JP5865493B2 - 低バンドギャップの共重合体及びその製造方法 - Google Patents
低バンドギャップの共重合体及びその製造方法 Download PDFInfo
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- JP5865493B2 JP5865493B2 JP2014520150A JP2014520150A JP5865493B2 JP 5865493 B2 JP5865493 B2 JP 5865493B2 JP 2014520150 A JP2014520150 A JP 2014520150A JP 2014520150 A JP2014520150 A JP 2014520150A JP 5865493 B2 JP5865493 B2 JP 5865493B2
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- 229920001577 copolymer Polymers 0.000 title claims description 108
- 238000000034 method Methods 0.000 title claims description 23
- 230000008569 process Effects 0.000 title claims description 6
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 31
- 238000006254 arylation reaction Methods 0.000 claims description 21
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 20
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 19
- 125000003545 alkoxy group Chemical group 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 14
- 239000010409 thin film Substances 0.000 claims description 13
- 150000001412 amines Chemical class 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 8
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 description 54
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 42
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 39
- YMMGRPLNZPTZBS-UHFFFAOYSA-N 2,3-dihydrothieno[2,3-b][1,4]dioxine Chemical compound O1CCOC2=C1C=CS2 YMMGRPLNZPTZBS-UHFFFAOYSA-N 0.000 description 33
- 239000000370 acceptor Substances 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 26
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 26
- 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 24
- 238000004770 highest occupied molecular orbital Methods 0.000 description 21
- 238000005160 1H NMR spectroscopy Methods 0.000 description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 18
- 239000007787 solid Substances 0.000 description 18
- CZDVJGBXKADLCY-UHFFFAOYSA-N thieno[3,4-b]pyrazine Chemical compound N1=CC=NC2=CSC=C21 CZDVJGBXKADLCY-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- -1 heteroaryl halides Chemical class 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 239000011541 reaction mixture Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- 230000003287 optical effect Effects 0.000 description 14
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 11
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- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 9
- QZVHYFUVMQIGGM-UHFFFAOYSA-N 2-Hexylthiophene Chemical compound CCCCCCC1=CC=CS1 QZVHYFUVMQIGGM-UHFFFAOYSA-N 0.000 description 9
- 238000003775 Density Functional Theory Methods 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000004364 calculation method Methods 0.000 description 9
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- 239000010410 layer Substances 0.000 description 9
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 9
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 8
- 101150065749 Churc1 gene Proteins 0.000 description 8
- 102100038239 Protein Churchill Human genes 0.000 description 8
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 8
- 238000000862 absorption spectrum Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 7
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- 238000006116 polymerization reaction Methods 0.000 description 7
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- XECCJSBEUDPALF-UHFFFAOYSA-N 5-(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound S1C=C2OCCOC2=C1C1=C2OCCOC2=CS1 XECCJSBEUDPALF-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- UDGKZGLPXCRRAM-UHFFFAOYSA-N 1,2,5-thiadiazole Chemical compound C=1C=NSN=1 UDGKZGLPXCRRAM-UHFFFAOYSA-N 0.000 description 5
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 description 5
- AHGHPBPARMANQD-UHFFFAOYSA-N 2,5-dibromo-3,4-dinitrothiophene Chemical compound [O-][N+](=O)C1=C(Br)SC(Br)=C1[N+]([O-])=O AHGHPBPARMANQD-UHFFFAOYSA-N 0.000 description 5
- AIIVDZFQFBEWIW-UHFFFAOYSA-N 5,7-dibromothieno[3,4-b]pyrazine Chemical compound N1=CC=NC2=C(Br)SC(Br)=C21 AIIVDZFQFBEWIW-UHFFFAOYSA-N 0.000 description 5
- 238000005700 Stille cross coupling reaction Methods 0.000 description 5
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
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- 230000001965 increasing effect Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
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- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 5
- AGZYNVVJQAOVRP-UHFFFAOYSA-N thiophene-3,4-diamine Chemical compound NC1=CSC=C1N AGZYNVVJQAOVRP-UHFFFAOYSA-N 0.000 description 5
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 125000001246 bromo group Chemical group Br* 0.000 description 4
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- KBVDUUXRXJTAJC-UHFFFAOYSA-N 2,5-dibromothiophene Chemical compound BrC1=CC=C(Br)S1 KBVDUUXRXJTAJC-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
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- 150000001875 compounds Chemical class 0.000 description 3
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- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 3
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
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- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
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- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
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- IVXQUINNUFGWID-UHFFFAOYSA-N tributyl-(5-tributylstannyl-2,3-dihydrothieno[3,4-b][1,4]dioxin-7-yl)stannane Chemical compound O1CCOC2=C([Sn](CCCC)(CCCC)CCCC)SC([Sn](CCCC)(CCCC)CCCC)=C21 IVXQUINNUFGWID-UHFFFAOYSA-N 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 1
- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical compound C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-UHFFFAOYSA-N 0.000 description 1
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 description 1
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- NLIJIXLRIYPOHM-UHFFFAOYSA-N 5-methylsulfanyl-1h-imidazole Chemical compound CSC1=CN=CN1 NLIJIXLRIYPOHM-UHFFFAOYSA-N 0.000 description 1
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
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- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- YJSKZIATOGOJEB-UHFFFAOYSA-N thieno[2,3-b]pyrazine Chemical compound C1=CN=C2SC=CC2=N1 YJSKZIATOGOJEB-UHFFFAOYSA-N 0.000 description 1
- BFLIRPGEXPAQAW-UHFFFAOYSA-N thiophene-2,3-diamine Chemical compound NC=1C=CSC=1N BFLIRPGEXPAQAW-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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Description
のうちから選択され、前記−R1はC1−C12アルキル基、C1−C12のアルキル基を含むアルコキシ、アミン、フェニル基であり、前記−Y−は−CH2−,−NH−又は−O−であり、前記−A1,−A2−は互いに異なってそれぞれ独立的に
,
のうちから選択され、前記−R2,−R3,−R4,−R5は互いに同じであるか異なってそれぞれ独立的に−H、C1−C12アルキル基、C1−C12のアルキル基を含むアルコキシ又はフェニル基であり、前記nは10−10,000の整数である共重合体に関するものである。
のうちから選択され、前記−R4,−R5は互いに同じであるか異なってそれぞれ独立的に−H,C1−C12アルキル、C1−C12アルコキシ又はフェニル基であり、前記nは10−10,000の整数である共重合体に関するものである。
のうちから選択され、前記−R1はC1−C12アルキル基、C1−C12のアルキル基を含むアルコキシ、アミン、フェニル基であり、前記−Y−は−CH 2 −,−NH−又は−O−であり、前記−A1−は
,
のうちから選択され、前記−R2,−R3,−R4,−R5は互いに同じであるか異なってそれぞれ独立的に−H,C1−C12アルキル基、C1−C12のアルキル基を含むアルコキシ又はフェニル基であり、前記nは10−10,000の整数である化2の共重合体の製造方法に関するものである。
のうちから選択され、前記−R1はCl−Cl2アルキル基、Cl−Cl2のアルキル基を含むアルコキシ、アミン、フェニル基であり、前記−Y−は−CH 2 −,−NH−又は−O−であり、前記−A1−,−A2−は互いに異なってそれぞれ独立的に
,
のうちから選択され、前記−R2,−R3,−R4,−R5は互いに同じであるか異なってそれぞれ独立的に−H,C1−C12アルキル基、C1−C12のアルキル基を含むアルコキシ又はフェニル基であり、前記nは10−10,000の整数であることを特徴とする化3の共重合体の製造方法に関するものである。
,
のうちから選択され、前記−L,−L2は互いに同じであるか異なってそれぞれ独立的に−Cl、−Br又は−Iのうちから選択され、前記−R1,−R2,−R3,−R1’は互いに同じであるか異なってそれぞれ独立的にヘキシル、C1−C12アルキル基、フェニル、C1−C12のアルキル基を含むアルコキシ、−H、アミン基であり、前記−Z−は
のうちから選択され、前記R4,R5は互いに同じであるか異なってそれぞれ独立的に−H、C1−C12アルキル基、C1−C12のアルキル基を含むアルコキシ、アミン又はフェニル基であり前記nは10−10,000の整数である化4の共重合体の製造方法に関するものである。
2;R=Sn(C4H9)3(90.0%)
4;R=Sn(C4H9)3(92.4%)
試薬及び条件:(i)LDA/THF,(Bu)3SnCl,0℃乃至室温;(ii)n−BuLi/THF/−80℃、CuCl2/−80℃乃至−40℃;(iii)n−BuLi/THF/−80℃、(Bu)3SnCl、THF(−80℃乃至室温)。
試薬及び条件:(i)H2SO4/F.H2SO4/F.HNO3,アイスバス乃至室温、3h;(ii)Sn/HCl,一晩0℃;(iii)水生グリオキサール、K2CO3、室温3h;(iv)NBS、AcOH/CHCl3、室温一晩
図3は、HT−BT−HT単位と共に(a)EDOT又は
<実施例3:電気化学的特性>
共重合体P1〜P6とPBTHTの電気化学的特性が循環電圧計(CV)によって調査された。P1〜P6の循環電圧グラフが図7に示されている。重合体のHOMO及びLUMOエネルギー順位(EHOMO及びELUMO)は以下の関係式によって決定される(23):EHOMO=‐EOX−4.4及びELUMO=‐Ered−4.4(eV単位)、ここでEox及びEredはAg/AgCl基準電極に対する重合体の開始酸化及び還元電位である。誘導されたEHOMO、ELUMO及び電気化学的バンドギャップ(Egec=ELUMO−EHOMO)が表2に要約されている。推定されたEgec値は角膜で推定された光学バンドギャップ(Egop)より多少高いが、これは重合体膜と電極表面との間に存在する界面障壁のためである可能性がある(22c,24)。HT上のヘキシル側鎖の位置を変更するだけでなく、重合体のバックボーンに追加のドナーやアクセプター部分を合体することで電気化学的挙動に目に見える効果が発揮される。図7は、P1〜P6の循環電圧グラフを示す図である。
[60]PCBM/A1の構造を有するBHJ光電地セルが製作され、ドナーとしてはその共重合体が、アクセプターとしてはPCBMが使用された。活性層の製造に使用される溶媒は電池の性能に強い影響を及ぼすと知られている。よって、ここでは優秀な品質のフィルムを得るためにクロロベンゼンを選択する。装置はソーラーシミュレーターAM1.5G(100mW/cm2)で電流‐電圧特性を応じに記録して特性化された。シミュレーションされた太陽光線(100mW/cm2)下で測定された電流‐電圧(I−V)曲線が図8に示される。関連するパラメータは表3に要約されている。図8は、共重合体(P1〜P6)のBHJ太陽電池の電流−電圧特性を示す図である(100mW/cm2の照査強度、PCBM)。
別途の言及がない限り、空気に敏感な試薬を含んだ全ての操作及び反応は乾燥した酸素無含有窒素雰囲気で行った。全ての試薬及び溶媒は商業的に販売されている製品を購入しており、使用する前に標準過程に従って乾燥させた。全ての反応はTLCで完了が確認された。
1H及び13C NMRスペクトルは内部基準でTMSを使用して25℃でCDCl3の中でVarian分光器(400MHz,1H;100MHz,13C)で測定され、化学的移動はppm単位で記録された。結合定数(J)の単位はHzである。フラッシュカラムクロマトグラフィはMerckシリカゲル60(分子サイズ230〜400メッシュ ASTM)を使用して行われた。このカラムクロマトグラフィに使用された同じ溶離液の中で、シリカゲルにトリエチルアミンを添加して中和されたシリカゲルを製造した。分析用薄膜クロマトグラフィ(TLC)はMerck 0.25mm 60Fシリカゲルが予めコーティングされているアルミニウム板とUV−254蛍光指示計を使用して行われた。UV−vis吸収スペクトルはCary UV−vis−NIR−5000分光光度計で純粋な重合体サンプルを対象に得られた。熱分解温度は窒素雰囲気で熱重量分析(TGA−TA機器 Q−50)で測定された。DSCは分当たり10℃の加熱速度で窒素雰囲気でTA機器(DSC−TA機器 Q−20)で行われた。CV測定はB級ソーラーシミュレータで行われた。ポテンショスタット/ガルバノスタット(SP−150 OMA Company);指示電解質はアセト二トリルに溶解されたテトラブチルアンモニウムヘキサフルオロフォスフェート(0.1M)であって、スキャン速度は50mV/sであった;電極が3つであるセルが使用された;プラチナワイヤと銀/塩化銀(0.1M KClの中のAg)がそれぞれカウンタ電極と基準電極として使用された。電気化学的測定対象として重合体膜はITOガラススライドの上で重合体−クロロベンゼン溶液からスピン
コーティングされた(約10mg/mL)。GPC分析はShimadzu(LC−20A Prominenceシリーズ)機器で行われた;クロロフォルムがキャリア溶媒(流速:1mL/分、30℃)として使用され、標準ポリスチレンサンプルを使用してキャリブレーション曲線が作成された。マイクロ波補助重合が集中マイクロ波合成システムCEM(Discover S−Class System)で行われた。低温反応は必ず低温槽(PSL1810−SHANGHA EYELA)で行われた。シリンジポンプであるKD Scientific(KDS−100)を使用して滴下過程の間に試薬を正確で精密な量で送達した。
(黄色の固体;1.69g,23%)1H NMR(CDCl3,400MHz,δ/ppm):6.22(s,1H,CHS)、4.29−4.16(m,8H,2XOCH2CH2O)、1.60−1.45(m,6H,3XCH3CH2CH2CH2)、1.34−1.30(m,6H,3XCH3CH2CH2),1.13−1.11(m,6H,3XCH3CH2),0.91−0.87(t,J=16Hz,9H,3XCH3)。13C NMR(CDCl3,100MHz,δ/ppm):147.06,141.13,137.68,136.69,115.52,110.43,106.80,96.90,64.88,64.48,28.96,27.04,13.58,10.48.C24H36O4S2Sn(571.38):理論値C50.45、H6.35,S11.22,Sn20.78;実測値C50.40、H6.39,S11.19。
ジエチルエテルで抽出し、無水硫酸ナトリウムで乾燥させた後、加熱せずに回転蒸発器で濃縮して3,4−ジアミノチオフェンの白色結晶生成物を得た(2.6g,61%)。1H NMR(CDCl3,400MHz,δ/ppm):6.16(s,2H,2XCHS)、δ3.36(s,br,4H,2XNH2)。13C NMR(CDCl3,100MHz,δ/ppm):137.2,101.7。C4H6N2S(114.17):
理論値C42.08、H5.30,N24.54,S28.09;実測値C42.18、H5.50,N24.66,S27.92。
Claims (6)
- 下記化3の構造を有する共重合体であって、
のうちから選択され、
前記−R1はC1−C12アルキル基、C1−C12のアルキル基を含むアルコキシ、アミン、フェニル基であり、
前記−Y−は−CH2−,−NH−又は−O−であり、
前記−A1,−A2−は互いに異なってそれぞれ独立的に
,
のうちから選択され、前記−R2,−R3,−R4,−R5は互いに同じであるか異なってそれぞれ独立的に−H、C1−C12アルキル基、C1−C12のアルキル基を含むアルコキシ又はフェニル基であり、
前記nは10−10,000の整数であることを特徴とする共重合体。
- 下記化8の構造を有する共重合体であって、
前記−R2,−R3は互いに同じであるか異なってそれぞれ独立的にヘキシル、C1−C12アルキル基、C1−C12のアルキル基を含むアルコキシ、アミン、−H又はフェニル基であり、
前記−R4,−R5は互いに同じであるか異なってそれぞれ独立的に−H,C1−C12アルキル基、C1−C12のアルキル基を含むアルコキシ、アミン又はフェニル基であり、
前記nは10−10,000の整数であることを特徴とする共重合体。 - 下記化12の第1単量体とA2の第2単量体をPdを含む触媒下で直接CHアリール化反応を行うステップを含む下記化3の共重合体の製造方法であって、
前記−D1−,−D2−は互いに同じであるか異なってそれぞれ独立的に
のうちから選択され、
前記−R1はCl−Cl2アルキル基、Cl−Cl2のアルキル基を含むアルコキシ、アミン、フェニル基であり、前記−Y−は−CH 2 −,−NH−又は−O−であり、
前記−A1−,−A2−は互いに異なってそれぞれ独立的に
,
のうちから選択され、前記−R2,−R3,−R4,−R5は互いに同じであるか異なってそれぞれ独立的に−H,C1−C12アルキル基、C1−C12のアルキル基を含むアルコキシ又はフェニル基であり、
前記nは10−10,000の整数であることを特徴とする化3の共重合体の製造方法。 - 下記化13の第1単量体と第2単量体をPdを含む触媒下で直接CHアリール化反応を行うステップを含む下記化4の共重合体の製造方法であって、
前記第2単量体は
,
のうちから選択され、
前記−R1,−R2,−R3,−R1’は互いに同じであるか異なってそれぞれ独立的にヘキシル、C1−C12アルキル基、フェニル、C1−C12のアルキル基を含むアルコキシ、−H、アミン基であり、
前記−Z−は
のうちから選択され、前記R4,R5は互いに同じであるか異なってそれぞれ独立的に−H、C1−C12アルキル基、C1−C12のアルキル基を含むアルコキシ、アミン又はフェニル基であり、
前記nは10−10,000の整数であることを特徴とする化4の共重合体の製造方法。 - 請求項1又は請求項2による共重合体を含む染料感応型太陽電池。
- 請求項1又は請求項2による共重合体を含む有機薄膜トランジスタ。
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