CN104114489B - 用于制备石墨烯纳米带的聚合物前体及其制备方法 - Google Patents
用于制备石墨烯纳米带的聚合物前体及其制备方法 Download PDFInfo
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- CN104114489B CN104114489B CN201280062080.2A CN201280062080A CN104114489B CN 104114489 B CN104114489 B CN 104114489B CN 201280062080 A CN201280062080 A CN 201280062080A CN 104114489 B CN104114489 B CN 104114489B
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- Prior art keywords
- alkyl
- alkynyl
- alkenyl
- polymer precursor
- oligophenylenes
- Prior art date
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 58
- 229910021389 graphene Inorganic materials 0.000 title claims description 56
- 239000002127 nanobelt Substances 0.000 title claims description 48
- 229920000642 polymer Polymers 0.000 title claims description 39
- 239000002243 precursor Substances 0.000 title claims description 38
- 238000002360 preparation method Methods 0.000 title claims description 29
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 17
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 12
- 150000002367 halogens Chemical class 0.000 claims abstract description 11
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 10
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 7
- 125000004171 alkoxy aryl group Chemical group 0.000 claims abstract description 5
- 125000002877 alkyl aryl group Chemical group 0.000 claims abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 23
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- 125000003342 alkenyl group Chemical group 0.000 claims description 15
- 239000004065 semiconductor Substances 0.000 claims description 14
- 125000000739 C2-C30 alkenyl group Chemical group 0.000 claims description 13
- 125000000304 alkynyl group Chemical group 0.000 claims description 10
- 230000005669 field effect Effects 0.000 claims description 8
- 239000010409 thin film Substances 0.000 claims description 5
- 125000000232 haloalkynyl group Chemical group 0.000 claims description 4
- 230000005693 optoelectronics Effects 0.000 claims description 4
- 238000012672 diels-alder polymerization Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000013086 organic photovoltaic Methods 0.000 claims 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 50
- -1 polyphenylene Polymers 0.000 description 48
- 239000002585 base Substances 0.000 description 27
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 239000000463 material Substances 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000000243 solution Substances 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 15
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 12
- 239000011541 reaction mixture Substances 0.000 description 12
- WIQXBJYQWBBHKZ-UHFFFAOYSA-N O=C1CC=C=C1 Chemical compound O=C1CC=C=C1 WIQXBJYQWBBHKZ-UHFFFAOYSA-N 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 9
- 238000010898 silica gel chromatography Methods 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000005698 Diels-Alder reaction Methods 0.000 description 8
- 229920000265 Polyparaphenylene Polymers 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 239000012043 crude product Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 239000004305 biphenyl Substances 0.000 description 6
- 235000010290 biphenyl Nutrition 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 description 6
- 235000011152 sodium sulphate Nutrition 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 5
- 238000006069 Suzuki reaction reaction Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000007766 curtain coating Methods 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 239000011630 iodine Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 5
- 235000015320 potassium carbonate Nutrition 0.000 description 5
- 238000007639 printing Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000031709 bromination Effects 0.000 description 4
- 238000005893 bromination reaction Methods 0.000 description 4
- 230000005587 bubbling Effects 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical group C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- 125000003438 dodecyl group Chemical class [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 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 3
- KTADSLDAUJLZGL-UHFFFAOYSA-N 1-bromo-2-phenylbenzene Chemical group BrC1=CC=CC=C1C1=CC=CC=C1 KTADSLDAUJLZGL-UHFFFAOYSA-N 0.000 description 3
- CTPUUDQIXKUAMO-UHFFFAOYSA-N 1-bromo-3-iodobenzene Chemical compound BrC1=CC=CC(I)=C1 CTPUUDQIXKUAMO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZSMCGIIWXAHJFU-UHFFFAOYSA-N C[Si](C)(C)C#CC=1C=C(C=CC=1)C=1C(C=CC=1)=O Chemical compound C[Si](C)(C)C#CC=1C=C(C=CC=1)C=1C(C=CC=1)=O ZSMCGIIWXAHJFU-UHFFFAOYSA-N 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003513 alkali Substances 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
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000295 complement effect Effects 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 239000003989 dielectric material Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 3
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 3
- CWMFRHBXRUITQE-UHFFFAOYSA-N trimethylsilylacetylene Chemical group C[Si](C)(C)C#C CWMFRHBXRUITQE-UHFFFAOYSA-N 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- JTEUQFURLJKAMI-UHFFFAOYSA-N 1-phenylbenzo[a]anthracene Chemical compound C1(=CC=CC2=CC=C3C=C4C=CC=CC4=CC3=C12)C1=CC=CC=C1 JTEUQFURLJKAMI-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 description 2
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- FXCLIEYDXXVEAI-UHFFFAOYSA-N benzene;dichloromethane Chemical compound ClCCl.C1=CC=CC=C1 FXCLIEYDXXVEAI-UHFFFAOYSA-N 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- JNTHRSHGARDABO-UHFFFAOYSA-N dibenzo[a,l]pyrene Chemical group C1=CC=CC2=C3C4=CC=CC=C4C=C(C=C4)C3=C3C4=CC=CC3=C21 JNTHRSHGARDABO-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution 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
- 239000010931 gold Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 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
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000001269 time-of-flight mass spectrometry Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 description 2
- BLSQLHNBWJLIBQ-OZXSUGGESA-N (2R,4S)-terconazole Chemical compound C1CN(C(C)C)CCN1C(C=C1)=CC=C1OC[C@@H]1O[C@@](CN2N=CN=C2)(C=2C(=CC(Cl)=CC=2)Cl)OC1 BLSQLHNBWJLIBQ-OZXSUGGESA-N 0.000 description 1
- QBLFZIBJXUQVRF-UHFFFAOYSA-N (4-bromophenyl)boronic acid Chemical compound OB(O)C1=CC=C(Br)C=C1 QBLFZIBJXUQVRF-UHFFFAOYSA-N 0.000 description 1
- PEZNEXFPRSOYPL-UHFFFAOYSA-N (bis(trifluoroacetoxy)iodo)benzene Chemical compound FC(F)(F)C(=O)OI(OC(=O)C(F)(F)F)C1=CC=CC=C1 PEZNEXFPRSOYPL-UHFFFAOYSA-N 0.000 description 1
- BBOLNFYSRZVALD-UHFFFAOYSA-N 1,2-diiodobenzene Chemical compound IC1=CC=CC=C1I BBOLNFYSRZVALD-UHFFFAOYSA-N 0.000 description 1
- KUBGQQGLLKNTCQ-UHFFFAOYSA-N 1-(2,3-dibromophenyl)-2,3,4,5,6-pentakis-phenylbenzene Chemical compound BrC=1C(=C(C=CC=1)C1=C(C(=C(C(=C1C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1)C1=CC=CC=C1)Br KUBGQQGLLKNTCQ-UHFFFAOYSA-N 0.000 description 1
- MPEOPBCQHNWNFB-UHFFFAOYSA-N 1-chloro-2-iodobenzene Chemical compound ClC1=CC=CC=C1I MPEOPBCQHNWNFB-UHFFFAOYSA-N 0.000 description 1
- UDHAWRUAECEBHC-UHFFFAOYSA-N 1-iodo-4-methylbenzene Chemical compound CC1=CC=C(I)C=C1 UDHAWRUAECEBHC-UHFFFAOYSA-N 0.000 description 1
- JVAQVYKSURQMBE-UHFFFAOYSA-N 11-(bromomethyl)tricosane Chemical compound CCCCCCCCCCCCC(CBr)CCCCCCCCCC JVAQVYKSURQMBE-UHFFFAOYSA-N 0.000 description 1
- LKHZWDIUNGOHBN-UHFFFAOYSA-N 2,3-dimethylbutane-2,3-diol;phenylboronic acid Chemical compound CC(C)(O)C(C)(C)O.OB(O)C1=CC=CC=C1 LKHZWDIUNGOHBN-UHFFFAOYSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-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
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241001331845 Equus asinus x caballus Species 0.000 description 1
- 230000005355 Hall effect Effects 0.000 description 1
- 238000006000 Knoevenagel condensation reaction Methods 0.000 description 1
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- 230000010748 Photoabsorption Effects 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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Abstract
一种通式(I)的低聚亚苯基单体,其中R1和R2彼此独立地为H、卤素、-OH、-NH2、-CN、-NO2;或直链或支化的饱和或不饱和C1-C40烃基,其可被卤素(F、Cl、Br、I)、-OH、-NH2、-CN和/或-NO2取代1-5次,且其中一个或多个CH2基团可被-O-或-S-代替;或任选取代的芳基、烷芳基或烷氧基芳基;且m表示0、1或2。
Description
本发明涉及用于制备石墨烯纳米带的聚合物前体、其制备方法、用于合成聚合物前体的低聚亚苯基单体,以及由所述聚合物前体和低聚亚苯基单体制备石墨烯纳米带的方法。
自从新近发现石墨烯(石墨的原子薄层)的诱人电子性质以来,石墨烯已在物理学、材料科学和化学方面受到相当多的关注。这些包括优异的载流子迁移率和量子霍尔效应。此外,石墨烯的化学稳定性和材料强度使得其成为从透明导电电极至电荷和能量储存装置的应用场合的理想候选者。
石墨烯纳米带(GNR)为衍生自母体石墨烯晶格的线性结构。其特性为由于提高的长宽比而导致的高形状各向异性。目前,在材料科学中正广泛讨论其在更小、更扁平且更快的碳基器件和集成电路中的应用。与石墨烯相反,扶手椅型GNR显示出可通过其宽度调节的带隙。当将GNR用于诸如必须桥接最小沟道宽度的场效应晶体管(FET)的器件中时,GNR的长度变得相关。这同样适用于在纳米级导电通路中潜在替代铜或金。同时,GNR的边缘结构具有强烈的影响。对较小纳米石墨烯的计算模拟和实验结果表明,在锯齿形成边缘处具有非键合π电子状态的GNR可用作自旋电子器件中的活性组件。
因为化学确定的GNR的设计、化学制备和加工的相当大的复杂性,因此这些结构中仅少数为人所知。最近这些年来,仅公开了有限数量的合成尝试以解决具有确定几何形状、宽度、长度、边缘结构和杂原子含量的GNR的制造问题。基于反应环境,GNR的自下而上合成制造的研究可进一步分为溶液和表面基路线。
对使用低聚亚苯基前体的溶液基方法而言,通常在第一步骤中制备聚合物,随后通过Scholl型氧化环化脱氢将其转化成石墨结构。然而,必须小心地调节母体单体的设计,以确保在化学辅助石墨化成最终GNR结构时芳族单元具有合适的排列。
J.Wu,L.Gherghel,D.Watson,J.Li,Z.Wang,C.D.Simpson,U.Kolb和K.Müllen,Macromolecules2003,36,7082-7089报道了通过可溶性支化聚亚苯基的分子内氧化环化脱氢而获得石墨纳米带的合成,所述支化聚亚苯基通过1,4-双(2,4,5-三苯基环戊二烯酮-3-基)苯和二乙炔基三联苯的反复Diels-Alder环加成而制备。所得石墨烯带不是线性的,相反由于聚亚苯基前体的结构设计而包含统计分布的“扭结”。
X.Yang,X.Dou,A.Rouhanipour,L.Zhi,H.J.和K.Müllen,JACSCommunications,网络公开03/07/2008报道了二维石墨烯纳米带的合成。1,4-二碘-2,3,5,6-四苯基苯与4-溴苯基硼酸的Suzuki-Miyaura偶合获得了二溴六苯基苯,将其转化成双硼酸酯。所述双硼酸酯与二碘苯的Suzuki-Miyaura聚合在强烈空间位阻反应中获得了聚亚苯基。所述聚亚苯基与作为氧化剂的FeCl3的分子内Scholl反应提供了石墨烯纳米带。
Y.Fogel,L.Zhi,A.Rouhanipour,D.Andrienko,H.J.和K.Müllen,Macromolecules2009,42,6878-6884报道了通过微波辅助Diels-Alder反应合成同系列的五种单分散带型聚亚苯基,其中在重复单元中具有刚性二苯并芘核。在引入多达6个二苯并芘单元的芳族骨架中,所得聚亚苯基带的尺寸为132-372个碳原子。由于该骨架的柔性和十二烷基链的周边取代,所述聚亚苯基带可溶于有机溶剂中。在进一步的反应步骤中,通过环化脱氢制备带型多环芳烃(PAH)。
就最终石墨烯纳米带而言,所有三种方法均具有缺点。
在第一种情况下,所得石墨烯纳米带由于其骨架中的统计排列的“扭结”而具有不良结构。此外,分子量由于A2B2型聚合方法对偏离化学计量比的敏感而受到限制。未在石墨烯纳米带中引入增溶性烷基侧链。
第二种情况由于A2B2型Suzuki方案的潜在A2B2化学计量比和1,4-二碘-2,3,5,6-四苯基苯的空间位阻也具有化学计量比的问题。
第三种情况使用逐步合成,其提供了石墨烯纳米带的确定切口(cutout),但无法实际制备高分子量物质。
本发明的目的是提供用于制备石墨烯纳米带的新颖方法。本发明的另一目的是提供用于制备石墨烯纳米带的合适聚合物前体,以及制备该聚合物前体的方法和合适的低聚亚苯基单体。
所述问题通过一种通式(I)的低聚亚苯基单体解决:
其中:
R1和R2彼此独立地为H、卤素、-OH、-NH2、-CN、-NO2;或直链或支化的饱和或不饱和C1-C40烃基,其可被卤素(F、Cl、Br、I)、-OR3、-NR3 2、-CN和/或-NO2取代1-5次,且其中一个或多个CH2基团可被-O-、-S-、-NR4-、-OC(O)-或-C(O)-代替;或任选取代的芳基、烷芳基或烷氧基芳基;
各R3彼此独立地为H、C1-C30烷基、C2-C30链烯基、C2-C30炔基、C1-C30卤代烷基、C2-C30卤代链烯基、C2-C30卤代炔基或C2-C30酰基;
各R4彼此独立地为H、C1-C30烷基、C2-C30链烯基、C2-C30炔基、C1-C30卤代烷基、C2-C30卤代链烯基、C2-C30卤代炔基或C2-C30酰基;且
m表示0、1或2。
优选地,R1和R2彼此独立地为H、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卤代链烯基或卤代炔基,例如C1-C30全氟烷基。更优选地,R1和R2彼此独立地为H、C1-C30烷基或C1-C30烷氧基。最优选地,R1和R2彼此独立地为H或C1-C30烷基。
可能的话,C1-C30烷基可为直链或支化的。
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、正癸基、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、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、十七烷氧基或十八烷氧基。
术语“烷硫基”意指与烷氧基相同的基团,不同之处在于醚连接链的氧原子被硫原子替代。
C2-C30链烯基为直链或支化的链烯基,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且可未被取代或被取代,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、顺式-3-甲基-2-戊-4-烯-1-炔基、反式-3-甲基-2-戊-4-烯-1-炔基、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基团,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”意指通过用卤素部分或完全取代上述烷基、链烯基和炔基而给出的基团。
C2-C30酰基为直链或支化的且可为饱和或不饱和的,例如乙酰基、丙酰基、异丁酰基、正丁酰基、戊酰基、己酰基、庚酰基、辛酰基、壬酰基、癸酰基或十二烷酰基。
芳基通常为C6-C30芳基,其可任选被取代,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、并四苯基(teracyl)、并五苯基(pentacyl)或并六苯基(hexacyl)。
在本发明的优选实施方案中,R1为直链或支化的C1-C30烷基且R2为H。
所述问题进一步通过一种用于制备石墨烯纳米带的具有通式(II)重复单元的聚合物前体解决:
其中:
R1和R2彼此独立地为H、卤素、-OH、-NH2、-CN、-NO2;或直链或支化的饱和或不饱和C1-C40烃基,其可被卤素(F、Cl、Br、I)、-OR3、-NR3 2、-CN和/或-NO2取代1-5次,且其中一个或多个CH2基团可被-O-、-S-、-NR4-、-OC(O)-或-C(O)-代替;或任选取代的芳基、烷芳基或烷氧基芳基;
各R3彼此独立地为H、C1-C30烷基、C2-C30链烯基、C2-C30炔基、C1-C30卤代烷基、C2-C30卤代链烯基、C2-C30卤代炔基或C2-C30酰基;
各R4彼此独立地为H、C1-C30烷基、C2-C30链烯基、C2-C30炔基、C1-C30卤代烷基、C2-C30卤代链烯基、C2-C30卤代炔基或C2-C30酰基;
m表示0、1或2;且
n表示2-900的数。
优选地,R1和R2彼此独立地为H、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卤代链烯基或卤代炔基,例如C1-C30全氟烷基。更优选地,R1和R2彼此独立地为H、C1-C30烷基或C1-C30烷氧基。最优选地,R1和R2彼此独立地为H或C1-C30烷基。
优选地,式(I)和式(II)中的R2为H。
优选地,式(I)和式(II)中的m表示0或1。更优选地,式(I)和式(II)中的m表示0。
在本发明的优选实施方案中,R1为直链或支化的C1-C30烷基且R2为H。
通式(I)的低聚亚苯基单体用于通过使其经由方案1的Diels-Alder反应而制备石墨烯纳米带制备用的具有通式(II)重复单元的聚合物前体。
Diels-Alder反应为用于构建官能分子和聚合物的广为人知的方案。通式(I)的低聚亚苯基单体至具有通式(II)重复单元的聚合物前体的Diels-Alder反应可在不同条件下实现。例如,Diels-Alder反应可在高沸点溶剂中在升高的温度下实施。合适的高沸点溶剂为二苯醚、1,1,2,2-四氯乙烷、1,2-二氯苯、1,2,4-三氯苯、硝基苯和二苯甲酮。
或者,Diels-Alder反应可在不使用溶剂下在200-300℃的温度下实施。方案1
一般而言,具有通式(II)重复单元的聚合物前体含有2-900个重复单元且具有1000-600000g/mo1的分子量。
本发明还涉及一种制备具有通式(II)重复单元的聚合物前体的方法,包括使通式(I)的低聚亚苯基单体Diels-Alder聚合。
本发明还涉及一种制备石墨烯纳米带的方法,包括根据方案2使具有通式(II)重复单元的聚合物前体环化脱氢。
由具有通式(II)重复单元的聚合物前体制备通式(III)的石墨烯纳米带可例如在DCM与硝基甲烷的混合物中使用氯化铁(III)作为氧化剂进行(方案2)。取决于温度和具有通式(II)重复单元的聚合物前体的性质,反应时间为2小时至10天。如果所述反应在约20℃下进行,则反应时间通常为2-4天。优选地,在反应期间,使惰性气体流通过反应混合物以避免副反应。
或者,通式(III)石墨烯纳米带的制备可使用处于无水DCM中的双(三氟乙酸)苯碘(III)(PIFA)和醚合三氟化硼或处于无水DCM中的五氯化钼(V)进行。
一般而言,通式(III)石墨烯纳米带的分子量为1000-600000g/mol。
方案2
通式(I)的低聚亚苯基单体可根据下文方案3-7合成,其涉及两种中间体3-溴苯偶酰4和取代的1,3-双(低聚亚苯基)丙-2-酮8,如下文方案7中所概述。所用的反应条件和溶剂纯粹是示意性的,当然也可使用其他条件和溶剂且由本领域技术人员确定。取决于所需的通式(III)石墨烯纳米带的宽度,可使不同取代的1,3-双(低聚亚苯基)丙-2-酮8(m=0、1或2)与3-溴苯偶酰4反应。合适的取代1,3-双(低聚亚苯基)丙-2-酮8例如为m=0的1,3-双(低聚亚苯基)丙-2-酮8-0(方案4)、m=1的1,3-双(低聚亚苯基)丙-2-酮8-1(方案5)和m=2的1,3-双(低聚亚苯基)丙-2-酮8-2(方案6)。
在第一反应序列中,中间体3-溴苯偶酰4可经由两步路线由市售1-溴-3-碘苯1和乙炔苯2合成(方案3)合成。1与2的Sonogashira偶合可用于构建3-溴二苯基乙炔3。所述反应可在碘化铜(I)和钯(II)催化剂的存在下在室温下于THF与三乙胺的混合物中实现。由于1-溴-3-碘苯1的碘碳键的较高反应性,所述偶合仅在所需的3位进行。
第二步骤包括使3-溴二苯基乙炔3的乙炔基氧化,从而获得3-溴苯偶酰4。该步骤可通过在于二甲亚砜中的碘存在下在升高的温度下搅拌溴二苯基乙炔3而实现。
方案3
方案4示意了由文献已知的卤代甲苯5起始制备取代的1,3-双(低聚亚苯基)丙-2-酮8-0的合成路线,其中X和Y独立地选自Cl、Br、I或H。第一步骤包括使卤代甲苯5的苄基位溴化,从而获得卤化苄基溴6。该步骤可通过在N-溴代琥珀酰亚胺(NBS)和过氧化苯甲酰的存在下在四氯化碳中于回流下加热卤代甲苯5而实现。卤代苄基溴6可进一步反应,从而获得卤代1,3-双(苯基)丙-2-酮7。这通过使用五羰基铁(0)、氢氧化钾和苄基三乙基氯化铵在二氯甲烷和水的反应混合物中于回流下加热卤代苄基溴6而实现。该反应序列的最后反应步骤可使用任何所需的取代或未取代卤化物R1X’或R2X’而实现,其中X’选自Cl、Br或I,且R1和R2如上文所定义。例如,取代的1,3-双(低聚亚苯基)丙-2-酮8-0可在室温下使用碘化锌(II)和钯(0)催化剂而获得。如果X和Y均为H,则省略该反应步骤。
方案4
取代的1,3-双(低聚亚苯基)丙-2-酮8-1(m=1)的合成示于方案5中。取代的1,3-双(低聚亚苯基)丙-2-酮8-1可经由四步路线由市售2-溴-1-碘-5-甲基苯9和苯基硼酸10起始合成。9与10的Suzuki交叉偶合可用于构建2-溴-5-甲基联苯11。所述反应可在碳酸钾和催化量的四(三苯基膦)钯(0)存在下在升高的温度下于甲苯、乙醇和水的反应混合物中实现。由于碘碳键的较高反应性,所述偶合主要在所需的1位碘原子处进行。下一步包括使2-溴-5-甲基联苯11的苄基位溴化,从而获得官能化的联苯12。该步骡可通过使用N-溴代琥珀酰亚胺(NBS)和过氧化苯甲酰在四氯化碳中于回流下加热溴-5-甲基联苯1l而实现。
方案5
官能化的联苯12可进一步反应,从而获得1,3-双(溴联苯)丙-2-酮13。这通过在五羰基铁(0)、氢氧化钾和苄基三乙基氯化铵的存在下在二氯甲烷与水的反应混合物中使官能化的联苯12沸腾而实现。在最后一步中,在碳酸钾和四(三苯基膦)钯(0)的存在下1,3-双(溴联苯)丙-2-酮13与芳基硼酸频哪醇酯14的Suzuki交叉偶合获得了取代的1,3-双(低聚亚苯基)丙-2-酮8-1(m=1)。R1和R2如上文所定义。
取代的1,3-双(低聚亚苯基)丙-2-酮8-2(m=2)的合成示于方案6中。取代的1,3-双(低聚亚苯基)丙-2-酮8-2的合成起始于市售2-溴-4-氯-1-碘苯16和上述取代的苯基硼酸频哪醇酯14。Suzuki交叉偶合可用于构建取代的2-溴-4-氯联苯17。所述反应可例如在碳酸钾和四(三苯基膦)钯(0)存在下在升高的温度下于甲苯、乙醇和水的反应混合物中实施。优选地,使用精确的1.00当量的取代苯基硼酸频哪醇酯14。随后,在第二Suzuki反应中,使用苯基硼酸10使2-溴-4-氯联苯17转化,从而获得取代的氯代三亚苯基18。所用的条件与前一步骤相同,但在较高的温度下。
方案6
取代三苯基硼酸频哪醇酯19可在乙酸钾作为碱和催化量的三(二亚苄基丙酮)二钯由(0)(Pd2(dba)3)和2-双环己基膦基-2',4',6'-三异丙基联苯(XPhos)的存在下在14-二烷中于回流下由氯代三亚苯基18制备。在使用碳酸钾作为碱和四(三苯基膦)钯(0)下,19与1,3-双(溴联苯)丙-2-酮13在甲苯、乙醇和水的混合物中于回流下的Suzuki交叉偶合获得了取代的1,3-双(低聚亚苯基)丙-2-酮8-2。
在得到中间体3-溴苯偶酰4和取代的1,3-双(低聚亚苯基)丙-2-酮8(m=0、1或2)的情况下,其偶合可使用Knoevenagel缩合进行(方案7)。这可通过在氢氧化四乙铵的存在下在80℃下于叔丁醇与水的混合物中使4与8反应而实现。在Sonogashira交叉偶合反应中,使用三甲基甲硅烷基乙炔、双(三苯基膦)氯化钯(II)和碘化铜(I)使所得的取代的2,5-双(低聚亚苯基)-3-(3-溴苯基)-4-苯基-2,4-环戊二烯酮20进一步反应。这获得了取代的2,5-双(低聚亚苯基)-3-(3-三甲基甲硅烷基乙酰基苯基)-4-苯基-2,4-环戊二烯酮21。使用碳酸钾作为碱最终导致形成通式(I)的低聚亚苯基单体。当使用1:1的THF与甲醇的混合物时,该反应进展良好。
方案7
使用本文所公开的石墨烯纳米带的各种制品也处于本发明的范围之内,所述制品包括电子器件、光学器件和光电子器件,如场效应晶体管(例如薄膜晶体管)、光伏器件、有机发光二极管(OLED)、互补金属氧化物半导体(CMOS)、互补逆变器、D触发器、整流器和环形振荡器,所述制品的制造方法也处于本发明的范围之内。
因此,本发明进一步提供了制备半导体材料的方法。所述方法可包括:制备包含溶解或分散于液体介质如溶剂或溶剂混合物中的一种或多种本文所公开的本发明石墨烯纳米带的组合物;将所述组合物沉积在基材上,以提供半导体材料前体,以及对所述半导体前体进行加工(例如加热)以提供包含一种或多种本文所公开的石墨烯纳米带的半导体材料(如薄膜半导体)。在各种实施方案中,所述液体介质可为有机溶剂、无机溶剂如水,或其组合。在一些实施方案中,所述组合物可进一步包含一种或多种添加剂,所述添加剂独立地选自:清洁剂、分散剂、粘合剂、相容剂、固化剂、引发剂、湿润剂、消泡剂、润湿剂、pH调节剂、生物杀伤剂和抑菌剂。例如,可包含表面活性剂和/或聚合物(例如聚苯乙烯、聚乙烯、聚α-甲基苯乙烯、聚异丁烯、聚丙烯、聚甲基丙烯酸甲酯等)作为分散割、粘合剂、相容剂和/或消泡剂。在一些实施方案中,沉积步骤可通过印刷进行,包括喷墨印刷和各种接触印刷技术(例如丝网印刷、凹版印刷、胶印、凹版移印、平版印刷、柔性版印刷和微接触印刷)。在其他实施方案中,沉积步骤可通过旋涂、液滴流延(drop-casting)、区域流延(zone-casting)、浸涂、刮刀涂覆、喷涂或真空过滤进行。
本发明进一步提供了制品,例如本文所述的各种器件,其包含具有本发明半导体材料和基材组分和/或介电组分的组合物。所述基材组分可选自掺杂硅、氧化铟锡(ITO)、ITO涂覆的玻璃、ITO涂覆的聚酰亚胺或其他塑料、铝或其他金属(单独或涂覆在聚合物或其他基材上)、掺杂聚噻吩等。所述介电组分可由如下材料制备:无机介电材料如各种氧化物(例如SiO2、A12O3、HfO2),有机介电材料如各种聚合材料(例如聚碳酸酯、聚酯、聚苯乙烯、聚卤乙烯、聚丙烯酸酯),和自组装超晶格/自组装纳米介电(SAS/SAND)材料(例如如Yoon,M-H.等,PNAS,102(13):4678-4682(2005)),以及混杂有机/无机介电材料(例如如US2007/0181961A1所述)。所述组合物还可包含一个或多个电接触点。源电极、漏电极和栅电极的合适材料包括金属(例如Au、A1、Ni、Cu)、透明导电氧化物(例如ITO、IZO、ZITO、GZO、GIO、GITO),和导电聚合物(例如聚(3,4-亚乙基二氧噻吩)聚(苯乙烯磺酸酯)(PEDOT:PSS)、聚苯胺(PANI)、聚吡咯(PPy)。本文所述的一种或多种组合物可体现在各种有机电子、光学和光电子器件中,如有机薄膜晶体管(OTFT),尤其是有机场效应晶体管(OFET),以及传感器、电容器、单极电路、互补电路(如逆变器电路)等。
可使用本发明石墨烯纳米带的其他制品为光伏器件或太阳能电池。本发明的化合物可显示出宽光吸收和/或极正向移动的还原电位,这使得其合乎该类应用的需要。因此,本文所述的石墨烯纳米带可在光伏设计中用作n型半导体,其包括形成p-n结的相邻p型半导体材料。所述化合物可呈薄膜半导体形式,其可沉积在基材上以形成复合物。本发明化合物在该类器件中的应用处于本领域技术人员的知识范围之内。
因此,本发明的另一方面涉及制造掺有本发明半导体材料的有机场效应晶体管的方法。本发明的半导体材料可用于制造各种有机场效应晶体管,包括顶栅顶接触电容器结构、顶栅底接触电容器结构、底栅顶接触电容器结构和底栅底接触电容器结构。
在某些实施方案中,可使用SiO2作为电介质而在顶接触几何结构中用本发明的石墨烯纳米带在掺杂硅基材上制造OTFT器件。在特定实施方案中,可在室温或升高的温度下沉积至少掺有本发明石墨烯纳米带的活性半导体层。在其他实施方案中,可通过本文所述的旋涂或印刷来施加至少掺有本发明石墨烯纳米带的活性半导体层。对顶接触器件而言,可使用掩模在膜顶部上图案化金属触点。
借助下文实施例更详细地阐述本发明。
实施例
附图简介:
图1:聚合物前体IIa的粗产物(表1,条目1,基体:TCNQ,线性模式)的MALDI-TOFMS分析。
图2:聚合物前体IIa的粗产物的MALDI-TOFMS分析(表1,条目1,基体:TCNQ,反射模式)。
图3:四聚、五聚、六聚和七聚聚合物前体IIa的化学式、精确质量和分子量。
(四聚体=C216H274,精确质量=2868.14,分子量=2870.49;五聚体=C270H342,精确质量=3584.68,分子量=3587.60;六聚体=C324H410,精确质量=4301.21,分子量=4304.72;七聚体=C378H478,精确质量=5017.74,分子量=5021.84)
图4:聚合物前体IIa在经GPC分级后的分子量分布(表1,条目2,THF,PSS)。
图5:石墨烯纳米带IIIa(粉末)的拉曼光谱。
图6:UV-VIS吸收光谱的对比:(a)处于THF(14μg/mL)中的聚合物前体IIa和(b)由处于THF中的分散体作为膜液滴流延于玻璃基材上的石墨烯纳米带IIIa。
图7:NMP剥离溶液中的石墨烯纳米带IIIa的UV-vis吸收光谱。
图8:石墨烯纳米带IIIa在各种栅极偏压VG下的输出特性。
图9:石墨烯纳米带IIIa在VSD=-60V的源极偏压下的传输曲线。
实施例1
3-溴二苯基乙炔(3)的制备
向1-溴-3-碘苯1(5.03g,17.8mmo1)和乙炔苯2(2.08g,20.4mmo1)于THF(50mL)与三乙胺(50mL)的混合物中的脱气溶液中添加碘化铜(I)(52.7mg,0.277mmo1)和二氯双(三苯基膦)钯(II)(376mg,0.536mmo1)。在室温下搅拌18小时之后,过滤反应混合物以移除沉淀物。滤液用乙醚稀释,并用氯化铵的饱和水溶液洗涤两次,用盐水洗涤三次,然后经硫酸钠干燥并真空浓缩。深褐色粗产物通过硅胶柱色谱法(洗脱液:己烷)纯化,获得无色油状标题化合物(4.46g,产率为98%)。
1 HNMR(300MHz,CD2Cl2):δ7.25(t,J=7.9Hz,1H),7.35-7.41(m,3H),7.46-7.57(m,4H),7.70(t,J=1.7Hz,1H)。
13 CNMR(75MHz,CDCl3):δ87.77,90.65,122.16,122.73,125.30,128.40,128.61,129.76,130.13,131.36,131.66,134.31。
元素分析:C14H9Br的计算值:C,65.40;H,3.53。实测值:C,65.53;H,3.65。
实施例2
3-溴苯偶酰(4)的制备
向3-溴二苯基乙炔3(6.38g,24.8mmo1)于DMSO(60mL)中的溶液中添加碘(3.15g,12.4mmo1)。使所述反应混合物脱气并在155℃下搅拌20小时。在冷却至室温之后,用亚硫酸钠的饱和水溶液猝灭反应,随后用二氯甲烷稀释。用二氯甲烷萃取水层三次并用水洗涤合并的有机层五次。在经硫酸钠干燥且真空浓缩之后,通过硅胶柱色谱法(洗脱液:30-50%二氯甲烷/己烷)纯化。获得黄色固体状标题化合物(4.47g,产率为62%)。
1 HNMR(300MHz,CD2Cl2):δ7.42(t,J=7.9Hz,1H),7.51-7.59(m,2H),7.71(tt,J=1.3,7.4Hz,1H),7.82(qd,J=0.99,8.0Hz,1H),7.89(td,J=1.2,7.8Hz,1H),7.93-7.98(m,2H),8.13(t,J=1.8Hz,1H)。
13 CNMR(75MHz,CD2Cl2):δ123.61,128.99,129.53,130.29,131.10,132.79,133.11,135.16,135.59,138.12,193.42,194.08。
元素分析:Cl4H9BrO2的计算值:C,58.16;H,3.14。实测值:C,58.21;H,3.32。
实施例3
3-(3-溴苯基)-2,5-双(4-十二烷基苯基)-4-苯基-2,4-环戊二烯酮(20a)的制备
在80℃下,向3-溴苯偶酰4(2.00g,6.92mmo1)和1,3-双(4-十二烷基苯基)丙-2-酮(8a)(3.79g,6.93mmo1)于叔丁醇(200mL)中的溶液中添加氢氧化四乙铵的水溶液(20%,2.05mL,2.77mmo1)。在80℃下搅拌50分钟之后,通过添加1NHCl(40mL)猝灭反应,用二氯甲烷萃取反应混合物三次。用水洗涤合并的有机萃取物三次,经硫酸钠干燥并蒸发,获得紫色粗产物。通过硅胶柱色谱法(洗脱液:20%二氯甲烷/己烷)纯化,获得紫色固体状标题化合物(5.05g,产率为91%)。
1 HNMR(300MHz,CD2Cl2):δ0.86-0.90(m,6H),1.23-1.37(m,36H),1.51-1.66(m,4H),2.52-2.62(m,4H),6.87-6.92(m,1H),6.93-6.98(m,2H),7.04-7.16(m,10H),7.18-7.32(m,3H),7.35-7.41(m,1H)。
13 CNMR(75MHz,CD2Cl2):δ14.30(2C),23.12(2C),29.75(2C),29.79(2C),29.92(2C),30.02(2C),30.07(2C),30.09(2C),30.11(2C),31.74(2C),32.36(2C),36.13(2C),122.25,125.64,126.36,128.12,128.46(2C),128.48(2C),128.60(2C),128.90,129.60(2C),129.97,130.25,130.34(2C),130.35(2C),131.61,132.46,133.63,136.13,143.13,143.38,152.58,152.63,154.27,200.93。
元素分析:C39H62O的计算值:C,79.57;H,8.44。实测值:C,79.59;H,8.56。
实施例4
2,5-双(4-十二烷基苯基)-3-苯基-4-(3-((三甲基甲硅烷基)乙炔基)-苯基)-2,4-环戊二烯酮(21a)的制备
向3-(3-溴苯基)-2,5-双(4-十二烷基苯基)-4-苯基-2,4-环戊二烯酮20a(3.00g,3.75mmol)和碘化铜(I)(73.5mg,0.386mmol)于三乙胺(200mL)中的脱气悬浮液中添加三甲基甲硅烷基乙炔(1.60mL,11.3mmol)和四(三苯基膦)钯(0)(438mg,0.379mmol)。在80℃下搅拌19小时之后,真空移除溶剂。将所得紫色固体溶于二氯甲烷中并氯化铵的饱和水溶液洗涤一次,然后用盐水洗涤两次。在经硫酸钠干燥并真空浓缩后,通过硅胶柱色谱法(洗脱液:15%二氯甲烷/己烷)的纯化,得到紫色固体状标题化合物(2.10g,产率为69%)。
1 HNMR(300MHz,CD2Cl2):δ0.19(s,9H),0.88(t,J=6.7Hz,6H),1.23-1.36(m,36H),1.55-1.65(m,4H),2.52-2.61(m,4H),6.87-6.92(m,1H),6.92-6.97(m,2H),7.04-7.29(m,13H),7.30-7.35(m,1H)。
13 CNMR(75MHz,CD2Cl2):δ0.10(3C),14.30(2C),23.12(2C),29.78(2C),29.82(2C),29.91(2C),30.01(2C),30.07(4C),30.10(2C),31.75(2C),32.35(2C),36.14(2C),95.25,104.61,123.49,125.52,126.01,128.27,128.41(2C),128.47(2C),128.53(2C),128.67,128.81,129.61(2C),129.82,130.34(4C),130.61,132.07,132.50,133.70,134.47,143.07,143.28,153.43,154.43,154.27,201.13。
元素分析:C58H76OSi的计算值:C,85.23;H,9.37。实测值:C,84.84;H,9.33。
实施例5
2,5-双(4-十二烷基苯基)-3-(3-乙炔基苯基)-4-苯基-2,4-环戊二烯酮(Ia)的制备
将甲醇(100mL)添加至2,5-双(4-十二烷基苯基)-3-苯基4-(3-((三甲基甲硅烷基)乙炔基)苯基)-2,4-环戊二烯酮21a(1.02g,1.25mmol)和氟化钾(361mg,6.21mmol)于THF(100mL)中的悬浮液中,并将反应混合物在40℃下搅拌5小时。在40℃下真空移除溶剂之后,通过硅胶柱色谱法(洗脱液:15%二氯甲烷/己烷)纯化,获得紫色固体状标题化合物(786mg,产率为84%)。
1 HNMR(300MHz,CD2Cl2):δ0.88(t,J=6.7Hz,6H),1.23-1.36(m,36H),1.51-1.65(m,4H),2.51-2.61(m,4H),3.04(s,1H),6.91-6.97(m,3H),7.04-7.30(m,13H),7.35-7.39(m,1H).
13 CNMR(75MHz,CD2Cl2):δ14.33(2C),23.14(2C),29.80(4C),29.93(2C),30.03(2C),30.09(4C),30.12(2C),31.75(2C),32.37(2C),36.14(2C),77.93,83.22,122.35,125.61,126.17,128.25,128.44(2C),128.48(2C),128.52,128.54,128.56(2C),128.84,129.63(2C),130.19,130.36(4C),132.28,133.00,133.69,134.44,143.08,143.27,153.21,154.34,201.06.
HRMS(ESI,正性):m/z,C55H69O[M+H]+的计算值为745.5348,实测值为745.5334。
实施例6
聚合物前体(IIa)的制备
方法1:在二苯醚溶液中Diels-Alder聚合
使用加热套回流2,5-双(4-十二烷基苯基)-3-(3-乙炔基苯基)-4-苯基-2,4-环戊二烯酮Ia于二苯醚中的脱气溶液。在冷却至室温之后,蒸出二苯醚并通过使用再循环凝胶渗透色谱法(GPC)系统(洗脱液:氯仿)分级所得的粗物质。
1 HNMR(300MHz,CD2Cl2):δ0.81-0.92(m,6H),1.00-1.68(m,40H),2.15-2.75(m,4H),6.15-7.38(m,18H)。
方法2:在纯净条件下Diels-Alder聚合
在25mLSchlenk管中,使用加热套将2,5-双(4-十二烷基苯基)-3-(3-乙炔基苯基)-4-苯基-2,4-环戊二烯酮Ia的紫色粉末加热至260℃。首先使所述粉末熔融,随后失去其紫色而变成浅黄色。在冷却至室温之后,将所得聚合物在THF中超声处理30分钟,滤出不溶性聚合物。真空浓缩滤液并通过凝胶渗透色谱法(洗脱液:二氯甲烷)分级。
表1聚合物前体IIa的反应条件和所得的分子量
a粗产物的GPC分析(THF,PSS,UV检测器)
b使用超声处理用THF由不溶性聚合物萃取粗产物。
聚合物前体IIa(表1,条目1)的粗产物在反射模式中的MALDI分析在2869、3587、4304、5021和5739处分别显示出四聚体、五聚体、六聚体、七聚体和八聚体的峰,这表明在反应期间,乙炔基和四苯基环戊二烯酮结构部分在其边缘处发生反应(图2)。
实施例7
石墨烯纳米带(IIIa)的制备
通过氩气鼓泡10分钟使聚合物前体IIa于非稳定化二氯甲烷中的溶液脱气。向所述脱气溶液中添加氧化铁(III)于硝基甲烷中的悬浮液。在持续氩气鼓泡下在室温搅拌3天之后,通过添加甲醇猝灭反应以形成黑色沉淀物。通过使用膜过滤器吸滤并用甲醇洗涤,获得黑色粉末状标题化合物。
尽管石墨烯纳米带IIIa在常规有机溶剂中的溶解性极差,但可借助超声处理使IIIa分散于THF中。由于分散体在超声处理停止之后立即开始重新聚集,因此无法分析分散体,但可通过将其液滴流延于玻璃基材上而制备IIIa的膜并测量固态UV-VIS吸收光谱(图6b)。这证实在聚合物前体IIa(图6a)脱氢环化成石墨烯纳米带IIIa(图6b)时,吸收带显著红移。石墨烯纳米带IIIa的光谱显示在570nm处存在吸收峰。
石墨烯纳米带IIIa的剥离在NMP中借助超声处理进行,由剥离溶液得到IIIa的UV-VIS吸收光谱(图7)。在550nm处观测到吸收峰。
通过在超声处理之后直接液滴流延IIIa于THF中的分散体而制造具有石墨烯纳米带IIIa的OFET装置,这证实在HMDS改性的OFET器件中,石墨烯纳米带IIIa的场效应迁移率μ最大=0.001cm2/vs且μ平均=0.00087cm2/vs(图8和图9)。
实施例8
1,3-双(4-(2-癸基十四烷基)苯基)丙-2-酮(8b)的制备
将无水N,N-二甲基乙酰胺(10mL)添加至处于装备有冷凝器的100mL双颈烧瓶中的锌(3.21g,49.1mmol)和碘(0.689mg,2.71mmo1)中,并在室温搅拌至碘的紫色消失。随后将2-癸基十四烷基溴(15.3g,36.7mmo1)添加至所述混合物中,并在80℃搅拌24小时以生成十二烷基溴化锌。将所述十二烷基溴化锌溶液经由插管添加至处于100mLSchlenk烧瓶中的1,3-双(4-溴苯基)丙-2-酮7b(2.00g,5.43mmo1)和二氯[1,1’-双(二苯基膦基)二茂铁]钯(II)(0.384g,0.544mmo1)中。将所述反应混合物在室温下搅拌18小时,随后用盐酸(2M,40mL)猝灭。用二氯甲烷苯取水层三次。用水洗涤合并的有机萃取物三次,经硫酸钠干燥并蒸发。粗物质通过硅胶柱色谱法(洗脱液:20%二氯甲烷/己烷)纯化,得到浅黄色油状标题化合物(4.13g,产率为86%)。
1 HNMR(300MHz,CD2Cl2)D:δ0.88(t,J=6.7Hz,12H),1.16-1.37(m,80H),1.55-1.67(m,2H),2.50(d,J=7.0Hz,4H),3.68(s,4H),7.01(d,J=8.1Hz,4H),7.09(d,J=8.1Hz,4H)。
13 CNMR(75MHz,CD2Cl2):δ14.36(4C),23.18(4C),26.99(4C),29.85(4C),30.16(16C),30.50(4C),32.42(4C),33.60(4C),40.12(2C),40.57(2C),49.13(2C),129.70(4C),129.86(4C),131.88(2C),141.11(2C),206.30。
元素分析:C63Hl10O的计算值:C,85.64;H,12.55。实测值:C,85.71;H,12.45。
实施例9
3-(3-溴苯基)-2,5-双(4-(2-癸基十四烷基)苯基)-4-苯基-2,4-环戊二烯酮(20b)的制备
在80℃下,向3-溴苯偶酰4(0.808g,2.79mmol)和1,3-双(4-(2-癸基十四烷基)苯基)丙-2-酮8b(2.55g,2.89mmol)于叔丁醇(70mL)中的溶液中添加氢氧化四乙铵的水溶液(20%,0.82mL,1.12mmol)。在80℃下搅拌40分钟之后,通过添加盐酸(2M,20mL)猝灭反应,真空浓缩反应混合物,随后用二氯甲烷苯取两次。用水洗涤合并的有机萃取物两次,经硫酸钠干燥并蒸发。通过硅胶柱色谱法(洗脱液:10%二氯甲烷/己烷)的纯化,获得紫色油状标题化合物(2.71g,产率为85%)。
1 HNMR(300MHz,CD2Cl2):δ0.88(t,J=6.7Hz,12H),1.15-1.35(m,80H),1.55-1.67(m,2H),2.50(t,J=6.4Hz,4H),6.87(td,J=1.1,7.9Hz,1H),6.92-6.98(m,2H),7.01-7.16(m,10H),7.18-7.32(m,3H),7.35-7.41(m,1H)。
13 CNMR(75MHz,CD2Cl2):δ14.33(4C),23.15(4C),26.96(4C),29.82(4C),30.12(16C),30.44(4C),32.39(4C),33.61(2C),33.64(2C),40.01(2C),40.78(2C),122.26,125.69,126.42,128.09,128.42,128.47(2C),128.49,128.91,129.30(2C),129.41(2C),129.65(2C),129.93,130.20(4C),131.62,132.56,133.66,136.13,142.12,142.39,152.55,154.22,200.95。
HRMS(ESI,正性):m/z,C77H116OBr[M+H]+的计算值为1135.8210,实测值为1135.8199。
实施例10
2,5-双(4-(2-癸基十四烷基)苯基)-3-苯基-4-(3-((三甲基甲硅烷基)-乙炔基)苯基-2,4-环戊二烯酮(21b)的制备
向3-(3-溴苯基)-2,5-双(4-(2-癸基十四烷基)苯基)-4-苯基-2,4-环戊二烯酮20b(1.53g,1.34mmol)和碘化铜(1)(30.0mg,0.158mmol)于三乙胺(100mL)中的脱气悬浮液中添加三甲基甲硅烷基乙炔(0.580mL,4.07mmol)和四(三苯基膦)钯(0)(158mg,0.137mmol)。在80℃下搅拌16小时之后,真空移除溶剂。通过硅胶柱色谱法(洗脱液:10%二氯甲烷/己烷)纯化,获得紫色油状标题化合物(1.23g,产率为79%)。
1 HNMR(300MHz,CD2Cl2):δ0.19(s,9H),0.88(t,J=6.8Hz,12H),1.16-1.36(m,80H),1.53-1.66(m,2H),2.45-2.53(m,4H),6.85-6.97(m,3H),7.00-7.29(m,13H),7.30-7.35(m,1H)。
13 CNMR(75MHz,CD2Cl2):δ0.05(3C),14.35(4C),23.16(4C),26.93(2C),26.97(2C),29.83(4C),30.13(16C),30.44(4C),32.40(4C),33.60(2C),33.66(2C),39.95,40.02,40.71,40.80,95.23,104.66,123.55,125.55,126.02,128.25,128.41(2C),128.49,128.52,128.83,129.30(2C),129.37(2C),129.68(2C),129.85,130.21(4C),132.10,132.55,133.75,134.55,142.07,142.24,153.42,154.43,201.17。
HRMS(ESI,正性):m/z,C83H124ONaSi[M+Na]+的计算值为1175.9319,实测值为1175.9371。
实施例11
2,5-双(4-(2-癸基十四烷基)苯基)-3-(3-乙炔基苯基)-4-苯基-2,4-环戊二烯酮(Ib)的制备
将甲醇(15mL)添加至2,5-双(4-(2-癸基十四烷基)苯基)-3-苯基-4-(3-((三甲基甲硅烷基)乙炔基)苯基-2,4-环戊二烯酮21b(110mg,0.0953mmol)和氟化钾(54.5mg,0.938mmol)于THF(15mL)中的悬浮液中,并将所述反应混合物在40℃下搅拌21小时。在40℃下真空移除溶剂之后,通过硅胶柱色谱法(洗脱液:10%二氯甲烷/己烷)纯化,获得紫色油状标题化合物(93.8mg,产率为91%)。
1 HNMR(300MHz,CD2Cl2):δ0.88(t,J=6.8Hz,12H),1.18-1.34(m,80H),1.54-1.67(m,2H),2.46-2.54(m,4H),3.03(s,1H),6.90-6.97(m,3H),7.01-7.30(m,13H),7.34-7.39(m,1H)。
13 CNMR(75MHz,CD2Cl2):δ14.32(4C),23.13(4C),26.93(4C),29.80(4C),30.10(16C),30.41(4C),32.37(4C),33.58(2C),33.62(2C),39.98(2C),40.75(2C),77.87,83.20,122.34,125.63,126.19,128.19,128.40(2C),128.46,128.50,128.83,129.28(2C),129.36(2C),129.66(2C),130.19(5C),132.26,133.06,133.69,134.43,142.07,142.25,153.18,154.29,201.09.
MS(MALDI-TOF):m/z(%),C79H116O的计算值:1081(43),1082(37),1083(16),1084(4);实测值:1081(34),1082(38),1083(21),1084(7)。
实施例12
聚合物前体(IIb)的制备
在25mLSchlenk管中,使用加热套将2,5-双(4-(2-癸基十四烷基)苯基)-3-(3-乙炔基苯基)-4-苯基-2,4-环戊二烯酮(Ib)的脱气溶液加热至260℃。首先使所述粉末熔融,随后失去其紫色而变成浅黄色。在冷却至室温之后,将所得聚合物在THF中超声处理30分钟,滤出不溶性聚合物。真空浓缩滤液并通过凝胶渗透色谱法(洗脱液:二氯甲烷)分级。
实施例13
石墨烯纳米带(IIIb)的制备
通过氩气鼓泡10分钟使聚合物前体IIb于非稳定化二氯甲烷中的溶液脱气。向所述脱气溶液中添加氯化铁(III)于硝基甲烷中的悬浮液。在持续氩气鼓泡下在室温下搅拌3天之后,通过添加甲醇猝灭所述反应,从而形成黑色沉淀物。通过使用膜过滤器吸滤并用甲醇洗涤,获得黑色粉末状标题化合物。
Claims (17)
1.一种通式(I)的低聚亚苯基单体
其中:
R1和R2彼此独立地为H、卤素、-OH、-NH2、-CN、-NO2;或直链或支化的饱和或不饱和C1-C40烃基,其可被卤素(F、Cl、Br、I)、-OR3、-NR3 2、-CN和/或-NO2取代1-5次,且其中一个或多个CH2基团可被-O-、-S-、-NR4-、-OC(O)-或-C(O)-代替;或任选取代的芳基、烷芳基或烷氧基芳基;
各R3彼此独立地为H、C1-C30烷基、C2-C30链烯基、C2-C30炔基、C1-C30卤代烷基、C2-C30卤代链烯基、C2-C30卤代炔基或C2-C30酰基;
各R4彼此独立地为H、C1-C30烷基、C2-C30链烯基、C2-C30炔基、C1-C30卤代烷基、C2-C30卤代链烯基、C2-C30卤代炔基或C2-C30酰基;且
m表示0、1或2。
2.如权利要求1的低聚亚苯基单体,其中R1和R2彼此独立地为H、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卤代链烯基或卤代炔基。
3.如权利要求1的低聚亚苯基单体,其中m表示0。
4.如权利要求1的低聚亚苯基单体,其中R1为直链或支化的C1-C30烷基且R2为H。
5.如权利要求1-4中任一项所定义的低聚亚苯基单体用于制备石墨烯纳米带制备用聚合物前体的用途。
6.一种用于制备石墨烯纳米带的聚合物前体,其具有通式(II)的重复单元:
其中:
R1和R2彼此独立地为H、卤素、-OH、-NH2、-CN、-NO2;或直链或支化的饱和或不饱和C1-C40烃基,其可被卤素(F、Cl、Br、I)、-OR3、-NR3 2、-CN和/或-NO2取代1-5次,且其中一个或多个CH2基团可被-O-、-S-、-NR4-、-OC(O)-或-C(O)-代替;或任选取代的芳基、烷芳基或烷氧基芳基;
各R3彼此独立地为H、C1-C30烷基、C2-C30链烯基、C2-C30炔基、C1-C30卤代烷基、C2-C30卤代链烯基、C2-C30卤代炔基或C2-C30酰基;
各R4彼此独立地为H、C1-C30烷基、C2-C30链烯基、C2-C30炔基、C1-C30卤代烷基、C2-C30卤代链烯基、C2-C30卤代炔基或C2-C30酰基;
m表示0、1或2;且
n表示2-100的数。
7.如权利要求6的聚合物前体,其中R1和R2彼此独立地为H、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C2-C30卤代炔基。
8.如权利要求6的聚合物前体,其中m表示0。
9.如权利要求6的聚合物前体,其中R1为直链或支化的C1-C30烷基且R2为H。
10.一种制备石墨烯纳米带的方法,其包括环化脱氢如权利要求6所定义的聚合物前体。
11.如权利要求10的方法,其中所述聚合物前体通过如权利要求1-4中任一项所定义的低聚亚苯基单体的Diels-Alder聚合制备。
12.一种石墨烯纳米带,其可通过如权利要求10的方法获得。
13.一种组合物,其包含溶解或分散于液体介质中的一种或多种如权利要求12的石墨烯纳米带。
14.一种电子、光学或光电子器件,其包含薄膜半导体,所述薄膜半导体包含一种或多种如权利要求12的石墨烯纳米带。
15.如权利要求14的器件,其中所述器件为有机场效应晶体管器件、有机光伏器件或有机发光二极管。
16.一种或多种如权利要求12的石墨烯纳米带在电子、光学或光电子器件中的用途。
17.如权利要求16的用途,其中所述器件为有机场效应晶体管器件、有机光伏器件或有机发光二极管。
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EP2845838A1 (en) | 2013-09-04 | 2015-03-11 | Basf Se | Purification process for graphene nanoribbons |
EP2907791A1 (en) * | 2014-02-13 | 2015-08-19 | Basf Se | Graphene nanoribbons with controlled zig-zag edge and cove edge configuration |
CN105502351B (zh) * | 2015-12-04 | 2017-10-20 | 华南理工大学 | 一种可溶性石墨烯纳米带及其合成方法与应用 |
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WO2017105470A1 (en) * | 2015-12-17 | 2017-06-22 | Intel Corporation | Low-defect graphene-based devices & interconnects |
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US11247905B2 (en) | 2016-11-18 | 2022-02-15 | The Regents Of The University Of California | Synthesis of graphene nanoribbons from monomeric molecular precursors bearing reactive alkyne moieties |
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