CN117467246B - Carbon fiber/glass fiber reinforced epoxy resin composite material and preparation method thereof - Google Patents
Carbon fiber/glass fiber reinforced epoxy resin composite material and preparation method thereof Download PDFInfo
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 78
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 78
- 239000002131 composite material Substances 0.000 title claims abstract description 72
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 59
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 59
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000003365 glass fiber Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 32
- 229920000570 polyether Polymers 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 16
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 15
- 238000001723 curing Methods 0.000 claims description 69
- 238000010438 heat treatment Methods 0.000 claims description 69
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 26
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 23
- 239000000835 fiber Substances 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- 230000000630 rising effect Effects 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000007598 dipping method Methods 0.000 claims description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims description 9
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000013007 heat curing Methods 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000032683 aging Effects 0.000 abstract description 12
- 239000011159 matrix material Substances 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 7
- 230000009471 action Effects 0.000 abstract description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 3
- 238000007259 addition reaction Methods 0.000 abstract description 2
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 2
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 12
- JUXXCHAGQCBNTI-UHFFFAOYSA-N 1-n,1-n,2-n,2-n-tetramethylpropane-1,2-diamine Chemical group CN(C)C(C)CN(C)C JUXXCHAGQCBNTI-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 150000001409 amidines Chemical class 0.000 description 6
- 239000002245 particle Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000010954 inorganic particle Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 1
- 239000011157 advanced composite material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002464 physical blending Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
Classifications
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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
-
- 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
-
- 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
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- 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
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
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- 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
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a carbon fiber/glass fiber reinforced epoxy resin composite material and a preparation method thereof, wherein single-end hydroxyl polyether and maleic anhydride are utilized to react to obtain single-end carboxylic acid polyether, then chopped carbon fiber and glass fiber are immersed in the single-end carboxylic acid polyether, polyether containing double bonds is coated on the surfaces of the chopped carbon fiber and the glass fiber, and the polyether and epoxy resin have better compatibility to improve the dispersion of the chopped carbon fiber and the glass fiber in a matrix, and meanwhile, the polyether can also improve the toughness of the epoxy resin; simultaneously, carbon-carbon double bonds are introduced into the surface of the nano titanium dioxide by modifying the nano titanium dioxide, then an addition reaction occurs between the carbon-carbon double bonds in the thermosetting forming process, and the nano titanium dioxide is introduced into the epoxy resin composite material by chemical action, so that the tensile strength of the composite material is further improved; in addition, the nano titanium dioxide has good ultraviolet aging resistance, and the aging resistance of the composite material is obviously improved.
Description
Technical Field
The invention relates to the technical field of epoxy resin matrix composite materials, in particular to a carbon fiber/glass fiber reinforced epoxy resin composite material and a preparation method thereof.
Background
Epoxy resin is an advanced composite resin matrix, and has excellent properties, particularly in terms of wear resistance, mechanical properties, adhesion, chemical stability, electrical insulation, adhesion to a substrate, and the like, so that the epoxy resin can be seen in the fields of machinery, chemical industry, construction, railway transportation, aerospace, and the like. However, the epoxy resin is crosslinked and solidified to form a three-dimensional network structure, the crosslinking density is increased, the internal stress is improved, and the solidified product is hard and brittle, has poor toughness and is easy to crack, so that the application of the epoxy resin in the high-strength and high-toughness composite material is limited, and the epoxy resin is required to be modified to achieve the purposes of reinforcing and toughening.
The prior method for toughening and modifying the epoxy resin generally comprises the following steps: inorganic particle toughened epoxy resin, interpenetrating network toughened epoxy resin and chemically modified toughened epoxy resin, wherein the inorganic particle toughened epoxy resin: adding dispersed phases such as rigid inorganic particles, rubber particles, thermoplastic resin, liquid crystal polymer, core-shell structure polymer and the like into epoxy resin; interpenetrating network toughened epoxy: forming an interpenetrating network or a semi-interpenetrating network or a sea-island structure in an epoxy resin system to achieve the aim of toughening; chemically modified toughened epoxy: the flexible chain segment is introduced into the main structure of the epoxy resin to achieve the purpose of toughening. Although the above methods can improve impact strength, they often do so at the expense of tensile strength of the material.
Chinese patent document CN201610235881.4 discloses a carbon fiber reinforced epoxy resin composite material, which comprises the following components in parts by weight: 45-60 parts of epoxy resin, 10-15 parts of toughening agent, 4-5 parts of slipping agent, 15-20 parts of curing agent, 1-2 parts of accelerator, 5-10 parts of thickener, 1-3 parts of release agent, 5-10 parts of compatibilizer, 10-15 parts of nano barium sulfate, 8-12 parts of UHMWPE and 10-16 parts of carbon fiber, and the prepared carbon fiber reinforced epoxy resin composite material has better scratch resistance, but the mechanical property of the composite material still needs to be improved.
The Chinese patent document CN202211085022.3 discloses a modified carbon fiber, a preparation method and application thereof and a modified carbon fiber epoxy resin composite material, and the surface of the carbon fiber is subjected to chemical activity and coarseness by introducing a graphene oxide film layer on the surface of the carbon fiber with pi-pi as acting force, so that the wettability with a resin matrix is improved, firm interaction is formed, the interface performance of the composite material is enhanced, but the aging resistance of the material is insufficient.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a carbon fiber/glass fiber reinforced epoxy resin composite material and a preparation method thereof, and the prepared composite material has good mechanical property and ageing resistance.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a preparation method of a carbon fiber/glass fiber reinforced epoxy resin composite material comprises the following steps:
S1, uniformly mixing single-end hydroxyl polyether and maleic anhydride, then adding a catalyst, namely p-toluenesulfonic acid, then introducing nitrogen, heating and stirring for reaction, adding chopped carbon fibers and glass fibers after the reaction is completed, dipping, taking out and drying to obtain modified composite fibers;
s2, dispersing nano titanium dioxide in an ethanol water solution, then adding a vinyl silane coupling agent into the solution, stirring the solution for 1 to 3 hours, and obtaining modified nano titanium dioxide through filtration, washing and drying;
And S3, uniformly mixing the epoxy resin, the modified composite fiber, the modified nano titanium dioxide, the curing agent and the azo diisobutylamidine hydrochloride, and placing the mixture into a forming die for heating, curing and forming to obtain the carbon fiber/glass fiber reinforced epoxy resin composite material.
Preferably, in the step S1, the mass ratio of the single-end hydroxyl polyether to the maleic anhydride to the p-toluenesulfonic acid to the chopped carbon fibers to the glass fibers is 100:8-12:1-2:5-10:5-10.
Preferably, in the step S1, the temperature of the heating and stirring reaction is 65-80 ℃, and the time of the heating and stirring reaction is 2-3 hours.
Preferably, in the step S2, the mass ratio of the nano titanium dioxide to the vinyl silane coupling agent is 8-10:1-3.
Preferably, in step S2, the vinyl silane coupling agent is selected from the group consisting of silane coupling agent A-151, silane coupling agent A-171, silane coupling agent A-172, and silane coupling agent A-173.
Preferably, in the step S3, the mass ratio of the epoxy resin to the modified composite fiber to the modified nano titanium dioxide to the curing agent to the azodiisobutylamidine hydrochloride is 80-100:10-20:5-10:10-15:1-3.
Preferably, in step S3, the curing agent is at least one selected from amine curing agents, polyamide curing agents, and imidazole curing agents.
Preferably, in step S3, the heat curing molding process is as follows: heating to 100-130 ℃ at the temperature rising rate of 10-15 ℃/min under the pressure of 0.2-0.3MPa, and curing for 1-2h; keeping the pressure unchanged, heating to 180-200 ℃ at a heating rate of 10-15 ℃/min, and curing for 10-20min.
The invention also provides the carbon fiber/glass fiber reinforced epoxy resin composite material prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention uses single-end hydroxyl polyether and maleic anhydride to react to obtain single-end carboxylic acid polyether, then the chopped carbon fiber and glass fiber are immersed in the single-end carboxylic acid polyether, the surfaces of the chopped carbon fiber and the glass fiber are coated with polyether containing double bonds, and the dispersion of the chopped carbon fiber and the glass fiber in the matrix is improved by using the better compatibility of the polyether and the epoxy resin, and meanwhile, the toughness of the epoxy resin can be improved by the polyether.
(2) The nano titanium dioxide belongs to inorganic rigid particles, has poor compatibility with an epoxy resin matrix, has low bonding strength when being directly blended, is easy to separate out, and has limited effect of improving the mechanical property of the composite material; in addition, the nano titanium dioxide has good ultraviolet aging resistance, and the aging resistance of the composite material is remarkably improved by introducing the nano titanium dioxide into the composite material.
Detailed Description
The present invention will be described in further detail with reference to the following preferred examples, but the present invention is not limited to the following examples.
Unless otherwise specified, the chemical reagents involved in the present invention are all commercially available.
A preparation method of a carbon fiber/glass fiber reinforced epoxy resin composite material comprises the following steps:
S1, uniformly mixing single-end hydroxyl polyether and maleic anhydride, adding a catalyst, namely p-toluenesulfonic acid, then introducing nitrogen, heating and stirring for reaction, adding chopped carbon fibers and glass fibers after the reaction is completed, dipping, taking out and drying to obtain the modified composite fibers.
In this step, the mass ratio of the single-ended hydroxyl polyether, maleic anhydride, p-toluenesulfonic acid, chopped carbon fibers and glass fibers is 100:8-12:1-2:5-10:5-10, and more preferably 100:8-10:1-2:6-8:6-8.
The temperature of the heating and stirring reaction is 65-80 ℃, more preferably 65 ℃, 70 ℃, 75 ℃ and 80 ℃.
The reaction time of heating and stirring is 2-3h, preferably 2h, 2.5h and 3h.
The soaking time is 1-5h, preferably 1h, 2h, 3h, 4h, 5h.
In the step, single-end hydroxyl polyether and maleic anhydride are utilized to react to obtain single-end carboxylic polyether, then chopped carbon fiber and glass fiber are immersed in the single-end carboxylic polyether, polyether containing double bonds is coated on the surfaces of the chopped carbon fiber and the glass fiber, and the dispersion of the chopped carbon fiber and the glass fiber in a matrix is improved by utilizing the good compatibility of the polyether and the epoxy resin, and meanwhile, the toughness of the epoxy resin can be improved by the polyether.
S2, dispersing nano titanium dioxide in ethanol water solution, then adding a vinyl silane coupling agent into the solution, stirring the solution for 1 to 3 hours, and obtaining the modified nano titanium dioxide through filtration, washing and drying.
In the step, the particle size of the selected nano titanium dioxide is 20-40nm;
the mass ratio of the nano titanium dioxide to the vinyl silane coupling agent is 8-10:1-3, and is more preferably 8:1, 8:2, 8:3, 9:1, 9:2, 9:3, 10:1, 10:2 and 10:3.
Wherein the vinyl silane coupling agent is selected from silane coupling agent A-151, silane coupling agent A-171, silane coupling agent A-172 or silane coupling agent A-173.
And S3, uniformly mixing the epoxy resin, the modified composite fiber, the modified nano titanium dioxide, the curing agent and the azo diisobutylamidine hydrochloride, and placing the mixture into a forming die for heating, curing and forming to obtain the carbon fiber/glass fiber reinforced epoxy resin composite material.
In this step, the mass ratio of the epoxy resin, the modified composite fiber, the modified nano titanium dioxide, the curing agent and the azobisisobutyrimidine hydrochloride is 80-100:10-20:5-10:10-15:1-3, preferably 80:15:5:10:1, 80:20:10:10:3, 90:15:10:15:2, 100:10:10:15:3, 100:20:10:15:3, 100:15:10:10:2.
In some embodiments, the epoxy resin may be a combination of one or more of bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin.
In some embodiments, the curing agent is at least one selected from amine curing agents, polyamide curing agents and imidazole curing agents, and in the embodiments of the application, the amine curing agent is selected, and the epoxy resin cured by the amine has excellent performance and excellent heat resistance and chemical stability.
The heating curing molding process comprises the following steps: heating to 100-130 ℃ at the temperature rising rate of 10-15 ℃/min under the pressure of 0.2-0.3MPa, and curing for 1-2h; keeping the pressure unchanged, heating to 180-200 ℃ at a heating rate of 10-15 ℃/min, and curing for 10-20min;
In some embodiments, the heat cure molding process is: heating to 100 ℃ at the temperature rising rate of 10 ℃/min under the pressure of 0.2MPa, and curing for 1h; then keeping the pressure unchanged, heating to 180 ℃ at a heating rate of 10 ℃/min, and curing for 10min;
In some embodiments, the heat cure molding process is: heating to 120 ℃ at the temperature rising rate of 15 ℃/min under the pressure of 0.25MPa, and curing for 2h; then keeping the pressure unchanged, heating to 200 ℃ at a heating rate of 15 ℃/min, and curing for 20min;
in some embodiments, the heat cure molding process is: heating to 130 ℃ at the temperature rising rate of 15 ℃/min under the pressure of 0.3MPa, and curing for 2h; then, the pressure was kept unchanged, and the mixture was heated to 200℃at a heating rate of 15℃per minute and cured for 20 minutes.
In the step, in the thermosetting molding process, under the action of an initiator azo diisobutylamidine hydrochloride, an addition reaction is carried out between carbon-carbon double bonds, nano titanium dioxide is introduced into the epoxy resin composite material through chemical action, the problem that the nano titanium dioxide is easy to separate out is solved, and the nano titanium dioxide is combined through chemical action, so that compared with physical blending, the bonding strength is obviously improved, and the mechanical property of the composite material is further improved; in addition, the nano titanium dioxide has good ultraviolet aging resistance, and the aging resistance of the composite material is remarkably improved by introducing the nano titanium dioxide into the composite material.
The invention is further illustrated by the following examples.
The brand of the single-end hydroxyl polyether used in the invention is polyether BPE-1000, and the molecular weight is 900-1100; the length of the chopped carbon fiber is 5-10mm; the length of the glass fiber is 3-6mm; the particle size of the nano titanium dioxide is 20-40nm; the model of the epoxy resin is epoxy resin E-51; the curing agent is tetramethyl propylene diamine, CAS number: 110-95-2.
Example 1
A preparation method of a carbon fiber/glass fiber reinforced epoxy resin composite material comprises the following steps:
S1, uniformly mixing 100g of single-end hydroxyl polyether and 8g of maleic anhydride, then adding 1g of catalyst p-toluenesulfonic acid, then introducing nitrogen to exhaust air, heating and stirring at 65 ℃ for reaction for 2 hours, adding 6g of chopped carbon fiber and 8g of glass fiber after the reaction is completed, dipping for 2 hours, taking out, and drying at 60 ℃ to obtain modified composite fibers;
S2, dispersing 8g of nano titanium dioxide in 100mL of 60wt% ethanol water solution, then adding 1g of silane coupling agent A-171 into the solution, stirring the solution for 2 hours, and filtering, washing and drying the solution to obtain modified nano titanium dioxide;
S3, uniformly mixing 80g of epoxy resin E-51, 15g of modified composite fiber, 5g of modified nano titanium dioxide, 10g of curing agent tetramethyl propylene diamine and 1g of azo diisobutyl amidine hydrochloride, and placing the mixture into a forming die for heating, curing and forming, wherein the heating, curing and forming process comprises the following steps: heating to 120 ℃ at the temperature rising rate of 10 ℃/min under the pressure of 0.2MPa, and curing for 2h; keeping the pressure unchanged, heating to 180 ℃ at a heating rate of 10 ℃/min, and curing for 10min to obtain the carbon fiber/glass fiber reinforced epoxy resin composite material.
Example 2
A preparation method of a carbon fiber/glass fiber reinforced epoxy resin composite material comprises the following steps:
S1, uniformly mixing 100g of single-end hydroxyl polyether and 12g of maleic anhydride, then adding 2g of catalyst p-toluenesulfonic acid, then introducing nitrogen to exhaust air, heating and stirring at 65 ℃ for reaction for 2 hours, adding 10g of chopped carbon fiber and 5g of glass fiber after the reaction is completed, dipping for 2 hours, taking out, and drying at 60 ℃ to obtain modified composite fibers;
s2, dispersing 10g of nano titanium dioxide in 100mL of 60wt% ethanol water solution, then adding 2g of silane coupling agent A-151 into the solution, stirring the solution for 2h, and filtering, washing and drying the solution to obtain modified nano titanium dioxide;
S3, uniformly mixing 100g of epoxy resin E-51, 20g of modified composite fiber, 8g of modified nano titanium dioxide, 15g of curing agent tetramethyl propylene diamine and 2g of azo diisobutyl amidine hydrochloride, and placing the mixture into a forming die for heating, curing and forming, wherein the heating, curing and forming process comprises the following steps: heating to 120 ℃ at the temperature rising rate of 10 ℃/min under the pressure of 0.2MPa, and curing for 1h; keeping the pressure unchanged, heating to 200 ℃ at a heating rate of 10 ℃/min, and curing for 10min to obtain the carbon fiber/glass fiber reinforced epoxy resin composite material.
Example 3
A preparation method of a carbon fiber/glass fiber reinforced epoxy resin composite material comprises the following steps:
S1, uniformly mixing 100g of single-end hydroxyl polyether and 10g of maleic anhydride, then adding 2g of catalyst p-toluenesulfonic acid, then introducing nitrogen to exhaust air, heating and stirring at 65 ℃ for reaction for 2 hours, adding 5g of chopped carbon fiber and 10g of glass fiber after the reaction is completed, dipping for 2 hours, taking out, and drying at 60 ℃ to obtain modified composite fibers;
S2, dispersing 10g of nano titanium dioxide in 100mL of 60wt% ethanol water solution, then adding 3g of silane coupling agent A-173 into the solution, stirring the solution for 2 hours, and filtering, washing and drying the solution to obtain modified nano titanium dioxide;
S3, evenly mixing 85g of epoxy resin E-51, 15g of modified composite fiber, 10g of modified nano titanium dioxide, 15g of curing agent tetramethyl propylene diamine and 2g of azo diisobutyl amidine hydrochloride, and placing the mixture into a forming die for heating, curing and forming, wherein the heating, curing and forming process comprises the following steps: heating to 120 ℃ at the temperature rising rate of 10 ℃/min under the pressure of 0.2MPa, and curing for 1h; keeping the pressure unchanged, heating to 200 ℃ at a heating rate of 10 ℃/min, and curing for 10min to obtain the carbon fiber/glass fiber reinforced epoxy resin composite material.
Example 4
A preparation method of a carbon fiber/glass fiber reinforced epoxy resin composite material comprises the following steps:
s1, uniformly mixing 100g of single-end hydroxyl polyether and 12g of maleic anhydride, then adding 2g of catalyst p-toluenesulfonic acid, then introducing nitrogen to exhaust air, heating and stirring at 65 ℃ for reaction for 2 hours, adding 10g of chopped carbon fiber and 10g of glass fiber after the reaction is completed, dipping for 2 hours, taking out, and drying at 60 ℃ to obtain modified composite fibers;
s2, dispersing 10g of nano titanium dioxide in 100mL of 60wt% ethanol water solution, then adding 2g of silane coupling agent A-173 into the solution, stirring the solution for 2h, and filtering, washing and drying the solution to obtain modified nano titanium dioxide;
S3, uniformly mixing 80g of epoxy resin E-51, 20g of modified composite fiber, 10g of modified nano titanium dioxide, 15g of curing agent tetramethyl propylene diamine and 3g of azo diisobutyl amidine hydrochloride, and placing the mixture into a forming die for heating, curing and forming, wherein the heating, curing and forming process comprises the following steps: heating to 120 ℃ at the temperature rising rate of 10 ℃/min under the pressure of 0.2MPa, and curing for 1h; keeping the pressure unchanged, heating to 200 ℃ at the heating rate of 10 ℃/min, and curing for 20min to obtain the carbon fiber/glass fiber reinforced epoxy resin composite material.
Example 5
A preparation method of a carbon fiber/glass fiber reinforced epoxy resin composite material comprises the following steps:
S1, uniformly mixing 100g of single-end hydroxyl polyether and 9g of maleic anhydride, then adding 1.5g of catalyst p-toluenesulfonic acid, then introducing nitrogen to exhaust air, heating and stirring at 70 ℃ for reaction for 2 hours, adding 8g of chopped carbon fiber and 8g of glass fiber after the reaction is completed, dipping for 2 hours, taking out, and drying at 60 ℃ to obtain modified composite fibers;
s2, dispersing 8g of nano titanium dioxide in 100mL of 60wt% ethanol water solution, then adding 1g of silane coupling agent A-151 into the solution, stirring the solution for 2 hours, and filtering, washing and drying the solution to obtain modified nano titanium dioxide;
S3, uniformly mixing 80g of epoxy resin E-51, 16g of modified composite fiber, 6g of modified nano titanium dioxide, 12g of curing agent tetramethyl propylene diamine and 1g of azo diisobutyl amidine hydrochloride, and placing the mixture into a forming die for heating, curing and forming, wherein the heating, curing and forming process comprises the following steps: heating to 120 ℃ at the temperature rising rate of 10 ℃/min under the pressure of 0.2MPa, and curing for 2h; keeping the pressure unchanged, heating to 180 ℃ at a heating rate of 10 ℃/min, and curing for 10min to obtain the carbon fiber/glass fiber reinforced epoxy resin composite material.
Comparative example 1
A preparation method of a carbon fiber/glass fiber reinforced epoxy resin composite material comprises the following steps:
85g of epoxy resin E-51, 5g of chopped carbon fiber, 10g of glass fiber, 10g of nano titanium dioxide and 15g of curing agent tetramethyl propylene diamine are uniformly mixed and placed into a forming die for heat curing forming, wherein the heat curing forming process comprises the following steps: heating to 120 ℃ at the temperature rising rate of 10 ℃/min under the pressure of 0.2MPa, and curing for 1h; keeping the pressure unchanged, heating to 200 ℃ at a heating rate of 10 ℃/min, and curing for 10min to obtain the carbon fiber/glass fiber reinforced epoxy resin composite material.
Comparative example 2
A preparation method of a carbon fiber/glass fiber reinforced epoxy resin composite material comprises the following steps:
S1, uniformly mixing 100g of single-end hydroxyl polyether and 10g of maleic anhydride, then adding 2g of catalyst p-toluenesulfonic acid, then introducing nitrogen to exhaust air, heating and stirring at 65 ℃ for reaction for 2 hours, adding 5g of chopped carbon fiber and 10g of glass fiber after the reaction is completed, dipping for 2 hours, taking out, and drying at 60 ℃ to obtain modified composite fibers;
S2, uniformly mixing 85g of epoxy resin E-51, 15g of modified composite fiber, 10g of nano titanium dioxide, 15g of curing agent tetramethyl propylene diamine and 2g of azo diisobutyl amidine hydrochloride, and placing the mixture into a forming die for heating, curing and forming, wherein the heating, curing and forming process comprises the following steps: heating to 120 ℃ at the temperature rising rate of 10 ℃/min under the pressure of 0.2MPa, and curing for 1h; keeping the pressure unchanged, heating to 200 ℃ at a heating rate of 10 ℃/min, and curing for 10min to obtain the carbon fiber/glass fiber reinforced epoxy resin composite material.
The composites prepared in examples 1-5 and comparative examples 1-2 were subjected to performance testing, wherein tensile strength and elongation at break were measured according to the method of GB/T2567-2021, impact strength was measured according to the method of GB/T2571-2021, and the test results are shown in the following table:
| tensile Strength (MPa) | Elongation at break (%) | Impact Strength (kJ/m 2) | |
| Example 1 | 86.4 | 6.3 | 33.5 |
| Example 2 | 89.3 | 6.7 | 33.8 |
| Example 3 | 91.7 | 7.1 | 33.9 |
| Example 4 | 93.6 | 7.8 | 34.1 |
| Example 5 | 87.5 | 6.4 | 33.6 |
| Comparative example 1 | 53.8 | 3.9 | 26.7 |
| Comparative example 2 | 74.2 | 4.7 | 29.8 |
And (3) testing ultraviolet aging resistance, wherein the aging conditions are as follows: the tensile strength and impact strength of the composite material are tested at the ultraviolet intensity of 1500uw/cm 2, the aging temperature of 60 ℃ and the aging time of 360 hours, the initial mechanical property strength is 100%, the retention rate of the mechanical property is calculated, and the test results are shown in the following table:
| Tensile Strength retention (%) | Impact retention (%) | |
| Example 1 | 89.3％ | 86.1％ |
| Example 2 | 89.8％ | 87.2％ |
| Example 3 | 91.5％ | 87.6％ |
| Example 4 | 92.1％ | 88.7％ |
| Example 5 | 89.4％ | 86.3％ |
| Comparative example 1 | 74.6％ | 71.5％ |
| Comparative example 2 | 82.4％ | 79.9％ |
Finally, it should be noted that: the above examples are not intended to limit the present invention in any way. Modifications and improvements will readily occur to those skilled in the art upon the basis of the present invention. Accordingly, any modification or improvement made without departing from the spirit of the invention is within the scope of the invention as claimed.
Claims (6)
1. The preparation method of the carbon fiber/glass fiber reinforced epoxy resin composite material is characterized by comprising the following steps of:
S1, uniformly mixing single-end hydroxyl polyether and maleic anhydride, then adding a catalyst, namely p-toluenesulfonic acid, then introducing nitrogen, heating and stirring for reaction, adding chopped carbon fibers and glass fibers after the reaction is completed, dipping, taking out and drying to obtain modified composite fibers;
s2, dispersing nano titanium dioxide in an ethanol water solution, then adding a vinyl silane coupling agent into the solution, stirring the solution for 1 to 3 hours, and obtaining modified nano titanium dioxide through filtration, washing and drying;
S3, uniformly mixing the epoxy resin, the modified composite fiber, the modified nano titanium dioxide, the curing agent and the azo diisobutylamidine hydrochloride, and placing the mixture into a forming die for heating, curing and forming to obtain the carbon fiber/glass fiber reinforced epoxy resin composite material;
In the step S1, the mass ratio of the single-end hydroxyl polyether to the maleic anhydride to the p-toluenesulfonic acid to the chopped carbon fiber to the glass fiber is 100:8-12:1-2:5-10:5-10;
In the step S2, the mass ratio of the nano titanium dioxide to the vinyl silane coupling agent is 8-10:1-3;
In the step S3, the mass ratio of the epoxy resin to the modified composite fiber to the modified nano titanium dioxide to the curing agent to the azodiisobutylamidine hydrochloride is 80-100:10-20:5-10:10-15:1-3.
2. The method for preparing a carbon fiber/glass fiber reinforced epoxy resin composite material according to claim 1, wherein in the step S1, the temperature of the heating and stirring reaction is 65-80 ℃, and the time of the heating and stirring reaction is 2-3 hours.
3. The method for producing a carbon fiber/glass fiber reinforced epoxy resin composite according to claim 1, wherein in step S2, the vinyl silane coupling agent is selected from the group consisting of silane coupling agent a-151, silane coupling agent a-171, silane coupling agent a-172 and silane coupling agent a-173.
4. The method for producing a carbon fiber/glass fiber reinforced epoxy resin composite according to claim 1, wherein in step S3, the curing agent is at least one selected from the group consisting of amine curing agents, polyamide curing agents, and imidazole curing agents.
5. The method for preparing a carbon fiber/glass fiber reinforced epoxy resin composite material according to claim 1, wherein in step S3, the heat curing molding process is as follows: heating to 100-130 ℃ at the temperature rising rate of 10-15 ℃/min under the pressure of 0.2-0.3MPa, and curing for 1-2h; keeping the pressure unchanged, heating to 180-200 ℃ at a heating rate of 10-15 ℃/min, and curing for 10-20min.
6. The carbon fiber/glass fiber reinforced epoxy resin composite material prepared by the preparation method according to any one of claims 1 to 5.
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