CN113549299A - Preparation method of high wear resistance and high toughness graphene nanosheets/epoxy resin composites - Google Patents
Preparation method of high wear resistance and high toughness graphene nanosheets/epoxy resin composites Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 80
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- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 79
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 66
- 239000002135 nanosheet Substances 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- -1 polysiloxane Polymers 0.000 claims abstract description 50
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- 229920000570 polyether Polymers 0.000 claims abstract description 44
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- 238000000498 ball milling Methods 0.000 claims abstract description 19
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- 239000000203 mixture Substances 0.000 claims description 28
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 8
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
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- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 claims description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 2
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 239000004844 aliphatic epoxy resin Substances 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920006295 polythiol Polymers 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 229920005989 resin Polymers 0.000 claims 1
- 239000011347 resin Substances 0.000 claims 1
- 239000002270 dispersing agent Substances 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 229910002804 graphite Inorganic materials 0.000 abstract 1
- 239000010439 graphite Substances 0.000 abstract 1
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 6
- DGUJJOYLOCXENZ-UHFFFAOYSA-N 4-[2-[4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenol Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 DGUJJOYLOCXENZ-UHFFFAOYSA-N 0.000 description 6
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- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical group [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 2
- 238000009435 building construction Methods 0.000 description 2
- 238000004100 electronic packaging Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229920000469 amphiphilic block copolymer Polymers 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000675 fabric finishing Substances 0.000 description 1
- 238000009962 finishing (textile) Methods 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- 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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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明公开了高耐磨和高韧性石墨烯纳米片/环氧树脂复合材料的制备方法，该方法采用一种嵌段共聚物—环氧基封端型聚醚聚硅氧烷作为石墨烯纳米片的分散剂，通过球磨石墨，将剥离的石墨烯纳米片均匀分散在环氧基封端型聚醚聚硅氧烷中，然后将混合浆液与环氧树脂共混并固化，制备石墨烯纳米片/环氧树脂复合材料。环氧基封端型聚醚聚硅氧烷嵌段结构中的有机硅和聚醚柔性链结构与石墨烯协同增韧环氧树脂，石墨烯的自润滑作用显著提高了环氧树脂的耐磨性，从而制备出高耐磨和高韧性的石墨烯纳米片/环氧树脂复合材料，该复合材料的高耐磨和高韧性以及优良的综合性能使其在研磨抛光、包装运输、电子电器和航空航天等领域具有极大的市场应用价值。
The invention discloses a preparation method of a graphene nanosheet/epoxy resin composite material with high wear resistance and high toughness. The method adopts a block copolymer-epoxy end-capped polyether polysiloxane as graphene nanosheet The dispersant of the sheet, by ball milling graphite, the exfoliated graphene nanosheets are uniformly dispersed in the epoxy-terminated polyether polysiloxane, and then the mixed slurry is blended with epoxy resin and cured to prepare graphene nanosheets. sheet/epoxy composite. The silicone and polyether flexible chain structures in the epoxy-terminated polyether polysiloxane block structure synergistically toughen epoxy resin with graphene, and the self-lubricating effect of graphene significantly improves the wear resistance of epoxy resin Therefore, graphene nanosheets/epoxy resin composites with high wear resistance and high toughness can be prepared. Aerospace and other fields have great market application value.
Description
Technical Field
The invention belongs to the field of polymer composite materials, and particularly relates to a preparation method of a graphene nanosheet/epoxy resin composite material with high wear resistance and high toughness.
Background
Due to good comprehensive performance, the epoxy resin is widely applied to the fields of electronic packaging, building construction, aerospace and the like. However, the epoxy resin still has some disadvantages in use, such as insufficient mechanical strength, toughness, wear resistance, heat conductivity, etc., which limits its application in various fields. Therefore, the reinforced modification of the epoxy resin is of great significance.
Graphene is considered to be a good filler for improving mechanical properties, wear resistance, flame retardance, heat conduction and electric conduction of high polymer materials due to a two-dimensional nano-layered structure and excellent comprehensive properties (Kim, et al macromolecules 2010,43, 6515-166530; Papageorgiouo, et al prog, Mater, Sci.2017,90, 75-127; Liang, et al, J.Mater, chem.C 2019,7, 2725-2733; Liushu, Sunju, and the like. However, the application of graphene in polymer modification still has a bottleneck to be solved urgently. On one hand, graphene sheets have strong van der waals force between layers, and are difficult to peel off in a high-molecular matrix by using a traditional dispersion method, and are dispersed in a form of single sheets and easy to agglomerate, so that the modification effect of the graphene sheets is reduced. For better dispersion effect, organic solvent is often adopted for dilution and dispersion (Yan red strong, Fangzhui, etc. a preparation method of graphene nanoplatelets/epoxy resin nanocomposite, CN 103396653A; Songhe river, Marmokun, etc. a preparation method of graphene epoxy resin composite, CN 103408895A). However, the introduction of organic solvent not only makes the preparation process complicated and increases energy consumption, but also pollutes environment. Secondly, due to the relative chemical inertness of the surface structure of graphene, the interaction force between graphene and macromolecules is weak, and the modification efficiency of graphene in the aspects of macromolecule mechanical property and heat conduction and electricity conduction is influenced. Therefore, before the graphene modified polymer material is used, the graphene is generally subjected to surface modification treatment (Toulongcheng, Wanyanjun, and the like, a preparation method of a functionalized graphene oxide/epoxy resin composite material, CN103627139AA, Rankine lacquer, Zhaoyuan, and the like, a thermal interface material of surface modified graphene-carbon nitride-epoxy resin and a preparation method thereof, CN 109337291A). However, the chemical surface modification process of graphene is complicated, the operation is complex, the industrial production is difficult, and a strong oxidant and an organic solvent are often used, so that the environment is polluted. Meanwhile, surface chemical modification can destroy the graphitized structure of graphene, so that excellent performances of graphene in the aspects of mechanics, heat conduction and electric conduction are reduced, while a modifier in a physical non-covalent bond modification method is high in cost, and the performance of epoxy resin is reduced by adding the modifier. Therefore, the good graphene dispersing agent and surface modifier are found to have great value for the application of graphene in the modification of high polymer materials.
Sundao 38495and the like utilize a block copolymer, i.e., isobutylene-b-propylene ethanol-b-isobutylene, as a dispersant to achieve good dispersion of graphene in an oily solvent (sundao 38495, litdan, a slurry and a preparation method and application thereof, CN 110484020A). Limeitai and the like adopt a polyether-polystyrene and other block copolymers as a dispersing agent to prepare a graphene solution (limeitai, sunzurchi, and the like, the block copolymers and a method for preparing graphene by using the block copolymers, CN107182213B) with good dispersion. The block copolymer has obvious toughening effect on epoxy resin (Huang Yajiang, Tang Dynasty, and the like, a reinforcing toughening agent, a toughened epoxy resin composite material and a preparation method thereof, CN107459612B, and amphiphilic block copolymer and inorganic nano filler for reinforcing the performance of thermosetting polymer, CN 101772546B).
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of a graphene nanosheet/epoxy resin composite material with high wear resistance and high toughness, the preparation method adopts a commercially available liquid fabric finishing agent, namely epoxy-terminated polyether polysiloxane, as a dispersing agent, and an organic silicon-oxygen chain in the structure of the polyether polysiloxane has strong interaction with a graphitized structure in graphene and can be used as a dispersing agent and a surface modifier of the graphene. Meanwhile, epoxy-terminated polyether can participate in epoxy resin curing, so that graphene and epoxy resin have strong interface interaction force. Therefore, the epoxy-terminated polyether polysiloxane and the graphene synergistically reinforce the modified epoxy resin.
In order to achieve the above purpose, the solution of the invention is:
a preparation method of a graphene nanosheet/epoxy resin composite material with high wear resistance and high toughness comprises the following steps:
1) adding graphite powder into epoxy-terminated polyether polysiloxane according to a certain mass ratio, and filling the mixture into a ball milling tank for ball milling to obtain graphene nanosheet/epoxy-terminated polyether polysiloxane mixed slurry.
2) The above steps are carried out. And mixing the graphene nanosheet/epoxy-terminated polyether polysiloxane mixed slurry with a certain amount of curing agent and epoxy resin, and stirring at a high speed for 30 minutes to obtain an epoxy resin mixture.
3) And vacuumizing the epoxy resin mixture, removing bubbles, pouring into a mold, and carrying out curing reaction to prepare the graphene nanosheet/epoxy resin composite material with high wear resistance and high toughness.
The mesh number of the graphite powder is 300-5000 meshes.
The epoxy-terminated polyether polysiloxane is colorless transparent or light yellow transparent liquid, and the viscosity is 100-3000 cP.
The midblock in the structure of the epoxy-terminated polyether polysiloxane is one or more copolymers of polydimethylsiloxane, polymethylphenylsiloxane and polydiphenylsiloxane. The molecular weight of the midblock is 500-5000 g/mol.
Two side blocks in the epoxy terminated polyether polysiloxane structure are one or two copolymers of polyoxyethylene ether and polyoxyethylene oxypropylene ether. The molecular weight of the two-side block is 500-10000 g/mol.
The end group in the epoxy terminated polyether polysiloxane structure is an epoxy group.
The mass ratio of the graphite powder to the epoxy-terminated polyether polysiloxane is 1: (3-200).
The ball milling equipment is a planetary ball mill, the grinding balls are zirconium dioxide balls, the ball milling rotating speed is 100-1000 rpm, and the ball milling time is 2-6 hours.
The epoxy resin is liquid epoxy resin, and specifically is one or a combination of more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin and aliphatic epoxy resin.
The curing agent is one or a combination of several of polyether amine, aliphatic amine, alicyclic amine, aromatic amine, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride and polythiol.
The epoxy resin composite material comprises the following components in percentage by mass: epoxy resin: 100 parts by mass; graphene nanosheet/epoxy-terminated polyether polysiloxane mixed slurry: 5-100 parts by mass; a curing agent; 10 to 120 parts by mass.
The curing process comprises the step-by-step heating curing, wherein the curing temperature of the first stage is 20-140 ℃, and the curing time is 30-90 minutes; the curing temperature of the second stage is 60-180 ℃, and the time is 60-300 minutes.
After the technical scheme is adopted, the invention has the following beneficial effects: 1) the invention adopts a commercial block copolymer-epoxy terminated polyether polysiloxane, wherein an organic silicon oxygen chain in the structure has strong interaction with a graphitized structure in graphene, and the block copolymer-epoxy terminated polyether polysiloxane can be used as a dispersing agent and a surface modifier of the graphene. Meanwhile, epoxy-terminated polyether can participate in epoxy resin curing, so that epoxy-terminated polyether polysiloxane modified graphene can be uniformly dispersed in epoxy resin and has strong interfacial interaction force with the epoxy resin. 2) The epoxy-terminated polyether polysiloxane is a block copolymer with high flexibility, has an obvious toughening effect on epoxy resin, and can be used for toughening the epoxy resin together with graphene. 3) The preparation method disclosed by the invention is simple in process, free of organic solvent, green and environment-friendly, and can meet the requirements of industrial production; 4) the epoxy resin composite material prepared by the invention not only has high wear resistance and high toughness, but also has other excellent performances such as heat conduction and the like, and has great application value in the fields of electronic packaging, building construction, aerospace and the like.
Drawings
FIG. 1 shows the chemical structure of epoxy-terminated polyether polysiloxane.
Detailed Description
In order to further explain the technical solution of the present invention, the present invention is explained in detail by the following specific examples.
Example 1
500-mesh graphite powder and epoxy terminated polyether polysiloxane (polydimethylsiloxane chain segment: 1000g/mol, epoxy polyether chain segment: 500g/mol) are mixed according to the mass ratio of 1: 199, and filling the mixture into a ball milling tank to perform ball milling for 2 hours at the rotating speed of 500rpm to prepare the graphene nanosheet/epoxy-terminated polyether polysiloxane mixed slurry. Then, 20g of the mixed slurry was mixed with 100g of bisphenol A epoxy resin (bisphenol A glycidyl ether), 85g of methyl hexahydrophthalic anhydride as a curing agent and 1.5g of 2, 4, 6-tris (dimethylaminomethyl) phenol as parts by mass, and stirred at a high speed for 30 minutes to obtain a black slurry epoxy resin mixture. A black paste epoxy resin mixture was obtained. And putting the mixture into an oven, vacuumizing for 10 minutes, removing bubbles introduced by stirring, pouring into a mold, and carrying out a curing reaction. The curing conditions were: curing for 60 minutes at 120 ℃, heating to 140 ℃ and curing for 4 hours to obtain the graphene nanosheet/epoxy resin composite material.
Example 2
Mixing 800-mesh graphite powder and epoxy terminated polyether polysiloxane (polydimethylsiloxane chain segment: 2000g/mol, epoxy polyether chain segment: 500g/mol) according to a mass ratio of 1: 99, and filling the mixture into a ball milling tank to perform ball milling for 4 hours at the rotating speed of 800rpm to prepare the graphene nanosheet/epoxy-terminated polyether polysiloxane mixed slurry. Then, 10g of the mixed slurry was mixed with 100g of bisphenol A epoxy resin (bisphenol A glycidyl ether), 85g of methyl hexahydrophthalic anhydride as a curing agent and 1.5g of 2, 4, 6-tris (dimethylaminomethyl) phenol as parts by mass, and stirred at high speed for 30 minutes to obtain a black slurry epoxy resin mixture. A black paste epoxy resin mixture was obtained. And putting the mixture into an oven, vacuumizing for 10 minutes, removing bubbles introduced by stirring, pouring into a mold, and carrying out a curing reaction. The curing conditions were: curing for 60 minutes at 120 ℃, heating to 140 ℃ and curing for 4 hours to obtain the graphene nanosheet/epoxy resin composite material.
Example 3
1500-mesh graphite powder and epoxy terminated polyether polysiloxane (polydimethylsiloxane chain segment: 3000g/mol, epoxy polyether chain segment: 500g/mol) are mixed according to the mass ratio of 1: 19, mixing, and ball-milling in a ball-milling tank at the rotating speed of 600rpm for 5 hours to prepare the graphene nanosheet/epoxy-terminated polyether polysiloxane mixed slurry. Then, 10g of the mixed slurry was mixed with 100g of bisphenol A epoxy resin (bisphenol A glycidyl ether), 85g of methyl hexahydrophthalic anhydride as a curing agent and 1.5g of 2, 4, 6-tris (dimethylaminomethyl) phenol as parts by mass, and stirred at high speed for 30 minutes to obtain a black slurry epoxy resin mixture. A black paste epoxy resin mixture was obtained. And putting the mixture into an oven, vacuumizing for 10 minutes, removing bubbles introduced by stirring, pouring into a mold, and carrying out a curing reaction. The curing conditions were: curing for 60 minutes at 120 ℃, heating to 140 ℃ and curing for 4 hours to obtain the graphene nanosheet/epoxy resin composite material.
Example 4
3000-mesh graphite powder and epoxy terminated polyether polysiloxane (polydimethylsiloxane chain segment: 2000g/mol, epoxy polyether chain segment: 500g/mol) are mixed according to the mass ratio of 1: 9, mixing, and putting the mixture into a ball milling tank to perform ball milling for 6 hours at the rotating speed of 1000rpm to prepare the graphene nanosheet/epoxy-terminated polyether polysiloxane mixed slurry. Then, 10g of the mixed slurry was mixed with 100g of bisphenol A epoxy resin (bisphenol A glycidyl ether), 85g of methyl hexahydrophthalic anhydride as a curing agent and 1.5g of 2, 4, 6-tris (dimethylaminomethyl) phenol as parts by mass, and stirred at high speed for 30 minutes to obtain a black slurry epoxy resin mixture. A black paste epoxy resin mixture was obtained. And putting the mixture into an oven, vacuumizing for 10 minutes, removing bubbles introduced by stirring, pouring into a mold, and carrying out a curing reaction. The curing conditions were: curing for 60 minutes at 120 ℃, heating to 140 ℃ and curing for 4 hours to obtain the graphene nanosheet/epoxy resin composite material.
Comparative example 1
1g of 3000-mesh graphite powder was added to 100g of bisphenol A epoxy resin (bisphenol A glycidyl ether), and the mixture was uniformly mixed, then 85g of a curing agent methylhexahydrophthalic anhydride and 1.5g of 2, 4, 6-tris (dimethylaminomethyl) phenol by mass were added and mixed, and the mixture was stirred at high speed for 30 minutes to obtain a black slurry epoxy resin mixture. A black paste epoxy resin mixture was obtained. And putting the mixture into an oven, vacuumizing for 10 minutes, removing bubbles introduced by stirring, pouring into a mold, and carrying out a curing reaction. The curing conditions were: curing for 60 minutes at 120 ℃, heating to 140 ℃ and curing for 4 hours to prepare the epoxy resin composite material.
Comparative example 2
100g of bisphenol A epoxy resin (bisphenol A glycidyl ether), 85g of a curing agent methylhexahydrophthalic anhydride and 1.5g of 2, 4, 6-tris (dimethylaminomethyl) phenol by mass were mixed and stirred at high speed for 30 minutes to obtain a black slurry epoxy resin mixture. A black paste epoxy resin mixture was obtained. And putting the mixture into an oven, vacuumizing for 10 minutes, removing bubbles introduced by stirring, pouring into a mold, and carrying out a curing reaction. The curing conditions were: curing for 60 minutes at 120 ℃, heating to 140 ℃ and curing for 4 hours to prepare the epoxy resin composite material.
In order to better illustrate the effects of the present invention, samples of examples and comparative examples were tested. The impact strength test is carried out according to the ASTM D6110-2017 standard, the abrasion resistance test is carried out according to the ASTM G9905 standard, and the thermal conductivity test is carried out according to the ASTM D5930-2017 standard. As can be seen from Table 1, the epoxy-terminated polyether polysiloxane and the carbon nanotubes cooperate to significantly improve the impact strength of the epoxy resin, which indicates that the toughness of the epoxy resin is significantly improved. Meanwhile, the wear resistance and the heat conductivity of the epoxy resin are improved. Therefore, the graphene nanosheet/epoxy resin composite material prepared by the method disclosed by the invention has the advantages of high wear resistance, high toughness and excellent comprehensive performance.
Table 1 results of performance testing
The above embodiments are not intended to limit the form and style of the present invention, and any suitable changes or modifications may be made by one of ordinary skill in the art without departing from the present invention.
Claims (10)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113881051A (en) * | 2021-11-05 | 2022-01-04 | 无锡东润电子材料科技有限公司 | Preparation method and application of multifunctional toughening agent for epoxy resin |
| CN115197540A (en) * | 2022-08-01 | 2022-10-18 | 哈尔滨工业大学（深圳） | A kind of preparation method and product of modified epoxy composite material suitable for marine environment |
| CN116284655A (en) * | 2023-01-10 | 2023-06-23 | 中威北化科技有限公司 | Preparation method of graphene-organosilicon synergistically-reinforced polyurethane grafted modified epoxy resin |
| WO2023197698A1 (en) * | 2022-04-14 | 2023-10-19 | 华南理工大学 | Heat-conduction-enhanced phase-change nanocapsule composite material, and preparation method therefor and use thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08176269A (en) * | 1994-12-27 | 1996-07-09 | Matsushita Electric Works Ltd | Epoxy resin composition for sealing |
| CN1279257A (en) * | 1999-06-30 | 2001-01-10 | 中国科学院化学研究所 | Polysiloxane modified epoxy resin composition |
| CN1982356A (en) * | 2005-12-15 | 2007-06-20 | 山东大易化工有限公司 | Epoxypropoxy end capped polyether and phenyl comodified polysiloxane, and preparation and use thereof |
| WO2017219944A1 (en) * | 2016-06-20 | 2017-12-28 | 山东欧铂新材料有限公司 | Method for preparing graphene-epoxy resin composite material |
| CN109265930A (en) * | 2018-07-24 | 2019-01-25 | 西北工业大学 | A kind of low-cost high-toughness self-lubricating epoxy resin and preparation method |
| CN110229464A (en) * | 2019-05-11 | 2019-09-13 | 常州宝利美石墨烯有限公司 | A kind of epoxy silicon oil modified graphene oxide and epoxy resin composite material preparation method |
| US20200190312A1 (en) * | 2016-09-06 | 2020-06-18 | Regents Of The University Of Minnesota | Synergistic toughening of epoxy modified by graphene and block copolymer |
| CN111607312A (en) * | 2020-06-04 | 2020-09-01 | 杭州每步材料科技有限公司 | Toughened abrasion-resistant epoxy resin daub and preparation method thereof |
| US20200291188A1 (en) * | 2019-03-13 | 2020-09-17 | Ele' Corporation | Epoxy-functionalized polyorganosiloxane toughener |
| CN112300666A (en) * | 2020-12-02 | 2021-02-02 | 陕西科技大学 | High-wear-resistance and corrosion-resistance graphene/epoxy super-slip coating and preparation method thereof |
-
2021
- 2021-07-22 CN CN202110831547.6A patent/CN113549299A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08176269A (en) * | 1994-12-27 | 1996-07-09 | Matsushita Electric Works Ltd | Epoxy resin composition for sealing |
| CN1279257A (en) * | 1999-06-30 | 2001-01-10 | 中国科学院化学研究所 | Polysiloxane modified epoxy resin composition |
| CN1982356A (en) * | 2005-12-15 | 2007-06-20 | 山东大易化工有限公司 | Epoxypropoxy end capped polyether and phenyl comodified polysiloxane, and preparation and use thereof |
| WO2017219944A1 (en) * | 2016-06-20 | 2017-12-28 | 山东欧铂新材料有限公司 | Method for preparing graphene-epoxy resin composite material |
| US20200190312A1 (en) * | 2016-09-06 | 2020-06-18 | Regents Of The University Of Minnesota | Synergistic toughening of epoxy modified by graphene and block copolymer |
| CN109265930A (en) * | 2018-07-24 | 2019-01-25 | 西北工业大学 | A kind of low-cost high-toughness self-lubricating epoxy resin and preparation method |
| US20200291188A1 (en) * | 2019-03-13 | 2020-09-17 | Ele' Corporation | Epoxy-functionalized polyorganosiloxane toughener |
| CN110229464A (en) * | 2019-05-11 | 2019-09-13 | 常州宝利美石墨烯有限公司 | A kind of epoxy silicon oil modified graphene oxide and epoxy resin composite material preparation method |
| CN111607312A (en) * | 2020-06-04 | 2020-09-01 | 杭州每步材料科技有限公司 | Toughened abrasion-resistant epoxy resin daub and preparation method thereof |
| CN112300666A (en) * | 2020-12-02 | 2021-02-02 | 陕西科技大学 | High-wear-resistance and corrosion-resistance graphene/epoxy super-slip coating and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 段志豪 等: "线性双端环氧基FB-450聚醚硅氧烷的合成", 《印染》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113881051A (en) * | 2021-11-05 | 2022-01-04 | 无锡东润电子材料科技有限公司 | Preparation method and application of multifunctional toughening agent for epoxy resin |
| WO2023197698A1 (en) * | 2022-04-14 | 2023-10-19 | 华南理工大学 | Heat-conduction-enhanced phase-change nanocapsule composite material, and preparation method therefor and use thereof |
| CN115197540A (en) * | 2022-08-01 | 2022-10-18 | 哈尔滨工业大学（深圳） | A kind of preparation method and product of modified epoxy composite material suitable for marine environment |
| CN115197540B (en) * | 2022-08-01 | 2023-08-08 | 哈尔滨工业大学（深圳） | Preparation method and product of modified epoxy composite material suitable for marine environment |
| CN116284655A (en) * | 2023-01-10 | 2023-06-23 | 中威北化科技有限公司 | Preparation method of graphene-organosilicon synergistically-reinforced polyurethane grafted modified epoxy resin |
| CN116284655B (en) * | 2023-01-10 | 2024-01-09 | 中威北化科技有限公司 | Preparation method of graphene-organosilicon synergistically-reinforced polyurethane grafted modified epoxy resin |
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