KR20140144148A - Dispersion stabilizer for graphene exfoliation, graphene-alkali metal salt complex including the same, and method for producing graphene using the same - Google Patents
Dispersion stabilizer for graphene exfoliation, graphene-alkali metal salt complex including the same, and method for producing graphene using the same Download PDFInfo
- Publication number
- KR20140144148A KR20140144148A KR20140069589A KR20140069589A KR20140144148A KR 20140144148 A KR20140144148 A KR 20140144148A KR 20140069589 A KR20140069589 A KR 20140069589A KR 20140069589 A KR20140069589 A KR 20140069589A KR 20140144148 A KR20140144148 A KR 20140144148A
- Authority
- KR
- South Korea
- Prior art keywords
- graphene
- group
- compound
- dispersion stabilizer
- alkali metal
- Prior art date
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 163
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 107
- 239000006185 dispersion Substances 0.000 title claims abstract description 103
- 239000003381 stabilizer Substances 0.000 title claims abstract description 94
- 229910052783 alkali metal Inorganic materials 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title abstract description 12
- 238000004299 exfoliation Methods 0.000 title abstract 3
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 59
- 239000010439 graphite Substances 0.000 claims abstract description 59
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 19
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 17
- 125000003118 aryl group Chemical group 0.000 claims abstract description 15
- 150000007942 carboxylates Chemical group 0.000 claims abstract description 7
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims abstract description 7
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 58
- 239000010410 layer Substances 0.000 claims description 41
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 238000000926 separation method Methods 0.000 claims description 26
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000011229 interlayer Substances 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 238000010298 pulverizing process Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- HBENZIXOGRCSQN-VQWWACLZSA-N (1S,2S,6R,14R,15R,16R)-5-(cyclopropylmethyl)-16-[(2S)-2-hydroxy-3,3-dimethylpentan-2-yl]-15-methoxy-13-oxa-5-azahexacyclo[13.2.2.12,8.01,6.02,14.012,20]icosa-8(20),9,11-trien-11-ol Chemical compound N1([C@@H]2CC=3C4=C(C(=CC=3)O)O[C@H]3[C@@]5(OC)CC[C@@]2([C@@]43CC1)C[C@@H]5[C@](C)(O)C(C)(C)CC)CC1CC1 HBENZIXOGRCSQN-VQWWACLZSA-N 0.000 claims description 2
- PHDIJLFSKNMCMI-ITGJKDDRSA-N (3R,4S,5R,6R)-6-(hydroxymethyl)-4-(8-quinolin-6-yloxyoctoxy)oxane-2,3,5-triol Chemical compound OC[C@@H]1[C@H]([C@@H]([C@H](C(O1)O)O)OCCCCCCCCOC=1C=C2C=CC=NC2=CC=1)O PHDIJLFSKNMCMI-ITGJKDDRSA-N 0.000 claims description 2
- JNPGUXGVLNJQSQ-BGGMYYEUSA-M (e,3r,5s)-7-[4-(4-fluorophenyl)-1,2-di(propan-2-yl)pyrrol-3-yl]-3,5-dihydroxyhept-6-enoate Chemical compound CC(C)N1C(C(C)C)=C(\C=C\[C@@H](O)C[C@@H](O)CC([O-])=O)C(C=2C=CC(F)=CC=2)=C1 JNPGUXGVLNJQSQ-BGGMYYEUSA-M 0.000 claims description 2
- VAVHMEQFYYBAPR-ITWZMISCSA-N (e,3r,5s)-7-[4-(4-fluorophenyl)-1-phenyl-2-propan-2-ylpyrrol-3-yl]-3,5-dihydroxyhept-6-enoic acid Chemical compound CC(C)C1=C(\C=C\[C@@H](O)C[C@@H](O)CC(O)=O)C(C=2C=CC(F)=CC=2)=CN1C1=CC=CC=C1 VAVHMEQFYYBAPR-ITWZMISCSA-N 0.000 claims description 2
- MWVKLRSIDOXBSE-UHFFFAOYSA-N 5-(1-piperidin-4-ylpyrazol-4-yl)-3-(6-pyrrolidin-1-yl-1,3-benzoxazol-2-yl)pyridin-2-amine Chemical compound NC1=NC=C(C2=CN(N=C2)C2CCNCC2)C=C1C(OC1=C2)=NC1=CC=C2N1CCCC1 MWVKLRSIDOXBSE-UHFFFAOYSA-N 0.000 claims description 2
- HIHOEGPXVVKJPP-JTQLQIEISA-N 5-fluoro-2-[[(1s)-1-(5-fluoropyridin-2-yl)ethyl]amino]-6-[(5-methyl-1h-pyrazol-3-yl)amino]pyridine-3-carbonitrile Chemical compound N([C@@H](C)C=1N=CC(F)=CC=1)C(C(=CC=1F)C#N)=NC=1NC=1C=C(C)NN=1 HIHOEGPXVVKJPP-JTQLQIEISA-N 0.000 claims description 2
- VCUKKMIXURRDKL-UHFFFAOYSA-N 9-(dimethylamino)-3-(4-ethylphenyl)pyrido[1,2]thieno[3,4-d]pyrimidin-4-one Chemical compound C1=CC(CC)=CC=C1N1C(=O)C(SC=2C3=C(N(C)C)C=CN=2)=C3N=C1 VCUKKMIXURRDKL-UHFFFAOYSA-N 0.000 claims description 2
- DGJMHKMYSDYOFP-MRXNPFEDSA-N C=CC(N(CCC1)C[C@@H]1N1N=C(C2=CN(CC(C3=CC=CC=C3)(F)F)N=N2)C2=C(N)N=CN=C12)=O Chemical compound C=CC(N(CCC1)C[C@@H]1N1N=C(C2=CN(CC(C3=CC=CC=C3)(F)F)N=N2)C2=C(N)N=CN=C12)=O DGJMHKMYSDYOFP-MRXNPFEDSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- HGDWHTASNMRJMP-UHFFFAOYSA-N [1-(hydroxyamino)-1-oxo-5-(3-phenoxyphenyl)pentan-2-yl]phosphonic acid Chemical compound ONC(=O)C(P(O)(O)=O)CCCC1=CC=CC(OC=2C=CC=CC=2)=C1 HGDWHTASNMRJMP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 2
- YBFBENHWPRGUMU-UHFFFAOYSA-N chembl398496 Chemical compound OC(=O)C1=CC=CC=C1NC(=O)N1CCN(C=2N=C3C=CC(O)=CC3=NC=2)CC1 YBFBENHWPRGUMU-UHFFFAOYSA-N 0.000 claims description 2
- AVAACINZEOAHHE-VFZPANTDSA-N doripenem Chemical compound C=1([C@H](C)[C@@H]2[C@H](C(N2C=1C(O)=O)=O)[C@H](O)C)S[C@@H]1CN[C@H](CNS(N)(=O)=O)C1 AVAACINZEOAHHE-VFZPANTDSA-N 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- JFOZKMSJYSPYLN-QHCPKHFHSA-N lifitegrast Chemical compound CS(=O)(=O)C1=CC=CC(C[C@H](NC(=O)C=2C(=C3CCN(CC3=CC=2Cl)C(=O)C=2C=C3OC=CC3=CC=2)Cl)C(O)=O)=C1 JFOZKMSJYSPYLN-QHCPKHFHSA-N 0.000 claims description 2
- GVOISEJVFFIGQE-YCZSINBZSA-N n-[(1r,2s,5r)-5-[methyl(propan-2-yl)amino]-2-[(3s)-2-oxo-3-[[6-(trifluoromethyl)quinazolin-4-yl]amino]pyrrolidin-1-yl]cyclohexyl]acetamide Chemical compound CC(=O)N[C@@H]1C[C@H](N(C)C(C)C)CC[C@@H]1N1C(=O)[C@@H](NC=2C3=CC(=CC=C3N=CN=2)C(F)(F)F)CC1 GVOISEJVFFIGQE-YCZSINBZSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 55
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 36
- 239000000243 solution Substances 0.000 description 25
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- 239000012044 organic layer Substances 0.000 description 21
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 239000002131 composite material Substances 0.000 description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- -1 binol sodium salt Chemical class 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 229940093499 ethyl acetate Drugs 0.000 description 7
- 235000019439 ethyl acetate Nutrition 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000003125 aqueous solvent Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 229940126214 compound 3 Drugs 0.000 description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- IYYIVELXUANFED-UHFFFAOYSA-N bromo(trimethyl)silane Chemical compound C[Si](C)(C)Br IYYIVELXUANFED-UHFFFAOYSA-N 0.000 description 3
- LGTLXDJOAJDFLR-UHFFFAOYSA-N diethyl chlorophosphate Chemical compound CCOP(Cl)(=O)OCC LGTLXDJOAJDFLR-UHFFFAOYSA-N 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 3
- ROIMNSWDOJCBFR-UHFFFAOYSA-N 2-iodothiophene Chemical compound IC1=CC=CS1 ROIMNSWDOJCBFR-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- ARYHTUPFQTUBBG-UHFFFAOYSA-N thiophen-2-ylboronic acid Chemical compound OB(O)C1=CC=CS1 ARYHTUPFQTUBBG-UHFFFAOYSA-N 0.000 description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-dioxonaphthalene Natural products C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 1
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 description 1
- ONBQEOIKXPHGMB-VBSBHUPXSA-N 1-[2-[(2s,3r,4s,5r)-3,4-dihydroxy-5-(hydroxymethyl)oxolan-2-yl]oxy-4,6-dihydroxyphenyl]-3-(4-hydroxyphenyl)propan-1-one Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1OC1=CC(O)=CC(O)=C1C(=O)CCC1=CC=C(O)C=C1 ONBQEOIKXPHGMB-VBSBHUPXSA-N 0.000 description 1
- YARBOAMGXZEJEN-UHFFFAOYSA-N 1-diphenylphosphanyl-n-(diphenylphosphanylmethyl)methanamine Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CNCP(C=1C=CC=CC=1)C1=CC=CC=C1 YARBOAMGXZEJEN-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- GZFGOTFRPZRKDS-UHFFFAOYSA-N 4-bromophenol Chemical compound OC1=CC=C(Br)C=C1 GZFGOTFRPZRKDS-UHFFFAOYSA-N 0.000 description 1
- SNFCXVRWFNAHQX-UHFFFAOYSA-N 9,9'-spirobi[fluorene] Chemical compound C12=CC=CC=C2C2=CC=CC=C2C21C1=CC=CC=C1C1=CC=CC=C21 SNFCXVRWFNAHQX-UHFFFAOYSA-N 0.000 description 1
- VNOYRIVFZFACDI-UHFFFAOYSA-N COCCOCCOCCOc1c(ccc2ccc(C(O)=O)c(cc3)c22)c2c3cc1 Chemical compound COCCOCCOCCOc1c(ccc2ccc(C(O)=O)c(cc3)c22)c2c3cc1 VNOYRIVFZFACDI-UHFFFAOYSA-N 0.000 description 1
- 229940126639 Compound 33 Drugs 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- FCSHMCFRCYZTRQ-UHFFFAOYSA-N N,N'-diphenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CC=C1 FCSHMCFRCYZTRQ-UHFFFAOYSA-N 0.000 description 1
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 description 1
- PNUZDKCDAWUEGK-CYZMBNFOSA-N Sitafloxacin Chemical compound C([C@H]1N)N(C=2C(=C3C(C(C(C(O)=O)=CN3[C@H]3[C@H](C3)F)=O)=CC=2F)Cl)CC11CC1 PNUZDKCDAWUEGK-CYZMBNFOSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- AOWWQAZKHKMWSA-OWOJBTEDSA-M [O-]C(c1ccc(/C=C/c2ccc(OCCOCCOCCO)[s]2)[s]1)=O Chemical compound [O-]C(c1ccc(/C=C/c2ccc(OCCOCCOCCO)[s]2)[s]1)=O AOWWQAZKHKMWSA-OWOJBTEDSA-M 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- HTRXGEPDTFSKLI-UHFFFAOYSA-N butanoic acid;ethyl acetate Chemical compound CCCC(O)=O.CCOC(C)=O HTRXGEPDTFSKLI-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- ARQRPTNYUOLOGH-UHFFFAOYSA-N chcl3 chloroform Chemical compound ClC(Cl)Cl.ClC(Cl)Cl ARQRPTNYUOLOGH-UHFFFAOYSA-N 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125773 compound 10 Drugs 0.000 description 1
- 229940126142 compound 16 Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- HXITXNWTGFUOAU-UHFFFAOYSA-N dihydroxy-phenylborane Natural products OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- PHWISQNXPLXQRU-UHFFFAOYSA-N n,n-dimethylcarbamothioyl chloride Chemical compound CN(C)C(Cl)=S PHWISQNXPLXQRU-UHFFFAOYSA-N 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical class [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- BYMHXIQVEAYSJD-UHFFFAOYSA-M sodium;4-sulfophenolate Chemical compound [Na+].OC1=CC=C(S([O-])(=O)=O)C=C1 BYMHXIQVEAYSJD-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-M toluene-4-sulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-M 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/16—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C317/22—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/205—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring the aromatic ring being a non-condensed ring
- C07C43/2055—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring the aromatic ring being a non-condensed ring containing more than one ether bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D495/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3834—Aromatic acids (P-C aromatic linkage)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6558—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system
- C07F9/65586—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system at least one of the hetero rings does not contain nitrogen as ring hetero atom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Description
본 발명은 그래핀 박리용 분산 안정제, 이를 포함하는 그래핀-알칼리 금속염 복합체, 및 이를 이용한 그래핀의 제조방법에 관한 것으로서, 더욱 상세하게는, 그래파이트로부터 그래핀을 효율적으로 박리할 수 있는 그래핀 박리용 분산 안정제, 이를 포함하는 그래핀-알칼리 금속염 복합체, 및 이를 이용한 그래핀의 제조방법에 관한 것이다.
The present invention relates to a dispersion stabilizer for graphene peeling, a graphene-alkali metal salt complex containing the same, and a method for producing graphene using the same, and more particularly, to a graphene- A dispersion stabilizer for peeling, a graphene-alkali metal salt complex containing the same, and a process for producing graphene using the same.
그래핀(graphene)은 탄소 원자가 6각형 벌집 모양으로 연결되어 2차원 시이트(sheet) 형상을 가지는 탄소 결정으로서, 다수의 그래핀 시이트가 적층되어 그래파이트(graphite)를 형성한다. 따라서, 그래파이트를 박리(exfoliation)시키면, 한층 또는 다수층으로 이루어진 시이트 형태의 그래핀을 얻을 수 있다. 그래핀은 금속의 성질 및 비금속의 성질을 모두 가지는 물질로서, 금속의 성질로서 양호한 전기 전도성 및 열 전도성을 가지며, 비금속의 성질로서 높은 열안정성 및 화학적 불활성을 가진다. 그래핀은 전기 소자, 배터리, 연료 전지, 내화성 재료 등의 다양한 용도에 적용될 수 있다.
A graphene is a carbon crystal having a two-dimensional sheet shape in which carbon atoms are connected in a hexagonal honeycomb shape, and a plurality of graphene sheets are laminated to form a graphite. Thus, when graphene is exfoliated, it is possible to obtain grafts in the form of a sheet composed of one or more layers. Graphene is a material having both metallic and non-metallic properties. It has good electrical conductivity and thermal conductivity as the nature of the metal, and has high thermal stability and chemical inertness as a non-metallic property. Graphene can be applied to various applications such as electric devices, batteries, fuel cells, refractory materials and the like.
전기적, 광학적 및 기계적 특성이 우수한 그래핀을 얻기 위해서는, 그래파이트로부터 그래핀을 효율적으로 박리하여야 한다. 그래파이트로부터 그래핀을 박리하는 방법으로는, 기계적 박리법과 화학적 박리법이 알려져 있다. 기계적 박리법은 기계적 분쇄 또는 접착 테이프를 이용하는 방법으로서, 그래파이트를 단순히 기계적으로 분쇄하거나, 그래파이트에 접착 테이프를 붙인 다음 떼어 내어, 접착 테이프에 부착되어 박리되는 그래핀을 얻는 방법이다. 화학적 박리법은, 그래파이트를 산화제로 산화시켜 산화 그래파이트를 제조한 다음, 산화 그래파이트의 면과 면 사이에 물 등의 용매를 삽입하여, 층과 층 사이의 간격을 증가시키고, 교반 또는 초음파 분쇄하여, 산화 그래핀을 박리시킨 다음, 이를 다시 환원시켜 그래핀을 제조하는 방법이다. 예를 들면, Chem. Commun., 2012, 48, 7732-7734 "Binol salt as a completely removable graphene surfactant"에는, 그래파이트를 산화시켜 그래핀 옥사이드(graphene oxide: GO)를 제조하고, 제조된 그래핀 옥사이드와 비놀(Binol) 및 수산화나트륨(NaOH)을 혼합하여, 비놀 나트륨염(Binol sodium salt)이 그래핀 옥사이드의 층과 층 사이에 삽입되도록 한 다음, 그래핀 옥사이드를 환원 및 박리시켜, 비놀 나트륨염이 삽입된 그래핀(그래핀 옥사이드의 환원 생성물)을 제조한 다음, 생성물을 물로 세척하여, 비놀 나트륨염을 제거함으로써, 순수한 그래핀을 얻는 방법이 개시되어 있다. 상기 비놀 나트륨염은 물에 대한 그래핀 옥사이드의 분산성(dispersity)을 향상시키고, 두 개의 나프탈렌 그룹이 그래핀의 분리 특성을 향상시킬 뿐만 아니라, 약한 π-π 상호 작용(interaction)으로 인하여, 수계 및 유기계 용매를 이용한 세척에 의하여, 환원된 그래핀의 특성에 영향을 미치지 않고, 그래핀으로부터 용이하게 제거될 수 있다.
In order to obtain graphene having excellent electrical, optical and mechanical properties, graphene must be efficiently removed from graphite. As a method of peeling off graphene from graphite, a mechanical peeling method and a chemical peeling method are known. The mechanical peeling method is a method of using mechanical pulverization or an adhesive tape, in which graphene is merely mechanically pulverized, or an adhesive tape is attached to graphite and then peeled off to obtain graphene which is adhered to the adhesive tape to be peeled off. The chemical peeling method is a method in which graphite is oxidized with an oxidizing agent to prepare oxidized graphite and then a solvent such as water is inserted between the surface and the surface of the oxidized graphite to increase the distance between the layer and the layer, The graphene oxide is peeled off, and then the oxide graphene is reduced to produce graphene. For example, Chem. (GB) discloses a process for producing graphene oxide (GO) by oxidizing graphite and a process for producing graphene oxide (GO) Sodium hydroxide (NaOH) was mixed so that a binol sodium salt was inserted between the layer and the graphene oxide layer. Then, the graphene oxide was reduced and separated to obtain graphene A reducing product of graphene oxide) is produced, and then the product is washed with water to remove the sodium salt of the nonanol to obtain pure graphene. The binol sodium salt improves the dispersibility of the graphene oxide to water and not only improves the separation characteristics of graphene but also improves the separation properties of graphene due to the weak < RTI ID = 0.0 > pi-pi < And washing with an organic solvent, it can be easily removed from the graphene without affecting the properties of the reduced graphene.
최근에는, 기계적 박리법으로 박리된 그래파이트에 분산제를 첨가하여, 용해도가 우수한 그래핀을 제조하는 방법도 연구되고 있다. 예를 들면, 그래파이트와 금속염 수용액을 혼합하여, 그래파이트 사이에 금속염을 삽입하거나(intercalation), 그래파이트 사이에 방향족 고리화합물을 삽입시켜 π-π 상호작용을 이용한 그래파이트의 분리 방법이 연구되고 있다(특허 공개 10-2012-0095907 등 참조). 상기 방법에서는, 수용액에 용해된 금속염 또는 방향족 화합물이 그래파이트의 층과 층 사이에 삽입(intercalation)되어, 그래파이트의 층간 거리를 증가시킨다.
Recently, a method for producing graphene having excellent solubility by adding a dispersant to graphite peeled by a mechanical peeling method has been studied. For example, there has been studied a method of separating graphite using π-π interaction by intercalating a metal salt between graphite and an aqueous solution of a metal salt, and inserting an aromatic ring compound between graphites 10-2012-0095907, etc.). In this method, a metal salt or an aromatic compound dissolved in an aqueous solution is intercalated between the layers of the graphite and the layer to increase the interlayer distance of the graphite.
본 발명의 목적은, 수계 및 유기계 용매에 대한 분산도가 우수할 뿐만 아니라, 그래파이트 내부에서 알칼리 금속염의 삽입(intercalation) 및 분산 특성을 향상시킬 수 있는 그래핀 박리용 분산 안정제 및 이를 포함하는 그래핀-알칼리 금속염 복합체를 제공하는 것이다.Disclosure of the Invention An object of the present invention is to provide a dispersion stabilizer for graphene peeling which is excellent in dispersibility in aqueous and organic solvents as well as capable of improving the intercalation and dispersion properties of alkali metal salts in graphite, - alkali metal salt complex.
본 발명의 다른 목적은, 그래핀의 대량 생산이 용이하며, 그래핀을 안정하고 간편하게 제조할 수 있는 그래핀의 제조방법을 제공하는 것이다.
It is another object of the present invention to provide a method for producing graphene which is easy to mass-produce graphene and can stably and easily produce graphene.
상기 목적을 달성하기 위하여, 본 발명은 하기 화학식 1의 구조를 가지는 그래핀 박리용 분산 안정제를 제공한다.In order to achieve the above object, the present invention provides a dispersion stabilizer for graphene peeling having a structure represented by the following general formula (1).
[화학식 1][Chemical Formula 1]
상기 화학식 1에서, Ar은 탄소수 4 내지 100의 방향족기이고, M은 알칼리 금속이고, X는 알칼리 금속 M과 이온 결합할 수 있는 옥사이드기(-O-), 카르복실레이트기(-COO-), 설포네이트기(-SO3-), 설포닐기(-SO2-) 또는 포스파이트기(-PO3-)이고, Y는 -CH2- 또는 -CF2- 이고, n은 0 내지 10의 정수이고, m은 1 내지 3의 정수이고, Z는 존재하지 않거나, -CH2-, -NH-, -O-, -S-, -SO2-, -CO- 또는 -CF2-이고, E는 -H, -CH3, -SH, -OH, -NH2 또는 -CH2NH2이고, p는 1 내지 100의 정수이며, l은 1 또는 2이다.
Wherein Ar is an aromatic group having 4 to 100 carbon atoms, M is an alkali metal, X is an oxide group (-O-), a carboxylate group (-COO-) capable of ionic bonding with an alkali metal M, , A sulfonate group (-SO 3 -), a sulfonyl group (-SO 2 -) or a phosphite group (-PO 3 -), Y is -CH 2 - or -CF 2 - M is an integer from 1 to 3 and Z is absent or is -CH 2 -, -NH-, -O-, -S-, -SO 2 -, -CO- or -CF 2 - E is -H, -CH 3, -SH, -OH , -NH 2 or -CH 2 NH 2, p is an integer from 1 to 100, l is 1 or 2.
또한, 본 발명은 그래핀의 층과 층 사이에 상기 화학식 1로 표시되는 그래핀 박리용 분산 안정제가 삽입되어 있는 그래핀-알칼리 금속염 복합체를 제공한다. 또한, 본 발명은, 용매의 존재 하에서, 상기 화학식 1로 표시되는 그래핀 박리용 분산 안정제와 그래파이트를 혼합하여, 그래파이트의 층과 층 사이에 그래핀 박리용 분산 안정제가 삽입되도록 함으로써, 그래파이트의 층간 간격을 증가시키는 단계; 상기 그래핀 박리용 분산 안정제가 삽입된 그래파이트를 분산시켜, 그래핀의 층과층 사이에 그래핀 박리용 분산 안정제가 삽입된 그래핀-알칼리 금속염 복합체를 제조하는 단계; 및 용매로 상기 그래핀-알칼리 금속염 복합체를 세척하여, 그래핀-알칼리 금속염 복합체로부터 그래핀 박리용 분산 안정제를 제거하는 단계를 포함하는 그래핀의 제조방법을 제공한다.
Further, the present invention provides a graphene-alkali metal salt complex having a graphene layer and a layer interposed therebetween, wherein the graphene dispersion stabilizer for graphening separation is embedded. The present invention also relates to a method for producing a graphite sheet by mixing the graphene dispersion stabilizer for graphening separation represented by the above formula (1) and graphite in the presence of a solvent to insert a dispersion stabilizer for graphening separation between the graphite layer and the layer, Increasing the interval; Preparing a graphene-alkali metal salt complex in which a dispersion stabilizer for graphening separation is dispersed to prepare a graphene layer and a layer in which a dispersion stabilizer for graphening separation is inserted; And washing the graphene-alkali metal salt complex with a solvent to remove a graphene-alkali metal salt complex and a dispersion stabilizer for graphen peeling.
본 발명에 따른 그래핀 박리용 분산 안정제는, 수계 및 유기계 용매에 대한 분산도가 우수할 뿐만 아니라, 그래파이트 내부에서 알칼리 금속염의 삽입 및 분산 특성을 향상시킬 수 있다. 소수성의 그래파이트들은 서로간의 강력한 인력으로 인해 응집되는 현상이 발생하는데, 본 발명에 따른 친수성기를 가지는 분산 안정제는 그래파이트들의 응집 현상을 방지하며, 분산 안정제를 변형하여 다양한 용매에 용이하게 분산되도록 할 수 있다. 또한, 본 발명에 따른 그래핀의 제조방법에 의하면, 그래핀을 안정하게 대량 생산할 수 있다.
The dispersion stabilizer for graphening separation according to the present invention not only has excellent dispersibility in aqueous and organic solvents but also improves the insertion and dispersion characteristics of alkali metal salts in graphite. The hydrophobic graphite particles aggregate due to strong attraction between them. The dispersion stabilizer having a hydrophilic group according to the present invention prevents agglomeration of graphite particles and can easily disperse the dispersion stabilizer in various solvents . Further, according to the method for producing graphene according to the present invention, graphene can be stably mass produced.
도 1은 본 발명에 따른 그래핀 박리용 분산 안정제를 이용하여 그래핀을 박리시키는 과정을 보여주는 모식도.
도 2는 NaOH 및 본 발명의 그래핀 박리용 분산 안정제를 사용하여 제조한 그래핀-그래핀 박리용 분산 안정제 복합체의 장기 안정성을 보여주는 사진.
도 3은 NaOH 및 본 발명의 그래핀 박리용 분산 안정제룰 사용하여 제조한 그래핀의 전자주사현미경 사진.1 is a schematic view showing a process of peeling off graphene using a dispersion stabilizer for graphening separation according to the present invention.
FIG. 2 is a photograph showing the long-term stability of a dispersion stabilizer composite for graphene-graphene peeling prepared using NaOH and the dispersion stabilizer for peeling off graphene of the present invention.
Fig. 3 is an electron micrograph of graphene prepared using NaOH and the dispersion stabilizer for graphene peeling of the present invention. Fig.
이하, 첨부된 도면을 참조하여 본 발명을 상세히 설명한다. 본 발명에 따른 그래핀 박리용 분산 안정제는 그래파이트의 층과 층 사이에서 삽입되어, 그래파이트의 층간 거리를 증가시킴으로써, 그래파이트로부터 그래핀의 박리를 촉진시키는 물질로서, 하기 화학식 1의 구조를 가진다. Hereinafter, the present invention will be described in detail with reference to the accompanying drawings. The dispersion stabilizer for graphening separation according to the present invention is a material which is inserted between a layer of graphite and a layer to increase the distance between layers of graphite, thereby promoting the separation of graphene from graphite.
상기 화학식 1에서, Ar은 탄소수 4 내지 100, 바람직하게는 탄소수 5 내지 50, 예를 들면 탄소수 6 내지 20의 방향족기이고, M은 Li, Na, K 등의 알칼리 금속이고, X는 알칼리 금속 M과 이온 결합할 수 있는 옥사이드기(Oxide, -O-), 카르복실레이트기(Carboxylate, -COO-), 설포네이트기(Sulfonate, -SO3-), 설포닐기(Sulfonyl, -SO2-) 또는 포스파이트기(Phosphite, -PO3-)이고, Y는 -CH2- 또는 -CF2- 이고, n은 0 내지 10, 바람직하게는 0 내지 5, 예를 들면 1, 2 또는 3의 정수이고, m은 방향족기 Ar에 연결되는 알칼리 금속 M을 포함하는 작용기의 개수로서, 1 내지 3의 정수이다. 또한, Z는 존재하지 않거나, -CH2-, -NH-, -O-, -S-, -SO2-, -CO- 또는 -CF2-이고, E는 -H, -CH3, -SH, -OH, -NH2 또는 -CH2NH2이고, p는 1 내지 100, 바람직하게는 1 내지 25, 예를 들면 2 내지 10의 정수이며, l은 방향족기 Ar에 연결되는 에틸렌글리콜 사슬의 개수로서, 1 또는 2이다.
Wherein Ar is an aromatic group having 4 to 100 carbon atoms, preferably 5 to 50 carbon atoms, such as 6 to 20 carbon atoms, M is an alkali metal such as Li, Na, K, and X is an alkali metal M (O), carboxylate group (-COO-), sulfonate group (-SO 3 -), sulfonyl group (-SO 2 -), Or phosphite group (Phosphite, -PO 3 -), Y is -CH 2 - or -CF 2 - and n is an integer of 0 to 10, preferably 0 to 5, such as 1, 2 or 3 And m is the number of functional groups containing an alkali metal M connected to the aromatic group Ar, and is an integer of 1 to 3. Also, Z is absent, -CH 2 -, -NH-, -O- , -S-, -SO 2 -, -CO- , or -CF 2 - and, E is -H, -CH 3, - SH, -OH, -NH 2 or -CH 2 NH 2 , p is an integer from 1 to 100, preferably from 1 to 25, such as from 2 to 10, and 1 is an ethylene glycol chain Is 1 or 2.
상기 화학식 1에서, 방향족기 Ar은 탄화수소 방향족기 또는 헤테로고리 방향족기를 하나 이상 포함할 수 있고, 바람직하게는 평면성을 가지는 방향족기이고, 예를 들면, 
In the formula 1, the aromatic group Ar may include at least one hydrocarbon aromatic group or a heterocyclic aromatic group, preferably an aromatic group having planarity, for example,
또한, 상기 알칼리 금속 M, X 및 Y의 결합 형태로는, 하기 결합 염(salt)들을 예시할 수 있다. 여기서, M, Y 및 n은 화학식 1에서 설명한 바와 같다.Examples of the bonding form of the alkali metals M, X and Y include the following bonding salts. Here, M, Y and n are as described in the formula (1).
상기 화학식 1로 표시되는 그래핀 박리용 분산 안정제의 구체적인 예로는 하기 화학식 1a 내지 1j로 표시되는 화합물을 예시할 수 있다. Specific examples of the dispersion stabilizer for graphene peeling represented by the above formula (1) include compounds represented by the following formulas (1a) to (1j).
[화합물 1a][Compound 1a]
[화합물 1b][Compound 1b]
[화합물 1c][Compound 1c]
[화합물 1d][Compound 1d]
[화합물 1e][Compound 1e]
[화합물 1f][Compound 1f]
[화합물 1g][Compound 1g]
[화합물 1h][Compound 1h]
[화합물 1i][Compound 1i]
[화합물 1j][Compound 1j]
[화합물 1k][Compound 1k]
[화합물 1l][Compound l]
[화합물 1m][Compound 1m]
[화합물 1n][Compound 1n]
[화합물 1o][Compound 1o]
[화합물 1p][Compound 1p]
[화합물 1q][Compound 1q]
도 1은 본 발명에 따른 그래핀 박리용 분산 안정제를 이용하여 그래핀을 박리시키는 과정을 보여주는 모식도이다. 도 1에 도시된 바와 같이, 본 발명에 따른 그래핀 박리용 분산 안정제는 그래파이트(도 1의 A)의 층과 층 사이에서 삽입되어(도 1의 B), 그래파이트의 층간 거리를 증가시킴으로써, 그래파이트로부터 그래핀을 박리시킨다(도 1의 C). 본 발명에 따른 그래핀 박리용 분산 안정제는, 알칼리 금속염 및 에틸렌글리콜(ethylene glycol) 형태의 친수성 알킬 체인을 가지는 방향족 화합물로서, 수계 및 유기계 용매에 대한 분산성(dispersity) 및 용해도가 우수하고, 그래파이트의 층과 층 사이로 효과적으로 침투(삽입)될 수 있다. 본 발명에 따른 그래핀 박리용 분산 안정제가 그래파이트의 층과 층 사이로 삽입되면, 알칼리 금속염이 그래파이트의 층과 층 사이로 침투(intercalation)하여 그래파이트의 층간 거리를 증가시키고, 또한, 분산 안정제의 평면성이 우수한 방향족 부분과 그래파이트 사이의 π-π 상호 작용에 의해, 그래파이트의 층간 분리가 더욱 촉진된다. 또한, 그래핀 박리용 분산 안정제의 한쪽 말단에 옥사이드기(-O-), 카르복실레이트기(-COO-), 설포네이트기(-SO3-), 설포닐기(-SO2-), 포스파이트기(-PO3-) 등을 도입하고, 이를 이용하여 금속염을 안정하게 배위시킴으로써, 금속염의 안정성을 향상시킬 수 있다. 본 발명에 따른 그래핀 박리용 분산 안정제에 있어서, 에틸렌글리콜 형태의 알킬 체인을 구성하는 산소 원자들은 비공유 전자쌍을 가지므로, 상기 산소 원자가 일부 알칼리 금속염(Li+, Na+, K+ 등)을 둘러 싸서, 크라운 에테르(crown ether)와 유사한 형태로 금속염을 안정하게 배위할 수 있다. 이 경우, 그래핀 박리용 분산 안정제의 양쪽 말단에 금속염이 위치하는 형태가 되므로, 그래핀 박리용 분산 안정제가 그래파이트의 층과 층 사이에 침투되는 경우, 그래파이트의 분산성을 더욱 향상시킬 수 있다. 본 발명에 따른 그래핀 박리용 분산 안정제는, 하기 실시예에 나타낸 바와 같이, 히드록시기를 가지는 방향족 화합물과 에틸렌글리콜 및 금속염을 반응시켜 제조할 수 있다.
1 is a schematic view showing a process of peeling graphene using a dispersion stabilizer for graphening separation according to the present invention. 1, the dispersion stabilizer for graphening separation according to the present invention is inserted between a layer of graphite (FIG. 1A) and a layer (FIG. 1B) to increase the interlayer distance of graphite, (Fig. 1 (C)). The dispersion stabilizer for graphening separation according to the present invention is an aromatic compound having an alkali metal salt and a hydrophilic alkyl chain in the form of ethylene glycol and is excellent in dispersibility and solubility in aqueous and organic solvents, (Inserted) between the layers and layers of the substrate. When the dispersion stabilizer for graphening separation according to the present invention is inserted between the graphite layer and the layer, the alkali metal salt intercalates between the graphite layer and the layer to increase the interlayer distance of the graphite, The π-π interaction between the aromatic portion and the graphite further promotes the delamination of the graphite. In addition, an oxide group (-O-), a carboxylate group (-COO-), a sulfonate group (-SO 3 -), a sulfonyl group (-SO 2 -), a phosphate group The stability of the metal salt can be improved by introducing a phosphate group (-PO 3 -) or the like and using it to stably coordinate the metal salt. In the dispersion stabilizer for graphene separation according to the present invention, the oxygen atoms constituting the alkyl chain in the ethylene glycol form have unshared electron pairs, so that the oxygen atoms are surrounded by some alkali metal salts (Li + , Na + , K + The metal salt can be stably trapped in a form similar to a crown ether. In this case, since the metal salt is located at both ends of the graphene dispersion stabilizer, when the dispersion stabilizer for graphen peeling penetrates between the graphite layer and the layer, the dispersibility of the graphite can be further improved. The dispersion stabilizer for graphening separation according to the present invention can be produced by reacting an aromatic compound having a hydroxy group with ethylene glycol and a metal salt as shown in the following examples.
본 발명에 따른 그래핀 박리용 분산 안정제를 이용하여 그래핀을 제조(박리)하기 위해서는, 먼저, 용매의 존재 하에서, 상기 화학식 1로 표시되는 그래핀 박리용 분산 안정제와 그래파이트를 혼합하여, 그래파이트의 층과 층 사이에 그래핀 박리용 분산 안정제가 삽입되도록 함으로써, 그래파이트의 층간 간격을 증가시킨다. 상기 화학식 1로 표시되는 그래핀 박리용 분산 안정제의 사용량은, 상기 그래핀 박리용 분산 안정제 및 그래파이트의 전체 함량에 대하여, 10 내지 90 중량%, 바람직하게는 50 내지 90 중량%, 더욱 바람직하게는 80 내지 90 중량%이다. 예를 들면, 상기 그래파이트에 대하여, 상기 그래핀 박리용 분산 안정제의 사용량은 중량비로 2 내지 10 배일 수 있다. 여기서, 상기 그래핀 박리용 분산 안정제의 사용량의 너무 작으면, 그래파이트의 박리가 불충분하게 수행될 우려가 있고, 상기 그래핀 박리용 분산 안정제의 사용량의 너무 많으면, 생성된 그래핀의 전기전도도가 저하될 우려가 있고, 특별한 이익이 없이, 경제적으로 바람직하지 못하다. 상기 그래핀 박리용 분산 안정제 및 그래파이트가 혼합되는 용매로는 통상의 수계 또는 유기계 용매를 특별한 제한 없이 사용할 수 있고, 예를 들면, 물, 에탄올, 이소프로필알콜, 디메틸설폭사이드, 디클로로메탄, 이황화탄소, 아세톤, 클로로포름, 사염화탄소, 1,4-디옥산, 메틸아세테이트, 피리딘, m-크레졸, 페놀, 디메틸포름아미드, 디메틸아세트아미드, 황산, N-메틸-2-피롤리돈 및 피리딘으로 이루어진 군에서 선택된 하나 이상의 용매를 사용할 수 있다. 상기 용매의 사용량은 특별히 제한되지 않고, 필요에 따라 설정될 수 있으나, 예를 들면, 상기 그래핀 박리용 분산 안정제 및 그래파이트 전체 100 중량부에 대하여, 500 내지 9900 중량부, 바람직하게는 2000 내지 9900 중량부이다. 여기서, 상기 용매의 사용량이 너무 적으면, 그래핀 박리용 분산 안정제 및 그래파이트가 충분히 용해되지 않을 우려가 있으며, 너무 많으면, 그래핀의 제조 효율이 저하될 우려가 있다. 상기 용매와 그래핀 박리용 분산 안정제 및 그래파이트의 혼합 온도도 필요에 따라 적절히 설정될 수 있으며, 예를 들면, 0 내지 200 ℃, 바람직하게는 25 내지 50 ℃이다.
In order to prepare (peel) the graphene using the dispersion stabilizer for graphening separation according to the present invention, first, the dispersion stabilizer for peeling the graphene represented by the above formula (1) and graphite are mixed in the presence of a solvent to prepare graphite And a dispersion stabilizer for separating graphene is inserted between the layer and the layer to increase the interlayer spacing of the graphite. The amount of the dispersion stabilizer for graphening separation represented by Formula 1 is 10 to 90% by weight, preferably 50 to 90% by weight, more preferably 50 to 90% by weight, based on the entire content of the dispersion stabilizer for graphitizing and graphite 80 to 90% by weight. For example, with regard to the graphite, the amount of the dispersion stabilizer for graphene peeling may be 2 to 10 times by weight. If the amount of the dispersion stabilizer for peeling the graphene is too small, the peeling of the graphite may be insufficiently performed. If the amount of the dispersion stabilizer for graphening is too large, the electrical conductivity of the resulting graphene is lowered And there is no special advantage, and it is economically undesirable. As the solvent in which the graphene dispersion stabilizer and graphite are mixed, a usual aqueous or organic solvent can be used without any particular limitation, and examples thereof include water, ethanol, isopropyl alcohol, dimethyl sulfoxide, dichloromethane, carbon disulfide , Acetone, chloroform, carbon tetrachloride, 1,4-dioxane, methyl acetate, pyridine, m-cresol, phenol, dimethylformamide, dimethylacetamide, sulfuric acid, N-methyl-2-pyrrolidone and pyridine One or more selected solvents may be used. The amount of the solvent to be used is not particularly limited and may be set as required. For example, the amount of the solvent is preferably 500 to 9900 parts by weight, more preferably 2000 to 9900 parts by weight per 100 parts by weight of the dispersion stabilizer for graphitizing and graphite, Parts by weight. If the amount of the solvent used is too small, there is a fear that the dispersion stabilizer for graphening and the graphite may not be sufficiently dissolved. If the amount is too large, there is a fear that the production efficiency of graphene is lowered. The mixing temperature of the solvent and the dispersion stabilizer for separating graphene and graphite may be suitably set as needed, for example, 0 to 200 ° C, preferably 25 to 50 ° C.
다음으로, 상기 그래핀 박리용 분산 안정제가 삽입된 그래파이트를 분산시켜, 그래핀의 층과 층 사이에 그래핀 박리용 분산 안정제가 삽입된 그래핀-알칼리 금속염 복합체를 제조한다. 상기 분산 단계는, 그래핀 박리용 분산 안정제가 삽입된 그래파이트 용액을 교반하거나 초음파 분쇄하는 등의 방법으로, 그래핀 박리용 분산 안정제가 삽입된 그래파이트를 박리 및 분쇄시켜 수행될 수 있다. 상기 그래핀-알칼리 금속염 복합체에 있어서, 상기 그래핀 박리용 분산 안정제의 함량은, 상기 그래핀-알칼리 금속염 복합체의 전체 함량에 대하여, 10 내지 90 중량%, 바람직하게는 50 내지 90 중량%, 더욱 바람직하게는 80 내지 90 중량%이다. 본 명세서에 있어서, 이와 같이 제조된 그래핀의 층과 층 사이에 그래핀 박리용 분산 안정제가 삽입된 복합체를 "그래핀-알칼리 금속염 복합체" 또는 "그래핀-그래핀 박리용 분산 안정제 복합체"라 하고, 상기 그래핀-알칼리 금속염 복합체를 포함하는 용액을 "그래핀-알칼리 금속염 복합체 잉크(ink)"라 한다. 이와 같이 잉크 상태의 복합체를 제조한 다음, 용매로 상기 그래핀-알칼리 금속염 복합체를 세척하여, 그래핀-알칼리 금속염 복합체로부터 그래핀 박리용 분산 안정제를 제거하면, 순순한 그래핀을 얻을 수 있다. 상기 세척 단계에 사용되는 용매로는 상기 그래핀 박리용 분산 안정제 및 그래파이트의 혼합에 사용되는 용매의 하나 이상을 필요에 따라 적절히 선택하여 사용할 수 있고, 바람직하게는 물을 사용할 수 있다.
Next, the graphite with the dispersion stabilizer for peeling off the graphene is dispersed to prepare a graphene-alkali metal salt complex in which a dispersion stabilizer for graphen peeling is inserted between the graphene layer and the layer. The dispersing step may be carried out by peeling and grinding graphite into which a dispersion stabilizer for graphening is inserted by stirring or ultrasonic pulverizing the graphite solution having the dispersion stabilizer for graphening removed. In the graphene-alkali metal salt composite, the content of the dispersion stabilizer for graphene peeling may be 10 to 90% by weight, preferably 50 to 90% by weight, more preferably 10 to 90% by weight based on the total content of the graphene- And preferably 80 to 90% by weight. In the present specification, the composite in which the dispersion stabilizer for graphening separation is inserted between the layer and the layer of graphene thus produced is referred to as "graphene-alkali metal salt complex" or "dispersion stabilizer composite for graphene- , And the solution containing the graphene-alkali metal salt complex is referred to as "graphene-alkali metal salt complex ink". The graphene-alkali metal salt complex is washed with a solvent after preparing the composite in the ink state, and the graphene-alkali metal salt complex is stripped of the dispersion stabilizer for graphen peeling, whereby pure graphene can be obtained. As the solvent used in the washing step, one or more of the solvents used for mixing the graphene dispersion stabilizer and the graphite may be appropriately selected and used. Preferably, water may be used.
본 발명에 따른 그래핀의 제조 방법에 의하면, 안전하고 저렴한 알칼리 금속염 및 친수성 알킬 체인을 가지는 유ㆍ무기 복합 화합물로서, 상기 화학식 1로 표시되는 그래핀 박리용 분산 안정제를 이용하여, 간단한 공정으로 그래핀을 박리함으로써, 단순히 알칼리 금속을 사용하여 그래파이트를 박리시키는 방법과 비교하여, 용이하고, 안정하며, 저렴하게 그래핀을 제조할 수 있다. 또한, 본 발명에 따른 그래핀의 제조 방법에 의하면, 환경적으로 바람직하지 못한 화학적 환원과정을 거치지 않고, 그래핀을 대량 생산할 수 있다. 본 발명에 따라 제조된 그래핀은, 대전방지막 등의 ESD (Electrostatic Discharge) 소자, 전자파 차폐 필름 등의 EMI(electromagnetic interference) 소자, 전극, 방열소재 등의 다양한 전기 및 전자 재료로 사용될 수 있다.
According to the method for producing graphene according to the present invention, as an organic-inorganic hybrid compound having a safe and cheap alkali metal salt and a hydrophilic alkyl chain, the dispersion stabilizer for graphening separation represented by the above formula (1) By separating the fins, graphene can be produced easily, stably, and inexpensively as compared with a method of simply peeling off graphite with an alkali metal. Further, according to the method for producing graphene according to the present invention, it is possible to mass produce graphene without an environmentally undesirable chemical reduction process. The graphene produced according to the present invention can be used as a variety of electrical and electronic materials such as electrostatic discharge (ESD) devices such as antistatic films, EMI (electromagnetic interference) devices such as electromagnetic wave shielding films, electrodes, and heat dissipation materials.
이하, 구체적인 실시예를 통하여 본 발명을 더욱 상세히 설명한다. 하기 실시예는 본 발명을 예시하기 위한 것으로서, 본 발명이 하기 실시예에 의해 한정되는 것은 아니다.
Hereinafter, the present invention will be described in more detail with reference to specific examples. The following examples illustrate the present invention and are not intended to limit the scope of the present invention.
[실시예 1] 그래핀 박리용 분산 안정제의 합성 [Example 1] Synthesis of dispersion stabilizer for graphene peeling
하기 반응식 1에 나타낸 바와 같이, 질소 분위기에서, 하이드로퀴논(Hydroquinone, 화합물 1) 10.00 g (90.82 mmol), p-벤조퀴논(benzoquinone) 980 mg (9.99 mmol), H2SO4 1.10 mL 및 트리에틸렌글리콜모노메틸에테르 (triethylene glycol monomethyl ether, p= 2) 14.5 mL (90.82 mmol)을 혼합하고, 80 ℃에서 24 시간 동안 교반하면서 반응시켰다. 디클로로메텐을 첨가하여, 반응액을 완전히 용해시키고, 물로 추출한 다음, 유기층을 MgSO4로 건조하고, 남은 유기층을 230 ℃, 1 mmHg의 조건에서 분별증류하여, 화합물 (2) 13.96 g을 얻었다(수율: 60%, 1H-NMR (CDCl3, Varian 400 MHz): δ 6.94 (1H, s), 6.74 (4H, s), 4.00-4.03 (2H, m), 3.79- 3.81 (2H, m), 3.64-3.71 (6H, m), 3.54-3.56 (2H, m), 3.36 (3H, s)).
As shown in Scheme 1, 10.00 g (90.82 mmol) of hydroquinone (compound 1), 980 mg (9.99 mmol) of p-benzoquinone, 1.10 mL of H 2 SO 4, 14.5 mL (90.82 mmol) of triethylene glycol monomethyl ether (p = 2) were mixed and reacted with stirring at 80 DEG C for 24 hours. Dichloromethane was added to dissolve the reaction solution completely and extracted with water. The organic layer was dried over MgSO 4 and the remaining organic layer was fractionally distilled at 230 ° C under 1 mmHg to obtain 13.96 g of compound (2) : 60%, 1 H-NMR (CDCl 3, Varian 400 MHz): δ 6.94 (1H, s), 6.74 (4H, s), 4.00-4.03 (2H, m), 3.79- 3.81 (2H, m), 3.64-3.71 (6H, m), 3.54-3.56 (2H, m), 3.36 (3H, s).
질소 분위기에서, 합성된 화합물 (2) 3.00 g을 이소프로필알콜(IPA) 42.0 mL에 용해시킨 후, 메탄올(MeOH) 20.0 mL에 NaOH 560 mg이 용해된 알칼리 금속 용액을 혼합하고, 80 ℃에서 24 시간 동안 교반하면서 반응시키고, IPA를 감압하여 제거하여, 펜옥사이드(Phenoxide type) 타입의 화합물 (3, M = Na) 3.0 g합성하였다(수율: 92 %, 1H-NMR (D2O, Varian 400 MHz): δ 6.65-6.67 (2H, d), 6.39-6.41 (2H, d), 3.94-3.95 (2H, m), 3.65- 3.67 (2H, m), 3.58-3.43 (8H, m), 3.20 (3H, s))After dissolving 3.00 g of the synthesized compound (2) in 42.0 mL of isopropyl alcohol (IPA) in a nitrogen atmosphere, 20.0 mL of methanol (MeOH) was mixed with an alkali metal solution in which 560 mg of NaOH was dissolved, (Yield: 92%, 1 H-NMR (D 2 O, Varian (R)) was synthesized in the same manner as in Example 1 , (2H, d), 3.94-3.95 (2H, m), 3.65-3.67 (2H, m), 3.58-3.43 (8H, m) 3.20 (3H, s))
[반응식 1][Reaction Scheme 1]
[실시예 2] 그래핀 박리용 분산 안정제의 합성 [Example 2] Synthesis of dispersion stabilizer for graphene peeling
하기 반응식 2에 나타낸 바와 같이, 질소 분위기에서, 실시예 1에서 합성된 화합물 (2) 1.00 g (3.9 mmol)을, 톨루엔(Toluene, PhMe) 10.0 mL에 용해시킨 후, NaH (60 % dispersion in mineral oil) 0.35 g (1.5 eq)을 넣고, 0 ℃에서 30분 동안 교반하면서 반응시킨 후, 1,3-프로판설톤(propanesultone, 화합물 (5)) 0.57 g (4.68 mmol)을 넣고, 110 ℃에서 4시간 동안 교반하면서 반응시켜, 알킬설포네이트(Alkylsurfonate) 타입의 화합물 (6, M = Na)을 합성하였다.1.00 g (3.9 mmol) of the compound (2) synthesized in Example 1 was dissolved in 10.0 mL of toluene (Toluene, PhMe) in a nitrogen atmosphere as shown in the following Reaction Scheme 2, and then 60% dispersion in mineral 0.57 g (4.68 mmol) of 1,3-propanesultone (compound (5)) was added thereto and the mixture was stirred at 110 ° C for 4 For 6 hours, to synthesize an alkylsulfonate type compound (6, M = Na).
[반응식 2][Reaction Scheme 2]
[실시예 3] 그래핀 박리용 분산 안정제의 합성 [Example 3] Synthesis of dispersion stabilizer for graphene peeling
하기 반응식 3에 나타낸 바와 같이, 질소 분위기에서, 소디움 4-하이드록시벤젠설포네이트 디하이드레이트(Sodium 4-hydroxybenzenesulfonate dehydrate, 화합물 7 ) 1.0 g (4.31 mmol), p-벤조퀴논 51.0 mg (0.474 mmol), H2SO4 0.1 mL 및 트리에틸렌글리콜 모노메틸에테르(p= 2) 0.690 mL (4.31 mmol)을 혼합하고, 80 ℃에서 24 시간 동안 교반하면서 반응시켰다. 반응 종결 후, 반응액을 냉각하고, 용매를 농축하고, 에탄올을 첨가한 다음, 반응액을 여과하였다. 여과물(Filtrate)을 메탄올에 용해시킨 후, 클로로포름(Chloroform)을 첨가하여, 결정을 생성시키고, 여과하여, 화합물 (8)를 합성하였다. 합성된 화합물 (8)에 2M NaOH 수용액(aq)을 천천히 첨가하면서, pH를 8로 맞춘 후, 에탄올로 침전시켜, 설포네이트(surfonate) 타입의 화합물 (9, M = Na)을 합성하였다.As shown in Scheme 3, 1.0 g (4.31 mmol) of sodium 4-hydroxybenzenesulfonate dehydrate (Compound 7) and 51.0 mg (0.474 mmol) of p-benzoquinone were mixed in a nitrogen atmosphere, 0.1 mL of H 2 SO 4 and 0.690 mL (4.31 mmol) of triethylene glycol monomethyl ether (p = 2) were mixed and reacted with stirring at 80 ° C for 24 hours. After completion of the reaction, the reaction solution was cooled, the solvent was concentrated, ethanol was added, and the reaction solution was filtered. The filtrate was dissolved in methanol, and then chloroform (Chloroform) was added to produce crystals and filtered to synthesize Compound (8). To the synthesized compound (8), 2M NaOH aqueous solution (aq) was added slowly and the pH was adjusted to 8, followed by precipitation with ethanol to synthesize a sulfonate type compound (9, M = Na).
[반응식 3][Reaction Scheme 3]
[실시예 4] 그래핀 박리용 분산 안정제의 합성 [Example 4] Synthesis of dispersion stabilizer for graphene peeling
하기 반응식 4에 나타낸 바와 같이, 4-브로모페놀(4-bromophenol, 화합물 10) 4.00 g (23.1 mmol), 2-[2-(2-메톡시에톡시)에톡시]-1-(4-메틸벤젠설포네이트)에탄 (2-[2-(2-methoxyethoxy)ethoxy]-1-(4-methylbenzenesulfonate)ethane, 화합물 11) 8.09 g (25.41 mmol) 및 K2CO3 7.70 g (55.4 mmol)을 반응기에 넣고 질소로 치환시킨 뒤, 무수 디메틸포름아미드(DMF) 60 ml를 넣어, 반응액을 용해시켰다. 반응액을 80 ℃에서 24시간 동안 교반하면서 반응시킨 후, 에틸아세테이트를 넣어 완전히 용해시키고, 물로 추출한 다음, 유기층을 MgSO4로 건조시키고, 남은 유기층을 농축하였다. 농축된 유기층을 헥산 : 에틸아세테이트 = 1:1 (부피비) 혼합 용액으로 전개하면서, 컬럼 정제하여 화합물 (12) 6.83 g을 얻었다(수율: 95%, 1H-NMR (DMSO, Varian 400 MHz): δ 7.36 (2H, d, J = 8.8 Hz), 6.80 (2H, d, J = 9.2 Hz), 4.1-4.07 (2H, m), 3.85- 3.83 (2H, m), 3.73-3.68 (6H, m), 3.55-3.53 (2H, m), 3.37 (3H, s)).
As shown in Scheme 4 below, 4.00 g (23.1 mmol) of 4-bromophenol (compound 10), 2- [2- (2-methoxyethoxy) ethoxy] 8.09 g (25.41 mmol) of Compound 2 and 7.70 g (55.4 mmol) of K 2 CO 3 were added to a solution of 2- [2- (2-methoxyethoxy) ethoxy] -1- (4-methylbenzenesulfonate) After the reaction mixture was purged with nitrogen, 60 ml of anhydrous dimethylformamide (DMF) was added to dissolve the reaction solution. After the reaction, while the reaction mixture was stirred at 80 ℃ for 24 hours, put in the ethyl acetate were completely dissolved, and then extracted with water, the organic layer was dried with MgSO 4, and concentrated to the remaining organic layer. Column chromatography was performed to obtain 6.83 g of compound (12) (yield: 95%, 1 H-NMR (DMSO, Varian 400 MHz)) as a concentrated organic layer was developed with a mixed solution of hexane: ethyl acetate = 1: 1 (volume ratio) (2H, m), 3.73-3.68 (6H, m), 7.38-7.28 (2H, m) ), 3.55-3.53 (2H, m), 3.37 (3H, s)).
얻어진 화합물 (12) 3.35 g (10.5 mmol)을 반응기에 넣고, 질소 치환한 다음, 무수 테트라히드로퓨란(THF) 30 ml를 첨가하여, 용해시켰다. 반응액을 -78 ℃로 냉각하고, n-부틸리튬(n-BuLi) 7.87 ml를 천천히 첨가한 후, 1.5시간 동안 교반하고, 디에틸클로로포스페이트(Diethyl chlorophosphate) 2.27 ml (15.75 mmol)를 첨가한 다음, 동일한 온도에서 3시간 동안 더 교반하면서 반응시켰다. 암모늄클로라이드를 첨가하여, 반응을 종료한 뒤, 에틸아세테이트를 첨가하여, 반응물을 완전히 용해시키고, 물로 추출한 다음, 유기층을 MgSO4로 건조하고, 남은 유기층을 농축하였다. 농축된 유기층을 에틸아세테이트 : 메탄올 = 10:1 (부피비)의 혼합 용액으로 전개하면서, 컬럼 정제하여 화합물 (13) 1.86 g을 얻었다(수율: 45%, 1H-NMR (CDCl3, Varian 400 MHz): δ 7.65 (2H, dd), 7.09 (2H, dd), 4.17-4.15 (2H, m), 3.99- 3.93 (4H, m), 3.76-3.74 (2H, m), 3.59-3.57 (2H, m), 3.53-3.50 (4H, m) 3.49-3.40 (2H, m) 3.32 (2H, s), 3.22 (3H, s), 1.21 (6H, m)).
3.35 g (10.5 mmol) of the obtained compound (12) was placed in a reactor, purged with nitrogen, and dissolved in 30 ml of anhydrous tetrahydrofuran (THF). The reaction solution was cooled to -78 ° C, 7.87 ml of n-butyllithium (n-BuLi) was slowly added, stirred for 1.5 hours, and 2.27 ml (15.75 mmol) of diethyl chlorophosphate was added Then, the reaction was carried out at the same temperature for 3 hours with further stirring. After completion of the reaction by adding ammonium chloride, ethyl acetate was added to completely dissolve the reaction product, and the reaction solution was extracted with water. The organic layer was dried over MgSO 4 and the remaining organic layer was concentrated. The obtained organic layer was subjected to column purification while developing with a mixed solution of ethyl acetate and methanol at a ratio of 10: 1 (volume ratio) to obtain 1.86 g of a compound (13) (yield: 45%, 1 H-NMR (CDCl 3 , Varian 400 MHz ): 隆 7.65 (2H, dd), 7.09 (2H, dd), 4.17-4.15 (2H, m), 3.99-3.93 (4H, m), 3.76-3.74 m), 3.53-3.50 (4H, m) 3.49-3.40 (2H, m) 3.32 (2H, s), 3.22 (3H, s), 1.21 (6H, m).
상기 화합물 (13) 1.74 g (4.62 mmol)을 아세토나이트릴(acetonitrile, MeCN) 16 ml에 용해시킨 후, 0 ℃로 냉각하고, 브로모트리메틸실란(Bromotrimethylsilane) 0.53 ml (3.99 mmol)을 첨가한 다음, 상온에서 17 시간 동안 반응시켜, 화합물 (14)을 합성하였다. 합성된 화합물 (14)에 2M NaOH 수용액(aq)을 천천히 첨가하면서, pH를 8로 맞춘 후, 에탄올로 침전시켜, 포스페이트(phosphate) 타입의 화합물 (15) 1.37 g을 얻었다(수율: 80%, 1H-NMR (D2O, Varian 400 MHz): δ 7.68 (2H, dd), 7.03 (2H, dd), 4.16-4.14 (2H, m), 3.81- 3.79 (2H, m), 3.66-3.65 (2H, m), 3.60-3.55 (4H, m), 3.49-3.47 (2H, m)).1.74 g (4.62 mmol) of the compound (13) was dissolved in 16 ml of acetonitrile (MeCN), cooled to 0 ° C, 0.53 ml (3.99 mmol) of bromotrimethylsilane was added , And the mixture was reacted at room temperature for 17 hours to synthesize Compound (14). The pH was adjusted to 8 while slowly adding 2M aqueous NaOH solution (aq) to the synthesized compound (14), and then precipitated with ethanol to obtain 1.37 g of a phosphate type compound (15) (yield: 80% 1 H-NMR (D 2 O , Varian 400 MHz): δ 7.68 (2H, dd), 7.03 (2H, dd), 4.16-4.14 (2H, m), 3.81- 3.79 (2H, m), 3.66-3.65 (2H, m), 3.60-3.55 (4H, m), 3.49-3.47 (2H, m)).
[반응식 4] [Reaction Scheme 4]
[실시예 5] 그래핀 박리용 분산 안정제의 합성 [Example 5] Synthesis of dispersion stabilizer for graphene peeling
하기 반응식 5에 나타낸 바와 같이, 9,9'-스피로바이플루오렌(9,9'- spirobifluorene, 화합물 16) 6.52 g (20.6 mmol)과 무수 FeCl3 10 mg을 클로로포롬(CHCl3) 60 ml에 용해시킨 후, 10 mL의 클로로포롬에 브로민(bromine) 2.24 mL (43.6 mmol)을 희석시킨 용액을, 0 ℃에서 1시간에 걸쳐 천천히 떨어뜨려 첨가하였다. 24시간 후, 반응물을 포화 소디움 싸이오설페이트(Na2S2O3) 용액과 물로 세척하여, 잔류 브로민을 제거하였다. 유기층을 소디움 설페이트로(Na2SO4)로 건조하고, 유기용매를 제거하고, CHCl3/에탄올(EtOH)로 재결정하여 화합물 (17) 8.8 g을 얻었다(수율: 88%, 1H-NMR (CDCl3, Varian 300 MHz): δ 7.83-7.80 (2H, d), 7.72-7.69 (2H, d), 7.52-7.49 (2H, dd), 7.41-7.37 (2H, t), 7.18-7.13 (2H, t), 6.84-6.83 (2H, d), 6.73-6.70 (2H, d)).
As shown in Scheme 5, 6.52 g (20.6 mmol) of 9,9'-spirobifluorene (Compound 16) and 10 mg of anhydrous FeCl 3 were dissolved in 60 ml of chloroform (CHCl 3 ) After dissolution, a solution of 2.24 mL (43.6 mmol) of bromine in 10 mL of chloroform was slowly added dropwise over 1 hour at 0 ° C. After 24 h, the reaction was washed with saturated sodium thiosulfate (Na 2 S 2 O 3 ) solution and water to remove the residual bromine. The organic layer with sodium sulfate (Na 2 SO 4) to the drying and removal of the organic solvent, and recrystallized from CHCl 3 / ethanol (EtOH) to give the compound (17) 8.8 g (Yield: 88%, 1 H-NMR ( CDCl 3, Varian 300 MHz): δ 7.83-7.80 (2H, d), 7.72-7.69 (2H, d), 7.52-7.49 (2H, dd), 7.41-7.37 (2H, t), 7.18-7.13 (2H , t), 6.84-6.83 (2H, d), 6.73-6.70 (2H, d).
화합물 (17) 2 g (4.21 mmol)을 50 mL 테트라하이드로퓨란(THF)에 용해시키고, -78 ℃로 냉각하고, n-부틸리튬(n-BuLi) 2.87 ml을 천천히 넣어준 후, 20분 후에 트리메틸보레이트(B(OMe)3) 0.65 g(6.31 mmol) 을 넣고, 약 20분 교반 후, 상온으로 온도를 상승시켰다. 다음으로, 과산화수소(H2O2) 10 mL와 소디움 옥사이드(NaOH) 0.5 g을 넣고, 12 시간 동안 교반하고, 메틸렌클로라이드(CH2Cl2)와 물로 추출한 다음, MgSO4로 유기층을 건조하고, 컬럼으로 분리하여 화합물 (18)을 얻었다. 메탄올 16 mL에 포타슘 하이드록사이드(KOH) 1.23 g(21.9 mmol)을 용해시킨 후, 화합물 (18) 3 g(7.30 mmol)을 0 ℃에서 첨가하였다. 반응액을 같은 온도에서 1시간 교반한 후, N,N-디메틸싸이오카바모일 클로라이드 (N,N-dimethylthiocarbamoyl chloride) 2.71 g (21.9 mmol)을 첨가하였다. 반응액의 온도를 60 ℃까지 올리고, 2시간 동안 교반한 후, 상온으로 냉각하여, 흰색의 고체 물질을 얻었다. 얻어진 물질을 MeOH/H2O (1:1 v/v) 혼합 용액으로 세척하고, 메틸렌클로라이드 및 핵산의 혼합 용액(CH2Cl2 : hexane = 2:1)으로 컬럼 정제하여 화합물 (19)를 얻었다.
2 g (4.21 mmol) of the compound (17) was dissolved in 50 mL of tetrahydrofuran (THF), cooled to -78 ° C, 2.87 mL of n- butyllithium (n-BuLi) was slowly added, 0.65 g (6.31 mmol) of trimethyl borate (B (OMe) 3 ) was added thereto, stirred for about 20 minutes, and then the temperature was raised to room temperature. Next, into a hydrogen peroxide (H 2 O 2) 10 mL and the sodium oxide (NaOH) 0.5 g, it was stirred for 12 h and methylene chloride (CH 2 Cl 2) and dried to extract the organic layer with MgSO 4 with water, The reaction mixture was separated into a column to obtain a compound (18). After dissolving 1.23 g (21.9 mmol) of potassium hydroxide (KOH) in 16 mL of methanol, 3 g (7.30 mmol) of compound (18) was added at 0 占 폚. After the reaction solution was stirred at the same temperature for 1 hour, 2.71 g (21.9 mmol) of N, N-dimethylthiocarbamoyl chloride was added. The temperature of the reaction solution was raised to 60 캜, stirred for 2 hours, and then cooled to room temperature to obtain a white solid material. The obtained material was washed with a mixed solution of MeOH / H 2 O (1: 1 v / v) and subjected to column purification using a mixed solution of methylene chloride and nucleic acid (CH 2 Cl 2 : hexane = 2: .
화합물 (19) 2 g(4.01 mmol)을 디페닐에테르(diphenylether) 3 mL에 용해시킨 후, 280 ℃에서 3.5 시간 동안 교반하였다. 반응액을 상온으로 냉각하고, 메탄올 40 mL 을 첨가하여, 노란 고체 물질 침전을 얻고, 감압 여과하였다. 여과된 고체 물질을 차가운 MeOH/H2O(1:1 v/v) 혼합 용액으로 세척하고, 에틸아세테이트(Ethylacetate) 10 mL 로 15분 동안 초음파 처리하여, 재결정시켜, 화합물 (20)을 얻었다. 질소 분위기에서, 얻어진 화합물 (20) 0.2 g(0.40 mmol) 및 포타슘하이드록사이드(KOH) 0.17 g (3.00 mmol)을 에탄올(EtOH) 5 mL에 용해시킨 후, 70 ℃에서 22 시간 동안 교반하였다. 반응액을 상온으로 냉각하고, H2O 20 mL 및 3M HCl(aq) 15 mL를 첨가하여, 침전된 화합물 (21)을 얻었다.
2 g (4.01 mmol) of the compound (19) was dissolved in 3 mL of diphenylether, and the mixture was stirred at 280 DEG C for 3.5 hours. The reaction solution was cooled to room temperature, and 40 mL of methanol was added to obtain a yellow solid substance precipitate, which was filtered under reduced pressure. The filtered solid material was washed with a cold MeOH / H 2 O (1: 1 v / v) mixed solution, sonicated with 10 mL of ethyl acetate (Ethylacetate) for 15 minutes and recrystallized to obtain compound (20). 0.2 g (0.40 mmol) of the obtained compound (20) and 0.17 g (3.00 mmol) of potassium hydroxide (KOH) were dissolved in 5 mL of ethanol (EtOH) and stirred at 70 캜 for 22 hours in a nitrogen atmosphere. The reaction solution was cooled to room temperature, and 20 mL of H 2 O and 15 mL of 3M HCl (aq) were added to obtain a precipitated compound (21).
화합물 (21) 2 g(2.34 mmol)을 디메틸포름아마이드(DMF) 20 mL 에 용해시킨 후, 2-(2-(2-메톡시에톡시에톡시)에틸-4-메틸설포네이트(2-(2-(2-methoxyethoxy ethoxy) ethyl-4-methylsulfonate) 2.24 g (7.02 mmol) 및 포타슘하이드록사이드(KOH) 0.39 g (7.02 mmol)을 첨가하였다. 반응액의 온도를 100 ℃로 온도를 올리고 4 시간 동안 교반한 후, 상온으로 온도를 내리고, 감압여과 후, DMF를 감압 증류하여 제거한 다음, 디클로로메탄(CH2Cl2)과 물로 반응물을 추출하고, 유기층을 MgSO4로 건조하고, 페트롤륨 에테르/디에틸에테르(petroleum ether/diethylether) 1:1 혼합 용액을 이용하여, 컬럼 정제하여 화합물 (22)를 얻었다. 화합물 (22) 3.35 g (5.84 mmol)을 반응기에 넣고, 질소 치환한 다음, 무수 테트라히드로퓨란(THF) 30 ml를 첨가하여, 용해시켰다. 반응액을 -78 ℃로 냉각하고, n-부틸리튬(n-BuLi) 4.37 ml를 천천히 첨가한 후, 1.5시간 동안 교반하고, 디에틸클로로포스페이트(Diethyl chlorophosphate) 1.26 ml (8.76 mmol)를 첨가한 다음, 동일한 온도에서 3시간 동안 더 교반하면서 반응시켰다. 암모늄클로라이드를 첨가하여, 반응을 종료한 뒤, 에틸아세테이트를 첨가하여, 반응물을 완전히 용해시키고, 물로 추출한 다음, 유기층을 MgSO4로 건조하고, 남은 유기층을 농축하였다. 농축된 유기층을 에틸아세테이트 : 메탄올 = 10:1 (부피비)의 혼합 용액으로 전개하면서, 컬럼 정제하여 화합물 (23)을 얻었다.
2 g (2.34 mmol) of the compound (21) was dissolved in 20 mL of dimethylformamide (DMF), and then 2- (2- (2- methoxyethoxyethoxy) ethyl- 2.24 g (7.02 mmol) of 2- (2-methoxyethoxyethoxy) ethyl-4-methylsulfonate and 0.39 g (7.02 mmol) of potassium hydroxide (KOH) were added. DMF was removed by distillation under reduced pressure, and the reaction product was extracted with dichloromethane (CH 2 Cl 2 ) and water. The organic layer was dried over MgSO 4 , filtered through petroleum ether 3.35 g (5.84 mmol) of the compound (22) was placed in a reactor, which was purged with nitrogen, and then anhydrous The reaction solution was cooled to -78 ° C, and 4.37 ml of n-butyllithium (n-BuLi) was slowly added thereto After the addition, stirring was carried out for 1.5 hours, 1.26 ml (8.76 mmol) of diethyl chlorophosphate was added and the reaction was allowed to proceed for further 3 hours at the same temperature. Ammonium chloride was added to terminate the reaction After the reaction mixture was completely dissolved and extracted with water, the organic layer was dried over MgSO 4 and the remaining organic layer was concentrated. The concentrated organic layer was washed with a mixture of ethyl acetate: methanol = 10: 1 (volume ratio) (23) was obtained.
화합물 (23) 2.91 g(4.62 mmol)을 아세토나이트릴(acetonitrile, MeCN) 16 ml에 용해시킨 후, 0 ℃로 냉각하고, 브로모트리메틸실란(Bromotrimethylsilane) 0.53 ml (3.99 mmol)을 첨가한 다음, 상온에서 17 시간 동안 반응시켜, 화합물 (24)을 합성하였다. 합성된 화합물 (24)에 2M NaOH 수용액(aq)을 천천히 첨가하면서, pH를 8로 맞춘 후, 에탄올로 침전시켜, 포스페이트(phosphate) 타입의 화합물 (25)를 얻었다.2.91 g (4.62 mmol) of the compound (23) was dissolved in 16 ml of acetonitrile (MeCN), followed by cooling to 0 ° C, adding 0.53 ml (3.99 mmol) of bromotrimethylsilane, Followed by reaction at room temperature for 17 hours to synthesize Compound (24). To the synthesized compound (24), 2M NaOH aqueous solution (aq) was slowly added and the pH was adjusted to 8, followed by precipitation with ethanol to obtain a phosphate type compound (25).
[반응식 5][Reaction Scheme 5]
[실시예 6] 그래핀 박리용 분산 안정제의 합성 [Example 6] Synthesis of dispersion stabilizer for graphene peeling
하기 반응식 6에 나타낸 바와 같이, 질소 분위기에서, 1,5-디히드록시나프탈렌(1,5-Dihydroxynaphthalene, 화합물 (26)) 14.55 g(90.82 mmol), p-벤조퀴논(benzoquinone) 980 mg(9.99 mmol), H2SO4 1.10 mL 및 트리에틸렌글리콜모노메틸에테르(triethyleneglycol monomethyl ether, p= 2) 14.5 mL (90.82 mmol)을 혼합하고, 80 ℃에서 24 시간 동안 교반하면서 반응시켰다. 디클로로메텐을 첨가하여, 반응액을 완전히 용해시키고, 물로 추출한 다음, 유기층을 MgSO4로 건조하고, 남은 유기층을 230 ℃, 1 mmHg의 조건에서 분별증류하여, 화합물 (27)을 얻었다. 질소 분위기에서, 합성된 화합물 (27) 3.00 g(9.79 mmol)을 이소프로필알콜(IPA) 42.0 mL에 용해시킨 후, 메탄올(MeOH) 20.0 mL에 NaOH 0.47 g이 용해된 알칼리 금속 용액을 혼합하고, 80 ℃에서 24 시간 동안 교반하면서 반응시키고, IPA를 감압 제거하여, 펜옥사이드(Phenoxide type) 타입의 화합물 (28)을 얻었다.14.55 g (90.82 mmol) of 1,5-dihydroxynaphthalene (compound (26)) and 980 mg (9.99 mmol) of benzoquinone were dissolved in a nitrogen atmosphere, mmol), H 2 SO 4 ( 1.10 mL) and triethyleneglycol monomethyl ether (p = 2) (14.5 mL, 90.82 mmol) were mixed and reacted at 80 ° C for 24 hours with stirring. Dichloromethane was added to dissolve the reaction solution completely and extracted with water. The organic layer was dried over MgSO 4 , and the remaining organic layer was fractionally distilled at 230 ° C and 1 mmHg to obtain Compound (27). 3.00 g (9.79 mmol) of the synthesized Compound (27) was dissolved in 42.0 mL of isopropyl alcohol (IPA) in a nitrogen atmosphere, and then an alkali metal solution in which 0.47 g of NaOH was dissolved was mixed with 20.0 mL of methanol (MeOH) The reaction was carried out with stirring at 80 DEG C for 24 hours, and IPA was removed under reduced pressure to obtain a phenoxide type compound (28).
[반응식 6][Reaction Scheme 6]
[실시예 7] 그래핀 박리용 분산 안정제의 합성 [Example 7] Synthesis of dispersion stabilizer for graphene peeling
하기 반응식 7에 나타낸 바와 같이, 2-요오드티오펜(화합물 (29), 2-iodo thiophene) 3 g (14.28 mmol)과 티오펜-2-보론산(화합물 (30), thiophene- 2-boronic acid) 1.66 g(13.00 mmol), 포타슘카보네이트(K2CO3) 4.93 g (35.7 mmol)을 H2O 1.65 mL 에 용해시킨 후, Pd-PSPEG-adppp complex(P-P chelate palladium complex of N-anchored 2-aza-1,3-bis(diphenylphosphino)propane ligand) 33 mg을 넣고, 50 ℃에서 12 시간 동안 교반한 다음, 잔류 반응물을 감압 여과하고, 헥산으로 컬럼 정제하여, 화합물 (31)을 얻었다. 화합물 (31) 3g (18.04 mmol)을 클로로포름(CHCl3) 200 mL에 용해시킨 후, N-브로모석신이미드(N-bromosuccineimide, NBS) 3.53 g(19.84 mmol)을 천천히 첨가하였다. 반응액을 24 시간 동안 교반하고, 메틸렌클로라이드(CH2Cl2)와 물로 추출한 후, 유기층을 MgSO4로 건조하고, 컬럼으로 분리하여 화합물 (32)를 얻었다. 화합물 (32) 3 g(9.26 mmol), 4-트리에틸렌글리콜 모노에틸에테르 페닐보로닉 엑씨드(4-triethyleneglycol monomethyleter phenylboronic acid, 화합물 (33)) 3.65 g (9.26 mmol), 포타슘카보네이트(K2CO3) 3.20 g(23.15 mmol) 및 Pd(PPh3)4 1.07 g(0.93 mmol)을 넣고, THF 50 mL에 용해시킨 후, 80 ℃에서 12시간 동안 교반하고, 반응액을 상온으로 냉각하고, 메틸렌클로라이드(CH2Cl2)와 물로 추출한 후, 유기층을 MgSO4로 건조하고, 컬럼으로 분리하여 화합물 (34)를 얻었다.
As shown in Scheme 7, 3 g (14.28 mmol) of 2-iodothiophene (compound (29), 2-iodo thiophene) was reacted with thiophene-2-boronic acid (compound (30), thiophene-2-boronic acid ) Was prepared by dissolving 1.66 g (13.00 mmol) of potassium carbonate (K 2 CO 3 ) (4.93 g, 35.7 mmol) in 1.65 mL of H 2 O and then adding Pd-PSPEG-adppp complex (PP chelate palladium complex of N-anchored 2- aza-1,3-bis (diphenylphosphino) propane ligand) was added and stirred at 50 ° C for 12 hours. The residual reaction product was filtered under reduced pressure and column-purified with hexane to obtain Compound (31). 3g (18.04 mmol) of the compound (31) was dissolved in 200 mL of chloroform (CHCl 3 ), and then 3.53 g (19.84 mmol) of N-bromosuccineimide (NBS) was added slowly. The reaction solution was stirred for 24 hours, and extracted with methylene chloride (CH 2 Cl 2 ) and water. The organic layer was dried over MgSO 4 and separated into a column to obtain a compound (32). 3.65 g (9.26 mmol) of 4-triethyleneglycol monomethylether phenylboronic acid (compound 33), 3 g (9.26 mmol) of potassium carbonate (K 2 CO 3) 3.20 g (23.15 mmol ) and placed Pd (PPh 3) 4 1.07 g (0.93 mmol), and was dissolved in THF 50 mL, was stirred at 80 ℃ for 12 hours, the reaction solution was cooled to room temperature, After extraction with methylene chloride (CH 2 Cl 2 ) and water, the organic layer was dried over MgSO 4 and separated into a column to obtain a compound (34).
화합물 (34) 5.07 g(10.5 mmol)을 반응기에 넣고, 질소 치환한 다음, 무수 테트라히드로퓨란(THF) 100 ml를 첨가하여 용해시켰다. 반응액을 -78 ℃로 냉각하고, n-부틸리튬(n-BuLi) 7.87 ml를 천천히 첨가한 후, 1.5시간 동안 교반하고, 디에틸클로로포스페이트(Diethyl chlorophosphate) 2.27 ml (15.75 mmol)를 첨가한 다음, 동일 온도에서 3시간 동안 더 교반하면서 반응시켰다. 암모늄클로라이드를 첨가하여, 반응을 종료한 뒤, 에틸아세테이트를 첨가하여, 반응물을 완전히 용해시키고, 물로 추출한 다음, 유기층을 MgSO4로 건조하고, 남은 유기층을 농축하였다. 농축된 유기층을 에틸아세테이트 : 메탄올 = 10:1 (부피비)의 혼합 용액으로 전개하면서, 컬럼 정제하여 화합물 (35)를 얻었다. 얻어진 화합물 (35) 2.50 g(4.62 mmol)을 아세토나이트릴(acetonitrile, MeCN) 16 ml에 용해시킨 후, 0 ℃로 냉각하고, 브로모트리메틸실란(Bromotrimethylsilane) 0.53 ml(3.99 mmol)을 첨가한 다음, 상온에서 17 시간 동안 반응시켜, 화합물 (36)을 합성하였다. 합성된 화합물 (36)에 2M NaOH 수용액(aq)을 천천히 첨가하면서, pH를 8로 맞춘 후, 에탄올로 침전시켜, 포스페이트(phosphate) 타입의 화합물 (37)을 얻었다.5.07 g (10.5 mmol) of the compound (34) was placed in a reactor, purged with nitrogen, and dissolved by adding 100 ml of anhydrous tetrahydrofuran (THF). The reaction solution was cooled to -78 ° C, 7.87 ml of n-butyllithium (n-BuLi) was slowly added, stirred for 1.5 hours, and 2.27 ml (15.75 mmol) of diethyl chlorophosphate was added Then, the reaction was carried out at the same temperature for 3 hours with further stirring. After completion of the reaction by adding ammonium chloride, ethyl acetate was added to completely dissolve the reaction product, and the reaction solution was extracted with water. The organic layer was dried over MgSO 4 and the remaining organic layer was concentrated. The concentrated organic layer was subjected to column purification while developing with a mixed solution of ethyl acetate: methanol = 10: 1 (volume ratio) to obtain a compound (35). 2.50 g (4.62 mmol) of the resulting compound (35) was dissolved in 16 ml of acetonitrile (MeCN), cooled to 0 ° C, 0.53 ml (3.99 mmol) of bromotrimethylsilane was added , And the mixture was reacted at room temperature for 17 hours to synthesize Compound (36). To the synthesized compound (36), 2M NaOH aqueous solution (aq) was slowly added and the pH was adjusted to 8, followed by precipitation with ethanol to obtain a phosphate type compound (37).
[반응식 7][Reaction Scheme 7]
[실시예 8] 그래핀-그래핀 박리용 분산 안정제 복합체의 제조 [Example 8] Production of dispersion stabilizer composite for graphene-graphene peeling
물 90 mL에 그래파이트 1 g을 넣은 후, 실시예 1에서 합성된 그래핀 박리용 분산 안정제(화합물 (3)) 5 g을 상온에서 물 10 mL에 완전히 용해시킨 용액을 첨가하였다. 그래파이트 및 그래핀 박리용 분산 안정제의 혼합 용액을 초음파 분쇄기로 6 시간 이상 분쇄하여, 그래핀-그래핀 박리용 분산 안정제 복합체를 제조하였다. 제조된 그래핀-그래핀 박리용 분산 안정제 복합체의 시간에 따른 분산 특성 및 화합물 (3) 대신 NaOH를 첨가한 경우의 분산 특성을 하기 표 1에 나타내었다. 하기 표 1에서, ○: 분산이 잘 됨, △: 약간 분산, X: 침전을 나타낸다.After adding 1 g of graphite to 90 mL of water, a solution in which 5 g of the dispersion stabilizer (compound (3)) for graphene peeling synthesized in Example 1 was completely dissolved in 10 mL of water at room temperature was added. A mixed solution of graphite and a dispersion stabilizer for graphen peeling was pulverized for 6 hours or more by an ultrasonic pulverizer to prepare a dispersion stabilizer composite for graphene-graphene peeling. The dispersion characteristics of the prepared dispersion stabilizer composite for graphene-graphen peeling and the dispersion characteristics when NaOH was added instead of the compound (3) are shown in Table 1 below. In Table 1, & cir &: indicates good dispersion, B: slightly dispersed, and X indicates precipitation.
또한, 상기 그래핀-그래핀 박리용 분산 안정제(화합물 (3)) 복합체 및 대조군으로 NaOH를 그래핀 박리용 분산 안정제로 사용하여 제조한 그래핀-그래핀 박리용 분산 안정제(NaOH) 복합체의 장기 안정성을 보여주는 사진을 도 2에 나타내었다. 도 2에 도시된 바와 같이, 화합물 3 및 NaOH 염을 이용하여 그래핀-그래핀 박리용 분산 안정제 복합체를 제조하면, 초기에는 모두 양호한 분산성을 보이지만(도 3의 A), 시간의 경과에 따라, 화합물 3을 이용한 그래핀-그래핀 분산 안정제 복합체는 우수한 분산 특성을 유지하는 반면, 그래핀-그래핀 박리용 분산 안정제(NaOH) 복합체는 분산 상태를 유지하지 못하고, 침천되었다(도 3의 B 및 C).
The dispersion stabilizer (compound (3)) for separating graphene-graphene and the dispersion stabilizer (NaOH) composite for separating graphene-graphene prepared by using NaOH as a control stabilizer A photograph showing the stability is shown in Fig. As shown in FIG. 2, when the dispersion stabilizer composite for graphene-graphene separation is prepared by using the compound 3 and the NaOH salt, all of the dispersions exhibit good dispersibility at the beginning (FIG. 3 A) , The graphene-graphene dispersion stabilizer composite using Compound 3 retained excellent dispersion characteristics, while the dispersion stabilizer (NaOH) composite for graphene-graphene peeling could not be maintained in the dispersed state (Fig. 3B And C).
[실시예 9] 분산 안정제가 제거된 그래핀의 제조 [Example 9] Production of graphene from which a dispersion stabilizer was removed
실시예 8에서 얻은 그래핀-그래핀 박리용 분산 안정제 복합체 잉크를 감압하여 필터링한 후, 물로 수회 세척하여, 그래핀-그래핀 박리용 분산 안정제 복합체로부터 그래핀 박리용 분산 안정제를 제거함으로써, 그래핀을 제조하였다. 0 내지 200 ℃의 온도에서, 남은 파우더(분산 안정제가 제거된 그래핀)를 물, 에탄올, 아이소프로필알콜, 디메틸설폭사이드, 디클로로메탄, 이황화탄소, 아세톤, 클로로포름, 사염화탄소, 1,4-디옥산, 메틸아세테이트, 피리딘, m-크레졸, 페놀, 디메틸포름아미드, 디메틸아세트아미드, 황산, N-메틸-2-피롤리돈 및 피리딘으로 이루어진 군에서 선택된 적어도 1종의 용매에 용해시켜, 그래핀 용액을 제조하였다.
The dispersion stabilizing agent composite ink for peeling the graphene-graphene dispersion obtained in Example 8 was filtered under reduced pressure, and then washed with water several times to remove the dispersion stabilizing agent for graphene peeling from the dispersion stabilizing agent composite for graphene-grape separation, Pin. The remaining powder (graphene from which the dispersion stabilizer is removed) is dissolved in water, ethanol, isopropyl alcohol, dimethyl sulfoxide, dichloromethane, carbon disulfide, acetone, chloroform, carbon tetrachloride, 1,4-dioxane Is dissolved in at least one solvent selected from the group consisting of methyl acetate, pyridine, m-cresol, phenol, dimethyl formamide, dimethylacetamide, sulfuric acid, N-methyl-2-pyrrolidone and pyridine, .
그래파이트, 그래핀 박리용 분산 안정제로서 NaOH를 사용하여 실시예 8 및 9와 동일한 방법으로 제조한 그래핀, 그래핀 박리용 분산 안정제로서 화합물 (3)의 화합물을 사용하여 실시예 8 및 9에 따라 제조한 그래핀의 전자주사현미경 사진(SEM: scanning electron microscope, Hitachi사 S-4800)을 각각 도 3의 A, B 및 C에 나타내었다. 도 3에 도시된 바와 같이, 분산 안정제로서 NaOH를 사용하면(도 3의 B), 그래파이트의 층간 간격을 약간 벌리지만, 분산 효과는 크지 않은 반면, 분산 안정제로서 화합물 3을 사용하면(도 3의 C), 그래파이트의 층과 층사이로 분산 안정제가 효과적으로 침투하여, 초음파 분쇄에 의해 그래파이트의 층간 사이를 효과적으로 벌리면서 그래핀이 제조된다.Graphene produced by the same method as in Examples 8 and 9 using NaOH as a dispersion stabilizer for graphite and graphening, and a compound of Compound (3) as a dispersion stabilizer for graphene peeling, A scanning electron microscope (SEM: scanning electron microscope, Hitachi S-4800) of the produced graphene is shown in Fig. 3, A, B and C, respectively. As shown in Fig. 3, when NaOH is used as the dispersion stabilizer (B in Fig. 3), the interlayer spacing of the graphite is slightly increased but the dispersing effect is not large. On the other hand, when the compound 3 is used as the dispersion stabilizer C), the dispersion stabilizer effectively penetrates between the layers of the graphite and the layers, and graphenes are produced while effectively spreading the space between the layers of the graphite by the ultrasonic pulverization.
Claims (10)
[화학식 1]
상기 화학식 1에서, Ar은 탄소수 4 내지 100의 방향족기이고, M은 알칼리 금속이고, X는 알칼리 금속 M과 이온 결합할 수 있는 옥사이드기(-O-), 카르복실레이트기(-COO-), 설포네이트기(-SO3-), 설포닐기(-SO2-) 또는 포스파이트기(-PO3-)이고, Y는 -CH2- 또는 -CF2- 이고, n은 0 내지 10의 정수이고, m은 1 내지 3의 정수이고, Z는 존재하지 않거나, -CH2-, -NH-, -O-, -S-, -SO2-, -CO- 또는 -CF2-이고, E는 -H, -CH3, -SH, -OH, -NH2 또는 -CH2NH2이고, p는 1 내지 100의 정수이며, l은 1 또는 2이다. A dispersion stabilizer for graphene peeling having a structure represented by the following formula (1).
[Chemical Formula 1]
Wherein Ar is an aromatic group having 4 to 100 carbon atoms, M is an alkali metal, X is an oxide group (-O-), a carboxylate group (-COO-) capable of ionic bonding with an alkali metal M, , A sulfonate group (-SO 3 -), a sulfonyl group (-SO 2 -) or a phosphite group (-PO 3 -), Y is -CH 2 - or -CF 2 - M is an integer from 1 to 3 and Z is absent or is -CH 2 -, -NH-, -O-, -S-, -SO 2 -, -CO- or -CF 2 - E is -H, -CH 3, -SH, -OH , -NH 2 or -CH 2 NH 2, p is an integer from 1 to 100, l is 1 or 2.
[화합물 1a]
[화합물 1b]
[화합물 1c]
[화합물 1d]
[화합물 1e]
[화합물 1f]
[화합물 1g]
[화합물 1h]
[화합물 1i]
[화합물 1j]
[화합물 1k]
[화합물 1l]
[화합물 1m]
[화합물 1n]
[화합물 1o]
[화합물 1p]
[화합물 1q]
[Compound 1a]
[Compound 1b]
[Compound 1c]
[Compound 1d]
[Compound 1e]
[Compound 1f]
[Compound 1g]
[Compound 1h]
[Compound 1i]
[Compound 1j]
[Compound 1k]
[Compound l]
[Compound 1m]
[Compound 1n]
[Compound 1o]
[Compound 1p]
[Compound 1q]
[화학식 1]
상기 화학식 1에서, Ar은 탄소수 4 내지 100의 방향족기이고, M은 알칼리 금속이고, X는 알칼리 금속 M과 이온 결합할 수 있는 옥사이드기(-O-), 카르복실레이트기(-COO-), 설포네이트기(-SO3-), 설포닐기(-SO2-) 또는 포스파이트기(-PO3-)이고, Y는 -CH2- 또는 -CF2- 이고, n은 0 내지 10의 정수이고, m은 1 내지 3의 정수이고, Z는 존재하지 않거나, -CH2-, -NH-, -O-, -S-, -SO2-, -CO- 또는 -CF2-이고, E는 -H, -CH3, -SH, -OH, -NH2 또는 -CH2NH2이고, p는 1 내지 100의 정수이며, l은 1 또는 2이다. A graphene-alkali metal salt complex in which a graphene dispersion stabilizing agent represented by the following general formula (1) is inserted between a graphene layer and a layer.
[Chemical Formula 1]
Wherein Ar is an aromatic group having 4 to 100 carbon atoms, M is an alkali metal, X is an oxide group (-O-), a carboxylate group (-COO-) capable of ionic bonding with an alkali metal M, , A sulfonate group (-SO 3 -), a sulfonyl group (-SO 2 -) or a phosphite group (-PO 3 -), Y is -CH 2 - or -CF 2 - M is an integer from 1 to 3 and Z is absent or is -CH 2 -, -NH-, -O-, -S-, -SO 2 -, -CO- or -CF 2 - E is -H, -CH 3, -SH, -OH , -NH 2 or -CH 2 NH 2, p is an integer from 1 to 100, l is 1 or 2.
상기 그래핀 박리용 분산 안정제가 삽입된 그래파이트를 분산시켜, 그래핀의 층과층 사이에 그래핀 박리용 분산 안정제가 삽입된 그래핀-알칼리 금속염 복합체를 제조하는 단계; 및
용매로 상기 그래핀-알칼리 금속염 복합체를 세척하여, 그래핀-알칼리 금속염 복합체로부터 그래핀 박리용 분산 안정제를 제거하는 단계를 포함하는 그래핀의 제조방법.
[화학식 1]
상기 화학식 1에서, Ar은 탄소수 4 내지 100의 방향족기이고, M은 알칼리 금속이고, X는 알칼리 금속 M과 이온 결합할 수 있는 옥사이드기(-O-), 카르복실레이트기(-COO-), 설포네이트기(-SO3-), 설포닐기(-SO2-) 또는 포스파이트기(-PO3-)이고, Y는 -CH2- 또는 -CF2- 이고, n은 0 내지 10의 정수이고, m은 1 내지 3의 정수이고, Z는 존재하지 않거나, -CH2-, -NH-, -O-, -S-, -SO2-, -CO- 또는 -CF2-이고, E는 -H, -CH3, -SH, -OH, -NH2 또는 -CH2NH2이고, p는 1 내지 100의 정수이며, l은 1 또는 2이다.Increasing the interlayer spacing of graphite by mixing a dispersion stabilizer for graphening separation represented by the following formula (1) and graphite in the presence of a solvent to insert a dispersion stabilizer for graphen peeling between the graphite layer and the layer;
Preparing a graphene-alkali metal salt complex in which a dispersion stabilizer for graphening separation is dispersed to prepare a graphene layer and a layer in which a dispersion stabilizer for graphening separation is inserted; And
And washing the graphene-alkali metal salt complex with a solvent to remove a graphene-alkali metal salt complex and a dispersion stabilizer for graphene peeling.
[Chemical Formula 1]
Wherein Ar is an aromatic group having 4 to 100 carbon atoms, M is an alkali metal, X is an oxide group (-O-), a carboxylate group (-COO-) capable of ionic bonding with an alkali metal M, , A sulfonate group (-SO 3 -), a sulfonyl group (-SO 2 -) or a phosphite group (-PO 3 -), Y is -CH 2 - or -CF 2 - M is an integer from 1 to 3 and Z is absent or is -CH 2 -, -NH-, -O-, -S-, -SO 2 -, -CO- or -CF 2 - E is -H, -CH 3, -SH, -OH , -NH 2 or -CH 2 NH 2, p is an integer from 1 to 100, l is 1 or 2.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020130065707 | 2013-06-10 | ||
| KR20130065707 | 2013-06-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20140144148A true KR20140144148A (en) | 2014-12-18 |
| KR102253512B1 KR102253512B1 (en) | 2021-05-18 |
Family
ID=52022468
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020140069589A KR102253512B1 (en) | 2013-06-10 | 2014-06-09 | Dispersion stabilizer for graphene exfoliation, graphene-alkali metal salt complex including the same, and method for producing graphene using the same |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR102253512B1 (en) |
| WO (1) | WO2014200232A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170126292A (en) * | 2016-05-09 | 2017-11-17 | 울산과학기술원 | Method for manufacturing graphene, dispersed composite of graphene and method for manufacturing dispersed composite of graphene |
| KR20180068717A (en) * | 2016-12-14 | 2018-06-22 | 주식회사 엘지화학 | Method for preparation of functionalized graphene |
| KR20200056406A (en) * | 2017-09-14 | 2020-05-22 | 그래프마테크 에이비 | Hybrid ionic graphene nanocomposite with layered structure |
| US10835886B2 (en) | 2014-12-12 | 2020-11-17 | Lg Chem, Ltd. | Block copolymer, and method for preparing graphene using the same |
| KR20230090618A (en) * | 2021-12-15 | 2023-06-22 | (주)플로우테크 | Method for massively manufacturing the graphene of the high quality |
| WO2023226000A1 (en) * | 2022-05-27 | 2023-11-30 | 宁德时代新能源科技股份有限公司 | Organic compound and use thereof, passivation film, solar cell and electronic device |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114744195B (en) * | 2022-03-18 | 2023-12-12 | 西安近代化学研究所 | Graphene-crown ether-metal ternary composite material, preparation method and application |
| CN115124562B (en) * | 2022-07-05 | 2024-02-20 | 辽宁大学 | Naphthyl high-reactivity graphene dispersing agent and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011162727A1 (en) * | 2010-06-25 | 2011-12-29 | National University Of Singapore | Methods of forming graphene by graphite exfoliation |
| KR20120095907A (en) * | 2009-11-12 | 2012-08-29 | 바이엘 테크놀로지 서비시즈 게엠베하 | Method for producing graphene solutions, graphene alkali metal salts, and graphene composite materials |
-
2014
- 2014-06-09 KR KR1020140069589A patent/KR102253512B1/en active IP Right Grant
- 2014-06-10 WO PCT/KR2014/005057 patent/WO2014200232A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120095907A (en) * | 2009-11-12 | 2012-08-29 | 바이엘 테크놀로지 서비시즈 게엠베하 | Method for producing graphene solutions, graphene alkali metal salts, and graphene composite materials |
| WO2011162727A1 (en) * | 2010-06-25 | 2011-12-29 | National University Of Singapore | Methods of forming graphene by graphite exfoliation |
Non-Patent Citations (3)
| Title |
|---|
| Chem. Soc. Rev., Vol. 41, pp. 666-686, 2012 * |
| J. Mater. Chem. C, Vol. 1, pp.1870-1875, 2013 * |
| J. Mater. Chem., Vol. 21, pp. 3462-3466, 2011 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10835886B2 (en) | 2014-12-12 | 2020-11-17 | Lg Chem, Ltd. | Block copolymer, and method for preparing graphene using the same |
| US11192085B2 (en) | 2014-12-12 | 2021-12-07 | Lg Chem, Ltd. | Block copolymer, and method for preparing graphene using same |
| KR20170126292A (en) * | 2016-05-09 | 2017-11-17 | 울산과학기술원 | Method for manufacturing graphene, dispersed composite of graphene and method for manufacturing dispersed composite of graphene |
| KR20180068717A (en) * | 2016-12-14 | 2018-06-22 | 주식회사 엘지화학 | Method for preparation of functionalized graphene |
| KR20200056406A (en) * | 2017-09-14 | 2020-05-22 | 그래프마테크 에이비 | Hybrid ionic graphene nanocomposite with layered structure |
| JP2020534193A (en) * | 2017-09-14 | 2020-11-26 | グラフマテック・アクチボラグ | Hybrid ionic graphene nanocomposite with layered structure |
| KR20230090618A (en) * | 2021-12-15 | 2023-06-22 | (주)플로우테크 | Method for massively manufacturing the graphene of the high quality |
| WO2023226000A1 (en) * | 2022-05-27 | 2023-11-30 | 宁德时代新能源科技股份有限公司 | Organic compound and use thereof, passivation film, solar cell and electronic device |
Also Published As
| Publication number | Publication date |
|---|---|
| KR102253512B1 (en) | 2021-05-18 |
| WO2014200232A1 (en) | 2014-12-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102253512B1 (en) | Dispersion stabilizer for graphene exfoliation, graphene-alkali metal salt complex including the same, and method for producing graphene using the same | |
| EP2903995B1 (en) | A process for the preparation of acylphosphanes | |
| CN108586318B (en) | Solution-processable thermally-activated delayed fluorescent material and preparation method thereof | |
| CN101643381A (en) | Diarylfluorene intermediate preparation method | |
| CN111233947A (en) | Structure of furanose cyclic phosphate ester flame retardant and preparation method thereof | |
| KR101871215B1 (en) | Method for synthesizing 2,6-bis[3'-(n-carbazolyl)phenyl]pyridine compound | |
| JP5584600B2 (en) | Lithium ionic liquid crystal compound, production method thereof and liquid crystal material | |
| JP2007153868A (en) | Ionic compound | |
| US8026394B2 (en) | Lithium salt and method for producing thereof | |
| CN1528738A (en) | Method for preparing 2-para octylphenyl ehtyl-2-amino propanediol | |
| CN101274942A (en) | Preparation of aryl phosphate | |
| US6657072B2 (en) | Method of preparing lithium complex salts for use in electrochemical cells | |
| JP5288779B2 (en) | 2,3-dicyanonaphthalene derivative | |
| CN104212432A (en) | Negative-positive double-ion surfactant and preparation method thereof | |
| US20110034717A1 (en) | Method for synthesizing 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and derivatives thereof | |
| Bauer et al. | Sugar-based monodentate phosphoramidite ligands for Cu-catalyzed enantioselective conjugate addition to enones | |
| JP6132656B2 (en) | Method for producing picene and derivatives thereof | |
| US10835895B2 (en) | Compound and synthesis method therefor | |
| JP5207516B2 (en) | Method for producing 2,3-dicyanonaphthalene derivative | |
| CN109232515B (en) | Crown ether compound and its preparing method | |
| FR2980478A1 (en) | LUMINESCENT PROBES FOR BIOLOGICAL MARKING AND IMAGING, AND PROCESS FOR PREPARING SAME. | |
| CN105085569B (en) | A kind of preparation method of 1,2- dioxanes derivative | |
| JP5054932B2 (en) | Process for producing ionic compounds | |
| CN108047087A (en) | 3 '-(4- bromonaphthalene -1- bases) [1,1 '-xenyl] -4- nitriles and its synthetic method | |
| JP3949481B2 (en) | Method for producing sulfonic acid amine salt |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant |