CN106632410B - 吡啶并噻吩基吡咯并吡咯二酮及其聚合物 - Google Patents
吡啶并噻吩基吡咯并吡咯二酮及其聚合物 Download PDFInfo
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- CN106632410B CN106632410B CN201611183130.9A CN201611183130A CN106632410B CN 106632410 B CN106632410 B CN 106632410B CN 201611183130 A CN201611183130 A CN 201611183130A CN 106632410 B CN106632410 B CN 106632410B
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- 229920000642 polymer Polymers 0.000 title claims abstract description 52
- -1 thienyl pyrrolo-pyrrole-dione Chemical compound 0.000 title claims abstract description 19
- 230000005669 field effect Effects 0.000 claims abstract description 18
- 239000004065 semiconductor Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000000376 reactant Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000003446 ligand Substances 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 claims description 2
- KYLUAQBYONVMCP-UHFFFAOYSA-N (2-methylphenyl)phosphane Chemical class CC1=CC=CC=C1P KYLUAQBYONVMCP-UHFFFAOYSA-N 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 claims description 2
- MSBPSFSYBUUPMC-UHFFFAOYSA-N furan-2-ylphosphane Chemical class PC1=CC=CO1 MSBPSFSYBUUPMC-UHFFFAOYSA-N 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical group [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 36
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 19
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 18
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 12
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- YKPJEYXZEBLYCI-UHFFFAOYSA-N pyrrolo[3,4-c]pyrrole Chemical class C1=NC=C2C=NC=C21 YKPJEYXZEBLYCI-UHFFFAOYSA-N 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- XIOFCJYPVMLOKU-UHFFFAOYSA-N 2-decyltetradecane Natural products CCCCCCCCCCCCC(C)CCCCCCCCCC XIOFCJYPVMLOKU-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- DBDCNCCRPKTRSD-UHFFFAOYSA-N thieno[3,2-b]pyridine Chemical compound C1=CC=C2SC=CC2=N1 DBDCNCCRPKTRSD-UHFFFAOYSA-N 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 125000004093 cyano group Chemical class *C#N 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- LULAYUGMBFYYEX-UHFFFAOYSA-N metachloroperbenzoic acid Natural products OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- LEIMLDGFXIOXMT-UHFFFAOYSA-N trimethylsilyl cyanide Chemical compound C[Si](C)(C)C#N LEIMLDGFXIOXMT-UHFFFAOYSA-N 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ZDQWESQEGGJUCH-UHFFFAOYSA-N Diisopropyl adipate Chemical compound CC(C)OC(=O)CCCCC(=O)OC(C)C ZDQWESQEGGJUCH-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229930192474 thiophene Natural products 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- XCMISAPCWHTVNG-UHFFFAOYSA-N 3-bromothiophene Chemical compound BrC=1C=CSC=1 XCMISAPCWHTVNG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000004847 absorption spectroscopy Methods 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- AKGGYBADQZYZPD-UHFFFAOYSA-N benzylacetone Chemical compound CC(=O)CCC1=CC=CC=C1 AKGGYBADQZYZPD-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004896 high resolution mass spectrometry Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- BBFCIBZLAVOLCF-UHFFFAOYSA-N pyridin-1-ium;bromide Chemical compound Br.C1=CC=NC=C1 BBFCIBZLAVOLCF-UHFFFAOYSA-N 0.000 description 2
- 150000003222 pyridines Chemical class 0.000 description 2
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- QYCIXUKZMDUDBK-UHFFFAOYSA-N thieno[3,2-b]pyridine-6-carbonitrile Chemical compound N#CC1=CN=C2C=CSC2=C1 QYCIXUKZMDUDBK-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- KVJHGPAAOUGYJX-UHFFFAOYSA-N 1,1,3,3-tetraethoxypropane Chemical compound CCOC(OCC)CC(OCC)OCC KVJHGPAAOUGYJX-UHFFFAOYSA-N 0.000 description 1
- TUCRZHGAIRVWTI-UHFFFAOYSA-N 2-bromothiophene Chemical class BrC1=CC=CS1 TUCRZHGAIRVWTI-UHFFFAOYSA-N 0.000 description 1
- JIZRGGUCOQKGQD-UHFFFAOYSA-N 2-nitrothiophene Chemical compound [O-][N+](=O)C1=CC=CS1 JIZRGGUCOQKGQD-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241001614291 Anoplistes Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000004816 dichlorobenzenes Chemical class 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004776 molecular orbital Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000004079 stearyl 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])[H] 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
-
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Abstract
本发明公开了一种吡啶并噻吩基吡咯并吡咯二酮聚合物。该吡啶并噻吩基吡咯并吡咯二酮聚合物的结构如式Ⅰ所示。以本发明吡啶并噻吩基吡咯并吡咯二酮为有机半导体层制备的有机场效应晶体管的空穴迁移率为1.31×10‑3cm2V‑ 1s‑1，开关比大于103‑104；在有机场效应晶体管器件中有非常高的的应用前景。
Description
技术领域
本发明属于材料领域，涉及一种吡啶并噻吩基吡咯并吡咯二酮及其聚合物。
背景技术
有机共轭聚合物为以π-共轭体系为骨架的一系列有机聚合物材料。由于聚合物材料是有小分子单体利用自聚合或者共聚合成的，所以聚合物的骨架结构可以利用对小分子的合成和修饰进行调整，进而调整其光电特性。同时，有机共轭聚合物在共轭骨架侧面一般都有助溶基团，可以通过该基团的引入调整溶解性。基于以上特殊溶解性以及粘附性的性质，有机共轭聚合物可以使用溶液法进行柔性、大面积加工制备，并且具有价格低廉，对塑料衬底兼容性好等优点，从而可以替代传统的以硅为基础的无机半导体材料。
基于聚合物的有机场效应晶体管(Polymer Based OrganicField-EffectTransistors,简称POFETs)则是一类以该类型的聚合物为半导体材料的有源器件。POFET器件在近年来引起了极为广泛的关注，并且取得了比较大的进展。器件的核心则是有机共轭聚合物材料。近年来，由于给体-受体型聚合物具有比较好的分子内以及分子间的相互作用，目前已经获取了比较高的空穴或者电子迁移率，从而受到了更多的关注与研究。其中，吡咯并吡咯二酮的结构被广泛应用于聚合物半导体材料研发领域。基于该结构的聚合物具有较低的分子能级，简单的合成路线和方法，使其具有广泛的应用到有机场效应晶体管的潜力。因而对吡咯并吡咯二酮前体进行化学修饰，并且合成基于该单体的新型聚合物材料具有十分重要的理论和应用意义。
发明内容
本发明的目的是提供一种吡啶并噻吩基吡咯并吡咯二酮及其聚合物。
本发明所提供的噻唑基吡咯并吡咯二酮聚合物，其结构通式如式I所示，
上述式I中，Ar为常见的给电子共聚单元，具体为如下基团的任意一种：
所述Ar基团中，Z为O、S或Se原子；R2为C1-C20的直链或支链烷基、F原子、含有氧原子或硫原子的C1-C20直链或支链烷基或C1-C20的碳氟直链或支链烷基；
均表示取代位；
R1为C10-C60的直链或支链烷基或为含有氧原子、硅原子、氮原子和氟原子中至少一种的C10-C60的直链或支链烷基；
n为共聚单元个数，具体为5-100；
X1至X4均选自N原子和C原子中的任意一种，且X1至X4中任意一个为N原子时，其余三个基团只能为C原子，且桥连键在N原子的邻位。
上述式I中，R1为C10-C60的直链或支链烷基。或者为含有氧原子、硅原子、氮原子或者氟原子等杂原子的烷基链。
上述式I中，n为具体为5-100；
具体的，R1为2-癸基十四烷基、4-癸基十四烷基或5-癸基十五烷基；
所述为如下基团中的任意一种：
均表示取代位；
所述式I所示聚合物为式VI所示聚合物：
所述式VI中，n为5-100，具体可为28。
本发明提供的制备所述式I所示聚合物的方法，包括如下步骤：
在催化剂和配体的作用下，将式II所示化合物双(溴代吡啶并噻吩基)-2,5-二(烷基)吡咯并[3,4-c]吡咯-1,4(2H,5H)-二酮与反应物a进行聚合反应，反应完毕得到所述式I所示聚合物；
所述式II中，R1、X1至X4的定义与式I中R1、X1至X4的定义相同；
所述反应物a为如下单体中的任意一种：
所述反应物a中，Z和R2的定义与式I中Z和R2的定义相同。
上述方法中，所述催化剂选自四(三苯基膦)钯、二(三苯基膦)二氯化钯、三(二亚苄基丙酮)二钯和二(二亚苄基丙酮)钯中的至少一种；
所述配体选自三苯基膦、三(邻甲苯基)膦和三(呋喃基)膦中的至少一种。
所述反应物a的投料摩尔份数为1.00份；
所述式II所示化合物的投料摩尔份数为0.95～1.05份；
所述催化剂的投料摩尔份数为0.01～0.10份；
所述配体的投料摩尔份数为0.02～0.30份；
所述反应物a与式II所示化合物、催化剂和配体的投料摩尔用量比具体为1.0：1.0：0.005:0.2；
所述聚合反应步骤中，温度为100～120℃，具体可为110℃；
时间为24～72小时，具体可为36小时；
所述聚合反应在溶剂中进行；所述溶剂具体为甲苯、氯苯和二氯苯中的至少一种。
另外，上述方法中作为起始原料的式II所示化合物也属于本发明的保护范围。
具体的，所述式II所示化合物具体可为3,6-双(3-溴噻吩并[3,2-b]吡啶-6-基)-2-5-二(2-癸基-十四烷-1-基)吡咯并[3,4-c]吡咯-1,4(2H,5H)-二酮。
该式II所示化合物双(溴代吡啶并噻吩基)-2,5-二(烷基)吡咯并[3,4-c]吡咯-1,4(2H,5H)-二酮可按照如下步骤制备而得：
(1)利用文献或者专利所报道的方法(US 2012/0245178；US 2014/0094456；10.1021/jo0340307)，合成相应的吡啶并噻吩中间体：
上述式III中，X1至X4的定义与前述式I中X1至X4的定义相同
(2)将步骤1)所得式III所示吡啶并噻吩与间氯过氧苯甲酸(m-CPBA)在二氯甲烷溶液中反应，反应完毕后得到式IV所示的吡啶并噻吩的氧化物；
上述式IV中，Y为N+–O-键，并且每个苯环上有且只有一个Y基团。
(3)将步骤2)所得式IV所示的吡啶并噻吩的氧化物与三乙胺、三甲基氰硅烷在乙腈溶液中反应，得到式V所示的氰基取代的吡啶并噻吩；
上述式V中，X1至X4的定义与前述式I中X1至X4的定义相同，并且氰基的位置在N原子的邻位。
(4)将步骤3)所得式V所示的氰基取代吡啶并噻吩与叔戊醇钠和丁二酸二异丙酯反应，反应完毕后得到式III所示的双(吡啶并噻吩-基)吡咯并[3,4-c]吡咯-1,4(2H,5H)-二酮；
上述式VI中，X1至X4的定义与前述式I中X1至X4的定义相同。
(5)将步骤4)所得式VI所示的双(吡啶并噻吩-基)吡咯并[3,4-c]吡咯-1,4(2H,5H)-二酮与碘代烷和碳酸钾反应，反应完毕后得到式VII所示的双(吡啶并噻吩-基)-2,5-二(烷基)吡咯并[3,4-c]吡咯-1,4(2H,5H)-二酮；
上述式VII中，R1、X1至X4的定义与前述式I中X1至X4的定义相同。
(6)将步骤5)所得式VII中双(吡啶并噻吩-基)-2,5-二(烷基)吡咯并[3,4-c]吡咯-1,4(2H,5H)-二酮与N-溴代丁二酰亚胺(NBS)反应，反应完毕后得到式II所示双(溴带吡啶并噻吩-基)-2,5-二(烷基)吡咯并[3,4-c]吡咯-1,4(2H,5H)-二酮；
上述方法的步骤1)中，可参考文献或者专利所报道的方法(US 2012/0245178；US2014/0094456；10.1021/jo0340307)；
所述步骤2)中，所述吡啶并噻吩与间氯过氧苯甲酸的投料摩尔用量比为1:2～5，优选1:2.5；反应步骤中，温度为0～60℃，时间为6～24小时；
所述步骤3)中，所述三甲基氰硅烷为商业化产品，所述吡啶并噻吩的氧化物与三乙胺、三甲基氰硅烷的投料摩尔用量比为1：1～3：2～5，优选1：1.5：2.5；反应步骤中，温度为100～130℃，时间为12～48小时；
所述步骤4)中，所述碘代烷为C5-C60的直链或支链碘代烷，所述氰基取代吡啶并噻吩与叔戊醇钠和丁二酸二异丙酯的投料摩尔用量比为2.0～2.5：2.5～4.0：1，优选2.5：3.75：1；反应步骤中，温度为90～120℃，时间为3～6小时；
所述步骤5)中，所述双(吡啶并噻吩-基)吡咯并[3,4-c]吡咯-1,4(2H,5H)-二酮与碘代烷和碳酸钾的投料摩尔用量比为1：2.5～4：1～3，优选1：3：3；反应步骤中，温度为100～120℃，时间为6～72小时；
所述步骤6)中，所述N-溴代丁二酰亚胺为商业产品，所述双(吡啶并噻吩-基)-2,5-二(烷基)吡咯并[3,4-c]吡咯-1,4(2H,5H)-二酮与N-溴代丁二酰亚胺的投料摩尔用量比为1：2.0～2.2，优选1：2.1；反应步骤中，温度为60～65℃，时间为24～72小时；
上述步骤1)至步骤6)所述反应均在溶剂中进行。所述步骤2)中，所述溶剂为二氯甲烷；所述步骤3)中，所述溶剂为预干燥的乙腈；所述步骤4)中，所述溶剂为叔戊醇；所述步骤5)中，所述溶剂为预干燥的N,N-二甲基甲酰胺；所述步骤6)中，所述溶剂为预干燥的三氯甲烷。
上述方法的合成路线如图1所示。
另外，上述本发明提供的式I所示聚合物在制备有机效应晶体管中的应用及以式I所示聚合物为半导体层的有机场效应晶体管，也属于本发明的保护范围。
本发明的优点在于：
1、合成方法具有常用简单方法，合成路线较短，反应产率较高，简单高效；原料为商业化产品，可以推广应用工业中的合成；
2、在聚合物主链中引入N原子能够有效的降低聚合物的分子轨道能级，提升骨架的共平面性，以及光热稳定性，可应用于其他光电器件以及功能材料中。
3.以本发明以吡啶并噻吩基吡咯并吡咯二酮聚合物为半导体层制备的POFET器件的迁移率(μ)和开关比比较高(μ可达1.31×10-3cm2V-1s-1，开关比为103-104)，在有机场效应晶体管半导体材料领域中有非常好的开发和应用前景。
附图说明
图1为本发明提供的制备式I所示化合物的合成路线。
图2为以本发明提供的吡啶并噻吩基吡咯并吡咯二酮聚合物的紫外可见吸收光谱图。
图3为以本发明提供的吡啶并噻吩基吡咯并吡咯二酮聚合物的循环伏安曲线图。
图4为以本发明提供的吡啶并噻吩基吡咯并吡咯二酮聚合物场效应晶体管的结构示意图。
图5为以本发明提供的噻唑基吡咯并吡咯二酮聚合物为半导体层的聚合物场效应晶体管的输出特性曲线图。
具体实施方式
下面结合具体实施例对本发明作进一步阐述，但本发明并不限于以下实施例。所述方法如无特别说明均为常规方法。所述原材料如无特别说明均能从公开商业途径获得。下述实施例中，所用Ar的双锡单体5,5’-双(三甲基锡基)-2,2’-联二噻吩为商业化产品或者可通过文献中的方法合成(10.1002/adma.201305981)。
实施例1、聚合物PPyDBT
1)噻吩并[3,2-b]吡啶的合成
将2-硝基噻吩(26g，200mmol)溶于390mL的浓盐酸中，在冰浴下分批加入锡粉(50g，420mmol)，待大部分锡粉溶解之后，加入140mL的乙醇和氯化锌(12g，88mmol)。将该混合物加热至85℃后，然后加入1,1,3,3-四乙氧基丙烷(34.4g，156mmol)，然后反应体系85℃反应1小时。待反应完毕之后，将反应物倒在冰上，用氨水中和至pH＝8后用二氯甲烷萃取后，无水硫酸钠干燥。减压条件下蒸干溶剂后，用硅胶色谱柱分离，洗脱液为石油醚：乙酸乙酯(10:1)。旋干溶剂得到无色油状液体6.57g，产率24.3％。
结构表征数据如下：
质谱：[MS(EI)]m/z:135.01
核磁氢谱和碳谱:1H-NMR(300MHz,CD2Cl2):δ(ppm)8.37(d,J＝4.8Hz,1H),7.90(d,J＝8.1Hz,1H),7.20(d,J＝7.8Hz,1H),7.52(d,J＝5.2Hz,1H),7.04(d,J＝5.2Hz,1H).13C-NMR(75MHz,CD2Cl2):δ161.63,146.25,146.04,133.15,130.84,119.61,118.21.
2)7-氧化-噻吩并[3,2-b]吡啶的合成
将噻吩并[3,2-b]吡啶(5.7g，41.5mmol)溶于20mL二氯甲烷中，在冰浴条件下分批加入间氯过氧苯甲酸(24.7g，含量70％，83mmol)。体系升到室温后反应2小时。反应完成后，减压蒸干溶剂得到白色固体4.38g，产物可以不经过提纯直接投下一步。
3)噻吩并[3,2-b]吡啶-6-腈的合成
氮气保护下，在三口瓶中将7-氧化-噻吩并[3,2-b]吡啶(4.38g，29mmol)，三乙胺(6mL，43.5mmol)溶于25mL预干燥的乙腈溶液中。在一个小时内，冰浴下滴加三甲基氰硅烷，之后110℃回流1小时。反应完毕后，将混合物倒入100mL水中，并且用二氯甲烷萃取，无水硫酸钠干燥。减压条件下蒸干溶剂后，用硅胶色谱柱分离，洗脱液为石油醚：二氯甲烷(2:1)。旋干溶剂得到白色固体3.3g，产率71.0％。
结构表征数据如下：
质谱：[MS(EI)]m/z:160.01
1H-NMR(300MHz,CD2Cl2):δ(ppm)8.13(d,J＝8Hz,1H),7.76(d,J＝6Hz,1H),7.60(d,J＝8Hz,1H)，7.31(d,J＝6Hz,1H).13C-NMR(75MHz,CD2Cl2):δ162.17,134.86,132.08,131.73,129.35,123.45,121.68,117.66.
4)3,6-双(噻吩并[3,2-b]吡啶-6-基)吡咯并[3,4-c]吡咯-1,4(2H,5H)-二酮的合成在氮气保护下，将特戊醇钠(1.72g,15.6mmol)溶于10mL特戊醇溶液中，110℃加热搅拌1h，将噻吩并[3,2-b]吡啶-6-腈(1g，6.24mmol)和丁二酸二异丙酯(0.89g，3.02mmol)溶于20mL的特戊醇中，一个小时以内滴加，滴加完成后110℃反应3小时。反应完毕后，将反应物倒入水和甲醇的混合溶剂中，抽滤并用甲醇洗涤，得到紫色固体1g。产物可以不经过提纯直接投下一步。
5)3,6-双(噻吩并[3,2-b]吡啶-6-基)-2-5-二(2-癸基-十四烷-1-基)吡咯并[3,4-c]吡咯-1，4(2H5H)-二酮的合成
在氮气保护下，将3,6-双(噻吩并[3,2-b]吡啶-6-基)吡咯并[3,4-c]吡咯-1,4(2H,5H)-二酮(0.91g，2.26mmol)、碳酸钾(0.78g，5.65mmol)、1-碘-2-癸基十四烷(4g，8.6mmol)以及10mL N,N-二甲基甲酰胺加入到50mL两口瓶中，110℃反应28小时。反应物降至室温后倒入300mL水中，三滤甲烷萃取，有机相用无水硫酸钠干燥。减压条件下蒸干溶剂后，用硅胶色谱柱分离，洗脱液为石油醚：四氢呋喃(6:1)。旋干溶剂得到深紫色固体0.56g，产率23％。
结构表征数据如下：
质谱：[HR-MS(EI)]m/z:理论值：1075.782997；实际值：1075.783060
1H-NMR(300MHz,CD2Cl2):δ(ppm)9.00(d,J＝9Hz,1H),8.22(d,J＝9Hz,1H),7.66(d,J＝6Hz,1H)，7.31(d,J＝6Hz,1H)，4.33(d,J＝6Hz,2H)，1.55-0.78(m，47H).13C-NMR(75MHz,CD2Cl2):δ162.54,160.98,145.20,144.45,133.14,131.41,130.14,122.99,121.81,111.72,46.26,38.54,31.94,31.57,30.07,29.68,29.56,29.38,26.53,22.71,13.91.
6)式II所示3,6-双(3-溴噻吩并[3,2-b]吡啶-6-基)-2-5-二(2-癸基-十四烷-1-基)吡咯并[3,4-c]吡咯-1,4(2H,5H)-二酮的合成
将3,6-双(噻吩并[3,2-b]吡啶-6-基)-2-5-二(2-癸基-十四烷-1-基)吡咯并[3,4-c]吡咯-1,4(2H,5H)-二酮(0.5g,0.46mmol)溶于10mlL氯仿溶液中，冰浴下分批次加入N-溴代丁二酰亚胺(0.18g,0.98mmol),0℃反应1小时。反应完毕后，将溶液倒入水中，用二氯甲烷萃取，无水硫酸镁干燥。溶剂蒸干后用硅胶色谱柱分离，洗脱液为石油醚：四氢呋喃(6:1)，旋干溶剂得到紫色固体0.42g,产率74％。
质谱：[HR-MS(TOF)]m/z：理论值1231.604021；测量值：1231.604099。
核磁氢谱和碳谱：1H-NMR(300MHz,CD2Cl2):δ(ppm)9.00(d,J＝9Hz,1H),8.07(d,J＝6Hz,1H),7.45(s,1H),4.27(d,J＝9Hz,2H),1.56-0.79(m,47H).13C-NMR(75MHz,CD2Cl2)δ162.41,161.50,144.88,144.26,134.01,130.30,124.69,123.84,119.87,111.92,46.34,38.56,31.93,31.57,30.04,29.70,29.66,29.54,29.35,26.53,22.67,13.86..
7)式I所示聚合物PPyDBT的合成
将式II所示3,6-双(3-溴噻吩并[3,2-b]吡啶-6-基)-2-5-二(2-癸基-十四烷-1-基)吡咯并[3,4-c]吡咯-1,4(2H,5H)-二酮(61.6mg,0.05mmol)、5,5’-双(三甲基锡基)-2,2’-联二噻吩(24.6mg,0.05mmol)、三(二亚苄基丙酮)二钯(2.25mg，0.0025mmol)、三(邻甲苯基)膦(3.03mg，0.01mmol)和甲苯(3mL)加入到反应瓶中，在氩气中进行三次冷冻-抽气-解冻循环除氧，然后将反应混合物加热到110℃反应36h。冷却后，加入80mL甲醇，室温下搅拌0.5h，过滤。得到的聚合物装入索氏提取器抽提。先用甲醇、丙酮、正己烷抽提至无色，除去小分子和催化剂，再用三氯甲烷提取得到最终产物43mg，产率69.5％。所得聚合物分子式如式VI所示。
分子量：GPC：Mn＝35.0kDa，PDI＝2.18，n为28。
核磁氢谱：1H NMR(300MHz,C2D2Cl4)δ(ppm):7.90(br,3H),6.97(br,2H),4.36(br,2H),1.69-0.82(m,47H)。
实施例2、实施例1所得化合物PPyDBT的光学、电学性能和场效应晶体管性能
1)化合物PPyDBT的光谱和电化学性能
图2为化合物PPyDBT在溶液和薄膜中的紫外可见吸收光谱。
由图2可知，PPyDBT的光学带隙为1.37eV，并且该聚合物具有比较强的分子内电荷转移峰，表明该聚合物主链的前线轨道重叠更好。
图3为化合物PPyDBT的循环伏安曲线。测定在CHI660c电化学工作站进行，用传统的三电极结构测试。测试在乙腈溶液中进行。
2)化合物PPyDBT的场效应晶体管性能
图4为有机场效应晶体管的结构示意图，如图所示，以高掺杂的硅片为衬底和栅电极，300纳米厚的二氧化硅为绝缘层，金为源电极和漏电极。源漏电极利用光刻的方法制备，基底依次在丙酮、二次水、乙醇中超声清洗后于80℃真空干燥，并用等离子体处理15分钟。然后用十八烷基三氯化硅烷(OTS)对已经活化的二氧化硅表面进行修饰，实施例1所得式I所示聚合物PPyDBT为半导体层，厚度为70nm。将聚合物材料溶于邻二氯苯中通过甩膜的方法在OTS修饰的基底上形成薄膜厚度为40nm)，并在热台上退火5分钟。所制备的场效应晶体管器件的电学性质在室温下用Keithley4200SCS半导体测试仪测量。
POFET性能的最重要的两个参数是：载流子的迁移率(μ)和器件的开关比(Ion/Ioff)。迁移率是指：在单位电场下，载流子的平均迁移速率(单位是cm2V-1s-1),它反映了在电场下的载流子如空穴或电子在半导体中的迁移能力。开关比的定义为：晶体管在“开”状态和“关”状态下的电流之比，它直接反映了器件开关性能的优劣。一个具有高性能并且能用实际应用的场效应晶体管，应当具有尽可能高的迁移率和开关比。
图5为基于PPyDBT所制备的场效应晶体管的转移特性曲线和输出特性曲线。
由上图可知，利用本发明实施例1所得聚合物场效应晶体管显示了很好的线性区和饱和区，说明基于吡啶并噻吩基吡咯并吡咯二酮的聚合物的OFET器件具有很好的场效应调控性能。
载流子迁移率可由方程计算得出：
IDS＝(W/2L)Ciμ(VG–VT)2(饱和区，VDS＝VG–VT)
其中，IDS为漏极电流，μ为载流子迁移率，VG为栅极电压，VT为阈值电压，W为沟道宽度(W＝1400微米)，L为沟道长度，Ci为绝缘体电容(单位面积电容(SiO2相对介电常数3.9，SiO2层300nm)。利用(IDS，sat)1/2对VG作图，并作线性回归，可由此回归线的斜率推算出载流子迁移率(μ)，由回归线与X轴的截点求得VT。迁移率可以根据公式从转移曲线的斜率计算得出。
开关比可由图5源漏电流的最大值与最小值之比得出。
以合成的PPyDBT聚合物为有机层做成了有机场效应晶体管器件，迁移率为1.31×10-3cm2V-1s-1，开关比为103-104。
实验结果表明，以吡啶并噻吩基吡咯并吡咯二酮为构架单元的聚合物是优良的聚合物半导体材料。本发明并不限于所报道的这一个材料，通过改变吡啶N上的相对位置或者使用不同的侧链取代基、给体共聚单元可以得到一系列的聚合物，且本发明给出的合成方法简单、有效，对于研究聚合物半导体材料的结构与性能的关系帮助巨大，对进一步设计和制备高性能的材料有着十分重要的指导意义。
Claims (13)
1.式I所示聚合物，
所述式I中，Ar为如下基团的任意一种：
所述Ar基团中，Z为S；R2为H；
均表示取代位；
R1为2-癸基十四烷基、4-癸基十四烷基或5-癸基十五烷基；
n为5-100；
所述为如下基团中的任意一种：
均表示取代位。
2.根据权利要求1所述的聚合物，其特征在于：
所述式I所示聚合物为式VI所示聚合物：
所述式VI中，n为5-100或28。
3.一种制备权利要求1-2任一所述式I所示聚合物的方法，包括如下步骤：
在催化剂和配体的作用下，将式II所示化合物与反应物a进行聚合反应，反应完毕得到所述式I所示聚合物；
所述式II中，R1和X的定义均与权利要求1中式I中的定义相同；
所述反应物a为如下单体中的任意一种：
所述反应物a中，Z和R2的定义与权利要求1式I中Z和R2的定义相同。
4.根据权利要求3所述的方法，其特征在于：所述催化剂选自四(三苯基膦)钯、二(三苯基膦)二氯化钯、三(二亚苄基丙酮)二钯和二(二亚苄基丙酮)钯中的至少一种；
所述配体选自三苯基膦、三(邻甲苯基)膦和三(呋喃基)膦中的至少一种。
5.根据权利要求4所述的方法，其特征在于：所述反应物a的投料摩尔份数为1.00份；
所述式II所示化合物的投料摩尔份数为0.95～1.05份；
所述催化剂的投料摩尔份数为0.01～0.10份；
所述配体的投料摩尔份数为0.02～0.30份。
6.根据权利要求5所述的方法，其特征在于：所述反应物a与式II所示化合物、催化剂和配体的投料摩尔用量比为1.0：1.0：0.005:0.2。
7.根据权利要求3所述的方法，其特征在于：所述聚合反应步骤中，温度为100℃～120℃；
时间为24小时～72小时。
8.根据权利要求3所述的方法，其特征在于：所述聚合反应步骤中，温度为110℃；
时间为36小时。
9.根据权利要求3-8中任一所述的方法，其特征在于：所述聚合反应在溶剂中进行。
10.根据权利要求9所述的方法，其特征在于：所述溶剂选自甲苯、氯苯和邻二氯苯中的至少一种。
11.式II所示化合物，
所述式II中，R1和X的定义均与权利要求1中式I中的定义相同。
12.权利要求1-2任一所述式I所示聚合物在制备有机效应晶体管中的应用。
13.一种有机场效应晶体管，其特征在于：所述有机场效应晶体管中，构成半导体层的材料为权利要求1-2任一所述式I所示聚合物。
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