CN117304652A - GO-SiO 2 Three-dimensional point plane nano material toughened epoxy resin composite material and preparation method thereof - Google Patents
GO-SiO 2 Three-dimensional point plane nano material toughened epoxy resin composite material and preparation method thereof Download PDFInfo
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- 150000001412 amines Chemical class 0.000 claims description 4
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 4
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of epoxy resin composite materials, in particular to a GO-SiO 2 Three-dimensional point plane nanomaterial toughened epoxy resin composite material and preparation method thereof, wherein mercapto-anchored Graphene Oxide (GO) and epoxy-anchored silicon dioxide (SiO) are adopted 2 ) The nanoparticles are hybridized by thiol-epoxy click chemistry to form a nanomaterial with a two-dimensional three-dimensional point-plane structure (GO-SiO 2 ) And an epoxy composite is prepared using a melt blending process. The invention uses covalent bonding methodSiO 2 Grafted onto GO, the interfacial compatibility and the dispersibility are effectively improved, so that the mixture can be mixed in a melt blending mode; and simultaneously, the epoxy resin composite material is cured in a mode of heating and curing at normal temperature, so that the internal stress in the EP curing process is reduced as much as possible, and the epoxy resin composite material with excellent mechanical properties is obtained.
Description
Technical Field
The invention relates to the technical field of epoxy resin composite materials, in particular to a GO-SiO 2 A three-dimensional point plane nano material toughened epoxy resin composite material and a preparation method thereof.
Background
Epoxy resins (EP) have been recognized as the most widely used thermosetting materials of strategic importance, since EP is an important organic matrix with excellent mechanical properties, thermal stability, low shrinkage, electrical insulation, strong adhesion, tribological properties and chemical resistance. The EP is widely applied to the industrial fields of chemical industry, light industry, water conservancy, traffic, machinery, electronics, household appliances, automobiles, aerospace and the like. In China, the main application fields of EP are the industries of paint, electronic vapor, composite materials and adhesives. However, the inherent brittleness and poor crack propagation resistance of EP's caused by their ultra-high crosslink density limit their applications. Therefore, the toughening modification of EP is an indispensable link. The toughening agents most commonly used in EP are mainly organic nanoparticles including core shell particles, spherical rubber particles, liquid rubber, glass microspheres, hyperbranched polymers and combinations thereof. Fillers of this type can improve the toughness of the EP at the cost of other important properties. In order to improve toughness and strength at the same time without sacrificing other properties, inorganic nanoparticles can also toughen EP in addition to organic nanoparticles. Typical inorganic nanoparticles are carbon nanotubes, graphene, fibers, organoclays, exfoliated montmorillonite, silica, alumina, and the like. Among the various nanofillers for preparing high performance epoxy nanocomposites, grapheme carbon nanomaterials are more attractive due to their unique physical properties.
Graphene Oxide (GO) is an oxide of graphene, and contains a large number of oxygen-containing groups such as hydroxyl groups and epoxy groups on the internal skeleton, and also has a large number of carbonyl groups and carboxyl groups on the lamellar edges. GO is an ideal nano filler, can be compounded with an EP matrix, and improves the mechanical property, the corrosion resistance, the thermal property and the like. However, due to pi-pi stacking effect and van der Waals forces, GO sheets are susceptible to irreversibly severe agglomeration in the EP matrix, resulting in weaker interactions between GO sheets and EP. Functionalization of GO is an effective measure to improve its dispersibility and interfacial compatibility in epoxy matrices.
In recent years, nano hybrid materials based on three-dimensional dot planar structures of GO are one of the research hot spots of resin-based composite materials in terms of enhancing resin properties or imparting some special functions to the resin. The different inorganic nano materials on the GO plane are linked with the GO material in a covalent/non-covalent mode, and cooperate with each other to endow the GO material with more excellent performance. For example low cost nano SiO 2 Has many excellent properties such as high strength, high toughness, corrosion resistance and high temperature resistance. But nano SiO 2 Because of its high specific surface area and polarity, it is easy to agglomerate. If nano SiO is to be used 2 Realizing effective bonding with GO sheet layer, and nano SiO on GO surface 2 Not only maintains the original functional characteristics, but also avoids nano SiO 2 Changing the state of close packing of GO nanoplatelets in the resin. Therefore, the nano hybrid material can play a role in synergistic enhancement in the resin matrix composite material, so that the composite resin has more outstanding mechanical, corrosion-resistant and thermal properties. However, due to SiO 2 Under the covering action of the GO surface, some functional groups originally positioned on the GO surface are eliminated, so that the interaction between the functional groups and the EP matrix is weakened. Thus, to improve GO-SiO 2 Interaction with EP matrix, necessary for GO-SiO 2 The structure of the hybrid material is regulated and controlled. Furthermore, in general, GO-SiO is prepared by sol-gel method, hydrothermal method, electrostatic assembly, etc 2 The hybrid material can effectively promote GO and SiO 2 The synergistic effect of the two materials, but the high production cost, long time, pollution and the like limit the development of the hybrid materials in the field.
Therefore, it is necessary to provide a GO-SiO which is simple in preparation method, good in compatibility with EP and excellent in reinforcing and toughening effects 2 Hybrid materials to solve the above problems.
Disclosure of Invention
The invention aims to provide a GO-SiO 2 Three-dimensional point plane nano material toughened epoxy resin composite material and preparation method thereof, and GO-SiO is adopted 2 GO-SiO enhancement by three-dimensional dot plane nanomaterials 2 Dispersibility in EP and through GO-SiO 2 The interface action with the resin matrix has good toughening effect on the epoxy resin composite material. In addition, no organic solvent participates in the operation process, so that the solvent removal operation is not needed before curing, the process steps are simplified, the product performance is improved, harmful substances are not generated, and the environment is not polluted.
To achieve the above object, in a first aspect, the present invention provides a GO-SiO 2 Toughened epoxy resin composites comprising epoxy resin (EP), GO-SiO 2 Three-dimensional dot plane nanomaterial and curing agent; prepared by a melt blending method;
the GO-SiO 2 The three-dimensional point planar nanomaterial comprises: mercapto-anchored (chemically modified) GO and epoxy-anchored SiO 2 And the mercapto-anchored GO and epoxy-anchored SiO 2 Covalent hybridization is performed between the two through a click chemistry method.
The invention adopts SiO anchored by epoxy groups 2 Thiol-epoxy covalent hybridization of thiol-anchored GO-microparticles with nanoparticles to obtain GO-SiO 2 The interfacial compatibility of the three-dimensional point planar nano material and the EP is obviously improved, so that the three-dimensional point planar nano material can be mixed with the EP through melt blending, and the dispersibility of the three-dimensional point planar nano material cannot be influenced, thereby not only improving the mechanical strength and toughness of the EP, but also omitting the steps of solvent addition and removal and reducing the influence of solvent residues on the performance of the composite material.
Further, the click chemistry method includes: anchoring the thiol-anchored GO (SGO) and epoxy-anchored SiO 2 (O-SiO 2 ) Stirring and reacting under the action of a catalyst to obtain SiO 2 Modified GO, namely the GO-SiO 2 Three-dimensional dot planar nanomaterial. Through covalent cross-linking of mercapto and epoxy, GO-SiO is obtained 2 The three-dimensional point plane nano material has the advantages of simple preparation method, high repeatability and convenient scaleAnd (5) preparing by chemical preparation.
The mercapto-anchored GO and epoxy-anchored SiO 2 The mass ratio of (1-2): (0.2-1), for example, 1:0.2,1:0.5,1:1,1.5:0.5,1.5:1,2:0.2,2:0.5, etc. The dispersibility and the toughness can be regulated and controlled by regulating and controlling the mass ratio of the two.
Further, the catalyst comprises 4-dimethylaminopyridine; further, the temperature of the stirring reaction is 105-110 ℃.
Specifically, the click chemistry method includes: 1-2 g SGO is added into 500-1000 mL DMF and is treated by ultrasonic for 30-60 min to form uniform suspension. Then, 0.2 to 1g of O-SiO 2 Adding the mixture into the suspension, and performing ultrasonic treatment for 30-60 min to form uniform suspension. Finally, adding 4-Dimethylaminopyridine (DMAP) catalyst, stirring and reacting for 6-8 h at 105-110 ℃. GO-SiO 2 Centrifuging the product, washing the product with absolute ethyl alcohol and deionized water for five times, and drying the product at 60-80 ℃ for 24-48 h to obtain SiO 2 Modified GO (GO-SiO) 2 )。
Further, the mercapto-anchored GO is a mercaptosilane coupling agent modified GO; the mercaptosilane coupling agent comprises: one or two of 3-mercaptopropyl trimethoxysilane (KH 590) and 3-mercaptopropyl triethoxysilane;
further, the preparation method of the mercaptosilane coupling agent modified GO comprises the following steps: dispersing GO in ethanol; under the condition that the pH value is 4-5, the sulfhydryl silane coupling agent is fully hydrolyzed in distilled water; then mixing the hydrolyzed mercaptosilane coupling agent with GO dispersion liquid, and stirring and reacting at 70-80 ℃; and finally centrifuging and washing the product, and then drying to obtain the GO modified by the mercaptosilane coupling agent.
Specifically, firstly, adding 1-2 g of GO into 500-1000 ml of ethanol, stirring for 30-60 min (the rotating speed is controlled at 200-500 r/min), and carrying out ultrasonic treatment for 1-2 h (the ultrasonic power is 100-150W, and the ultrasonic treatment time is 60-120 min) to uniformly disperse GO in an ethanol solution; 10-20 mL KH590 and 50-100 mL deionized water are taken in a beaker, acetic acid is added to adjust the pH to 4-5, stirring is carried out for 1-3 hours, KH590 is fully hydrolyzed, then the hydrolyzed KH590 is slowly dripped into GO dispersion liquid through a constant pressure separating funnel, and stirring reaction is carried out for 6-8 hours at 70-80 ℃. And finally centrifuging the product (the centrifuging time is 10-30 min, the rotating speed is 3000-5000 r/min), washing 2-5 times by absolute ethyl alcohol and 2-5 times by distilled water, and then drying at 60-80 ℃ for 24-48 h to obtain the GO (SGO) modified by KH 590.
Further, the epoxy-anchored SiO 2 SiO modified by epoxy silane coupling agent 2 The method comprises the steps of carrying out a first treatment on the surface of the The epoxy silane coupling agent includes: one or two of 3-glycidoxypropyl trimethoxysilane (KH 560) and 3-glycidoxypropyl triethoxysilane.
Further, the epoxy silane coupling agent modified SiO 2 The preparation method of (2) comprises the following steps: siO is made of 2 Dispersing in ethanol; under the condition that the pH value is 4-5, the epoxy silane coupling agent is fully hydrolyzed in distilled water; then the hydrolyzed epoxy silane coupling agent and SiO 2 Mixing the dispersion liquid, and stirring and reacting at 70-80 ℃; finally centrifuging and washing the product, and then drying to obtain SiO modified by epoxy silane coupling agent 2 。
Specifically, first, 1 to 2g of SiO is added into 500 to 1000mL of ethanol 2 Stirring for 30-60 min, and ultrasonic treating for 1-2 hr to make SiO 2 Uniformly dispersing in an ethanol solution, taking 10-20 mL of KH560 and 50-100 mL of deionized water in a beaker, adding acetic acid to adjust the pH to 4-5, stirring for 1-3 h to fully hydrolyze the KH560, slowly dripping the hydrolyzed KH560 into the GO dispersion liquid through a constant pressure separating funnel, and stirring and reacting for 6-8 h at 70-80 ℃. Finally centrifuging the product, washing the product for 2 to 5 times by absolute ethyl alcohol and washing the product by deionized water for 2 to 5 times, and then drying the product at 60 to 80 ℃ for 24 to 48 hours to obtain the SiO modified by KH560 2 (O-SiO 2 )。
SiO was quenched with gamma-glycidoxypropyl trimethoxysilane (KH 560) 2 Surface modification (O-SiO) 2 ) GO surface is modified with gamma-mercaptopropyl trimethoxysilane (KH 590). SiO is then reacted by mercapto-epoxy click chemistry 2 Uniformly bonds to the GO surface. SiO (SiO) 2 Of surfacesThe epoxy group not only has good compatibility in EP, but also establishes covalent connection with the EP under the bridging action of the curing agent, thereby effectively enhancing the interface interaction between the GO and the epoxy matrix. Furthermore, siO 2 And the special three-dimensional point plane structure is formed by the GO, so that the load can be effectively transmitted, and the mechanical property of the EP can be improved.
Further, the slice diameter of the GO is 10-20 mu m; and/or, the SiO 2 Is a microsphere with the diameter of 15-50 nm. Spherical SiO 2 The nano hybrid material with a three-dimensional point plane structure is formed by clicking on chemical connection to the flaky GO, and the effect of reinforcing the EP resin is more remarkable.
Further, the GO-SiO 2 The addition amount of the three-dimensional point plane nano material is 0.01 to 0.5wt.% of the mass of the epoxy resin; preferably 0.1 to 0.5wt.%, for example 0.1%, 0.2%, 0.3%, 0.4%, 0.5% etc.
Further, the GO-SiO 2 The toughened epoxy resin composite material comprises the following components in parts by weight: 100 parts of epoxy resin and GO-SiO 2 0.01 to 0.5 part of three-dimensional point plane nano material, 35 to 60 parts of curing agent and 0.1 to 0.5 part of defoaming agent.
The GO-SiO 2 The toughened epoxy resin composite material comprises the following components in parts by weight: 100 parts of epoxy resin and GO-SiO 2 0.01 to 0.5 part of three-dimensional point plane nano material, 35 to 60 parts of curing agent and 0.1 to 0.5 part of defoaming agent.
Further, the epoxy resin comprises E51, E44 or NPEL-128;
and/or, the defoamer comprises one or more of silicone and polyether defoamers;
and/or the curing agent comprises one or more of polyetheramine and fatty amine types; the polyetheramine comprises D2000, T5000, or T403; the fatty amine type boanka ethylenediamine, diethylenetriamine or triethylenetetramine.
In a second aspect, the present invention provides a GO-SiO as described in any one of the above 2 The preparation method of the toughened epoxy resin composite material comprises the following steps: heating epoxy resin to 60-100 ℃, and then adding an antifoaming agent and the GO-SiO 2 Stirring and ultrasonic treating the three-dimensional point plane nano material, adding a curing agent, uniformly stirring, defoaming, and finally pouring into a mold for curing to obtain the GO-SiO 2 Toughening epoxy resin composite materials.
Further, the power of the ultrasonic treatment is 100-150W, and the ultrasonic time is 60-120 min;
and/or, the deaerating comprises: vacuumizing for 30-60 min in a vacuum drying oven with the vacuum degree below 0.1MPa for defoaming;
and/or, the curing comprises the steps of curing for 15-30 hours at normal temperature and then curing in an oven; the oven curing comprises the steps of curing for 2-4 hours at 80-100 ℃, and then heating to 120-150 ℃ for curing for 2-4 hours. By means of the mode of temperature rising and curing at normal temperature, internal stress in the EP curing process can be reduced as much as possible, and therefore the epoxy resin composite material with excellent mechanical properties can be obtained more favorably.
Further, the mold is a silica gel mold. The mold is typically coated with a release agent, which is a dry fluorine release agent.
The beneficial effects of the invention are as follows:
(1) The invention uses sulfhydryl-epoxy group click chemistry reaction to make SiO 2 Covalently bonded to the GO surface, the GO-SiO thus obtained 2 The interface compatibility of the three-dimensional point plane nano material and the EP is high, and SiO 2 The epoxy group on the surface not only has good compatibility in EP, but also establishes covalent connection with EP under the bridging action of the curing agent, thereby effectively enhancing the interface interaction between GO and the epoxy matrix. Furthermore, siO 2 And the special three-dimensional point plane structure is formed by the GO, so that the load can be effectively transmitted, and the mechanical property of the EP can be improved.
(2) According to the invention, the nano hybrid material with the three-dimensional point-plane structure is added into the EP by adopting a melt blending method to prepare the epoxy composite material, so that the steps of adding and removing the solvent are omitted, and the influence of the solvent residue on the performance of the composite material is reduced.
(3) The GO modified by the nano particles enhances the interface combination effect between GO and EP, and the three-dimensional point plane structure forms a disperse phase in the EP network, thereby playing a role in the EP composite materialGood toughening effect. 0.1wt.% GO-SiO 2 The tensile strength of the EP composite material is increased from 47.45+/-2.32 MPa to 65.79+/-2.87 MPa, the bending strength is increased from 93.08 +/-5.07 MPa to 126.73 +/-4.38 MPa, the bending modulus is increased from 2562.70 +/-105.85 MPa to 3706.75 +/-100.06 MPa, and the impact strength is increased from 8.57+/-0.56 kJ/m 2 Raised to 13.85+/-0.69 kJ/m 2 . The material is also changed from obvious brittle fracture to plastic fracture, so that the toughness is effectively improved.
Drawings
In order to more clearly illustrate the invention or the technical solutions of the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the invention, and other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows the mechanical properties of EP and its composites: (a) tensile strength; (b) a tensile stress-strain curve; (c) flexural strength and flexural modulus; (d) a bending stress-strain curve;
FIG. 2 is an impact strength of EP and its composites;
in FIG. 3, (a) is a pure EP impact profile, (b) is 0.1wt.% GO-SiO 2 Impact profile of EP;
FIG. 4 is SiO 2 And O-SiO 2 Is (a); GO, SGO and GO-SiO 2 Is (b);
FIG. 5 GO, SGO and GO-SiO 2 (a) a raman spectrum and (b) an XRD spectrum;
in FIG. 6, (a) GO and (b) GO-SiO 2 SEM images of (scale bar 500 nm); (c) GO and (d) GO-SiO 2 A TEM image of (a); a TEM micrograph (e) of the region I, EDS (f), and an elemental map (g) C, (h) O, (I) S, (j) Si elemental map (scale bar 100 nm);
in FIG. 7 (a) 0.1wt.% GO-SiO 2 Physical map of GO ultrasound 1h dispersed in EP, (b) 0.1wt.% GO-SiO 2 A physical image of GO dispersed in EP after 24h of standing, (c) 20-fold optical microscope magnification of A area samplingImage, (d) 20 x magnification of the image of the B region sample, (e) 0.1wt.% GO/EP and (f) 0.1wt.% GO-SiO 2 EP optical microscope image.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but 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.
The bisphenol A type epoxy resin used in the invention is of the type of Nanya 128, has an epoxy equivalent of 184-190 g/eq and a viscosity of 12000-15000 cps/25 ℃, and is purchased from the chemical industry Co. The curing agent is polyetheramine, model 3628K, available from Guangzhou Huabang chemical Co. Graphene Oxide (GO), model SE-2430, available from Heizhou, sixth element materials technologies Co., ltd. SiO (SiO) 2 (99.5%, 20.+ -.5 nm), 4-Dimethylaminopyridine (DMAP), 3-glycidoxypropyl trimethoxysilane (KH 560) were purchased from Shanghai Mei Lin Shenghua Co. Defoamer (DF-450) is supplied by Dongguande Feng Xiaopao agent Co. Glacial acetic acid is supplied by Miou reagent Inc. of Tianjin, and 3-mercaptopropyl trimethoxysilane (KH 590) is supplied by Shanghai Jiding Biotechnology Inc.
The die used in the embodiment of the invention is a silica gel die manufactured according to the sample size required by GB/T2567-2021 performance test.
Example 1 pure epoxy resin
1. The pure EP is prepared from the following raw materials in parts by weight: 100 parts of bisphenol A epoxy resin, 50 parts of curing agent and 0.3 part of defoaming agent.
2. The preparation method comprises the following steps:
pure EP: 0.3wt.% (mass fraction of defoamer to EP) of defoamer was added to EP, stirred for 30min, then sonicated at 40 ℃ for 1h, then bubble removed in a vacuum oven at 0.1MPa for 1h. And adding a curing agent (the mass ratio of the EP to the curing agent is 2:1) into the mixture, and uniformly stirring. The mixture was then poured into a mold, cured at room temperature for 24 hours, then cured in an oven at 100 ℃ for 2 hours, and cured at 150 ℃ for 4 hours to give a pure EP material.
The tensile strength, the bending modulus and the impact strength of the composite material are tested by adopting a GB/T2567-2021 resin casting body performance test method. Of these, FIG. 1 shows the tensile strength (a in FIG. 1), flexural strength and flexural modulus (c in FIG. 1) of pure EP materials of 47.45.+ -. 2.32MPa, 93.08.+ -. 5.07MPa and 2562.70.+ -. 105.85MPa, respectively. FIG. 2 shows that the impact strength of the pure EP material is 8.57.+ -. 0.56kJ/m 2 。
Example 2 GO nanomaterial toughened EP composite
1. The GO nano material toughened EP composite material is prepared from the following raw materials in parts by weight: 0.1 part of GO nano material, 100 parts of bisphenol A epoxy resin, 50 parts of curing agent and 0.3 part of defoaming agent.
2. The preparation method comprises the following steps:
heating the EP at 80 ℃, reducing the viscosity of the EP, adding 0.3wt.% of defoamer, adding GO with the mass fraction of 0.1% into the EP, stirring for 30min, continuing to ultrasonically treat the EP at 40 ℃ for 1h to uniformly disperse the GO in the EP, and then removing bubbles in a vacuum drying oven at 0.1MPa for 1h. And adding a curing agent into the mixture, and uniformly stirring. The mixture was then poured into a mold, cured at ambient temperature for 24 hours, cured in an oven at 100 ℃ for 2 hours, and cured at 150 ℃ for 4 hours, yielding 0.1wt.% GO/EP composite.
The tensile strength, flexural modulus and impact strength of the composite materials were tested using GB/T2567-2021 resin casting performance test methods, as shown in FIG. 1. It can be seen that the tensile strength, flexural strength and flexural modulus of the GO/EP composite material are increased from 47.45.+ -. 2.32MPa, 93.08.+ -. 5.07MPa and 2562.70.+ -. 105.85MPa to 53.37.+ -. 3.24MPa, 104.38.+ -. 4.62MPa and 2860.86.+ -. 111.20MPa, respectively. FIG. 2 shows impact strength of 8.57.+ -. 0.56kJ/m 2 Raised to 10.68+/-0.89 kJ/m 2 。
Example 3 SGO nanomaterial toughened EP composites
1. The SGO nano material toughened EP composite material is prepared from the following raw materials in parts by weight: 0.1 part of SGO nano material, 100 parts of bisphenol A epoxy resin, 50 parts of curing agent and 0.3 part of defoaming agent.
2. The preparation method comprises the following steps:
(1) Thiol covalent anchoring GO: firstly, adding 1g of GO into 450mL of ethanol, stirring for 30min, uniformly dispersing the GO in an ethanol solution by ultrasonic treatment for 1h, taking 10mL of KH590 and 50mL of deionized water in a beaker, adding acetic acid to adjust the pH to 4, and stirring for 2h to fully hydrolyze the KH 590. The hydrolyzed KH590 was then slowly added dropwise to the GO dispersion via a constant pressure separatory funnel and reacted at 78 ℃ with stirring for 6h. Finally, the product was centrifuged and washed five times with absolute ethanol and distilled water, and then dried at 60 ℃ for 24 hours to obtain KH590 modified GO (SGO).
(2) Composite material: heating the EP at 80 ℃, reducing the viscosity of the EP, adding 0.3wt.% of defoamer, adding SGO with mass fraction of 0.1% into the EP, stirring for 30min, then performing ultrasonic treatment at 40 ℃ for 1h to uniformly disperse GO in the EP, and then removing bubbles for 1h in a vacuum drying oven with pressure of 0.1 MPa. And adding a curing agent into the mixture, and uniformly stirring. The mixture was then poured into a mold, cured at ambient temperature for 24 hours, then cured in an oven at 100 ℃ for 2 hours, and cured at 150 ℃ for 4 hours, yielding 0.1wt.% SGO/EP composite.
The tensile strength, flexural modulus and impact strength of the composite materials were tested using GB/T2567-2021 resin casting performance test methods, as shown in FIG. 1. As can be seen, the tensile strength, flexural strength and flexural modulus of the SGO/EP composite material are respectively improved from 47.45+ -2.32 MPa, 93.08 + -5.07 MPa and 2562.70 + -105.85 MPa to 58.51 + -3.88 MPa, 109.67 + -3.56 MPa and 3040.91 + -91.23 MPa, and the impact strength is improved from 8.57+ -0.56 kJ/m in FIG. 2 2 Raised to 11.87+/-0.43 kJ/m 2 。
Example 4, GO&SiO 2 Nanometer mixed material toughened EP composite material
1、GO&SiO 2 The nano mixed material toughened EP composite material is prepared from the following raw materials in parts by weight: GO (GO)&SiO 2 0.1 part of nano material, 100 parts of bisphenol A epoxy resin, 50 parts of curing agent and 0.3 part of defoaming agent.
2. The preparation method comprises the following steps:
(1) Thiol covalent anchoring GO: prepared as in example 2.
(2) Epoxy group covalent anchoring SiO 2 : covalent anchoring of epoxy silane coupling agents to SiO 2 The specific steps on the nanoparticle are: first, 1g of SiO was added to 450mL of ethanol 2 Stirring for 30min, and performing ultrasonic treatment for 1h to make SiO 2 Uniformly dispersing in ethanol solution, taking 10mL of KH560 and 50mL of distilled water in a beaker, stirring for 2h to fully hydrolyze the KH560, slowly dripping the hydrolyzed KH560 into GO dispersion liquid through a constant pressure separating funnel, and stirring for reaction for 6h at 78 ℃. Finally centrifuging the product, washing the product with deionized water and absolute ethyl alcohol for five times, and then drying the product at 60 ℃ for 24 hours to obtain KH560 modified SiO 2 (O-SiO 2 )。
(3)GO&SiO 2 Nano material: the material combines SGO and O-SiO by simple physical mixing 2 Doping is carried out at a mass ratio of 5:1.
(4) Composite material: heating EP at 80deg.C, reducing viscosity of EP, and adding GO with mass fraction of 0.1%&SiO 2 To EP, 0.3wt.% of an antifoaming agent was added, stirred for 30min, then sonicated at 40 ℃ for 1h, then de-bubbled in a vacuum oven. And adding a curing agent into the mixture, and uniformly stirring. Then pouring the mixture into a mold, curing for 24 hours at normal temperature, curing for 2 hours in a baking oven at 100 ℃ and curing for 4 hours at 150 ℃ to obtain GO&SiO 2 EP composite materials.
The tensile strength, flexural modulus and impact strength of the composite materials were tested using GB/T2567-2021 resin casting performance test methods, as shown in FIG. 1. It can be seen that GO&SiO 2 The tensile strength, bending strength and bending modulus of the EP composite material are respectively improved from 47.45+/-2.32 MPa, 93.08 +/-5.07 MPa and 2562.70 +/-105.85 MPa to 60.71 +/-2.95 MPa, 115.44 +/-4.18 MPa and 3528.17 +/-85.83 MPa, and the impact strength is 8.57+/-0.56 kJ/m in FIG. 2 2 Raised to 12.32+/-0.64 kJ/m 2 。
Example 5 GO-SiO 2 Three-dimensional point plane nano material toughened EP composite material
1、GO-SiO 2 Three-dimensional point plane nano material toughened EP composite materialThe raw materials with the following weight proportions are prepared: GO-SiO 2 0.1 part of three-dimensional point plane nano material, 100 parts of bisphenol A epoxy resin, 50 parts of curing agent and 0.3 part of defoaming agent.
2. The preparation method comprises the following steps:
(1) Thiol covalent anchoring GO: prepared as in example 2.
(2) Epoxy group covalent anchoring SiO 2 : prepared as in example 3.
(3)GO-SiO 2 Three-dimensional dot plane nanomaterial: 1g SGO was added to 500mL DMF and sonicated for 30min to form a homogeneous suspension. Then, 0.2. 0.2g O-SiO 2 Adding into the suspension, and performing ultrasonic treatment for 30min to form uniform suspension. Finally, 4-Dimethylaminopyridine (DMAP) catalyst was added and the reaction was stirred at 105℃for 7h. GO-SiO 2 Centrifuging the product, washing with absolute ethanol and deionized water for five times, and drying at 60deg.C for 24 hr to obtain SiO 2 Modified GO (GO-SiO) 2 )。
(4) Composite material: heating EP at 80deg.C, reducing EP viscosity, adding 0.3wt.% defoamer, and adding GO-SiO 0.1% by mass 2 Added to EP, stirred for 30min, then sonicated at 40 ℃ for 1h, then de-bubbled in a vacuum oven. And adding a curing agent into the mixture, and uniformly stirring. Then pouring the mixture into a mold, curing for 24 hours at normal temperature, curing for 2 hours in a baking oven at 100 ℃ and curing for 4 hours at 150 ℃ to obtain GO-SiO 2 EP composite materials.
The tensile strength, flexural modulus and impact strength of the composite materials were tested using GB/T2567-2021 resin casting performance test methods, as shown in FIG. 1. It can be seen that GO-SiO 2 The tensile strength, bending strength and bending modulus of the EP composite material are respectively improved from 47.45+/-2.32 MPa, 93.08 +/-5.07 MPa and 2562.70 +/-105.85 MPa to 65.79+/-2.87 MPa, 126.73 +/-4.38 MPa and 3706.75 +/-100.06 MPa, and the impact strength is 8.57+/-0.56 kJ/m in FIG. 2 2 Raised to 13.85+/-0.69 kJ/m 2 。
FIG. 1 is a bending test of the EP composite material prepared by a universal tester. According to GB/T2567-2021 resin casting Performance testThe standard in method was used for preparing bars. FIG. 2 is a test of a specimen using a ZBC-4C pendulum impact tester manufactured by Shenzhen Sansi Material detection Co. As can be seen from FIG. 1, the GO-SiO produced in example 5 is compared to the pure EP material produced in comparative example 1 2 The tensile strength of the EP composite material is improved by 38.65 percent, the bending strength is improved by 36.15 percent, and the bending modulus is improved by 44.64 percent. As can be seen from fig. 2, the impact strength is improved by 61.61%. And by comparison it was found that the properties exhibited by the addition of different modified GO to EP are also different. Addition of 0.1wt.% GO-SiO in EP 2 The mechanical properties of the composite are best.
Fig. 3 shows a fault structure of the composite material observed by a scanning electron microscope model TESCAN MIRA LMS manufactured by tesken, inc, and analyzed for a failure mode to obtain a toughening mechanism, and a sample is subjected to metal spraying treatment before testing. As can be seen from fig. 3, the fracture surface of the pure EP prepared in example 1 has a less corrugated structure with a small number of branches (a in fig. 3). In contrast, GO-SiO in example 5 2 the/EP composite exhibits a large number of corrugations (b in FIG. 3) in the fracture cross section, and has a large number of lines and branches of bands and streamlines, GO-SiO 2 The flakes were well dispersed in the EP matrix and no significant platelet aggregation was observed. The formation of waves is accompanied by the generation of new fracture surfaces, GO-SiO 2 The breaking of the/EP composite consumes more energy. This illustrates GO-SiO 2 Has stronger interfacial adhesion with the EP matrix, so the EP impact performance is improved.
FIG. 4 is a representation of nanomaterials using a VECTOR-22 instrument from Bruker instruments, germany, and analysis of the functional groups on the surface of GO and its composites using a Fourier transform infrared spectrometer to determine the class of compounds and to determine if the chemical reaction process is proceeding successfully. From FIG. 4 a, it can be seen that the epoxy group is at 896cm -1 An asymmetric stretching vibration peak appears at the position. 2929cm -1 And 2863cm -1 The new characteristic peak at this point is O-SiO 2 In spectrum-CH 2 Is a tensile vibration of the steel sheet. KH560 is at SiO 2 Surface anchoring was successful. FIG. 4b can be found at 1442cm -1 、1241cm -1 、1083cm -1 The characteristic peaks at the positions respectively belong to the tensile vibration of C-S, C-Si and Si-O-C. Wherein, the stretching vibration peak of the Si-O-C bond is generated by hydrolysis after KH590 reacts with hydroxyl on GO. The new peaks also indicate that thiol groups have been successfully anchored to the GO surface. 900cm -1 The Si-OH peak at the site is a functional group generated by the hydrolysis of alkoxy groups, 794cm -1 A new stretching vibration peak appears nearby, which is Si-O-Si bond formed by the reaction between the silane coupling agents after alkoxy hydrolysis. In GO-SiO 2 2564cm in the spectrum of -1 the-SH peak at the spot disappeared, 1454cm -1 C-S-C bond appears nearby, indicating GO and SiO 2 The nano particles successfully react through a mercapto-epoxy clicking reaction.
Fig. 5a is a raman spectroscopy test of nanomaterial using a raman spectrometer (inVia Reflex) for structural analysis. The test parameters are as follows: infrared semiconductor laser with 785nm excitation light source and 500cm scanning range -1 -2800cm -1 The scan time was 10s. Structural changes during GO modification were analyzed using raman spectroscopy. As can be seen from FIG. 5a, I of GO and SGO D /I G Values of 1.36 and 1.44, respectively, indicate that GO surface grafting of silane chains reduces GO order. Furthermore, due to SiO 2 Introduction of NPs, I D /I G An increase in value to 1.75 indicates GO-SiO 2 The degree of disorder of the structure is further increased. FIG. 5b shows the analysis of the crystal structure of the nanomaterial by using a Bruker D8 Discover X-ray diffractometer, with the following test parameters: the copper target K alpha rays are adopted, the scanning range is 5-90 degrees, the scanning speed is 12 degrees/min, and the scanning time is 0.2s. GO has a narrow and strong diffraction peak at 12.24 °. After KH590 modification, a broader diffraction peak appears at 9.48. According to bragg equation 2dsin θ=nλ, SGO has an interlayer spacing 1.29 times that of GO due to grafting KH590 on the GO surface. For GO-SiO 2 A weak broad diffraction peak was observed around 6.02℃indicating amorphous SiO 2 NPs have been anchored at the GO surface. Calculated GO-SiO 2 Is 2.03 times higher than GO, indicating SiO 2 Aggregation of nanoparticles at the GO surface increases the interlayer spacing of GO. In addition, in the case of the optical fiber,the crystallinity of GO decreases and disorder increases, consistent with the results of raman analysis. FIG. 5b shows the same weight of GO and GO-SiO in a test tube 2 And (3) powder. It can be seen that due to SiO 2 Nanoparticles attached to GO layer, GO-SiO 2 Is larger than the volume of GO. SiO (SiO) 2 The nano particles are assembled on the surface of the GO through covalent bonds, so that the re-accumulation of the GO layer is prevented, and the dispersibility of the GO in the EP matrix is improved.
Fig. 6 shows a microstructure of a nanomaterial observed by a scanning electron microscope model TESCAN MIRA LMS manufactured by tesken, inc, and analyzed for lamellar structure, wrinkles, surface roughness, and the like, and a FEI Talos F200S transmission electron microscope of samer feier technology, inc. From the figure, it can be seen that SEM images of GO show an irregular layered two-dimensional structure with partial folds and overlaps. In GO-SiO 2 Surface, some SiO 2 The nanoparticles are uniformly coated on the GO surface. At the same time, the surface of GO is due to SiO 2 Is roughened by the loading of (2), indicating SiO 2 The nanoparticle is assembled with GO by reaction. To further characterize SiO 2 The dispersed state of the nano particles on the surface of GO, and the GO-SiO are observed through TEM 2 Is a topographical feature of (c). GO presents a transparent structure with many small folds and a large specific surface area. For GO-SiO 2 Coating a layer of SiO on the surface of GO 2 And (3) nanoparticles. Then, GO-SiO was further confirmed by EDS spectra and elemental mapping 2 C, O, si and S elements. The S element in the thiol group of KH590 is shown, and also exhibits sparse and uniform distribution. And a large amount of O element and Si element exist, further proving SiO 2 Nanoparticles have been successfully assembled on GO surfaces.
Fig. 7 is a view of the dispersion of nanomaterials in a dispersion medium using a WMS-1037 optical microscope manufactured by Chongqing ott optical instruments, inc. From the figure, it can be seen that GO and GO-SiO after ultrasound 2 Are well dispersed in EP. However, after 24h of standing, GO precipitated at the bottom of the bottle and the upper layer was significantly layered. And GO-SiO 2 Only generatePartially precipitates and can remain stable. This illustrates SiO 2 Is beneficial to the dispersion and inhibition of reagglomeration of GO, and improves GO-SiO 2 The dispersibility in the epoxy matrix helps to improve the mechanical properties of the EP composite.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. GO-SiO 2 The toughened epoxy resin composite material is characterized by comprising epoxy resin and GO-SiO 2 The three-dimensional point plane nano material and the curing agent are prepared by adopting a melt blending method as main raw materials;
the GO-SiO 2 The three-dimensional point planar nanomaterial comprises: mercapto-anchored GO and epoxy-anchored SiO 2 And the mercapto-anchored GO and epoxy-anchored SiO 2 Covalent hybridization is performed between the two through a click chemistry method.
2. The GO-SiO according to claim 1 2 The toughened epoxy resin composite material is characterized in that the click chemistry method comprises: anchoring the thiol-anchored GO and epoxy-anchored SiO 2 Stirring and reacting under the action of a catalyst to obtain SiO 2 Modified GO, namely the GO-SiO 2 Three-dimensional dot plane nanomaterial;
the mercapto-anchored GO and epoxy-anchored SiO 2 The mass ratio of (1-2): (0.2-1).
3. The GO-SiO according to claim 2 2 The toughened epoxy resin composite material is characterized in that the catalyst comprises 4-dimethylaminopyridine;
and/or the temperature of the stirring reaction is 105-110 ℃.
4. The GO-SiO according to claim 1 2 The toughened epoxy resin composite material is characterized in that the mercapto-anchored GO is GO modified by a mercapto silane coupling agent; the mercaptosilane coupling agent comprises: one or two of 3-mercaptopropyl trimethoxysilane and 3-mercaptopropyl triethoxysilane;
and/or, the preparation method of the GO modified by the mercaptosilane coupling agent comprises the following steps: dispersing GO in ethanol; under the condition that the pH value is 4-5, the sulfhydryl silane coupling agent is fully hydrolyzed in distilled water; then mixing the hydrolyzed mercaptosilane coupling agent with GO dispersion liquid, and stirring and reacting at 70-80 ℃; and finally centrifuging and washing the product, and then drying to obtain the GO modified by the mercaptosilane coupling agent.
5. The GO-SiO according to claim 1 2 Toughened epoxy resin composites characterized in that the epoxy-anchored SiO 2 SiO modified by epoxy silane coupling agent 2 The method comprises the steps of carrying out a first treatment on the surface of the The epoxy silane coupling agent includes: one or two of 3-glycidoxypropyl trimethoxysilane and 3-glycidoxypropyl triethoxysilane.
And/or, the epoxy silane coupling agent modified SiO 2 The preparation method of (2) comprises the following steps: siO is made of 2 Dispersing in ethanol; under the condition that the pH value is 4-5, the epoxy silane coupling agent is fully hydrolyzed in distilled water; then the hydrolyzed epoxy silane coupling agent and SiO 2 Mixing the dispersion liquid, and stirring and reacting at 70-80 ℃; finally centrifuging and washing the product, and then drying to obtain SiO modified by epoxy silane coupling agent 2 。
6. GO-SiO according to any one of claims 1-5 2 The toughened epoxy resin composite material is characterized in that the diameter of the GO sheet layer is 10-20 mu m;
and/or, the SiO 2 Is a microsphere with the diameter of 15-50 nm.
7. GO-SiO according to any one of claims 1-6 2 The toughened epoxy resin composite material is characterized in that the GO-SiO 2 The addition amount of the three-dimensional point plane nano material is 0.01 to 0.5wt.% of the mass of the epoxy resin; preferably 0.1 to 0.5wt.%;
and/or the GO-SiO 2 The toughened epoxy resin composite material comprises the following components in parts by weight: 100 parts of epoxy resin and GO-SiO 2 0.01 to 0.5 part of three-dimensional point plane nano material, 35 to 60 parts of curing agent and 0.1 to 0.5 part of defoaming agent.
8. The GO-SiO of claim 7 2 A toughened epoxy resin composite material, wherein the epoxy resin comprises E51, E44 or NPEL-128;
and/or, the defoamer comprises one or more of silicones and polyethers;
and/or the curing agent comprises one or more of polyetheramine and fatty amine types; the polyetheramine comprises D2000, T5000, or T403; the fatty amine type boanka ethylenediamine, diethylenetriamine or triethylenetetramine.
9. A GO-SiO according to any one of claims 1-8 2 The preparation method of the toughened epoxy resin composite material is characterized by comprising the following steps: heating epoxy resin to 60-100 ℃, and then adding an antifoaming agent and the GO-SiO 2 Stirring and ultrasonic treating the three-dimensional point plane nano material, adding a curing agent, uniformly stirring, defoaming, and finally pouring into a mold for curing to obtain the GO-SiO 2 Toughening epoxy resin composite materials.
10. The GO-SiO according to claim 9 2 The preparation method of the toughened epoxy resin composite material is characterized in that the power of ultrasonic treatment is 100-150W, and the ultrasonic time is 60-120 min;
and/or, the deaerating comprises: vacuumizing for 30-60 min in a vacuum drying oven with the vacuum degree below 0.1MPa for defoaming;
and/or, the curing comprises the steps of curing for 15-30 hours at normal temperature and then curing in an oven; the oven curing comprises the steps of curing for 2-4 hours at 80-100 ℃, and then heating to 120-150 ℃ for curing for 2-4 hours;
and/or the mould is a silica gel mould.
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