CN116790138B - Modified graphene and preparation method of modified graphene slurry - Google Patents
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000002002 slurry Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 39
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 22
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000006185 dispersion Substances 0.000 claims abstract description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 60
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 41
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 39
- 239000013067 intermediate product Substances 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 28
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 24
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 17
- -1 amino-protected N-methyl ethylenediamine Chemical class 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- DYHSDKLCOJIUFX-UHFFFAOYSA-N tert-butoxycarbonyl anhydride Chemical compound CC(C)(C)OC(=O)OC(=O)OC(C)(C)C DYHSDKLCOJIUFX-UHFFFAOYSA-N 0.000 claims description 14
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 14
- 125000004651 chloromethoxy group Chemical group ClCO* 0.000 claims description 13
- 239000000706 filtrate Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 239000003607 modifier Substances 0.000 claims description 12
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 12
- 238000002390 rotary evaporation Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 11
- 238000000967 suction filtration Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 8
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 8
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 8
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 8
- 239000012065 filter cake Substances 0.000 claims description 8
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- DYPJJAAKPQKWTM-UHFFFAOYSA-N 2-chloropropane-1,3-diol Chemical compound OCC(Cl)CO DYPJJAAKPQKWTM-UHFFFAOYSA-N 0.000 claims description 6
- JNTPTNNCGDAGEJ-UHFFFAOYSA-N 6-chlorohexan-1-ol Chemical compound OCCCCCCCl JNTPTNNCGDAGEJ-UHFFFAOYSA-N 0.000 claims description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- KFIGICHILYTCJF-UHFFFAOYSA-N n'-methylethane-1,2-diamine Chemical compound CNCCN KFIGICHILYTCJF-UHFFFAOYSA-N 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 150000002009 diols Chemical class 0.000 claims description 4
- 230000001804 emulsifying effect Effects 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 4
- 239000004417 polycarbonate Substances 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000000543 intermediate Substances 0.000 claims description 2
- 125000006239 protecting group Chemical group 0.000 claims description 2
- 230000009615 deamination Effects 0.000 claims 1
- 238000006481 deamination reaction Methods 0.000 claims 1
- 229920002635 polyurethane Polymers 0.000 abstract description 14
- 239000004814 polyurethane Substances 0.000 abstract description 14
- 238000004132 cross linking Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 239000004480 active ingredient Substances 0.000 abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 8
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
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- 230000003993 interaction Effects 0.000 description 3
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
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- WOAZEKPXTXCPFZ-UHFFFAOYSA-N dimethyl(phenyl)azanium;chloride Chemical compound Cl.CN(C)C1=CC=CC=C1 WOAZEKPXTXCPFZ-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
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- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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Abstract
The invention discloses modified graphene and a preparation method of modified graphene slurry, which belong to the technical field of graphene modification. According to the invention, part of organic molecular chains on the surface of the graphene can be intercalated into the lamellar layers of the graphene, so that the distance between the lamellar layers is increased, and the dispersion of the graphene in the slurry is facilitated; from the aspect of an introduced molecular chain structure, the alcohol hydroxyl contained on the modified graphene can promote polyurethane crosslinking, promote the generation of a crosslinked network structure, and the polyethylene glycol molecular chain contained on the modified graphene has extremely high hydrophilicity, so that the modified graphene has a polyurethane-philic component and a hydrophilic component, can play a bridging role between polyurethane and water, and further promotes the uniformity and stability of active ingredients in the slurry.
Description
Technical Field
The invention belongs to the technical field of graphene modification, and particularly relates to modified graphene and a preparation method of modified graphene slurry.
Background
With the enhancement of environmental awareness, the development of functional coatings with water-based polymers as matrixes and water as solvents is receiving more and more attention in the field. Graphene is a two-dimensional honeycomb crystal structure formed by closely arranging sp2 hybridized carbon atoms, and belongs to graphite materials. The composite material has excellent Young's modulus (1100 GPa), high thermal conductivity (about 5000 J.K.s) -1, high carrier mobility (2X 10 5cm2·(V·s)-1) and high specific surface area (theoretical calculation value 2630m 2.g-1), quantum Hall effect and quantum tunneling effect, and also has excellent impermeability, so that the composite material has great application prospect in the field of functional coatings.
The Waterborne Polyurethane (WPU) is an important branch of functional paint, and the main dispersion medium is water, so that the waterborne polyurethane has the advantages of no toxicity, low VOCs, low viscosity, high flexibility, strong cohesiveness, high wear resistance and the like. However, the key of graphene as a reinforcing filler to play a role in the aqueous polyurethane emulsion is whether the graphene has good dispersibility and interface interaction.
Therefore, how to improve the dispersibility and stability of graphene and to uniformly and stably disperse in water has become one of the problems to be solved by various research and development enterprises and many first-line researchers in the field.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides modified graphene and a preparation method of modified graphene slurry.
The aim of the invention can be achieved by the following technical scheme:
The preparation method of the modified graphene comprises the following steps:
S1, adding amino-protected N-methyl ethylenediamine, triethylamine and tetrahydrofuran into a dry three-neck flask, placing the flask in an ice bath, stirring and mixing, slowly dripping 2-chloro-1, 3-propanediol into the flask through a constant pressure dropping funnel under stirring when the temperature of the system is stabilized at 0-2 ℃, reacting for 3 hours at normal temperature after the dripping is finished, filtering to remove salt, and removing tetrahydrofuran through reduced pressure rotary evaporation to obtain an intermediate product 1; the ratio of the amounts of amino-protected N-methyl ethylenediamine, triethylamine and 2-chloro-1, 3-propanediol was 0.1mol:10.1g:0.1mol;
Under the action of triethylamine, nucleophilic substitution reaction is carried out on-NH-on an amino-protected N-methyl ethylenediamine molecule and-Cl on a 2-chloro-1, 3-propanediol molecule to obtain an intermediate 1, and the process is as follows:
S2, continuously introducing nitrogen into a three-neck flask with a stirrer, a thermometer and a condenser tube for 10min (replacing air in the flask), adding phosphorus oxychloride, dioxane and N, N-dimethylaniline (acid binding agent), stirring and dissolving uniformly, then dropwise adding a dioxane solution of an intermediate product 1, controlling the reaction temperature to be not higher than 40 ℃ in the dropwise adding process, heating to 100 ℃ after the dropwise adding process is completed, preserving heat for reaction for 12h, cooling to below 30 ℃, removing generated N, N-dimethylaniline hydrochloride by suction filtration, removing dioxane from filtrate by reduced pressure distillation, washing twice with distilled water, separating a lower organic phase, then adding ethyl acetate, drying with anhydrous magnesium sulfate, suction filtration, and removing ethyl acetate by reduced pressure distillation of filtrate to obtain an intermediate product 2; the ratio of the dosage of phosphorus oxychloride, N-dimethylaniline and the intermediate product 1 is 15.3g to 24.2g to 24.8g;
Under the action of N, N-dimethylaniline, phosphorus oxychloride and two-OH on the molecule of the intermediate product 1 undergo substitution and cyclization reactions to obtain an intermediate product 2, wherein the process is as follows:
S3, adding dichloromethane into a four-neck flask, introducing nitrogen, continuously (removing air in the flask) for 10min, adding an intermediate product 2 and triethylamine, stirring and uniformly mixing, dropwise adding ethylenediamine by adopting a constant pressure funnel, reacting for 4h under normal temperature after the dropwise adding is finished, removing generated triethylamine hydrochloride by suction filtration after the reaction is finished, and distilling filtrate under reduced pressure to obtain an intermediate product 3; the ratio of the amounts of intermediate 2, triethylamine and ethylenediamine was 32.9g:10.1g:6g;
Mixing the intermediate product 3 with saturated hydrogen chloride solution of THF (tetrahydrofuran) according to a solid-to-liquid ratio of 1g to 8mL, stirring for 5h at room temperature, filtering, leaching a filter cake with diethyl ether, and vacuum drying to obtain an intermediate product 4;
Nucleophilic substitution reaction is carried out on-Cl on the intermediate product 2 molecules and-NH 2 on ethylenediamine molecules, a substitution reaction is carried out by controlling the molar ratio of the-Cl to the-NH 2 to be close to 1:1, an intermediate product 3 is obtained, the intermediate product 3 is subjected to Boc protecting group removal under an acidic condition, and-NH 2 is formed, so that an intermediate product 4 is obtained, and the reaction process is as follows:
S4, adding chloromethoxy polyethylene glycol and acetonitrile into a three-neck flask, stirring and dissolving uniformly, adding potassium carbonate, potassium iodide and an intermediate product 4, carrying out reflux reaction for 24 hours under the dark condition and nitrogen protection at 85 ℃, carrying out suction filtration (removing potassium carbonate and potassium iodide salt) after the reaction is finished, taking filtrate, and carrying out reduced pressure rotary evaporation (removing solvent acetonitrile) to obtain a modifier; the dosage ratio of chloromethoxy polyethylene glycol, acetonitrile, potassium carbonate, potassium iodide and intermediate 4 is 0.1mol:500mL:2.3g:1.2g:25.2g;
Nucleophilic substitution reaction is carried out on-NH 2 on the molecule of the intermediate product 4 and end-Cl on chloromethoxy polyethylene glycol, and a substitution reaction is carried out by controlling the molar ratio of the two to be close to 1:1, so as to obtain the modifier, wherein the process is as follows:
S5, mixing graphene oxide with DMF (N, N-dimethylformamide), performing ultrasonic dispersion for 1h, adding a modifier and DCC (dicyclohexylcarbodiimide) in a stirring state, performing magnetic stirring reaction for 24h in an oil bath at 90 ℃, performing centrifugal separation after the reaction is finished, washing 3-4 times with an ethanol aqueous solution, and finally performing vacuum drying and grinding on a filter cake to obtain the pre-modified graphene; the dosage ratio of graphene oxide, modifier and DCC is 5g to 40.5g to 10.3g;
Under the action of DCC, performing amidation reaction on-COOH on the surface of graphene oxide and-NH 2 on the modifier molecules to enable the modifier molecules to be grafted on the surface of graphene oxide, so as to obtain pre-modified graphene;
S6, ultrasonically dispersing the pre-modified graphene in DMSO, then adding 6-chloro-n-hexanol, heating to 50 ℃, stirring and reacting for 4 hours, centrifuging, washing 3-4 times by using an ethanol aqueous solution after the reaction is finished, and finally vacuum drying and grinding a filter cake to obtain the modified graphene; the dosage ratio of the pre-modified graphene to the 6-chloro-n-hexanol is 10g to 13.6g;
substitution reaction is carried out on-NH-and 6-chloro-n-hexanol on a molecular chain of a modifier grafted on the surface of the pre-modified graphene to obtain the modified graphene, wherein the chemical molecular chain structure grafted on the surface of the modified graphene is shown as follows:
Through chemical modification of graphene, six-membered rings and long molecular chains are introduced into the graphene, part of organic molecular chains can be intercalated into the lamellar layers of the graphene, and the distance between the lamellar layers is increased, so that the dispersion of the graphene in the slurry is facilitated;
The chemical molecular chain structure is known to contain a plurality of alcoholic hydroxyl groups, polyethylene glycol molecular chains, phosphate groups and N-containing groups; the alcoholic hydroxyl groups can participate in the reaction process in the preparation process of the slurry (the aqueous polyurethane emulsion polymerization process), so that a crosslinking effect is achieved, the generation of a crosslinked network structure of a polyurethane matrix can be promoted, the water resistance and the mechanical strength of the slurry after the slurry is solidified into a film can be improved, the interaction force of graphene and the slurry matrix (the aqueous polyurethane) can be improved, and the dispersion effect of the graphene in the matrix can be improved; the polyethylene glycol molecular chain belongs to a long chain with good hydrophilicity and strong water solubility, so that the dispersion performance of the modified graphene in a slurry solvent (water) can be effectively promoted, and the modified graphene has a polyurethane-philic component and a hydrophilic component, so that the bridging effect between polyurethane and water can be achieved, and the uniformity and stability of active ingredients in the slurry can be further promoted; it is pointed out that the P-N synergistic flame retardant component is also introduced on the surface of the graphene through modification and uniformly distributed in the slurry, so that the flame retardant property of the slurry can be improved to a certain extent, and the flame retardant effect is stable and durable due to the higher interaction force of the flame retardant component and the matrix.
Further, the amino-protected N-methyl ethylenediamine is prepared by the steps of:
Adding N-methyl ethylenediamine and triethylamine into a three-necked flask, dissolving di-tert-butyl dicarbonate into diethyl ether, dropwise dripping the di-tert-butyl dicarbonate into the three-necked flask through a constant pressure funnel, stirring and reacting for 10 hours at a constant temperature of 3 ℃, removing a solvent (diethyl ether) through rotary evaporation after the reaction is finished, and finally carrying out recrystallization and purification by using a mixed solution of dichloromethane and diethyl ether (the volume ratio of dichloromethane to diethyl ether is 1:1) to obtain amino-protected N-methyl ethylenediamine; the dosage ratio of N-methyl ethylenediamine, triethylamine and di-tert-butyl dicarbonate is 7.4g:10.1g:21.8g;
By reacting di-tert-butyl dicarbonate with-NH 2 on N-methyl ethylenediamine, protecting-NH 2 on N-methyl ethylenediamine by tert-butyl (Boc) to obtain amino-protected N-methyl ethylenediamine, the process is as follows:
Further, the chloromethoxy polyethylene glycol is prepared by the following steps:
Adding methoxy polyethylene glycol and dried potassium carbonate into a three-neck flask, adding dichloromethane, starting magnetic stirring after the temperature of the system is raised to 45 ℃, starting to dropwise add mixed solution (with the concentration of 1 mol/L) of thionyl chloride and dichloromethane, carrying out reflux reaction for 24 hours at 45 ℃ after the dropwise adding is finished, carrying out suction filtration (removing potassium carbonate salt) after the reaction is finished, taking filtrate, and carrying out reduced pressure rotary evaporation (removing solvent dichloromethane and residual raw material thionyl chloride) to obtain chloromethoxy polyethylene glycol; the dosage ratio of the mixture of methoxypolyethylene glycol, potassium carbonate, thionyl chloride and dichloromethane is 0.1mol:13.8g:120mL; preferably, the methoxypolyethylene glycol has a molecular weight of 560 (i.e., n=11);
under the action of thionyl chloride, the terminal-OH of methoxy polyethylene glycol is subjected to chlorination reaction to obtain chloromethoxy polyethylene glycol, wherein the reaction process is as follows:
the invention also aims to provide a preparation method of the modified graphene slurry, which comprises the following steps:
the method comprises the steps of firstly, ultrasonically dispersing modified graphene in deionized water to form graphene dispersion liquid with the mass fraction of 10% for later use;
Secondly, adding IPDI (isophorone diisocyanate), PCD (polycarbonate diol) and a catalyst DBTDL (dibutyl tin dilaurate) into a reaction kettle, reacting for 2 hours at 55 ℃, then adding DMPA (dimethylolpropionic acid) in three times, heating to 60 ℃ for reacting for 6 hours, and adding proper amount of acetone to regulate the viscosity to obtain a waterborne polyurethane prepolymer; IPDI, PCD, DBTDL, DMPA is used in a mass ratio of 24.1:70.9:0.15:5;
thirdly, adding triethylamine into the waterborne polyurethane prepolymer, stirring at room temperature for neutralization for 30min, dripping the mixture into graphene dispersion liquid, emulsifying for 2h at a high speed, adding a proper amount of hydrazine hydrate, and reducing at 90 ℃ for 30min to obtain slurry; the dosage ratio of the triethylamine, the prepolymer and the graphene dispersion liquid is 0.22g to 5g to 8-10mL.
The invention has the beneficial effects that:
According to the preparation method, the graphene oxide is subjected to chemical modification, the surface of the graphene oxide is grafted with the organic molecular chains, part of the organic molecular chains can be intercalated into the lamellar layers of the graphene, and the distance between the lamellar layers is increased, so that the graphene is dispersed in the slurry; from the aspect of an introduced molecular chain structure, the alcohol hydroxyl contained on the modified graphene can promote polyurethane crosslinking, promote the generation of a crosslinked network structure, and the polyethylene glycol molecular chain contained on the modified graphene has extremely high hydrophilicity, and the modified graphene has both a polyurethane-philic component and a hydrophilic component, so that the modified graphene can play a bridging role between polyurethane and water, and further promote the uniformity and stability of active ingredients in slurry; thereby obtaining the graphene polyurethane slurry with uniform and stable texture, and having important application value in the field of functional coatings.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Preparing amino-protected N-methyl ethylenediamine:
7.4g of N-methyl ethylenediamine and 10.1g of triethylamine are added into a three-necked flask, 21.8g of di-tert-butyl dicarbonate is dissolved in 50mL of diethyl ether, the mixture is dropwise added into the three-necked flask through a constant pressure funnel, the mixture is stirred and reacted for 10 hours at the constant temperature of 3 ℃, after the reaction is finished, the solvent (diethyl ether) is removed through rotary evaporation, and finally, the mixture of dichloromethane and diethyl ether (the volume ratio of dichloromethane to diethyl ether is 1:1) is used for recrystallization and purification, so that the amino-protected N-methyl ethylenediamine is obtained.
Example 2
Preparation of chloromethoxy polyethylene glycol:
56g of methoxy polyethylene glycol (with molecular weight of 560) and 13.8g of dried potassium carbonate are added into a three-necked flask, methylene dichloride is added, after the temperature of the system is raised to 45 ℃, magnetic stirring is started, 120mL of mixed solution of thionyl chloride and methylene dichloride (with concentration of 1 mol/L) is started to be dropwise added, after the dropwise addition is finished, reflux reaction is carried out for 24 hours at 45 ℃, suction filtration (removing potassium carbonate salt) is carried out after the reaction is finished, filtrate is taken, and reduced pressure rotary evaporation (removing solvent methylene dichloride and residual raw material thionyl chloride) is carried out, thus obtaining the chloromethoxy polyethylene glycol.
Example 3
Preparing modified graphene:
s1, adding 17.4g of the amino-protected N-methyl ethylenediamine prepared in the embodiment 1, 10.1g of triethylamine and 60mL of tetrahydrofuran into a dry three-neck flask, placing the flask into an ice bath, stirring and mixing, slowly dripping 11g of 2-chloro-1, 3-propanediol into the flask through a constant pressure dropping funnel under stirring when the system temperature is stabilized at 0-2 ℃, reacting for 3 hours at normal temperature after the dripping is finished, filtering to remove salt, and removing the tetrahydrofuran through reduced pressure rotary evaporation to obtain an intermediate product 1;
S2, continuously introducing nitrogen into a three-neck flask with a stirrer, a thermometer and a condenser tube for 10min (replacing air in the flask), adding 15.3g phosphorus oxychloride, 80mL dioxane and 24.2g N, N-dimethylaniline (acid binding agent), stirring and dissolving uniformly, then dropwise adding 50mL dioxane solution containing 24.8g intermediate product 1, controlling the reaction temperature to be not higher than 40 ℃, heating to 100 ℃ after the dropwise adding, preserving heat for reaction for 12h, cooling to below 30 ℃, filtering to remove generated N, N-dimethylaniline hydrochloride, distilling the filtrate under reduced pressure to remove dioxane, washing twice with distilled water, separating out a lower organic phase, then adding ethyl acetate, drying with anhydrous magnesium sulfate, filtering, and distilling the filtrate under reduced pressure to remove ethyl acetate to obtain an intermediate product 2;
S3, adding 100mL of dichloromethane into a four-necked flask, introducing nitrogen, continuously adding 32.9g of intermediate product 2 and 10.1g of triethylamine after continuously heating for 10min (removing air in the flask), stirring and uniformly mixing, dropwise adding 6g of ethylenediamine by adopting a constant pressure funnel, reacting for 4h at normal temperature after the dropwise adding is finished, removing generated triethylamine hydrochloride by suction filtration after the reaction is finished, and obtaining intermediate product 3 after reduced pressure distillation of filtrate;
35.2g of intermediate 3 was mixed with 282mL of saturated solution of THF (tetrahydrofuran) in hydrogen chloride, stirred at room temperature for 5h, filtered, the filter cake rinsed with diethyl ether and dried in vacuo to give intermediate 4;
S4, adding 57.8g of chloromethoxy polyethylene glycol prepared in the example 2 and 500mL of acetonitrile into a three-necked flask, stirring and dissolving uniformly, adding 2.3g of potassium carbonate, 1.2g of potassium iodide and 25.2g of intermediate product 4, carrying out reflux reaction for 24 hours under the conditions of 85 ℃ and darkness and nitrogen protection, carrying out suction filtration (removing potassium carbonate and potassium iodide salt) after the reaction is finished, taking filtrate, and carrying out reduced pressure rotary evaporation (removing solvent acetonitrile) to obtain a modifier;
S5, mixing 5g of graphene oxide with 120mL of DMF, performing ultrasonic dispersion for 1h, adding 40.5g of modifier and 10.3g of DCC (DCC) under stirring, performing magnetic stirring reaction for 24h at 90 ℃, performing centrifugal separation after the reaction is finished, washing with ethanol aqueous solution for 4 times, and finally performing vacuum drying and grinding on a filter cake to obtain the pre-modified graphene;
S6, dispersing 10g of pre-modified graphene in 80mL of DMSO (dimethyl sulfoxide) by ultrasonic, adding 13.6g of 6-chloro-n-hexanol, heating to 50 ℃, stirring for reaction for 4 hours, centrifuging, washing with an ethanol water solution for 4 times after the reaction is finished, and finally, vacuum drying and grinding a filter cake to obtain the modified graphene.
Example 4
Preparing modified graphene slurry:
the method comprises the steps of firstly, ultrasonically dispersing modified graphene prepared in the embodiment 3 in deionized water to form graphene dispersion liquid with the mass fraction of 10% for later use;
Secondly, adding 24.1g of IPDI (isophorone diisocyanate), 70.9g of PCD (polycarbonate diol) and 0.15g of catalyst DBTDL (dibutyl tin dilaurate) into a reaction kettle, reacting for 2 hours at 55 ℃, adding 5g of DMPA (dimethylolpropionic acid) in three times, heating to 60 ℃ for reacting for 6 hours, and adding 20mL of acetone to adjust the viscosity to obtain an aqueous polyurethane prepolymer;
Thirdly, adding 4.4g of triethylamine into 100g of the waterborne polyurethane prepolymer, stirring at room temperature for neutralization for 30min, then dripping into 160mL of graphene dispersion liquid, emulsifying for 2h at a high speed, finally adding 5mL of hydrazine hydrate, and reducing at 90 ℃ for 30min to obtain slurry.
Example 5
Preparing modified graphene slurry:
the method comprises the steps of firstly, ultrasonically dispersing modified graphene prepared in the embodiment 3 in deionized water to form graphene dispersion liquid with the mass fraction of 10% for later use;
Secondly, adding 24.1g of IPDI (isophorone diisocyanate), 70.9g of PCD (polycarbonate diol) and 0.15g of catalyst DBTDL (dibutyl tin dilaurate) into a reaction kettle, reacting for 2 hours at 55 ℃, adding 5g of DMPA (dimethylolpropionic acid) in three times, heating to 60 ℃ for reacting for 6 hours, and adding 20mL of acetone to adjust the viscosity to obtain an aqueous polyurethane prepolymer;
Thirdly, adding 4.4g of triethylamine into 100g of aqueous polyurethane prepolymer, stirring at room temperature for neutralization for 30min, then dripping into 200mL of graphene dispersion liquid, emulsifying for 2h at a high speed, finally adding 5mL of hydrazine hydrate, and reducing at 90 ℃ for 30min to obtain slurry.
Comparative example
The modified graphene in the embodiment 4 is changed into common graphene oxide and polyethylene glycol 2000 with the same quality, and the rest raw materials and the preparation process are unchanged to obtain the slurry.
The slurries obtained in example 4, example 5 and comparative example were coated on a 40 μm PET film with a 12 μm bar and, after drying, the following performance tests were performed:
tensile test: cutting the dried composite film into 16mm x 2mm dumbbell-shaped splines, and testing the stress-strain condition of the cured film; stretching rate: 10mm/min;
Stability test: placing 50mL of slurry in a sealed container, sealing at 25 ℃, standing for 14d, and observing the appearance condition of the slurry;
Flame retardancy: the oxygen index is tested according to standard method ISO 4589-3:1996; the test of the smoky burn time was carried out according to standard method GB/T5455-1997;
The results are shown in the following table:
As can be seen from the data in the table, the modified graphene slurry obtained by the invention has higher stability and dispersibility and certain flame retardant property; according to the data of the comparative example, after the graphene oxide is modified, the formation of a polyurethane crosslinking structure can be promoted, the performances such as mechanical strength and the like can be further improved, the bridging effect between polyurethane and water can be also achieved, the stability and the dispersibility of the slurry can be further improved, and certain flame retardant property can be given to the slurry.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (2)
1. The preparation method of the modified graphene is characterized by comprising the following steps of:
S1, adding amino-protected N-methyl ethylenediamine, triethylamine and tetrahydrofuran into a dry three-neck flask, placing the flask in an ice bath, stirring and mixing, slowly dripping 2-chloro-1, 3-propanediol into the flask through a constant pressure dropping funnel under stirring when the temperature of the system is stabilized at 0-2 ℃, reacting for 3 hours at normal temperature after the dripping is finished, filtering to remove salt, and removing tetrahydrofuran through reduced pressure rotary evaporation to obtain an intermediate product 1; the ratio of the amounts of amino-protected N-methyl ethylenediamine, triethylamine and 2-chloro-1, 3-propanediol was 0.1mol:10.1g:0.1mol;
S2, continuously introducing nitrogen into the three-neck flask for 10min, adding phosphorus oxychloride, dioxane and N, N-dimethylaniline, stirring and dissolving uniformly, then dropwise adding a dioxane solution of the intermediate product 1, controlling the reaction temperature to be not higher than 40 ℃ in the dropwise adding process, heating to 100 ℃ after the dropwise adding process is finished, preserving heat for reaction for 12h, cooling to below 30 ℃, and performing aftertreatment to obtain an intermediate product 2; the ratio of the dosage of phosphorus oxychloride, N-dimethylaniline and the intermediate product 1 is 15.3g to 24.2g to 24.8g;
S3, adding dichloromethane into a four-neck flask, introducing nitrogen, continuously adding an intermediate product 2 and triethylamine after 10min, stirring and uniformly mixing, dropwise adding ethylenediamine by adopting a constant pressure funnel, reacting for 4h at normal temperature after the dropwise adding is finished, removing generated triethylamine hydrochloride by suction filtration after the reaction is finished, and distilling filtrate under reduced pressure to obtain an intermediate product 3; deamination protecting group of intermediate 3 under acidic condition to obtain intermediate 4; the ratio of the amounts of intermediate 2, triethylamine and ethylenediamine was 32.9g:10.1g:6g;
S4, adding chloromethoxy polyethylene glycol and acetonitrile into a three-neck flask, stirring and dissolving uniformly, adding potassium carbonate, potassium iodide and an intermediate product 4, carrying out reflux reaction for 24 hours under the dark condition and nitrogen protection at 85 ℃, carrying out suction filtration after the reaction is finished, taking filtrate, and carrying out reduced pressure rotary evaporation to obtain a modifier; the dosage ratio of chloromethoxy polyethylene glycol, acetonitrile, potassium carbonate, potassium iodide and intermediate 4 is 0.1mol:500mL:2.3g:1.2g:25.2g;
S5, mixing graphene oxide with N, N-dimethylformamide, performing ultrasonic dispersion for 1h, adding a modifier and dicyclohexylcarbodiimide in a stirring state, performing magnetic stirring reaction for 24h in an oil bath at 90 ℃, performing centrifugal separation after the reaction is finished, washing 3-4 times with an ethanol aqueous solution, and finally performing vacuum drying and grinding on a filter cake to obtain pre-modified graphene; the dosage ratio of graphene oxide, modifier and dicyclohexylcarbodiimide is 5g to 40.5g to 10.3g;
S6, ultrasonically dispersing the pre-modified graphene in DMSO, then adding 6-chloro-n-hexanol, heating to 50 ℃, stirring and reacting for 4 hours, centrifuging, washing 3-4 times by using an ethanol aqueous solution after the reaction is finished, and finally vacuum drying and grinding a filter cake to obtain the modified graphene; the dosage ratio of the pre-modified graphene to the 6-chloro-n-hexanol is 10g to 13.6g;
the amino-protected N-methyl ethylenediamine in step S1 is prepared by the steps of:
Adding N-methyl ethylenediamine and triethylamine into a three-necked flask, dissolving di-tert-butyl dicarbonate into diethyl ether, dropwise dripping the di-tert-butyl dicarbonate into the three-necked flask through a constant pressure funnel, stirring and reacting for 10 hours at a constant temperature of 3 ℃, removing diethyl ether through rotary evaporation after the reaction is finished, and finally carrying out recrystallization and purification by using a mixed solution of dichloromethane and diethyl ether to obtain amino-protected N-methyl ethylenediamine;
The chloromethoxy polyethylene glycol in the step S4 is prepared by the following steps:
Adding methoxy polyethylene glycol and dried potassium carbonate into a three-neck flask, adding dichloromethane, starting magnetic stirring after the temperature of the system is raised to 45 ℃, starting to dropwise add mixed solution of thionyl chloride and dichloromethane, carrying out reflux reaction for 24 hours at 45 ℃ after the dropwise adding is finished, carrying out suction filtration after the reaction is finished, taking filtrate, and carrying out reduced pressure rotary evaporation to obtain the chloromethoxy polyethylene glycol.
2. The preparation method of the modified graphene slurry is characterized by comprising the following specific steps of:
the method comprises the steps of firstly, ultrasonically dispersing modified graphene in deionized water to form graphene dispersion liquid with the mass fraction of 10% for later use;
Secondly, adding isophorone diisocyanate, polycarbonate diol and catalyst dibutyltin dilaurate into a reaction kettle, reacting for 2 hours at 55 ℃, then adding dimethylolpropionic acid three times, heating to 60 ℃ for reacting for 6 hours, and adding proper amount of acetone to regulate the viscosity to obtain a waterborne polyurethane prepolymer;
Thirdly, adding triethylamine into the waterborne polyurethane prepolymer, stirring at room temperature for neutralization for 30min, dripping the mixture into the graphene dispersion liquid, emulsifying for 2h at a high speed, adding a proper amount of hydrazine hydrate, and reducing at 90 ℃ for 30min to obtain slurry.
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