TW201504242A - 以稠合二酮基吡咯并吡咯為主之聚合物 - Google Patents
以稠合二酮基吡咯并吡咯為主之聚合物 Download PDFInfo
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- TW201504242A TW201504242A TW103121620A TW103121620A TW201504242A TW 201504242 A TW201504242 A TW 201504242A TW 103121620 A TW103121620 A TW 103121620A TW 103121620 A TW103121620 A TW 103121620A TW 201504242 A TW201504242 A TW 201504242A
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- Prior art keywords
- alkyl
- group
- substituted
- halogen
- alkoxy
- Prior art date
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- 229920000642 polymer Polymers 0.000 title claims abstract description 158
- 239000004065 semiconductor Substances 0.000 claims abstract description 30
- 238000013086 organic photovoltaic Methods 0.000 claims abstract description 13
- 230000005669 field effect Effects 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 239000006096 absorbing agent Substances 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 427
- 229910052739 hydrogen Inorganic materials 0.000 claims description 176
- 239000001257 hydrogen Substances 0.000 claims description 150
- -1 nitro, cyano, vinyl Chemical group 0.000 claims description 134
- 125000003118 aryl group Chemical group 0.000 claims description 110
- 125000003545 alkoxy group Chemical group 0.000 claims description 100
- 229910052736 halogen Inorganic materials 0.000 claims description 97
- 150000002367 halogens Chemical class 0.000 claims description 93
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 85
- 125000001072 heteroaryl group Chemical group 0.000 claims description 65
- GBXQPDCOMJJCMJ-UHFFFAOYSA-M trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C GBXQPDCOMJJCMJ-UHFFFAOYSA-M 0.000 claims description 62
- 229910052760 oxygen Inorganic materials 0.000 claims description 57
- 150000002431 hydrogen Chemical class 0.000 claims description 56
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 54
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 54
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 49
- 150000001875 compounds Chemical class 0.000 claims description 47
- 239000001301 oxygen Substances 0.000 claims description 43
- 125000005843 halogen group Chemical group 0.000 claims description 39
- 125000003342 alkenyl group Chemical group 0.000 claims description 38
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 38
- 229910052786 argon Inorganic materials 0.000 claims description 34
- 125000004434 sulfur atom Chemical group 0.000 claims description 34
- GJVFBWCTGUSGDD-UHFFFAOYSA-L pentamethonium bromide Chemical compound [Br-].[Br-].C[N+](C)(C)CCCCC[N+](C)(C)C GJVFBWCTGUSGDD-UHFFFAOYSA-L 0.000 claims description 33
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 32
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 28
- 229910052717 sulfur Inorganic materials 0.000 claims description 28
- 229910052799 carbon Inorganic materials 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 24
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 claims description 22
- 125000001188 haloalkyl group Chemical group 0.000 claims description 21
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 20
- 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 claims description 19
- 125000000304 alkynyl group Chemical group 0.000 claims description 14
- 125000005842 heteroatom Chemical group 0.000 claims description 13
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- 229910052740 iodine Inorganic materials 0.000 claims description 9
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 8
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 8
- 125000000623 heterocyclic group Chemical group 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- RFCAUADVODFSLZ-UHFFFAOYSA-N 1-Chloro-1,1,2,2,2-pentafluoroethane Chemical compound FC(F)(F)C(F)(F)Cl RFCAUADVODFSLZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 4
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 125000003107 substituted aryl group Chemical group 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- PLXPTFQGYWXIEA-UHFFFAOYSA-N nitroformonitrile Chemical group [O-][N+](=O)C#N PLXPTFQGYWXIEA-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 26
- 239000000203 mixture Substances 0.000 description 66
- 239000010410 layer Substances 0.000 description 54
- 238000007639 printing Methods 0.000 description 50
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 45
- 239000000976 ink Substances 0.000 description 41
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 40
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 36
- 238000009472 formulation Methods 0.000 description 34
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 32
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical class [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 31
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 29
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 230000015572 biosynthetic process Effects 0.000 description 24
- 238000003786 synthesis reaction Methods 0.000 description 23
- 239000011541 reaction mixture Substances 0.000 description 22
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 19
- 239000004793 Polystyrene Substances 0.000 description 18
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 17
- 239000002585 base Substances 0.000 description 17
- 125000004432 carbon atom Chemical group C* 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 239000002253 acid Substances 0.000 description 16
- 239000011230 binding agent Substances 0.000 description 16
- 229920002223 polystyrene Polymers 0.000 description 16
- 239000011734 sodium Substances 0.000 description 16
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 15
- 125000001931 aliphatic group Chemical group 0.000 description 14
- 239000000049 pigment Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 13
- 235000019439 ethyl acetate Nutrition 0.000 description 13
- 229910003472 fullerene Inorganic materials 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000000178 monomer Substances 0.000 description 11
- KCTFIWDZXROTJT-FQEVSTJZSA-N 1-[(2s)-2,3-dihydroxypropyl]-5-[[4-[[6-(2,2,2-trifluoroethyl)thieno[2,3-d]pyrimidin-4-yl]amino]piperidin-1-yl]methyl]indole-2-carbonitrile Chemical compound C=1C=C2N(C[C@H](O)CO)C(C#N)=CC2=CC=1CN(CC1)CCC1NC1=NC=NC2=C1C=C(CC(F)(F)F)S2 KCTFIWDZXROTJT-FQEVSTJZSA-N 0.000 description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- 239000012212 insulator Substances 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 238000002844 melting Methods 0.000 description 10
- 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 10
- TVTJUIAKQFIXCE-HUKYDQBMSA-N 2-amino-9-[(2R,3S,4S,5R)-4-fluoro-3-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-7-prop-2-ynyl-1H-purine-6,8-dione Chemical compound NC=1NC(C=2N(C(N(C=2N=1)[C@@H]1O[C@@H]([C@H]([C@H]1O)F)CO)=O)CC#C)=O TVTJUIAKQFIXCE-HUKYDQBMSA-N 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 9
- 229910052731 fluorine Inorganic materials 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 9
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 9
- 0 CC(*)(C*)c1c(C)c([s]c(C2=C(C3O)C4=C5N3C(*)=C(*)c3c5[s]c5c3[s]c(-c3c(C)c(*)c(C6=SC(*(*)*)=C(*)*6)[s]3)c5*)c3C(*)=C(*)N2C4=O)c3[s]1 Chemical compound CC(*)(C*)c1c(C)c([s]c(C2=C(C3O)C4=C5N3C(*)=C(*)c3c5[s]c5c3[s]c(-c3c(C)c(*)c(C6=SC(*(*)*)=C(*)*6)[s]3)c5*)c3C(*)=C(*)N2C4=O)c3[s]1 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 150000002430 hydrocarbons Chemical group 0.000 description 8
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 8
- QBWKPGNFQQJGFY-QLFBSQMISA-N 3-[(1r)-1-[(2r,6s)-2,6-dimethylmorpholin-4-yl]ethyl]-n-[6-methyl-3-(1h-pyrazol-4-yl)imidazo[1,2-a]pyrazin-8-yl]-1,2-thiazol-5-amine Chemical compound N1([C@H](C)C2=NSC(NC=3C4=NC=C(N4C=C(C)N=3)C3=CNN=C3)=C2)C[C@H](C)O[C@H](C)C1 QBWKPGNFQQJGFY-QLFBSQMISA-N 0.000 description 7
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 7
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 235000019198 oils Nutrition 0.000 description 7
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 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 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 229910052737 gold Inorganic materials 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 6
- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- 238000004528 spin coating Methods 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- AOSZTAHDEDLTLQ-AZKQZHLXSA-N (1S,2S,4R,8S,9S,11S,12R,13S,19S)-6-[(3-chlorophenyl)methyl]-12,19-difluoro-11-hydroxy-8-(2-hydroxyacetyl)-9,13-dimethyl-6-azapentacyclo[10.8.0.02,9.04,8.013,18]icosa-14,17-dien-16-one Chemical compound C([C@@H]1C[C@H]2[C@H]3[C@]([C@]4(C=CC(=O)C=C4[C@@H](F)C3)C)(F)[C@@H](O)C[C@@]2([C@@]1(C1)C(=O)CO)C)N1CC1=CC=CC(Cl)=C1 AOSZTAHDEDLTLQ-AZKQZHLXSA-N 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 125000004648 C2-C8 alkenyl group Chemical group 0.000 description 5
- 229940126657 Compound 17 Drugs 0.000 description 5
- 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 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 101150003085 Pdcl gene Proteins 0.000 description 5
- 125000004414 alkyl thio group Chemical group 0.000 description 5
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- 239000011593 sulfur Substances 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 4
- YSUIQYOGTINQIN-UZFYAQMZSA-N 2-amino-9-[(1S,6R,8R,9S,10R,15R,17R,18R)-8-(6-aminopurin-9-yl)-9,18-difluoro-3,12-dihydroxy-3,12-bis(sulfanylidene)-2,4,7,11,13,16-hexaoxa-3lambda5,12lambda5-diphosphatricyclo[13.2.1.06,10]octadecan-17-yl]-1H-purin-6-one Chemical compound NC1=NC2=C(N=CN2[C@@H]2O[C@@H]3COP(S)(=O)O[C@@H]4[C@@H](COP(S)(=O)O[C@@H]2[C@@H]3F)O[C@H]([C@H]4F)N2C=NC3=C2N=CN=C3N)C(=O)N1 YSUIQYOGTINQIN-UZFYAQMZSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- OPFJDXRVMFKJJO-ZHHKINOHSA-N N-{[3-(2-benzamido-4-methyl-1,3-thiazol-5-yl)-pyrazol-5-yl]carbonyl}-G-dR-G-dD-dD-dD-NH2 Chemical compound S1C(C=2NN=C(C=2)C(=O)NCC(=O)N[C@H](CCCN=C(N)N)C(=O)NCC(=O)N[C@H](CC(O)=O)C(=O)N[C@H](CC(O)=O)C(=O)N[C@H](CC(O)=O)C(N)=O)=C(C)N=C1NC(=O)C1=CC=CC=C1 OPFJDXRVMFKJJO-ZHHKINOHSA-N 0.000 description 4
- 229910003849 O-Si Inorganic materials 0.000 description 4
- 229910003872 O—Si Inorganic materials 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 238000006069 Suzuki reaction reaction Methods 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 4
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 4
- 239000002041 carbon nanotube Substances 0.000 description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 125000000392 cycloalkenyl group Chemical group 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
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- WKGAHGXHQGURDG-UHFFFAOYSA-N benzenecarboximidamide;hydrobromide Chemical compound Br.NC(=N)C1=CC=CC=C1 WKGAHGXHQGURDG-UHFFFAOYSA-N 0.000 description 1
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- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006367 bivalent amino carbonyl group Chemical group [H]N([*:1])C([*:2])=O 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
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- XNEYCQMMVLAXTN-UHFFFAOYSA-N carbonic acid;magnesium Chemical compound [Mg].OC(O)=O XNEYCQMMVLAXTN-UHFFFAOYSA-N 0.000 description 1
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- 150000007942 carboxylates Chemical class 0.000 description 1
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- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 229940125758 compound 15 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000012937 correction 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
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical group CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- UZVGSSNIUNSOFA-UHFFFAOYSA-N dibenzofuran-1-carboxylic acid Chemical compound O1C2=CC=CC=C2C2=C1C=CC=C2C(=O)O UZVGSSNIUNSOFA-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
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- HDZRDZCQFYUOHE-UHFFFAOYSA-N ditert-butyl-(1-phenylindol-2-yl)phosphane Chemical compound CC(C)(C)P(C(C)(C)C)C1=CC2=CC=CC=C2N1C1=CC=CC=C1 HDZRDZCQFYUOHE-UHFFFAOYSA-N 0.000 description 1
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- 150000002170 ethers Chemical class 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
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- 239000010433 feldspar Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
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- 238000009499 grossing Methods 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 125000005446 heptyloxy 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])O* 0.000 description 1
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- 229920006270 hydrocarbon resin Polymers 0.000 description 1
- DOUHZFSGSXMPIE-UHFFFAOYSA-N hydroxidooxidosulfur(.) Chemical group [O]SO DOUHZFSGSXMPIE-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
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- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
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- 239000001023 inorganic pigment Substances 0.000 description 1
- 229910002094 inorganic tetrachloropalladate Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000001977 isobenzofuranyl group Chemical group C=1(OC=C2C=CC=CC12)* 0.000 description 1
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- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
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- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
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- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 description 1
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- 230000001590 oxidative effect Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- ZVSLRJWQDNRUDU-UHFFFAOYSA-L palladium(2+);propanoate Chemical compound [Pd+2].CCC([O-])=O.CCC([O-])=O ZVSLRJWQDNRUDU-UHFFFAOYSA-L 0.000 description 1
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- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 description 1
- WOTPFVNWMLFMFW-ISLYRVAYSA-N para red Chemical compound OC1=CC=C2C=CC=CC2=C1\N=N\C1=CC=C(N(=O)=O)C=C1 WOTPFVNWMLFMFW-ISLYRVAYSA-N 0.000 description 1
- JQQSUOJIMKJQHS-UHFFFAOYSA-N pentaphenyl group Chemical group C1=CC=CC2=CC3=CC=C4C=C5C=CC=CC5=CC4=C3C=C12 JQQSUOJIMKJQHS-UHFFFAOYSA-N 0.000 description 1
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- 125000001644 phenoxazinyl group Chemical group C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
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- 239000011591 potassium Substances 0.000 description 1
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- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
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- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical group CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
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- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
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- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
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- 238000001226 reprecipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 125000006413 ring segment Chemical group 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- MABNMNVCOAICNO-UHFFFAOYSA-N selenophene Chemical compound C=1C=C[se]C=1 MABNMNVCOAICNO-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 238000007764 slot die coating Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- DVUVKWLUHXXIHK-UHFFFAOYSA-N tetraazanium;tetrahydroxide Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[OH-].[OH-].[OH-].[OH-] DVUVKWLUHXXIHK-UHFFFAOYSA-N 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- VJYJJHQEVLEOFL-UHFFFAOYSA-N thieno[3,2-b]thiophene Chemical compound S1C=CC2=C1C=CS2 VJYJJHQEVLEOFL-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- BWHOZHOGCMHOBV-BQYQJAHWSA-N trans-benzylideneacetone Chemical compound CC(=O)\C=C\C1=CC=CC=C1 BWHOZHOGCMHOBV-BQYQJAHWSA-N 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
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- 238000009736 wetting Methods 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
-
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Abstract
本發明係關於包含一或多個式
□之(重複)單元之聚合物,
其中
Y為式□之基團;及其作為IR吸收
劑,在有機裝置中、尤其有機光伏打裝置及光電二極體中、或含有二極體及/或有機場效電晶體之裝置中作為有機半導體的用途。本發明聚合物可具有於有機溶劑中之極佳溶解性及極佳成膜特性。此外,當將本發明聚合物用於有機場效電晶體、有機光伏打裝置及光電二極體時,可觀測到高能量轉換效率、極佳場效遷移率、良好開/關電流比及/或極佳穩定性。
Description
本發明係關於包含一或多個式(I)之(重複)單元的聚合物及其作為IR吸收劑,在有機裝置中、尤其有機光伏打裝置及光電二極體中、或含有二極體及/或有機場效電晶體之裝置中作為有機半導體的用途。本發明聚合物可具有有機溶劑中之極佳溶解性及極佳成膜特性。此外,當本發明聚合物用於有機場效電晶體、有機光伏打裝置及光電二極體時,可觀測到高能量轉換效率、極佳場效遷移率、良好開/關電流比及/或極佳穩定性。
近年來,二酮基吡咯并吡咯(DPP)已成為尤其在太陽能電池中具有有前景之光電特性之寡聚物及聚合物之一種廣泛研究之有機構築嵌段。參見D.Chandran及Kwang-Sup Lee,Macromolecular Research 21(2013)272。
US2011/0004004係關於式
化合物:及其在
如二極體、有機場效電晶體及/或太陽能電池之有機裝置中作為有機半導體之用途。
WO2011/144566係關於包含一或多個式之(重複)單
元之聚合物,式或
之聚合物,其中A為式
之基團,及其在有機裝置中、
尤其有機光伏打裝置(太陽能電池)及光電二極體中、或含有二極體及/或有機場效電晶體之裝置中作為有機半導體的用途。Daniel T Gryko等人,Organic Letters 14(2012)2670揭示π-膨脹二酮基吡咯并吡咯之合成方法。三步策略似乎極普遍且由製備二酮基吡咯并吡咯開始,隨後用溴乙醛二乙醇縮乙醛進行N-烷基化並進行親電子芳族取代。最終反應區域選擇性地提供螢光染料。
WO2013/092474(PCT/EP2012/075762)(享有早於本發明之優先權日期,但在本發明之優先權日期之後公佈)係關於公式(III)化合物:
其中Ar指示同芳族或雜芳族系統。
PCT/EP2014/054060(享有早於本發明之優先權日期,但在本發明
之優先權日期之後公佈)係關於式之新穎化合
物,其可用作具有獨特結構及特性之雜環染料。此等化合物可以三步合成由簡單基質獲得。
本發明之一個目標為提供聚合物,其在用於有機場效電晶體、有機光伏打裝置(太陽能電池)及光電二極體時展示高能量轉換效率、極佳場效遷移率、良好開/關電流比及/或極佳穩定性。本發明之另一目標為提供具有極低能帶隙之聚合物,其亦可用作紅外(IR)吸收劑。
該目標已藉由包含一或多個式
之(重複)單元的(共軛)聚
合物解決,其中
Y為式之基團;
a為0、1、2或3,a'為0、1、2或3;b為0、1、2或3;b'為0、1、2或3;c為0、1、2或3;c'為0、1、2或3;Ar及Ar'指示同芳族或雜芳族系統,其可將經取代或未經取代。
R1、R1'、R2及R2'可相同或不同且選自以下:氫、C1-C100烷基,其可視情況經C1-C12烷基、C1-C12烷氧基、鹵素、C5-C12環烷基、硝基、氰基、乙烯基、烯丙基、C6-C24芳基、C2-C20雜芳基、矽烷基或矽氧烷基取代一或多次;及/或可視情況雜有-O-、-S-、-NR39-、CONR39-、NR39CO-、-COO-、-CO-或-OCO-,C2-C100烯基,其可視情況經C1-C12烷基、C1-C12烷氧基、鹵素、C5-C12環烷基、硝基、氰基、乙烯基、烯丙基、C6-C24芳基、C2-C20雜
芳基、矽烷基或矽氧烷基取代一或多次;及/或可視情況雜有-O-、-S-、-NR39、CONR39-、NR39CO-、-COO-、-CO-或-OCO-,C3-C100炔基,其可視情況經C1-C12烷基、C1-C12烷氧基、鹵素、C5-C12環烷基、硝基、氰基、乙烯基、烯丙基、C6-C24芳基、C2-C20雜芳基、矽烷基或矽氧烷基取代一或多次;及/或可視情況雜有-O-、-S-、-NR39-、CONR39-、NR39CO-、-COO-、-CO-或-OCO-,C3-C12環烷基,其可視情況經C1-C12烷基、C1-C12烷氧基、鹵素、C5-C12環烷基、硝基、氰基、乙烯基、烯丙基、C6-C24芳基、C2-C20雜芳基、矽烷基或矽氧烷基取代一或多次;及/或可視情況雜有-O-、-S-、-NR39-、CONR39-、NR39CO-、-COO-、-CO-或-OCO-,C6-C24芳基,其可視情況經C1-C12烷基、C1-C12烷氧基、鹵素、C5-C12環烷基、硝基、氰基、乙烯基、烯丙基、C6-C24芳基、C2-C20雜芳基、矽烷基或矽氧烷基取代一或多次;C2-C20雜芳基,其可視情況經C1-C12烷基、C1-C12烷氧基、鹵素、C5-C12環烷基、硝基、氰基、乙烯基、烯丙基、C6-C24芳基、C2-C20雜芳基、矽烷基或矽氧烷基取代一或多次;-CO-C1-C18烷基、-CO-C5-C12環烷基或-COO-C1-C18烷基;R39為氫、C1-C18烷基、C1-C18鹵烷基、C7-C25芳基烷基或C1-C18醯基,
Ar1、Ar1'、Ar2、Ar2'、Ar3及Ar3'彼此獨立地為
諸如 ,諸如
,其中
X為-O-、-S-、-NR8-、-Si(R11)(R11')-、-Ge(R11)(R11')-、-C(R7)(R7')-、-C(=O)-、-C(=CR104R104')-、
,尤其或 ,諸如
,諸如
,其中、
X1為S、O、NR107-、-Si(R117)(R117')-、Ge(R117)(R117')-、-
C(R108)(R109)-、-C(=O)-、-C(=CR104R104')-、
R3及R3'彼此獨立地為氫;鹵素;鹵化C1-C25烷基,尤其CF3;氰基;C1-C25烷基,尤其C3-C25烷基,其可視情況雜有一或多個氧或硫原子;C7-C25芳基烷基或C1-C25烷氧基;R4、R4'、R5、R5'、R6及R6'彼此獨立地為氫;鹵素;鹵化C1-C25烷基,尤其CF3;氰基;C1-C25烷基,尤其C3-C25烷基,其可視情況雜有一或多個氧或硫原子;C7-C25芳基烷基或C1-C25烷氧基;R7、R7'、R9及R9'彼此獨立地為氫;C1-C25烷基,尤其C3-C25烷基,其可視情況雜有一或多個氧或硫原子;或C7-C25芳基烷基,R8及R8'彼此獨立地為氫;C6-C18芳基;經C1-C18烷基或C1-C18烷氧基取代之C6-C18芳基;或C1-C25烷基,尤其C3-C25烷基,其可視情況雜有一或多個氧或硫原子;或C7-C25芳基烷基,
R11及R11'彼此獨立地為C1-C25烷基,尤其C1-C8烷基;C7-C25芳基烷基;或苯基,其可經C1-C8烷基及/或C1-C8烷氧基取代一至三次;R12及R12'彼此獨立地為氫;鹵素;氰基;C1-C25烷基,尤其C3-C25烷基,其可視情況雜有一或多個氧或硫原子;C1-C25烷氧基;C7-C25芳基烷基;或,其中R13為C1-C10烷基或三(C1-C8烷基)矽烷基;R104及R104'彼此獨立地為氫;C1-C18烷基;氰基;COOR103;C6-C10芳基,其可視情況經G取代;或C2-C8雜芳基,其可視情況經G取代,R103及R103'彼此獨立地為C1-C100烷基,尤其C3-C25烷基;經E取代及/或雜有D之C1-C25烷基;C7-C25芳基烷基;C6-C24芳基;經G取代之C6-C24芳基;C2-C20雜芳基;或經G取代之C2-C20雜芳基,R105、R105'、R106及R106'彼此獨立地為氫;鹵素;氰基;C1-C25烷基,其可視情況雜有一或多個氧或硫原子;C7-C25芳基烷基;或C1-C18烷氧基,R107為氫;C7-C25芳基烷基;C6-C18芳基;經C1-C18烷基或C1-C18烷氧基取代之C6-C18芳基;C1-C18全氟烷基;C1-C25烷基;尤其C3-C25烷基,其可雜有-O-或-S-;或-COOR103;R103係如上文所定義;R108及R109彼此獨立地為H;C1-C25烷基;經E取代及/或雜有D之C1-C25烷基;C7-C25芳基烷基;C6-C24芳基;經G取代之C6-C24芳基;C2-C20雜芳基;經G取代之C2-C20雜芳基;C2-C18烯基;C2-C18炔基;C1-C18烷氧基;經E取代及/或雜有D之C1-C18烷氧基;或C7-C25芳烷基,或R108及R109一起形成式=CR110R111之基團,其中R110及R111彼此獨立地為H;C1-C18烷基;經E取代及/或雜有D之C1-C18烷基;C6-C24芳基;經G取代之C6-C24芳基;或C2-C20雜芳基;
或經G取代之C2-C20雜芳基,或R108及R109一起形成五或六員環,其視情況可經以下取代:C1-C18烷基、經E取代及/或雜有D之C1-C18烷基、C6-C24芳基、經G取代之C6-C24芳基、C2-C20雜芳基、經G取代之C2-C20雜芳基、C2-C18烯基、C2-C18炔基、C1-C18烷氧基、經E取代及/或雜有D之C1-C18烷氧基、或C7-C25芳烷基,D為-CO-、-COO-、-S-、-O-或-NR112-,E為C1-C8硫烷氧基、C1-C8烷氧基、CN、-NR112R113、-CONR112R113或鹵素,G為E或C1-C18烷基,及R112及R113彼此獨立地為H;C6-C18芳基;經C1-C18烷基或C1-C18烷氧基取代之C6-C18芳基;C1-C18烷基;或雜有-O-之C1-C18烷基,R114為C1-C25烷基,尤其C3-C25烷基,其可視情況雜有一或多個氧或硫原子,R115及R115'彼此獨立地為氫;鹵素;氰基;C1-C25烷基,尤其C3-C25烷基,其可視情況雜有一或多個氧或硫原子;C1-C25烷氧基;C7-C25芳基烷基;或,其中R116為C1-C10烷基或三(C1-C8烷基)矽烷基;R117及R117'彼此獨立地為C1-C25烷基,尤其C1-C8烷基;C7-C25芳基烷基;或苯基,其可經C1-C8烷基及/或C1-C8烷氧基取代一至三次;R118、R119、R120及R121彼此獨立地為氫;鹵素;鹵化C1-C25烷基,尤其CF3;氰基;C1-C25烷基,尤其C3-C25烷基,其可視情況雜有一或多個氧或硫原子;C7-C25芳基烷基;或C1-C25烷氧基;R122及R122'彼此獨立地為氫;C6-C18芳基;經C1-C18烷基或C1-C18烷氧基取代之C6-C18芳基;或C1-C25烷基,尤其C3-C25烷基,其可視情況雜有一或多個氧或硫原子;或C7-C25芳基烷基。
本發明之聚合物較佳為共軛聚合物。較佳為包含式(I)之重複單元的聚合物。
在一較佳實施例中,本發明係針對包含式
之重複單元的聚合物,其
中Y為式之基團,a為0或1,a'為0或1,b為
0,b'為0,c為0且c'為0;且Ar1及Ar1'係如上文所定義。
在該實施例中,聚合物較佳包含一或多個式之
(重複)單元,其中Y為式之基團,其中a為0、
1、2或3,尤其0或1;a'為0、1、2或3,尤其0或1;其中Ar1、Ar1'、Ar及Ar'以及R1、R1'、R2及R2'係如技術方案1所定義。
更佳地,a為0,a'為0,b為0,b'為0,c為0且c'為0。
在一較佳實施例中,Ar1及Ar1'彼此獨立地為下式之基團:(XIa);(XIb);(XIc);(XIe);(XIf);(XIk);(XIm);(XIn);(XIq);(XIr);(XIu);(XIw);(XIx);(XIII),諸如(XIIIa)及(XIIIb);或(XIV),諸如(XIVb)。較佳地,Ar1及Ar1'彼此獨立地為式XIa、XIb、XIe、XIf、XIr或XIIIa之基團。更佳地,Ar1及Ar1'彼此獨立地為式
XIa、XIb或XIf之基團,最佳為式XIa之基團。
R1、R1'、R2及R2'較佳選自氫:C1-C100烷基,其可視情況經C1-C12烷基、C1-C12烷氧基、鹵素、C5-C12環烷基、硝基、氰基、乙烯基、烯丙基、C6-C24芳基或C2-C20雜芳基取代一或多次;及/或可視情況雜有-O-、-S-、-NR39-、-COO-、-CO-或-OCO-,C2-C100烯基,其可視情況經C1-C12烷基、C1-C12烷氧基、鹵素、C5-C12環烷基、硝基、氰基、乙烯基、烯丙基、C6-C24芳基或C2-C20雜芳基取代一或多次;及/或可視情況雜有-O-、-S-、-NR39-、-COO-、-CO-或-OCO-,C3-C100炔基,其可視情況經C1-C12烷基、C1-C12烷氧基、鹵素、C5-C12環烷基、硝基、氰基、乙烯基、烯丙基、C6-C24芳基或C2-C20雜芳基取代一或多次;及/或可視情況雜有-O-、-S-、-NR39-、-COO-、-CO-或-OCO-,C3-C12環烷基,其可視情況經C1-C12烷基、C1-C12烷氧基、鹵素、C5-C12環烷基、硝基、氰基、乙烯基、烯丙基、C6-C24芳基或C2-C20雜芳基取代一或多次;及/或可視情況雜有-O-、-S-、-NR39-、-COO-、-CO-或-OCO-,C6-C24芳基,其可視情況經C1-C12烷基、C1-C12烷氧基、鹵素、C5-C12環烷基、硝基、氰基、乙烯基、烯丙基、C6-C24芳基或C2-C20雜芳基取代一或多次;C2-C20雜芳基,其可視情況經C1-C12烷基、C1-C12烷氧基、鹵素、C5-C12環烷基、硝基、氰基、乙烯基、烯丙基、C6-C24芳基或C2-C20雜芳基取代一或多次;-CO-C1-C18烷基、-CO-C5-C12環烷基或-COO-C1-C18烷基,其中R39為C1-C18烷基。
本發明聚合物或包含本發明聚合物之有機半導電材料、層或組
分宜可於有機光伏打裝置(太陽能電池)中、光電二極體中、有機場效電晶體(OFET)中、作為IR吸收劑、於薄膜電晶體(TFT)中、積體電路(IC)中、射頻識別(RFID)標記、裝置或組件中、有機發光二極體(OLED)中、有機發光電晶體(OLET)中、平板顯示器中、顯示幕之背光中、雷射二極體中、光導體中、光偵測器、電子照相記錄裝置中、有機記憶體裝置中、感測器裝置中、聚合物發光二極體(PLEDS)中之電荷注入層、電荷遷移層或夾層中、有機電漿子發射二極體(OPED)中、肖特基二極體(Schottky diode)中、平坦化層中、抗靜電膜中、聚合物電解質膜(PEM)中、導電基板中、導電圖案中、電池中之電極材料中、配向層中、生物感應器中、生物晶片中、安全標記中、安全裝置中及偵測及鑑別DNA序列之組件或裝置中使用。
術語聚合物包含寡聚物以及聚合物。本發明寡聚物之重量均分子量為<4,000道爾頓。本發明聚合物之重量平均分子量較佳為4,000道爾頓或4,000道爾頓以上,尤其4,000至2,000,000道爾頓,極尤其10,000至1,000,000道爾頓,更佳10,000至100,000道爾頓且最佳20,000至60,000道爾頓。分子量根據高溫凝膠滲透層析(HT-GPC)使用聚苯乙烯標準物來測定。本發明聚合物之多分散性較佳為1.01至10,更佳1.1至3.0,最佳1.5至2.5。本發明聚合物較佳為共軛聚合物。
本發明寡聚物之重量平均分子量較佳低於4,000道爾頓。
在本發明之一實施例中,聚合物為式
之聚合物,其中n通常在4至
1000,尤其4至200,極尤其5至150之範圍內。
在R1、R1'、R2及R2'之定義中,矽烷基或矽氧烷基意謂-SiR161R162R163或-O-SiR161R162R163。
R161、R162及R163彼此獨立地為氫、C1-C25烷基、可視情況經C1-C4烷基取代之C3-C12環烷基、C1-C25鹵烷基、C2-C25烯基、-O-SiR164R165R166、-(O-SiR164R165)d-R166、C1-C25烷氧基、C3-C24(雜)芳氧基、NR167R168、鹵素、C1-C25醯氧基、苯基、經C1-C25烷基、鹵素、氰基或C1-C25烷氧基取代1至3次之苯基;較佳為氫、C1-C25烷基、可視情況經C1-C4烷基取代之C3-C12環烷基、C1-C25鹵烷基、C2-C25烯基、-O-SiR164R165R166、-(O-SiR164R165)d-R166或苯基;更佳為C1-C8烷基、可視情況經C1-C4烷基取代之C5-C6環烷基、C1-C8鹵烷基、C2-C8烯基、-O-SiR164R165R166、-(O-SiR164R165)d-R166或苯基;最佳為C1-C8烷基、C1-C8鹵烷基、尤其經氟原子取代一或多次之C1-C8烷基、-O-SiR164R165R166或-(O-SiR164R165)d-R166。
R164、R165及R166彼此獨立地為氫;C1-C25烷基、視情況經C1-C4烷基取代之C3-C12環烷基、C1-C25鹵烷基、C2-C25烯基、-O-SiR169R170R171、-(O-SiR169R170)d-R171、C1-C25烷氧基、C3-C24(雜)芳氧基、NR167R168、鹵素、C1-C25醯氧基、苯基、經C1-C25烷基、鹵素、氰基或C1-C25烷氧基取代1至3次之苯基;較佳為氫;C1-C25烷基、C1-C25鹵烷基、C2-C25烯基、-O-SiR169R170R171、;-(O-SiR169R170)d-R171或苯基;更佳為C1-C8烷基、C1-C8鹵烷基、C2-C8烯基、-O-SiR169R170R171、-(O-SiR169R170)d-R171或苯基;最佳為C1-C8烷基、C1-C8鹵烷基、尤其經氟原子取代一或多次之C1-C8烷基、-O-SiR169R170R171或-(O-SiR169R170)d-R171。
R169、R170及R171彼此獨立地為氫、C1-C25烷基、可視情況經C1-C4烷基取代之C3-C12環烷基、C1-C25鹵烷基、C2-C25烯基、-O-Si(CH3)3、C1-C28烷氧基、C3-C24(雜)芳氧基、NR167R168、鹵素、C1-C25醯氧基、苯基、經C1-C25烷基、鹵素、氰基或C1-C25烷氧基取代1至3次之苯基;較佳為氫、C1-C25烷基、C1-C25鹵烷基、C2-C25烯基、-O-
Si(CH3)3或苯基;更佳為C1-C8烷基、C1-C8鹵烷基、C2-C8烯基、-O-Si(CH3)3或苯基;最佳為C1-C8烷基、C1-C8鹵烷基,尤其經氟原子取代一或多次之C1-C8烷基;或-O-Si(CH3)3。
d為1至50,較佳1至40,甚至更佳1至30,又更佳1至20,更佳1至15,又更佳1至10,且甚至更佳1至5,且最佳1至3之整數。
R167及R168彼此獨立地為氫、C1-C25烷基、C1-C25鹵烷基、C3-C25烯基或苯基;較佳為C1-C25烷基、C1-C25鹵烷基或苯基;最佳為C1-C25烷基。
在一尤其較佳實施例中,R161、R162及R163彼此獨立地為C1-C25烷基,尤其C1-C8烷基;C1-C25鹵烷基,尤其C1-C8鹵烷基,諸如-CF3、-(CH2)2CF3、-(CH2)2(CF2)5CF3及-(CH2)2(CF2)6CF3;C2-C25烯基,尤其C2-C8烯基;C3-C12環烷基,尤其C5-C6環烷基,其可視情況經C1-C4烷基取代;苯基,-O-SiR164R165R166或-(O-SiR164R165)d-R166。在基團-O-SiR164R165R166之情況下,R164、R165及R166彼此獨立地為C1-C8烷基、C1-C8鹵烷基、C2-C8烯基或苯基。在基團-(O-SiR164R165)d-R166之情況下,R164及R165彼此獨立地為C1-C8烷基,R166為C1-C8烷基或苯基且d為2至5整數。
下文展示式-SiR161R162R163或-O-SiR161R162R163之基團之實例:
(*表明與碳原子鍵結,連接矽烷基或矽氧
烷基)。
R1、R1'、R2及R2'可相同或不同且較佳選自氫,C1-C100烷基,其可視情況經C1-C12烷基、C1-C12烷氧基、鹵素、C5-C12環烷基、氰基、C6-C24芳基、C2-C20雜芳基取代一或多次及/或可能、視情況雜有-O-、-S-、-COO-或-OCO-,C2-C100烯基,其可視情況經C1-C12烷基、C1-C12烷氧基、鹵素、C5-C12環烷基、氰基、C6-C24芳基、C2-C20雜芳基取代一或多次及/或可視情況雜有-O-、-S-、-COO-或-OCO-,C3-C100炔基,其可視情況經C1-C12烷基、C1-C12烷氧基、鹵素、C5-C12環烷基、氰基、C6-C24芳基、C2-C20雜芳基取代一或多次及/或可視情況雜有-O-、-S-、-COO-或-OCO-,C4-C12環烷基,其可視情況經C1-C12烷基、C1-C12烷氧基、鹵素、C5-C12環烷基、氰基、C6-C24芳基、C2-C20雜芳基取代一或多次及/或可視情況雜有-O-、-S-、-COO-或-OCO-,C6-C24芳基,其可視情況經C1-C12烷基、C1-C12烷氧基、鹵素、C5-C12環烷基、氰基、C6-C24芳基、C2-C20雜芳基取代一或多次,C2-C20雜芳基,其可視情況經C1-C12烷基、C1-C12烷氧基、鹵
素、C5-C12環烷基、氰基、C6-C24芳基、C2-C20雜芳基、-CO-C1-C18烷基、-CO-C5-C12環烷基及-COO-C1-C18烷基取代一或多次。
更佳地,R1、R1'、R2及R2'選自氫、C1-C50烷基、C1-C50鹵烷基、C7-C25芳基烷基、C2-C50烯基、C2-C50鹵烯基、烯丙基C5-C12環烷基、苯基或萘基,其可視情況經C1-C12烷基或C1-C12烷氧基、-CO-C1-C18烷基、-CO-C5-C12環烷基及-COO-C1-C18烷基取代一或多次。甚至更佳地,R1、R1'、R2及R2'為C1-C50烷基。又更佳地,R1、R1'、R2及R2'為C1-C36烷基,諸如甲基、乙基、正丙基、異丙基、正丁基、第二丁基、異丁基、第三丁基、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、異庚基、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及2-乙基己基、正壬基、癸基、十一烷基,尤其正十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、2-乙基-己基、2-丁基-己基、2-丁基-辛基、2-己基癸基、2-癸基-十四烷基、十七烷基、十八烷基、二十烷基、二十一烷基、二十二烷基或二十四烷基。較佳地,R1及R1'具有相同含義且獨立地R2及R2'具有相同含義。
更佳地,若R1及R1'為氫,則R2及R2'不為氫,或若R1及R1'不為氫,則R2及R2'為氫。
最佳地,R2及R2'為氫且R1及R1'不為氫。
基團R1、R2、R1'及R2'宜可由式表示,其中m1=n1+2
且m1+n124。諸如R1、R2、R1'及R2'之對掌性側鏈任一者均可為均勻對掌性或外消旋的,其可影響化合物之形態。
較佳地,R103彼此獨立地為C1-C25烷基、經鹵素取代之C1-C25烷
基、C7-C25芳基烷基或苯基;更佳為C1-C25烷基。
在一較佳實施例中,Ar1及Ar1'彼此獨立地為下式之基團:(XIa);(XIb);(XIc);(XIe);(XIf);(XIk);(XIm);(XIn);(XIq);(XIr);(XIu);(XIw);(XIx);(XIII),諸如(XIIIa)及(XIIIb);或(XIV),諸如(XIVb)。較佳地,Ar1及Ar1'彼此獨立地為式XIa、XIb、XIe、XIf、XIr或XIIIa之基團。更佳地,Ar1及Ar1'彼此獨立地為式XIa、XIb或XIf之基團,最佳為式XIa之基團。
較佳地,R3及R3'彼此獨立地為氫、鹵素、CF3、氰基、C1-C25烷基或C1-C25烷氧基;更佳為CF3、氰基或C1-C25烷基;最佳為氫、或C1-C25烷基。
較佳地,R104及R104'彼此獨立地為氫、氰基或C1-C25烷基基團,更佳為氫或C1-C25烷基,最佳為氫。
較佳地,R4、R4'、R5、R5'、R6及R6'彼此獨立地為氫、鹵素、CF3、氰基、C1-C25烷基或C1-C25烷氧基,更佳為氫、CF3、氰基或C1-C25烷基;最佳為氫或C1-C25烷基。
較佳地,R7、R7'、R9及R9'彼此獨立地為氫、C1-C25烷基,更佳為C4-C25烷基。
較佳地,R8及R8'彼此獨立地為氫、C1-C25烷基、可視情況雜有一或多個氧或硫原子之C1-C25烷基、或C7-C25芳基烷基,更佳為氫或C1-C25烷基。
較佳地,R11及R11'彼此獨立地為C1-C25烷基、尤其C1-C8烷基或苯基;更佳為C1-C8烷基。
較佳地,R12及R12'彼此獨立地為氫、C1-C25烷基、C1-C25烷氧基或,其中R13為C1-C10烷基或三(C1-C8烷基)矽烷基,更佳為氫、C1-C25烷基或C1-C25烷氧基。
較佳地,Ar2、Ar2'、Ar3、Ar3'、Ar4及Ar4'彼此獨立地具有Ar1之
含義。
在一較佳實施例中,Ar2、Ar2'、Ar3、Ar3'、Ar4及Ar4'彼此獨立地為下式之基團:(XIa);(XIb);(XIc);(XIe);(XIf);(XIk);(XIm);(XIn);(XIr);(XIx);(XIz);(XIIj);(XIII),諸如(XIIIa)及(XIIIb);或(XIV),諸如(XIVb)。較佳地,Ar2、Ar2'、Ar3、Ar3'、Ar4及Ar4'彼此獨立地為式XIa、XIb、XIf、XIr、XIIj或XIIIa之基團更佳地,Ar2、Ar2'、Ar3、Ar3'、Ar4及Ar4'彼此獨立地為式XIa、XIb、XIf或XIIj之基團,最佳為式XIa之基團。
較佳地,R105、R105'、R106及R106'彼此獨立地為氫、鹵素、氰基、C1-C25烷基或C1-C18烷氧基,更佳為C1-C25烷基或C1-C18烷氧基,最佳為氫或C1-C25烷基。
R107較佳為氫、C1-C25烷基、可視情況雜有一或多個氧或硫原子之C1-C25烷基、或C7-C25芳基烷基,更佳為氫或C1-C25烷基,最佳為C4-C25烷基。
較佳地,R108及R109彼此獨立地為H、C1-C25烷基、經E取代及/或雜有D之C1-C25烷基、C7-C25芳基烷基、C2-C18烯基或C7-C25芳烷基,或R108及R109一起形成5或6員環,其可視情況經C1-C18烷基、經E取代及/或雜有D之C1-C18烷基、C6-C24芳基、經G取代之C6-C24芳基取代,D為-CO-、-COO-、-S-或-O-,E為C1-C8硫烷氧基、C1-C8烷氧基、CN或鹵素,G為E或C1-C18烷基。更佳地,R108及R109彼此獨立地為H、C1-C25烷基或C7-C25芳基烷基。最佳地,R108及R109彼此獨立地為H或C1-C25烷基。
D較佳為-CO-、-COO-、-S-或-O-,更佳為-COO-、-S-或-O-,最佳為-S-或-O-。
較佳地,E為C1-C8硫烷氧基、C1-C8烷氧基、CN或鹵素,更佳為C1-C8烷氧基、CN或鹵素,最佳為鹵素,尤其F。
較佳地,R112及R113彼此獨立地為H;C1-C18烷基;或雜有-O-之C1-C18烷基,更佳為H或C1-C18烷基;最佳為C1-C18烷基。
在一較佳實施例中,本發明係針對包含一或多個式
之(重複)單元之聚合物,其中Y為式
之基團,其中
R1、R1'、R2及R2'可不同,但較佳相同,較佳選自氫、C1-C50烷基、C1-C50鹵烷基、C7-C25芳基烷基、C2-C50烯基、C2-C50鹵烯基、烯丙基、C5-C12環烷基、苯基及萘基,其可視情況經C1-C12烷基或C1-C12烷氧基、-CO-C1-C18烷基、-CO-C5-C12環烷基及-COO-C1-C18烷基取代一或多次;更佳為C1-C50烷基;最佳為C1-C38烷基;a為0、1、2或3,a'為0、1、2或3;其中Ar1及Ar1'係如上文所定義;且R103、R103'、D及E係如上文所定義。
較佳地,a為0、1或2,a'為0、1或2。
a及a'可不同,但較佳相同,a及a'較佳為0或1,更佳為0。
在式(基團Y)中,
Ar及Ar'為彼此獨立地選擇之同雜芳族或雜芳族系統,其可經取代或未經取代。同芳族或雜芳族體系(Ar及Ar')可不同,但較佳相同。
同芳族或雜芳族系統(分別為Ar及Ar')較佳選自由以下組成之群:苯、呋喃、噻吩、吡咯、硒吩、苯并呋喃、苯并噻吩、吲哚、苯并硒吩、噻吩并[2,3-b]噻吩、噻吩并[3,2-b]噻吩及9H-茀,其可視情
況經取代。Ar及Ar'較佳彼此獨立地選自 尤其
及,其中點線表示與6員環鍵結(點線指示在
氮原子之對位與碳原子鍵結,點線指示在氮原子之間位與碳
原子鍵結)。
R1、R1'、R2及R2'可相同或不同且係選自氫或C1-C38烷基,尤其其中在R1、R2對中,一者為氫且另一者為C8-C36烷基,且在R1'、R2'對中,一者為氫且另一者為C8-C36烷基。
R99'"為氫、C1-C25烷基或經一或多個鹵素原子取代及/或雜有一或多個氧原子之C1-C25烷基,或兩個部分R99可形成5或6員烷基環。
在另一個較佳實施例中,Ar及Ar'彼此獨立地選自
,諸如 諸如
諸如
,諸如 或,諸如
R91、R91'及R91"彼此獨立地為H;鹵素、尤其F;氰基;C1-C25烷氧基;經一或多個鹵素原子、尤其F取代之C1-C25烷基;或C1-C25烷基,R92為H;鹵素、尤其F;氰基;C1-C25烷氧基;或C1-C25烷基,R95、R96、R97及R98彼此獨立地為H;鹵素、尤其F;氰基;C1-C25烷基;C1-C25烷氧基;或經一或多個鹵素原子、尤其F取代之C1-C25烷基;X91為O、S、Se或NR94,X92為O、S、CR99R99'或NR130,X93為O、S或NR130,X94為O、S或NR130,R94及R130彼此獨立地為氫;C6-C18芳基;經C1-C18烷基、鹵素、尤其F取代之C6-C18芳基;或C1-C18烷氧基;可視情況雜有一或多個氧或硫原子及/或視情況經一或多個鹵素原子、尤其F取代之C1-C25烷基;或C7-C25芳基烷基,及R99、R99'、R99"及R99*彼此獨立地為氫、C1-C25烷基或經一或多個鹵素原子取代及/或雜有一或多個氧原子之C1-C25烷基,或兩個部分R99及R99'或R99"及R99*可形成5或6員烷基環,其可視情況經一或多個鹵素原子取代及/或雜有一或多個氧原子。較佳地,R99、R99'、R99"及R99*彼此獨立地為氫、C1-C25烷基或經一或多個鹵素原子取代及/或雜有一或多個氧原子之C1-C25烷基。更佳地,R99、R99'、R99"及R99*彼此獨立地為氫、C1-C25烷基或雜有一或多個氧原子之C1-C25烷基。最佳
地,R99、R99'、R99"及R99*彼此獨立地為C3-C25烷基或雜有一或多個氧原子之C3-C25烷基。
R121、R122、R123、R124及R125彼此獨立地為氫、鹵素、C6-C18芳基;經C1-C18烷基、鹵素取代之C6-C18芳基;或C1-C18烷氧基;可視情況雜有一或多個氧或硫原子及/或視情況經一或多個鹵素原子、尤其F取代之C1-C25烷基;或C7-C25芳基烷基;較佳為氫、鹵素、C1-C18烷氧基或C1-C25烷基;最佳為氫。
較佳地,X91為O、S或Se,更佳地,X91為O或S,最佳地X91為S。
較佳地,X92、X93及X94為O或S,更佳為S。
較佳地,R94為氫或可視情況雜有一或多個氧或硫原子之C1-C25烷基。更佳地,R94為C1-C25烷基。
R95、R96、R97及R98較佳為氫;鹵素、尤其F;C1-C25烷基或經一或多個鹵素原子、尤其F取代之C1-C25烷基;更佳為氫或C1-C25烷基,最佳為H。
在一較佳實施例中,本發明係針對包含一或多個式
之(重複)單元之聚合物,
其中a、b、c、a'、b'、c'、Ar1、Ar1'、Ar2、Ar2'、Ar3及Ar3'係如上文所定義,Y為下式之基團:
,其中
R1、R1'、R2及R2'可相同或不同且選自氫或C1-C38烷基;R91、R91'及R91"彼此獨立地為H;鹵素、尤其F;氰基;C1-C25烷氧基;經一或多個鹵素原子、尤其F取代之C1-C25烷基;或C1-C25烷基,R92為H;鹵素、尤其F;氰基;C1-C25烷氧基;或C1-C25烷基,R94為氫;C6-C18芳基;經C1-C18烷基、鹵素、尤其F取代之C6-C18芳基;或C1-C18烷氧基;可視情況雜有一或多個氧或硫原子及/或視情況經一或多個鹵素原子、尤其F取代之C1-C25烷基;或C7-C25芳基烷基;及R99'"為氫、C1-C25烷基或經一或多個鹵素原子取代及/或雜有一或
多個氧原子之C1-C25烷基,或兩個基團R99可形成5或6員烷基環。
包含重複單元(I)及式(Ya)、(Yb)、(Yc)、(Yd)、(Ye)、(Yf)、(Yg)、(Yh)、(Yi)、(Yj)、(Yk)、(Yl)、(Ym)、(Yn)及(Yo)之Y的聚合物較佳。包含重複單元(I)及式(Ya)、(Yb)、(Yd)、(Yf)、(Yh)、(Yi)、(Yj)、(Ym)及(Yo)之Y的聚合物更佳。包含重複單元(I)及式(Yb)、(Yd)、(Yj)及(Yo)之Y的聚合物最佳。
R91較佳為H、C1-C25烷氧基或C1-C25烷基;更佳為氫或C1-C25烷基,最佳為氫。
R91'較佳為H、C1-C25烷氧基或C1-C25烷基;更佳為氫或C1-C25烷基,最佳為氫。
R91"較佳為H、C1-C25烷氧基或C1-C25烷基;更佳為氫或C1-C25烷基,最佳為氫。
R92較佳為H、C1-C25烷氧基或C1-C25烷基;更佳為氫或C1-C25烷基,最佳為氫。
在式Ya至Yo之重複單元中,R2及R2'為氫的重複單元更佳。R1及R1'可不同,但較佳相同且選自C1-C25烷基、C2-C25烯基、可視情況雜有一或多個氧原子及/或視情況經基團ESi或一或多個鹵素原子、尤其F取代之C2-C25烯基;C3-C10雜芳基;經鹵素、C1-C18烷基或C1-C18烷氧基取代之C3-C10雜芳基;或可視情況雜有一或多個氧原子及/或視情況經基團ESi或一或多個鹵素原子、尤其F取代之C1-C25烷基。更佳地,R1為C1-C25烷基或可視情況雜有一或多個氧原子及/或視情況經基團ESi或一或多個氟原子取代之C1-C25烷基。最佳地,R1為C1-C25烷基。
在另一個較佳實施例中,本發明係針對包含一或多個式
之(重複)單元之聚合物,
其中
a、b、c、a'、b'、c'、Ar1、Ar1'、Ar2、Ar2'、Ar3及Ar3'係如上文所定義,Y為下式之基團:
,其中
R1、R1'、R2及R2'可相同或不同且選自氫或C1-C38烷基;R99、R99'、R99"及R99*彼此獨立地為氫、C1-C25烷基或雜有一或多個氧原子之C1-C25烷基;較佳為C3-C25烷基或雜有一或多個氧原子之C3-C25烷基;
R121、R122、R123、R124及R125彼此獨立地為氫、鹵素、C1-C18烷氧基或C1-C25烷基;較佳為氫;及R130為氫;C6-C18芳基;經C1-C18烷基、鹵素、尤其F取代之C6-C18芳基;或C1-C18烷氧基;可視情況雜有一或多個氧或硫原子及/或視情況經一或多個鹵素原子、尤其F取代之C1-C25烷基;或C7-C25芳基烷基。
在該實施例中,包含重複單元(I)及式(Yo*)、(Yp)、(Yw)、(Yx)、(Yy)、(Yz)、(Yaa)、(Yab)、(Yac)、(Yad)、(Yae)、(Yaf)、(Yag)、(Yah)、(Yai)、(Yaj)、(Yak)、(Yal)、(Yam)及(Yan)之Y的聚合物為較佳。包含重複單元(I)及式(Yo*)、(Yw)、(Yx)、(Yy)、(Yz)、(Yac)、(Yad)、(Yaf)、(Yag)、(Yah)、(Yai)、(Yak)、(Yal)、(Yam)及(Yan)之Y的聚合物為更佳。包含重複單元(I)及式(Yo*)、(Yw)、(Yac)、(Yaf)、(Yag)、(Yah)、(Yak)及(Yam)之Y的聚合物甚至更佳。包含重複單元(I)及式(Yo*)、(Yaf)及(Yah)之Y,尤其重複單元(I)及式(Yo*)之Y的聚合物為最佳。
在式Yo*至Yan之重複單元中,R2及R2'為氫的重複單元更佳。R1及R1'可不同,但較佳相同,且係選自氫、C1-C25烷基、C2-C25烯基、可視情況雜有一或多個氧原子及/或視情況經基團ESi或一或多個鹵素原子、尤其F取代之C2-C25烯基;C3-C10雜芳基;經鹵素、C1-C18烷基或C1-C18烷氧基取代之C3-C10雜芳基;或可視情況雜有一或多個氧原子及/或視情況經基團ESi或一或多個鹵素原子、尤其F取代之C1-C25烷基。更佳地,R1為氫、C1-C25烷基或可視情況雜有一或多個氧原子及/或視情況經基團ESi或一或多個氟原子取代之C1-C25烷基。最佳地,R1為氫或C1-C25烷基。在另一個較佳實施例中,式Yo*至Yan之重複單元中之R1、R1'、R2及R2'為氫。
在另一個實施例中,本發明係針對包含式及
之(重複)單元之聚合物,其中
其中A為式(I)之重複單元,及-COM1-為具有Ar1之含義的重複單元,其中Ar1係如上文所定義
或為式之基團,
s為1,t為1,u為0或1,v為0或1,及Ar14、Ar15、Ar16及Ar17彼此獨立地為下式之基團:
其中X5及X6中之一者為N且另一者為CR14,及R17及R17'彼此獨立地為H或C1-C25烷基。
較佳地,Ar14、Ar15、Ar16及Ar17彼此獨立地為式或
之基團,最佳為式之基團。
在一較佳實施例中,-COM1-為下式之基團:(XIa);(XIb);(XIc);(XIe);(XIf);(XIk);(XIm);(XIn);(XIr);(XIx);(XIz);(XIIj);(XIII),諸如(XIIIa)或(XIIIb);或(XIV),諸如(XIVb)。較佳地,-COM1-為式XIa、XIb、XIf、XIr、XIIj或XIIIa之基團。更佳地,-COM1-為式XIa、XIb、XIf或XIIj之基團;最佳為式XIa之基團。
式之基團之實例為
在一尤其較佳實施例中,重複單元-COM1-為下式之基團:
,其中R3及R3'彼此獨立地為氫或C1-C25烷
基,R104及R104'較佳彼此獨立地為氫、氰基或C1-C25烷基,且R17及R17'彼此獨立地為H或C1-C25烷基、尤其C6-C25烷基,其可視情況雜有一或多個氧原子。
在另一個較佳實施例中,重複單元-COM1-為下式之基團:
,其中
R4及R5彼此獨立地為氫或C1-C25烷基;
R12及R12'為H或C1-C25烷基;R105、R105'、R106及R106'彼此獨立地為氫、鹵素、氰基、C1-C25烷基或C1-C25烷氧基,尤其為氫或C1-C25烷基;R107為C1-C25烷基,及R108及R109彼此獨立地為C1-C25烷基,其可雜有一或多個氧原子。
在本發明之一較佳實施例中,聚合物為包含式
之重複單元的共聚物,尤其式
之共聚物,其中A及COM1係如上文所定義;
n為產生4,000至2,000,000道爾頓,更佳10,000至1,000,000且最佳10,000至100,000道爾頓之分子量的數目。n通常在4至1000,尤其4至200,極尤其5至150之範圍內。
在一較佳實施例中,本發明係針對A為式(Ya)、(Yb)、(Yc)、(Yd)、(Ye)、(Yf)、(Yg)、(Yh)、(Yi)、(Yj)、(Yk)、(Yl)、(Ym)、(Yn)或(Yo),尤其式(Ya)、(Yb)、(Yd)、(Yf)、(Yh)、(Yi)、(Yj)、(Ym)或(Yo),且極尤其式(Yb)、(Yd)、(Yj)或(Yo)之重複單元的聚合
物,且為下式之基團: 或,其中R3、R3'、R17及R17'彼此獨
立地為氫或C1-C25烷基,且R104及R104'較佳彼此獨立地為氫、氰基或C1-C25烷基。
在另一個較佳實施例中,本發明係針對A為式(Yo*)、(Yw)、(Yx)、(Yy)、(Yz)、(Yac)、(Yad)、(Yaf)、(Yag)、(Yah)、(Yai)、(Yak)、(Yal)、(Yam)或(Yan),尤其式(Yo*)、(Yw)、(Yac)、(Yaf)、(Yag)、(Yah)、(Yak)或(Yam),極尤其式(Yo*)、(Yaf)或(Yah)之重複
單元的聚合物,且為下式之基團: 或,其中R3、R3'、R17及R17'彼
此獨立地為氫或C1-C25烷基,且R104及R104'較佳彼此獨立地為氫、氰基或C1-C25烷基。在重複單元(Yo*)、(Yaf)或(Yah)中,(Yo*)更佳。
在另一個較佳實施例中,本發明係針對A為式(Ya)、(Yb)、(Yc)、(Yd)、(Ye)、(Yf)、(Yg)、(Yh)、(Yi)、(Yj)、(Yk)、(Yl)、(Ym)、(Yn)或(Yo),尤其式(Ya)、(Yb)、(Yd)、(Yf)、(Yh)、(Yi)、(Yj)、(Ym)或(Yo),且極尤其式(Yb)、(Yd)、(Yj)或(Yo)之重複單元
的聚合物,且為下式之基團: 或,其中
R4及R5彼此獨立地為氫或C1-C25烷基;R12及R12'為H或C1-C25烷基;R105、R105'、R106及R106'彼此獨立地為氫、鹵素、氰基、C1-C25烷基或C1-C25烷氧基,尤其為氫或C1-C25烷基;R107為C1-C25烷基,R108及R109彼此獨立地為C1-C25烷基,其可雜有一或多個氧原子。
在另一個較佳實施例中,本發明係針對A為式(Yo*)、(Yw)、(Yx)、(Yy)、(Yz)、(Yac)、(Yad)、(Yaf)、(Yag)、(Yah)、(Yai)、(Yak)、(Yal)、(Yam)或(Yan),尤其式(Yo*)、(Yw)、(Yac)、(Yaf)、(Yag)、(Yah)、(Yak)或(Yam),極尤其式(Yo*)、(Yaf)或(Yah)之重複單元的聚合物,且
為下式之基團: 或,其中
R4及R5彼此獨立地為氫或C1-C25烷基;R12及R12'為H或C1-C25烷基;R105、R105'、R106及R106'彼此獨立地為氫、鹵素、氰基、C1-C25烷
基或C1-C25烷氧基,尤其為氫或C1-C25烷基;R107為C1-C25烷基,R108及R109彼此獨立地為C1-C25烷基,其可雜有一或多個氧原子。在(Yo*)、(Yaf)或(Yah)重複單元中,(Yo*)更佳。
在式VII'之聚合物中,如技術方案9中所定義之式(Ia-1)、(Ia-2)、(Ia-3)、(Ia-4)、(Ia-5)、(Ia-6)、(Ia-7)、(Ia-8)、(Ia-9)、(Ia-10)、(Ia-11)、(Ia-12)、(Ia-13)、(Ia-14)、(Ia-15)、(Ia-16)、(Ia-17)、(Ia-18)、(Ia-19)、(Ia-20)、(Ia-21)、(Ia-22)、(Ia-23)、(Ia-24)、(Ia-25)、(Ia-26)、(Ia-27)、(Ia-28)、(Ia-29)及(Ia-30)之聚合物較佳。
n較佳為4至1000,尤其4至200,極尤其5至100,R1較佳為C1-C38烷基,尤其C8-C36烷基,R2為氫;R3及R3'較佳為氫、鹵素、氰基、C1-C25烷基或C1-C25烷氧基,尤其為氫或C1-C25烷基;R17及R17'較佳為H或C1-C25烷基;R91、R91'及R91"較佳為H或C1-C25烷基,R92為H或C1-C25烷基,及R99為C1-C25烷基或C1-C25烷基。
根據本發明之一個實施例,式之聚合物(Ia-1)、(Ia-3)、(Ia-4)、(Ia-6)、(Ia-7)、(Ia-8)、(Ia-9)、(Ia-10)、(Ia-11)、(Ia-13)、(Ia-15)及(Ia-17)更佳。
聚合物之實例為技術方案10中所示之聚合物P-1至P-25。與聚合物P-15相比,聚合物P-1至P-14及P-16至P-25較佳。
本發明之聚合物可包含2種以上不同重複單元,諸如與彼此不同
之重複單元A、B及D。若聚合物包含式及之重複單
元,則其較佳為式之(無規)共聚物,其中x=0.995至
0.005,γ=0.005至0.995,尤其x=0.2至0.8,y=0.8至0.2,且其中x+y=1。A為式(I)之重複單元,D*為重複單元-COM1-,且B為重複單元-COM1-或式(I)之重複單元;其限制條件為A、B及D*彼此不同。對於A及-COM1-,應用與上文相同之偏好。
可例如藉由鈴木反應(Suzuki reaction)來獲得式VII之共聚物。芳族酸鹽與鹵化物(尤其為溴化物)之縮合反應(通常稱作「鈴木反應」)容許存在如N.Miyaura及A.Suzuki在Chemical Reviews,第95卷,第457-2483頁(1995)中所報導之各種有機官能基。較佳催化劑為2-二環己基膦基-2',6'-二-烷氧基聯苯/乙酸鈀(II)、三烷基-鏻鹽/鈀(0)衍生物及三烷基膦/鈀(0)衍生物。尤其較佳之催化劑為2-二環己基膦基-2',6'-二-甲氧基聯苯(sPhos)/乙酸鈀(II)及四氟硼酸三第三丁基鏻((t-Bu)3P*HBF4)/參(二亞苄基丙酮)二鈀(0)(Pd2(dba)3)及三第三丁基膦(t-Bu)3P/參(二亞苄基丙酮)二鈀(0)(Pd2(dba)3)。此反應可應用於製備高分子量聚合物及共聚物。
為製備對應於式VII之聚合物,在Pd及三苯膦之催化作用下,使式X10-A-X10之二鹵化物與一定(等莫耳)量之對應於式X11-COM1-X11之二酸或二酸鹽反應;或使式X10-COM1-X10之二鹵化物與一定(等莫耳)量對應於式X11-A-X11之二酸或二酸鹽之反應,其中X10為鹵素,尤其Br或I;且X11在每次出現時獨立地為-B(OH)2、-B(OY1)2、
或,其中Y1在每次出現時獨立地為C1-C10烷基且
Y2在每次出現時獨立地為C2-C10伸烷基,諸如-CY3Y4-CY5Y6或-CY7Y8-CY9Y10-CY11Y12-,其中Y3、Y4、Y5、Y6、Y7、Y8、Y9、Y10、Y11及Y12彼此獨立地為氫或C1-C10烷基,尤其-C(CH3)2C(CH3)2-、-
CH2C(CH3)2CH2-或-C(CH3)2CH2C(CH3)2-,且Y13及Y14彼此獨立地為氫或C1-C10烷基。該反應一般在約0℃至180℃下在諸如甲苯、二甲苯之芳族烴溶劑中進行。其他溶劑,諸如二甲基甲醯胺、二噁烷、二甲氧基乙烷及四氫呋喃亦可單獨或與芳族烴混合使用。使用鹼水溶液,較佳碳酸鈉或碳酸氫鈉、磷酸鉀、碳酸鉀或碳酸氫鉀作為酸、酸鹽之活化劑且作為HBr淨化劑。聚合反應可耗時0.2至100小時。諸如氫氧化四烷銨之有機鹼及諸如TBAB之相轉移催化劑可促進硼之活性(參見例如Leadbeater&Marco;Angew.Chem.Int.Ed.Eng.42(2003)1407及其中所引用之參考文獻)。反應條件之其他變化由T.I.Wallow及B.M.Novak在J.Org.Chem.59(1994)5034-5037中;及M.Remmers,M.Schulze及G.Wegner在Macromol.Rapid Commun.17(1996)239-252中提供。可能藉由使用過量二溴化物、二酸或二酸鹽或鏈終止劑來控制分子量。
根據WO2010/136352中所述之方法,聚合可在以下存在下進行:a)催化劑/配位體系統,其包含鈀催化劑及有機膦或鏻化合物,b)鹼,c)溶劑或溶劑之混合物,其特徵在於
有機膦為式之經三取代膦,或其鏻鹽,其中
X"獨立於Y"表示氮原子或C-R2"基團且Y"獨立於X"表示氮原子或C-R9"基團,兩個R1"基團中之各R1"獨立於另一者表示選自以下群組之基團:C1-C25烷基;C3-C20環烷基,其尤其包括單環與雙環及三環環烷基;C5-C14芳基,其尤其包括苯基、萘基、茀基;C2-C13雜芳基,其
中選自N、O、S群之雜原子的數目可為1至2;其中兩個基團R1"亦可彼此鍵聯,且其中上文所提及之基團R1"本身各自可彼此獨立地經選自以下群組之取代基單或多取代:氫、C1-C20烷基、C2-C20烯基、C3-C8環烷基、C2-C9雜烷基、C5-C10芳基、C2-C9雜芳基(其中來自群組N、O、S之雜原子的數目可為1至4)、C1-C20烷氧基、C1-C10鹵基烷基、羥基、形式NH-(C1-C20烷基)、NH-(C5-C10芳基)、N(C1-C20烷基)2、N(C1-C20烷基)(C5-C10芳基)、N(C5-C10芳基)2、N(C1-C20烷基/C5-C10芳基3)3 +、NH-CO-C1-C20烷基、NH-CO-C5-C10芳基之胺基、形式COOH及COOQ之羧根基(其中Q表示單價陽離子或C1-C8烷基)、C1-C6醯氧基、亞磺酸根基、形式SO3H及SO3Q'之磺酸根基(其中Q'表示單價陽離子、C1-C20烷基或C5-C10芳基)、三C1-C6烷基矽烷基(其中兩個所提及之取代基亦可彼此橋接),R2"至R9"表示氫、烷基、烯基、環烷基、芳族或雜芳族芳基、O-烷基、NH-烷基、N-(烷基)2、O-(芳基)、NH-(芳基)、N-(烷基)(芳基)、O-CO-烷基、O-CO-芳基、F、Si(烷基)3、CF3、CN、CO2H、COH、SO3H、CONH2、CONH(烷基)、CON(烷基)2、SO2(烷基)、SO(烷基)、SO(芳基)、SO2(芳基)、SO3(烷基)、SO3(芳基)、S-烷基、S-芳基、NH-CO(烷基)、CO2(烷基)、CONH2、CO(烷基)、NHCOH、NHCO2(烷基)、CO(芳基)、CO2(芳基)基團,其中兩個或兩個以上相鄰基團各獨立於另一者亦可彼此鍵聯,使得存在縮合環系統且其中在R2"至R9"中,烷基表示具有1至20個碳原子之烴基,其在各情況下可為直鏈或分支鏈的,烯基表示2至20個碳原子之單或多不飽和烴基,其在各情況下可直鏈或分支鏈的,環烷基表示3至20個碳原子之烴,芳基表示5至14員芳族基團,其中芳基中之1至4個碳原子亦可藉由來自群組氮、氧及硫之雜原子替換,使得存在5至14員雜芳族基團,其中基團R2"至R9"亦可如R1"所定義進行進一步取代。
有機膦及其合成描述於WO2004101581中。
較佳有機膦係選自下式之三取代膦:
1)R5"及R6"一起形成環。2)R3"及R4"一起形成環
較佳催化劑之實例包括以下化合物:乙醯基丙酮酸鈀(II)、鈀(0二亞苄基丙酮錯合物、丙酸鈀(II),Pd2(dba)3:[參(二亞苄基丙酮)二鈀(0)],Pd(dba)2:[雙(二亞苄基丙酮)鈀(0)],Pd(PR3)2,其中PR3為式VI之經三取代膦,Pd(OAc)2:[乙酸鈀(II)],氯化鈀(II),溴化鈀(II),四氯鈀(II)酸鋰,PdCl2(PR3)2;其中PR3為式VI之經三取代膦;鈀(0)二烯丙醚錯合物,硝酸鈀(II),PdCl2(PhCN)2:[二氯雙(苯甲腈)鈀(II)],
PdCl2(CH3CN):[二氯雙(乙腈)鈀(II)],及PdCl2(COD):[二氯(1,5-環辛二烯)鈀(II)]。
尤其較佳為PdCl2、Pd2(dba)3、Pd(dba)2、Pd(OAc)2或Pd(PR3)2。最佳為Pd2(dba)3及Pd(OAc)2。
鈀催化劑在反應混合物中以催化量存在。術語「催化量」係指明顯低於(雜)芳族化合物之1當量,較佳以所用(雜)芳族化合物之當量計0.001至5莫耳%,最佳0.001至1莫耳%的量。
反應混合物中膦或鏻鹽之量較佳為以所用(雜)芳族化合物之當量計0.001至10莫耳%,最佳為0.01至5莫耳%。Pd:膦之較佳比率為1:4。
鹼可選自所有水性及非水性鹼,且可為無機或有機的。在反應混合物中,每一硼官能基較佳存在至少1.5當量之該鹼。適合之鹼為例如鹼金屬及鹼土金屬之氫氧化物、羧酸鹽、碳酸鹽、氟化物及磷酸鹽,諸如鈉及鉀之氫氧化物、乙酸鹽、碳酸鹽、氟化物及磷酸鹽,亦或金屬醇化物。亦可使用鹼之混合物。鹼較佳為鋰鹽,諸如鋰之醇鹽(諸如甲醇鋰及乙醇鋰)、氫氧化鋰、甲酸鋰、碳酸鋰、氟化鋰及/或磷酸鋰。
目前最佳之鹼為水性LiOH×H2O(LiOH之單水合物)及(無水)LiOH。
反應通常在0℃至180℃,較佳20℃至160℃,更佳40℃至140℃且最佳40℃至120℃下進行。聚合反應可耗時0.1小時,尤其0.2至100小時。
在本發明之一較佳實施例中,溶劑為THF,鹼為LiOH*H2O,且反應在THF之回流溫度(約65℃)下進行。
舉例而言,溶劑係選自甲苯、二甲苯、苯甲醚、THF、2-甲基四氫呋喃、二噁烷、氯苯、氟苯或包含一或多種溶劑(如THF/甲苯)及視情況選用之水的溶劑混合物。最佳為THF或THF/水。
聚合宜在以下存在下進行:a)乙酸鈀(II)或Pd2(dba)3,(參(二亞苄基丙酮)二鈀(0))及有機膦A-1至A-13,b)LiOH或LiOH×H2O;及c)THF及視情況選用之水。若使用LiOH之單水合物,則不需要添加水。
聚合最佳在以下存在下進行:a)乙酸鈀(II)或Pd2(dba)3(參(二亞苄基丙酮)二鈀(0))及
b)LiOH×H2O;及c)THF。鈀催化劑之存在量較佳為以所用(雜)芳族化合物之當量計約0.5莫耳%。反應混合物中膦或鏻鹽之量較佳為以所用(雜)芳族化合物之當量計約2莫耳%。Pd:膦之較佳比率為約1:4。
聚合反應較佳在不存在氧氣之情況下於惰性條件下進行。使用氮氣且更佳氬氣作為惰性氣體。
WO2010/136352中所述之方法適合於大規模應用,可容易進行且可以高產率、高純度及高選擇性將起始物質轉化為各別聚合物。該方法可提供重量平均分子量為至少10,000,更佳至少20,000,最佳至少30,000之聚合物。目前最佳之聚合物的重量平均分子量為30,000至80,000道爾頓。分子量根據高溫凝膠滲透層析(HT-GPC)使用聚苯乙烯標準物來測定。聚合物之多分散性較佳為1.01至10,更佳為1.1至3.0,最佳為1.5至2.5。
必要時,單官能性芳基鹵化物或芳基酸酯(諸如
(X2為Br、-B(OH)2、-
B(OY1)2、、-BF4Na或-BF4K)可用作此類反應中
之鏈終止劑,其將致使形成末端芳基。
可能藉由控制鈴木反應中單體饋料之次序及組成來控制所得共聚物中單體單元之定序。
本發明聚合物亦可藉由施蒂勒偶合(Stille coupling)合成(參見例如Babudri等人,J.Mater.Chem.,2004,14,11-34;J.K.Stille,Angew.Chemie Int.Ed.Engl.1986,25,508)。為製備對應於式VII之聚合物,在惰性溶劑中於0℃至200℃範圍內之溫度下,在含鈀催化劑存在下,使式X10-A-X10之二鹵化物與式X11'-COM1-X11'之化合物反應,或使式
X10-COM1-X10之二鹵化物與式X11'-A-X11'之化合物反應,其中X11'為基團-SnR207R208,R209及X10如上文所定義,其中R207、R208及R209相同或不同,且為H或C1-C6烷基,其中兩個基團視情況形成常見環且此等基團視情況為分支鏈或非分支鏈的。本文中必須確保所用所有單體之整體具有有機錫官能基與鹵素官能基之高平衡比。另外,可證明宜在反應結束時藉由以單官能試劑封端來移除任何過量反應性基團。為實施此方法,較佳將錫化合物及鹵素化合物引入一或多種惰性有機溶劑中且在0℃至200℃、較佳30℃至170℃之溫度下攪拌1小時至200小時、較佳5小時至150小時之時間。粗產物可藉由熟習此項技術者已知且適合各自聚合物之方法(例如重複再沈澱或甚至藉由透析)來純化。
適用於所描述方法之有機溶劑為例如醚類,例如乙醚、二甲氧基乙烷、二乙二醇二甲醚、四氫呋喃、二噁烷、二氧雜環戊烷、二異丙基醚及第三丁基甲基醚;烴類,例如己烷、異己烷、庚烷、環己烷、苯、甲苯及二甲苯;醇類,例如甲醇、乙醇、1-丙醇、2-丙醇、乙二醇、1-丁醇、2-丁醇及第三丁醇;酮類,例如丙酮、乙基甲基酮及異丁基甲基酮;醯胺類,例如二甲基甲醯胺(DMF)、二甲基乙醯胺及N-甲基吡咯啶酮;腈類,例如乙腈、丙腈及丁腈;及其混合物。
應類似於鈴木變化形式之描述來選擇鈀及膦組分。
或者,亦可藉由根岸反應(Negishi reaction)使用鋅試劑A-(ZnX12)2(其中X12為鹵素及鹵化物)與COM1-(X23)2(其中X23為鹵素或三氟甲磺酸根)或使用A-(X23)2與COM1-(ZnX23)2來合成本發明聚合物。參見例如E.Negishi等人,Heterocycles 18(1982)117-22。
或者,亦可藉由檜山反應(Hiyama reaction)使用有機矽試劑A-(SiR210R211R212)2(其中R210、R211及R212相同或不同且為鹵素或C1-C6烷基)與COM1-(X23)2(其中X23為鹵素或三氟甲磺酸根)或使用A-(X23)2與COM1-(SiR210R211R212)2來合成本發明聚合物。參見例如T.Hiyama等
人,Pure Appl.Chem.66(1994)1471-1478及T.Hiyama等人,Synlett(1991)845-853。
可經由二鹵化物X10-A-X10(其中X10為鹵素,較佳為溴)之山本偶合(Yamamoto coupling)來獲得類型(A)n之均聚物。或者,可例如用FeCl3作為氧化劑經由單元X10-A-X10(其中X10為氫)之氧化聚合來獲得類型(A)n之均聚物。
式化合物為產生
本發明聚合物之中間物且描述於PCT/EP2012/075762及EP13157961.7(US61/773166)(其以引用的方式併入本文中)及Daniel T.Gryko等人Org.Lett.,14(2012)2670中。a、a'、b、b'、c、c'、Y、Ar1、Ar1'、Ar2、Ar2'、Ar3及Ar3'係如上文所定義,且X2及X2'彼此獨立地為鹵素,尤其Br或I;ZnX12;-SnR207R208R209,其中R207、R208及R209相同或不同且為H或C1-C6烷基,其中兩個基團視情況形成共用環且此等基團視情況為分支鏈或非分支鏈的;-SiR210R211R212,其中R210、R211及R212相同或不同且為鹵素或C1-C6烷基;X12為鹵素原子,極尤其為I或Br;-OS(O)2CF3;-OS(O)2-芳基,尤其為
;-OS(O)2CH3;-B(OH)2;-B(OY1)2; ;-BF4Na或-BF4K,其中Y1在每次出現時獨立地為C1-C10烷基
且Y2在每次出現時獨立地為C2-C10伸烷基,諸如-CY3Y4-CY5Y6-或-CY7Y8-CY9Y10-CY11Y12-,其中Y3、Y4、Y5、Y6、Y7、Y8、Y9、Y10、Y11及Y12彼此獨立地為氫或C1-C10烷基,尤其為-C(CH3)2C(CH3)2-、-C(CH3)2CH2C(CH3)2-或-CH2C(CH3)2CH2-,且Y13及Y14彼此獨立地為氫或C1-C10烷基。式(V)化合物可用於生產聚合物。
X2及X2'較佳為相同的。
對於a、a'、b、b'、c、c'、Y、Ar1、Ar1'、Ar2、Ar2'、Ar3及Ar3',應用與上文針對式(I)之重複單元所述之相同偏好。
式之化合物(其中R1、R2及Ar係如上文所定
義)可藉由以下來獲得:在鹼存在下使式之二
酮基吡咯并吡咯與
式之化合物反應,其中X2為Cl、Br或I;接著在酸
存在下使所獲得之式之N-烷基化衍生物經歷分
子內縮合。
烷基化反應較佳在硫酸氫四丁基銨或K2CO3存在下於二甲基甲醯
胺(DMF)中進行。
環化反應較佳在三氟甲烷磺酸存在下於二氯甲烷中進行。
如以下反應方案中所示,化合物(5)可例如以DPP衍生物(2)為起始物質來製備:
在-30℃與+50℃之間,較佳在-10℃與室溫之間的溫度下,例如在0℃下,在如氯仿之適合溶劑中使用兩當量之N-溴基丁二醯亞胺進行溴化。
或者,式之化合物(其中R1、R2及Ar如上文
所定義)可藉由以下來獲得:在鹼存在下使式
之二酮基吡咯并吡咯與式之化合物反應,其中X2為Cl、
Br或I;接著在酸存在下使獲得之式之N-烷基化
繞射物經歷分子內縮合。在縮醛及縮酮中,氧可視情況經硫原子置換。
R70及R71彼此獨立地為C1-C25烷基,其可視情況經C1-C8烷基、C1-C8烷氧基取代一或多次及/或可視情況雜有-O-、-S-、-NR39-。較佳地,R70及R71彼此獨立地為C1-C25烷基,尤其為C1-C4烷基。R70及R71視情況可形成5或6員環。
烷基化反應較佳在硫酸氫四丁基銨或K2CO3存在下於二甲基甲醯胺(DMF)中進行。環化反應較佳在三氟甲烷磺酸存在下於二氯甲烷中進行。
以下式(IN-1)至(IN-17)之化合物為生產式化合
物之中間物:
,其中R3為氫;
鹵素、尤其F;氰基;C1-C25烷氧基;經一或多個鹵素原子、尤其F取
代之C1-C25烷基;C1-C25烷基、 或,其中
R22至R25及R29至R33彼此獨立地表示H、F、氰基、C1-C25烷氧基、經一或多個鹵素原子、尤其F取代之C1-C25烷基;或C1-C25烷基;且R26為H、F、氰基、苯基、C1-C25烷氧基、經一或多個鹵素原子取代之C1-C25烷基或C1-C25烷基;R99、R99'、R99"及R99*彼此獨立地為氫、C1-C25烷基或雜有一或多個氧原子之C1-C25烷基;較佳為C3-C25烷基或雜有一或多個氧原子之C3-C25烷基;R121、R122、R123、R124及R125彼此獨立地為氫、鹵素、C1-C18烷
氧基或C1-C25烷基;較佳為氫;及R130為氫;C6-C18芳基;經C1-C18烷基、鹵素、尤其F取代之C6-C18芳基;或C1-C18烷氧基;可視情況雜有一或多個氧或硫原子及/或視情況經一或多個鹵素原子、尤其F取代之C1-C25烷基;或C7-C25芳基烷基。參見PCT/EP2014/054060。
在本發明之上下文中,除非另有說明,否則術語鹵素、C1-C25烷基(C1-C18烷基)、C2-C25烯基(C2-C18烯基)、C2-25炔基(C2-18炔基)、脂族基、脂族烴基、伸烷基、伸烯基、環脂族烴基、環烷基、環烯基、C1-C25烷氧基(C1-C18烷氧基)、C1-C18全氟烷基、胺甲醯基、C6-C24芳基(C6-C18芳基)、C7-C25芳烷基及雜芳基各自如下定義:鹵素為氟、氯、溴及碘。
若可能,C1-C25烷基(C1-C18烷基)通常為直鏈或分支鏈的。實例為甲基、乙基、正丙基、異丙基、正丁基、第二丁基、異丁基、第三丁基、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、異庚基、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及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-C8烷基通常為甲基、乙基、正丙基、異丙基、正丁基、第二丁基、異丁基、第三丁基、正戊基、2-戊基、3-戊基、2,2-二甲基-丙基、正己基、正庚基、正辛基、1,1,3,3-四甲基丁基及2-乙基己基。C1-C4烷基通常為甲基、乙基、正丙基、異丙基、正丁基、第二丁基、異丁基、第三丁基。
C2-C25烯基(C2-C18烯基)為直鏈或分支鏈烯基,諸如乙烯基、烯丙基、甲基烯丙基、異丙烯基、2-丁烯基、3-丁烯基、異丁烯基、正
戊-2,4-二烯基、3-甲基-丁-2-烯基、正辛-2-烯基、正十二-2-烯基、異十二烯基、正十二-2-烯基或正十八-4-烯基。
C2-25炔基(C2-18炔基)為直鏈或分支鏈炔基,且較佳為可未經取代或經取代之C2-8炔基,諸如乙炔基、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、順-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。
相比於脂族烴基,脂族基可經任何非環取代基取代,但較佳未經取代。較佳取代基為C1-C8烷氧基或C1-C8烷硫基,如下文進一步例示。術語「脂族基」亦包含某些非相鄰碳原子經氧置換之烷基,如-CH2-O-CH2-CH2-O-CH3。後一基團可視為經-O-CH2-CH2-O-CH3取代之甲基。
具有至多25個碳原子之脂族烴基為具有至多25個碳原子之直鏈或分支鏈烷基、烯基或炔基(alkynyl)(亦拼寫為炔基(alkinyl)),如上文所例示。
伸烷基為二價烷基,亦即具有兩個(而非一個)自由價數之烷基,例如三亞甲基或四亞甲基。
伸烯基為二價烯基,亦即具有兩個(而非一個)自由價數之烯基,例如-CH2-CH=CH-CH2-。
相比於脂族烴基,脂族基可經任何非環取代基取代,但較佳未經取代。較佳取代基為C1-C8烷氧基或C1-C8烷硫基,如下文進一步例示。術語「脂族基」亦包含某些非相鄰碳原子經氧置換之烷基,如-CH2-O-CH2-CH2-O-CH3。後一基團可視為經-O-CH2-CH2-O-CH3取代之甲基。
環脂族烴基為可經一或多個脂族及/或環脂族烴基取代之環烷基
或環烯基。
環脂族-脂族基為經環脂族基取代之脂族基,其中術語「環脂族」及「脂族」具有本文中所給定之含義且其中游離價數延伸自脂族部分。因此,環脂族-脂族基為例如環烷基-烷基。
環烷基-烷基為經環烷基取代之烷基,例如環己基-甲基。
「環烯基」意謂含有一或多個雙鍵之不飽和脂環烴基,諸如環戊烯基、環戊二烯基、環己烯基及其類似基團,其可未經取代或經一或多個脂族及/或環脂族烴基取代及/或與苯基縮合。
舉例而言,環烷基或環烯基,尤其環己基可與苯基縮合一或兩次,該苯基可經C1-C4烷基取代一至三次。此類縮合環己基之實例為下式之基團:
,尤其
或,其可在苯基部分經C1-C4烷基取代
一至三次。
式XII之二價基團(其中R28及R27在一起表示伸烷基或伸烯基,其皆可經由氧及/或硫鍵結至噻吩基且皆可具有至多25個碳原子)為例如下式之基團:
其中A表示具有至多25個碳原子之直鏈或分支鏈伸烷基,較佳為可經一或多個烷基取代之伸乙基或伸丙基,且Y表示氧或硫。舉例而言,式-Y-A-O-之二價基團表示-O-CH2-CH2-O-或-O-CH2-CH2-CH2-O-。
式XI之基團(其中R22至R26中彼此相鄰之兩個基團一起表示具有至多8個碳原子之伸烷基或伸烯基,由此形成環)為例如下式之基團:
或,其中在式XXXII之基團中,R23及R24
在一起表示1,4-伸丁基且在式XXXIII之基團中,R23及R24一起表示1,4-伸丁-2-烯基。
C1-C25烷氧基(C1-C18烷氧基)為直鏈或分支鏈烷氧基,例如甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、第二丁氧基、第三丁氧基、戊氧基、異戊氧基或第三戊氧基、庚氧基、辛氧基、異辛氧基、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、十七烷氧基及十八烷氧基。C1-C8烷氧基之實例為甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、第二丁氧基、異丁氧基、第三丁氧基、正戊氧基、2-戊氧基、3-戊氧基、2,2-二甲基丙氧基、正己氧基、正庚氧基、正辛氧基、1,1,3,3-四甲基丁氧基及2-乙基己氧基,較佳為C1-C4烷氧基,通常諸如甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、第二丁氧基、異丁氧基、第三丁氧基。術語「烷硫基」意謂如烷氧基相同之基團,但其中改用硫原子置換醚鍵之氧原子。
C1-C18全氟烷基(尤其為C1-C4全氟烷基)為分支或未分支基團,諸如-CF3、-CF2CF3、-CF2CF2CF3、-CF(CF3)2、-(CF2)3CF3及-C(CF3)3。
術語「胺甲醯基」通常為C1-18胺甲醯基,較佳為C1-8胺甲醯基,其可未經取代或經取代,諸如胺甲醯基、甲基胺甲醯基、乙基胺甲醯基、正丁基胺甲醯基、第三丁基胺甲醯基、二甲基胺甲醯基氧基、N-嗎啉基胺甲醯基或吡咯啶并胺甲醯基。
環烷基通常為C3-C12環烷基,諸如環戊基、環己基、環庚基、環
辛基、環壬基、環癸基、環十一烷基、環十二烷基,較佳環戊基、環己基、環庚基或環辛基,其可未經取代或經取代。環烷基,尤其環己基可與可經C1-C4-烷基、鹵素及氰基取代一至三次之苯基縮合一或兩
次。此類縮合環己基之實例為:或
尤其或,其中R151、R152、R153、
R154、R155及R156彼此獨立地為C1-C8烷基、C1-C8烷氧基、鹵素及氰基,尤其為氫。
C6-C24芳基(C6-C18芳基)通常為苯基、茚基、薁基、萘基、聯苯基、as-二環戊二烯并苯基、s-二環戊二烯并苯基、苊基、茀基、菲基、茀蒽基、聯伸三苯基、基、稠四苯基、苉基、苝基、稠五苯基、稠六苯基、芘基或蒽基,較佳為苯基、1-萘基、2-萘基、4-聯二苯、9-菲基、2-茀基或9-茀基、3-聯二苯或4-聯二苯,其可未經取代或經取代。C6-C12芳基之實例為苯基、1-萘基、2-萘基、3-聯二苯或4-聯二苯、2-茀基或9-茀基、或9-菲基,其可未經取代或經取代。
C7-C25芳烷基通常為苄基、2-苄基-2-丙基、β-苯基-乙基、α,α-二甲基苄基、ω-苯基-丁基、ω,ω-二甲基-ω-苯基-丁基、ω-苯基-十二烷基、ω-苯基十八烷基、ω-苯基-二十烷基或ω-苯基-二十二烷基,較佳為C7-C18芳烷基,諸如苄基、2-苄基-2-丙基、β-苯基-乙基、α,α-二甲基苄基、ω-苯基-丁基、ω,ω-二甲基-ω-苯基-丁基、ω-苯基-十二烷基
或ω-苯基十八烷基,且尤其較佳為C7-C12芳烷基,諸如苄基、2-苄基-2-丙基、β-苯基-乙基、α,α-二甲基苄基、ω-苯基-丁基、ω,ω-二甲基-ω-苯基-丁基,其中脂族烴基與芳族烴基可未經取代或經取代。較佳實例為苄基、2-苯基乙基、3-苯基丙基、萘基乙基、萘基甲基及異丙苯基。
雜芳基通常為C2-C20雜芳基,亦即具有5至7個環原子之環或縮合環系統,其中氮、氧或硫為可能之雜原子,且通常為具有5至30個原子之具有至少6個共軛π電子之不飽和雜環基,諸如噻吩基、苯并[b]噻吩基、二苯并[b,d]噻吩基、噻噁基、呋喃基、呋喃甲基、2H-哌喃基、苯并呋喃基、異苯并呋喃基、二苯并呋喃基、苯氧基噻吩基、吡咯基、咪唑基、吡唑基、吡啶基、聯吡啶基、三嗪基、嘧啶基、吡嗪基、噠嗪基、吲哚嗪基、異吲哚基、吲哚基、吲唑基、嘌呤基、喹嗪基、喹啉基(chinolyl)、異喹啉基、酞嗪基、啶基、喹喏啉基、喹唑啉基、啉基、喋啶基、咔唑基、咔啉基、苯并三唑基、苯并噁唑基、啡啶基、吖啶基、嘧啶基、啡啉基、啡嗪基、異噻唑基、啡噻嗪基、異噁唑基、呋呫基或啡噁嗪基,其可未經取代或經取代。
上文所提及之基團之可能取代基為C1-C8烷基、羥基、巰基、C1-C8烷氧基、C1-C8烷硫基、鹵素、鹵基-C1-C8烷基、氰基、胺甲醯基、硝基或矽烷基,尤其為C1-C8烷基、C1-C8烷氧基、C1-C8烷硫基、鹵素、鹵基-C1-C8烷基或氰基。
雜有一或多個O之C1-C18烷基為例如(CH2CH2O)1-9-Rx(其中Rx為H或C1-C10烷基)、CH2-CH(ORy')-CH2-O-Ry(其中Ry為C1-C18烷基且Ry'涵蓋與Ry相同之定義或為H)。
若取代基(諸如R3)在一基團中出現一次以上,則其在每次出現時可不同。
含有本發明聚合物之混合物產生包含本發明聚合物(通常為5重量
%至99.9999重量%,尤其為20重量%至85重量%)及至少另一材料之半導體層。該另一材料可為(但不限於)與本發明聚合物相同但具有不同分子量之部分、本發明之另一聚合物、半導電聚合物、有機小分子、碳奈米管、富勒烯衍生物、無機粒子(量子點、量子棒、量子三角架、TiO2、ZnO等)、導電粒子(Au、Ag等)、絕緣體材料(如關於閘極介電質所述之絕緣材料(PET、PS等))。本發明聚合物可與以下中所述之小分子摻合:例如WO2009/047104、WO2010108873(PCT/EP2010/053655)、WO09/047104、US6,690,029、WO2007082584及WO2008107089:WO2007082584:
WO2008107089:
其中Y1'及Y2'中之一者表示-CH=或=CH-且另一者表示-X*-,Y3'及
Y4'中之一者表示-CH=或=CH-且另一者表示-X*-,X*為-O-、-S-、-Se-或-NR"-,R*為具有1至20個C原子之環狀、直鏈或分支鏈烷基或烷氧基,或具有2至30個C原子之芳基,其全部視情況經氟化或全氟化,R'為H、F、Cl、Br、I、CN、具有1至20個C原子且視情況氟化或全氟化之直鏈或分支鏈烷基或烷氧基、具有6至30個C原子且視情況氟化或全氟化之芳基、或CO2R",其中R"為H、具有1至20個C原子且視情況氟化之烷基或具有2至30個C原子且視情況氟化之芳基,R'''為具有1至10個C原子之H或環狀、直鏈或分支鏈烷基,y為0或1,x為0或1。
聚合物可含有小分子,或兩種或兩種以上小分子化合物之混合物。
因此,本發明亦係關於包含本發明聚合物之有機半導體材料、
層或組件。
本發明之聚合物可用作半導體裝置中之半導體層。因此,本發明亦係關於包含本發明聚合物、或有機半導體材料、層或組之半導體裝置。半導體裝置尤其為有機光伏打(PV)裝置(太陽能電池)、光電二極體或有機場效電晶體。
本發明聚合物可單獨或組合用作半導體裝置之有機半導體層。該層可藉由任何適用之手段來提供,諸如氣相沈積(對於具有相對低分子量之材料)及印刷技術。本發明化合物可充分溶於有機溶劑中且可進行溶液沈積並圖案化(例如藉由旋塗、浸塗、槽模塗佈、噴墨印刷、凹版印刷、柔版印刷、平版印刷、網版印刷、微接觸(波)印刷、滴落鑄造或區域鑄造或其他已知技術)。
本發明聚合物可用於包含複數個OTFT之積體電路以及各種電子物品中。此類物品包括例如射頻識別(RFID)標籤、用於可撓性顯示器(適用於例如個人電腦、蜂巢式電話或手持型裝置)之底板、智慧卡、記憶體裝置、感測器(例如光、影像、生物、化學、機械或溫度感測器),尤其為光電二極體或安全裝置及其類似物。
本發明之另一態樣為包含一或多種本發明之聚合物或化合物之有機半導體材料、層或組件。另一個態樣為本發明之聚合物或材料在有機光伏打(PV)裝置(太陽能電池)、光電二極體或有機場效電晶體(OFET)中之用途。另一個態樣為包含本發明之聚合物或材料的有機光伏打(PV)裝置(太陽能電池)、光電二極體或有機場效電晶體(OFET)。
本發明聚合物通常用作薄有機層或膜(厚度較佳小於30微米)形式之有機半導體。本發明半導體層之厚度通常為至多1微米(=1μm),但必要時其可更厚。對於各種電子裝置應用,厚度亦可小於約1微米厚。舉例而言,對於OFET中之用途,層厚度通常可為100nm或100
nm以下。層之確切厚度將視例如使用層之電子裝置的需求而定。
舉例而言,OFET中汲極與源極之間的作用半導體通道可包含本發明之層。
本發明之OFET裝置較佳包含:- 源極電極,- 汲極電極,- 閘極電極,- 半導體層,- 一或多個閘極絕緣體層,及- 視情況選用之基板,其中該半導體層包含一或多種本發明聚合物。
OFET裝置中之閘極、源極及汲極電極以及絕緣及半導體層可以任何順序排列,其限制條件為源極及汲極電極與閘極電極由絕緣層隔開,閘極電極與半導體層皆接觸絕緣層且源極電極與汲極電極皆接觸半導體層。
OFET較佳包含具有第一側面及第二側面之絕緣體、位於絕緣體之第一側面上的閘電極、位於絕緣體之第二側面上的包含本發明聚合物之層、及位於聚合物層上之汲電極及源電極。
OFET裝置可為頂閘極裝置或底閘極裝置。
OFET裝置之適合結構及製造方法為熟習此項技術者所已知,且描述於例如WO03/052841之文獻中。
閘極絕緣體層可包含例如含氟聚合物,如市售Cytop 809M®或Cytop 107M®(來自Asahi Glass)。閘極絕緣體層較佳藉由例如旋塗、刮刀塗布、線棒式塗佈、噴塗或浸塗或其他已知方法,自包含絕緣體材料及一或多種具有一或多個氟原子之溶劑(含氟溶劑)、較佳全氟溶劑之調配物沈積。適合全氟溶劑為例如FC75®(可自Acros購得,目錄
編號12380)。其他適合含氟聚合物及含氟溶劑自先前技術已知,如全氟聚合物鐵氟龍(Teflon)AF® 1600或2400(來自DuPont)或Fluoropel®(來自Cytonix)或全氟溶劑FC 43®(Acros,編號12377)。
包含本發明聚合物之半導體層可另外包含至少另一種材料。該另一材料可為(但不限於)本發明之另一聚合物、半導體聚合物、聚合黏合劑、不同於本發明聚合物之有機小分子、碳奈米管、富勒烯衍生物、無機粒子(量子點、量子棒、量子三角架、TiO2、ZnO等)、導電粒子(Au、Ag等)、及絕緣體材料(如關於閘極介電質所述之絕緣體材料(PET、PS等))。如上所述,半導體層亦可由一或多種本發明聚合物之混合物與聚合黏合劑組成。本發明聚合物與聚合黏合劑之比率可在5%至95%內變化。較佳地,聚合黏合劑為半結晶性聚合物,諸如聚苯乙烯(PS)、高密度聚乙烯(HDPE)、聚丙烯(PP)及聚甲基丙烯酸甲酯(PMMA)。藉由此技術,可避免電學效能之劣化(參見WO2008/001123A1)。
本發明聚合物宜用於有機光伏打(PV)裝置(太陽能電池)。因此,本發明提供包含本發明聚合物之PV裝置。此構造之裝置亦將具有整流特性,因此亦可稱為光電二極體。光響應裝置可應用作為自光產生電之太陽能電池及量測或偵測光之光偵測器。
PV裝置依序包含:(a)陰極(電極),(b)視情況存在之過渡層,諸如鹼金屬鹵化物,尤其氟化鋰,(c)光敏層,(d)視情況存在之平滑層,(e)陽極(電極),(f)基板。
光敏層包含本發明聚合物。較佳地,光敏層由本發明之共軛聚
合物作為電子供體及受體材料(如富勒烯,尤其官能化之富勒烯PCBM)作為電子受體來製備。如上所述,光敏層亦可含有聚合黏合劑。式I之聚合物與聚合黏合劑的比率可在5%至95%內變化。較佳地,聚合黏合劑為半結晶性聚合物,諸如聚苯乙烯(PS)、高密度聚乙烯(HDPE)、聚丙烯(PP)及聚甲基丙烯酸甲酯(PMMA)。
對於異質接面太陽能電池,作用層較佳包含重量比為1:1至1:3之本發明聚合物與富勒烯(諸如[60]PCBM(亦即6,6-苯基-C61-丁酸甲酯)或[70]PCBM)之混合物。適用於本發明之富勒烯可具有較寬的尺寸範圍(每分子中碳原子之數目)。如本文所使用之術語富勒烯包括各種純碳籠狀分子,包括巴克敏斯特富勒烯(C60)及相關「球形」富勒烯以及碳奈米管。富勒烯可選自在例如C20至C1000範圍內之此項技術中已知之彼等富勒烯。較佳地,富勒烯係選自C60至C96之範圍。最佳地,富勒烯為C60或C70,諸如[60]PCBM或[70]PCBM。亦可容許利用化學改質之富勒烯,其限制條件為改質之富勒烯保留受體型及電子遷移率特性。受體材料亦可為選自由以下組成之群的材料:任何半導電聚合物(諸如本發明聚合物),其限制條件為該等聚合物保持受體型及電子遷移率特徵;有機小分子;碳奈米管;無機粒子(量子點、量子棒、量子三角架、TiO2、ZnO等)。
光敏層由本發明聚合物作為電子供體及富勒烯(尤其官能化富勒烯PCBM)作為電子受體來製備。此兩種組分與溶劑混合且以溶液形式藉由例如旋塗法、滴落鑄造法、朗繆爾-布勞傑特(Langmuir-Blodgett,「LB」)法、噴墨印刷法及滴液法塗覆至平滑層上。壓輥或印刷方法亦可用以用此類光敏層塗佈較大表面。替代典型之甲苯,較佳使用諸如氯苯之分散劑作為溶劑。在此等方法中,鑒於簡化操作及成本,真空沈積法、旋塗法、噴墨印刷法及鑄造法尤其較佳。
在藉由使用旋塗法、鑄造法及噴墨印刷法形成層之情況下,可
使用藉由以0.01至90重量%之濃度將組合物溶解或分散於適當有機溶劑中製備之溶液及/或分散液來進行塗佈,該等合適有機溶劑為諸如苯、甲苯、二甲苯、四氫呋喃、甲基四氫呋喃、N,N-二甲基甲醯胺、丙酮、乙腈、苯甲醚、二氯甲烷、二甲基亞碸、氯苯、1,2-二氯苯及其混合物。
光伏打(PV)裝置亦可由為了吸收更多太陽光譜而彼此疊放處理之多接面太陽能電池組成。此類結構例如描述於App.Phys.Let.90,143512(2007),Adv.Funct.Mater.16,1897-1903(2006)及WO2004/112161中。
所謂的『串聯太陽能電池』以此順序包含:(a)陰極(電極),(b)視情況存在之過渡層,諸如鹼金屬鹵化物,尤其氟化鋰,(c)光敏層,(d)視情況存在之平滑層,(e)中間電極(諸如Au、Al、ZnO、TiO2等)(f)視情況存在之匹配能階之額外電極,(視情況存在之過渡層,諸如鹼金屬鹵化物,尤其氟化鋰,(h)光敏層,(i)視情況存在之平滑層,(j)陽極(電極),(k)基板。
亦可如例如在US20070079867及US 20060013549中所描述在纖維上處理PV裝置。
由於其極佳自組織特性,故包含本發明聚合物之材料或薄膜亦可單獨或與其他材料一起用於LCD或OLED裝置中之配向層中或用作該配向層,如例如US2003/0021913中所述。
本發明之另一目的為提供當用於有機場效電晶體、有機光伏打裝置(太陽能電池)及光電二極體時,顯示高能量轉換效率、極佳場效遷移率、良好開/關電流比及/或極佳穩定性之化合物。
此外,本發明聚合物可用作IR吸收劑。
因此,本發明聚合物尤其可用於安全印刷、不可見及/或IR可讀棒編碼、塑膠之雷射焊接、使用IR輻射器使表面塗層固化、印記之乾燥及固化、調色劑於紙或塑膠上之固定、電漿顯示器面板之光學濾光片、紙或塑膠之雷射標記、塑膠預型件之發熱及使各應用熱屏蔽。
在另一態樣中,本發明提供用於安全印刷之印刷墨水調配物,其包含至少一種本發明聚合物,諸如選自P-1至P-14及P-16至P-25之聚合物。
在另一態樣中,本發明提供一種安全文件,其包含基板及至少一種本發明之聚合物或化合物。安全文件可為銀行鈔票、護照、支票、憑證(voucher)、身分識別或交易卡、印花稅票及稅收標籤。
在另一態樣中,本發明提供一種可藉由印刷方法獲得之安全文件,其中採用包含至少一種本發明之聚合物或化合物之印刷墨水調配物。
本發明之聚合物或化合物,諸如選自P-1至P-14及P-16至P-25之聚合物宜可用於安全印刷之印刷墨水調配物中。
在安全印刷中,將本發明之聚合物或化合物添加至印刷墨水調配物中。適合印刷墨水為用於噴墨印刷、柔版印刷、網版印刷、凹版印刷、平版印刷、雷射印刷或凸版印刷及用於電子照相術之以顏料或染料為主之基於水、基於油或基於溶劑之印刷墨水。用於此等印刷方法之印刷墨水通常包含溶劑、黏合劑以及各種添加劑,諸如塑化劑、抗靜電劑或蠟。用於平版印刷及凸版印刷之印刷墨水通常調配成高黏度糊狀印刷墨水,而用於柔版印刷及凹版印刷之印刷墨水通常調配成
具有相對低黏度之液體印刷墨水。
尤其用於安全印刷之本發明之印刷墨水調配物較佳包含a)至少一種本發明之聚合物或化合物,諸如選自聚合物P-1至P-14及P-16至P-25之聚合物,b)聚合黏合劑,c)溶劑,d)視情況選用之至少一種著色劑,及e)視情況選用之至少一種其他添加劑。
適合之印刷墨水組分為習知的且為熟習此項技術者所熟知。此類組分之實例描述於「Printing Ink Manual」,第4版,Leach R.H.等人(編),Van Nostrand Reinhold,Wokingham,(1988)中。印刷墨水及其配方之詳述亦揭示於「Printing Inks」-Ullmann's Encyclopedia of Industrial Chemistry,第6版,1999 Electronic Release中。IR吸收凹版墨水調配物之配方描述於US 20080241492 A1中。上文所提及之文獻之揭示內容以引用的方式併入本文中。
本發明之印刷墨水調配物一般含有以印刷墨水調配物之總重量計0.0001至25重量%,較佳0.001至15重量%,尤其0.01至5重量%之組分a)。
本發明之印刷墨水調配物一般含有以印刷墨水調配物之總重量計5至74重量%,較佳10至60重量%,更佳15至40重量%之組件b)。
本發明之印刷墨水調配物之適合聚合黏合劑b)例如選自天然樹脂、酚類樹脂、酚改質樹脂、醇酸樹脂、聚苯乙烯均及共聚物、萜類樹脂、聚矽氧樹脂、聚胺基甲酸酯樹脂、尿素-甲醛樹脂、三聚氰胺樹脂、聚醯胺樹脂、聚丙烯酸酯、聚甲基丙烯酸酯、氯化橡膠、乙烯基酯樹脂、丙烯酸樹脂、環氧樹脂、硝化纖維、烴類樹脂、乙酸纖維素及其混合物。
本發明之印刷墨水調配物亦可包含藉由固化方法形成聚合黏合劑之組分。因此,本發明之印刷墨水調配物亦可調配成可能量固化的,例如能夠藉由UV光或EB(電子束)輻射固化。在此實施例中,黏合劑包含一或多種可固化單體及/寡聚物。相應調配物在此項技術中已知且可見於標準教科書中,諸如1997-1998中由John Wiley & Sons聯合SITA Technology Limited以7卷出版之系列「Chemistry & Technology of UV & EB Formulation for Coatings,Inks & Paints」。
適合單體及寡聚物(亦稱為預聚物)包含環氧丙烯酸酯、丙烯酸化油、丙烯酸胺基甲酸酯、丙烯酸聚酯、聚矽氧丙烯酸酯、丙烯酸化胺及丙烯酸系飽和樹脂。進一步詳述及實例在藉由G Webster編之「Chemistry & Technology of UV & EB Formulation for Coatings,Inks & Paints」,第II卷:Prepolymers & Reactive Diluents中提供。
若採用可固化聚合黏合劑,則其可含有反應性稀釋劑,亦即充當溶劑且當固化時併入聚合黏合劑中之單體。反應性單體通常選自丙烯酸酯或甲基丙烯酸酯,且可為單官能性或多官能性的。多官能性單體之實例包含丙烯酸聚酯或甲基丙烯酸聚酯、多元醇丙烯酸酯或多元醇甲基丙烯酸酯以及聚醚丙烯酸酯或聚醚甲基丙烯酸酯。
在印刷墨水調配物藉由UV輻射固化之情況下,通常必需包含至少一種光引發劑以在曝露於UV輻射時引發單體之固化反應。適用光引發劑之實例可見於標準教科書中,諸如J.V.Crivello & K.Dietliker之「Chemistry & Technology of UV & EB Formulation for Coatings, Inks & Paints」,第III卷,「Photoinitiators for Free Radical Cationic and Anionic Polymerisation」,第2版,G.Bradley編且在1998藉由John Wiley & Sons聯合SITA Technology Limited出版。亦可有利地包括敏化劑以及光引發劑以實現高效固化。
本發明之印刷墨水調配物一般含有以印刷墨水調配物之總重量
計1至94.9999重量%,較佳5至90重量%,尤其10至85重量%之溶劑c)。
適合溶劑係選自水、有機溶劑及其混合物。就本發明之目的而言,將亦充當溶劑之反應性單體視為上文所提及之黏合劑組分b)之一部分。
溶劑之實例包含水;醇,例如乙醇、1-丙醇、2-丙醇、乙二醇、丙二醇、二乙二醇及乙氧基丙醇;酯,例如乙酸乙酯、乙酸異丙酯、乙酸正丙酯及乙酸正丁酯;烴,例如甲苯、二甲苯、礦物油及植物油;及其混合物。
本發明之印刷墨水調配物可含有其他著色劑d)。較佳地,印刷墨水調配物含有以印刷墨水調配物之總重量計0至25重量%,更佳0.1至20重量%,尤其1至15重量%之著色劑d)。
適合著色劑d)會選擇習知染料且尤其習知顏料。在本發明之上下文中,術語「顏料」廣泛用以鑑別所有顏料及填充劑,實例為彩色顏料、白色顏料及無機填充劑。此等顏料包括無機白色顏料,諸如二氧化鈦(較佳呈金紅石形式)、硫酸鋇、氧化鋅、硫化鋅、鹼性碳酸鉛、三氧化二銻、鋅鋇白(硫化鋅+硫酸鋇);或彩色顏料,實例為氧化鐵、碳黑、石墨、鋅黃、鋅綠、群青、錳黑、銻黑、錳紫、巴黎藍(Paris blue)或施魏因富特綠(Schweinfurt green)。除無機顏料以外,本發明之印刷墨水調配物亦可包含有機彩色顏料,實例為棕色、藤黃、卡塞爾棕(Cassel brown)、甲苯胺紅、對位紅、漢薩黃(Hansa yellow)、靛藍、偶氮染料、蒽醌及靛藍類染料以及二噁嗪、喹吖啶酮、酞菁、異吲哚啉酮及金屬錯合物顏料。亦適合的為包含空氣以增加光散射之合成白色顏料,諸如Rhopaque®分散體。適合填充劑為例如鋁矽酸鹽,諸如長石;矽酸鹽,諸如高嶺土、滑石、雲母、菱鎂礦;鹼土金屬碳酸鹽,諸如碳酸鈣(呈例如方解石或白堊形式)、碳酸
鎂、白雲石;鹼土金屬硫酸鹽,諸如硫酸鈣;二氧化矽等。
本發明之印刷墨水調配物可含有至少一種添加劑e)。較佳地,印刷墨水調配物含有以印刷墨水調配物之總重量計0至25重量%,更佳0.1至20重量%,尤其1至15重量%之至少一種組分e)。
適合添加劑(組分e))係選自塑化劑、蠟、乾燥劑、抗靜電劑、螯合劑、抗氧化劑、穩定劑、黏著促進劑、表面活性劑、流動控制劑、消泡劑、殺生物劑、增稠劑等及其組合。此等添加劑尤其用於印刷墨水之應用相關特性之精細調節,該等特性之實例為黏著力、耐磨性、乾燥速率或滑動性。
詳言之,本發明之用於安全印刷之印刷墨水調配物較佳含有a)0.0001至25重量%之至少一種本發明之聚合物或化合物,諸如選自聚合物P-1至P-14及P-16至P-25之聚合物,b)5至74重量%之至少一種聚合黏合劑,c)1至94.9999重量%之至少一種溶劑,d)0至25重量%之至少一種著色劑,及e)0至25重量%之至少一種其他添加劑,其中組分a)至e)之總和總計達100%。
本發明之印刷墨水調配物宜以習知方式,例如藉由混合個別組分來製備。
可在本發明之印刷墨水調配物之前塗覆底漆。舉例而言,塗覆底漆以改良對基板之黏著力。亦可塗覆例如呈保護所印刷影像之覆蓋物形式之額外印刷漆。
以下實例僅出於說明之目的而納入且不限制申請專利範圍之範疇。除非另有規定,否則所有份數及百分比均以重量計。重量平均分子量(Mw)及多分散性(Mw/Mn=PD)藉由高溫凝膠滲透層析法(HT-GPC)來測定[裝置:GPC PL 220,來自Polymer laboratories(Church
Stretton,UK;現為Varian)產生來自折射率(RI)之響應,層析條件:管柱:3「PLgel Olexis」管柱,來自Polymer Laboratories(Church Stretton,UK);平均粒度為13ìm(尺寸300×8mm I.D.),移動相:1,2,4-三氯苯,藉由真空蒸餾純化並藉由丁基羥基甲苯(BHT,200mg/l)穩定,層析溫度:150℃;移動相流速:1ml/min;溶質濃度:約1mg/ml;注射立體:200ìl;偵測:RI,分子量校準之程序:相對校正藉由使用一組10個獲自Polymer Laboratories(Church Stretton,UK)之聚苯乙烯校正標準物進行,分子量跨越1,930,000Da-5,050Da之範圍,亦即PS 1,930,000、PS 1,460,000、PS 1,075,000、PS 560,000、PS 330,000、PS 96,000、PS 52,000、PS 30,300、PS 10,100、PS 5,050Da。使用多項式校正來計算分子量。
在以下實例中提供之所有聚合物結構均為經由所述聚合程序而獲得之聚合物產物的理想化表示。若超過兩種組分與彼此共聚合,則視聚合條件而定,聚合物中之次序可為交替或隨機的。
a)7-溴化-9,9-二(2-甲氧基乙基)-9H-茀-2-甲腈2:在室溫下在氬氣下攪拌2,7-二溴-9H-茀(11.34g,35mmol)、碘化鉀(100mg,0.60mmol)及150ml THF之混合物。小心地逐份添加氫化鈉(7.00g,175mmol,於礦物油中60%)且再攪拌混合物15min。隨後逐滴添加1-氯-2-甲氧乙烷(9.6ml,105mmol)且在室溫下攪拌反應混合物3天。藉由逐滴添加200ml水淬滅反應。用6M HCl酸化所得黑色混合物(顏色消失)且用二氯甲烷萃取三次。用水洗滌合併之有機層兩次且經硫酸鈉
乾燥。減壓移除溶劑且自乙醇再結晶獲得之固體殘餘物,得到13.40g(87%)呈白色粉末狀之2,7-二溴-9,9-二(2-甲氧基乙基)-9H-茀1。熔點:138-140℃。1H NMR(500MHz,CDCl3)δ 7.55(d,J=1.4Hz,2H),7.53(d,J=8.1Hz,2H),7.49(dd,J=8.1,1.7Hz,2H),3.02(s,6H),2.68(dd,J=8.4,6.7Hz,4H),2.49-2.15(m,4H)。13C NMR(126MHz,CDCl3)δ 150.8,138.4,130.8,126.5,121.8,121.3,68.1,58.4,51.7,39.4。HRMS(EI)C19H20Br2O2(M+)之計算值:437.9830,實驗值:437.9831。
b)在160℃下在氬氣下於緊閉壓力容器中攪拌2,7-二溴-9,9-二(2-甲氧基乙基)-9H-茀1(13.21g,30mmol)、氰化銅(I)(2.78g,31mmol)及100ml DMF。在40h之後,使反應混合物冷卻且添加26g FeCl3‧6H2O於40ml濃鹽酸及10ml水中之溶液。在90℃下攪拌所得混合物20min,冷卻,用水稀釋且用5份二氯甲烷萃取。合併有機層,用水洗滌兩次且經MgSO4乾燥。產物藉由矽膠層析(氯仿→氯仿:乙酸乙酯9:1)純化且自乙醇再結晶。獲得5.20g(45%)呈灰白色粉末狀之2。熔點:193-196℃。1H NMR(500MHz,CDCl3)δ 7.75(dd,J=7.9,0.6Hz,1H),7.70(dd,J=1.4,0.6Hz,1H),7.66(dd,J=7.9,1.4Hz,1H),7.64-7.59(m,2H),7.55(dd,J=8.1,1.8Hz,1H),2.99(s,6H),2.78-2.70(m,2H),2.70-2.62(m,2H),2.41-2.27(m,4H)。13C NMR(126MHz,CDCl3)δ 151.9,149.6,143.8,137.5,131.9,131.1,127.0,126.8,123.4,122.2,120.5,119.30,110.7,68.0,58.4,52.0,39.2。HRMS(ESI)C20H20BrNO2Na(M+Na+)之計算值:408.0570,實驗值:408.0575。
c)3,6-雙(7-溴-9,9-二(2-甲氧基乙基)-9H-茀-2-基)-1,4-二酮基吡咯并[3,4-c]吡咯4:在氬氣氛圍下,於裝備有回流冷凝器及電磁攪拌器之三頸燒瓶中置放20ml第三戊醇、催化量之氯化鐵(III)及鈉(0.690g,30mmol)。在回流下加熱混合物直至鈉完全反應。接著使反應混合物冷卻至90℃且添加7-溴-9,9-二(2-甲氧基乙基)-9H-茀-2-甲腈(2,4.87g,12.6mmol)。接著加熱混合物至110℃且逐滴添加1.23ml(6.0mmol)丁二酸二異丙酯3(30min)。在110℃下反應16h之後,使混合物冷卻且添加30ml水/乙酸1:1。回流所得懸浮液幾分鐘且冷卻至30℃。接著濾出所獲得之顏料的沈澱,用熱水及甲醇洗滌若干次且真空乾燥。獲得1.66g(32%)呈深棕色粉末狀之4。熔點:>400℃。1H NMR(500MHz,CDCl3:TFA-d 4:1)δ 8.48(br s,2H),8.22(br s,2H),7.96(br s,2H),7.72(d,J=8.0Hz,2H),7.69-7.62(m,4H),3.17(s,6H),3.11-2.95(m,8H),2.59(br s,4H),2.50(br s,4H)。HRMS(ESI)C44H42Br2N2O6Na(M+Na+)之計算值:875.1301,實驗值:875.1307。
d)2,5-雙(2,2-二乙氧基乙基)-3,6-雙(7-溴-9,9-二(2-甲氧基乙基)-9H-茀-2-基)-1,4-二酮基吡咯并[3,4-c]吡咯5:在氬氣氛圍下將3,6-雙(7-溴-9,9-二(2-甲氧基乙基)-9H-茀-2-基)-1,4-二酮基吡咯并[3,4-c]吡咯(4,684mg,0.80mmol)、硫酸氫四丁銨(TBAHS,14mg,0.04mmol)、碳酸鉀(1.66g,12mmol)及20ml DMF之混合物加熱至130℃。接著藉由注射器逐滴添加溴乙醛二乙醇縮乙醛(1.20ml,8.0mmol)(30min)。在130℃下攪拌反應混合物16h,冷卻且用水及二氯
甲烷稀釋。用五份二氯甲烷萃取水層,用水及鹽水洗滌合併之有機層且經硫酸鈉乾燥。蒸發溶劑,且藉由管柱層析(二氯甲烷:丙酮19:1→9:1)分離產物且自CHCl3/MeOH再結晶。獲得440mg(51%)呈橙黃色螢光粉末狀之5。熔點:197-199℃。1H NMR(500MHz,CDCl3)δ 8.23(d,J=1.1Hz,2H),8.16(dd,J=8.0,1.5Hz,2H),7.82(d,J=8.0Hz,2H),7.65-7.60(m,4H),7.53(dd,J=8.2,1.7Hz,2H),4.97(t,J=5.6Hz,2H),3.90(d,J=5.6Hz,4H),3.73(dq,J=9.3,7.0Hz,4H),3.55(dq,J=9.4,7.0Hz,4H),3.05(s,12H),2.85-2.73(m,8H),2.45(ddd,J=15.0,9.5,5.7Hz,4H),2.34(ddd,J=13.5,9.6,5.4Hz,4H),1.19(t,J=7.0Hz,12H)。13C NMR(126MHz,CDCl3)δ 163.4,152.1,149.1(2信號),142.3,138.5,130.9,129.7,127.1,126.8,124.3,122.5,121.8,120.3,109.6,100.4,68.3,63.8,58.4,51.8,45.8,39.3,15.5。HRMS(ESI)C56H66Br2N2O10Na(M+Na+)之計算值:1107.2982,實驗值:1107.3010。
e)2,5-雙(2,2-二乙氧基乙基)-3,6-雙(7-溴-9,9-二(2-甲氧基乙基)-9H-茀-2-基)-1,4-二酮基吡咯并[3,4-c]吡咯(6=化合物I-8):將(5,435mg,0.40mg)溶解於8ml氯仿中。隨後緩慢添加三氟甲烷磺酸(0.78ml,8.8mmol)且在60℃下攪拌反應混合物1h。接著使反應混合物冷卻且緩慢添加三乙胺(1.4ml,10mmol)以中和酸。用二氯甲烷稀釋所獲得之深藍色混合物,用水洗滌3次且經硫酸鈉乾燥。蒸發溶劑
且使固體殘餘物自CHCl3/MeOH再結晶。獲得329mg(91%)呈深紫色結晶狀之6。熔點:354-356℃。1H NMR(500MHz,CDCl3)δ 9.26(s,2H),7.91(d,J=7.3Hz,2H),7.84(s,2H),7.70(d,J=8.1Hz,2H),7.67(d,J=1.4Hz,2H),7.57(dd,J=8.1,1.8Hz,2H),6.88(d,J=7.3Hz,2H),3.01(s,12H),2.92-2.78(m,8H),2.61(ddd,J=14.5,8.9,5.7Hz,4H),2.40(ddd,J=14.1,9.0,5.5Hz,4H)。13C NMR(126MHz,CDCl3)δ 155.8,152.7,150.0,144.4,141.4,137.8,134.6,131.1,127.2,124.1,123.6,123.2,122.7,122.3,117.4,112.3,101.5,68.4,58.3,51.9,39.5。HRMS(ESI)C48H42Br2N2O6(M+)之計算值:900.1410,實驗值:900.1396。
f)(化合物7=聚合物P-11)在鈴木反應條件下使1當量化合物6及1當量噻吩-雙酸酯[175361-81-6]共聚合以得到聚合物P-11。
a)根據Org.Lett.2012,第2670頁合成單體10;使DPP顏料8[84632-54-2]與2當量苯甲醯甲溴[70-11-1]及鹼反應得到烷基化DPP 9:
b)在酸性條件下實現化合物10之環閉合:
c)接著使用實例1f)之聚合條件藉由1當量化合物10及1當量二酸酯11之鈴木共聚合來製備聚合物P-2:
a)根據化合物2合成化合物14:
或者,化合物14可藉由以下途徑合成:
在氬氣氛圍下,於三頸燒瓶(250mL)中置放2-溴-9H-茀([1133-80- 8],37.86g,0.15mol)、氰化銅(I)(21.68g,0.242mol)及二甲基甲醯胺(190mL)。在氬氣下將所得懸浮液加熱至回流。在152℃(油浴,165℃)下在氬氣下攪拌反應混合物17h。使反應混合物冷卻至室溫,接著傾入具有氫氧化銨之冷水中(600mL有冰之冷水,200mL 25%NH4OH水溶液)且攪拌2h。藉由過濾收集所形成之淺棕色沈澱。依序用稀氫氧化銨(800mL)、水(800mL)洗滌固體得到粗產物。用二氯甲烷(6×100mL)自漏斗洗滌潤濕產物且用水(200mL)、飽和NaCl(50mL)洗滌合併之有機物相且經Na2SO4(40.0g)乾燥。此後,濾出Na2SO4,用二氯甲烷(2×50mL)洗滌。蒸發溶劑。在40℃下真空乾燥原始產物[2523-48-0]2h。產量28.58g(99.6%)。熔點:88-90℃。粗產物未經進一步純化即用於下一步驟中。
向9H-茀-2-甲腈(25.39g,0.132mol)於CH2Cl2(200mL)中之攪拌溶液中添加Br2(27.2mL,0.53mol,4.0eq)。經由捕集器將自溶液析出之HBr引導至NaOH之洗滌溶液中。攪拌混合物16h。濾出黃色沈澱,用5% NaHSO3(500mL)、水(4×500mL)洗滌且在50℃下經蒸發器乾燥1h且在室溫下真空(油泵)乾燥隔夜。分離粗灰色固體。產量16.45g 45.8%。
用200mL二氯甲烷洗滌過濾器漏斗且與濾液合併。在分離之後,用二氯甲烷(200mL)萃取水層。用水(4×400mL)、鹽水(100mL)洗滌合併之有機層且經Na2SO4乾燥。濾出(洗滌,100mL CH2Cl2)乾燥劑且在蒸發溶劑之後使殘餘物真空乾燥。產量17.46g 48.6%。總產量94.4%之產物[656238-34-5]。熔點:166-173℃,精確熔點:172℃。
在氬氣下將27.2g(0.1mol)7-溴-9H-茀-2-甲腈及碘化鉀(0.9g)溶
解於150mL二甲亞碸中。使溶液冷卻至10℃且逐滴添加1-溴辛烷(44.6g,0.23mol)且在氬氣下以小份添加氫氧化鉀(34.0g,0.6mol)。在20℃下監測溫度。之後,在室溫下攪拌反應混合物隔夜。用乙醚(250mL)稀釋混合物,接著經由矽藻土(40.0g)過濾且用乙醚(150mL,50mL)洗滌。將濾液傾入有冰之去離子水(500mL)中。
收集有機相且用水(3×100mL)、鹽水(50mL)洗滌且經硫酸鈉(50g)乾燥。溶液經由矽藻土(50.0g)及二氧化矽(80g)過濾,用乙醚(3×100mL)洗滌且濃縮,得到呈黃色油狀之粗產物(51.86g)。藉由自甲醇(80mL)、異丙醇(10mL)及乙醚(2mL)之混合物再結晶分離產物,得到產物[428865-55-8]。產量33.89g(68.1%),熔點:50.0-54.0℃,精確熔點:48.3-52.2℃,1H NMR(500MHz,CDCl3)δ:7.74(dd,J=7.9,0.5Hz,1H,),7.58-7.68(m 3H),7.49-7.53(m,2H),1.95(ddd,J=9.5,6.3,2.8Hz,4H,CH2CH2(CH2)5CH3),1.03-1.25(m,20H,CH2CH2(CH2)5CH3),0.83(t,J=7.2Hz,6H,CH2CH2(CH2)5CH3),0.55(m,4H,CH2CH2(CH2)5CH3)。
b)在氬氣下反應燒瓶(250mL)中裝入40ml 2-甲基-2-丁醇、2.0g(86.9mmol)鈉及30mg氯化鐵(III)。在氬氣下加熱反應混合物至100℃。攪拌反應混合物1h至所有鈉均溶解之時。接著使反應混合物冷卻至90℃且一次性添加7-溴-9,9-二辛基-9H-茀-2-甲腈(10.14g,20.5mmol)(用20ml 2-甲基-2-丁醇洗滌)。攪拌反應物10分鐘,升溫至110℃且經由注射器添加1.98g(9.79mmol)丁二酸二異丙酯。在氬氣下於
油浴中在110℃下攪拌反應混合物隔夜。第二天,使反應混合物冷卻至60℃,藉由添加25mL AcOH、25mL水及25mL EtOH淬滅。在100℃下1h之後,在室溫下持續攪拌隔夜。第二天添加100mL水且經G3過濾器過濾原始產物。向殘餘物濾餅中以小份添加水(25mL)及EtOH(600mL),接著藉由過濾分離產物且在室溫下真空(油泵)乾燥。產量2.49g(23.7%)之式15化合物。將此化合物直接用於下一反應中以得到化合物16。
c)在氬氣氛圍下將3,6-雙(7-溴-9,9-二辛基-9H-茀-2-基)-1,4-二酮基吡咯并[3,4-c]吡咯(1.24g,1.16)、碳酸鉀(2.40g,17.4mmol)及25ml NMP之混合物加熱至120℃。接著藉由注射器添加溴乙醛二乙醇縮乙醛(1.70ml,10.0mmol)。在120℃下攪拌反應混合物1h,接著藉由注射器添加第二份溴乙醛二乙醇縮乙醛(1.70ml,10.0mmol)且在130℃下繼續反應隔夜。第二天,使反應混合物冷卻且用水淬滅。用三份己烷萃取產物。用水及鹽水洗滌合併之有機層兩次。最後經硫酸鈉乾燥,蒸發溶劑且藉由管柱層析(己烷:乙酸乙酯29:1→19:1)純化產物。在真空(油泵)乾燥隔夜之後,獲得0.723g(48%)呈紅橙色螢光固體狀之式16化合物。
d)在氬氣氛圍下,將二縮醛3,6-雙(7-溴-9,9-二辛基-9H-茀-2-基)-2,5-雙(2,2-二乙氧基乙基)-1,4-二酮基吡咯并-[3,4-c]吡咯(677,0.519mmol)溶解於10ml氯仿中。隨後緩慢添加三氟甲烷磺酸(0.92ml,10.4mmol)且在60℃下攪拌反應混合物1h。接著使反應混合物冷卻且緩慢添加三乙胺(1.75ml,12.6mmol)於5ml CHCl3中之溶液以中和酸。將獲得之深藍色混合物置放於500ml錐形瓶中且添加200ml EtOH。使所得懸浮液冷卻且濾出沈澱且真空乾燥,得到呈深藍色粉末狀之式17化合物(=化合物(I-9))。產量:536mg(92%)。
1H NMR(500MHz,CDCl3)δ 9.19(s,2H,9-H及20-H),7.91(d,J=7.3Hz,2H,1-H及12-H),7.83(s,2H,3-H及14-H),7.70(d,J=7.9Hz,2H,4-H及5-H),7.59-7.50(m,4H,7-H及18-H+,5-H及16-H),6.88(d,J=7.4Hz,2H,2-H及13-H),2.29-2.15(m,4H,CH2CH2(CH2)5CH3),2.12-1.98(m,4H,CH2CH2(CH2)5CH3),1.32-0.94(m,40H,CH2CH2(CH2)5CH3),0.78(t,J=7.1Hz,12H,CH2CH2(CH2)5CH3),0.72-0.62(m,8H,CH2CH2(CH2)5CH3)。
經由化合物17及化合物[924894-85-9]之鈴木聚合反應根據聚合物
P-11獲得聚合物P-12(化合物18)。
在氬氣下添加500mg化合物17及186.8mg化合物[239075-02-6]至25ml四氫呋喃中。接著添加48.24mg膦配位體[740815-37-6]以及8mg乙酸鈀(II)。接著將混合物加熱至回流。接著添加112.47mg LiOH單水合物且在回流下加熱混合物隔夜。使混合物冷卻且傾入水中。過濾沈澱且用水及甲醇洗滌。接著用庚烷、四氫呋喃及甲苯對濾餅進行索司勒(Soxhlet)萃取。四氫呋喃溶離份含有重量平均分子量(Mw)為20,246Da且多分散性(PDI)為2.52之聚合物19。甲苯溶離份含有Mw為28,825Da且PDI為1.72之聚合物19。
聚合物P-22(化合物20)類似於聚合物P-21(化合物19)經由化合物17及化合物[175361-81-6]之鈴木聚合反應獲得。四氫呋喃溶離份含有Mw為27,769Da且PDI為2.04之聚合物20。甲苯溶離份含有Mw為54,561Da且PDI為1.70之聚合物20。
在氬氣下將1000mg化合物17及520.76mg錫化合物[14275-61-7]添加至無水甲苯中。接著添加29.78mg四(三苯基膦)鈀且將混合物加熱至回流隔夜。使反應混合物冷卻且傾入甲醇中。過濾沈澱且用甲醇及丙酮洗滌濾餅。接著用庚烷、四氫呋喃及甲苯對濾餅進行索司勒萃取。四氫呋喃溶離份含有Mw為30,484Da且PDI為3.14之聚合物21。甲苯溶離份含有Mw為65,063Da且PDI為2.83之聚合物21。
a)化合物22之合成類似於化合物14之合成藉由用1-溴-十二烷對化合物[656238-34-5]烷基化來進行。
1H NMR(500MHz,CDCl3)δ:7.73(d,J=7.8Hz,1H,),7.63(dd,J=7.9,1.2Hz,1H),7.61-7.58(m,3H),7.49-7.52(m2H),1.95(ddd,J=9.9,6.4,2.8Hz,4H,CH2CH2(CH2)9CH3),1.30-1.10(m,36H,CH2CH2(CH2)9CH3),0.83(t,J=7.1Hz,6H,CH2CH2(CH2)9CH3),0.55(m,4H,CH2CH2(CH2)9CH3)。
b)化合物23之合成類似於化合物15之合成藉由化合物22及化合物3之縮合反應進行。
1H NMR(500MHz,CDCl3:TFA-d 4:1)δ 8.41(br s,2H,在茀基處1-H),8.20(br d,J=6.4Hz,2H,在茀基處3-H),7.90(d,J=7.9Hz,2H,在茀基處4-H),7.72-7.56(m,6H,5-H,在茀基處6-H及8-H),2.19(td,J=10.0,3.8Hz,4H,CH2CH2(CH2)9CH3),2.08(td,J=10.0,3.8Hz,4H,CH2CH2(CH2)9CH3),1.38-0.96(m,72H,CH2CH2(CH2)9CH3),0.86(t,J=6.2Hz,12H,CH3),0.82-0.64(m,8H,CH2CH2(CH2)9CH3)。
c)化合物24之合成類似於化合物16之合成藉由用溴乙醛二乙醇縮乙醛對化合物23烷基化來進行。
1H NMR(500MHz,CDCl3)δ,8.16(s,2H),8.15(dd,J=7.9,1.2Hz,1H,),7.80(d,J=7.9Hz,1H,),7.61(d,J=7.9Hz,1H),7.47-7.60(m 3H),).4.99(t,J=5.6Hz,2H,NCH2CH(OEt)2),3.90(d,J=5.8Hz,4H,NCH2CH(OEt)2),3.73(dq,J=9.5,7.1Hz,4H,OCH2CH3),3.55(dq,
J=9.2,7.0Hz,4H,OCH2CH3),2.05(ddd,J=13.4,10.1,6.4Hz,4H,CH2CH2(CH2)9CH3),1.96(ddd,J=13.4,10.1,6.4Hz,4H,CH2CH2(CH2)9CH3),1.00-1.30(m,96H,CH2CH2(CH2)9CH3及OCH2CH3),0.85(t,J=7.0Hz,12H,CH2CH2(CH2)9CH3),0.62-0.71(m,8H,CH2CH2(CH2)9CH3)。
d)化合物25之合成類似於化合物17之合成藉由在酸性條件下使化合物24發生閉環反應來進行。
1H NMR(500MHz,CDCl3)δ 9.19(s,2H,9-H及20-H),7.91(d,J=6.7Hz,2H,1-H及12-H),7.83(s,2H,3-H及14-H),7.69(d,J=7.9Hz,2H,4-H及15-H),7.60-7.50(m,4H,7-H及18-H+,5-H及16-H),6.87(d,J=7.3Hz,2H,2-H及13-H),2.28-2.18(m,4H,CH2CH2(CH2)9CH3),2.09-1.98(m,4H,CH2CH2(CH2)9CH3),1.24-1.00(m,72H,CH2CH2(CH2)9CH3),0.82(t,J=7.1Hz,12H,CH2CH2(CH2)9CH3),0.73-0.63(m,8H,CH2CH2(CH2)9CH3)。
聚合物P-24(化合物26)類似於聚合物P-21(化合物19)經由化合物25及化合物[175361-81-6]之鈴木聚合反應獲得。四氫呋喃溶離份含有Mw為44,416Da且PDI為1.73之聚合物26。
聚合物P-25(化合物27)類似於聚合物P-23(化合物21)經由化合物25及化合物[14275-61-7]之施蒂勒聚合反應獲得。四氫呋喃溶離份含有Mw為124,676Da且PDI為4.58之聚合物27。
以聚合物P-22為主之有機場效應電晶體(OFET)之製造及電表徵
將聚合物P-22以0.75重量%之濃度溶解於甲苯中且隨後塗佈於具有經微影圖案化金觸點之PET基板上,充當OFET之源極及汲極觸點。100μl調配物藉由標準刀片塗佈機以20mm/s之塗佈速度進行塗佈,從而在整個基板之上產生均勻半導體層。在塗佈完成之後,即刻將基板輸送至預加熱之加熱板上且在90℃下加熱30s。接下來,將由
Cytop CTL-809M組成之閘極電介質層旋塗於有機半導體之上(1200rpm,30s)。在旋塗之後,再次將基板輸送至加熱板上且在100℃下再退火5Min。最後。藉由真空蒸發沈積50nm厚之遮蔽罩圖案化金閘極電極以使BGTC組態中之FET完善。
在通道長度L=10μm且通道寬度W=250μm之情況下,對此代表性裝置,電洞遷移率計算為μ約為1×10-4cm2/Vs。臨限電壓為-6.5V,而開/關比率為1.06×102。
以聚合物P-25為主之有機場效應電晶體(OFET)之製造及電表徵
樣品製備及電表徵與應用實例1中所述相同。
在通道長度L=10μm且通道寬度W=250μm之情況下,對於此代表性裝置,電洞遷移率計算為μ約為4×10-5cm2/Vs。臨限電壓為-8V,而開/關比率為1.1×101。
將聚合物P-21於甲苯中之溶液刮塗於頂閘極底接觸電晶體(金觸點,通道長度為100μm及200μm,通道寬度為10000μm)上。將Cytop用作介電質。經測量兩種通道長度之電洞遷移率皆為0.001cm2/Vs。
Claims (17)
- 一種聚合物,其包含一或多個式 之(重複)單元,其 中 Y為式之基團; a為0、1、2或3,a'為0、1、2或3;b為0、1、2或3;b'為0、1、2或3;c為0、1、2或3;c'為0、1、2或3;Ar及Ar'指示同芳族或雜芳族系統,其可經取代或未經取代,R1、R1'、R2及R2'可相同或不同且係選自:氫、C1-C100烷基,其可視情況經C1-C12烷基、C1-C12烷氧基、鹵素、C5-C12環烷基、硝基、氰基、乙烯基、烯丙基、C6-C24芳基、C2-C20雜芳基、矽烷基或矽氧烷基取代一或多次;及/或可視情況雜有-O-、-S-、-NR39-、CONR39-、NR39CO-、-COO-、-CO-或-OCO-,C2-C100烯基,其可視情況經C1-C12烷基、C1-C12烷氧基、鹵素、C5-C12環烷基、硝基、氰基、乙烯基、烯丙基、C6-C24芳基、C2-C20雜芳基、矽烷基或矽氧烷基取代一或多次;及/或可視情況雜有-O-、-S-、-NR39-、CONR39-、NR39CO-、-COO-、-CO-或-OCO-,C3-C100炔基,其可視情況經C1-C12烷基、C1-C12烷氧基、鹵 素、C5-C12環烷基、硝基、氰基、乙烯基、烯丙基、C6-C24芳基、C2-C20雜芳基、矽烷基或矽氧烷基取代一或多次;及/或可視情況雜有-O-、-S-、-NR39-、CONR39-、NR39CO-、-COO-、-CO-或-OCO-,C3-C12環烷基,其可視情況經C1-C12烷基、C1-C12烷氧基、鹵素、C5-C12環烷基、硝基、氰基、乙烯基、烯丙基、C6-C24芳基、C2-C20雜芳基、矽烷基或矽氧烷基取代一或多次;及/或可視情況雜有-O-、-S-、-NR39-、CONR39-、NR39CO-、-COO-、-CO-或-OCO-,C6-C24芳基,其可視情況經C1-C12烷基、C1-C12烷氧基、鹵素、C5-C12環烷基、硝基、氰基、乙烯基、烯丙基、C6-C24芳基、C2-C20雜芳基、矽烷基或矽氧烷基取代一或多次;C2-C20雜芳基,其可視情況經C1-C12烷基、C1-C12烷氧基、鹵素、C5-C12環烷基、硝基、氰基、乙烯基、烯丙基、C6-C24芳基、C2-C20雜芳基、矽烷基或矽氧烷基取代一或多次;-CO-C1-C18烷基、-CO-C5-C12環烷基或-COO-C1-C18烷基;R39為氫、C1-C18烷基、C1-C18鹵烷基、C7-C25芳基烷基或C1-C18醯基, Ar1、Ar1'、Ar2、Ar2'、Ar3及Ar3'彼此獨立地為
- 如請求項1之聚合物,其為包含一或多個式之 (重複)單元之聚合物,其中Y為式 之基團,其中 a為0、1、2或3,a'為0、1、2或3;其中Ar1、Ar1'、Ar及Ar'及R1、R1'、R2及R2'係如請求項1所定義。
- 如請求項1或2之聚合物,其包含一或多個以下式之(重複)單元:
- 如請求項3之聚合物,其包含一或多個以下式之(重複)單元:
- 如請求項1或2之聚合物,其包含式及之(重 複)單元,其中A為式(I)之重複單元,及-COM1-為重複單元,其具有Ar1之含義,其中Ar1係如請求項1 所定義,或為式之基團, s為1,t為1,u為0或1,v為0或1,及Ar14、Ar15、Ar16及Ar17彼此獨立地為以下式之基團:
- 如請求項5之聚合物,其為式之聚合物, 其中A及COM1係如請求項5所定義;且n為4至1000,尤其4至200,極尤其5至150。
- 如請求項5之聚合物,其中A為如請求項3所定義之式(Ya)、(Yb)、(Yd)、(Yj)、(Yo*),尤其(Yo)、(Yaf)或(Yah);或如請求項4所定義之式(Ya')、(Yb')、(Yd')、(Yj')、(Yo')、(Yaf’)或 (Yah')之重複單元,且為式,尤其
- 如請求項5之聚合物,其中為式 尤其或之基團;其中 R108及R109彼此獨立地為C1-C25烷基,其可雜有一或多個氧原 子。
- 如請求項5之聚合物,其為以下式之聚合物:
- 如請求項9之聚合物,其為以下式之聚合物:
- 一種有機半導體材料、層或組件,其包含如請求項1至10中任一項之聚合物。
- 一種半導體裝置,其包含如請求項1至10中任一項之聚合物及/或如請求項11之有機半導體材料、層或組件。
- 如請求項12之半導體裝置,其為有機光伏打裝置、光電二極體或有機場效電晶體。
- 一種製備有機半導體裝置之方法,該方法包含將如請求項1至10中任一項之聚合物於有機溶劑中之溶液及/或分散液施用於適合基板上且移除該溶劑。
- 一種如請求項1至10中任一項之聚合物及/或如請求項11之有機半導體材料、層或組件的用途,其係於PV裝置中、光電二極體中、作為IR吸收劑或於有機場效電晶體中使用。
- 一種下式之化合物, ,其中 X2及X2'彼此獨立地為鹵素,尤其Br或I;ZnX12;-SnR207R208R209,其中R207、R208及R209係相同或不同且為H或C1-C6烷基,其中兩個基團視情況形成共用環且此等基團視情況為分支鏈或非分支鏈的;-SiR210R211R212,其中R210、R211及R212係相同或不同且為鹵素或C1-C6烷基;X12為鹵素原子,極尤其為I或 Br;-OS(O)2CF3;-OS(O)2-芳基,尤其為;- OS(O)2CH3;-B(OH)2;-B(OY1)2;;- BF4Na或-BF4K,其中Y1在每次出現時獨立地為C1-C10烷基且Y2在每次出現時獨立地為C2-C10伸烷基,諸如-CY3Y4-CY5Y6-或-CY7Y8-CY9Y10-CY11Y12-,其中Y3、Y4、Y5、Y6、Y7、Y8、Y9、Y10、Y11及Y12彼此獨立地為氫或C1-C10烷基,尤其為-C(CH3)2C(CH3)2-、-C(CH3)2CH2C(CH3)2-或-CH2C(CH3)2CH2-,且Y13及Y14彼此獨立地為氫或C1-C10烷基; Y為式之基團; a為0、1、2或3,a'為0、1、2或3;b為0、1、2或3;b'為0、1、2或3;c為0、1、2或3;c'為0、1、2或3; Ar及Ar'彼此獨立地為,諸如
- 如請求項16之化合物,其為以下式之化合物:
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