CN115490996A - Epoxy resin composite material and processing method thereof - Google Patents
Epoxy resin composite material and processing method thereof Download PDFInfo
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- CN115490996A CN115490996A CN202211194418.1A CN202211194418A CN115490996A CN 115490996 A CN115490996 A CN 115490996A CN 202211194418 A CN202211194418 A CN 202211194418A CN 115490996 A CN115490996 A CN 115490996A
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 65
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 238000003672 processing method Methods 0.000 title claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 68
- 238000010438 heat treatment Methods 0.000 claims abstract description 49
- 238000003756 stirring Methods 0.000 claims abstract description 46
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 40
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 36
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- 239000000126 substance Substances 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 18
- 238000001291 vacuum drying Methods 0.000 claims description 17
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 claims description 10
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical group CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 8
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical group C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- MWQBWSPPTQGZII-UHFFFAOYSA-N ethoxy(phenyl)phosphinic acid Chemical compound CCOP(O)(=O)C1=CC=CC=C1 MWQBWSPPTQGZII-UHFFFAOYSA-N 0.000 claims description 7
- UVBBCQLPTZEDHT-UHFFFAOYSA-N pent-4-en-1-amine Chemical compound NCCCC=C UVBBCQLPTZEDHT-UHFFFAOYSA-N 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 238000009849 vacuum degassing Methods 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 4
- 238000010907 mechanical stirring Methods 0.000 claims description 4
- 239000012044 organic layer Substances 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000003607 modifier Substances 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims 2
- 238000000746 purification Methods 0.000 claims 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 16
- 239000003063 flame retardant Substances 0.000 abstract description 16
- 239000011159 matrix material Substances 0.000 abstract description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 9
- 230000002195 synergetic effect Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 4
- 230000003993 interaction Effects 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical class OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02W30/62—Plastics recycling; Rubber recycling
Abstract
The invention discloses an epoxy resin composite material and a processing method thereof, belonging to the technical field of composite materials and comprising the following raw materials in parts by weight: 100 parts of epoxy resin, 4-7 parts of modified graphene oxide, 18-25 parts of curing agent and 9-12 parts of accelerator; stirring, mixing and ultrasonically treating the raw materials, and curing by gradient heating to obtain the epoxy resin composite material. According to the invention, modified graphene oxide is adopted as a raw material, an organic molecular chain is grafted on the surface of the graphene oxide, the organic molecular chain belongs to a multi-element synergistic flame-retardant component, and the synergistic flame-retardant effect is exerted in a condensed phase and a gas phase, so that the epoxy resin has good flame retardance; in addition, the organic molecular chain has good compatibility with a matrix, and benzene rings contained in the organic molecular chain and benzene rings in epoxy resin have pi-pi interaction, so that the interface compatibility of graphene oxide and the epoxy resin matrix is improved, and the mechanical property and the flame retardant property of the composite material are improved.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to an epoxy resin composite material and a processing method thereof.
Background
As an important thermosetting polymer, epoxy resin has excellent mechanical properties, adhesive properties, dimensional stability and chemical resistance, and is widely applied to the fields of adhesives, coatings, electronic packaging, composite material manufacturing and the like.
The nanometer reinforced material has powerful promotion effect on the future development of aerospace industry due to light weight, high strength and multiple functions. And among them, graphene is the more of the blur in the nanoenhancer family. In recent years, graphene reinforced nanocomposites have been stronger and lighter than other nanoreinforced composites, which is why graphene is one of the best candidates for composite design as reinforcement. In addition, the graphene has excellent mechanical properties and outstanding electrical and thermal properties, and a better choice is provided for the design, preparation and application of a structure-function integrated material in the development of aerospace industry in the future. However, graphene itself is a two-dimensional nanomaterial and cannot be independently applied, so that the graphene is an important way for realizing application. The graphene and the epoxy resin are made into the composite material, so that the composite material has good comprehensive performance, and researches show that good and bad dispersibility of the graphene in a matrix are decisive factors influencing high and low performance of the composite material.
In addition, the epoxy resin has poor flame retardancy, the oxygen index of the epoxy resin is usually 18-22, and the epoxy resin belongs to flammable materials, so that the application of the epoxy resin in some fields with high requirements on fire safety is limited.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an epoxy resin composite material and a processing method thereof.
The epoxy resin composite material adopts the modified graphene oxide as a raw material, and an organic molecular chain is grafted on the surface of the graphene oxide, belongs to multi-element (N, P and S) synergistic flame-retardant components, and can play a synergistic flame-retardant role in a condensed phase and a gas phase, so that the epoxy resin has good flame retardance; in addition, the organic molecular chain has good compatibility with a matrix, and benzene rings contained in the organic molecular chain and benzene rings in epoxy resin have pi-pi interaction, so that the interface compatibility of graphene oxide and the epoxy resin matrix is improved, uniform dispersion in the composite material is realized, and the mechanical property and the flame retardant property of the composite material are improved.
The purpose of the invention can be realized by the following technical scheme:
an epoxy resin composite material comprises the following raw materials in parts by weight: 100 parts of epoxy resin, 4-7 parts of modified graphene oxide, 18-25 parts of curing agent and 9-12 parts of accelerator.
Further, the curing agent is methyl tetrahydrophthalic anhydride.
Further, the accelerator is 2,4, 6-tris (dimethylaminomethyl) phenol.
Further, the epoxy resin is bisphenol a type epoxy resin or bisphenol F type epoxy resin.
Further, the modified graphene oxide is prepared by the following steps:
s1, adding ethyl phenylphosphonate and toluene into a four-neck flask provided with a mechanical stirring device and a condenser, uniformly stirring, adding phosphorus pentasulfide, introducing nitrogen, raising the temperature to 55 ℃, stirring for 2 hours, cooling to 40 ℃, adding phosphorus pentasulfide again, introducing nitrogen, reacting for 15 hours, stopping heating, cooling to room temperature, removing a solvent by rotary evaporation, adding chloroform into the obtained oily liquid, oscillating, filtering, transferring the liquid into a three-neck flask, adding saturated NaHCO, reacting for 15 hours, adding 3 Stirring the solution under nitrogen for 20min, separating the organic layer, and adding anhydrous Na 2 SO 4 Drying, suction filtering, vacuum rotary evaporating to remove chloroform, and weighing the product with acetonitrileCrystallizing, and finally drying in a vacuum drying oven at 40 ℃ for 8 hours to obtain a modified substance; the ratio of the dosage of the ethyl phenylphosphonate, the toluene and the phosphorus pentasulfide is 0.5 mol;
phenylphosphonic acid ethyl ester and P 2 S 5 The chemical reaction is carried out to generate a modified product, and the reaction process is as follows:
s2, mixing graphene oxide and DMF (N, N-dimethylformamide), performing ultrasonic treatment at room temperature for 10min, transferring the mixed solution into a three-neck flask, adding 4-penten-1-amine into the system, continuously stirring for 1h, then adding EDC-HCl (1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and a coupling agent), transferring the three-neck flask into a water bath at 60 ℃, continuously stirring for reacting for 6h, performing centrifugal separation, washing for 4-5 times by using absolute ethyl alcohol to remove unreacted substances, and finally, putting the product into a vacuum drying oven at 50 ℃ and drying to constant weight to obtain grafted graphene; the dosage ratio of the graphene oxide, DMF, 4-pentenyl-1-amine and EDC-HCl is 0.1g;
the surface of the graphene oxide contains a large number of oxygen-containing functional groups, and the step utilizes-COOH on the surface of the graphene oxide and-NH on 4-penten-1-amine molecules 2 The reaction is carried out, 4-pentene-1-amine molecular chains are grafted on the surface of graphene oxide through amido bonds to form grafted graphene, and the reaction process is as follows:
s3, mixing the grafted graphene and DMF, performing room temperature ultrasound for 10min, transferring the mixed solution to a four-neck flask provided with a mechanical stirrer, a condenser pipe and a nitrogen inlet and outlet, adding a modifier, introducing nitrogen, heating to 80 ℃, stirring for reaction for 6h, cooling to room temperature, performing centrifugal separation, washing with absolute ethyl alcohol for 4-5 times to remove unreacted substances, and finally, putting the product in a 50 ℃ vacuum drying oven for drying to constant weight to obtain modified graphene oxide; the dosage ratio of the grafted graphene to the modified substance to the DMF is 0.1g;
the molecular chain grafted on the surface of the grafted graphene oxide contains C = C, unsaturated carbon-carbon double bonds and the graft are subjected to chemical reaction to obtain the modified graphene oxide, and the reaction process is as follows:
grafting an organic molecular chain on the surface of the obtained modified graphene oxide, wherein the grafted organic molecular chain contains a sulfur-containing group, a phosphate group, a nitrogen-containing group and a benzene ring; during the combustion process, sulfuric acid (strong acid), polyphosphoric acid and pyrophosphoric acid compounds generated by the S element can promote the further degradation of the flame retardant, so that the condensed phase flame retardant capability can be enhanced, the residual carbon content of the substances can be increased, and the epoxy resin composite material has better carbon forming capability; in addition, during the combustion process, the sulfur and nitrogen-containing non-combustible gas (SO) can be decomposed and generated 2 、NO x ) Diluting oxygen, and decomposing to generate P and OP free radicals in the high-temperature combustion process to combine with OH and H free radicals with high activity to terminate the chain reaction of gas phase so as to achieve the quenching effect; therefore, the organic molecular chain grafted on the surface of the graphene oxide belongs to a multi-element (N, P and S) synergistic flame-retardant component, and can play a synergistic flame-retardant role in a condensed phase and a gas phase, so that the epoxy resin has good flame retardance; in addition, it needs to be further explained that-OH, epoxy group and the like contained in the graphene oxide can generate a chemical bonding effect with an epoxy resin matrix, the introduced organic molecular chain has good compatibility with the matrix, and a benzene ring contained in the graphene oxide has pi-pi interaction with a benzene ring in the epoxy resin, so that the modified graphene oxide has good interface compatibility with the epoxy resin matrix, can realize uniform dispersion in the composite material, and improves the mechanical property and the flame retardant property of the composite material.
A processing method of an epoxy resin composite material comprises the following steps:
mixing epoxy resin and a curing agent, heating in a 70 ℃ water bath, magnetically stirring at a rotating speed of 450r/min for 1h, stopping stirring, adding modified graphene oxide, continuously stirring for 2h, then adding an accelerant, heating in a 60 ℃ water bath, magnetically stirring for 30min at 500r/min, ultrasonically dispersing for 30min (500W power), placing the mixed solution after ultrasonic dispersion into a vacuum drying oven, heating at 70 ℃ and vacuum degassing for 2h, pouring the mixed solution into a polytetrafluoroethylene mold, placing the polytetrafluoroethylene mold into a drying oven for gradient heating and curing, and performing gradient heating and curing parameters: heating at 120 ℃ for 2h, heating at 150 ℃ for 2h, heating at 100 ℃ for 12h, and naturally cooling to room temperature to obtain the epoxy resin composite material.
The invention has the beneficial effects that:
the epoxy resin composite material adopts the modified graphene oxide as a raw material, and an organic molecular chain is grafted on the surface of the graphene oxide, belongs to multi-element (N, P and S) synergistic flame-retardant components, and can play a synergistic flame-retardant role in a condensed phase and a gas phase, so that the epoxy resin has good flame retardance; in addition, the organic molecular chain has good compatibility with a matrix, and benzene rings contained in the organic molecular chain and benzene rings in epoxy resin have pi-pi interaction, so that the interface compatibility of graphene oxide and the epoxy resin matrix is improved, uniform dispersion in the composite material is realized, and the mechanical property and the flame retardant property of the composite material are improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The modified graphene oxide is prepared by the following steps:
s1, adding 0.5mol of ethyl phenylphosphonate and 300mL of toluene into a four-neck flask provided with a mechanical stirring device and a condenser tube, uniformly stirring,adding 0.125mol of phosphorus pentasulfide, introducing nitrogen, raising the temperature to 55 ℃, stirring for 2h, reducing the temperature to 40 ℃ after the reaction is finished, adding 0.125mol of phosphorus pentasulfide again, introducing nitrogen, reacting for 15h, stopping heating, cooling to room temperature, removing the solvent by rotary evaporation, adding 200mL of chloroform into the obtained oily liquid, performing oscillation suction filtration, transferring the liquid into a three-neck flask, adding 300mL of saturated NaHCO 3 Stirring the solution under nitrogen for 20min, separating the organic layer, and adding anhydrous Na 2 SO 4 Drying, suction filtering, vacuum rotary evaporating to remove chloroform, recrystallizing the product with acetonitrile, and finally drying in a vacuum drying oven at 40 ℃ for 8h to obtain a modified substance;
s2, mixing 0.1g of graphene oxide and 60mL of DMF (N, N-dimethylformamide), performing ultrasonic treatment at room temperature for 10min, transferring the mixed solution into a three-neck flask, adding 120mL of 4-penten-1-amine into the system, continuously stirring for 1h, then adding 5mg of EDC-HCl (1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and a coupling agent), transferring the three-neck flask into a water bath at 60 ℃, continuously stirring for reaction for 6h, performing centrifugal separation, washing for 4 times by using absolute ethyl alcohol to remove unreacted substances, and finally, putting the product into a vacuum drying oven at 50 ℃ and drying to constant weight to obtain grafted graphene;
s3, mixing 0.1g of grafted graphene with 300mL of DMF, performing ultrasonic treatment at room temperature for 10min, transferring the mixed solution to a four-neck flask provided with a mechanical stirrer, a condenser pipe and a nitrogen inlet and outlet, adding 0.36g of modified substance, introducing nitrogen, heating to 80 ℃, stirring for reaction for 6h, cooling to room temperature, performing centrifugal separation, washing for 4 times with absolute ethyl alcohol to remove unreacted substances, and finally, putting the product in a 50 ℃ vacuum drying oven to dry to constant weight to obtain the modified graphene oxide.
Example 2
The modified graphene oxide is prepared by the following steps:
s1, adding 1.0mol of ethyl phenylphosphonate and 600mL of toluene into a four-neck flask provided with a mechanical stirring device and a condenser tube, uniformly stirring, adding 0.25mol of phosphorus pentasulfide, introducing nitrogen, raising the temperature to 55 ℃, stirring for 2h, reducing the temperature to 40 ℃, adding 0.25mol of phosphorus pentasulfide again, introducing nitrogen, reacting for 15h,stopping heating, cooling to room temperature, removing the solvent by rotary evaporation, adding 400mL of chloroform into the obtained oily liquid, performing suction filtration by oscillation, transferring the liquid into a three-neck flask, and adding 600mL of saturated NaHCO 3 Stirring the solution for 20min under nitrogen protection, separating the solution to obtain organic layer, and adding anhydrous Na 2 SO 4 Drying, suction filtering, vacuum rotary evaporating to remove chloroform, recrystallizing the product with acetonitrile, and finally drying in a vacuum drying oven at 40 ℃ for 8h to obtain a modified substance;
s2, mixing 0.2g of graphene oxide and 120mL of DMF (N, N-dimethylformamide), performing ultrasonic treatment at room temperature for 10min, transferring the mixed solution to a three-neck flask, adding 240mL of 4-pentene-1-amine into the system, continuously stirring for 1h, then adding 10mg of EDC-HCl (1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and a coupling agent), transferring the three-neck flask to a water bath at 60 ℃, continuously stirring for reacting for 6h, performing centrifugal separation, washing with absolute ethyl alcohol for 5 times to remove unreacted substances, and finally putting the product into a vacuum drying oven at 50 ℃ to dry to constant weight to obtain grafted graphene;
s3, mixing 0.2g of grafted graphene with 600mL of DMF (dimethyl formamide), performing ultrasonic treatment at room temperature for 10min, transferring the mixed solution to a four-neck flask with a mechanical stirrer, a condenser pipe and a nitrogen inlet and outlet, adding 0.72g of modified substance, introducing nitrogen, heating to 80 ℃, stirring for reaction for 6h, cooling to room temperature, performing centrifugal separation, washing for 5 times with absolute ethyl alcohol to remove unreacted substances, and finally, putting the product into a 50-DEG vacuum drying oven to be dried to constant weight to obtain the modified graphene oxide.
Example 3
An epoxy resin composite material comprises the following raw materials by weight: 1000g of bisphenol A epoxy resin, 40g of modified graphene oxide, 180g of methyl tetrahydrophthalic anhydride and 90g of 2,4, 6-tris (dimethylaminomethyl) phenol;
the epoxy resin composite material is processed by the following processing method:
mixing bisphenol A epoxy resin and methyl tetrahydrophthalic anhydride, heating in 70 ℃ water bath, magnetically stirring at the rotating speed of 450r/min for 1h, stopping stirring, adding modified graphene oxide, continuously stirring for 2h, then adding 2,4, 6-tris (dimethylaminomethyl) phenol, heating in 60 ℃ water bath, magnetically stirring at 500r/min for 30min, ultrasonically dispersing for 30min (500W power), placing the mixed solution after ultrasonic dispersion into a vacuum drying oven, heating at 70 ℃ and vacuum degassing for 2h, pouring the mixed solution into a polytetrafluoroethylene mold, placing into a drying oven for gradient heating and curing, wherein the gradient heating and curing parameters are as follows: heating at 120 ℃ for 2h, heating at 150 ℃ for 2h, heating at 100 ℃ for 12h, and naturally cooling to room temperature to obtain the epoxy resin composite material.
Example 4
An epoxy resin composite material comprises the following raw materials by weight: 1000g of bisphenol F epoxy resin, 55g of modified graphene oxide, 215g of methyl tetrahydrophthalic anhydride and 105g of 2,4, 6-tris (dimethylaminomethyl) phenol;
the epoxy resin composite material is processed by the following processing method:
mixing bisphenol F type epoxy resin and methyl tetrahydrophthalic anhydride, heating in 70 ℃ water bath, magnetically stirring at the rotating speed of 450r/min for 1h, stopping stirring, adding modified graphene oxide, continuously stirring for 2h, then adding 2,4, 6-tris (dimethylaminomethyl) phenol, heating in 60 ℃ water bath, magnetically stirring at 500r/min for 30min, ultrasonically dispersing for 30min (500W power), placing the mixed solution after ultrasonic dispersion into a vacuum drying box, heating at 70 ℃ and vacuum degassing for 2h, pouring the mixed solution into a polytetrafluoroethylene mold, placing into a drying box for gradient heating and curing, wherein the gradient heating and curing parameters are as follows: heating at 120 ℃ for 2h, heating at 150 ℃ for 2h, heating at 100 ℃ for 12h, and naturally cooling to room temperature to obtain the epoxy resin composite material.
Example 5
An epoxy resin composite material comprises the following raw materials by weight: 1000g of bisphenol A epoxy resin, 70g of modified graphene oxide, 250g of methyl tetrahydrophthalic anhydride and 120g of 2,4, 6-tris (dimethylaminomethyl) phenol;
the epoxy resin composite material is processed by the following processing method:
mixing bisphenol A epoxy resin and methyl tetrahydrophthalic anhydride, heating in 70 ℃ water bath, magnetically stirring at the rotating speed of 450r/min for 1h, stopping stirring, adding modified graphene oxide, continuously stirring for 2h, then adding 2,4, 6-tris (dimethylaminomethyl) phenol, heating in 60 ℃ water bath, magnetically stirring at 500r/min for 30min, ultrasonically dispersing for 30min (500W power), placing the mixed solution after ultrasonic dispersion into a vacuum drying oven, heating at 70 ℃ and vacuum degassing for 2h, pouring the mixed solution into a polytetrafluoroethylene mold, placing into a drying oven for gradient heating and curing, wherein the gradient heating and curing parameters are as follows: heating at 120 ℃ for 2h, heating at 150 ℃ for 2h, heating at 100 ℃ for 12h, and naturally cooling to room temperature to obtain the epoxy resin composite material.
Comparative example
The modified graphene oxide in example 3 was replaced with ordinary graphene oxide, and the remaining raw materials and preparation process were unchanged.
The epoxy resin composites obtained in examples 3 to 5 and comparative example were processed into test specimens and subjected to the following performance tests:
and (3) testing mechanical properties: testing by using a universal testing machine, wherein the tensile speed is as follows: 50mm/min;
limiting oxygen index test (LOI): testing by adopting an intelligent oxygen index tester according to the ASTM D-2863 standard;
vertical burning test (UL-94): testing by a vertical combustion tester according to the ASTM D-3810 standard;
the results obtained are shown in the following table:
| example 3 | Example 4 | Example 5 | Comparative example | |
| Tensile strength/MPa | 82.5 | 80.9 | 81.6 | 76.4 |
| Impact Strength/kJ.m -2 | 6.38 | 6.21 | 6.35 | 5.95 |
| LOI index/% | 27.9 | 27.5 | 27.8 | 20.5 |
| UL-94 rating | V-0 | V-0 | V-0 | Grade free |
As can be seen from the data in the table above, the epoxy resin composite material obtained by the invention has good mechanical properties and flame retardant properties; and the data of the comparative example show that the graphene oxide can endow the composite material with flame retardant property after being modified, can be more uniformly dispersed in the composite material, and can improve the mechanical property of the composite material.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only, and it will be appreciated by those skilled in the art that various modifications, additions and substitutions can be made to the embodiments described without departing from the scope of the invention as defined in the appended claims.
Claims (10)
1. The epoxy resin composite material is characterized by comprising the following raw materials in parts by weight: 100 parts of epoxy resin, 4-7 parts of modified graphene oxide, 18-25 parts of curing agent and 9-12 parts of accelerator;
further, the modified graphene oxide is prepared by the following steps:
s1, adding ethyl phenylphosphonate and toluene into a four-neck flask provided with a mechanical stirring device and a condenser, uniformly stirring, adding phosphorus pentasulfide, introducing nitrogen, raising the temperature to 55 ℃, stirring for 2 hours, cooling to 40 ℃ after the stirring, adding phosphorus pentasulfide again, introducing nitrogen, reacting for 15 hours, stopping heating, cooling to room temperature, removing a solvent by rotary evaporation, and purifying to obtain a modified substance;
s2, mixing graphene oxide and DMF, performing ultrasonic treatment at room temperature for 10min, transferring the mixed solution to a three-neck flask, adding 4-pentene-1-amine into the system, continuing stirring for 1h, then adding EDC-HCl, transferring the three-neck flask to a water bath at 60 ℃, continuing stirring for reaction for 6h, performing centrifugal separation, washing for 4-5 times by using absolute ethyl alcohol to remove unreacted substances, and finally, putting the product into a vacuum drying oven at 50 ℃ and drying to constant weight to obtain grafted graphene;
s3, mixing the grafted graphene and DMF, performing room temperature ultrasound for 10min, transferring the mixed solution to a four-neck flask provided with a mechanical stirrer, a condenser pipe and a nitrogen inlet and outlet, adding the modifier, introducing nitrogen, heating to 80 ℃, stirring for reaction for 6h, cooling to room temperature, performing centrifugal separation, washing with absolute ethyl alcohol for 4-5 times to remove unreacted substances, and finally, putting the product in a 50 ℃ vacuum drying oven for drying to constant weight to obtain the modified graphene oxide.
2. The epoxy resin composite material as claimed in claim 1, wherein the specific operation of purification in step S1 is as follows: adding chloroform into the obtained oily liquid, oscillating, filtering, transferring the liquid into a three-neck flask, and adding saturated NaHCO 3 Stirring the solution for 20min under nitrogen protection, separating the solution to obtain organic layer, and adding anhydrous Na 2 SO 4 Drying, suction filtering, vacuum rotary evaporating to remove chloroform, recrystallizing the product with acetonitrile, and finally drying in a vacuum drying oven at 40 ℃ for 8h to obtain the modified substance.
3. The epoxy resin composite material as claimed in claim 1, wherein the ratio of the amounts of ethyl phenylphosphonate, toluene and phosphorus pentasulfide used in step S1 is 0.5 mol.
4. The epoxy resin composite material as claimed in claim 1, wherein the ratio of the usage amounts of graphene oxide, DMF, 4-penten-1-amine, EDC-HCl in step S2 is 0.1g.
5. The epoxy resin composite material as claimed in claim 1, wherein the ratio of the amounts of the grafted graphene, the modified material and DMF in step S3 is 0.1g.
6. The epoxy resin composite material as claimed in claim 1, wherein the curing agent is methyl tetrahydrophthalic anhydride.
7. The epoxy resin composite as claimed in claim 1, wherein the accelerator is 2,4, 6-tris (dimethylaminomethyl) phenol.
8. The epoxy resin composite material according to claim 1, wherein the epoxy resin is a bisphenol A type epoxy resin or a bisphenol F type epoxy resin.
9. The processing method of the epoxy resin composite material as claimed in claim 1, comprising the steps of:
mixing epoxy resin and a curing agent, heating in a 70 ℃ water bath, magnetically stirring at the rotating speed of 450r/min for 1h, stopping stirring, adding modified graphene oxide, continuously stirring for 2h, then adding an accelerant, heating in a 60 ℃ water bath, magnetically stirring at 500r/min for 30min, further ultrasonically dispersing for 30min, placing the mixed solution after ultrasonic dispersion into a vacuum drying oven, heating at 70 ℃ for vacuum degassing for 2h, pouring the mixed solution into a polytetrafluoroethylene mold, placing into a drying oven for gradient heating and curing, and naturally cooling to room temperature after curing is completed to obtain the epoxy resin composite material.
10. The processing method of epoxy resin composite material as claimed in claim 9, wherein the ultrasonic power is 500W; gradient heating curing parameters: heating at 120 deg.C for 2h, heating at 150 deg.C for 2h, and heating at 100 deg.C for 12h.
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