CN117801150B - Dispersing agent for epoxy resin-graphene system and preparation method thereof - Google Patents
Dispersing agent for epoxy resin-graphene system and preparation method thereof Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 86
- 239000002270 dispersing agent Substances 0.000 title claims abstract description 73
- 239000004593 Epoxy Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 239000000178 monomer Substances 0.000 claims description 75
- 238000003756 stirring Methods 0.000 claims description 46
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims description 38
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 29
- 229940126062 Compound A Drugs 0.000 claims description 27
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 16
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 14
- GVLQQPDTOWRBRC-UHFFFAOYSA-N 2-bromo-n-(2-bromoethyl)ethanamine Chemical compound BrCCNCCBr GVLQQPDTOWRBRC-UHFFFAOYSA-N 0.000 claims description 13
- CNQRHSZYVFYOIE-UHFFFAOYSA-N (4-iodophenyl)methanol Chemical compound OCC1=CC=C(I)C=C1 CNQRHSZYVFYOIE-UHFFFAOYSA-N 0.000 claims description 12
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 claims description 9
- FXORZKOZOQWVMQ-UHFFFAOYSA-L dichloropalladium;triphenylphosphane Chemical compound Cl[Pd]Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 FXORZKOZOQWVMQ-UHFFFAOYSA-L 0.000 claims description 9
- 238000011049 filling Methods 0.000 claims description 9
- XGWFJBFNAQHLEF-UHFFFAOYSA-N 9-anthroic acid Chemical compound C1=CC=C2C(C(=O)O)=C(C=CC=C3)C3=CC2=C1 XGWFJBFNAQHLEF-UHFFFAOYSA-N 0.000 claims description 8
- -1 silver hexafluoroantimonate Chemical compound 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 39
- 239000002131 composite material Substances 0.000 abstract description 8
- 230000008859 change Effects 0.000 abstract description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 28
- 239000003822 epoxy resin Substances 0.000 description 23
- 229920000647 polyepoxide Polymers 0.000 description 23
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 15
- 230000001276 controlling effect Effects 0.000 description 13
- 230000000694 effects Effects 0.000 description 8
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 7
- 239000004342 Benzoyl peroxide Substances 0.000 description 7
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 7
- 235000019400 benzoyl peroxide Nutrition 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 102000004005 Prostaglandin-endoperoxide synthases Human genes 0.000 description 3
- 108090000459 Prostaglandin-endoperoxide synthases Proteins 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229910021392 nanocarbon Inorganic materials 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- IBODDUNKEPPBKW-UHFFFAOYSA-N 1,5-dibromopentane Chemical compound BrCCCCCBr IBODDUNKEPPBKW-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
-
- 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
- C08K2201/001—Conductive 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)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of composite materials, in particular to a dispersing agent for an epoxy resin-graphene system and a preparation method thereof, wherein a main chain with a large pi-bond structure in a dispersing agent structure for the epoxy resin-graphene system improves the conductivity of the dispersing agent; the epoxy resin-graphene composite material has an amino ring structure, so that the impact resistance and the curing speed of the epoxy resin-graphene composite material after the dispersing agent is used are improved; the dispersing agent does not react with graphene to change the body structure of the graphene, and pi-pi bonds are utilized to attract the graphene, so that the dispersing performance and mechanical performance of the graphene are improved.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a dispersing agent for an epoxy resin-graphene system and a preparation method thereof.
Background
The epoxy resin has the characteristics of high adhesiveness, high strength, wear resistance, corrosion resistance and the like, and has wide application in the fields of construction, electronics, automobiles, aerospace, medical treatment and the like, but the epoxy resin has high chemical crosslinking density, low molecular chain flexibility and large internal stress of a structure after being cured, the cured epoxy resin shows rigidity and brittleness behaviors, and the crack resistance expansibility is poor, so that the application of the epoxy resin is limited.
Graphene is a two-dimensional material composed of carbon atoms, and has advantages such as high conductivity, high strength, transparency, toughness, good chemical stability, and the like. Researchers find that the problem of epoxy resin can be solved by doping graphene and epoxy resin, but graphene is easy to agglomerate in an epoxy resin matrix due to large surface area and strong van der Waals force, so that the crack development direction of the epoxy resin becomes single when the epoxy resin is subjected to external force, and therefore, how to solve the dispersibility of the graphene in the epoxy resin becomes a hot spot of current research. The methods commonly used at present are as follows: 1. the surface of the nano carbon material is directly modified, so that different types of functional groups are grafted on the surface of the nano carbon material, and the dispersion performance of the nano carbon material is improved. 2. The graphene can be well dispersed in the epoxy resin by adding the dispersing agent.
For example, CN113896871B, an epoxy-graphene system dispersing agent and a preparation method thereof, discloses a dispersing agent which has simple synthesis method and high yield, has good dispersing effect on graphene, graphene oxide or graphite sheets under the epoxy-graphene system, and can effectively toughen an epoxy resin matrix. In addition, as CN114479546B, a preparation method and application of an easily dispersible graphene slurry, which provides a graphene dispersing agent structure, and the graphene slurry with stable dispersibility can be directly obtained when the graphene slurry is prepared by stripping through optimization of a graphene dispersing agent and a solvent, so that the graphene dispersing agent structure can be used for preparing graphene heavy anti-corrosion coating and graphene heat conduction slurry. However, the flexibility and conductivity of the epoxy resin composite material are also problems to be solved, and the above two publications do not mention and solve the problems.
Therefore, development of a dispersant for graphene, which does not change the structure of graphene itself, can increase the dispersibility of graphene and can also increase the curing speed, impact resistance and conductivity of an epoxy resin-graphene composite, is urgent.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a dispersing agent for an epoxy resin-graphene system and a preparation method thereof, wherein the dispersing agent can accelerate the curing speed of epoxy resin, improve the dispersity and stability of graphene in the epoxy resin system, and simultaneously increase the flexibility and conductivity of an epoxy resin-graphene composite material.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the invention provides a dispersing agent for an epoxy resin-graphene system, which has the structural formula:
Wherein a=2b, and a, b are positive integers.
In the epoxy resin-graphene system, the shielding effect of the epoxy resin is stronger, the conductivity of the graphene is weakened, the conductivity of the epoxy resin-graphene system can be increased by introducing a large pi bond structure, meanwhile, the dispersing agent also has pi-pi bonds instead of pi-pi bonds generated by reacting with the graphene, the mechanical property and the dispersibility of the graphene are enhanced through pi-pi bond action on the basis of not changing the structure of the graphene, and in addition, the cyclic amino structure in the dispersing agent can increase the curing speed of the epoxy resin and improve the shock resistance of the system.
In some embodiments, the dispersant for the epoxy-graphene system has a molecular weight of 2000 to 13000.
The applicant researches and discovers that the molecular weight of the dispersing agent can be specifically regulated to enable solids to be more easily adsorbed to form a thicker adsorption layer, so that aggregation of solid particles is prevented, and the dispersing effect is improved; in addition, the dispersing agent has better steric hindrance, and can better prevent the sedimentation and aggregation of solid particles, thereby improving the suspension performance and stability of the whole system.
The invention further provides a preparation method of the dispersing agent for the epoxy resin-graphene system, which comprises the following steps:
S1, mixing copper iodide, triphenylphosphine palladium dichloride, 4-iodobenzyl alcohol and triethylamine, filling N 2, stirring, dropwise adding phenylacetylene, heating to 40-50 ℃, and stirring for 16-18 hours under temperature control to obtain a compound A;
S2, mixing the compound A with 9-anthracene carboxylic acid, adding a solvent, adding a first catalyst, adjusting the pH of the reaction solution, heating to 100-110 ℃, and stirring for 2-4 hours to obtain a monomer B;
s3, mixing another compound A with glycidol, adding a solvent, adding a second catalyst, heating to 60-70 ℃ by microwaves, and reacting for 4-6 hours to obtain a monomer C;
S4, adding the monomer C into water, adding a third catalyst, controlling the temperature to be 35-45 ℃, stirring for 4-10 hours to obtain an intermediate, adding the intermediate into a solvent, adding an acid binding agent, heating to 60-80 ℃, dropwise adding 2-bromo-N- (bromoethyl) ethylamine, and stirring for 16-24 hours to obtain a monomer D;
S5, mixing the monomer B and the monomer D, adding a solvent, filling N 2, adding an initiator, heating to 80-90 ℃, and stirring for 4-6 hours to obtain the dispersing agent for the epoxy resin-graphene system.
In some embodiments, the molar ratio of phenylacetylene to 4-iodobenzyl alcohol in step S1 is 1 (1-1.3).
Preferably, the molar ratio of phenylacetylene to 4-iodobenzyl alcohol in step S1 is 1:1.2.
The invention can lead the reaction to be more complete and the yield to be higher by controlling the proportion of phenylacetylene and 4-iodobenzyl alcohol.
In some embodiments, the molar ratio of phenylacetylene to copper iodide in step S1 is 1 (0.01-0.02); the addition amount of triphenylphosphine or triphenylphosphine palladium dichloride in the step S1 is 8-10wt% of phenylacetylene; the volume of triethylamine in the step S1 is 10-14 times of the mass volume of phenylacetylene.
Preferably, in the step S1, the molar ratio of phenylacetylene to copper iodide is 1:0.015; the addition amount of the triphenylphosphine or the triphenylphosphine palladium dichloride in the step S1 is 9 weight percent of phenylacetylene; the volume of triethylamine in the step S1 is 12 times of the mass volume of phenylacetylene.
In some embodiments, the molar ratio of compound A to 9-anthranilic acid in step S2 is 1 (1 to 1.3).
Preferably, the molar ratio of the compound A to the 9-anthracene carboxylic acid in the step S2 is 1:1.2.
In some embodiments, the first catalyst in the step S2 is thionyl chloride, and the pH value of the reaction solution is adjusted to 1-3.
Preferably, in the step S2, the first catalyst is thionyl chloride, and the pH value of the reaction solution is adjusted to 2.
In some embodiments, the solvent in step S2 is N, N-dimethylformamide and/or toluene, and the volume is 8 to 12 times the mass of compound a.
Preferably, the solvent in the step S2 is toluene, and the volume is 10 times the mass of the compound a.
Toluene and N, N-dimethylformamide can generate an azeotropic effect with water, and the applicant finds that the azeotropic effect of toluene is better than that of N, N-dimethylformamide, and the azeotropic effect can discharge water generated in a reaction liquid and promote the forward progress of an esterification reaction.
In some embodiments, in step S3, the molar ratio of compound A to glycidol is 1 (1.2-1.4).
Preferably, in the step S3, the molar ratio of the compound a to the glycidol is 1:1.3.
The hydroxyl group in glycidol reacts with the hydroxyl group on 4-iodobenzyl alcohol to form an ether bond, and at the same time, the hydroxyl group can open the ring of the epoxy group in glycidol, and the generated hydroxyl group reacts with glycidol again, so that the molar ratio of the compound A to glycidol needs to be controlled to make the reaction more complete.
In some embodiments, the second catalyst in step S3 is a combination of 8 to 10wt% tetrakis (triphenylphosphine) palladium of compound a and 8 to 10wt% silver hexafluoroantimonate of compound a.
Preferably, the second catalyst in the step S3 is a combination of 9wt% of tetrakis (triphenylphosphine) palladium of the compound a and 9wt% of silver hexafluoroantimonate of the compound a.
In some embodiments, the solvent in step S3 is dichloroethane or toluene, and the volume is 8 to 12 times the mass of compound a.
Preferably, the solvent in the step S3 is dichloroethane, and the volume is 10 times the mass of the compound a.
In some embodiments, the third catalyst in step S4 is a cyclooxygenase enzyme added in an amount of 5 to 10wt% of monomer C; the water in the step S4 is deionized water, and the volume of the water is 5 to 10 times of the mass of the monomer C; the solvent in the step S4 is one or more of acetonitrile, methanol, ethanol, ethyl acetate and dichloromethane, and the volume of the solvent is 10-14 times of the mass of the monomer C.
Preferably, the third catalyst in the step S4 is cyclooxygenase, and the addition amount is 8wt% of the monomer C; the water in the step S4 is deionized water, and the volume of the water is 8 times of the mass of the monomer C; the solvent in the step S4 is acetonitrile, and the volume is 12 times of the mass of the monomer C.
The end group in the monomer C structure is an epoxy group, the epoxy group is soaked in alkaline solution, and is ring-opened into hydroxyl under the action of polar groups under the action of alkaline solution, so that the subsequent reaction is convenient to carry out.
In some embodiments, in step S4, the molar ratio of monomer C to 2-bromo-N- (bromoethyl) ethylamine is 1 (1 to 1.4).
Preferably, in the step S4, the molar ratio of the monomer C to the 2-bromo-N- (bromoethyl) ethylamine is 1:1.2.
The epoxy group is ring-opened to generate two hydroxyl groups, and the 2-bromo-N- (bromoethyl) ethylamine also contains two halogens; in addition, the acid generated by the reaction can be prevented from being excessively fast by controlling the dropping rate, so that the temperature of the system is severely raised.
In some embodiments, the acid-binding agent in step S4 is one or more of K 2CO3、Na2CO3, calcium carbonate, and triethylamine, and the molar ratio of monomer C to acid-binding agent is 1 (1.2-1.4).
Preferably, in the step S4, the acid-binding agent is K 2CO3, and the molar ratio of the monomer C to the acid-binding agent is 1:1.3.
In some embodiments, the molar ratio of monomer B to monomer D in step S5 is 1 (0.5-0.7).
Preferably, in the step S5, the molar ratio of the monomer B to the monomer D is 1:0.6.
In some embodiments, the solvent in the step S5 is one or more of toluene, N-dimethylformamide, isobutanol and chloroform, and the volume is 10-12 times of the total mass of the monomer B and the monomer D; the initiator in the step S5 is azodiisobutyronitrile or/and benzoyl peroxide, and the addition amount is 1-5 wt% of the total mass of the monomer B and the monomer D.
Preferably, the solvent in the step S5 is N, N-dimethylformamide, and the volume is 11 times of the total mass of the monomer B and the monomer D; the initiator in the step S5 is benzoyl peroxide, and the addition amount is 3wt% of the total mass of the monomer B and the monomer D.
Compared with the prior art, the invention has the following beneficial effects:
(1) The large pi bond structure in the dispersing agent structure for the epoxy resin-graphene system can avoid the influence caused by the shielding effect of the epoxy resin and improve the conductivity of the epoxy resin-graphene system.
(2) The amino ring structure in the dispersing agent structure for the epoxy resin-graphene system can increase the shock resistance of the epoxy resin-graphene system, accelerate the curing speed of the epoxy resin and save the later preparation process time.
(3) According to the dispersing agent structure for the epoxy resin-graphene system, pi-pi bonds in the dispersing agent structure are avoided, the dispersing agent does not damage the graphene body structure, the adsorption capacity of graphene is improved on the basis of weakening the graphene performance, and the dispersibility and mechanical properties of graphene in epoxy resin are improved.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is obvious 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.
The sources of the raw materials used in the following examples and comparative examples are as follows:
cyclooxygenase was purchased from Tianjin Sidian chemical technology Co.
Other raw materials are commercially available without specific description.
Example 1
The preparation method of the dispersing agent for the epoxy resin-graphene system of the embodiment comprises the following steps:
s1, mixing 2.8g of copper iodide, 9g of triphenylphosphine palladium dichloride, 275.0g of 4-iodobenzyl alcohol and 1200ml of triethylamine, charging N 2, stirring, dropwise adding 100g of phenylacetylene, controlling the temperature to 45 ℃, and stirring for 17 hours to obtain a compound A;
S2, mixing 100g of the compound A with 128.2g of 9-anthracene carboxylic acid, adding 1000ml of toluene, adding thionyl chloride to adjust the pH value to 2, and stirring at 105 ℃ for 3 hours to obtain a monomer B;
S3, mixing 100g of the compound A with 46.3g of glycidol, adding 1000ml of dichloroethane, adding 9g of tetra (triphenylphosphine) palladium and 9g of silver hexafluoroantimonate, and heating to 65 ℃ by microwaves for reacting for 5 hours to obtain a monomer C;
S4, adding 100g of monomer C into 800ml of deionized water, adding 8g of epoxy hydrolase, controlling the temperature to be 40 ℃, stirring for 7 hours to obtain an intermediate, adding the intermediate into 1200ml of acetonitrile, adding 68g of K 2CO3, heating to 70 ℃, dropwise adding 104.9g of 2-bromo-N- (bromoethyl) ethylamine, and stirring for 20 hours to obtain a monomer D;
S5, mixing 100g of the monomer B with 51.1g of the monomer D, adding 1100ml of N, N-dimethylformamide, filling N 2 g of benzoyl peroxide, and stirring for 5 hours at the temperature of 85 ℃ to obtain the dispersing agent for the epoxy resin-graphene system.
Example 2
The preparation method of the dispersing agent for the epoxy resin-graphene system of the embodiment comprises the following steps:
S1, mixing 1.9g of copper iodide, 8g of triphenylphosphine palladium dichloride, 229.1g of 4-iodobenzyl alcohol and 1000ml of triethylamine, charging N 2, stirring, dropwise adding 100g of phenylacetylene, controlling the temperature to 40 ℃, and stirring for 16 hours to obtain a compound A;
s2, mixing 100g of a compound A with 106.8g of 9-anthracene carboxylic acid, adding 800ml of toluene, adding thionyl chloride to adjust the pH value to 1, and stirring at 100 ℃ for 2 hours to obtain a monomer B;
S3, mixing 100g of the compound A with 42.7g of glycidol, adding 900ml of dichloroethane, adding 9g of tetra (triphenylphosphine) palladium and 9g of silver hexafluoroantimonate, and heating to 65 ℃ by microwaves for reacting for 5 hours to obtain a monomer C;
S4, adding 100g of monomer C into 700ml of deionized water, adding 7g of epoxy hydrolase, controlling the temperature to be 40 ℃, stirring for 6 hours to obtain an intermediate, adding the intermediate into 1100ml of acetonitrile, adding 66g of K 2CO3, heating to 70 ℃, dropwise adding 100g of 2-bromo-N- (bromoethyl) ethylamine, and stirring for 18 hours to obtain a monomer D;
s5, mixing 100g of the monomer B with 53g of the monomer D, adding 1100ml of N, N-dimethylformamide, filling N 2, adding 2.5g of benzoyl peroxide, and stirring for 4 hours at the temperature of 85 ℃ to obtain the dispersing agent for the epoxy resin-graphene system.
Example 3
The preparation method of the dispersing agent for the epoxy resin-graphene system of the embodiment comprises the following steps:
S1, mixing 2.1g of copper iodide, 9g of triphenylphosphine palladium dichloride, 250g of 4-iodobenzyl alcohol and 1100ml of triethylamine, charging N 2, stirring, dropwise adding 100g of phenylacetylene, controlling the temperature to 45 ℃, and stirring for 17 hours to obtain a compound A;
S2, mixing 100g of the compound A with 109g of 9-anthracene carboxylic acid, adding 900ml of toluene, adding thionyl chloride to adjust the pH value to 2, and stirring for 3 hours at the temperature of 105 ℃ to obtain a monomer B;
S3, mixing 100g of the compound A with 49.9g of glycidol, adding 1200ml of dichloroethane, adding 10g of tetra (triphenylphosphine) palladium and 10g of silver hexafluoroantimonate, and heating to 70 ℃ by microwaves for reacting for 6 hours to obtain a monomer C;
S4, adding 100g of monomer C into 1000ml of deionized water, adding 10g of epoxy hydrolase, controlling the temperature to be 45 ℃, stirring for 10 hours to obtain an intermediate, adding the intermediate into 1400ml of acetonitrile, adding 73.3g of K 2CO3, heating to 80 ℃, dropwise adding 122.4g of 2-bromo-N- (bromoethyl) ethylamine, and stirring for 24 hours to obtain a monomer D;
S5, mixing 100g of the monomer B with 52g of the monomer D, adding 1100ml of N, N-dimethylformamide, filling N 2, adding 3.5g of benzoyl peroxide, and stirring for 4 hours at the temperature of 85 ℃ to obtain the dispersing agent for the epoxy resin-graphene system.
Example 4
The preparation method of the dispersing agent for the epoxy resin-graphene system of the embodiment comprises the following steps:
S1, mixing 3.7g of copper iodide, 10g of triphenylphosphine palladium dichloride, 297.9g of 4-iodobenzyl alcohol and 1400ml of triethylamine, charging N 2, stirring, dropwise adding 100g of phenylacetylene, controlling the temperature to 50 ℃, and stirring for 18 hours to obtain a compound A;
S2, mixing 100g of the compound A with 130g of 9-anthracene carboxylic acid, adding 1100ml of toluene, adding thionyl chloride to adjust the pH value to 2, and stirring for 3 hours at the temperature of 105 ℃ to obtain a monomer B;
s3, mixing 100g of the compound A with 48g of glycidol, adding 800ml of dichloroethane, adding 8g of tetrakis (triphenylphosphine) palladium and 8g of silver hexafluoroantimonate, and heating to 60 ℃ by microwaves for reacting for 4 hours to obtain a monomer C;
S4, adding 100g of monomer C into 800ml of deionized water, adding 8g of epoxy hydrolase, controlling the temperature to be 40 ℃, stirring for 7 hours to obtain an intermediate, adding the intermediate into 1200ml of acetonitrile, adding 68g of K 2CO3, heating to 70 ℃, dropwise adding 104.9g of 2-bromo-N- (bromoethyl) ethylamine, and stirring for 20 hours to obtain a monomer D;
S5, mixing 100g of the monomer B with 42.6g of the monomer D, adding 1000ml of N, N-dimethylformamide, filling N 2, adding 1g of benzoyl peroxide, and stirring for 6 hours at the temperature of 80 ℃ to obtain the dispersing agent for the epoxy resin-graphene system.
Example 5
The preparation method of the dispersing agent for the epoxy resin-graphene system of the embodiment comprises the following steps:
s1, mixing 2.8g of copper iodide, 9g of triphenylphosphine palladium dichloride, 275.0g of 4-iodobenzyl alcohol and 1200ml of triethylamine, charging N 2, stirring, dropwise adding 100g of phenylacetylene, controlling the temperature to 45 ℃, and stirring for 17 hours to obtain a compound A;
s2, mixing 100g of the compound A with 138.9g of 9-anthracene carboxylic acid, adding 1200ml of toluene, adding thionyl chloride to adjust the pH value to 3, and stirring at the temperature of 110 ℃ for 4 hours to obtain a monomer B;
S3, mixing 100g of the compound A with 44g of glycidol, adding 1000ml of dichloroethane, adding 9g of tetra (triphenylphosphine) palladium and 9g of silver hexafluoroantimonate, and heating to 65 ℃ by microwaves for reacting for 5 hours to obtain a monomer C;
s4, adding 100g of monomer C into 500ml of deionized water, adding 5g of epoxy hydrolase, controlling the temperature to be 35 ℃, stirring for 4 hours to obtain an intermediate, adding the intermediate into 1000ml of acetonitrile, adding 62.8g of K 2CO3, heating to 60 ℃, dropwise adding 87.4g of 2-bromo-N- (bromoethyl) ethylamine, and stirring for 16 hours to obtain a monomer D;
S5, mixing 100g of the monomer B with 59.6g of the monomer D, adding 1200ml of N, N-dimethylformamide, filling N 2 g of benzoyl peroxide, and stirring for 6 hours at the temperature of 90 ℃ to obtain the dispersing agent for the epoxy resin-graphene system.
Example 6
This example provides a method for preparing a dispersant, which is similar to example 1, except that the stirring time is extended to 9 hours in step S5.
Example 7
This example provides a method for preparing a dispersant, which is similar to example 1, except that the stirring time is shortened to 2 hours in step S5.
Example 8
This example provides a method for preparing a dispersant, and the specific embodiment is the same as example 1, except that the amount of monomer D added is 86g.
Example 9
This example provides a method for preparing a dispersant, and the specific embodiment is the same as example 1, except that the amount of glycidol added is 75g.
Comparative example 1
This comparative example provides a process for the preparation of a dispersant, the specific embodiment being the same as example 1, except that styrene of equal molar mass is used instead of phenylacetylene.
Comparative example 2
This comparative example provides a process for the preparation of a dispersant, the embodiment being identical to example 1, except that benzoic acid of equivalent molar mass is used instead of 9-anthranilic acid.
Comparative example 3
This comparative example provides a process for the preparation of a dispersant, the specific embodiment being the same as example 1, except that monomer C of equal molar mass is used instead of monomer D in step S5.
Comparative example 4
This comparative example provides a process for the preparation of a dispersant, the specific embodiment being the same as example 1, except that 1, 5-dibromopentane of equivalent molar mass was used instead of 2-bromo-N- (bromoethyl) ethylamine.
Performance test:
(1) Dispersion properties
Mixing the dispersing agents prepared in each example and comparative example with graphene and methanol according to the mass ratio of 1:5:30, carrying out ultrasonic oscillation for 2 hours, and standing at room temperature to observe the dispersion stability of the graphene;
(2) Curing speed
The dispersing agent prepared in each example and comparative example is mixed with E-51 resin and graphene according to the mass ratio of 0.5:13:2, and the curing time is detected by adopting paperless recorder equipment on the premise of no external curing agent.
(3) Impact resistance
The test was conducted according to the standard published by JC/T-1015-2016, and further, the conductivity was tested, and the test results are shown in Table 1.
TABLE 1
As can be seen from table 1, the dispersing agents for epoxy resin-graphene systems prepared in examples 1 to 5 have good dispersing effect, high impact strength, fast curing speed and good conductivity. Example 6 the molecular weight of the dispersant was too high due to the prolonged stirring time in step S5, the solubility thereof was lowered, a small amount of oily matter was precipitated after standing for 36 hours, and the viscosity of the system was increased due to the increase in the molecular weight thereof, resulting in an increase in the curing time; example 7 a small amount of precipitation occurred after standing for 36 hours due to the too low molecular weight of the dispersant caused by the shortened stirring time in step S5; in the embodiment 8, the molar ratio of the monomer B to the monomer D is changed, so that the curing speed of the dispersing agent is increased, but the graphene cannot be uniformly dispersed in the epoxy resin due to the excessively high curing speed, so that a small amount of precipitation occurs after the dispersing agent is kept stand for 12 hours; comparative example 1 the dispersant structure does not have a large pi bond structure due to the use of styrene of the same molar mass instead of phenylacetylene, resulting in a reduced conductive property of the dispersant; comparative example 2 uses benzoic acid with the same molar mass to replace 9-anthracene formic acid, so that pi-pi bond structure in a dispersing agent system is reduced, the attraction capacity to graphene is reduced, and the graphene is agglomerated after standing for 36 hours and is precipitated; comparative example 3 the impact resistance of the dispersant is reduced and the curing time is prolonged by using monomer C of the same molar mass instead of monomer D; comparative example 4 the use of 1, 5-dibromopentane in place of 2-bromo-N- (bromoethyl) ethylamine, which had equivalent molar mass, prevented the dispersant from reacting with the epoxy resin, and prolonged the cure time. The detection result shows that the dispersing agent for the epoxy resin-graphene system prepared by the invention can increase the dispersibility of graphene in epoxy resin in actual use, and can increase the impact strength, the curing speed and the conductivity of the epoxy resin-graphene composite material.
Finally, it should be noted that the above-mentioned embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same, and although the present invention has been described in detail with reference to examples, it should be understood by those skilled in the art that modifications and equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention, and all such modifications and equivalents are intended to be encompassed in the scope of the claims of the present invention.
Claims (10)
1. The dispersing agent for the epoxy resin-graphene system is characterized by having the structural formula:
Wherein a=2b, and a, b are positive integers.
2. The dispersant for epoxy resin-graphene system according to claim 1, wherein the molecular weight of the dispersant for epoxy resin-graphene system is 2000 to 13000.
3. A method for preparing the dispersant for epoxy resin-graphene system according to claim 1 or 2, comprising the steps of:
S1, mixing copper iodide, triphenylphosphine palladium dichloride, 4-iodobenzyl alcohol and triethylamine, filling N 2, stirring, dropwise adding phenylacetylene, heating to 40-50 ℃, and stirring for 16-18 hours to obtain a compound A;
S2, mixing the compound A with 9-anthracene carboxylic acid, adding a solvent, adding a first catalyst, adjusting the pH of the reaction solution, heating to 100-110 ℃, and stirring for 2-4 hours to obtain a monomer B;
s3, mixing another compound A with glycidol, adding a solvent, adding a second catalyst, heating to 60-70 ℃ by microwaves, and reacting for 4-6 hours to obtain a monomer C;
S4, adding the monomer C into water, adding a third catalyst, controlling the temperature to be 35-45 ℃, stirring for 4-10 hours to obtain an intermediate, adding the intermediate into a solvent, adding an acid binding agent, heating to 60-80 ℃, dropwise adding 2-bromo-N- (bromoethyl) ethylamine, and stirring for 16-24 hours to obtain a monomer D;
S5, mixing the monomer B and the monomer D, adding a solvent, filling N 2, adding an initiator, heating to 80-90 ℃, and stirring for 4-6 hours to obtain the dispersing agent for the epoxy resin-graphene system.
4. The method for preparing a dispersant for epoxy resin-graphene system according to claim 3, wherein the molar ratio of phenylacetylene to 4-iodobenzyl alcohol in step S1 is 1 (1-1.3).
5. The method for preparing a dispersant for epoxy resin-graphene system according to claim 3, wherein the molar ratio of compound A to 9-anthranilic acid in step S2 is 1 (1-1.3).
6. The method for preparing a dispersing agent for an epoxy resin-graphene system according to claim 3, wherein the first catalyst in the step S2 is thionyl chloride, and the pH value of the reaction solution is adjusted to 1-3.
7. The method for preparing a dispersant for epoxy resin-graphene system according to claim 3, wherein the molar ratio of compound A to glycidol in step S3 is 1 (1.2-1.4).
8. The method for preparing a dispersant for epoxy resin-graphene system according to claim 3, wherein the second catalyst in the step S3 is a combination of 8 to 10mol% tetrakis (triphenylphosphine) palladium of the compound a and 8 to 10mol% silver hexafluoroantimonate of the compound a.
9. The method for preparing a dispersant for epoxy resin-graphene system according to claim 3, wherein the molar ratio of monomer C to 2-bromo-N- (bromoethyl) ethylamine in step S4 is 1 (1-1.4).
10. The method for preparing a dispersant for epoxy resin-graphene system according to claim 3, wherein the molar ratio of monomer B to monomer D in step S5 is 1 (0.5-0.7).
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