CN115490996B - Epoxy resin composite material and processing method thereof - Google Patents
Epoxy resin composite material and processing method thereof Download PDFInfo
- Publication number
- CN115490996B CN115490996B CN202211194418.1A CN202211194418A CN115490996B CN 115490996 B CN115490996 B CN 115490996B CN 202211194418 A CN202211194418 A CN 202211194418A CN 115490996 B CN115490996 B CN 115490996B
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- graphene oxide
- stirring
- heating
- composite material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 59
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 59
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 238000003672 processing method Methods 0.000 title abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 67
- 238000010438 heat treatment Methods 0.000 claims abstract description 48
- 238000003756 stirring Methods 0.000 claims abstract description 47
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 39
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 9
- 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 32
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 18
- 239000000126 substance 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
- 238000001723 curing Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 claims description 12
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 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
- 238000001914 filtration Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000012044 organic layer Substances 0.000 claims description 8
- UVBBCQLPTZEDHT-UHFFFAOYSA-N pent-4-en-1-amine Chemical compound NCCCC=C UVBBCQLPTZEDHT-UHFFFAOYSA-N 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 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
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene 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
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 238000009849 vacuum degassing Methods 0.000 claims description 5
- 238000010907 mechanical stirring Methods 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
- 238000010025 steaming Methods 0.000 claims description 4
- 239000003607 modifier Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 claims 3
- 238000000034 method Methods 0.000 claims 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims 2
- 238000013007 heat curing Methods 0.000 claims 1
- 239000012264 purified product Substances 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 5
- 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
- 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
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 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
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 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
- 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
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003973 paint 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
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004634 thermosetting polymer Substances 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses an epoxy resin composite material and a processing method thereof, which belong to the technical field of composite materials and comprise 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; and stirring, mixing and ultrasonic treatment of the raw materials, and gradient heating and curing to obtain the epoxy resin composite material. According to the invention, modified graphene oxide is used as a raw material, and an organic molecular chain is grafted on the surface of the graphene oxide, wherein the organic molecular chain belongs to a multielement synergistic flame retardant component, and a 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 better compatibility with the matrix, and benzene rings contained on the organic molecular chain and benzene rings in the epoxy resin have pi-pi interaction, so that the interfacial 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 resins are widely used in the fields of adhesives, paints, electronic packaging, composite material manufacturing, and the like because of their excellent mechanical properties, adhesive properties, dimensional stability, and chemical resistance.
The nano reinforcing material has strong pushing effect on the future development of aerospace industry due to the light weight, high strength and multifunction. And graphene is more a seeker in the nano-reinforcement family. In recent years, graphene reinforced nanocomposites have been stronger than other nanocomposites and lighter in weight, which is why graphene is one of the best candidates for reinforcement in composite design. And the graphene has excellent mechanical properties and attractive excellent electrical and thermal properties, and provides a better choice for the design, preparation and application of structure-function integrated materials in the future aerospace industry development. However, graphene is a two-dimensional nanomaterial and cannot be independently applied, so that the preparation of the graphene is an important way for realizing application. The graphene and the epoxy resin are manufactured 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 for influencing the performance of the composite material.
In addition, epoxy resins are poor in flame retardance, and their oxygen index is generally 18-22, which is a flammable material, which limits the application of epoxy resins in some fields with high requirements on fire safety.
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.
According to the epoxy resin composite material, modified graphene oxide is used as a raw material, and an organic molecular chain is grafted on the surface of the graphene oxide, wherein the organic molecular chain belongs to a multielement (N, P, S) synergistic flame-retardant component, so that a synergistic flame-retardant effect can be exerted in a condensed phase and a gas phase, and the epoxy resin has good flame retardance; in addition, the organic molecular chain has better compatibility with the matrix, and benzene rings contained on the organic molecular chain and benzene rings in the epoxy resin have pi-pi interaction, so that the interfacial compatibility of graphene oxide and the epoxy resin matrix is improved, uniform dispersion in the composite material is realized, and the mechanical property and flame retardant property of the composite material are improved.
The aim of the invention can be achieved 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-necked flask provided with a mechanical stirring device and a condenser tube, stirring uniformly, adding phosphorus pentasulfide, introducing nitrogen, raising the temperature to 55 ℃ and stirring for 2 hours, reducing the temperature to 40 ℃ after the completion of the stirring, adding phosphorus pentasulfide again, introducing nitrogen for reacting for 15 hours, stopping heating, cooling to room temperature, removing the solvent by rotary evaporation, adding chloroform into the obtained oily liquid, oscillating and suction-filtering, transferring the liquid into a three-necked flask, adding saturated NaHCO 3 Stirring the solution under nitrogen protection for 20min, separating to obtain organic layer, and collecting the organic layer with anhydrous Na 2 SO 4 Drying, suction filtering, vacuum rotary steaming to remove chloroform, recrystallizing the product with acetonitrile, and finally drying in a vacuum drying oven at 40 ℃ for 8 hours to obtain a modified substance; the dosage ratio of the ethyl phenylphosphonate, the toluene and the phosphorus pentasulfide is 0.5mol:300mL:0.25mol, wherein the amounts of the phosphorus pentasulfide added in the two steps are the same;
ethyl phenylphosphonate 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) and then carrying out ultrasonic treatment at room temperature for 10min, transferring the mixed solution into a three-neck flask, adding 4-pentene-1-amine into a 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 ℃ for continuously stirring and reacting for 6h, carrying out centrifugal separation, washing with absolute ethyl alcohol for 4-5 times to remove unreacted substances, and finally, putting the product into a vacuum drying box at 50 ℃ for drying to constant weight to obtain grafted graphene; graphene oxide, DMF, 4-pentene-1-amine and EDC-HCl are used in a ratio of 0.1g to 60mL to 120mL to 5mg;
the graphene oxide surface contains a large number of oxygen-containing functional groups, and the step utilizes-COOH on the surface and-NH on 4-pentene-1-amine molecules 2 The preparation method comprises the steps of reacting, namely grafting a 4-pentene-1-amine molecular chain on the surface of graphene oxide through an amide bond to form grafted graphene, wherein the reaction process is as follows:
s3, mixing the grafted graphene and DMF, performing ultrasonic treatment at room temperature for 10min, transferring the mixed solution into 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, drying the product in a vacuum drying oven at 50 ℃ to constant weight to obtain modified graphene oxide; the dosage ratio of the grafted graphene to the modified DMF is 0.1g to 0.36g to 300mL;
the molecular chain grafted on the surface of the grafted graphene oxide contains C=C, and unsaturated carbon-carbon double bonds and grafts react chemically to obtain modified graphene oxide, wherein the reaction process is as follows:
the surface of the obtained modified graphene oxide is grafted with an organic molecular chain, wherein the grafted organic molecular chain contains a sulfur-containing group, a phosphate group, a nitrogen-containing group and a benzene ring; in the combustion process, sulfuric acid (strong acid), polyphosphoric acid and pyrophosphoric acid compounds generated by S element can promote further degradation of the flame retardant, further enhance the flame retardant capability of condensed phases and increase the carbon residue of substances, so that the epoxy tree is enabledThe fat composite material has better char forming capability; in addition, during the combustion process, the sulfur and nitrogen-containing nonflammable gas (SO 2 、NO x ) Diluting oxygen, and decomposing to generate P and OP free radicals and high-activity OH and H free radicals in the high-temperature combustion process to terminate the gas-phase chain reaction, thereby achieving the quenching effect; therefore, the organic molecular chain grafted on the surface of the graphene oxide belongs to a multielement (N, P, 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 is further described that-OH, epoxy group and the like contained in the graphene oxide can generate chemical bonding action with the epoxy resin matrix, the introduced organic molecular chain has better compatibility with the matrix, and benzene rings contained in the graphene oxide and benzene rings in the epoxy resin have pi-pi interaction, so that the modified graphene oxide and the epoxy resin matrix have good interface compatibility, uniform dispersion in the composite material can be realized, and the mechanical property and flame retardant property of the composite material are improved.
A processing method of an epoxy resin composite material comprises the following steps:
mixing epoxy resin and a curing agent, heating in a water bath at 70 ℃, magnetically stirring at a rotating speed of 450r/min for 1h, stopping stirring, adding modified graphene oxide, continuously stirring for 2h, then adding an accelerator, heating in a water bath at 60 ℃, magnetically stirring at 500r/min for 30min, ultrasonically dispersing for 30min (500W power), placing the ultrasonically dispersed mixed solution in a vacuum drying oven, heating at 70 ℃ for vacuum degassing for 2h, pouring the mixed solution into a polytetrafluoroethylene mold, placing the polytetrafluoroethylene mold into the drying oven for gradient heating and curing, and carrying out 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:
according to the epoxy resin composite material, modified graphene oxide is used as a raw material, and an organic molecular chain is grafted on the surface of the graphene oxide, wherein the organic molecular chain belongs to a multielement (N, P, S) synergistic flame-retardant component, so that a synergistic flame-retardant effect can be exerted in a condensed phase and a gas phase, and the epoxy resin has good flame retardance; in addition, the organic molecular chain has better compatibility with the matrix, and benzene rings contained on the organic molecular chain and benzene rings in the epoxy resin have pi-pi interaction, so that the interfacial compatibility of graphene oxide and the epoxy resin matrix is improved, uniform dispersion in the composite material is realized, and the mechanical property and flame retardant property of the composite material are improved.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the 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-necked flask equipped with a mechanical stirring device and a condenser pipe, stirring uniformly, adding 0.125mol of phosphorus pentasulfide, introducing nitrogen, raising the temperature to 55 ℃, stirring for 2 hours, reducing the temperature to 40 ℃ after the completion, adding 0.125mol of phosphorus pentasulfide again, introducing nitrogen for reacting for 15 hours, stopping heating, cooling to room temperature, removing the solvent by rotary evaporation, adding 200mL of chloroform into the oily liquid, oscillating and filtering, transferring the liquid into a three-necked flask, and adding 300mL of saturated NaHCO 3 Stirring the solution under nitrogen protection for 20min, separating to obtain organic layer, and collecting the organic layer with anhydrous Na 2 SO 4 Drying, suction filtering, vacuum rotary steaming to remove chloroform, recrystallizing the product with acetonitrile, and finally drying in a vacuum drying oven at 40 ℃ for 8 hours to obtain a modified substance;
s2, mixing 0.1g of graphene oxide with 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-pentene-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 ℃ for continuously stirring and reacting for 6h, performing centrifugal separation, washing with absolute ethyl alcohol for 4 times to remove unreacted substances, and finally, putting the product into a vacuum drying box at 50 ℃ for drying to constant weight to obtain grafted graphene;
s3, mixing 0.1g of grafted graphene with 300mL of DMF (dimethyl formamide), performing ultrasonic treatment at room temperature for 10min, transferring the mixed solution into a four-necked flask with a mechanical stirrer, a condenser tube 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 with absolute ethyl alcohol for 4 times to remove unreacted substances, and finally, drying the product in a vacuum drying oven at 50 ℃ 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-necked flask equipped with a mechanical stirring device and a condenser pipe, stirring uniformly, adding 0.25mol of phosphorus pentasulfide, introducing nitrogen, raising the temperature to 55 ℃, stirring for 2 hours, reducing the temperature to 40 ℃ after the completion, adding 0.25mol of phosphorus pentasulfide again, introducing nitrogen for reacting for 15 hours, stopping heating, cooling to room temperature, removing the solvent by rotary evaporation, adding 400mL of chloroform into the oily liquid, oscillating and filtering, transferring the liquid into a three-necked flask, and adding 600mL of saturated NaHCO 3 Stirring the solution under nitrogen protection for 20min, separating to obtain organic layer, and collecting the organic layer with anhydrous Na 2 SO 4 Drying, suction filtering, vacuum rotary steaming to remove chloroform, recrystallizing the product with acetonitrile, and finally drying in a vacuum drying oven at 40 ℃ for 8 hours to obtain a modified substance;
s2, mixing 0.2g of graphene oxide with 120mL of DMF (N, N-dimethylformamide), performing ultrasonic treatment at room temperature for 10min, transferring the mixed solution into 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 into a water bath at 60 ℃ for continuously stirring and 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 box at 50 ℃ for drying 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 into a four-necked flask with a mechanical stirrer, a condenser tube 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 with absolute ethyl alcohol for 5 times to remove unreacted substances, and finally, drying the product in a vacuum drying oven at 50 ℃ to constant weight to obtain the modified graphene oxide.
Example 3
An epoxy resin composite material comprises the following raw materials in parts by weight: 1000g of bisphenol A epoxy resin, 40g of modified graphene oxide, 180g of methyltetrahydrophthalic 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 a water bath at 70 ℃, magnetically stirring at a 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 a water bath at 60 ℃, magnetically stirring at 500r/min for 30min, ultrasonically dispersing for 30min (500W power), placing the ultrasonically dispersed mixed solution in a vacuum drying oven, heating at 70 ℃ for vacuum degassing for 2h, pouring the mixed solution into a polytetrafluoroethylene mold, placing into the 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.
Example 4
An epoxy resin composite material comprises the following raw materials in parts by weight: 1000g of bisphenol F type epoxy resin, 55g of modified graphene oxide, 215g of methyltetrahydrophthalic 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 epoxy resin and methyl tetrahydrophthalic anhydride, heating in a water bath at 70 ℃, magnetically stirring at a 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 a water bath at 60 ℃, magnetically stirring at 500r/min for 30min, ultrasonically dispersing for 30min (500W power), placing the ultrasonically dispersed mixed solution in a vacuum drying oven, heating at 70 ℃ for vacuum degassing for 2h, pouring the mixed solution into a polytetrafluoroethylene mold, placing into the 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.
Example 5
An epoxy resin composite material comprises the following raw materials in parts by weight: 1000g of bisphenol A epoxy resin, 70g of modified graphene oxide, 250g of methyltetrahydrophthalic 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 a water bath at 70 ℃, magnetically stirring at a 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 a water bath at 60 ℃, magnetically stirring at 500r/min for 30min, ultrasonically dispersing for 30min (500W power), placing the ultrasonically dispersed mixed solution in a vacuum drying oven, heating at 70 ℃ for vacuum degassing for 2h, pouring the mixed solution into a polytetrafluoroethylene mold, placing into the 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.
Comparative example
The modified graphene oxide in example 3 is changed into common graphene oxide, and the rest raw materials and the preparation process are unchanged.
The epoxy resin composites obtained in examples 3-5 and comparative examples were processed into test samples and subjected to the following performance tests:
mechanical property test: testing by a universal testing machine, wherein the stretching speed is as follows: 50mm/min;
limiting oxygen index test (LOI): testing according to ASTM D-2863 standard by using an intelligent oxygen index tester;
vertical burn test (UL-94): testing according to ASTM D-3810 standard using a vertical burning tester;
the results 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 | No grade |
As can be seen from the data in the table, the epoxy resin composite material obtained by the invention has good mechanical property and flame retardant property; 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 improves the mechanical property of the composite material.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, 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 present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. 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 merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (7)
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;
the modified graphene oxide has the following structural formula:
s1, adding ethyl phenylphosphonate and toluene into a four-necked flask provided with a mechanical stirring device and a condenser tube, stirring uniformly, adding phosphorus pentasulfide, introducing nitrogen, raising the temperature to 55 ℃ and stirring for 2 hours, reducing the temperature to 40 ℃ after the completion of the stirring, adding phosphorus pentasulfide again, introducing nitrogen for reacting for 15 hours, stopping heating, cooling to room temperature, removing the solvent by rotary evaporation, and purifying to obtain a modified substance; the dosage ratio of the ethyl phenylphosphonate, the toluene and the phosphorus pentasulfide is 0.5mol:300mL:0.25mol, wherein the amounts of the phosphorus pentasulfide added in the two steps are the same;
s2, mixing graphene oxide and DMF, performing ultrasonic treatment at room temperature for 10min, transferring the mixed solution into a three-neck flask, adding 4-pentene-1-amine into the system, continuously stirring for 1h, then adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, transferring the three-neck flask into a water bath at 60 ℃ for continuously stirring and reacting for 6h, performing centrifugal separation, washing with absolute ethyl alcohol for 4-5 times to remove unreacted substances, and finally, putting the product into a vacuum drying oven at 50 ℃ for drying to constant weight to obtain grafted graphene; graphene oxide, DMF, 4-pentene-1-amine, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride in an amount ratio of 0.1g to 60mL to 120mL to 5mg;
s3, mixing the grafted graphene and DMF, performing ultrasonic treatment at room temperature for 10min, transferring the mixed solution into 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, drying the product in a vacuum drying oven at 50 ℃ to constant weight to obtain modified graphene oxide; the ratio of the dosage of the grafted graphene, the modified matter and the DMF is 0.1g to 0.36g to 300mL.
2. An epoxy resin composite according to claim 1, wherein the purified product of step S1 hasAnd (3) body operation: adding chloroform into the oily liquid, oscillating, filtering, transferring the liquid into a three-necked flask, adding saturated NaHCO 3 Stirring the solution under nitrogen protection for 20min, separating to obtain organic layer, and collecting the organic layer with anhydrous Na 2 SO 4 Drying, suction filtering, vacuum rotary steaming to remove chloroform, recrystallizing the product with acetonitrile, and finally drying in a vacuum drying oven at 40 ℃ for 8 hours to obtain a modified substance.
3. An epoxy resin composite according to claim 1, wherein the curing agent is methyltetrahydrophthalic anhydride.
4. An epoxy resin composite according to claim 1, wherein the accelerator is 2,4, 6-tris (dimethylaminomethyl) phenol.
5. An epoxy resin composite according to claim 1, wherein the epoxy resin is bisphenol a type epoxy resin or bisphenol F type epoxy resin.
6. The method for processing an epoxy resin composite material according to claim 1, comprising the steps of:
mixing epoxy resin and a curing agent, heating in a water bath at 70 ℃, magnetically stirring at a rotating speed of 450r/min for 1h, stopping stirring, adding modified graphene oxide, continuously stirring for 2h, then adding an accelerator, heating in a water bath at 60 ℃, magnetically stirring at 500r/min for 30min, performing ultrasonic dispersion for 30min, placing the mixed solution after ultrasonic dispersion in a vacuum drying oven, heating at 70 ℃ for vacuum degassing for 2h, pouring the mixed solution into a polytetrafluoroethylene mould, placing the polytetrafluoroethylene mould into the drying oven for gradient heating and curing, and naturally cooling to room temperature after curing is completed to obtain the epoxy resin composite material.
7. The method for processing an epoxy resin composite material according to claim 6, wherein the ultrasonic power is 500W; gradient heat curing parameters: heating at 120deg.C for 2h, heating at 150deg.C for 2h, and heating at 100deg.C for 12h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211194418.1A CN115490996B (en) | 2022-09-28 | 2022-09-28 | Epoxy resin composite material and processing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211194418.1A CN115490996B (en) | 2022-09-28 | 2022-09-28 | Epoxy resin composite material and processing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115490996A CN115490996A (en) | 2022-12-20 |
| CN115490996B true CN115490996B (en) | 2023-06-27 |
Family
ID=84472045
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211194418.1A Active CN115490996B (en) | 2022-09-28 | 2022-09-28 | Epoxy resin composite material and processing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115490996B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107663278A (en) * | 2017-09-26 | 2018-02-06 | 广州埃米石墨烯投资管理有限公司 | A kind of epoxy resin highly effective flame-retardant agent dispersing liquid and preparation method thereof |
| CN108586807A (en) * | 2018-05-25 | 2018-09-28 | 南京林业大学 | A kind of flame retarding function graphite alkene and its preparation and application |
| CN111763406A (en) * | 2020-08-05 | 2020-10-13 | 兰州交通大学 | Preparation process of graphene nanocomposite |
| CN113512274A (en) * | 2021-08-22 | 2021-10-19 | 华北科技学院(中国煤矿安全技术培训中心) | Modified graphene oxide and preparation method and application thereof |
| CN114426701A (en) * | 2022-01-11 | 2022-05-03 | 桂林理工大学 | Preparation of P-N compound and graphene oxide synergistic flame retardant and application of P-N compound and graphene oxide synergistic flame retardant in epoxy resin |
-
2022
- 2022-09-28 CN CN202211194418.1A patent/CN115490996B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107663278A (en) * | 2017-09-26 | 2018-02-06 | 广州埃米石墨烯投资管理有限公司 | A kind of epoxy resin highly effective flame-retardant agent dispersing liquid and preparation method thereof |
| CN108586807A (en) * | 2018-05-25 | 2018-09-28 | 南京林业大学 | A kind of flame retarding function graphite alkene and its preparation and application |
| CN111763406A (en) * | 2020-08-05 | 2020-10-13 | 兰州交通大学 | Preparation process of graphene nanocomposite |
| CN113512274A (en) * | 2021-08-22 | 2021-10-19 | 华北科技学院(中国煤矿安全技术培训中心) | Modified graphene oxide and preparation method and application thereof |
| CN114426701A (en) * | 2022-01-11 | 2022-05-03 | 桂林理工大学 | Preparation of P-N compound and graphene oxide synergistic flame retardant and application of P-N compound and graphene oxide synergistic flame retardant in epoxy resin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115490996A (en) | 2022-12-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Paluvai et al. | Synthesis and modifications of epoxy resins and their composites: a review | |
| Cheng et al. | Improving interfacial properties and thermal conductivity of carbon fiber/epoxy composites via the solvent-free GO@ Fe3O4 nanofluid modified water-based sizing agent | |
| CN103665769B (en) | The preparation method of the multiple dimensioned fiber prepreg material of nano-micrometre | |
| CN105064030A (en) | Carbon fiber sizing agent and preparation method thereof | |
| CN114920713A (en) | Flame-retardant curing agent, and preparation method and application of reactive epoxy resin | |
| CN115010993A (en) | Preparation method and application of graphene oxide hybrid flame retardant | |
| Venu et al. | Thermal decomposition behavior and flame retardancy of bioepoxies, their blends and composites: A comprehensive review | |
| CN115490996B (en) | Epoxy resin composite material and processing method thereof | |
| CN106832786A (en) | A kind of high flame retardant composition epoxy resin | |
| CN112194822B (en) | Phosphorus-containing flame retardant, preparation method and modified epoxy resin | |
| CN113462154B (en) | High-heat-resistance cyanate resin and preparation method thereof | |
| CN112852112A (en) | Synergistic system epoxy resin composite material of phosphorus-containing ionic liquid and carbon nano material and preparation method thereof | |
| CN111748178A (en) | Epoxy resin composition and preparation method and application thereof | |
| CN114292404B (en) | POSS modified oxazoline derivative, preparation method thereof and epoxy resin composition | |
| CN113788823B (en) | Biological-based epoxy resin based on vanillin and preparation method thereof | |
| CN106592241A (en) | Modified epoxy resin small filament bundle universal carbon fiber sizing agent, and preparation method and application thereof | |
| CN109553929B (en) | Nano flame-retardant epoxy resin composite material and preparation method thereof | |
| CN115594943A (en) | Modified carbon nanotube flame-retardant reinforced epoxy resin and preparation method thereof | |
| CN114685937A (en) | Flame-retardant epoxy resin composite material and preparation method thereof | |
| KR20220088019A (en) | Thermosetting resin composition with high toughness and flame retardant | |
| CN110643168A (en) | Black phosphorus nanosheet flame-retardant polyphenyl ether resin and preparation method thereof | |
| CN110194939A (en) | A kind of the two-component epoxy pouring sealant and its application method of high heat conductive insulating | |
| CN113980458B (en) | Carbon fiber composite material for aviation and preparation method thereof | |
| CN104341759A (en) | Nanoscale flame retardant reinforced polycarbonate and preparation method | |
| CN114316274B (en) | POSS modified urea derivative, preparation method thereof and epoxy resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240204 Address after: 401520 No. 566 Yinxiang Avenue, Tuchang Town, Hechuan District, Chongqing (self committed) Patentee after: Chongqing Huiyue Enterprise Management Service Co.,Ltd. Country or region after: China Address before: No. 118, Guoxiang Road, Zhongzhuang Town, Yiyuan County, Zibo City, Shandong Province, 256100 Patentee before: Shandong bokesaisi New Material Technology Co.,Ltd. Country or region before: China |
|
| TR01 | Transfer of patent right |