CN102459399A - 制备区域规则的聚-(3-取代的)噻吩、硒吩、噻唑和硒唑的方法 - Google Patents
制备区域规则的聚-(3-取代的)噻吩、硒吩、噻唑和硒唑的方法 Download PDFInfo
- Publication number
- CN102459399A CN102459399A CN2010800314475A CN201080031447A CN102459399A CN 102459399 A CN102459399 A CN 102459399A CN 2010800314475 A CN2010800314475 A CN 2010800314475A CN 201080031447 A CN201080031447 A CN 201080031447A CN 102459399 A CN102459399 A CN 102459399A
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- Prior art keywords
- substituted
- alkyl
- dihalo
- organic
- thiophene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 229930192474 thiophene Natural products 0.000 title claims description 23
- 150000003577 thiophenes Chemical class 0.000 title claims description 10
- 150000003557 thiazoles Chemical class 0.000 title claims description 6
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- 150000005082 selenophenes Chemical class 0.000 title 1
- 239000011701 zinc Substances 0.000 claims abstract description 33
- -1 3-substituted thiophene Chemical class 0.000 claims abstract description 31
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 31
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 18
- 239000011777 magnesium Substances 0.000 claims abstract description 18
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920001519 homopolymer Polymers 0.000 claims abstract description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 125000006649 (C2-C20) alkynyl group Chemical group 0.000 claims description 6
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 6
- 125000001072 heteroaryl group Chemical group 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000001475 halogen functional group Chemical group 0.000 claims 2
- 239000003054 catalyst Substances 0.000 abstract description 3
- 230000000630 rising effect Effects 0.000 abstract description 3
- 125000002734 organomagnesium group Chemical group 0.000 abstract 3
- 229920001577 copolymer Polymers 0.000 abstract 2
- 229910018583 Ni(O) Inorganic materials 0.000 abstract 1
- WXHIJDCHNDBCNY-UHFFFAOYSA-N palladium dihydride Chemical compound [PdH2] WXHIJDCHNDBCNY-UHFFFAOYSA-N 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 22
- 239000010410 layer Substances 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 239000004065 semiconductor Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 239000002585 base Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- JEDHEMYZURJGRQ-UHFFFAOYSA-N 3-hexylthiophene Chemical compound CCCCCCC=1C=CSC=1 JEDHEMYZURJGRQ-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000002800 charge carrier Substances 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
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- 0 *c(cc([s]1)Br)c1Br Chemical compound *c(cc([s]1)Br)c1Br 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000005669 field effect Effects 0.000 description 3
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-Bis(diphenylphosphino)propane Substances C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- IDIAJXCQVAOTOR-UHFFFAOYSA-M [Br-].CCCCCCC=1C=C([Zn+])SC=1Br Chemical compound [Br-].CCCCCCC=1C=C([Zn+])SC=1Br IDIAJXCQVAOTOR-UHFFFAOYSA-M 0.000 description 2
- ITPFBKSKXYDHSZ-UHFFFAOYSA-M [Br-].CCCCCCc1cc(Br)sc1[Zn+] Chemical compound [Br-].CCCCCCc1cc(Br)sc1[Zn+] ITPFBKSKXYDHSZ-UHFFFAOYSA-M 0.000 description 2
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229910052728 basic metal Inorganic materials 0.000 description 2
- 150000003818 basic metals Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- WUOIAOOSKMHJOV-UHFFFAOYSA-N ethyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(CC)C1=CC=CC=C1 WUOIAOOSKMHJOV-UHFFFAOYSA-N 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- XQJNXCHDODCAJF-UHFFFAOYSA-N 2-bromo-3-hexylthiophene Chemical class CCCCCCC=1C=CSC=1Br XQJNXCHDODCAJF-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- 229920001621 AMOLED Polymers 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical class [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- AAXGWYDSLJUQLN-UHFFFAOYSA-N diphenyl(propyl)phosphane Chemical compound C=1C=CC=CC=1P(CCC)C1=CC=CC=C1 AAXGWYDSLJUQLN-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 238000001914 filtration Methods 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- NDJKXXJCMXVBJW-UHFFFAOYSA-N heptadecane Chemical compound CCCCCCCCCCCCCCCCC NDJKXXJCMXVBJW-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 1
- 230000005426 magnetic field effect Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
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- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- LQERIDTXQFOHKA-UHFFFAOYSA-N nonadecane Chemical compound CCCCCCCCCCCCCCCCCCC LQERIDTXQFOHKA-UHFFFAOYSA-N 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
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- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
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- 230000009257 reactivity Effects 0.000 description 1
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- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
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- 241000894007 species Species 0.000 description 1
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- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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Abstract
本发明涉及一种通过如下步骤制备3-取代的噻吩、3-取代的硒吩、3-取代的噻唑或3-取代的硒唑的区域规则均聚物或共聚物的方法:a)使3-取代的2,5-二卤代噻吩、2,5-二卤代硒吩、2,5-二卤代噻唑或2,5-二卤代硒唑与反应性锌、镁和/或有机镁卤化物反应得到含有一种卤代锌或一种卤代镁基团的有机锌或有机镁中间体,b)使有机锌或有机镁中间体与Ni(II)、Ni(0)、Pd(II)或Pd(0)催化剂接触以引发聚合反应,和c)使有机锌或有机镁中间体聚合以得到3-取代的噻吩、3-取代的硒吩、3-取代的噻唑或3-取代的硒唑的区域规则的头-尾均聚物或共聚物,其特征在于聚合反应在时间t1期间于从较低温度T1升至较高温度T2的温度下进行,其中T1为-40℃至5℃且T2为-20℃至40℃,其中T2-T1为至少10℃且平均升高率(T2-T1)/t1为0.05-1℃/分钟。
Description
本发明涉及一种制备区域规则的聚-(3-取代的)噻吩、硒吩、噻唑和硒唑的方法。
在20世纪下半叶,为(微)电子部件开发的复杂结构单元是基于无机电极、绝缘体和半导体的场效应晶体管(FET)。这些材料已经证明可靠、高效,且性能根据著名的摩尔定律周期性增强。不与传统硅技术竞争,基于分子和聚合材料的有机FET(OFET)可以发现在低性能记忆元件以及集成的光电器件中大规模应用,例如在活性基材有机发光二极管显示器、RFID标签、智能ID标签和传感器中的像素驱动和开关元件。
由于多个导电或半导电有机聚合物的开发,那些作为活性层因此半导体在有机薄膜晶体管(OTFT)中的应用已经日益得到关注。
与迄今使用的无机半导体相比,有机半导体在OTFT中的使用具有许多优点。它们可以从纤维到膜的任何形式加工,呈现出高机械柔韧性,可以在低成本下生产且具有低重量。然而显著的优点是可以在大气压下通过将该层从溶液中沉积在聚合物衬底上,例如通过印刷技术而生产整个半导体组件,以得到廉价可生产的FET。
电子装置的性能基本取决于半导体材料的载荷子迁移率和在接通状态和断开状态之间的电流比(通断比)。因此理想的半导体具有在关闭状态最小的电导率和在开通状态最大的载荷子迁移率(迁移率高于10-3cm2V-1s-1,通断比高于102)。另外,半导体材料必须对氧化相对稳定,即必须具有足够高的电离势,因为其氧化降解降低组分的性能。
在现有技术中,区域规则的头-尾聚(3-烷基噻吩),尤其是聚(3-己基噻吩)(P3HT)已经建议用作半导体材料,因为它显示了在1·10-5和0.1cm2V-1s-1之间的载荷子迁移率。区域规则的聚(3-烷基噻吩)在磁场效应晶体管和光伏电池中作为活性空穴传输层已经显示良好的性能。然而,载荷子迁移率和因此这些应用的性能已经显示强烈地依赖于聚合物骨架的烷基侧链的区域规则性。高区域规则性是指高度的头-尾耦合和少量的头-头或尾-尾耦合。高区域规则性导致这些聚合物以固体状态填料良好并因此导致高载荷子迁移率。通常为良好性能需要区域规则性大于90%。
例如在概述R.D.McCullough,Ad.Mater.,1998,10(2),93-116及其中引用的参考文献中已经报导了多种生产高区域规则聚(3-烷基噻吩)的方法。WO 93/15086公开了由2,5-二溴-3-烷基噻吩开始制备高区域规则的聚(3-烷基噻吩),其中将离析物加入高反应性″Rieke锌″(Zn*)的溶液中以形成异构体2-溴-3-烷基-5-(溴代锌)噻吩和2-(溴代锌)-3-烷基-5-溴代噻吩的混合物。加入作为镍交叉耦合催化剂的Ni(dppe)Cl2(1,2-二(二苯基膦基)乙烷氯化镍(II))导致形成区域规则的头-尾(HT)聚(3-烷基噻吩)。
根据EP 1 028 136,2,5-二溴-3-烷基噻吩与甲基溴化镁在THF中反应。同样为两种区域异构体混合物的所得有机镁中间体随后与镍(II)催化剂Ni(dppe)Cl2反应得到区域规则的聚合物。
本发明的目的是提供一种由3-取代的2,5-二卤代噻吩或2,5-二卤代硒吩开始制备区域规则的聚(3-取代的噻吩)或聚(3-取代的硒吩)的改进方法,该方法得到具有更高区域规则性的聚(3-取代的噻吩)或聚(3-取代的硒吩)。
该问题通过一种通过如下步骤制备3-取代的噻吩、3-取代的硒吩、3-取代的噻唑和/或3-取代的硒唑的区域规则均聚物或共聚物的方法而解决:
a)使3-取代的2,5-二卤代噻吩、2,5-二卤代硒吩、2,5-二卤代噻唑或2,5-二卤代硒唑与反应性锌、镁或有机镁卤化物反应得到含有一种卤代锌或一种卤代镁基团的有机锌或有机镁中间体,
b)使所述有机锌或有机镁中间体与Ni(II)、Ni(0)、Pd(II)和Pd(0)催化剂接触以引发聚合反应,和
c)使所述有机锌或有机镁中间体聚合以得到3-取代的噻吩、3-取代的硒吩、3-取代的噻唑或3-取代的硒唑的区域规则的头-尾均聚物或共聚物,
其特征在于所述聚合反应在时间t1期间于从较低温度T1升至较高温度T2的温度下进行,其中T1为-40℃至5℃且T2为-20℃至40℃,其中T2-T1为至少10℃且平均升高率(T2-T1)/t1为0.05-1℃/分钟。
在第一步骤a)中,3-取代的2,5-二卤代噻吩与反应性锌或有机镁卤化物反应得到含有一种卤代锌或一种卤代镁基团的有机锌或有机镁中间体。优选3-取代的2,5-二卤代噻吩、2,5-二卤代硒吩、2,5-二卤代噻唑或2,5-二卤代硒唑为通式(I)的化合物:
其中
R独立地选自a)C1-20烷基,b)C2-20烯基,c)C2-20炔基,d)C1-20烷氧基,e)C1-20烷硫基,f)-C(O)-C1-20-烷基,g)-C(O)-C2-20-烯基,h)-C(O)O-C2-20炔基,i)-C(O)O-C1-20-烷基,j)-C(O)O-C2-20-烯基,k)-Y-C3-10环烷基,l)-Y-C6-14芳基,m)-Y-3-12员杂环烷基,或n)-Y-5-14员杂芳基,
其中所述C1-20烷基、C2-20烯基、C2-20炔基、C3-10环烷基、C6-14芳基、3-12员杂环烷基和5-14员杂芳基各自任选被1-4个R1基团取代,
R1独立地选自a)-S(O)m-C1-20烷基,b)-S(O)m-OC1-20烷基,c)-S(O)m-OC6-14芳基,d)-C(O)-OC1-20烷基,e)-C(O)-OC6-14芳基,f)C1-20烷基,g)C2-20烯基,h)C2-20炔基,i)C1-20烷氧基,j)C3-10环烷基,k)C6-14芳基,l)3-12员杂环烷基,或m)5-14员杂芳基,
Y独立地选自二价C1-6烷基、O、S、C(O)、C(O)O,或共价键,
V为S或Se,
W为CH或N,
X选自Cl、Br和I。
在优选实施方案中,R独立地选自如上所定义的a)C1-20烷基,d)C1-20烷氧基和f)-C(O)-C1-20-烷基。更优选R独立地选自如上所定义的a)C1-20烷基和d)C1-20烷氧基。尤其是R为C1-20烷基。R特别优选为线性或支化C6-C20烷基,例如正丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、正十一烷基、正十二烷基、正十三烷基、正十四烷基、正十五烷基、正十六烷基、正十七烷基、正十八烷基、正十九烷基、正二十烷基、1-甲基戊基、1-甲基己基、2-甲基戊基、2-乙基己基和2,7-二甲基辛基。
反应性锌为由前述零价锌金属颗粒以细碎粉末的形式构成的高反应性零价锌金属类,且可以如WO 93/15086中所述制备。反应性锌通常由还原锌(II)盐,可以是任何不合有酸性质子的各种阴离子的抗衡离子,例如硫酸盐、硝酸盐、亚硝酸盐、乙酸盐、氰化物,或卤化物而制备。还原剂为碱金属或碱金属配合物,优选碱金属和萘的配合物,尤其是锂和萘的配合物。例如反应性锌类可以通过在碱金属如锂和有效催化量的电子转移化合物如萘存在下在THF或乙二醇二甲醚(1,2-二甲氧基乙烷)中还原ZnCl2或Zn(CN)2而制备。
3-取代的2,5-二卤代噻吩与反应性锌的反应通常在排除水和氧气下进行。通常反应在与用于生产高反应性锌类相同的介质中进行。优选反应在醚、聚醚或烃类溶剂中进行,最优选反应在THF中进行。
使用轻微摩尔过量的反应性锌。优选每当量的3-取代的2,5-二卤代噻吩或2,5-二卤代硒吩使用至少1.2当量的反应性锌。反应性锌与3-取代的2,5-二卤代噻吩区域选择性反应,其中区域选择性通常为至少80%。例如反应性锌与3-己基-2,5-二溴代噻吩在室温下反应得到以约9∶1比例的2-溴-5-溴代锌-3-己基噻吩(IIa)和5-溴-2-溴代锌-3-己基噻吩(IIb)的区域异构体混合物。
或者,3-取代的2,5-二卤代噻吩可以与有机镁卤化物反应。有机镁卤化物可以为任何格氏(Grignard)试剂R-MgX,其中X为Cl、Br或I,但通常为Cl或Br,且R通常为任何烷基、乙烯基或苯基,例如CH2-CH=CH2、-C3H7、-C6H13、-C12H29、异丙基和叔丁基。优选3-取代的2,5-二卤代噻吩或2,5-二卤代硒吩溶于有机溶剂中,并将有机镁卤化物在惰性气体气氛下,优选在0-25℃的温度下加入溶液中。或者有机镁卤化物溶于有机溶剂中并将离析物加入溶液中。待加入溶液中的离析物本身还可以溶于溶剂中,然后两种溶液混合。有机镁卤化物相对于离析物以优选0.9-1.05当量,最优选0.95-0.98当量的比例加入。优选溶剂选自线性或环状有机醚且包括二乙醚、THF、2-甲基四氢呋喃、四氢吡喃和二烷。反应通常在无氧气和水存在下进行。离析物和有机镁卤化物反应生成格氏中间体产物,其通常为式IIIa和IIIb的区域异构体的混合物。
如WO 2005/014691中所述,有机镁中间体,或式IIIa和IIIb的中间体混合物还可以通过使用纯镁代替有机镁卤化物产生。
在步骤b)中,使有机锌或有机镁中间体与Ni(0)、Ni(II)、Pd(0)或Pd(II)催化剂接触以引发聚合反应。合适的Ni(0)或Ni(II)催化剂例如为Ni(dPPP)Cl2(其中dppp=1,3-二(二苯基膦基)丙烷)、Ni(dppe)Cl2(其中dppe=1,2-二(二苯基膦基)乙烷)、四(三苯基膦基)镍(0)、Ni(acac)Cl2(其中acac=乙酰丙酮化物)、二(三苯基膦基)二羰基镍(0)、二(1,5-环辛二烯)镍(0)和四(三苯基膦基)镍(0)。催化剂还可以相对于有机锌或有机镁中间体以通常0.1-1摩尔%的量加入。Ni(II)催化剂通常用作在溶剂中,通常在烃类、醚类或环状醚溶剂如THF中的浆料。根据本发明,含有步骤a)的有机锌或有机镁中间体的溶液冷却至-40℃至5℃或以下的温度,并将含有催化剂如Ni(II)催化剂的溶液以混合物的温度不超过起始温度T1的方式加入。通常混合步骤b)例如通过一次或在例如1-120秒的短时间内加入含有催化剂的溶液而快速进行。
在步骤c)中有机锌或有机镁中间体在催化剂存在下聚合以得到区域规则的头-尾聚(3-取代的噻吩)、聚(3-取代的硒吩)、聚(3-取代的噻唑)或聚(3-取代的硒唑)。聚合反应在时间t1期间于从-40℃至5℃的较低温度T1升至-20℃至40℃的较高温度T2的升高温度下进行,其中T2-T1为至少10℃且平均升高率(T2-T1)/t1为0.05-1℃/分钟。起始温度T1可以取决于所用催化剂的反应性。在一个优选实施方案中。T1为0-5℃且T2为10-40℃,且(T2-T1)/t1为0.1-1℃/分钟。因此t1为10-400分钟。通常t1为15-240分钟,优选15-120分钟,更优选20-90分钟。通常在温度不连续升高的情况下温度在t1内持续升高,优选实际升高率在t1时间内的任何时间下不超过10℃/分钟。实际升高率可以遵循线性或指数函数或任何其它函数,然而,平均升高率在如上所定义的限度内。
通常聚合反应到达T2后于T2下在另一时间t2期间继续。通常t2为0-600分钟。通常t2为30-240分钟。
根据本发明,通过在升高的温度下进行聚合反应,实现更高的区域规则性。通过1H-NMR测定的区域规则性通常为≥97%,优选≥98%,尤其是≥99%。相反,若反应从聚合开始在温度T2下进行,则得到<97%的更低区域规则性。
产物可以使用己烷和丙酮作为萃取剂通过索氏萃取纯化。产物可以进一步通过沉淀纯化。
聚合物可以由如现有技术已知的多个基团封端。优选终端基团为H,取代或未取代的苯基或取代或未取代的噻吩,对此没有限制。
根据本发明生产的共聚物可以用于生产光学、电子和半导体材料,尤其是在场效应晶体管(FET)中作为电荷传输材料,例如作为集成电路(IC)、RFID标签、背板像素驱动的组件。具体而言,它们可以用于有机光电部件。或者它们可以在有机发光二极管(OLED)中在电致发光显示器中使用或用作背光照明,例如液晶显示器(LCD),用于光电应用中或用于传感器,用于电子照相记录和其它半导体应用。
本发明的另一方面涉及本发明聚合物的氧化和还原形式。电子得失导致高电导率的高离域离子形式的形成。这可以在暴露于常见掺杂剂时出现。合适的掺杂剂和掺杂方法为本领域技术人员已知,例如来自EP 0 528 662、US 5,198,153或WO 96/21659。
本发明聚合物的传导形式可以作为有机“金属”用于应用中,例如但不限于,作为电荷注入层和ITO平面层用于有机发光二极管应用中,作为平板显示器和触摸屏的膜、抗静电膜、印刷传导衬底、图形或段片用于电子应用中如印刷电路板和电容器。
因为根据本发明生产的聚合物溶于有机溶剂或水,它们可以由溶液施用至衬底上。因此该层可用廉价的方法,例如用涂敷方法如旋涂或印刷技术如照相凹版印刷而施用。
合适的溶剂或溶剂混合物例如包含醚类、芳烃,尤其是氯代溶剂。
FET和其它包含半导体材料如二极管的组件可以有利地用于ID标签或安全标签以表明真实性并防止伪造有价值物品如支票、信用卡,身份证件如ID卡或驾照或其它具有金钱优点的证件如橡皮图章、邮票或门票等。
或者,根据本发明生产的聚合物可以在有机发光二极管(OLED)中,例如在显示器中或作为液晶显示器(LCD)的背光照明使用。通常OLED具有多层结构。发光层通常在一种或多种电子-和/或空穴传输层之间嵌入。当应用电压时,电子或空穴可以在发光层的方向上移动,其中它们重组以激发发光层中发光化合物的随后发光。根据其电子和光学性能,聚合物、材料和层可以发现用于一种或多种传输层和/或发光层。当化合物、材料或层为电致发光或具有电致发光基团或化合物时,它们特别适用于发光层。
如同加工用于OLED的合适聚合物,该选择为常识且例如描述于Synthetic Materials,111-112(2000),31-34或J.Appl.Phys.,88(2000),7124-7128中。
实施例
除非另有说明,所有定量数据(百分数、ppm等)基于重量,基于混合物总重量。
实施例1
制备有机锌化合物
将带有磁力搅拌器的5L烧瓶通过重复排空并引入氩气而惰性化,并借助塑料管填充有活性锌(Rieke Metals Inc.,100g/l,226g锌)的悬浮液。在以内部温度不超过0℃的速度下在搅拌下小心滴加958.0g 2,5-二溴-3-己基噻吩(2.873mol)之前,内部温度通过冷却达到约-10℃。反应混合物回到室温并再搅拌10h。在搅拌器已经关闭之后,未消耗的锌沉积下来。上清溶液用钢管小心取出并用无水THF稀释至0.5M的浓度。产物混合物的转化率和组成通过气相色谱法测定。转化率>99%,并形成以摩尔比9∶1的2-溴-3-己基-5-噻吩基溴化锌和5-溴-3-己基-2-噻吩基溴化锌的异构体混合物。
实施例2a-2g
聚合成聚(3-己基噻吩)
在氮气气氛下将140g实施例1(70mmol异构体混合物)的溶液引入惰性化烧瓶中并回到起始温度(见表)。在15gTHF中悬浮的131.2mg[1,2-二(二苯基膦基)乙烷]二氯化镍(II)(0.249mmol)快速加入此溶液中。然后反应混合物的温度在定义的时间内以定义的升温速度升高(见表1)。反应转化率通过取样和GC分析监测。最后通过加入5ml浓盐酸停止反应且聚合物在1.5L甲醇中立即沉降。聚合物作为固体过滤出来,洗涤并干燥。
测定分子量
聚(3-己基噻吩)溶于氯仿(约0.05重量%)中并用THF作为洗脱剂用标准GPC装置分析(进样:WATERS 717自动进样器;体积100μl;流速:1ml/分钟;泵:WATERS 515型,双柱塞泵;检测:WATERS Lambda-Max481 UV检测器450nm,WATERS 410差示折射仪,测定温度35℃,柱设定:Polymer Laboratories的PL-凝胶柱,4个柱子各自长度30cm且直径0.77,交联聚苯乙烯-二乙烯基苯基体,粒径5μm,孔径:
测定区域规则性
少量粗聚合物(约5mg)溶于1ml氘代氯仿中并填入NMR管中。记录样品的1H NMR光谱并用软件Mestre-C Version 2.3评价。使用头-尾和头-头键合之比以测定聚合物后轮的区域规则性。为此,α-亚甲基质子的信号是合适的,该信号在头-尾键合的情况下出现在2.80nm处且在头-头键合的情况下出现在2.59nm处。借助于分析软件整合在对应信号A下的面积。区域规则性通过如下公式计算:
结果总结于下表中。
表1
实施例3
试验工厂规模合成
60L钢釜用溶剂通过沸腾清洗,然后在减压(10毫巴)下于80℃下干燥并用氮气重复吹扫。首先在THF中加入24kg 2-溴-3-己基-5-噻吩基溴化锌和5-溴-3-己基-2-噻吩基溴化锌的异构体混合物(0.5M,异构体比例约9∶1)并在搅拌下冷却至4℃。在冷却之后,经由惰性弹管快速加入在400gTHF中悬浮的23.68g[1,2-二(二苯基膦基)乙烷]二氯化镍(II)(44.84mmol)。然后反应混合物在90分钟内加热至30℃。将釜内容物未稀释泵入250kg甲醇中并用一点THF(约5kg)洗涤该釜。固体借助赛茨滤菌器(直径30cm,40μm金属网筛过滤器)滤出并用250kg甲醇再次洗涤。这得到1.6kg具有重均分子量30kg mol-1的聚合物(多分散性约1.9)。
实施例4
实验室规模纯化用于电子组件的聚(3-己基噻吩)
10g粗聚合物在索氏萃取器中首先用己烷然后用丙酮萃取。然后固体残余物溶于氯仿中并在甲醇中沉淀,用甲醇洗涤,滤出并在40℃下减压干燥。该程序重复两次。这得到没有单体残余物的纯聚(3-己基噻吩)且其残留金属含量小于10ppm。
实施例5
表征FET中的聚(3-己基噻吩)
为了生产场效应晶体管(FET),具有200nm厚度,热生长二氧化硅的掺杂硅片用作衬底。用平板印刷结构化金的源极/漏极(厚度约40mm)。电介质边界层通过气相沉积用六甲基二硅氮烷改性。聚(3-己基噻吩)层通过旋涂(5000rpm,30s)由40mg/ml氯苯构成的溶液而施用。在表征之前,膜在90℃下短时间干燥。
所有步骤在无保护性气体气氛下进行。FET特性在黄光下用Keithley4200半导体参数分析仪记录,并取平均值。结果再现于下表2中。
表2
实施例2 | μsat/cm2V-1s-1 | 通断比(0-60V) | 启动压 |
a | 0.15(空穴) | 103 | +20V |
c(组合物) | 0.01(空穴) | 103 | +15V |
发现根据本发明生产的具有更高区域规则性的材料在FET中具有明显比对比材料更高的电荷迁移率。
Claims (9)
1.一种通过如下步骤制备3-取代的噻吩、3-取代的硒吩、3-取代的噻唑或3-取代的硒唑的区域规则均聚物或共聚物的方法:
a)使3-取代的2,5-二卤代噻吩、2,5-二卤代硒吩、2,5-二卤代噻唑或2,5-二卤代硒唑与反应性锌、镁和/或有机镁卤化物反应得到含有一种卤代锌或一种卤代镁基团的有机锌或有机镁中间体,
b)使所述有机锌或有机镁中间体与Ni(II)、Ni(0)、Pd(II)或Pd(0)催化剂接触以引发聚合反应,和
c)使所述有机锌或有机镁中间体聚合以得到3-取代的噻吩、3-取代的硒吩、3-取代的噻唑或3-取代的硒唑的区域规则的头-尾均聚物或共聚物,
其特征在于所述聚合反应在时间t1期间于从较低温度T1升至较高温度T2的温度下进行,其中T1为-40℃至5℃且T2为-20℃至40℃,其中T2-T1为至少10℃且平均升高率(T2-T1)/t1为0.05-1℃/分钟。
2.根据权利要求1的方法,其中T1为0-5℃且T2为10-40℃。
3.根据权利要求1或2的方法,其中t1为15-120分钟。
4.根据权利要求1-3中任一项的方法,其中所述聚合反应在时间t2期间于T2下继续。
5.根据权利要求4的方法,其中t2为30-240分钟。
6.根据权利要求1-5中任一项的方法,其中所述3-取代的2,5-二卤代噻吩、2,5-二卤代硒吩、2,5-二卤代噻唑或2,5-二卤代硒唑为通式(I)的化合物:
其中
R独立地选自a)C1-20烷基,b)C2-20烯基,c)C2-20炔基,d)C1-20烷氧基,e)C1-20烷硫基,f)-C(O)-C1-20烷基,g)-C(O)-C2-20烯基,h)-C(O)O-C2-20炔基,i)-C(O)O-C1-20烷基,j)-C(O)O-C2-20烯基,k)-Y-C3-10环烷基,l)-Y-C6-14芳基,m)-Y-3-12员杂环烷基,或n)-Y-5-14员杂芳基,
其中所述C1-20烷基、C2-20烯基、C2-20炔基、C3-10环烷基、C6-14芳基、3-12员杂环烷基和5-14员杂芳基各自任选被1-4个R1基团取代,
R1独立地选自a)-S(O)m-C1-20烷基,b)-S(O)m-OC1-20烷基,c)-S(O)m-OC6-14芳基,d)-C(O)-OC1-20烷基,e)-C(O)-OC6-14芳基,f)C1-20烷基,g)C2-20烯基,h)C2-20炔基,i)C1-20烷氧基,j)C3-10环烷基,k)C6-14芳基,l)3-12员杂环烷基,或m)5-14员杂芳基,
Y独立地选自二价C1-6烷基、O、S、C(O)、C(O)O,或共价键,
V为S或Se,
W为CH或N,
X选自Cl、Br和I。
7.根据权利要求6的方法,其中V为S。
8.根据权利要求7的方法,其中W为CH。
9.根据权利要求7或8的方法,其中R为C1-20烷基或C1-20烷氧基。
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