CN104080758A - 石墨烯纳米带前体和适于制备其的单体 - Google Patents
石墨烯纳米带前体和适于制备其的单体 Download PDFInfo
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- CN104080758A CN104080758A CN201280064363.0A CN201280064363A CN104080758A CN 104080758 A CN104080758 A CN 104080758A CN 201280064363 A CN201280064363 A CN 201280064363A CN 104080758 A CN104080758 A CN 104080758A
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- Prior art keywords
- halogen
- alkyl
- monomer
- aryl
- graphene nanobelt
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 50
- 239000002243 precursor Substances 0.000 title claims abstract description 32
- 239000000178 monomer Substances 0.000 title claims description 37
- 239000002074 nanoribbon Substances 0.000 title abstract 2
- 238000002360 preparation method Methods 0.000 title description 4
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 19
- 150000002367 halogens Chemical class 0.000 claims abstract description 18
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 8
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 8
- 125000002877 alkyl aryl group Chemical group 0.000 claims abstract description 7
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 7
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 7
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 239000002127 nanobelt Substances 0.000 claims description 37
- -1 aryl rings pentadienones Chemical class 0.000 claims description 33
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical compound C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-UHFFFAOYSA-N 0.000 claims description 7
- 150000001721 carbon Chemical group 0.000 claims description 7
- 125000002252 acyl group Chemical group 0.000 claims description 6
- 125000004171 alkoxy aryl group Chemical group 0.000 claims description 6
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims description 4
- 238000006000 Knoevenagel condensation reaction Methods 0.000 claims description 3
- 238000005698 Diels-Alder reaction Methods 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- 125000005843 halogen group Chemical group 0.000 abstract 1
- 125000003107 substituted aryl group Chemical group 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 39
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 26
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- 239000002585 base Substances 0.000 description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 239000000126 substance Substances 0.000 description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 14
- 238000005481 NMR spectroscopy Methods 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000012043 crude product Substances 0.000 description 8
- 238000006356 dehydrogenation reaction Methods 0.000 description 8
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 6
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 238000001237 Raman spectrum Methods 0.000 description 5
- 239000012230 colorless oil Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 229960001866 silicon dioxide Drugs 0.000 description 5
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 238000001254 matrix assisted laser desorption--ionisation time-of-flight mass spectrum Methods 0.000 description 4
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- MEENTMAAPFUEFN-UHFFFAOYSA-N 1-dodecyl-4-phenylbenzene Chemical compound C1=CC(CCCCCCCCCCCC)=CC=C1C1=CC=CC=C1 MEENTMAAPFUEFN-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 125000001475 halogen functional group Chemical group 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000007243 oxidative cyclization reaction Methods 0.000 description 3
- JUKHVNMXKSHNQY-UHFFFAOYSA-N penta-3,4-dien-2-one Chemical compound CC(=O)C=C=C JUKHVNMXKSHNQY-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- 125000000739 C2-C30 alkenyl group Chemical group 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000006117 Diels-Alder cycloaddition reaction Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- FQQOMPOPYZIROF-UHFFFAOYSA-N cyclopenta-2,4-dien-1-one Chemical compound O=C1C=CC=C1 FQQOMPOPYZIROF-UHFFFAOYSA-N 0.000 description 2
- 229940117389 dichlorobenzene Drugs 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000000232 haloalkynyl group Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- ILPBINAXDRFYPL-UHFFFAOYSA-N 2-octene Chemical compound CCCCCC=CC ILPBINAXDRFYPL-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- YXYKIXHQDOQFFJ-UHFFFAOYSA-N C(CCCCCCCCCCC)ON(C1=CC=CC=C1)OCCCCCCCCCCCCCC Chemical compound C(CCCCCCCCCCC)ON(C1=CC=CC=C1)OCCCCCCCCCCCCCC YXYKIXHQDOQFFJ-UHFFFAOYSA-N 0.000 description 1
- 244000178870 Lavandula angustifolia Species 0.000 description 1
- 235000010663 Lavandula angustifolia Nutrition 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- YSNYZCPALUKLFL-UHFFFAOYSA-N [O].CCCCCCCCCCC Chemical compound [O].CCCCCCCCCCC YSNYZCPALUKLFL-UHFFFAOYSA-N 0.000 description 1
- MEWQFMZMPMAMTG-UHFFFAOYSA-N [O].CCCCCCCCCCCCCCC Chemical compound [O].CCCCCCCCCCCCCCC MEWQFMZMPMAMTG-UHFFFAOYSA-N 0.000 description 1
- PNNXBWWSFIVKQW-UHFFFAOYSA-N [O].CCCCCCCCCCCCCCCC Chemical compound [O].CCCCCCCCCCCCCCCC PNNXBWWSFIVKQW-UHFFFAOYSA-N 0.000 description 1
- FVXZXFWDTIMEMA-UHFFFAOYSA-N [O].CCCCCCCCCCCCCCCCC Chemical compound [O].CCCCCCCCCCCCCCCCC FVXZXFWDTIMEMA-UHFFFAOYSA-N 0.000 description 1
- CIGIRZIOSVQVKQ-UHFFFAOYSA-N [O].CCCCCCCCCCCCCCCCCC Chemical compound [O].CCCCCCCCCCCCCCCCCC CIGIRZIOSVQVKQ-UHFFFAOYSA-N 0.000 description 1
- PHCRNOUPAWMIFE-UHFFFAOYSA-N [O].O(CCCCC)CCCCCCC Chemical group [O].O(CCCCC)CCCCCCC PHCRNOUPAWMIFE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005418 aryl aryl group Chemical class 0.000 description 1
- 238000005801 aryl-aryl coupling reaction Methods 0.000 description 1
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005100 correlation spectroscopy Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000000755 henicosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000001102 lavandula vera Substances 0.000 description 1
- 235000018219 lavender Nutrition 0.000 description 1
- 125000002463 lignoceryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 238000003808 methanol extraction Methods 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002460 pentacosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
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Abstract
提供了包含通式(I)重复单元的石墨烯纳米带前体。其中R1,R2各自为H;卤素;-OH;-NH2;-CN;-NO2;或烃基,其具有1-40个碳原子且可为直链或支化的、饱和或不饱和的且被卤素(F、Cl、Br、I)、-OH、-NH2、-CN和/或-NO2单取代或多取代,其中一个或多个CH2基团也可被-O-、-S-、-C(O)O-、-O-C(O)-、-C(O)-、-NH-或-NR-替代,其中R为任选取代的C1-C40烃基;或任选取代的芳基、烷芳基或烷氧基芳基。(I)
Description
本发明涉及石墨烯纳米带前体、可通过氧化环化脱氢(分子内Scholl反应)由其获得的石墨烯纳米带、制备所述石墨烯纳米带前体的方法、适于制备所述石墨烯纳米带前体的单体和制备所述单体的方法。
石墨烯纳米带(GNR)为源自石墨烯结构的确定部分。其由以蜂窝形式排列的sp2杂化碳原子单层带组成且具有高长度:宽度的边长比,从而使得其为准一维碳的多晶型物。由于所述带的宽度与其长度相比较小,因此在石墨烯纳米带中,边缘结构对石墨烯的电子性能的影响不可忽视。借助边缘结构,可以以受控方式影响石墨烯纳米带的电子性能。
石墨烯本身已用于有机电子器件,例如在场效应晶体管中作为透明电极材料或作为活性材料。然而,石墨烯不具有天然带隙,从而无法在电子器件电路中用作半导体。然而,理论模型已显示,通过控制宽度和边缘结构可在石墨烯纳米带中获得合成带隙。为了获得该类半导电石墨烯纳米带,需要具有“扶手椅”边缘结构且宽度<10nm的结构确定的无缺陷石墨烯带。这些迄今为止尚不能获得。
无法通过诸如如下方法的“自上而下”法来控制所得石墨烯纳米带的尺寸和边缘结构:石墨烯氧化物的还原(S.Stankovich,D.Dikin,R.Piner,K.Kohlhaas,A.Kleinhammes,Y.Jia,Y.Wu,S.Nguyen,R.Ruoff,Carbon2007,45,1558)、光刻法(M.Han,B.,Y.Zhang,P.Kim,Phys.Rev.Lett,2007,98,206805;Z.Chen,Y.Lin,M.Rooks,P.Avouris,Physica E,2007,40,228)、碳纳米管的解压(a)L.Jiao,X.Wang,G.Diankov,H.Wang,H.Dai,Nat.Nanotechnol.2010,5,321;b)D.Kosynkin,A.Higginbotham,A.Sinitskii,J.Lomeda,A.Dimiev,B.Price,J.Tour,Nature2009,458,872)或石墨烯的机械离层(X.Li,X.Wang,L.Zhang,S.Lee,H.Dai,Science2008,219,1229)。相反,有机“自下而上”合成允许在原子水平上控制结构且因此适于制备具有精确限定结构的GNR。
X.Yang,X.Dou,A.Rouhanipour,L.Zhi,H.Rader,K.Müllen,J.Am.Chem.Soc.2008,130,4216公开了根据下文方案1通过合适聚合物前体的环化脱氢而制备石墨烯纳米带。
方案1
所述合成基于在最后反应步骤中通过氧化环化脱氢(分子内Scholl反应)而转化成二维石墨烯结构的经修饰聚合物前体的研发。然而,无法实现完全环化脱氢,因此由于存在缺陷而不能进行电子性能研究。
方案2显示了获得聚合物前体的聚合反应。
方案2
在Suzuki缩聚期间单体的强空间位阻导致聚合物的最大长度为约10nm,这是因为单体3中的碘官能团被邻位的两个苯基显著屏蔽,从而使得偶联反应变得更困难。此外,碳-碘键可容易地热断裂,并导致链终止。同时,在聚合物中存在由于烷基重叠所导致的空间位阻,这在随后的环化脱氢步骤中与这些基团相邻的芳基-芳基键的形成并导致不完全的环化脱氢。已发现的另一缺点是聚合物骨架的聚对亚苯基结构,其仅允许沿聚合物链具有低水平的柔性。这可导致在获得较高分子量之前,分子的聚集和沉淀提高,即使在聚合期间。
此外,在A2+B2型聚合反应的情况下,所述单体必须以精确化学计量量使用,这是因为否则的话仅能获得低聚合度。
本发明的目的是提供一种制备石墨烯纳米带的方法以及合适的石墨烯纳米带前体,其不具有现有技术的缺点。本发明的一个特定目的是提供能形成具有“扶手椅”边缘结构的无缺陷石墨烯纳米带的石墨烯纳米带前体。
所述目的由包含通式(I)的重复单元的石墨烯纳米带前体和可通过氧化环化脱氢由其获得的石墨烯纳米带实现:
其中:
R1,R2各自为H;卤素;-OH;-NH2;-CN;-NO2;烃基,其具有1-40个碳原子且可为直链或支化的、饱和或不饱和的且被卤素(F、Cl、Br、I)、-OH、-NH2、-CN和/或-NO2单取代或多取代,其中一个或多个CH2基团也可被-O-、-S-、-C(O)O-、-O-C(O)-、-C(O)-、-NH-或-NR-替代,其中R为任选取代的C1-C40烃基;或任选取代的芳基、烷芳基或烷氧基芳基。
所述目的是通过一种制备石墨烯纳米带前体的方法以及通式(II)单体单元本身实现,所述方法包括通式(II)的单体单元的Yamamoto偶联反应,
其中:
R1、R2各自为H;卤素;-OH;-NH2;-CN;-NO2;或烃基,其具有1-40个碳原子且可为直链或支化的、饱和或不饱和的且被卤素(F、Cl、Br、I)、-OH、-NH2、-CN和/或-NO2单取代或多取代,其中一个或多个CH2基团也可被-O-、-S-、-C(O)O-、-O-C(O)-、-C(O)-、-NH-或-NR-替代,其中R为任选取代的C1-C40烃基;或任选取代的芳基、烷芳基或烷氧基芳基,且
X为卤素、三氟甲磺酸酯基或重氮基。
一般而言,R1、R2各自为H或可被所述取代基单至五取代的饱和或单至五烯属和/或炔属不饱和烃基。
优选R1,R2为H或可被所述取代基单至五取代的直链或支化饱和烃基。
优选R1,R2各自独立地为氢、C1-C30烷基、C1-C30烷氧基、C1-C30烷硫基、C2-C30链烯基、C2-C30炔基、C1-C30卤代烷基、C2-C30卤代链烯基和卤代炔基,例如C1-C30全氟烷基。
C1-C30烷基可为直链或(可能的话)支化的。
实例为甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、正戊基、2-戊基、3-戊基、2,2-二甲基丙基、1,1,3,3-四甲基戊基、正己基、1-甲基己基、1,1,3,3,5,5-六甲基己基、正庚基、异庚基、1,1,3,3-四甲基丁基、1-甲基庚基、3-甲基庚基、正辛基、1,1,3,3-四甲基丁基和2-乙基己基、正壬基、癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基、十八烷基、二十烷基、二十一烷基、二十二烷基、二十四烷基或二十五烷基。
C1-C30烷氧基为直链或支化的烷氧基,例如甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、仲丁氧基、叔丁氧基、戊氧基、异戊氧基或叔戊氧基、庚氧基、辛氧基、异辛氧基、壬氧基、癸氧基、十一烷氧基、十二烷氧基、十四烷氧基、十五烷氧基、十六烷氧基、十七烷氧基和十八烷氧基。
术语“烷硫基”意指与烷氧基相同,区别之处在于醚桥中的氧原子被硫原子替代。
C2-C30链烯基为直链或支化的,例如乙烯基、烯丙基、甲基烯丙基、异丙烯基、2-丁烯基、3-丁烯基、异丁烯基、正戊-2,4-二烯基、3-甲基-丁-2烯基、正辛-2-烯基、正十二碳-2-烯基、异十二碳烯基、正十二碳-2-烯基或正十八碳-4-烯基。
C2-C30炔基为直链或支化的,例如乙炔基、1-丙炔-3-基、1-丁炔-4-基、1-戊炔-5-基、2-甲基-3-丁炔-2-基、1,4-戊二炔-3-基、1,3-戊二炔-5-基、1-己炔-6-基、顺-3-甲基-2-戊烯-4-炔-1-基、反-3-甲基-2-戊烯-4-炔-1-基、1,3-己二炔-5-基、1-辛炔-8-基、1-壬炔-9-基、1-癸炔-10-基或1-二十四炔-24-基。
C1-C30全氟烷基为支化或未支化的,例如-CF3、-CF2CF3、-CF2CF2CF3、-CF(CF3)2、-(CF2)3CF3或-C(CF3)3。
术语“卤代烷基、卤代链烯基和卤代炔基”意指部分地或完全被卤素取代的烷基、链烯基和炔基。
芳基通常为C6-C30芳基且可任选被取代,例如苯基、4-甲基苯基、4-甲氧基苯基、萘基、联苯基、联三苯基、芘基、芴基、菲基、蒽基、tetracyl、pentacyl和hexacyl。
优选地,X=Cl或Br。更优选地,R1,R2各自为H或C8-C30烷基,尤其为H或C10-C26烷基。
优选地,R2=H。
由本发明的单体单元(II)起始通过Yamamoto偶联反应,可制备通常具有3-100个,优选5-50个重复单元(I)的石墨烯纳米带。此外,Yamamoto聚合反应不像A2+B2型聚合反应那样对化学计量敏感。
在形成石墨烯纳米带前体的聚合步骤期间和在该前体随后环化脱氢以获得石墨烯纳米带期间,石墨烯纳米带前体分子的具有角度的骨架降低了空间位阻。这允许引入空间要求苛刻的烷基,从而额外产生提高的溶解性。在聚合期间,具有相对较高柔性的具有角度的聚合物骨架的较高扭转水平抑制了分子的聚集,因此可获得较高分子量。
用于制备通式(II)单体的合成方案示于方案3中。
方案3
由已包含两个柔性间联苯单元的1,3-二(联苯-3-基)丙-2-酮7起始,与4,4'-二卤代苯甲偶酰的Knoevenagel缩合引入了用于随后Yamamoto聚合的两个卤素官能团,从而获得四芳基环戊二烯酮8。环戊二烯酮8通过与任选官能化的二苯乙炔10的Diels-Alder环加成转化,从而单体6。该反应可在微波反应器中进行。
石墨烯纳米带前体对应于方案4在镍催化剂存在下通过Yamamoto聚合由单体6合成。合适的催化剂体系包含处于作为溶剂的甲苯/DMF混合物中的Ni(COD)2、1,5-环辛二烯和2,2'-联吡啶。所形成的聚合物可通过添加氯苯或溴苯而“封端”,即可将端卤素官能团置换成苯基。
方案4
获得石墨烯纳米带的石墨烯纳米带前体11的环化脱氢可借助分子内Scholl反应使用例如氯化铁(III)作为路易斯酸和氧化剂进行。
一般而言,所得石墨烯纳米带的分子量为2000-100 000,优选为4000-50 000,这些分子量可借助GPC测定。
石墨烯纳米带也可在金属表面上制备。这通过升华将单体沉积至表面上而实现。这产生了双自由基,所述双自由基随温度升高而聚合,从而获得石墨烯纳米带前体。在最后步骤中,对基板进一步的热处理导致环化脱氢,从而获得成品石墨烯纳米带(参见Cai,J.等;Nature466,470-473(2010))。
通过下文实施例详细说明本发明。
实施例
附图显示了:
图1 所合成单体6a-c的叠加MALDI-TOF质谱;
图2 所合成单体6a-c的1H NMR谱的相关芳族区域;
图3 聚合物前体11a-c的MALDI-TOF质谱;
图4 GNR12b的拉曼光谱;
图5 GNR12a,b的IR光谱。
实施例1-3
单体合成
用于制备通式(II)6a-6c单体的合成方案示于方案5中。
方案5
使用四丁基氢氧化铵作为碱由已包含两个柔性间联苯单元的1,3-二(联苯-3-基)丙-2-酮7进行与4,4'-二溴苯甲偶酰9a或4,4'-二氯苯甲偶酰9b的Knoevenagel缩合引入了用于随后Yamamoto聚合的两个卤素官能团。四芳基环戊二烯酮8a和8b无法通过柱色谱法从反应物中移除,然而产物可选择性地从DCM沉淀于甲醇中。因此,获得呈紫色固体形式的8a(产率为77%)和8b(53%)。在最后的反应步骤中,引入增溶基团并通过与官能化二苯乙炔的Diels-Alder环加成使所述环戊二烯酮转化,从而获得目标化合物。由于高空间要求,因此该反应必须在微波反应器中在220℃和300瓦下经24小时反应时间实施。在用硅胶柱色谱法纯化并反复再沉淀之后,借助循环GPC来纯化所有单体。尽管产率相应降低,但该高纯度是在聚合中获得高分子量所必需的。因此,以40%的产率获得呈无色固体形式的不含烷基的单体6a。8b与4,4'-二(十二烷基)二苯乙炔10b的加成获得单体6b,产率为56%;与4,4'-双(2-癸基十四烷基)二苯乙炔10c的反应获得单体6c,产率为41%。这两种烷基化产物均呈无色油状物获得。
实施例
实施例1a 2,5-二([1,1'-联苯]-3-基)-3,4-双(4-溴苯基)环戊-2,4-二烯酮(8a)
在80℃下向2.84g4,4'-二溴苯甲偶酰(7.73mmol)和2.80g1,3-二(联苯-3-基)丙-2-酮(7,7.73mmol)于30ml叔丁醇中的脱气溶液中添加甲醇-四丁基氢氧化铵溶液(1M,2.84ml,2.84mmol)。将所述反应溶液在80℃下搅拌20分钟,然后通过添加水终止。用二氯甲烷萃取3次,用饱和氯化钠溶液洗涤所收集的有机相并经硫酸镁干燥,然后在减压下蒸出溶剂。通过柱色谱法(硅胶,洗脱液:具有20%DCM的己烷)纯化粗产物,获得2.85g呈紫色蜡形式的四芳基环戊二烯酮8a(53%,4.10mmol)。元素分析测量值:C70.5;H3.3%(C41H26Br2O的计算值:C70.9;H3.8%);1H NMR(700MHz,d8-THF)δ=7.51-7.49(m,4H,CH),7.49-7.46(m,4H,CH),7.41(dd,J=8.2,1.1Hz,4H,CH),7.36(t,J=7.8Hz,4H,CH),7.32(t,J=8.0Hz,2H,CH),7.29-7.25(m,2H,CH),7.25-7.22(m,2H,CH),7.01-6.99(m,4H,CH);13C NMR(175MHz,d8-THF)δ=154.28,141.92,141.83,133.58,132.72,132.34,132.30,132.12,129.99,129.89,129.71,129.53,128.26,127.80,127.21,126.74,123.92;MS(FD,8kV):m/z(%):693.8(100)[M+](C41H26Br2O的计算值:694.0);Rf(具有6%乙酸乙酯的己烷)=0.47。
实施例1b 1,2-双(4-溴苯基)-3,6-双(联苯-3-基)-4,5-二苯基苯(6a)
在微波反应器中在300瓦功率和7巴最大压力下将300mg2,5-二([1,1'-联苯]-3-基)-3,4-双(4-溴苯基)环戊-2,4-二烯酮(8a,0.432mmol)和77.0mg4,4'-二溴二苯乙炔(0.432mmol)于3ml二苯基醚中的脱气溶液加热至230℃,保持3×12小时。在冷却至室温后,用己烷稀释反应溶液并通过柱色谱法(二氧化硅,具有6%乙酸乙酯的己烷)纯化。在借助循环GPC纯化并在高真空下干燥之后,获得145mg呈无色晶体形式的单体6a(40%,0.172mmol)。元素分析测量值:C76.7;H3.1%(C54H36Br2的计算值:C76.8;H4.3%);1H NMR(700MHz,d8-THF)δ=7.30-7.25(m,4H,CH),7.23-7.17(m,6H,CH),7.13(d,J=1.5Hz,1H,CH),7.12-7.11(m,1H,CH),7.11-7.09(m,4H,CH),7.09-7.06(m,2H,CH),6.95(s,1H,CH),6.94(br s,2H,CH),6.93(s,1H,CH),6.91(t,J=4.1Hz,2H,CH),6.89(d,J=8.0Hz,2H,CH),6.85(d,J=7.0Hz,4H,CH),6.83(d,J=2.0Hz,2H,CH),6.81(d,J=1.4Hz,1H,CH),6.79(d,J=8.3Hz,2H,CH),6.78(s,1H,CH);13C NMR(125MHz,d2-TCE)δ=141.05,140.74,140.20,140.00,139.44,139.03,138.52,133.03,132.92,131.30,131.15,130.26,129.92,129.85,128.42,127.17,126.87,126.62,126.52,125.20,124.15,120.18,119.51;MS(MALDI-TOF):m/z(%):845.1(100)[M+](C54H36Br2的计算值:844.1);Rf(具有6%乙酸乙酯的己烷)=0.40;m.p.(℃):在>400℃时分解。
实施例2a 2,5-二([1,1'-联苯]-3-基)-3,4-双(4-氯苯基)环戊-2,4-二烯酮(8b)
在80℃下向940mg4,4'-二氯苯甲偶酰(3.37mmol)和1.22g1,3-二(联苯-3-基)丙-2-酮(7,3.37mmol)于20ml叔丁醇中的脱气溶液中添加甲醇-四丁基氢氧化铵溶液(1M,1.7ml,1.7mmol)。将所述反应溶液在80℃下搅拌20分钟,然后通过添加水终止反应。用二氯甲烷将所述混合物萃取3次,用饱和氯化钠溶液洗涤所收集的有机相并经硫酸镁干燥,然后在减压下蒸出溶剂。通过柱色谱法(硅胶,洗脱液:具有20%DCM的己烷)来纯化粗产物,获得1.56g呈淡紫色固体形式的四芳基环戊二烯酮8b(77%,2.58mmol)。元素分析测量值:C81.3;H3.3%(C41H26Cl2O的计算值:C81.3;H4.3%);1HNMR(700MHz,d8-THF)δ=7.52(s,2H,CH),7.50(d,J=7.8Hz,2H,CH),7.42(d,J=7.2Hz,4H,CH),7.36(t,J=7.7Hz,4H,CH),7.32(m,6H,CH),7.27(t,J=7.3Hz,2H,CH),7.23(d,J=7.8Hz,2H,CH),7.06(d,J=8.5Hz,4H,CH);13C NMR(175MHz,d8-THF)δ=199.86,154.28,141.91,141.82,135.61,133.14,132.14,132.10,129.98,129.90,129.70,129.69,129.52,128.27,127.78,127.20,126.73;MS(MALDI-TOF):m/z(%):604.6(100)[M+](C41H26Cl2O的计算值:604.1);Rf(具有10%乙酸乙酯的己烷)=0.47。
实施例2b 1,2-双(4-氯苯基)-3,6-双(联苯-3-基)-4,5-双(4-十二烷基苯基)苯(6b)
在微波反应器中在300瓦功率和7巴最大压力下将1.84g2,5-二([1,1'-联苯]-3-基)-3,4-双(4-氯-苯基)环戊-2,4-二烯酮(8b,3.03mmol)和1.72g4,4'-二(十二烷基)二苯乙炔(3.34mmol)于12ml二苯基醚和5ml碳酸亚丙酯中的脱气溶液加热至230℃,保持2×12小时。在冷却至室温后,用己烷稀释所述反应溶液并通过柱色谱法(二氧化硅,具有6%乙酸乙酯的己烷)纯化。在借助循环GPC纯化并在高真空下干燥后,获得1.85g呈无色油状物的单体6b(56%,1.69mmol)。元素分析测量值:C85.6;H7.9%(C78H84Cl2的计算值:C85.8;H7.8%);1H NMR(700MHz,d8-THF)δ=7.27(dt,J=7.7,4.0Hz,4H,CH),7.22-7.16(m,6H,CH),7.10(d,J=10.0Hz,4H,CH),6.94(t,J=7.7Hz,4H,CH),6.91(s,2Hv),6.88(d,J=8.4Hz,2H,CH),6.87-6.81(m,2H,CH),6.81-6.77(m,2H,CH),6.77-6.70(br m,6H,CH),6.66(d,J=7.5Hz,2H,CH),2.41-2.28(m,4H,α-CH2),1.44-1.34(m,4H,(β-CH2),1.34-1.03(m,36H,-CH2-),0.89(t,J=6.9Hz,6H,-CH3);13C NMR(175MHz,d8-THF)δ=142.44,142.42,142.27,141.88,141.74,140.76,140.74,140.68,140.59,140.56,140.14,140.10,139.09,139.05,134.18,134.14,134.06,134.01,132.56,132.50,132.47,132.30,132.26,131.69,131.41,129.37,128.20,128.07,127.90,127.88,127.84,127.81,127.80,127.74,125.14,125.12,36.36,36.33,33.06,32.37,32.34,30.85,30.81,30.77,30.75,30.61,30.60,30.51,30.00,29.98,25.94,25.82,23.74,14.62;MS(MALDI-TOF):m/z(%):1091.0(100)[M+](C78H84Cl2的计算值:1090.6);Rf(具有6%乙酸乙酯的己烷)=0.65。
实施例3 1,2-双(4-氯苯基)-3,6-双(联苯-3-基)-4,5-双(4-(2-癸基十四烷基)十二烷基苯基)苯(6c)
在微波反应器中在300瓦功率和7巴最大压力下将636mg2,5-二([1,1'-联苯]-3-基)-3,4-双(4-氯苯基)环戊-2,4-二烯酮(8b,1.05mmol)和895mg4,4'-双(2-癸基十四烷基)二苯乙炔(1.05mmol)于10ml二苯基醚中的脱气溶液加热至230℃,保持2×12小时。在冷却至室温后,用己烷稀释所述反应溶液并通过柱色谱法(二氧化硅,具有6%乙酸乙酯的己烷)纯化。在借助循环GPC纯化并在高真空下干燥后,获得613mg呈无色油状物的单体6c(41%,0.429mmol)。元素分析测量值:C86.0;H9.7%(C102H132Cl2的计算值:C85.8;H9.3%);1H NMR(700MHz,d8-THF)δ=7.29-7.25(m,4H,CH),7.20(m,6H,CH),7.14(s,1H,CH),7.11(d,J=10.0Hz,3H,CH),6.95-6.88(m,9H,CH),6.85(d,J=8.4Hz,1H,CH),6.81(d,J=8.0Hz,1H,CH),6.79(d,J=7.8Hz,2H,CH),6.77(d,J=7.7Hz,1H,CH),6.73(d,J=7.8Hz,2H,CH),6.69(t,J=7.6Hz,2H,CH),6.64(d,J=7.9Hz,2H,CH),2.33-2.24(m,4H,α-CH2),1.44-1.37(m,2H,β-CH2),1.35-0.95(brm,80H,-CH2-),0.89(m,12H,-CH3);13C NMR(175MHz,d8-THF)δ=142.43,142.41,142.20,142.18,141.94,141.77,140.69,140.65,140.55,140.52,140.10,140.07,139.61,139.08,134.13,134.04,133.98,132.48,132.31,132.13,131.70,131.37,129.41,128.67,128.53,128.21,128.07,127.87,127.77,125.08,40.92,40.61,33.94,33.86,33.81,33.08,33.06,31.20,31.12,31.10,30.89,30.86,30.82,30.54,30.52,27.49,27.45,25.93,25.82,23.76,23.75,14.63;MS(MALDI-TOF):m/z(%):1427.8(100)[M+](C102H132Cl2的计算值:1428.0);Rf(具有6%乙酸乙酯的己烷)=0.76。
图1显示了所合成的单体6a-c的叠加MALDI-TOF质谱。在全部三种情况下,均可获得呈纯净形式的产物且可确保不再存在会在随后的聚合期间导致链生长终止的副产物。单体的精确结构通过1H NMR谱证实。
图2显示了以d8-THF记录的单体6a-c的1H NMR谱的相关芳族区域(700MHz,RT)。单体6a-c的1H NMR谱仅可困难地解析,这是因为全部34-36个芳族质子均显示出非常类似的化学位移。信号处于6.6-7.3ppm的窄范围内,且一些叠加。借助DOSY(扩散序谱),可测定样品中的分子扩散性质,且COSY实验可测定NMR中共轭质子的信号间的耦合。
实施例4-6
聚合物合成
在证实单体6a-c的结构和纯度之后,根据方案6通过Yamamoto聚合来合成相应的聚合物。
方案6
方案6显示了石墨烯纳米带前体11a-c的合成,这通过在甲苯/DMF中使用Ni(COD)2、1,5-环辛二烯和2,2'-联吡啶催化二卤代单体6a-c的Yamamoto聚合实现。产率为(i)84%、(ii)86%、(iii)67%。由于催化活性镍(0)试剂在Yamamoto缩聚中对水和氧极为敏感,因此所有单体单元6均在将其用于聚合之前在高真空下干燥。在手套箱中在氩气气氛下称取由59.4mgNi(COD)2、23.4mg1,5-环辛二烯和33.7mg2,2'-联吡啶(各自为0.216mmol)组成的催化剂混合物并在微波相容玻璃反应容器中与溶剂一起制备,用具有隔片的气密性铝盖密封并保护以免任何入射光。使用微波反应器实施所述反应获得了明显提高的反应速率和高于溶剂沸点的反应温度的优点。在60℃下将催化剂热活化20分钟后,将0.09mmol单体于1ml无水甲苯中的脱气溶液穿过隔片引入反应容器中,并在300瓦微波功率和80℃下聚合10小时。使用约50mg/ml的单体浓度来促进高分子量的获得。为了将聚合物封端,最后添加溴苯/氯苯于甲苯中的脱气溶液(0.5ml,0.01摩尔浓度),并将混合物再加热至80℃达20分钟。为了纯化产物和移除催化剂残余物,将反应溶液滴加至HCl/甲醇混合物中并搅拌过夜。在离心机中移除所得的沉淀并在甲醇中用THF反复再沉淀,然后将其滤出并在减压下干燥。获得呈无色固体形式的不含烷基的聚合物11a和具有十二烷基链的11b,产率为84-86%。只有通过引入支化的2-癸基十四烷基,才能将熔点降至聚合物11c在室温下以无色油状物存在的程度。在随后环化脱氢以获得相应GNR之前,通过手动制备型GPC分馏来移除低分子量低聚物。这是可能的,因为全部三种聚合物完全可溶于常见的有机溶剂如THF、DCM或甲苯中。
实施例4
所用单体为76.0mg1,2-双(4-溴苯基)-3,6-双(联苯-3-基)-4,5-二苯基苯(6a,0.09mmol)。在反应结束并冷却至室温后,已形成无色沉淀物。在纯化粗产物后,获得43.7mg呈无色固体形式的聚合物11a(84%)。GPC分析:Mn=0.11×104g/mol,Mw=0.15×104g/mol,多分散性D=1.35(UV检测器,PS标样),DSC(℃):无转变。
实施例5
所用单体为98.3mg1,2-双(4-溴苯基)-3,6-双(联苯-3-基)-4,5-双(4-十二烷基苯基)苯(6b,0.09mmol)。在反应结束并冷却至室温后,反应溶液已变成深褐色,并在烧瓶壁上存在黑色沉淀物。在纯化粗产物后,获得79.0mg呈无色固体形式的聚合物11b(86%)。GPC分析:Mn=0.93×104g/mol,Mw=1.25×104g/mol,多分散性D=1.34(UV检测器,PS标样),DSC(℃):无转变。
实施例6
所用单体为128.6mg1,2-双(4-溴苯基)-3,6-双(联苯-3-基)-4,5-双(4-(2-癸基十四烷基)十二烷基苯基)苯(6c,0.09mmol)。在反应结束并冷却至室温后,反应溶液已变成深褐色,并在烧瓶壁上存在黑色沉淀物。在纯化粗产物后,获得81.9mg呈无色油状物形式的聚合物11c(67%)。GPC分析:Mn=0.35×104g/mol,Mw=0.48×104g/mol,多分散性D=1.37(UV检测器,PS标样),DSC(℃):无转变。
通过MALDI-TOF MS和GPC分析来测定在聚合物11a-c中获得的分子量。由于无合适标样用于GPC分析,因此使用聚苯乙烯标样,这些因为该聚合物具有呈角度的骨架。MALDI-TOF MS存在由于样品的多分散性而不可检测高分子量物质的限制。因此,此处获得的数据仅允许得出样品中的最低分子量。对聚合物前体11a-c记录的MALDI-TOF质谱再现于图3中。
借助MALDI-TOF MS的聚合物11a-c分析显示,在所有情况下均观察到极规整的信号图案,因此在信号间隔与相应重复单元的计算分子量之间存在高水平的对应性。在11a的情况下,强信号归因于完全脱溴的产物。弱信号因在电离期间银离子的吸附而产生,且未在反射器模式下观察到。可检测到至多5000g/mol的分子量,这对应于7个重复单元的最大值。在具有十二烷基链的聚合物11b的情况下,检测到至多20 000g/mol的分子量(19个重复单元)。在聚合物11c的情况下,检测到摩尔质量为至多10 000g/mol的7个重复单元。
由于全部三种聚合物11a-c(除烷基外)均具有相同的重复单元,因此可容易地将分子量转化成链长度。该长度对应于在环化脱氢后GNR随后的纵向尺寸。对具有十二烷基链的石墨烯纳米带前体11b而言,20 000g/mol的摩尔质量对应于随后的宽度为2.1nm且长度为约12nm的石墨烯带(约1.2nm/重复单元)。
实施例7-9
环化脱氢
聚合物前体11a-c获得相应GNR12a-c的环化脱氢根据方案7借助分子内Scholl反应使用氯化铁(III)作为路易斯酸和氧化剂而进行。
方案7
所述反应通常以1mg/ml的极低聚合物浓度在未经稳定的二氯甲烷中进行以防止发生分子内的芳基-芳基偶联。在整个反应时间内用氩气流使反应溶液脱气以驱出氧气和所形成的HCl。在反应开始时,快速添加呈处于硝基甲烷中的浓溶液形式的每个所形成的键为6当量的氯化铁(III)(每个重复单元90当量),并将所述混合物在室温下搅拌3天。在结束环化脱氢后,用甲醇沉淀GNR并进一步纯化。
获得呈黑色固体的不含烷基的GNR12a和具有十二烷基的GNR12b,产率为64%和98%,其不溶于标准有机溶剂如甲苯、THF、四氯乙烷或氯仿中。在石墨烯带宽度为2.1nm的情况下,π-π相互作用如此强烈,以至于在12b的情况下两个十二烷基/重复单元不足以防止聚集。因此,为了进行后处理,通过用THF和甲醇实施索格利特萃取来除去粗产物的所有可溶性杂质,最后在高真空下干燥。相反,获得可溶于标准有机溶剂如THF或甲苯中的呈黑色固体形式的具有2-癸基十四烷基链的GNR12c,产率为81%。因此,通过在甲醇中由THF反复再沉淀来实施纯化,随后用丙酮实施索格利特萃取,以除去杂质、副产物和无机残余物。
实施例7
使50mg聚合物前体11a与1.12g FeCl3(6.87mmol,溶解于4ml硝基甲烷中)反应。在3天反应时间后,已形成黑色沉淀物,将其在离心机中移除。对纯化而言,在每种情况下均用THF和甲醇对粗产物实施2天索格利特萃取,最后在高真空下干燥。因此,获得呈黑色不溶固体形式的32.0mg GNR12a(64%)。DSC(℃):无转变。
实施例8
使76.6mg聚合物前体11b与1.10g FeCl3(6.76mmol,溶解于3.5ml硝基甲烷中)反应。在3天反应时间后,已形成黑色沉淀物,将其在离心机中移除。对纯化而言,在每种情况下均用THF和甲醇对粗产物实施2天索格利特萃取,最后在高真空下干燥。因此,获得呈黑色不溶固体形式的72.9mg GNR12b(98%)。DSC(℃):无转变。
实施例9
使38.11mg聚合物前体11c与410mg FeCl3(2.53mmol,溶解于1.3ml硝基甲烷中)反应。在添加甲醇后,形成黑色沉淀物,将其在离心机中移除并通过在甲醇中由THF再沉淀且随后用丙酮实施2天索格利特萃取来除去所有杂质、副产物和无机残余物。在高真空下干燥后,获得呈黑色固体形式的30.2mg GNR12c(81%)。DSC(℃):无转变。
借助拉曼和IR光谱证实GNR12a-c的完全环化脱氢和无缺陷结构。图4显示了使用激光在λ=488nm处激发在薄粉末膜中记录的GNR12b拉曼光谱。拉曼光谱能获得与GNR中π-体系程度有关的信息,且因此能计算共轭长度。通过IR吸收测量,可检测所有样品在4050cm-1处的能带的存在,这是苯基环的自由旋转的特征,且在完全环化脱氢的情况下不再可检测到。
GNR12b为唯一在固态下未显示出荧光的样品,因此允许使用488nm的激光激发波长在薄粉末膜上记录拉曼光谱。所得光谱示于图4中。获得对1331cm-1处的特征D能带和1579cm-1处的尖锐G能带二者的良好分辨率。这些能带的位置与由文献已知的石墨烯带的值良好吻合,这证实样品的石墨烯特征。在多重这些波数下,也可发现二阶和三阶信号。对GNR12b的尺寸La的计算而言,一阶D能带与G能带的积分(I)之比由式l(D)/l(G)=C(λ)/La换算。C(λ)为波长依赖性因子,对于λ=488nm,假定值C(λ)=4.4nm。因此,计算尺寸为4.6-4.7nm,这对应于约8个重复单元且分子量为约8000g/mol的石墨烯带。
此外,通过IR光谱证实GNR12a和12b的环化脱氢的完全性。图5显示了GNR12a和12b的IR光谱。4050cm-1处的能带为在每种情况下苯基环自由旋转的特征,且在聚合物前体11a和11b的光谱中清楚观察到该能带(上部线条)。在环化脱氢结束后,完全不存在该能带(下部线条),这排除了分子中未缩合苯基环的存在,且因此证实完全环化脱氢。
Claims (5)
1.一种石墨烯纳米带前体,其包含通式(I)的重复单元:
其中:
R1,R2各自为H;卤素;-OH;-NH2;-CN;-NO2;或烃基,其具有1-40个碳原子且可为直链或支化的、饱和或不饱和的且被卤素(F、Cl、Br、I)、-OH、-NH2、-CN和/或-NO2单取代或多取代,其中一个或多个CH2基团也可被-O-、-S-、-C(O)O-、-O-C(O)-、-C(O)-、-NH-或-NR-替代,其中R为任选取代的C1-C40烃基;或任选取代的芳基、烷芳基或烷氧基芳基。
2.一种石墨烯纳米带,其可通过使如权利要求1的石墨烯纳米带前体在溶液中或在金属表面上环化脱氢而获得。
3.一种制备石墨烯纳米带前体的方法,其包括通式(II)单体的Yamamoto偶联反应,
其中:
R1,R2各自为H;卤素;-OH;-NH2;-CN;-NO2;或烃基,其具有1-40个碳原子且可为直链或支化的、饱和或不饱和的且被卤素(F、Cl、Br、I)、-OH、-NH2、-CN和/或-NO2单取代或多取代,其中一个或多个CH2基团也可被-O-、-S-、-C(O)O-、-O-C(O)-、-C(O)-、-NH-或-NR-替代,其中R为任选取代的C1-C40烃基;或任选取代的芳基、烷芳基或烷氧基芳基,且
X为卤素、三氟甲磺酸酯基或重氮基。
4.一种制备通式(II)单体的方法,其包括如下步骤:
(i)通过Knoevenagel缩合使1,3-二(联苯-3-基)丙-7-酮7
与4,4'-二卤代苯甲偶酰9反应
从而获得四芳基环戊二烯酮8:
(ii)通过Diels-Alder反应使四芳基环戊二烯酮8与二苯乙炔10反应
从而获得通式(II)的单体:
其中:
R1、R2各自为H;卤素;-OH;-NH2;-CN;-NO2;或烃基,其具有1-40个碳原子且可为直链或支化的、饱和或不饱和的且被卤素(F、Cl、Br、I)、-OH、-NH2、-CN和/或-NO2单取代或多取代,其中一个或多个CH2基团也可被-O-、-S-、-C(O)O-、-O-C(O)-、-C(O)-、-NH-或-NR-替代,其中R为任选取代的C1-C40烃基;或任选取代的芳基、烷芳基或烷氧基芳基,且
X为卤素、三氟甲磺酸酯基或重氮基。
5.一种用于通过Yamamoto偶联反应来制备石墨烯纳米带前体的通式(II)的单体:
其中:
R1、R2各自为H;卤素;-OH;-NH2;-CN;-NO2;或烃基,其具有1-40个碳原子且可为直链或支化的、饱和或不饱和的且被卤素(F、Cl、Br、I)、-OH、-NH2、-CN和/或-NO2单取代或多取代,其中一个或多个CH2基团也可被-O-、-S-、-C(O)O-、-O-C(O)-、-C(O)-、-NH-或-NR-替代,其中R为任选取代的C1-C40烃基;或任选取代的芳基、烷芳基或烷氧基芳基,且
X为卤素、三氟甲磺酸酯基或重氮基。
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