TW200930743A - Process for preparation of regioregular conducting block copolymers - Google Patents
Process for preparation of regioregular conducting block copolymers Download PDFInfo
- Publication number
- TW200930743A TW200930743A TW097141826A TW97141826A TW200930743A TW 200930743 A TW200930743 A TW 200930743A TW 097141826 A TW097141826 A TW 097141826A TW 97141826 A TW97141826 A TW 97141826A TW 200930743 A TW200930743 A TW 200930743A
- Authority
- TW
- Taiwan
- Prior art keywords
- block copolymer
- substituted
- thiophene
- benzene
- regular
- Prior art date
Links
- 229920001400 block copolymer Polymers 0.000 title claims abstract description 218
- 238000000034 method Methods 0.000 title claims abstract description 120
- 230000008569 process Effects 0.000 title claims description 10
- 238000002360 preparation method Methods 0.000 title description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 64
- 239000002184 metal Substances 0.000 claims abstract description 64
- 239000003054 catalyst Substances 0.000 claims abstract description 57
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims abstract description 12
- -1 biphenylyl Chemical group 0.000 claims description 106
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 81
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 75
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 68
- 239000000178 monomer Substances 0.000 claims description 64
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 60
- 125000003118 aryl group Chemical group 0.000 claims description 50
- 125000000217 alkyl group Chemical group 0.000 claims description 48
- 229930192474 thiophene Natural products 0.000 claims description 43
- 125000001424 substituent group Chemical group 0.000 claims description 34
- 239000011701 zinc Substances 0.000 claims description 33
- 238000006116 polymerization reaction Methods 0.000 claims description 29
- 125000001072 heteroaryl group Chemical group 0.000 claims description 27
- 229910052725 zinc Inorganic materials 0.000 claims description 23
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 21
- 125000000623 heterocyclic group Chemical group 0.000 claims description 21
- 229910052759 nickel Inorganic materials 0.000 claims description 21
- 150000003577 thiophenes Chemical class 0.000 claims description 21
- RKCAIXNGYQCCAL-UHFFFAOYSA-N porphin Chemical compound N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 RKCAIXNGYQCCAL-UHFFFAOYSA-N 0.000 claims description 20
- SDUHMTJLVJVDQH-UHFFFAOYSA-N thiophene;zinc Chemical compound [Zn].C=1C=CSC=1 SDUHMTJLVJVDQH-UHFFFAOYSA-N 0.000 claims description 20
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 19
- 229920001577 copolymer Polymers 0.000 claims description 18
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 238000006467 substitution reaction Methods 0.000 claims description 15
- 239000003153 chemical reaction reagent Substances 0.000 claims description 14
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 14
- ICMAFTSLXCXHRK-UHFFFAOYSA-N Ethyl pentanoate Chemical compound CCCCC(=O)OCC ICMAFTSLXCXHRK-UHFFFAOYSA-N 0.000 claims description 13
- 125000004122 cyclic group Chemical group 0.000 claims description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 12
- 239000011777 magnesium Substances 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 11
- 125000003545 alkoxy group Chemical group 0.000 claims description 11
- 230000005669 field effect Effects 0.000 claims description 11
- 229910052749 magnesium Inorganic materials 0.000 claims description 11
- 239000011591 potassium Substances 0.000 claims description 11
- 229910052700 potassium Inorganic materials 0.000 claims description 11
- 125000005843 halogen group Chemical group 0.000 claims description 10
- 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 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 125000004414 alkyl thio group Chemical group 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 150000004795 grignard reagents Chemical class 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 9
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 239000007818 Grignard reagent Substances 0.000 claims description 8
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 8
- 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 8
- 239000010409 thin film Substances 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 7
- 150000004696 coordination complex Chemical class 0.000 claims description 7
- 150000002825 nitriles Chemical class 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 150000002576 ketones Chemical class 0.000 claims 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 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 5
- 235000010290 biphenyl Nutrition 0.000 claims description 5
- 239000004305 biphenyl Substances 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 5
- 150000002602 lanthanoids Chemical class 0.000 claims description 5
- DEPMYWCZAIMWCR-UHFFFAOYSA-N nickel ruthenium Chemical compound [Ni].[Ru] DEPMYWCZAIMWCR-UHFFFAOYSA-N 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims 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 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 150000002240 furans Chemical class 0.000 claims description 4
- 229920001519 homopolymer Polymers 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 150000002923 oximes Chemical class 0.000 claims description 4
- 150000003233 pyrroles Chemical class 0.000 claims description 4
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 4
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 claims description 3
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 claims description 3
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 claims description 2
- 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 claims description 2
- NSYFIAVPXHGRSH-UHFFFAOYSA-N 2,5-dibromo-3-hexylthiophene Chemical compound CCCCCCC=1C=C(Br)SC=1Br NSYFIAVPXHGRSH-UHFFFAOYSA-N 0.000 claims description 2
- XWUCFAJNVTZRLE-UHFFFAOYSA-N 7-thiabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound C1=C(S2)C=CC2=C1 XWUCFAJNVTZRLE-UHFFFAOYSA-N 0.000 claims description 2
- 229910021587 Nickel(II) fluoride Inorganic materials 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- DBJLJFTWODWSOF-UHFFFAOYSA-L nickel(ii) fluoride Chemical compound F[Ni]F DBJLJFTWODWSOF-UHFFFAOYSA-L 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 claims 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 claims 1
- ATRJNSFQBYKFSM-UHFFFAOYSA-N 2,3-dibromothiophene Chemical compound BrC=1C=CSC=1Br ATRJNSFQBYKFSM-UHFFFAOYSA-N 0.000 claims 1
- PJRGDKFLFAYRBV-UHFFFAOYSA-N 2-phenylthiophene Chemical compound C1=CSC(C=2C=CC=CC=2)=C1 PJRGDKFLFAYRBV-UHFFFAOYSA-N 0.000 claims 1
- DVGKRPYUFRZAQW-UHFFFAOYSA-N 3 prime Natural products CC(=O)NC1OC(CC(O)C1C(O)C(O)CO)(OC2C(O)C(CO)OC(OC3C(O)C(O)C(O)OC3CO)C2O)C(=O)O DVGKRPYUFRZAQW-UHFFFAOYSA-N 0.000 claims 1
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 claims 1
- 125000006267 biphenyl group Chemical group 0.000 claims 1
- XESLIEMIJSFBOC-UHFFFAOYSA-N ethene;thiophene Chemical compound C=C.C=1C=CSC=1 XESLIEMIJSFBOC-UHFFFAOYSA-N 0.000 claims 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims 1
- PFZLGKHSYILJTH-UHFFFAOYSA-N thieno[2,3-c]thiophene Chemical compound S1C=C2SC=CC2=C1 PFZLGKHSYILJTH-UHFFFAOYSA-N 0.000 claims 1
- VJYJJHQEVLEOFL-UHFFFAOYSA-N thieno[3,2-b]thiophene Chemical compound S1C=CC2=C1C=CS2 VJYJJHQEVLEOFL-UHFFFAOYSA-N 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 72
- 239000000463 material Substances 0.000 description 55
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Classifications
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- 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
- 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
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/10—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aromatic carbon atoms, e.g. polyphenylenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
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- 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
- C08G61/125—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 oxygen atom in the ring
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/151—Copolymers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/50—Photovoltaic [PV] devices
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
Description
200930743 九、發明說明: 【發明所屬之技術領域】 本發明係關於製備具有高位置選擇性之位置規則性導電 嵌段共聚物之方法。 【先前技術】 近來人們對導電聚合物極為關注,此乃因 . 綱性、導電性-及其他有價值特性。導電聚:=用 於各種應用之電子組件中,例如電晶體、二極體、三極 ° 冑、及整流器。因純度低而導致的不規則導電性經常妨礙 導電聚合物在該等及其他應用中之使用。 存在若干種製備諸如聚噻吩等導電聚合物之已知合成方 法。然而,該等已知技術經常提供具有低於最佳之位置規 則度之經取代聚噻吩。人們期望高位置規則性導電聚合 物,此乃因單體定向對聚合物導電性具有較強影響。高位 置規則性導電聚合物使得可改良封裝及優化微結構,從而 改良電荷載流子遷移率。 ’ 缺乏期望機械及加工特性亦妨礙了導電聚合物在該等及 其他應用中之使用。改良導電聚合物之可加工性 紅-方法係經由合成嵌段共㈣來改良。嵌段共聚物具 有吸引力是因為其使得設計者可藉由謹慎選擇適當我段鍵 &來疋製嵌段共聚物之可加工性及機械特性。 因此業内仍需要合成尚純度及高位置規則性導電嵌段 共聚物之改良方法。業内亦需要具有高純度位置規則性導 電嵌段共聚物組件之裝置以改良製造及裝置作業之便利 I35320.doc 200930743 性。 【發明内容】BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of preparing a positionally-regular conductive block copolymer having high positional selectivity. [Prior Art] Recently, attention has been paid to conductive polymers, which are due to their properties, electrical conductivity, and other valuable properties. Conductive Poly: = Used in electronic components for a variety of applications, such as transistors, diodes, triodes, and rectifiers. Irregular conductivity due to low purity often hampers the use of conductive polymers in such and other applications. There are several known synthetic methods for preparing conductive polymers such as polythiophenes. However, such known techniques often provide substituted polythiophenes having suboptimal positional rules. High position regular conductive polymers are expected because of the strong influence of monomer orientation on polymer conductivity. The high position of the regular conductive polymer allows improved package and optimized microstructure to improve charge carrier mobility. The lack of desirable mechanical and processing properties also hinders the use of conductive polymers in these and other applications. Improved Processability of Conductive Polymers Red-methods are modified by the synthesis of blocks (4). Block copolymers are attractive because they allow the designer to tailor the processability and mechanical properties of the block copolymer by carefully selecting the appropriate section of the & Therefore, there is still a need in the art for an improved method of synthesizing a regular-purity and high-position regular conductive block copolymer. There is also a need in the industry for a device having a high purity positionally oriented conductive block copolymer assembly to improve the ease of manufacture and operation. I35320.doc 200930743. [Summary of the Invention]
本發明係關於製備位置規則性導電敌段共聚物之方法以 及由此製備之位置規則性導電嵌段共聚物。本文所揭示製 備位置規則性導電嵌段共聚物之方法採用活化金屬,其將 金屬原子直接插入鹵素-芳香族或鹵素-雜芳香族碳鍵中。 較佳地,活化金屬係裏克(Rieke)鋅(Zn*)。若(例如)使用鎳 (II)或鉑觸媒來完成聚合,則可獲得位置規則性導電嵌段 共聚物。 位置規則性導電嵌段共聚物可為(例如)包括兩種或更多 種具有相同環系統(例如噻吩)之單體之嵌段共聚物,或由 兩種或更多種具有不同環系統(例如噻吩及苯)之單體組成 之嵌段共聚物。 較佳地,位置規則性導電嵌段共聚物係(例如)包括未經 取代售吩、3-取代噻吩、3,4-二取代噻吩、或其組合之聚 噻吩嵌段共聚物,或包括聚噻吩嵌段及另一芳香族或雜芳 香族導電聚合物嵌段之嵌段共聚物。 本發明亦係關於具有優良導電特性之位置規則性導電嵌 段共聚物。位置規則性導電嵌段共聚物之特徵在於其單體 組成、其位置規則度、及其物理特性,例如其分子量及數 量平均刀子量、其聚合度分佈性、其導電性、其由其製備 特徵直接決定之純度、以及其他特性。位置規則性導電嵌 段共聚物之特徵亦在於其製備方法。 本發明亦係關於藉由本文所述方法製備之位置規則性導 135320.doc 200930743 電嵌’又共聚物薄膜。位置規則性導電嵌段共聚物薄膜可包 括穆·雜劑。 本發明亦提供電子裝置’其包括(例如)用藉由本文所述 任一方法製備之位置規則性導電嵌段共聚物構建之電路。 電子裝置可為薄膜電晶體、場效應電晶體、射頻識別標 記、平板顯示器、光伏打裝置、電致發光顯示裝置、感測 器裝置、及電子照相裝置、或有機發光二極體(〇led)。 本發明提供製備位置規則性導電嵌段共聚物之方法,其 包括:a)將錄(11)觸媒與第一單趙·金屬錯合物合併以提供The present invention relates to a process for preparing a positionally oriented conductive segment copolymer and a positionally oriented conductive block copolymer prepared thereby. The method of preparing a positionally oriented conductive block copolymer disclosed herein employs an activated metal which directly inserts a metal atom into a halogen-aromatic or halogen-heteroaromatic carbon bond. Preferably, the metal is Rieke zinc (Zn*). If the polymerization is completed, for example, using nickel (II) or a platinum catalyst, a positionally regular conductive block copolymer can be obtained. The positionally-regular conductive block copolymer may be, for example, a block copolymer comprising two or more monomers having the same ring system (e.g., thiophene), or two or more having different ring systems ( For example, a block copolymer composed of monomers of thiophene and benzene). Preferably, the positionally-regular conductive block copolymer is, for example, a polythiophene block copolymer comprising unsubstituted phenanthrene, 3-substituted thiophene, 3,4-disubstituted thiophene, or a combination thereof, or includes poly A block copolymer of a thiophene block and another aromatic or heteroaromatic conductive polymer block. The present invention is also directed to a positionally constrained electrically conductive block copolymer having excellent electrical conductivity. The positional regular conductive block copolymer is characterized by its monomer composition, its positional regularity, and its physical properties, such as its molecular weight and number average knife amount, its degree of polymerization distribution, its electrical conductivity, and its preparation characteristics. Directly determine the purity, and other characteristics. The positionally regular electrically conductive block copolymer is also characterized by its method of preparation. The present invention is also directed to a positional regular guide 135320.doc 200930743 prepared by the method described herein. The positionally regular conductive block copolymer film may comprise a mu of a dopant. The invention also provides an electronic device' comprising circuitry constructed, for example, from a positionally-regular conductive block copolymer prepared by any of the methods described herein. The electronic device may be a thin film transistor, a field effect transistor, a radio frequency identification mark, a flat panel display, a photovoltaic device, an electroluminescence display device, a sensor device, an electrophotographic device, or an organic light emitting diode (〇led) . The present invention provides a method of preparing a positionally oriented conductive block copolymer comprising: a) combining a (11) catalyst with a first single Zhao metal complex to provide
❹ 位置規則性導電嵌段共聚物中間趙,其中該第—單體-金 屬錯合物係藉由包括以下步驟之方法來製備:將第一種二 函素-單體與活化金屬、格氏試劑(Grignard叫咖)或 RZnX、R2ZnX、或尺321^試劑合併,其中尺係(^ ^2)烷 基,Μ係鎂、錳、鋰、鈉或鉀,且α、或厂· b) 將第二單體-金屬錯合物與位置規則性導電嵌段共聚物中 間體合併以提供位置規則性導電嵌段共聚物,其中該第二 單體-金屬錯合物係藉由包括以下步驟之方法來製備:將 第二種二齒素-單體與活化金屬、格氏試劑、或RZnX、 R2ZnX、或R3ZnM試劑合併,其中尺係(C2_Ci2)烷基,μ係 鎂、錳、鋰、鈉、或鉀,且X係F、a、Br、或1;其中各 二鹵素_單體皆獨立地為經兩個鹵素取代之芳香族或雜芳 香族基團,其申該等鹵素相同或不同,且其中若該等二鹵 素-單體具有相同環系統,則至少一個二齒素-單體經取 代,且若兩個二_素_單體皆具有相同環系統且經取代, 135320.doc 200930743 則該等取代基不同。 在實施例卜使用錄⑴)觸媒且以任一順序合併錄 觸媒與第一單體金屬錯合物。在另-實施例中,將錄⑻ 觸媒添加至第—單體·金屬錯合物t以提供位置規則性導 , f嵌段共聚物中間體。在另-實施例中,將第—單體·金 屬錯口物添加至錄(η)觸媒中以提供位置規則性導電嵌段 ' 共聚物中間體。 在一實施例中,芳香族或雜芳香族基團可為苯、噻吩、 料"夫續、苯胺、伸苯基伸乙締基、伸嗟吩基伸乙烯 基、雙-伸嗟吩基伸乙稀基、乙炔、苐、伸芳基、異硫 萘、對苯硫醚、噻吩并[2,3_b]售吩、噻吩并[2,3<搾吩、 噻吩并[2,3-d]嗟吩、萘、苯并[2,3]嗟吩、苯并[3,4]㈣、 聯苯基、或聯嘆吩基’且其中芳香族或雜芳香族基團具有 0至約3個非鹵素取代基。 在另一實施<列中’上述芳香族或雜芳㈣基團之取代基 _ 各自獨立地為可視需要經約1至約5個酯、輞、腈、胺基、 芳基、雜芳基、或雜環基取代之(Ci_C24)烷基、(Ci C24)烷 硫基、(CrC24)烷基曱矽烷基、或(Ci_C24)烷氧基,且烷基 - 中烷基鏈之一或多個碳原子可視需要由約1至約10個〇、s . 或NH基團替換。 在另一實施例中,第一種二_素_單體及第二種二鹵素_ 單體各自獨立地選自由以下組成之群:2,5_二函素_噻吩、 2,5-二鹵素比略、2,5-二商素-咬喃、二鹵素苯、2,% 二鹵素-3-取代噻吩、2,5-二函素取代吡咯、2,弘二齒素_ 135320.doc •9- 200930743 3-取代呋喃、1,3-二函素-2-取代苯、以-二齒素-4-取代 苯、1,3-二鹵素-5-取代苯、1,3_二齒素取代苯、1>3_二 齒素_2,4-二取代苯、M-二画素-2,5-二取代苯、以-二齒 素_2,6-二取代苯、1,3_二自素_4,5-二取代苯、丨,3-二齒素_ 4.6- 二取代苯、1,3-二函素_2,4,5-三取代苯、丨,3·二齒素_ • :/义三取代苯〜以-二函素冬今乂-三取代苯’^-二函素- - 2-取代苯、Μ-二鹵素-3-取代苯、M-二齒素-5-取代苯、 1,4-二鹵素-6-取代苯、1,4-二齒素_2,3-二取代苯、L4-二 Ο 鹵素-2,5-二取代苯、M-二鹵素-2,6-二取代苯、L4-二鹵 素-3,5-二取代苯、1,4_二鹵素_3,6-二取代苯、L4-二幽素- 3.5.6- 三取代苯、2,5·二齒素-3,4-二取代噻吩、2,5-二齒素· 3,4-二取代0比哈、2,5-二鹵素-3,4-二取代*夫嗔、及其組 合0 在一實施例中,第一種二鹵素-單體係二溴己基 嘆吩且第二種二齒素_單體係5-(2_5_二溴嗔吩_3-基)戊酸乙 酯。在另一實施例中,位置規則性導電嵌段共聚物包括未 經取代嘆吩、3-取代嗔吩、3,4-二取代雀吩、或其組合。 在另一實施例中’位置規則性導電嵌段共聚物係HT聚(3-取代噻吩)嵌段共聚物或HT聚(3,4_二取代嗟吩)欲段共聚 . 物。 在一實施例中,HT聚(3-取代噻吩)嵌段共聚物係經複數 個直鏈(Ci-Ci2)烷基取代且經複數個經酯基取代之直鏈(Cr C12)烷基取代。在另一實施例中,HT聚(3-取代噻吩)嵌段 共聚物係經複數個己基取代且經複數個經乙基酯基單取代 135320.doc • 10· 200930743 之戊基取代。 在一實施例中’活化金屬係銘、鍾、銅、辞、鎂、約、 欽、鐵、错、錄、姻、或其組合。在另一實施例中,活化 金屬係裏克鋅(Zn*)。 在另一實施例中’位置規則性導電嵌段共聚物之位置規 則度大於約87% ’或較佳為至少約92%,或更佳為至少約 97%。 在一實施例中,位置規則性導電嵌段共聚物係經複數個 直鍵(C丨-C12)院基取代且經複數個經酯基取代之直鏈(C1 _ C〗2)烷基取代》在另一實施例中,位置規則性導電嵌段共 聚物係經複數個己基取代且經複數個經乙基酯基單取代之 戊基取代。在另一實施例中,位置規則性導電嵌段共聚物 之重量平均分子量為約5,000至約200,000,或較佳為約 40,000至約 60,000 〇 在一實施例中,所製備位置規則性導電嵌段共聚物聚合 度分佈性指數為約1至約2.5,或較佳為約1.2至約2.2。在 另一實施例中’鎳(II)觸媒係或衍生自Ni(dppe)Cl2、 Ni(dPPP)Cl2、NKPPh^Bi·2、1,5-環辛二烯雙(三苯基)鎳、 二氣(2,2’_二吡啶)鎳、四(三苯基膦)鎳、Ni〇、ν%、位置 Positioning of a regular conductive block copolymer intermediate, wherein the first monomer-metal complex is prepared by a method comprising the steps of: first element-monomer and activated metal, Grignard Reagent (Grignard called coffee) or RZnX, R2ZnX, or ruler 321 ^ reagent combined, wherein the ruler (^ ^ 2) alkyl, lanthanide magnesium, manganese, lithium, sodium or potassium, and α, or plant · b) will The second monomer-metal complex is combined with the positionally-regular conductive block copolymer intermediate to provide a positionally-regular conductive block copolymer, wherein the second monomer-metal complex is comprised of the following steps The method comprises the steps of: combining a second dentate-monomer with an activated metal, a Grignard reagent, or a RZnX, R2ZnX, or R3ZnM reagent, wherein the ft (C2_Ci2) alkyl group, the μ system of magnesium, manganese, lithium, sodium Or potassium, and X is F, a, Br, or 1; wherein each dihalogen-monomer is independently an aromatic or heteroaromatic group substituted by two halogens, the halogens being the same or different And wherein if the dihalogen-monomers have the same ring system, at least one dentate-monomer is substituted And if the two bis-monomers all have the same ring system and are substituted, 135320.doc 200930743 then the substituents are different. In the examples, the recording (1) catalyst was used and the recording medium and the first monomer metal complex were combined in either order. In another embodiment, the (8) catalyst is added to the first monomer/metal complex t to provide a positional regular, f block copolymer intermediate. In another embodiment, a first monomeric metal disorder is added to the (η) catalyst to provide a positionally regular conductive block 'copolymer intermediate. In one embodiment, the aromatic or heteroaromatic group may be benzene, thiophene, benzoic acid, aniline, phenylene extended phenyl group, thiophene extended vinyl group, bis-extended thiophene extended ethylene Base, acetylene, anthracene, aryl, isothionaphthalene, p-phenylene sulfide, thieno[2,3_b], thieno[2,3< thiophene, thieno[2,3-d] porphin , naphthalene, benzo[2,3]porphin, benzo[3,4](tetra),biphenyl, or conjugated phenyl] and wherein the aromatic or heteroaromatic group has from 0 to about 3 non-halogen Substituent. In another embodiment, the substituents of the above aromatic or heteroaryl (tetra) groups are each independently from about 1 to about 5 esters, hydrazines, nitriles, amine groups, aryl groups, heteroaryl groups, as desired. Or a heterocyclic group substituted with (Ci_C24)alkyl, (Ci C24)alkylthio, (CrC24)alkyldecyl, or (Ci_C24)alkoxy, and one or more alkyl-alkyl chains The carbon atoms may optionally be replaced by from about 1 to about 10 hydrazine, s. or NH groups. In another embodiment, the first dioxin monomer and the second dihalo monomer are each independently selected from the group consisting of: 2,5-difunctional thiophene, 2,5-di Halogen ratio, 2,5-di-business-bite, dihalobenzene, 2,% dihalo-3-substituted thiophene, 2,5-difunctional substituted pyrrole, 2, Hong dentate _ 135320.doc • 9- 200930743 3-Substituted furan, 1,3-difunctional-2-substituted benzene, bis-dentate-4-substituted benzene, 1,3-dihalo-5-substituted benzene, 1,3_two-tooth Substituted benzene, 1>3_didentate-2,4-disubstituted benzene, M-dimorph-2,5-disubstituted benzene, bis-dentate-2,6-disubstituted benzene, 1,3 _Seconazole _4,5-disubstituted benzene, hydrazine, 3- dentate _ 4.6-disubstituted benzene, 1,3-difunctional 2,4,5-trisubstituted benzene, anthracene, 3·2 Phytosin _ • : / sense trisubstituted benzene ~ to - dimerin winter 乂 - trisubstituted benzene '^-difunctional - 2-substituted benzene, fluorene-dihalo-3-substituted benzene, M-dentate 5--5-substituted benzene, 1,4-dihalo-6-substituted benzene, 1,4-dentate-2,3-disubstituted benzene, L4-diindole halogen-2,5-disubstituted benzene, M -dihalo-2,6-disubstituted benzene, L4-dihalogen-3,5-disubstituted benzene, 1,4_dihalogen _3,6-disubstituted benzene, L4-diponectin- 3.5.6-trisubstituted benzene, 2,5·didentin-3,4-disubstituted thiophene, 2,5-didentate·3,4- Disubstituted 0-H, 2,5-dihalo-3,4-disubstituted*, and combinations thereof 0 In one embodiment, the first dihalogen-single system dibromohexyl sinter and second A dentate-single system of ethyl 5-(2-5-dibromophenant-3-yl)pentanoate. In another embodiment, the positionally regular conductive block copolymer comprises unsubstituted singly, 3-substituted porphin, 3,4-disubstituted finch, or a combination thereof. In another embodiment, the <positionally-preferred conductive block copolymer is a HT poly(3-substituted thiophene) block copolymer or HT poly(3,4-disubstituted porphin). In one embodiment, the HT poly(3-substituted thiophene) block copolymer is substituted with a plurality of linear (Ci-Ci2) alkyl groups and substituted with a plurality of linear (Cr C12) alkyl groups substituted with an ester group. . In another embodiment, the HT poly(3-substituted thiophene) block copolymer is substituted with a plurality of hexyl groups and substituted with a plurality of ethyl ester groups monosubstituted 135320.doc • 10·200930743. In one embodiment, the 'metal auxiliaries, bells, copper, rhodium, magnesium, about, chin, iron, erroneous, recorded, marital, or combinations thereof. In another embodiment, the metal is activated by zinc (Zn*). In another embodiment, the positional regular conductive block copolymer has a positionality of greater than about 87% or preferably at least about 92%, or more preferably at least about 97%. In one embodiment, the positionally-regular conductive block copolymer is substituted with a plurality of linear (C丨-C12) substituents and substituted with a plurality of linear (C1 _ C 2) alkyl groups substituted with an ester group. In another embodiment, the positionally-regular conductive block copolymer is substituted with a plurality of hexyl groups and substituted with a plurality of pentyl groups monosubstituted with ethyl ester groups. In another embodiment, the positionally regular conductive block copolymer has a weight average molecular weight of from about 5,000 to about 200,000, or preferably from about 40,000 to about 60,000 Å. In one embodiment, the positionally oriented conductive block is prepared. The copolymer polymerization degree distribution index is from about 1 to about 2.5, or preferably from about 1.2 to about 2.2. In another embodiment, 'nickel (II) catalyst or derived from Ni(dppe)Cl2, Ni(dPPP)Cl2, NKPPh^Bi.2, 1,5-cyclooctadiene bis(triphenyl)nickel , two gas (2,2'-dipyridine) nickel, tetrakis(triphenylphosphine) nickel, Ni〇, ν%,
NiC12、NiBr2、Nil2、NiAs、Ni(dmph)2、BaNiS、或其組 合0 在另一實施例中’採用約0.01 m〇l %至約1 〇〇 m〇l %錄 (Η)觸媒’或較佳約0.1 mol %至約5 mol % ’或更佳約〇. 1 mol %至約3 mol %。在另一實施例中,採用約〇 〇1 m〇1 % 135320.doc 11 200930743 至約100 mol %鉑觸媒,或較佳約(M mol %至約5 mol %, 或更佳約0· 1 mol %至約3 mol 0/〇。 在一實施例中,本發明提供製備位置規則性HT聚(3-取 代噻吩)嵌段共聚物之方法’其包括:a)將鎳(11)觸媒與第 一噻吩-辞錯合物合併以提供位置規則性HT聚(3-取代噻吩) 中間體;b)將第二噻吩-鋅錯合物與位置規則性ht聚(3 _ 取代噻吩)中間體合併以提供位置規則性HT聚(3-取代噻吩) 嵌段共聚物。 在另一實施例中,以任一順序合併鎳(Π)觸媒與第一噻 吩-鋅錯合物。在另一實施例中,合併鎳(H)觸媒與第一噻 吩-鋅錯合物以提供位置規則性HT聚(3-取代噻吩)中間體。 在一實施例中’合併第一噻吩-鋅錯合物與鎳(π)觸媒以提 供位置規則性ΗΤ聚(3-取代噻吩)中間體。 在一實施例中’提供包括用位置規則性導電嵌段共聚物 或位置規則性ΗΤ聚(3-取代噻吩)嵌段共聚物構建之電路之 電子裝置。在另一實施例中,裝置為薄膜電晶體、場效應 電晶體、射頻識別標記、平板顯示器、光伏打裝置、電致 發光顯示裴置、感測器裝置 '及電子照相裝置、或有機發 光二極體。 在另一實施例中,提供位置規則性導電嵌段共聚物或位 置規則性ΗΤ聚(3-取代噻吩)嵌段共聚物。在一實施例中, 粗位置規則性導電欲段共聚物或粗位置規則性Ητ聚(3 _取 代隹吩)嵌段共聚物之位置規則度為至少約8 7 %,較佳大於 約92%,更佳大於約95%。 135320.doc •12· 200930743 在另一實施例中,提供導電嵌段共聚物,其具有至少約 92%之位置規則度;重量平均分子量為約30,000至約 70,000 ;且電導為約10·5至約10·6西門子/cm ° 【實施方式】 定義 本文所用某些術語具有以下含義。本說明書中所用所有 其他術語及詞組皆具有如熟習此項技術者所瞭解之一般含 義。該等一般含義可藉由參照技術辭典來獲得,例如 w Hawley's ,第 11 版,Sax 及NiC12, NiBr2, Nil2, NiAs, Ni(dmph)2, BaNiS, or a combination thereof 0 In another embodiment, 'using about 0.01 m〇l% to about 1 〇〇m〇l% of the catalyst (Η) catalyst' Or preferably from about 0.1 mol% to about 5 mol%' or more preferably from about 1 mol% to about 3 mol%. In another embodiment, about 1 m 〇 1 % 135320.doc 11 200930743 to about 100 mol % platinum catalyst, or preferably about (M mol % to about 5 mol %, or better about 0. 1 mol % to about 3 mol 0 / 〇. In one embodiment, the present invention provides a method of preparing a positionally regular HT poly(3-substituted thiophene) block copolymer, which comprises: a) contacting nickel (11) The medium is combined with a first thiophene-conjugate to provide a positionally regular HT poly(3-substituted thiophene) intermediate; b) a second thiophene-zinc complex with a positionally regular ht poly(3 _ substituted thiophene) The intermediates are combined to provide a positionally regular HT poly(3-substituted thiophene) block copolymer. In another embodiment, the nickel (ruthenium) catalyst is combined with the first thiophene-zinc complex in either order. In another embodiment, a nickel (H) catalyst is combined with a first thiophene-zinc complex to provide a positionally regular HT poly(3-substituted thiophene) intermediate. In one embodiment, the first thiophene-zinc complex and the nickel (π) catalyst are combined to provide a positionally regular fluorene (3-substituted thiophene) intermediate. In one embodiment, an electronic device comprising a circuit constructed using a positionally regular conductive block copolymer or a positionally regular condensed (3-substituted thiophene) block copolymer is provided. In another embodiment, the device is a thin film transistor, a field effect transistor, a radio frequency identification mark, a flat panel display, a photovoltaic device, an electroluminescent display device, a sensor device, and an electrophotographic device, or an organic light emitting device Polar body. In another embodiment, a positionally regular conductive block copolymer or a positionally regular fluorene (3-substituted thiophene) block copolymer is provided. In one embodiment, the coarse-position regular conductive segment copolymer or the coarse-position regular Ητ poly(3 _ substituted porphin) block copolymer has a positional regularity of at least about 87%, preferably greater than about 92%. More preferably, it is greater than about 95%. 135320.doc • 12· 200930743 In another embodiment, a conductive block copolymer is provided having a positional regularity of at least about 92%; a weight average molecular weight of from about 30,000 to about 70,000; and a conductance of about 10.5 to About 10.6 Siemens/cm ° [Embodiment] Definitions Certain terms used herein have the following meanings. All other terms and phrases used in the specification have the generic meaning as understood by those skilled in the art. These general meanings can be obtained by reference to technical dictionaries such as w Hawley's, 11th edition, Sax and
Lewis,Van Nostrand Reinhold,New York,N.Y.,1987及 77^ MercA/ni/ex,第 11版,Merck & Co.,'Rahway N.J. 1989。 本文所用詞語"及/或"意指與此詞語相關之任一條目、條 目之任一組合、或所有條目。 除非上下文另外明確指出,否則本文所用單數形式"一" 及"該"包括複數含義。因此,舉例而言,提及"調配物"時 A 其包括複數種該等調配物,以使化合物X之調配物包括化 合物X之各種調配物。 本文所用詞語"約"意指在指定數值的10%範圍内變化, 例如約50%意指自45%至55%變化。對於整數範圍而言, . 詞語”約"可包括比所述整數大或小一或二之整數。 本文所用術語"活化金屬"係指金屬粉末、金屬粉塵、或 金屬顆粒,其已經化學方式、熱學方式、電化學方式、或 超音波方式活化。通常"活化金屬"價態為零。 本文所用術語"活化鋅"係指鋅粉末、辞粉塵、或鋅顆 135320.doc 13 200930743 粒,其已經化學方式、熱學方式、電化學方式、或超音波 方式活化》舉例而言,辞可藉由添加少量l2、鹵代碳化合 物、鹵代矽化合物、或Hg(:l2以化學方式來活化。鋅之電化 學活化可藉由施加正極電壓來實施。熱活化可藉由在真空中 加熱辞顆粒或鋅粉末來實施。活化亦可藉由超音波來實施。 本文所用術語"烷基"係指具有(例如)〗至3〇個碳原子、且 經常具有1至12個碳原子之具支鏈、無支鏈、或環狀烴。 實例包括(但不限於)甲基、乙基、卜丙基(正丙基)、2丙基 (異丙基)、1· 丁基(正丁基)、2-甲基-1-丙基(異丁基)、2_ 丁 基(第二丁基)、2-甲基-2-丙基(第三丁基)、i•戊基(正戊 基)、2-戊基、3-戊基、2-甲基-2-丁基、3-甲基-2-丁基、3-曱基-1-丁基、2-甲基-1-丁基、ι_己基、2_己基、3 -己基、 2- 甲基-2-戊基、3 -甲基-2-戊基、4-甲基-2-戊基、3 -甲基_ 3- 戊基、2-甲基-3-戊基、2,3-二甲基-2-丁基、3,3-二曱基_ 2-丁基、己基、辛基、癸基、十二烷基、及諸如此類。烷 基可未經取代或經取代。視需要烷基亦可部分或完全不飽 和。因此,提及烷基時其包括烯基及炔基。如上文所闞述及 例示,烷基可為單價烴基,或其可為二價烴基(即伸烷基)。 本文所用術語"烷硫基"係指烷基_S_基團,其中烧基係如 本文所定義。在一實施例中’烷硫基包括(例如)甲硫基、 乙硫基、正丙基硫基、異丙基硫基、正丁基硫基、第三丁 基硫基、第一 丁基硫基、正戊基硫基、正己基硫基、ι,2· 二甲基丁硫基、及諸如此類。烷硫基中之烷基可未經取代 或經取代。 135320.doc • 14- 200930743 本文所用術語"烷基曱矽烷基"係指烷基-SiH2-或烧基· SiR2_基團,其中烧基係如本文所定義,且各r獨立地為η 或烷基。可藉由熟習此項技術者所知多種技術中之任一種 用烧基甲碎烧基來取代嗟吩’通常藉由使嚷吩與院基甲# 烷基鹵化物偶合來達成’多種該等技術揭示於AldrichLewis, Van Nostrand Reinhold, New York, N.Y., 1987 and 77^ MercA/ni/ex, 11th ed., Merck & Co., 'Rahway N.J. 1989. The term " and/or " as used herein means any entry, any combination of terms, or all entries associated with this term. The singular forms """ &"""""""" Thus, for example, reference to "mixture"" includes a plurality of such formulations such that the formulation of Compound X includes various formulations of Compound X. The term "about" as used herein means to vary within 10% of the specified value, for example about 50% means to vary from 45% to 55%. For the range of integers, the word "about" may include an integer one or two greater than the integer. The term "activated metal" as used herein refers to metal powder, metal dust, or metal particles, which have Chemical, thermal, electrochemical, or ultrasonic activation. Usually "activated metal" is zero. The term "activated zinc" as used herein refers to zinc powder, repulsive dust, or zinc 135320. Doc 13 200930743 granules, which have been chemically, thermally, electrochemically, or ultrasonically activated. For example, the words can be added by adding a small amount of l2, a halogenated carbon compound, a halogenated hydrazine compound, or Hg (:l2). It is chemically activated. Electrochemical activation of zinc can be carried out by applying a positive voltage. Thermal activation can be carried out by heating the particles or zinc powder in a vacuum. Activation can also be carried out by ultrasonic waves. "Alkyl" means a branched, unbranched, or cyclic hydrocarbon having, for example, from 3 to 3 carbon atoms, and often from 1 to 12 carbon atoms. Examples include Not limited to) methyl, ethyl, propyl (n-propyl), 2-propyl (isopropyl), 1 butyl (n-butyl), 2-methyl-1-propyl (isobutyl), 2_ butyl (t-butyl), 2-methyl-2-propyl (t-butyl), i-pentyl (n-pentyl), 2-pentyl, 3-pentyl, 2-methyl -2-butyl, 3-methyl-2-butyl, 3-mercapto-1-butyl, 2-methyl-1-butyl, i-hexyl, 2-hexyl, 3-hexyl, 2- Methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 3-methyl-3-ethylpentyl, 2-methyl-3-pentyl, 2, 3-dimethyl-2-butyl, 3,3-didecyl-2-butyl, hexyl, octyl, decyl, dodecyl, and the like. The alkyl group may be unsubstituted or substituted. The alkyl group may also be partially or completely unsaturated, as desired. Thus, when referring to an alkyl group, it includes alkenyl and alkynyl groups. As exemplified and exemplified above, the alkyl group may be a monovalent hydrocarbon group, or it may be a divalent hydrocarbon group ( That is, an alkyl group. The term "alkylthio" as used herein refers to an alkyl-S- group, wherein the alkyl group is as defined herein. In one embodiment, the alkylthio group includes, for example, methyl sulfide. Base, Thio, n-propylthio, isopropylthio, n-butylthio, tert-butylthio, first butylthio, n-pentylthio, n-hexylthio, ι, 2· Dimethyl butylthio, and the like. The alkyl group in the alkylthio group may be unsubstituted or substituted. 135320.doc • 14- 200930743 The term "alkylalkylalkyl" as used herein refers to alkyl-SiH2 a - or a thiol-SiR2_ group, wherein the alkyl group is as defined herein, and each r is independently η or alkyl. Replacing the porphin with a burnt-based alkyl group by any of a variety of techniques known to those skilled in the art will generally be accomplished by coupling the porphin to the alkyl halide of the compound. Technology revealed in Aldrich
Handbook of Fine Chemicals, 2007-2008, Milwaukee,WI 中。 本文所用術語"烷氧基"係指烷基-〇·基團,其中炫基係 如本文所定義。在一實施例中’烷氧基包括(例如)甲氧 基、乙氧基、正丙氧基、異丙氧基、正丁氧基、第三丁氧 基、第二丁氧基、正戊氧基、|己氧基、1,2_二曱基丁氧 基、及諸如此類。烷氧基中之烷基可未經取代或經取代。 本文所用術語"芳基"係指藉由自母體芳香族環系統之單 碳原子移除一個氫原子衍生之芳香族烴基。該基團可位於 母鳢環系統之飽和或不飽和碳原子處。芳基可具有6至18 個碳原子。芳基可具有單環(例如苯基)或多個縮合(稠合) 環’其中至少一個環為芳香族(例如萘基、二氫菲基、苐 基、或蒽基)。通常芳基包括(但不限於)衍生自苯、萘、 蒽、聯苯基、及諸如此類之基團。芳基可未經取代或視需 要經取代,如上文針對烷基所述。 本文所用術語"嵌段共聚物"係指藉由偶合官能性多價聚 合物製備之任何聚合物,例如AB嵌段共聚物。某些實施 例之嵌段共聚物可為AB嵌段共聚物,其中a嵌段為第一單 體且B嵌段為第二單體,其中第一及第二單體各不相同。 某些實施例之嵌段共聚物亦可為ABA嵌段共聚物或ABc嵌 135320.doc -15- 200930743 段共聚物,其中A嵌段為第一單體,其中B嵌段為第二單 體,且其中C嵌段為第三單體,其中第一、第二及第三單 體各不相同。此外,某些實施例之嵌段共聚物可為Ab嵌 段共聚物,例如其中A嵌段為聚噻吩,且B嵌段為另一導 電聚合物’例如聚(β比咯)。某些實施例之嵌段共聚物亦可 為ΑΒΑ嵌段共聚物或ABC嵌段共聚物,其中a嵌段為聚噻 吩,其中B嵌段為另一導電聚合物,例如聚(吡咯),且其 中C嵌段為另一導電聚合物,例如聚(笨胺)。 本文所用術語"導電聚合物"係指可傳導電流之聚合物。 通常導電聚合物係主鏈中主要含有sp2_雜化碳原子之聚合 物,該等碳原子亦可經對應雜原子替換。在最簡單之情況 下’此意指在主鏈中雙鍵與單鍵交替存在。"主要"意指天 然存在的導致共軛阻斷之缺陷不影響術語"導電聚合物,,之 適用性。此外,若(例如)主鏈中存在芳基胺單元及/或某些 雜環(即經由N、〇或S原子共軛)及/或有機金屬錯合物(即 經由金屬原子共軛),則術語"導電"亦用於此申請案文本 中。相反’諸如簡單烷基橋、(硫)醚、酯、醯胺、或亞醯 胺連接等單元定義為非導電鏈段。部分導電聚合物欲意指 主鏈中相對較長導電部分由非導電部分中斷或側鏈中含有 相對較長導電部分但主鏈不導電之聚合物。本文所用術語 "導電聚合物”在屬類上亦係指均聚物、隨機共聚物、支化 聚合物、嵌段共聚物、及諸如此類。 本文所用術語"膜,,或"薄膜"係指顯示機械穩定性及撓性 之自樓式或獨立式膜,以及位於支撐基材上或兩基材之間 135320.doc -16- 200930743 之塗層或層。 本文所用術語"格氏試劑,,係指經由炫基或芳基齒化物在 鎂金屬上之作用形成之組合物。 本文所用術語”齒素"係指氟、氯、?臭、或埃基團、取代 基、或自由基。 本文所用術語"雜芳基•,在本文令定義為單環、二環、或 三環系統’其含有-個、兩個或三個芳香族環且芳香族環 中含有至少-個氮、氧、或硫原且其可未經取代或經 (例如)一或多個(且具體而言丨至3個)取代基取代,如上 文"經取代”之定義中所述。雜芳基之實例包括(但不限 於降批略基、3H令朵基、4H•啥嗪基、。丫咬基苯并间 嗟吩基、苯并嗟唾基、弄琳基、㈣基、苯并吼味基、 啐啉基、二苯并[b,d]呋喃基、呋咕基、呋喃基、咪唑基、 味二峻基(imidizolyi)、^坐基、,嗪基、㈣基、異苯并 吱味基、異巧卜朵基、異噎琳基、異嗟峻基異嗯峻基萘 咬基、鳴唾基、萘嵌間二氮雜苯基、菲咬基、菲你基、吩 «比嗪基、吩嗪基、吩嘆嗪基、吩嚼硫基、吩料基、呔嗪 基喋啶基、嘌呤基、β比喃基、吼嗪基、„比唑基、噠嗪 基、吼啶基、嘧啶基、吼咯基、喹唑啉基、喹啉基、喹噁 啉基、噻二唑基、噻蒽基、噻唑基、噻吩基、三唑基、四 唑基、及咕噸基。在一實施例中術語"雜芳基"表示含有5 或6個環原子之單環芳香族環,其含有碳原子及丄、2、3或 4個獨立選自非過氧化物氧、硫及N(z)之雜原子其中冗不 存在或為H'〇、烷基、芳基、或(CiC6)烷基芳基。在另 135320.doc •17· 200930743 實1中雜芳基表示自具有約8至約1〇個環原子之 稠u f雜環何生者,尤其苯基衍^物或藉由使伸丙基、 三亞甲基、或四亞甲基二價自由基與其稠合而衍生者。 ❹ ❹ 喃 基 基 基 本文所用術語"雜環"或"雜環基"係指飽和或部分不飽和 環系統,其含有至少一個選自氧、氮及硫之群之雜原子, 且視需要經-❹個如本文術語"經取代"中所定義之基團 取代。雜環可為含有—或多個雜原子之單環、二環或三環 基團。雜環基團亦可含有與環連接之氧代基(=0)β雜環基 之非限制性實例包括1,3-二氫苯并呋喃、1,3-二氧戊環、 1,4-二噁烷、丨,4_二噻烷、吡喃、2_吡唑啉、4好_吡 苯并二氫吡喃基、咪唑啶基、咪唑啉基、二氫吲哚 異苯并二氫吡喃基、異二氩吲哚基、嗎啉、六氫吡嗪 /、氫吡啶、六氫吡啶基、吡唑啶、吡唑啶基、吡唑啉 吡咯啶 '吡咯啉、奎寧環、及硫嗎啉。術語"雜環"亦 包括(例如,但不限於)以下文獻中所述雜環之單價自由 基.Paquette,Leo A.,Principles of Modern HeterocyclicHandbook of Fine Chemicals, 2007-2008, Milwaukee, WI. The term "alkoxy" as used herein, refers to an alkyl-oxime group, wherein the leuco group is as defined herein. In one embodiment 'alkoxy includes, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, second butoxy, n-pentyl Oxy, hexyloxy, 1,2-didecylbutoxy, and the like. The alkyl group in the alkoxy group may be unsubstituted or substituted. The term "aryl" as used herein refers to an aromatic hydrocarbon radical derived by the removal of one hydrogen atom from a single carbon atom of the parent aromatic ring system. This group may be at the saturated or unsaturated carbon atom of the parent ring system. The aryl group may have 6 to 18 carbon atoms. The aryl group may have a single ring (e.g., phenyl) or a plurality of condensed (fused) rings wherein at least one of the rings is aromatic (e.g., naphthyl, dihydrophenanthrenyl, fluorenyl, or fluorenyl). Typically aryl groups include, but are not limited to, groups derived from benzene, naphthalene, anthracene, biphenyl, and the like. The aryl group may be unsubstituted or substituted as desired, as described above for the alkyl group. The term "block copolymer" as used herein refers to any polymer prepared by coupling a functional polyvalent polymer, such as an AB block copolymer. The block copolymer of certain embodiments may be an AB block copolymer wherein the a block is a first monomer and the B block is a second monomer, wherein the first and second monomers are each different. The block copolymer of some embodiments may also be an ABA block copolymer or an ABc embedded 135320.doc -15-200930743 segment copolymer, wherein the A block is the first monomer, and the B block is the second monomer. And wherein the C block is a third monomer, wherein the first, second and third monomers are each different. Further, the block copolymer of certain embodiments may be an Ab block copolymer, for example, wherein the A block is a polythiophene and the B block is another conductive polymer 'e such as poly(β pyrrole). The block copolymer of certain embodiments may also be a hydrazine block copolymer or an ABC block copolymer, wherein the a block is a polythiophene, wherein the B block is another conductive polymer, such as poly(pyrrole), and Wherein the C block is another conductive polymer such as poly(stupylamine). The term "conductive polymer" as used herein refers to a polymer that conducts electrical current. Usually, the conductive polymer is a polymer mainly containing sp2-hybridized carbon atoms in the main chain, and these carbon atoms may also be replaced by corresponding hetero atoms. In the simplest case, this means that double bonds and single bonds alternate in the main chain. "Main" means that the natural deficiencies that lead to conjugate blocking do not affect the term "conductive polymer," its applicability. Further, if, for example, an arylamine unit and/or a certain heterocyclic ring (ie, conjugated via an N, hydrazine or S atom) and/or an organometallic complex (ie, conjugated via a metal atom) are present in the backbone, The term "conductive" is also used in the text of this application. In contrast, units such as simple alkyl bridges, (thio)ethers, esters, decylamines, or hydrazine amine linkages are defined as non-conductive segments. A partially conductive polymer is intended to mean a relatively long conductive portion of the main chain which is interrupted by a non-conductive portion or which has a relatively long conductive portion in the side chain but which is not electrically conductive. The term "conductive polymer" as used herein also refers to homopolymers, random copolymers, branched polymers, block copolymers, and the like. The term "film, or "film"; means a self-propelled or free-standing film that exhibits mechanical stability and flexibility, and a coating or layer on the support substrate or between 135320.doc -16- 200930743. The term " A reagent, which is a composition formed by the action of a leukotriene or an aryl dentate on a magnesium metal. The term "dentate" as used herein refers to fluorine, chlorine, ? Stinky, or an ionic group, a substituent, or a free radical. The term "heteroaryl" as used herein, is defined herein as a monocyclic, bicyclic, or tricyclic system which contains one, two or three aromatic rings and contains at least one nitrogen in the aromatic ring. Oxygen, or sulphur and which may be unsubstituted or substituted, for example, by one or more (and in particular 丨 to 3) substituents, as described above in the definition of "substituted". Heteroaryl Examples include, but are not limited to, down-reacting, 3H, aryl, 4H, pyridazinyl, acenaphthyl benzophenanyl, benzinium, lindenyl, (tetra), benzopyrene Tertyl, porphyrin, dibenzo[b,d]furanyl,furazanyl,furyl,imidazolyl,imidizolyi,isosyl,zino,(tetra),isobenzo吱味基, 异巧卜基基, 异噎琳基, 异嗟峻基异 峻 基 萘 萘 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Biazinyl, phenazinyl, phenazinyl, benzylthio, phenyl, pyridazinyl, fluorenyl, beta-pyranyl, pyridazinyl, benzylazolyl, pyridazinyl, Acridinyl, pyrimidinyl, Rupyl, quinazolinyl, quinolyl, quinoxalinyl, thiadiazolyl, thioxyl, thiazolyl, thienyl, triazolyl, tetrazolyl, and xanthene. In one embodiment The term "heteroaryl" denotes a monocyclic aromatic ring containing 5 or 6 ring atoms containing carbon atoms and deuterium, 2, 3 or 4 independently selected from non-peroxide oxygen, sulfur and N (z) a hetero atom in which it is vacant or is H' 〇, alkyl, aryl, or (CiC6)alkylaryl. In another 135320.doc •17· 200930743, the heteroaryl group represents from about 8 to A thick uf heterocyclic ring of about 1 ring atom, especially a phenyl derivative or a derivative obtained by condensing a propyl group, a trimethylene group or a tetramethylene divalent radical. The term "heterocyclic ring" or "heterocyclic group" as used in the basic text of 喃 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基Substituting a group as defined in the term "substituted" as needed. The heterocyclic ring may be a monocyclic, bicyclic or tricyclic ring containing - or a plurality of heteroatoms. Non-limiting examples of heterocyclic groups which may also contain an oxo (=0) beta heterocyclyl group attached to the ring include 1,3-dihydrobenzofuran, 1,3-dioxolane, 1,4-Dioxane, anthracene, 4_dithiane, pyran, 2_pyrazoline, 4-pyridolohydropyranyl, imidazolidinyl, imidazolinyl, dihydroindole Benzodihydropyranyl, iso-dihydroarsenyl, morpholine, hexahydropyrazine/hydropyridine, hexahydropyridyl, pyrazolidine, pyrazolidinyl, pyrazolinium pyrrolidine 'pyrroline, Quinine ring, and thiomorpholine. The term "heterocycle" also includes (for example, without limitation) monovalent free radicals of the heterocyclic ring described in the following literature. Paquette, Leo A., Principles of Modern Heterocyclic
Chemistry (W.A. Benjamin, New York, 1968),尤其第 i、 3、4、6、7 及 9 章,The Chemistry of Heterocyclic Compounds, A Series of Monographs(John Wiley & Sons »Chemistry (W.A. Benjamin, New York, 1968), especially chapters i, 3, 4, 6, 7 and 9, The Chemistry of Heterocyclic Compounds, A Series of Monographs (John Wiley & Sons »
New York,1950年至今),尤其第 13、14、16、19、及 28 卷,及《/. dm. C/ze/n· S〇c· i960,52,5566。在本發明—實施 例中,"雜環"包括本文所定義之”碳環",其中一或多個(例 如1、2、3或4個)碳原子已經雜原子(例如〇、N或S)替換》 本文所用術語"高位置規則度"係指化合物或聚合物具有 135320.doc • 18 · 200930743 至少約85%之位置規則度、較佳至少約87%之位置規則 度、更佳至少約90%之位置規則度、甚至更佳至少約92% 之位置規則度、更佳至少·約95%之位置規則度、更佳至少 約97%之位置規則度、或最佳至少約99%之位置規則度。New York, 1950 to present, especially Volumes 13, 14, 16, 19, and 28, and /. dm. C/ze/n·S〇c·i960, 52, 5566. In the present invention - an embodiment, "heterocycle" includes a "carbocycle" as defined herein, wherein one or more (e.g., 1, 2, 3 or 4) carbon atoms have been heteroatoms (e.g., hydrazine, N or S) Replacement The term "high positionality" as used herein refers to a compound or polymer having a positional regularity of at least about 85%, preferably at least about 87% of the positional regularity of 135320.doc • 18 · 200930743 More preferably, at least about 90% of the positionality, even better, at least about 92% of the positionality, preferably at least about 95% of the positionality, preferably at least about 97% of the positionality, or preferably At least about 99% of the positional regularity.
❹ 本文所用術語"HT聚(經取代噻吩)嵌段共聚物”係指在ht 聚(3_取代噻吩)嵌段共聚物或ht聚(3,4-二取代噻吩)嵌段 共聚物中單體頭-尾定向^ HT聚(經取代嘴吩)嵌段共聚物 中所表現位置規則度百分比可藉由標準ιΗ 術來確 定。位置規則度百分比可藉由各種技術來提高,包括(例如) 索克斯累特提取(Soxhlet extraction)、沈殿、及重結晶。 本文所用術語"金屬觸媒"係指用於單體_金屬錯合物之聚 合觸媒。 本文所用術語"單體_金屬錯合物"係指與金屬原子(例如 鋅)相連之單體部分(例如㈣)。單體_金屬錯合物通常係 單體金屬齒化物錯合物(例如嗟吩辞自化物錯合物)。"齒 化物"或”齒素"基團可為氟、氣、漠或碘。 本文所用詞語”較佳"及”較 校佳地係扎在某些情況下可提 供一定優勢之本發明眘尬 實施例。,然巾,在相同或其他情況下 其他實施例亦可係較佳。 p* ^ 卜徒及一或多個較佳實施例 時並不表不其他實施例 6 士政』用且並不意欲將其他實施例 自本發明範圍中排除。 本文所用術語"位置規 ^ , 幻性係扣其中單體實質上以頭-尾 疋向排列之聚合物β皇包 a J而S ,儘管多種習用聚合物具有完 全α·α偶合’但其係頭_ 取』具有- 碩尾、及尾·尾定向之混合物。 135320.doc 19 200930743术语 The term "HT poly(substituted thiophene) block copolymer" as used herein means in ht poly(3_substituted thiophene) block copolymer or ht poly(3,4-disubstituted thiophene) block copolymer Monomer head-to-tail orientation ^ The percentage of positional regularity exhibited in the HT poly (substituted phenotype) block copolymer can be determined by standard ι Η. The percentage of positional regularity can be improved by various techniques, including (for example) Soxhlet extraction, sedimentation, and recrystallization. The term "metal catalyst" as used herein refers to a polymerization catalyst for monomer-metal complexes. The term "single A body-metal complex refers to a monomer moiety (eg, (iv)) attached to a metal atom (eg, zinc). The monomer-metal complex is typically a monomeric metal tooth complex complex (eg, porphin) Compound complex). The "dental" " or dentate" group can be fluorine, gas, desert or iodine. As used herein, the terms "better" and "preferably" are preferred embodiments of the present invention that provide advantages in some cases. However, other embodiments may be preferred in the same or other circumstances. </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> and one or more preferred embodiments are not intended to be used in the context of the present invention. As used herein, the term "positional rules", phantom buckles, in which the monomers are substantially aligned in a head-to-tail orientation, are agglomerated, although a variety of conventional polymers have a full alpha·alpha coupling' The head _ takes a mixture of - tail, tail and tail orientation. 135320.doc 19 200930743
因此f用聚合物並非具有完全位置規則性(先前稱作 位置特異性及立體特異性),即全部係暑頭、頭·尾、或 尾-尾定向。習用聚合物亦非完全位置隨機性,即每種定 向含量相等(25%頭-尾及頭-尾、25%頭_尾及頭頭、25% 尾-尾及頭-尾、25%尾-尾及頭_頭)。Therefore, the polymer for f does not have full positional regularity (previously referred to as positional specificity and stereospecificity), i.e., all of the head, tail, tail, or tail-tail orientation. Conventional polymers are also not completely random in position, ie each orientation is equal (25% head-tail and head-tail, 25% head_tail and head, 25% tail-tail and head-tail, 25% tail-tail And head _ head).
頭-尾及頭-尾連接Head-to-tail and head-to-tail connections
R RR R
頭-尾及頭·頭連接Head-to-tail and head-to-head connection
尾-尾及頭-頭連接 -20· 135320.doc 200930743Tail-tail and head-to-head connection -20· 135320.doc 200930743
尾-尾及頭-頭連接 關於術語位置隨機性及位置規則性(或位置選擇性)之其 他闡述及論述參見美國專利第5,756,053號,其係以引用 ❹ 方式併入本文争。 本文所用術語”裏克鋅(Zn*)”係指藉由美國專利第 5’756,653號中所述方法製備之鋅之活化形式,該專利係以 引用方式併入本文中。 本文所用術語"室溫"係指約23〇c。 本文所用術語"經取代”意欲表示在使用’’經取代"之表達 式中所不基團上一或多個(例如1、2、3、4或5個,在某些 φ 實施例中為1、2或3個,且在其他實施例中為1或2個)氫原 子經選自所述有機或無機基團者替代,或經熟習此項技術 者已知之適宜有機或無機基團替代,前提係不超過所示原 子之常價’且取代產生穩定化合物。所述適宜有機或無機 • 基團包括(例如)烷基、烯基 '炔基、烷氧基、齒素、鹵代 烧基、經基、羥基烷基、芳基、雜芳基、雜環基、環烷 基、燒酿基、烷氧基羰基、胺基、烷基胺基、二烷基胺 基、二氣甲硫基、二氟曱基、醯胺基、硝基、三氟曱基、 二氣甲氧基、羧基、羧基烷基、酮基、硫代基、烷硫基、 135320.doc 21 200930743 烧基亞績醯基、烧基續酿基、院基甲碎烧基、及氰基。此 外,所述適宜基團可包括(例如)-X、-R、-CT、-OR、-SR、-S_ 、-NR2、-NR3、=NR、-CX3、-CN、-OCN、-SCN、-N=C=0、 -NCS、-NO、-N02、=N2、-N3、NC( = 0)R、-C( = 0)R、 -C(=0)NRR -S(=0)2〇-、-S(=0)20H、-S(=0)2R、-0S(=0)20R、 ' -S(=0)2NR、-S(=0)R、-0P(=0)02RR、-P(=0)02RR、-P(=0)(C〇2、 -P( = 0)(0H)2、-C( = 0)R、-C( = 0)x、-C(S)R、-C(0)0R、 -c(0)cr、-C(S)OR、-C(0)SR、-C(S)SR、-C(0)NRR、 O -C(S)NRR、-C(NR)NRR,其中各X獨立地為鹵素(或"鹵素"基 團):F、Cl、Br、或I,且各R獨立地為Η、烷基、芳基、 雜環基、保護基團或前藥部分。熟習此項技術者可容易地 理解,當取代基為酮基(即=〇)或硫代基(即=S)或類似基團 時,經取代原子上兩個氫原子被替代。 本文所用術語”穩定化合物"及"穩定結構"意欲表示化合 物或聚合物足夠堅固以在自反應混合物分離為有用純度時 保持不變。本發明化合物及聚合物通常為穩定化合物。中 間體及金屬錯合物可稍微不穩定或為本發明方法之不可分 離組份。 - 本文所用術語"噻吩-鋅錯合物π係指與辞原子相連之噻吩 部分。噻吩-鋅錯合物通常為噻吩-鋅鹵化物錯合物。”鹵化 物"或"鹵素"基團可為氟、氣、溴或碘。 當然,對於任一含有一或多個取代基之上述基團而言, 應理解該等基團不含有任何立體上不合實際及/或合成上 不可行之取代或取代模式。此外,本發明化合物包括所有 135320.doc •22· 200930743 自該等化合物之取代產生之立體化學異構體。 本發明係關於製備位置規則性導電嵌段共聚物之方法以 及藉此製備之位置規則性導電嵌段共聚物。本文所揭示製 備位置規則性導電嵌段共聚物之方法採用活化金屬,其將 金屬原子直接插入鹵素-芳香族或鹵素-雜芳香族碳鍵辛。 若(例如)使用鎳(II)觸媒或鉑觸媒來完成聚合,則可獲得位 置規則性導電嵌段共聚物。 位置規則性導電嵌段共聚物可為(例如)包括兩種或更多 種具有相同環系統(例如噻吩)之單體之嵌段共聚物,或由 兩種或更多種具有不同環系統(例如噻吩及苯)之單體組成 之嵌段共聚物。 較佳地’位置規則性導電嵌段共聚物係(例如)包括未經 取代噻吩、3-取代噻吩、3,4-二取代噻吩、或其組合之聚 噻吩嵌段共聚物’或包括聚噻吩嵌段及另一芳香族或雜芳 香族導電聚合物嵌段之嵌段共聚物。 本發明亦係關於具有優良導電特性之位置規則性導電嵌 段共聚物。位置規則性導電嵌段共聚物之特徵在於其單體 組成、其位置規則性程度、及其物理特性,例如其分子量 及數量平均分子量、其聚合度分佈性、其導電性、其由其 製備特徵直接決定之純度、以及其他特性。位置規則性導 電嵌段共聚物之特徵亦在於其製備方法。 本發明亦係關於藉由本文所述方法製備之位置規則性導 電嵌段共聚物薄膜。位置規則性導電嵌段共聚物薄臈可包 括摻雜劑。 135320.doc •23· 200930743 本發明亦提供電子裝置,其包括(例如)用藉由本文所述 任一方法製備之位置規則性導電嵌段共聚物構建之電路。 電子裝置可為薄膜電晶體、場效應電晶體、射頻識別標 記、平板顯示器、光伏打裝置、電致發光顯示裝置、感測 器裝置、及電子照相裝置、或有機發光二極體(OLED)。 通用製備方法 本文提供多種製備位置規則性導電嵌段共聚物之實例性 方法。該等方法意欲闡述該等製備之性質而不意欲限制可 用方法之範圍。某些化合物可用作製備本發明其他化合物 或聚合物之中間體。 製備位置規則性導電嵌段共聚物之一般方案闡述於下文 方案1中。 在方案1中’位置規則性導電嵌段共聚物係藉由以下步 驟來製備:a)合併鎳(11)觸媒與第一單體-金屬錯合物(有 機金屬I)以提供位置規則性導電嵌段共聚物中間體,其中 該第一單體-金屬錯合物係藉由包括以下步驟之方法來製 備:合併第一種二齒素-單體與活化金屬、格氏試劑、或 RZnX、R2ZnX、或 R3znM試劑,其中 R係(c2-C12)烷基,Μ 係鎂、錳、鋰、鈉或鉀,且χ係F、c卜; b)合併第 二單體-金屬錯合物(有機金屬Π)與位置規則性導電嵌段共 聚物中間體以提供位置規則性導電嵌段共聚物,其中該第 二單體-金屬錯合物係藉由包括以下步驟之方法來製備: 合併第二種二鹵素-單體與活化金屬、格氏試劑或RZnX、 R2ZnX、或R3ZnM試劑,其中烷基,M係鎂、 135320.doc -24· 200930743 錳、鋰、鈉或鉀,且X係F、a、Br、或1,其中各二鹵素- 單體獨立地為經兩個相同或不同南素原子取代之芳香族或 雜芳香族基團,且其中若二函素-單體具有相同環系統, 則至少一個二鹵素-單體經取代,且若該兩個二齒素-單體 皆具有相同環系統且皆經取代,則該等取代基各不相同。 以任一順序合併鎳(11)觸媒與第—單體_金屬錯合物。舉 . 例而言,將鎳(Π)觸媒與第一單體-金屬錯合物合併以提供 _ 位置規則性導電嵌段共聚物中間體。或者,將第一單體_ 纟屬錯合物與錄(Π)觸媒合併以提供位置規則性導電嵌段 共聚物中間體。 方案1.Tail-Tail and Head-Head Connections For further explanations and discussion of the term positional randomness and positional regularity (or positional selectivity), see U.S. Patent No. 5,756,053, which is incorporated herein by reference. The term "Rick Zinc (Zn*)" as used herein refers to an activated form of zinc prepared by the method described in U.S. Patent No. 5,756,653, the disclosure of which is incorporated herein by reference. The term "room temperature" as used herein refers to about 23 〇c. The term "substitution" as used herein is intended to mean one or more of the groups that are not used in the expression ''substitution'" (e.g. 1, 2, 3, 4 or 5, in certain φ embodiments) 1 or 2 or 3 in other embodiments, and 1 or 2 in other embodiments) a hydrogen atom is replaced by a member selected from the group consisting of the organic or inorganic group, or a suitable organic or inorganic group known to those skilled in the art. The group substitution, provided that it does not exceed the constant value of the indicated atom 'and the substitution produces a stable compound. The suitable organic or inorganic group includes, for example, an alkyl group, an alkenyl 'alkynyl group, an alkoxy group, a dentate group, a halogen group. Alkyl, thiol, hydroxyalkyl, aryl, heteroaryl, heterocyclyl, cycloalkyl, aryl, alkoxycarbonyl, amine, alkylamino, dialkylamino, Methylthio, difluoroindenyl, decylamino, nitro, trifluoromethyl, dimethoxy, carboxy, carboxyalkyl, keto, thio, alkylthio, 135320.doc 21 200930743 a base group, a base group, a base group, and a cyano group. Further, the suitable group may include, for example, -X, - R, -CT, -OR, -SR, -S_, -NR2, -NR3, =NR, -CX3, -CN, -OCN, -SCN, -N=C=0, -NCS, -NO, -N02 , =N2, -N3, NC( = 0)R, -C( = 0)R, -C(=0)NRR -S(=0)2〇-, -S(=0)20H, -S( =0) 2R, -0S(=0)20R, '-S(=0)2NR, -S(=0)R, -0P(=0)02RR, -P(=0)02RR, -P(= 0)(C〇2, -P( = 0)(0H)2, -C( = 0)R, -C( = 0)x, -C(S)R, -C(0)0R, -c (0)cr, -C(S)OR, -C(0)SR, -C(S)SR, -C(0)NRR, O-C(S)NRR, -C(NR)NRR, each of which X is independently halogen (or "halogen" group): F, Cl, Br, or I, and each R is independently hydrazine, alkyl, aryl, heterocyclyl, protecting group or prodrug moiety It will be readily understood by those skilled in the art that when the substituent is a keto group (i.e., = oxime) or a thio group (i.e., =S) or the like, two hydrogen atoms on the substituted atom are replaced. The terms "stabilizing compound" and "stabilizing structure" are intended to mean that the compound or polymer is sufficiently strong to remain unchanged when separated from the reaction mixture to useful purity. The compounds and polymers of the invention are generally stable compounds. Intermediates and metals The compound may be somewhat unstable or may be an inseparable component of the process of the invention. - The term "thiophene-zinc complex π as used herein refers to a thiophene moiety attached to a diatom atom. The thiophene-zinc complex is typically thiophene- Zinc halide complex. The "halide" or "halogen" group may be fluorine, gas, bromine or iodine. Of course, for any of the above groups containing one or more substituents, it is understood that the groups do not contain Any substitution or substitution pattern which is sterically impractical and/or synthetically infeasible. Furthermore, the compounds of the invention include all stereochemical isomers resulting from the substitution of such compounds by 135320.doc • 22 200930743. A method of preparing a positionally oriented conductive block copolymer and a positionally regular conductive block copolymer prepared thereby. The method of preparing a positionally regular conductive block copolymer disclosed herein employs an activated metal which directly inserts a metal atom into a halogen - Aromatic or halogen-heteroaromatic carbon bond. If the polymerization is carried out, for example, using a nickel (II) catalyst or a platinum catalyst, a positionally regular conductive block copolymer can be obtained. The copolymer may be, for example, a block copolymer comprising two or more monomers having the same ring system (e.g., thiophene), or two or more having different ring systems A block copolymer composed of a monomer such as thiophene and benzene. Preferably, the position-regular conductive block copolymer (for example) includes unsubstituted thiophene, 3-substituted thiophene, 3,4-disubstituted a thiophene block copolymer or a combination thereof, or a block copolymer comprising a polythiophene block and another aromatic or heteroaromatic conductive polymer block. The present invention is also directed to a position having excellent electrical conductivity properties. Regular conductive block copolymer. The positional regular conductive block copolymer is characterized by its monomer composition, its degree of positional regularity, and its physical properties, such as its molecular weight and number average molecular weight, its degree of polymerization distribution, Electrical conductivity, purity directly determined by its preparation characteristics, and other characteristics. The positional regular conductive block copolymer is also characterized by its method of preparation. The present invention also relates to a positionally regular conductive prepared by the method described herein. a block copolymer film. The positionally regular conductive block copolymer thin layer may include a dopant. 135320.doc • 23· 200930743 The present invention also provides an electronic device, A circuit comprising, for example, a positionally-regular conductive block copolymer prepared by any of the methods described herein. The electronic device can be a thin film transistor, a field effect transistor, a radio frequency identification tag, a flat panel display, a photovoltaic device An electroluminescent display device, a sensor device, and an electrophotographic device, or an organic light emitting diode (OLED). General Preparation Methods Various exemplary methods of preparing a positionally regular conductive block copolymer are provided herein. It is intended to describe the nature of such preparations and is not intended to limit the scope of the methods available. Certain compounds are useful as intermediates in the preparation of other compounds or polymers of the invention. A general scheme for preparing positionally regular conductive block copolymers is set forth in Scheme 1 below. In Scheme 1, the 'positional regular conductive block copolymer is prepared by the following steps: a) combining a nickel (11) catalyst with a first monomer-metal complex (organic metal I) to provide a position A regular conductive block copolymer intermediate wherein the first monomer-metal complex is prepared by a process comprising the steps of: And a first dentate-monomer and an activated metal, a Grignard reagent, or a RZnX, R2ZnX, or R3znM reagent, wherein the R is a (c2-C12) alkyl group, and the lanthanum is magnesium, manganese, lithium, sodium or potassium. And the lanthanide F, c; b) combining the second monomer-metal complex (organometallic ruthenium) with the positionally regular conductive block copolymer intermediate to provide a positionally regular conductive block copolymer, wherein the The dimonomer-metal complex is prepared by a process comprising the steps of: combining a second dihalogen-monomer with an activated metal, a Grignard reagent or an RZnX, R2ZnX, or R3ZnM reagent, wherein the alkyl group, the M system Magnesium, 135320.doc -24· 200930743 Manganese, lithium, sodium or potassium, and X is F, a, Br, or 1, wherein each dihalogen-monomer is independently substituted by two identical or different sulphur atoms. An aromatic or heteroaromatic group, and wherein if the dimeric-monomer has the same ring system, at least one dihalogen-monomer is substituted, and if the two dentate-monomers have the same ring system And all substituted, the substituents are different. The nickel (11) catalyst and the first monomer-metal complex are combined in either order. For example, a nickel (ruthenium) catalyst is combined with a first monomer-metal complex to provide a _ positionally regular conductive block copolymer intermediate. Alternatively, the first monomer oxime complex is combined with a ruthenium catalyst to provide a positionally regular conductive block copolymer intermediate. plan 1.
其中 A、Β及〇各自鉬a E可不存在,或也為&、氮、氧、磷、矽、或碳; 一 |、氮、氧、碟、矽、或碳,且在E不 I35320.doc -25· 200930743 存在時B與D形成鍵; Χι及X2各自獨立地為鹵素; m及n表示為使嵌段共聚物具有期望分子量而存在的單 體單元之數量;Wherein A, Β and 〇 each of molybdenum a E may be absent, or also &, nitrogen, oxygen, phosphorus, antimony, or carbon; a |, nitrogen, oxygen, dish, sputum, or carbon, and in E not I35320. Doc -25· 200930743 When present, B and D form a bond; Χι and X2 are each independently halogen; m and n represent the number of monomer units present for the block copolymer to have a desired molecular weight;
Ri、R2、R3、R4、R5及R6各自獨立地不存在,或為視需 要經約1至約5個酯、酮、腈、胺基、_素、芳基、雜芳 基、或雜環基取代之统基、炫硫基、燒基甲石夕院基、或烧 氧基’且烷基中烷基鏈之一或多個碳原子可視需要由約j 至約10個Ο、S、及/或NP基團替換,其中P係上文所述取 代基或氣保護基團,且M*係活化金屬、格氏試劑、或 RZnX、R2ZnX4 R3ZnM試劑’其中 &係(C2_Ci2)烧基,μ係 鎂、錳、鋰、鈉或鉀,且X係F、C1、,其中環形表 示芳香族結構,其中A、B、D及E基團具有維持中性環結 構所需之額外氫原子,Ni(II)觸媒為可達成單體_金屬錯合 物聚合之任一鎳(Π)觸媒,且 在一實施例中,本發明提供製備位置規則性導電嵌段共 聚物之方法,其包括:a)在可提供活性聚合之條件下合 併鎳(II)觸媒與第一單體_金屬錯合物以提供位置規則性導 電嵌段共聚物中間體,其中該第一單體-金屬錯合物係藉 由包括以下步驟之方法來製備:合併第一種二鹵素-單體 與活化金屬、格氏試劑、或RZnX、R2ZnX或R3ZnM試劑, 其中R係(CVC,2)烧基,μ係鎂、猛、鐘、納或鉀,且X係 F、Cl、Br或I ; b)合併第二單體金屬錯合物與位置規則 性導電嵌段共聚物中間體以提供位置規則性導電嵌段共聚 135320.doc -26- 200930743 物其中該第二單體-金屬錯合物係藉由包括以下步驟之 方法來製備:合併第二種二_素_單體與活化金屬、格氏 試劑、或RZnX、R2ZnX或R3ZnM試劑,其中厌係(〇:2(:12)烷 基,熥係鎂、錳、鋰、鈉或鉀,且X係F、Cl、Br或I,其 中各二鹵素-單體獨立地為經兩個相同或不同鹵素原子取 代之芳香族或雜芳香族基團,且其中若二鹵素單體具有 相同環系統,則至少一個二齒素_單體經取代,且若該兩 個二函素-單體皆具有相同環系統且皆經取代,則該等取 代基各不相同》 在另一實施例中’方法另外包括用視需要與第一單體_ 金屬錯合物相同之第三單體-金屬錯合物使位置規則性導 電嵌段共聚物鍵延長。在另一實施例中,方法另外包括使 位置規則性導電AB嵌段共聚物鏈延長以形成位置規則性 導電ΑΒΑ嵌段共聚物。 在一實施例中’方法另外包括鏈延長步驟以形成位置規 則性導電ABC嵌段共聚物。在另一實施例中,位置規則性 導電AB嵌段共聚物係位置規則性聚噻吩嵌段共聚物。 可使用各種活化金屬來形成第一單體-金屬錯合物及第 二單體-金屬錯合物。適宜活化金屬可包括(例如)鋅、銘、 錳、銅及諸如此類。較佳地,使用裏克辞(Zn*)。 通常,各單體-金屬錯合物形成溫度為至少約,較 佳至少約〇°C,且更佳至少約23。〇。通常各單體_金屬錯合 物之形成溫度不超過約100°c,較佳不超過約60〇c,且更 佳不超過約4〇°c。 135320.doc • 27· 200930743 通常各單體-金屬錯合物之形成在至少約5分鐘内可充分 完成’且較佳在至少約30分鐘内充分完成。通常反應時間 不超過約24小時,更佳不超過約8小時,且甚至更佳不超 過約1小時。 第一單體-金屬錯合物與第二單體_金屬錯合物形成位置 規則性導電嵌段共聚物之較佳聚合反應條件包括(例如)惰 性氣氛(例如氮、氦、或氬)之使用及適宜溫度及時間。 ❹Ri, R2, R3, R4, R5 and R6 are each independently absent or, if desired, from about 1 to about 5 esters, ketones, nitriles, amines, auxins, aryls, heteroaryls, or heterocycles. a substituent, a thiol group, a pyroline group, or an alkoxy group, and one or more carbon atoms of the alkyl chain in the alkyl group may be from about j to about 10 Ο, S, as desired. And/or NP group substitution, wherein P is a substituent or a gas protecting group as described above, and an M* system activating metal, a Grignard reagent, or a RZnX, R2ZnX4 R3ZnM reagent 'where & (C2_Ci2) alkyl group , μ is magnesium, manganese, lithium, sodium or potassium, and X is F, C1, wherein the ring represents an aromatic structure, wherein the groups A, B, D and E have additional hydrogen atoms required to maintain the neutral ring structure. , the Ni(II) catalyst is any nickel (Π) catalyst that can achieve polymerization of the monomer-metal complex, and in one embodiment, the present invention provides a method for preparing a positionally-regular conductive block copolymer, It comprises: a) combining a nickel (II) catalyst with a first monomer-metal complex under conditions which provide living polymerization to provide a positionally regular conductive block copolymer intermediate, The first monomer-metal complex is prepared by a method comprising the steps of: combining a first dihalogen-monomer with an activated metal, a Grignard reagent, or an RZnX, R2ZnX or R3ZnM reagent, wherein the R system (CVC, 2) a base, μ system of magnesium, fierce, bell, nano or potassium, and X series F, Cl, Br or I; b) combined second monomer metal complex and positional regular conductive block copolymerization The intermediate is provided to provide a positional regular conductive block copolymer 135320.doc -26- 200930743 wherein the second monomer-metal complex is prepared by a method comprising the steps of: combining the second bis- _ Monomer and activated metal, Grignard reagent, or RZnX, R2ZnX or R3ZnM reagent, wherein the ruthenium (〇: 2 (: 12) alkyl, lanthanide magnesium, manganese, lithium, sodium or potassium, and X series F, Cl , Br or I, wherein each dihalogen-monomer is independently an aromatic or heteroaromatic group substituted by two identical or different halogen atoms, and wherein if the dihalogen monomer has the same ring system, then at least one The dentate-monomer is substituted, and if the two dimeric-monomers all have the same ring system and are substituted, then The substituents are different. In another embodiment, the method additionally comprises the use of a third monomer-metal complex which is the same as the first monomer-metal complex, to position the regular conductive block copolymer. The bond is extended. In another embodiment, the method additionally comprises extending the positionally regular conductive AB block copolymer chain to form a positionally regular conductive block copolymer. In one embodiment, the method additionally includes a chain extension step A positionally regular conductive ABC block copolymer is formed. In another embodiment, the positionally regular conductive AB block copolymer is a positionally regular polythiophene block copolymer. Various activating metals can be used to form the first monomer-metal complex and the second monomer-metal complex. Suitable activating metals can include, for example, zinc, indium, manganese, copper, and the like. Preferably, Rick (Zn*) is used. Typically, each monomer-metal complex formation temperature is at least about, preferably at least about 〇 ° C, and more preferably at least about 23. Hey. Typically, the monomer-metal complex is formed at a temperature of no more than about 100 ° C, preferably no more than about 60 ° C, and more preferably no more than about 4 ° C. 135320.doc • 27· 200930743 Typically, the formation of each monomer-metal complex is fully accomplished in at least about 5 minutes and is preferably fully completed in at least about 30 minutes. Typically, the reaction time is no more than about 24 hours, more preferably no more than about 8 hours, and even more preferably no more than about 1 hour. Preferred polymerization conditions for the first monomer-metal complex and the second monomer-metal complex to form a positionally-regular conductive block copolymer include, for example, an inert atmosphere (e.g., nitrogen, helium, or argon). Use and suitable temperature and time. ❹
通常將第一單體-金屬錯合物添加至金屬觸媒中以提供 位置規則性導電嵌段共聚物中間趙。亦可將金屬觸媒添加 至第-單體-金屬中以提供位置規則性導電嵌段共聚物中 間體。 通常聚合溫度為至少-78。。,較佳至少(TC,且更佳至少 23C。通常,聚合溫度不超過所用溶劑之沸點,較佳不超 過60°C ’且更佳不超過4〇t。 通常聚合反應在至少2小時内充分完成,且較佳在至少 J時内充刀凡成。通常聚合反應不超過72小時更佳不 超過48小時,且甚至更佳不超㈣小時。 可在與製備單體·金屬錯合物時所用溶劑相同之溶劑中 實施聚合反應。可在不分離任何中間體之情況下實施整個 反應序列。 適宜二自素·單體可包括(例如)㈣二由素取代或未經取 :«C:C3°)方基單體或二齒素取代或未經取代(c3-c3。)雜芳 基早體。芳香族或雜芳香族單體可為(例如)苯、售吩…比 嘻、咳鳴、苯胺、伸苯基伸乙烯基、伸噻吩基伸乙烯基、 135320.doc -28- 200930743 雙-伸噻吩基伸乙烯基、 — —^ 乙炔苐、伸方基、異硫萘、對 本朗、喧吩并[2,3姻吩、嘴吩扣〜]售吩嗟吩并 [2’3-d]嗟吩、萘、苯并[2,3]嗟吩、苯并[3,4]喧吩、聯苯 基、或聯嗔吩基、及諸如此類。芳香族或雜芳香族單體可 具有〇個至約3個非_素取代基。取代基各自獨立地為可視 需要經約1至約5個酯、酮、腈、胺基、芳基、雜芳基、或 雜環基取代之(C丨-C24)烷基、(C丨-C24)烷硫基、(C丨-C24)烷 基曱矽烷基、或(C^C^)烷氧基,且烷基中烷基鏈之一或The first monomer-metal complex is typically added to the metal catalyst to provide a positionally oriented conductive block copolymer intermediate. A metal catalyst may also be added to the first monomer-metal to provide a positionally regular conductive block copolymer intermediate. Usually the polymerization temperature is at least -78. . Preferably, it is at least (TC, and more preferably at least 23 C. Usually, the polymerization temperature does not exceed the boiling point of the solvent used, preferably does not exceed 60 ° C ' and more preferably does not exceed 4 〇 t. Usually the polymerization reaction is sufficient for at least 2 hours. It is completed, and preferably filled in at least J. Usually, the polymerization reaction does not exceed 72 hours, more preferably does not exceed 48 hours, and even more preferably does not exceed (four) hours. It can be used in the preparation of monomer/metal complexes. The polymerization is carried out in the same solvent as the solvent used. The entire reaction sequence can be carried out without isolating any of the intermediates. Suitable dioxins·monomers can include, for example, (d) di- ordinarily substituted or not taken: «C: C3°) a quaternary monomer or a dentate substituted or unsubstituted (c3-c3.)heteroaryl precursor. The aromatic or heteroaromatic monomer may be, for example, benzene, phenanthrene, cough, aniline, phenyl extended vinyl, thiophene extended vinyl, 135320.doc -28- 200930743 bis-thenylene-based extension Vinyl, —^^ acetylene oxime, exo-group, isothionaphthalene, benzophenone, porphin [2,3 吩, mouth 〜 ] ] ] ] 售 售 售 售 2 2 2 2 2 [2'3-d] 嗟Naphthalene, benzo[2,3] porphin, benzo[3,4] porphin, biphenyl, or hydrazino, and the like. The aromatic or heteroaromatic monomer may have from one to about three non-protein substituents. The substituents are each independently (C丨-C24)alkyl, optionally substituted with from about 1 to about 5 esters, ketones, nitriles, amines, aryl, heteroaryl, or heterocyclic groups, (C丨- C24) alkylthio, (C丨-C24)alkyldecyl, or (C^C^)alkoxy, and one of the alkyl chains in the alkyl group or
❹ 多個碳原子可視需要由約1至約10個0、S或NH基團替換。 適宜二齒素-單體包括(例如)2,5-二參素-噻吩、2,5·二鹵 素-吡咯、2,5-二鹵素-呋喃、1,3-二齒素苯、2,5-二齒素-3-取代噻吩、2,5-二鹵素-3-取代吡咯、2,5-二i素-3-取代呋 喃、1,3-二函素-2-取代苯、L3·二邊素_4-取代苯、込3-二 鹵素-5-取代苯、ι,3-二鹵素_6_取代苯、L3-二齒素_2,4_一 取代苯、1,3-二_素-2,5-二取代苯、二齒素·2,6-二取 代苯、1,3-二函素-4,5-二取代苯、L3-二齒素_4,6_二取代 苯、1,3-二自素-2,4,5-三取代笨、L3·二鹵素_2’4,6_二取代 苯、1,3_二鹵素-2,5,6-三取代苯、二鹵素_2_取代苯、 1,4-二函素-3-取代苯、1,4_二齒素-5-取代苯、Μ·二函素_ 6-取代苯、1,4-二鹵素-2,3-二取代苯、Μ.二鹵素-2’5_二 取代苯、U4-二函素-2,6-二取代苯、Μ·二函素·3,5·二取 代苯、1,4-二邊素-3,6-二取代苯、Μ_二齒素_3,5,6_三取代 苯、2,5-二i素·3,4-二取代嘍吩、2’5_二.素_3’4·二取代 吡洛、2,5-二齒素_3,4-工取代呋喃、或其組合。 135320.doc • 19- 200930743 在較佳實施例令,製備經取代HT聚噻吩嵌段共聚物之 方法展示於下文方案2中。 在方案2中,藉由包括以下步驟之方法來製備位置規則 性ΗΤ聚(3-取代噻吩)嵌段共聚物:合併鎳(π)觸媒與第一 噻吩··鋅錯合物以提供位置規則性ΗΤ聚(3-取代噻吩)中間 體,b)合併第二噻吩-鋅錯合物與位置規則性^17聚(3取 代噻吩)中間體以提供位置規則性HT聚(3_取代噻吩)嵌段共 聚物》以任一順序合併鎳(11)觸媒與第一噻吩_鋅錯合物。 舉例而s,將鎳(II)觸媒與第一噻吩_鋅錯合物合併以提供 位置規則性HT聚(3-取代噻吩)中間體,或者,將第一噻吩_ 鋅錯合物與鎳(π)觸媒合併以提供位置規則性111聚(3_取代 噻吩)中間體。 方案2.多个 Multiple carbon atoms may optionally be replaced by from about 1 to about 10 0, S or NH groups. Suitable dentate-monomers include, for example, 2,5-di-s-thiophene, 2,5-dihalo-pyrrole, 2,5-dihalo-furan, 1,3-dentary benzene, 2, 5-Bidentate-3-substituted thiophene, 2,5-dihalo-3-substituted pyrrole, 2,5-diiso-3-substituted furan, 1,3-difunctional-2-substituted benzene, L3 · Bismuth _4-substituted benzene, 込3-dihalo-5-substituted benzene, iota, dihalo _6_substituted benzene, L3-didentin_2, 4-substituted benzene, 1,3 - bis-2,5-disubstituted benzene, dentate, 2,6-disubstituted benzene, 1,3-biphenyl-4,5-disubstituted benzene, L3-dentate _4,6 _Disubstituted benzene, 1,3-dimorph-2,4,5-trisubstituted stupid, L3·dihalogen-2'4,6-disubstituted benzene, 1,3_dihalogen-2,5,6 -trisubstituted benzene, dihalo-2-substituted benzene, 1,4-difunctional-3-substituted benzene, 1,4-didentin-5-substituted benzene, fluorene dimer/6-substituted benzene, 1,4-dihalo-2,3-disubstituted benzene, fluorene dihalo-2'5-disubstituted benzene, U4-difunctional-2,6-disubstituted benzene, fluorene disaccharide·3, 5. Disubstituted benzene, 1,4-dimerin-3,6-disubstituted benzene, Μ_ dentate _3,5,6_trisubstituted benzene, 2,5-dii s 3,4- Disubstituted porphin, 2'5_di. _3'4· Los substituted pyrazole, 2,5-substituted furan tooth element _3,4- workers, or a combination thereof. 135320.doc • 19-200930743 In a preferred embodiment, the process for preparing a substituted HT polythiophene block copolymer is shown in Scheme 2 below. In Scheme 2, a positionally regular fluorene (3-substituted thiophene) block copolymer is prepared by a process comprising the steps of: combining a nickel (π) catalyst with a first thiophene·zinc complex to provide a position Regularly condensed (3-substituted thiophene) intermediates, b) combined second thiophene-zinc complexes with a positionally regular 1717 poly(3-substituted thiophene) intermediate to provide positional regular HT poly(3_substituted thiophene) The block copolymers combine the nickel (11) catalyst with the first thiophene-zinc complex in either order. For example, s, a nickel (II) catalyst is combined with a first thiophene-zinc complex to provide a positionally regular HT poly(3-substituted thiophene) intermediate, or the first thiophene-zinc complex is combined with nickel. The (π) catalysts combine to provide a positional regularity 111 poly(3_substituted thiophene) intermediate. Scenario 2.
r2R2
ZnX:ZnX:
135320.doc ·30· 200930743 其中又丨及又2各自獨立地為鹵素,心及心各自獨立地為視 需要經約1至約5個酯、酮、腈、胺基、鹵素、芳基、雜芳 基、或雜環基取代之烧基、烧硫基、烧基甲梦烧基、或烧 氧基,且院基中炫基鏈之一或多個碳原子視需要由〗個或 10個0、S、及/或NP基團替換,其中p為上述取代基或氮 保護基團’且其中心及尺2不可同時不存在,Zn*為裏克 鋅’ Ni(II)觸媒為可達成噻吩鋅錯合物聚合之任何鎳(〗〗)觸 媒,且m孕η,其中m及η表示為使嵌段共聚物具有期望分 子量而存在的單體單元之數量。 在一實施例中’本發明提供製備位置規則性ΗΤ聚(3·取 代噻吩)嵌段共聚物之方法,其包括勾在可提供活性聚合 之條件下合併鎳(II)觸媒與第一噻吩_鋅錯合物以提供位置 規則性ΗΤ聚(3-取代噻吩)中間體;b)合併第二噻吩-鋅錯 合物與位置規則性HT聚(3-取代噻吩)中間體以提供位置規 則性HT聚(3-取代噻吩)嵌段共聚物,其中至少一種單體_金 屬錯合物經取代’且若該兩種單體-金屬錯合物皆經取 代’則該等取代基各不相同。 在另一實施例中,方法另外包括用視需要與第一噻吩_ 鋅錯合物相同之第三噻吩-鋅錯合物使位置規則性Ητ聚(3_ 取代0S吩)嵌段共聚物鏈延長。在另一實施例中,方法另 外包括使位置規則性HT聚(3-取代噻吩)AB嵌段共聚物鏈延 長以形成位置規則性HT聚(3·取代噻吩)ΑΒΑ嵌段共聚物。 在一實施例中’方法另外包括鏈延長步驟以形成位置規 則性HT聚(3-取代噻吩)ABC嵌段共聚物。 135320.doc •31 _ 200930743 第一及第二噻吩·鋅錯合物係藉由美國專利第5 756 653 號令所述方法來製備,該專利係以引用方式併人本文中。 此方法包括將第-及第二2,5_二由素·嗟吩與裏克辞(㈣ 合併以提供第一及第二噻吩_鋅錯合物。 可將2,5-二由素_噻吩溶於適宜溶劑中,例如醚性溶劑, 例如四氫呋喃。可將反應燒瓶冷卻,之後引入活化鋅,較 佳引入裏克鋅(Zn*)試劑。可將裏克鋅(Zn*)添加至反應燒 瓶中並授拌足夠長時間以藉由使_代鋅(Ζηχ)基團與嗟吩 中個χ(鹵素)基團交換來形成嘆吩-辞錯合物。 在噻吩-鋅錯合物形成後,可將鎳(11)觸媒添加至含有噻 吩-鋅錯合物之反應容器中。可將所得混合物攪拌足夠長 時間以使得形成聚噻吩,其通常可自反應混合物中沈澱。 或者在噻吩-鋅錯合物形成後,可將噻吩_鋅錯合物添·加至 含有鎳(II)觸媒之燒瓶中。可藉由將反應混合物轉移至一 定體積的聚噻吩實質上不溶於其中之溶劑中來分離聚噻 吩。其他處理可包括過濾、用曱醇洗滌、及在高度真空下 乾燥。可用(例如)諸如己烷等烴溶劑藉由索克斯累特提取 實施額外純化。 可在任一適宜有效溫度下實施聚噻吩之形成。在一實施 例中,在約-100°c至約150°C之溫度下實施聚合。在另一 實施例中,在約-20°C至約10CTC之溫度下實施聚合。可在 與製備隹吩鋅錯合物時所用溶劑相同之溶劑中實施聚合。 使用Ni(II)觸媒之聚合反應步鈿可在約〇。〇至此反應步驟中 所用溶劑之沸點左右溫度下實施。通常使用Ni(II)觸媒之 135320.doc -32- 200930743 聚合反應步驟係在約〇°C至約25°C下實施。 活化金屬 活化金屬係高反應性金屬,其具有較大表面積且缺乏鈍 化表面氧化物。舉例而言,活化金屬可為金屬粉末、金屬 粉塵、或金屬顆粒。活化金屬可藉由(例如)化學方法、熱 學方法、電化學方法、或超音波方法來活化❶通常活化金 屬價態為零。較佳地,活化金屬為裏克金屬,其係藉由本 發明一發明者Reuben D. Rieke博士所研發之方法來製備。 裏克法通常涉及用鹼金屬還原無水金屬鹵化物(例如F、 Cl、Br、或I)之四氫呋喃懸浮液。裏克法中所用驗金屬通 常包括(例如)鉀、鈉及鋰。舉例而言,裏克鎂之製備使用 鉀作為還原劑,如下所述:135320.doc ·30· 200930743 wherein 丨 and 2 are each independently halogen, and the heart and heart are each independently from about 1 to about 5 esters, ketones, nitriles, amines, halogens, aryls, An aryl group, or a heterocyclic group-substituted alkyl group, a sulfur-burning group, a pyridyl group, or an alkoxy group, and one or more carbon atoms of the thiol chain in the hospital base are optionally or 10 0, S, and/or NP group substitution, wherein p is the above substituent or nitrogen protecting group ' and its center and the ruler 2 are not simultaneously absent, and Zn* is a Rick zinc 'Ni(II) catalyst Any nickel (") catalyst that polymerizes the thiophene zinc complex is reached, and m is pregnant, wherein m and η are the number of monomer units present to provide the block copolymer with the desired molecular weight. In one embodiment, the invention provides a method of preparing a positionally regular fluorene (3. substituted thiophene) block copolymer comprising combining a nickel (II) catalyst with a first thiophene under conditions which provide living polymerization. -Zinc complex to provide a positionally regular fluorene (3-substituted thiophene) intermediate; b) combining a second thiophene-zinc complex with a positionally regular HT poly(3-substituted thiophene) intermediate to provide a positional rule a HT poly(3-substituted thiophene) block copolymer in which at least one monomer-metal complex is substituted 'and if the two monomer-metal complexes are substituted' then the substituents are not the same. In another embodiment, the method additionally comprises extending the positional regular Ητ poly(3_substituted OSE) block copolymer chain with a third thiophene-zinc complex as desired for the first thiophene-zinc complex. . In another embodiment, the method further comprises extending the positionally regular HT poly(3-substituted thiophene) AB block copolymer chain to form a positionally regular HT poly(3. substituted thiophene) fluorene block copolymer. In one embodiment, the method additionally includes a chain extension step to form a positionally regular HT poly(3-substituted thiophene) ABC block copolymer. 135320.doc •31 _ 200930743 The first and second thiophene-zinc complexes are prepared by the method described in U.S. Patent No. 5,756,653, the disclosure of which is incorporated herein by reference. The method comprises combining the first and second 2,5-di- quinone porphin with Rick ((iv) to provide the first and second thiophene-zinc complex. 2,5-di- _ The thiophene is dissolved in a suitable solvent, such as an ethereal solvent, such as tetrahydrofuran. The reaction flask can be cooled, followed by the introduction of activated zinc, preferably with the introduction of a Zn* (Zn*) reagent. The Zn* can be added to the reaction. The flask is stirred for a sufficient period of time to form a singular-synthesis complex by exchanging a zinc-based (Ζηχ) group with a quinone (halogen) group in the porphin. Formation of the thiophene-zinc complex Thereafter, a nickel (11) catalyst may be added to the reaction vessel containing the thiophene-zinc complex. The resulting mixture may be stirred for a sufficient time to form a polythiophene, which may typically be precipitated from the reaction mixture. After the zinc complex is formed, the thiophene-zinc complex can be added to the flask containing the nickel (II) catalyst. The reaction mixture can be substantially insoluble in the volume by transferring the polythiophene. The polythiophene is separated in a solvent. Other treatments may include filtration, washing with decyl alcohol, and at height Drying under vacuum can be carried out by, for example, a hydrocarbon solvent such as hexane by Soxhlet extraction. The formation of polythiophene can be carried out at any suitable effective temperature. In one embodiment, at about -100° The polymerization is carried out at a temperature of from c to about 150 ° C. In another embodiment, the polymerization is carried out at a temperature of from about -20 ° C to about 10 CTC, which may be the same solvent as that used in the preparation of the zinc phenanthrene complex. The polymerization is carried out in a polymerization process using a Ni(II) catalyst, which can be carried out at a temperature of about 〇. 〇 to the boiling point of the solvent used in the reaction step. Usually, Ni(II) catalyst is used as 135320.doc -32- 200930743 The polymerization step is carried out at a temperature of from about 〇 ° C to about 25 ° C. The activated metal activates a metal-based highly reactive metal having a large surface area and lacking a passivated surface oxide. For example, the activated metal may be a metal powder , metal dust, or metal particles. The activated metal can be activated by, for example, a chemical method, a thermal method, an electrochemical method, or an ultrasonic method, and the valence state of the activated metal is usually zero. Preferably, the activated metal is Rick metal, which is prepared by a method developed by Dr. Reuben D. Rieke, an inventor of the present invention. Rick process generally involves the reduction of tetrahydrofuran of an anhydrous metal halide (e.g., F, Cl, Br, or I) with an alkali metal. Suspensions. The metals used in the Rick process typically include, for example, potassium, sodium, and lithium. For example, Rick magnesium is prepared using potassium as a reducing agent, as described below:
MgCl2 + 2 K — Mg + 2 KC1 多種活化金屬係藉由此方法來製備,包括(例如)銘、 猛、銅、鋅、鎖、約、欽、鐵、钻、錄、及銦。在某些情 況下,反應係用催化量之電子載流子(例如聯苯基或萘)來 實施。活化金屬通常係在原位使用。 適宜活化金屬包括(例如)銘、猛、銅、鋅、鎮、約、 鈦、鐵、鈷、鎳、銦、或其組合。較佳地,活化金屬係裏 克鋅》 2,5-二由素-嘆吩 在較佳實施例中,二鹵素-單體係二自素-噻吩。2,5_二 鹵素-噻吩可為2,5-二南素-3-取代噻吩、未經取代2,5-二鹵 素-噻吩、或2,5-二齒素-3,4-二取代噻吩》二_素噻吩通常 135320.doc •33- 200930743 為一氟-、二氣_、二溴_或二蛾_嗟吩,其可未經取代或在3 位及/或4位經取代。亦可使用2 5-二函素噻吩、2 5•二鹵 素-3-取代噻吩與2,5_二函素_3,4_二取代噻吩之組合。 適宜未經取代二鹵素噻吩可包括(例如)2,5-二氟嗟吩、 2.5- 二氣噻吩、2,5-二溴噻吩、2,5-二块噻吩、2-氟-5-氣噻 吩、2-氟-5-溴噻吩、2-氟·5-碘噻吩、2-氣-5-氟噻吩、2· 氯-5-溴嗟吩、2-氣-5-峨售吩、2-溴-5-氟嗟吩、2-溴-5-氣 嗟吩、2-溴-5-碘噻吩、2-碘-5-氟噻吩、2-碘-5-氣嘆吩、 及2-碘-5-溴噻吩。該等在3_及/或4·位未經取代之2,5_二鹵 素隹吩可用於製備包括(例如)未經取代聚噻吩嵌段及一或 多個經取代聚噻吩嵌段之嵌段共聚物。舉例而言,未經取 代聚噻吩可與3-取代聚噻吩嵌段及/或3,4-二取代聚噻吩嵌 段組合。或者’ 3-取代聚噻吩可與3,4-二取代聚噻吩嵌段 組合。 上文所列二齒素噻吩可在3及/或4位經以下基團取代: $ 可視需要經約1至約5個酯、酮、腈、胺基、芳基、雜芳基 或雜環基取代之((:「(:24)烷基、(C丨-C24)烷硫基、(Ci-C24) 烷基甲矽烷基、或(C^C^)烷氧基,且烷基中烷基鏈之一 或多個碳原子可視需要由約1至約10個0、S或NH基團替 換。 適宜2,5-二函素-3-取代噻吩可包括(例如)2,5-二氟-3-己 基噻吩、2,5-二氣-3·己基噻吩、2,5-二溴-3-己基噻吩、 2.5- 二碘-3-己基噻吩、2-氟-3-己基-5-氣噻吩、2-氟-3-己 基-5-溴噻吩、2-氟-3-己基-5-碘噻吩、2-氯-3-己基_5_氟噻 135320.doc -34- 200930743 吩、2-氯-3-己基-5-溴噻吩、2-氣-3-己基-5-碘噻吩、2-溴-3-己基-5-氟嘆吩、2-漠-3-己基-5-氣嘆吩、2-漠-3-己基-5-碘噻吩、2-碘-3-己基-5-氟噻吩、2-碘-3-己基-5-氣噻吩、 2- 碘-3-己基-5-溴"塞吩、5-(2-5-二氟嗟吩-3-基)戊酸乙酯、 5-(2-5-二氣嗟吩-3-基)戊酸乙S旨、5-(2-5-二演嘴吩-3-基)戊 酸乙酯、5-(2-5-二碘噻吩-3-基)戊酸乙酯、5-(2-氟-5-氣噻 吩-3_基)戊酸乙酯、5-(2-氟-5-溴嘆吩-3-基)戊酸乙酯、5-(2-氟-5-埃嗟吩-3-基)戊酸乙g旨、5-(2-氣-5-漠售吩-3-基)戊 酸乙醋、5-(2-氣-5-蛾〇塞吩-3-基)戊酸乙醋、5-(2-漠-5-氣 噻吩-3-基)戊酸乙酯、5-(2·溴-5-氣噻吩-3-基)戊酸乙酯、 5-(2-溴-5-峨嘆吩-3-基)戊酸乙酯、5-(2-蛾-5-氣嗟吩-3-基) 戊酸乙酯、5-(2-碘-5-溴噻吩-3-基)戊酸乙酯、及5_(2_峨_ 5-氟嗟吩-3-基)戊酸乙酯。較佳地,2,5-二幽素_3_取代嗟 吩係2-溴-3 -己基-5-蛾嘴吩或5-(2-漠-5-峨嗟吩_3_基)戊酸 乙酯。 適宜2,5-二i素-3,4-二取代噻吩可包括(例如)5 (2 5_二 氟-3-己基嚷吩-3-基)戊酸乙酯、5-(2-5-二氣_3_己基喧吩· 3- 基)戊酸乙酯、5-(2-5-二溴-3-己基噻吩-3-基)戊酸乙酯、 5-(2-5二蛾-3·己基喧吩-3-基)戊酸乙酯、5-(2-1-5-氣·3_ 己基售吩·3-基)戊酸乙醋、5-(2-氟-5-漠-3-己基喧吩_3_基) 戊酸乙酯、5-(2-氟-3-己基-5-碘噻吩-3-基)戊酸乙酯、5_ (2-氣-3-己基-5-氟嘴吩-3-基)戊酸乙酯、5-(2-氣_3·己基·5· 漠嘆吩-3-基)戍酸乙g旨、5-(2 -氣-3-己基-5-破嗟吩_3_基)戊 酸乙酯、5-(2-溴-5-氣-3-己基售吩-3-基)戊酸乙酯、5_(2_ 135320.doc -35- 200930743 演-3-己基-5-埃嘆吩-3-基)戊酸乙醋、5_(2_硬_3_己基_5_氣 嗟吩-3-基)戊酸乙酯、5-(2-峨-3-己基_5-溴售吩-3-基)戊酸 乙醋、及5-(2-破-5-氟-3-己基嘆吩_3-基)戊酸乙醋。 溶劑 該等方法中所用溶劑可為非質子性有機溶劑。可使用一 或多種溶劑化合物或混合物。適宜溶劑包括醚性或聚醚性 溶劑。該等溶劑之實例包括乙醚、曱基·第三丁基醚、四 氫呋喃(THF)、二噁烷、二乙二醇二甲醚、三甘醇二甲 $ _、1,2-二甲氧基乙烧(DME或乙二醇二曱謎)、及諸如此 類。溶劑通常為四氳夫味。 聚合反應觸媒 在該等方法之聚合反應中可使用多種金屬觸媒。金屬觸 媒可包含有機金屬化合物或過渡金屬錯合物。舉例而言, 金屬觸媒可為鎳、鉑、或鈀化合物^較佳地,金屬觸媒為 錄(Η)觸媒’其可提供位置選擇性聚喧吩嵌段共聚物。 多 在一實施例方法中用於形成位置規則性聚噻吩嵌段共聚 物之觸媒係Ni(II)觸媒。使用有效量之Ni(II)觸媒以使得可 在少於約5天時間内使用足量觸媒來實施反應。此通常為 約0.01-10莫耳%(m〇l %)之量,然而,可使用任一量之鎳 觸媒,例如50 mol %、100 m〇l %或更多。端視所存在 嘆吩單體之量’通常使用約〇. 1 mol %鎳(II)觸媒至約5 mol %鎳(II)觸媒,或較佳地使用 約0.1 mol %錄(II)觸媒至約3 mol %鎳(π)觸媒。 適宜錄(Π)觸媒之實例包括(例如)Ni(PR3)2X2(其中R係 135320.doc -36· 200930743 (C丨-c20)烷基、(C6-C20)芳基’且X為齒素)、NiLX2(其中L 係適宜鎳(Π)配體且X為鹵素)。適宜鎳(π)配體包括丨,2-雙 (二苯基膦基)乙烷、1,3-二苯基膦基丙烷、[2,2-二甲基_ 1,3-二氧戊環-4,5-二基)雙(亞甲基)]二苯基膦、雙(三苯基 膦)、及(2,2'_二吡啶)配體。其他適宜Ni(II)觸媒包括 Ni(CN),2、NiO、Ni(CN)5-3、Ni2Cl8·4、NiF2、NiCl2、 NiBr2、Nil2、NiAs、Ni(dmph)2(其中 dmph 係二曱基乙二 肟)、BaNiS、[NiX(QAS)]+(其中X為鹵素且QAS係As(鄰 C6H4AsPh2)3)、[NiP(CH2CH2CH2AsMe2)3CN]+、[Ni(NCS)6]·4、 KNiX3(其中 X為齒素)、[Ni(NH3)6]+2、及[Ni(bipy)3]+2(其中 bipy為二°比咬)。 通常鎳觸媒亦包括1,2-雙(二苯基膦基)乙烷鎳(Π)氣化物 (Ni(dppe)Cl2)、1,3-二苯基膦基丙烷鎳(π)氣化物 (Ni(dppp)Cl2)、I,5·環辛二烯雙(三苯基)鎳、二溴雙(三苯 基膦)鎳、二氣(2,2,_二吡啶)鎳、及四(三苯基膦)鎳(〇)。 熟習此項技術者已知之一般技術及方法可用於本文方法 中’例如實施聚合及分離並純化產物之各種標準程序。 聚合物結構及導電聚合物之特性 通常導電聚合物係有機聚合物,由於其具有共軛主鏈妗 構,其在某些條件下顯示高導電性(相對於傳統聚合材料 之導電性)。當該等材料經摻雜、經氧化、或經還原時, 其作為電洞或電子導體之性能提高。在對導電聚合物實施 低氧化(或還原)後,在通常稱作摻雜之過程中,自價帶頂 端移除-電子(或添加至導帶底端)從而產生自由基陽離子 135320.doc •37· 200930743 (或極化子)。極化子之形成在若干單體單元產生部分離域 作用。在進一步氧化後,可自單獨聚合物鏈段移除另一電 子由此產生兩個獨立極化子。 或者,可移除不成對電子以產生雙陽離子(或雙極化 子)。在所施加電場中,極化子及雙極化子二者皆具有流 動性且可藉由雙鍵及單鍵之離域作用沿聚合物鏈移動。此 氧化態之改變導致形成稱為雙極化子之新能態。價帶中某 些殘留電子易達到該等能級,從而使聚合物可用作導體。 ® 此共軛結構之共軛度取決於在固態下聚合物鏈形成平面構 型之程度。此乃因環-環共輛取決於π_軌道重疊。若特定環 扭曲脫離平面,則不能發生重疊且共概帶結構可中斷。某 些較小扭曲係無害的,此乃因(例如)嗟吩環之間之重疊程 度隨該等環間二面角之餘弦而改變。 共軛聚合物作為有機導體之性能亦可取決於聚合物在固 態下之形態。電子特性可取決於聚合物鏈之間之電連接性 〇 及鏈間電荷輸送。電荷輸送路徑可沿聚合物鏈或位於相鄰 鏈間。由於帶電荷部分對環間雙鍵數量(環平面性指標)具 有依賴性,因此平面主鏈構型可促進沿鏈之輸送。此鏈間 導電機制可涉及平面聚合物鏈段之堆積(稱為π-堆積)或鏈 * ㈣躍機制,其中激子或電子可穿過空間或其他基質經随 道到達或"跳躍”至靠近其離去鏈之另一鏈。因此,可在固 •4下驅使聚合物鏈有序化之方法可有助於改良導電聚合物 之14能。衆所周知’導電聚合物薄膜之吸光度特性反映在 固態下發生之增強之再堆積。 135320.doc -38 - 200930743 為有效使用共輛聚合物,有利地藉由可自聚合介質移除 有機及離子雜質之方法來製備該等聚合物。舉例而言,雜 質(尤其金屬離子)在此材料中之存在對導電聚合物之性能 可具有嚴重危害性效應。該等效應包括(例如)電荷定位或 捕獲、激子淬熄、電荷遷移率降低、諸如相分離等介面形 態效應、及將聚合物氧化或還原為可能不適合於特定應用 之非典型導電狀態。存在若干種可自共軛聚合物移除雜質 之方法。大多數該等方法可藉由將聚合物溶於常見有機及 © 極性溶劑中之能力來促進。 位置規則性導電嵌段共聚物係藉由本文所述方法來製 備。聚嗟吩及其他類型非嘆吩聚合物之欲段共聚物之聚合 闡述於(例如)Yokozawa 等人,Po/ywer >/〇Μ"«α/,36(2),65 (2004)中。嵌段共聚物為業内人士所熟知。例如,參見 Yang(編輯),The Chemistry of Nanostructured Materials * 第 317-327 頁("Block Copolymers in Nanotechnology")(2003)。 拔段共聚物亦闡述於(例如Copo/ywer·?, Overview awcf CWi/cfl/ ,Noshay 及 McGrath,Academic Press, 1977中。舉例而言,此文章闡述A-B二嵌段共聚物(第5 章)、A-B-A三嵌段共聚物(第6章)、及-(AB)n-多嵌段共聚 物(第7章),其在本發明中可形成基礎嵌段共聚物類型。包 括(例如)聚噻吩在内之其他嵌段共聚物闡述於(例如)以下 文獻中:Francois等人,办《ίΛ. Mei.,69,463-466 (1995); Yang 等人,26,1188-1190,(1993) ; Widawski 等人,iWziwre,369, 387-389 (1994) ; Jenekhe 等人, 135320.doc -39- 200930743 279, 1903-1907 (1998) ; Wang等人,乂如 〜C.,122, 6855-6861 (2000) ; Li 等人, 32,3034-3044 (1999);及 Hempenius等人,j 5〇c·,120, 2798-2804 (1998)。 位置規則性導電嵌段共聚物之衍生物可為經修飾聚合 物,例如聚(3-取代噻吩),其保留原料聚合物之基本主鏈 結構,但在結構上對原料聚合物進行了修飾。衍生物可與 原料聚合物組合在一起以形成相關聚合物家族。衍生物一 ® 般保留諸如導電性等原料聚合物特性。 此外,位置規則性導電嵌段共聚物可包含具有經摻雜或 未經摻雜之共軛結構之導電嵌段,及一或多個其他非導電 嵌段。非導電嵌段可包括各種合成聚合物,包括(例如)縮 合聚合物、加成聚合物、及開環聚合物,例如胺基甲酸 酯、聚醯胺、聚酯、聚醚、乙烯基聚合物、芳香族聚合 物、脂肪族聚合物、雜原子聚合物、矽氧烷、丙烯酸酯、 ❹ 甲基丙烯酸酯、磷腈、矽烷、及諸如此類。可使用無機及 有機聚合物作為非導電部分。 若需要,可將位置規則性導電嵌段共聚物與其他組份摻 σ 該等其他組份包括(例如)無機玻璃及金屬以及其他聚 - «物’例如無機聚合物及有機聚合物以及相同類型(例如 兩種聚噻吩類型)或不同類型(例如聚噻吩與非聚噻吩)之其 他導電聚合物。可使用嵌段共聚物作為促相容劑。 位置規則性聚(3_取代嘍吩)嵌段共聚物 在較佳實施例中’位置規則性導電嵌段共聚物係位置規 135320.doc 200930743 則性聚(3-取代噻吩)嵌段共聚物。具有優良π-共軛、電傳 遞、及固態形態之材料可藉由使用位置特異性化學偶合方 法來製備,該方法產生具有大於95% 2,5,-偶合之具有烷基 取代基之聚(3-取代噻吩)嵌段共聚物。 與具有烧基、芳基、及燒基/芳基取代基之位置隨機性 聚(3-取代噻吩)類似,具有烷基、芳基、及烷基/芳基取代 基之位置規則性聚(3-取代噻吩)嵌段共聚物可溶於常見有 機溶劑中且在藉由沈積方法(例如旋塗、液滴澆注、浸 塗、喷塗、及印刷技術(例如喷墨印刷、膠版印刷、及轉 移塗佈印刷))施加時表現增強之可加工性。因此,與位置 隨機性聚(3-取代噻吩)嵌段共聚物相比,該等材料在大面 積模式中具有更佳之加工性》此外,由於其2,5,-環-環偶 合具有均一性’故其表現出明顯的π-共輛迹象及對應於該 等材料中π-π *吸收之可見光吸收之高消光係數。此吸收決 疋導帶結構之品質’當具有烧基、芳基、或院基/芳基取 代基之位置規則性聚(3-取代噻吩)嵌段共聚物用於有機電 子裝置中時,可使用該結構,且由此決定該裝置之效率及 性能。 聚(3-取代噻吩)嵌段共聚物之位置規則性之另一優點在 於在固態下其可自組裝且形成高度有序化結構。該等結構 傾向於經由π·堆積基元並置噻吩環系統且使得可經由此單 獨聚合物間之鍵結佈置改良鏈間電荷輸送,從而增強與位 置隨機性聚合物相比之導電特性。因此,可瞭解該等材料 之形態學優點。 135320.doc -41 · 200930743 如同使用聚嗟吩之情況,據顯示具有院基、芳基、及烷 基-芳基取代基之各種聚(3·取代料)嵌段共聚物可溶於諸 如甲苯及二甲苯等常見有機溶劑中。該等材料皆具有共同 的與聚喧吩類似之共^-電子帶結構,此使其成為適用於 電子應用中之P-型導體’但由於其溶解性其在很大程度上 比聚噻吩更易&加工&純化。彳將該等材料製成寡聚體 鏈,例如(3-烷基噻吩)n、(3-芳基噻吩)。、或(3_烷基/芳基 噻吩)n,其中η係數值為2-10之重複單元數量,或將其製成 η為1 1-350或更高之聚合物,但對該等材料而言,η最常見 數值為50-200。 取代基效應 由於導電聚合物之電子特性源自聚合物主鏈之共輛帶結 構’因此任何可增加或降低主鏈„_結構内電子密度之因素 皆可直接影響導電聚合物之帶隙及能級。因此,鍵結至主 鏈且含有吸電子取代基之取代基可降低共軛主鏈之電子密 度並降低聚合物之HOMO。鍵結至主鏈且含有電子釋放官 能團之取代基可具有相反效應。取代效應之性質為熟習此 項技術者已知且詳細闡述於關於有機化學之一般文本中 (例如,參見March,J.,Advanced Organic Chemistry,第 二版 ’ John Wiley & Sons,New-York公司,1985及其中所 引用參考文獻)。在兩種情況下,聚合物能級改變之量值 取決於取代基之具體官能團、官能團與共軛主鏈鍵結之長 度或性質、以及聚合物内其他功能特徵之存在。 在聚(3-烷基噻吩)情況下,通常包括可提高溶解度之院 135320.doc •42- 200930743 基取代基,其具有電子釋放效應,從而相對於聚噻吩提高 聚合物之HOMO。舉例而言,已顯示作為聚噻吩之3_取代 基或4·取代基組份之氟取代基自聚噻吩均聚物吸電子從 而降低導電聚合物之H〇M〇。可看出,在3位上之烷氧基 取代基可用於減小位置規則性聚(3_取代噻吩)之帶隙。在 每種該等情況下’對能級之操縱皆係藉由修飾均聚物主鏈 來達成。在許多情況下,期望將特定官能團納入導電聚合 物中以賦予其特殊性質。舉例而言,引入聚(3_己基·噻吩) 之院基取代基以使聚合物可溶於常見有機溶劑中。然而, 對於其中需要低HOMO之應用而言,此電子釋放官能團實 際上賦予與期望電子效應相反之效應。 因此’經由其可平衡及調節導電聚合物之電子、光學及 物理特性以提供可滿足不同性能需求之材料之靈活合成方 法為有機裝置研發提供了實際益處。 藉由本文所揭示方法製備之經改良位置規則性導電嵌段 共聚物可包括不同嵌段鍵段之各種組合,該等嵌段鏈段包 括(例如)未經取代聚噻吩、3-取代聚噻吩及3,4-二取代聚 喧吩。 該等取代基可為根據上文取代基定義所列述之任一基 團。在一實施例中’噻吩係3-取代噻吩,其中取代基為烷 基、烧硫基、烧基甲石夕院基、或炫氧基。取代基可視需要 經其他官能團取代,例如(但不限於)約1至約5個酯、酮、 腈、胺、函素、芳基、雜環基、及雜芳基。烷基、烷硫 基、烧基甲矽烷基或烷氧基中烷基鏈之一或多個碳原子亦 135320.doc •43- 200930743 可由一或多個雜原子替換,例如〇、s、Np基團(其中p係 取代基或氮保護基團)、或其組合。 通常較佳包括可改良聚嗟吩谈段共聚物溶解性之取代 基。該等取代基較佳可包括含有至少約5或6個碳原子之基 . 目例如己基、己氧基、己基硫基、及己基甲石夕烧基。在 某一實施例中,直接鍵結至3位之取代基較佳可為雜原 子,例如硫、矽、氧、或氮原子。雜原子可經其他適宜基 ®取代,例如上文經取代定義中所述者。在嗟吩3位之雜 原子可藉由(例如)以下方式進一步增強聚噻吩嵌段共聚物 之導電.使得喧吩環系統之芳香族電子可發生離域作 用,及/或使得聚合物之封裝可發生改良且微結構可進行 優化,從而改良電荷載流子遷移率。在本發明另一態樣 中,較佳可藉由一或多個(例如丨至1〇個、丨至5個或丨至^ 個)亞甲基(其視需要由一或多個雜原子替換)將芳基、雜芳 基、或雜環基取代基與噻吩環間隔開來(例如聚乙烯或聚 ❹ 乙烯亞胺基,其中該基圏包括約2至約1〇個重複單元)。在 噻吩單體3位之取代基可藉由提供空間體積來影響聚合反 應之位向化學從而改良產物聚噻吩嵌段共聚物之位置規則 性。 - 產物聚噻吩嵌段共聚物上之末端基團(位於聚合物末端 噻吻2·或5-位之基團)可為氫或鹵素。聚噻吩嵌段共聚物之 末端基團亦可為院基或官能化烧基,其可藉由用有機金屬 物質(例如有機-鋅試劑)終止聚合反應來獲得。 藉由本文所述方法製備之聚噻吩嵌段共聚物之重量平均 135320.doc • 44 - 200930743 分子量可為約5,000至約2〇〇 〇〇〇,較佳為約2〇 〇〇〇至約 80,000,且更佳為約4〇,_至約6〇,_,如使用存於四氣 呋喃中之聚苯乙烯標準品藉由Gpc所測定。聚合度分佈性 指數(PDI)可為約丨至約25,或較佳為約丨」至約24,或更 佳為約1.2至約2.2。 在處理後未經任何純化之情況下,藉由本發明方法製備 之聚噻吩嵌段共聚物之位置規則度通常為至少約87%。諸 如用己烷實施索克斯累特提取等簡單純化技術可將位置規 則度改良至大於約94%,較佳大於約95%,更佳大於約 97%,更佳大於約98%,或甚至更佳大於約99〇/〇。 在聚合後可藉由在甲醇中沈澱並隨後對所沈澱聚合物實 施簡單過濾來分離粗聚嗔吩嵌段共聚物。相對於先前技術 之粗產物’粗聚噻吩嵌段共聚物具有優良特性。粗聚噻吩 嵌段共聚物具有較已知製備方法為高之位置規則性,此可 減少為電子應用提供可用材料所需的純化工作量。 較高位置規則性使聚噻吩嵌段共聚物具有較高導電性。 在經#雜時’位置規則性3 _取代聚嗟吩之導電性可為約 1’000西門子/cm、+/-約400西門子/cm。位置隨機性3_取代 聚嘆吩喪段共聚物通常以約5-1〇西門子/cm導電。此外, 未經摻雜位置規則性3-取代聚噻吩嵌段共聚物以約1〇-5至 約10 6西門子/cm(半導體範圍)導電且未經摻雜位置隨機性 聚噻吩嵌段共聚物以約10·9西門子/cm導電。 摻雜 在較佳實施例中,位置規則性導電嵌段共聚物可以氧化 135320.doc 45· 200930743 方式或還原方式經摻雜。添加摻雜劑可導致個別聚合物分 子中共軛π系統之範圍擴展。不需要將共軛兀系統之範圍擴 展至整個分子範圍上。必須充分擴展單個分子中π共軛系 統之範圍以使得在去除溶劑後個別分子中之π共軛部分與 相鄰分子中之π共軛部分的一部分相鄰。在π共軛系統中電 子實質上在整個π共軛鍵範圍内發生離域。該等電子係更 鬆散之鍵結且可用於電傳導中。在施加電場時,電子可沿 個別分子流動且在相鄰分子之π共軛部分重疊之區域中可 自一分子跳躍至相鄰分子上。 亦可藉由在電化學電池中將位置規則性導電嵌段共聚物 限定在電極表面並將其置於氧化電位下而以電化學方式達 成摻雜》 可引入位置規則性導電嵌段共聚物基質中之摻雜劑包括 (例如)埃(Id、溴(Βι*2)、氣化鐵、及各種坤酸鹽或錄鹽。 其他摻雜劑可包括(例如)各種已知鏽鹽、碘鑌鹽、硼酸 鹽、甲苯磺酸鹽、三氟甲磺酸鹽、及磺醯氧基亞胺。位置 規則性導電嵌段共聚物可藉由(例如)以下方法來摻雜:將 聚合物溶於適宜有機溶劑中並將摻雜劑添加至溶液中,隨 後蒸發溶劑。可使用此技術之多種變化形式且該等技術為 熟習此項技術者所熟知。例如,參見美國專利第5,〗98,丨53 號,其係以引用方式併入本文中。 在導電薄膜應用中,電導率可介於約lxl〇-s s/cm至約 104 s/cm之間,但更通常其在約! s/cm至約5〇〇 s/cm範圍 内。在聚噻吩嵌段共聚物係位置規則性聚(3_取代噻吩)嵌 135320.doc -46· 200930743 段共聚物(其中3-取代基為烷基、芳基、或烷基/芳基部分 且在3-取代基之a*.位具有氧取代或在3取代基之α·或卜 位具有雜原子)之情況下’㈣薄膜之期望特徵為在正常 使用條件下其導電性能保留數千小時且在較高溫度及/或 濕度下能滿足it宜裝置應力測試要求。此匕有利於穩定電荷 遷移率之作業範圍且使得可藉由控制摻雜物質之數量及種 類來調節特性並藉由調節一級結構來完善調節該等特性之 能力。 可用於如上所述調節導電特性之氧化劑有許多種。藉由 控制暴露於聚噻吩嵌段共聚物中之摻雜劑之量,可控制所 得導電溥膜。由於其高蒸氣壓力及在有機溶劑中之高溶解 度,可將鹵素施加至氣相中或溶液中。相對於中性狀態之 材料,聚噻吩嵌段共聚物之氧化可大幅度降低材料之溶解 性°然而’可製備各種溶液並將其塗佈至裝置上。 適宜摻雜劑亦可包括(例如)三氯化鐵、三氣化金、五氟 化坤、驗金屬之次氣酸鹽、質子酸(例如苯確酸及其衍生 物、丙酸、及其他有機羧酸及磺酸)、亞硝鑌鹽(例如 NOPF6或NOBF4)、或有機氧化劑(例如四氰醌、二氣二氰 酿)、及高價碘氧化劑(例如亞碘醯苯及二乙醯氧基埃苯)e 聚°塞吩嵌段共聚物亦可藉由添加含有酸或氧化性官能團之 聚合物(例如聚(苯乙烯磺酸))來氧化。 添加摻雜劑所用溶劑並未加以特別限定。可使用一或多 種溶劑化合物或混合物。亦可使用有機溶劑。舉例而言, 可使用_、酯及醇。可使用水。可使用極性溶劑。可使用 135320.doc •47· 200930743 非質子溶劑。可使用分子量低於2〇〇、或低於1〇〇 g/m〇i之 溶劑。 用於添加摻雜劑之適宜溶劑包括(例如)二甲基甲醯胺 (DMF)、二氧戊環、甲基乙基酮、mibk、乙二醇二曱 ㈣丁腈、環戊嗣、環己_、吼咬、氯仿、硝基甲烷、2_ 硝基甲烷、二氣乙烯、四氣乙烯、碳酸丙烯酯、喹啉、環 己嗣、1,4-二氧戊環、二甲亞碾(DMS〇)、硝基苯、氣苯、 及甲基-2-"比嘻咬_。 ® 其他组份 在較佳實施例中,位置規則性導電嵌段共聚物亦可包括 或多種其他適宜組份,例如敏化劑、穩定劑、抑制劑、 鍵轉移劑、共反應單體或寡聚物、表面活性化合物、满滑 齊J潤展劑、分散劑、疏水劑、黏合劑、流動改良劑、稀 釋劑著色劑、染料、顏料、或推雜劑。可藉由以下方式 將該等可選組份添加至聚合物組合物中:將位置規則性導 e €嵌段共聚物溶於適宜有機溶劑中並將該組份添加至溶液 中,隨後蒸發溶劑。在本發明某些實施例中,諸如聚噻吩 嵌段共聚物等位置規則性導電嵌段共聚物明顯可用作實質 上純淨之聚合物或經摻雜聚合物。 薄膜 在較佳實μ例中,位4規則性導電嵌段共聚物可呈薄膜 形式。可溶位置規則性導電嵌段共聚物之高導電性薄膜可 用於多種應用中’包括(例如)多種類型之二極體。在其中 性形式或未經摻雜形式中,可溶位置規則性導電嵌段共聚 135320.doc -48· 200930743 物提供可藉由以下技術施加之能力··旋轉澆注、液滴澆 注絲網印刷、喷墨、及諸如轉移塗佈或輥塗等標準印刷 技術。端視所添加摻雜劑之量,可將導電性自中性或半導 體狀態調節至高導電狀態,從而使材料特異性適合給定應 用。一般而言,可使經摻雜位置規則性導電嵌段共聚物之 導電薄膜在可見光區變透3月。此使得其適合料透明導 . 體。此特性組合使得其適合用於諸如二極體及發光二極體 等電子裝置中》 ° 已顯示在二極體以及發光二極趙及固態照明t位置規則 生導電嵌段共聚物(尤其經摻雜位置規則性導電嵌段共聚 物)適合用作陽性電荷載流子,亦稱為電洞注入層。此端 視其氧化容易程度以及其在捧雜狀態下之穩定性而定。導 電薄膜之性能係藉由評估其高電導率值、良好電子性能、 及高熱穩定性來量測。電導率通常係藉由以下方法來量 測:σ=Ι/(4.53 VW),其中電導率〇係以s/咖來量測,卜電 ❹ 流⑽P),電麼(V),且薄膜厚度(cm)。此數值通常 係藉由標準四點探針法來量測,其中電流流經兩電極之間 電位係Ί由另肖電極來量測。可藉由諸如s腹及輪廊 ' 術等不同方法來測定厚度。 冑用可溶位置規則性導電嵌段共聚物來構建導電層或膜 β在極體中提供若干優勢,例如在裝置製造期間使材料 及組件易於加工。在其中性或未經摻雜形式中,位置規則 性導電嵌段共聚物提供可使用以下技術來施加聚㈣嵌段 共聚物層之能力:旋轉淹注、液滴洗注、絲網印刷、噴 135320.doc -49- 200930743 墨、及諸如轉移塗佈或輥塗等標準印刷技術。該等方法容 許原位溫和加工及對所施加導電材料體積實施精確控制。 一般而言’可使用用於可印刷或經印刷電子裝置之方法。 可使用微影餘刻及奈米银刻方法。 使用位置規則性導電嵌段共聚物可在此應用中提供若干 優勢。該等優勢中最重要者係經由控制薄膜形態、選擇所 用氧化劑及所用氧化劑數量來調節裝置導電性之能力。當 該等材料係以中性或未經摻雜狀態形成時,可藉助氧化之 量謹慎調節導電性。與使用其他導電聚合物相比,使用該 等材料之另一關鍵益處係位置規則性導電嵌段共聚物之經 氧化或"經摻雜"導電狀態之穩定性。該等材料之選擇性溶 解亦容許選擇性應用及去除裝置中該等材料之膜。 此外’導電聚合物闡述於The Encyclopedia of P〇丨ymerMgCl2 + 2 K — Mg + 2 KC1 A variety of activated metals are prepared by this method, including, for example, Ming, Meng, Cu, Zinc, Lock, Hex, Zinc, Iron, Drill, Record, and Indium. In some cases, the reaction is carried out with a catalytic amount of electron carriers such as biphenyl or naphthalene. The activated metal is usually used in situ. Suitable activating metals include, for example, Ming, Meng, copper, zinc, town, about, titanium, iron, cobalt, nickel, indium, or combinations thereof. Preferably, the activated metal is a zinc chromite 2,5-di- sulphate. In a preferred embodiment, the dihalogen-single system is a bis-thiophene. 2,5-dihalo-thiophene can be 2,5-dinan-3-substituted thiophene, unsubstituted 2,5-dihalo-thiophene, or 2,5-didentin-3,4-disubstituted Thiophene bis-thiophene is usually 135320.doc •33- 200930743 is a monofluoro-, di-, _, or di-molybdenum phenanthrene which may be unsubstituted or substituted at the 3 and/or 4 positions. A combination of 2 5-difunctional thiophene, 2 5•dihalo-3-substituted thiophene and 2,5-difunctional _3,4-disubstituted thiophene can also be used. Suitable unsubstituted dihalothiophenes may include, for example, 2,5-difluorophene, 2.5-dithiophene, 2,5-dibromothiophene, 2,5-dithiophene, 2-fluoro-5-gas. Thiophene, 2-fluoro-5-bromothiophene, 2-fluoro-5-iodothiophene, 2-gas-5-fluorothiophene, 2·chloro-5-bromophene, 2-gas-5-fluorene, 2 -bromo-5-fluorophene, 2-bromo-5-phenethiophene, 2-bromo-5-iodothiophene, 2-iodo-5-fluorothiophene, 2-iodo-5-azone, and 2- Iodine-5-bromothiophene. The 2,5-dihaloquinones which are unsubstituted at the 3_ and/or 4' position may be used to prepare, for example, an unsubstituted polythiophene block and one or more substituted polythiophene blocks. Segment copolymer. For example, an unsubstituted polythiophene can be combined with a 3-substituted polythiophene block and/or a 3,4-disubstituted polythiophene block. Alternatively, the '3-substituted polythiophene can be combined with a 3,4-disubstituted polythiophene block. The dentate thiophenes listed above may be substituted at the 3 and/or 4 positions by the following groups: $ 1 to about 5 esters, ketones, nitriles, amines, aryls, heteroaryls or heterocycles as desired. Substituted ((:"(:24)alkyl, (C丨-C24)alkylthio, (Ci-C24)alkylcarboxyalkyl, or (C^C^)alkoxy, and in alkyl One or more carbon atoms of the alkyl chain may optionally be replaced by from about 1 to about 10 0, S or NH groups. Suitable 2,5-difunctional-3-substituted thiophenes may include, for example, 2,5- Difluoro-3-hexylthiophene, 2,5-dioxa-3-hexylthiophene, 2,5-dibromo-3-hexylthiophene, 2.5-diiodo-3-hexylthiophene, 2-fluoro-3-hexyl- 5-oxythiophene, 2-fluoro-3-hexyl-5-bromothiophene, 2-fluoro-3-hexyl-5-iodothiophene, 2-chloro-3-hexyl_5-fluorothia 135320.doc -34- 200930743 Phenyl, 2-chloro-3-hexyl-5-bromothiophene, 2-ox-3-hexyl-5-iodothiophene, 2-bromo-3-hexyl-5-fluoroseptene, 2-oxa-3-hexyl- 5- annole, 2-oxa-3-hexyl-5-iodothiophene, 2-iodo-3-hexyl-5-fluorothiophene, 2-iodo-3-hexyl-5-athiophene, 2-iodo-3 -hexyl-5-bromo"cephene, ethyl 5-(2-5-difluorophenanthr-3-yl)pentanoate, 5-(2-5-dioxaphen-3-yl) Ethyl valerate, ethyl 5-(2-5-di-n-phen-3-yl)pentanoate, ethyl 5-(2-5-diiodothiophen-3-yl)pentanoate, 5- Ethyl (2-fluoro-5-athiophen-3-yl)pentanoate, ethyl 5-(2-fluoro-5-bromothin-3-yl)pentanoate, 5-(2-fluoro-5- Ethyl-3-yl)pentanoic acid, ethyl 5-(2-a-5-methanol-3-phenoxy)pentanoic acid, 5-(2-a-5-mothose-phenophene- 3-ethyl) ethyl valerate, ethyl 5-(2-indol-5-oxythiophen-3-yl)pentanoate, ethyl 5-(2·bromo-5-athiophen-3-yl)pentanoate , 5-(2-bromo-5-acanthen-3-yl)pentanoic acid ethyl ester, 5-(2- moth-5- gas porphin-3-yl) valeric acid ethyl ester, 5-(2- Ethyl iodo-5-bromothiophen-3-yl)pentanoate, and ethyl 5-(2_峨-5-fluorononin-3-yl)pentanoate. Preferably, 2,5-diphthoquinone_ 3_Substituted porphin 2-bromo-3-hexyl-5-mothole or 5-(2-di-5-峨嗟- _3_yl)pentanoic acid ethyl ester. Suitable 2,5-di-i The -3,4-disubstituted thiophene may include, for example, ethyl 5(2 5 -difluoro-3-hexylindol-3-yl)pentanoate, 5-(2-5-digas_3_hexylfluorene). Phenyl-3-yl)ethyl valerate, ethyl 5-(2-5-dibromo-3-hexylthiophen-3-yl)pentanoate, 5-(2-5-dimoth-3-hexyl porphin- 3-yl)ethyl valerate, 5-(2- 1-5-Gas·3_ hexyl sold phen-3-yl) Ethyl valerate, 5-(2-Fluoro-5-indol-3-hexyl porphin-3-yl) Ethyl valerate, 5-(2 -Ethylfluoro-3-hexyl-5-iodothiophen-3-yl)pentanoate, ethyl 5-(2-ethane-3-hexyl-5-fluoroindol-3-yl)pentanoate, 5-(2 - gas _3 · hexyl · 5 · desert phen-3-yl) bismuth citrate, 5-(2- gas-3-hexyl-5-breaking porphin-3-yl) valeric acid ethyl ester, 5 -(2-Bromo-5-gas-3-hexyl phenyl-3-yl) pentanoic acid ethyl ester, 5_(2_ 135320.doc -35- 200930743 -3-hexyl-5-ept-3-yl Ethyl valerate, ethyl 5-(2_hard_3_hexyl_5_ginophen-3-yl)pentanoate, 5-(2-indole-3-hexyl-5-bromo benzene-3- Ethyl valerate, and 5-(2-But-5-fluoro-3-hexyl septin-3-yl)pentanoic acid vinegar. Solvent The solvent used in these methods may be an aprotic organic solvent. One or more solvent compounds or mixtures can be used. Suitable solvents include etheric or polyether solvents. Examples of such solvents include diethyl ether, decyl-tert-butyl ether, tetrahydrofuran (THF), dioxane, diethylene glycol dimethyl ether, triethylene glycol dimethyl _, 1,2-dimethoxy group. Ethylene (DME or ethylene glycol dice), and the like. The solvent is usually a four-milk flavor. Polymerization Catalyst A variety of metal catalysts can be used in the polymerization of such methods. The metal catalyst may comprise an organometallic compound or a transition metal complex. For example, the metal catalyst can be a nickel, platinum, or palladium compound. Preferably, the metal catalyst is a ruthenium catalyst which provides a positionally selective polyporphin block copolymer. A catalyst Ni(II) catalyst for forming a positionally regular polythiophene block copolymer is used in an embodiment method. An effective amount of Ni(II) catalyst is used to effect the reaction using a sufficient amount of catalyst in less than about 5 days. This is usually in the range of about 0.01 to 10 mol% (m〇l%), however, any amount of nickel catalyst may be used, for example, 50 mol%, 100 m〇% or more. The amount of the oscillating monomer present in the end view is usually about 1 mol % nickel (II) catalyst to about 5 mol % nickel (II) catalyst, or preferably about 0.1 mol % recorded (II) Catalyst to about 3 mol% nickel (π) catalyst. Examples of suitable (Π) catalysts include, for example, Ni(PR3)2X2 (wherein R is 135320.doc -36·200930743 (C丨-c20) alkyl, (C6-C20) aryl' and X is a tooth And NiLX2 (wherein L is a suitable nickel (ruthenium) ligand and X is a halogen). Suitable nickel (π) ligands include hydrazine, 2-bis(diphenylphosphino)ethane, 1,3-diphenylphosphinopropane, [2,2-dimethyl-1,3-dioxol Cyclo-4,5-diyl)bis(methylene)]diphenylphosphine, bis(triphenylphosphine), and (2,2'-bipyridine) ligands. Other suitable Ni(II) catalysts include Ni(CN), 2, NiO, Ni(CN)5-3, Ni2Cl8·4, NiF2, NiCl2, NiBr2, Nil2, NiAs, Ni(dmph)2 (where dmph is two曱基乙二肟), BaNiS, [NiX(QAS)]+ (where X is halogen and QAS is As (o-C6H4AsPh2)3), [NiP(CH2CH2CH2AsMe2)3CN]+, [Ni(NCS)6]·4 , KNiX3 (where X is dentate), [Ni(NH3)6]+2, and [Ni(bipy)3]+2 (where bipy is a two-degree bite). Usually, the nickel catalyst also includes 1,2-bis(diphenylphosphino)ethane nickel (Π) vapor (Ni(dppe)Cl2), 1,3-diphenylphosphinopropane nickel (π) vapor. (Ni(dppp)Cl2), I,5·cyclooctadiene bis(triphenyl)nickel, dibromobis(triphenylphosphine)nickel, digas (2,2,-dipyridine)nickel, and four (triphenylphosphine) nickel (ruthenium). The general techniques and methods known to those skilled in the art can be used in the methods herein such as performing various standard procedures for polymerization and separation and purification of products. Properties of Polymer Structures and Conductive Polymers Generally, conductive polymers are organic polymers which, due to their conjugated backbone structure, exhibit high electrical conductivity (relative to the conductivity of conventional polymeric materials) under certain conditions. When the materials are doped, oxidized, or reduced, their performance as a hole or electron conductor is improved. After the low-oxidation (or reduction) of the conductive polymer, in the process commonly referred to as doping, the -electron (or added to the bottom end of the conduction band) is removed from the valence band to generate a radical cation 135320.doc • 37· 200930743 (or polaron). The formation of polarons acts in the separation domain of several monomer unit generating moieties. After further oxidation, another electron can be removed from the individual polymer segments thereby creating two independent polarons. Alternatively, unpaired electrons can be removed to produce a dication (or bipolar). In the applied electric field, both the polaron and the bipolaron are fluid and can move along the polymer chain by the delocalization of double bonds and single bonds. This change in oxidation state results in the formation of a new energy state called a bipolaron. Some of the residual electrons in the valence band are susceptible to these levels, allowing the polymer to act as a conductor. The degree of conjugation of this conjugated structure depends on the extent to which the polymer chain forms a planar configuration in the solid state. This is because the ring-ring common vehicle depends on the π_track overlap. If a particular ring is twisted off the plane, no overlap can occur and the common band structure can be interrupted. Some minor distortions are harmless because, for example, the degree of overlap between the porphin rings varies with the cosine of the dihedral angle between the rings. The properties of the conjugated polymer as an organic conductor may also depend on the morphology of the polymer in its solid state. Electronic properties may depend on the electrical connectivity between the polymer chains and the charge transport between the chains. The charge transport path can be along the polymer chain or between adjacent chains. Since the charged moiety has a dependency on the number of double bonds between the rings (ring planarity index), the planar main chain configuration promotes transport along the chain. This interchain electrical conduction mechanism may involve a stacking of planar polymer segments (referred to as π-stacking) or a chain* (four) hopping mechanism in which excitons or electrons may pass through space or other matrix to arrive or "jump" Close to the other chain of the leaving chain. Therefore, the method of ordering the polymer chain under the solid 4 can help to improve the 14 energy of the conductive polymer. It is known that the absorbance characteristics of the conductive polymer film Reflecting the enhanced re-stacking that occurs in the solid state. 135320.doc -38 - 200930743 In order to effectively use a co-polymer, it is advantageous to prepare the polymer by removing organic and ionic impurities from the polymerization medium. In particular, the presence of impurities (especially metal ions) in this material can have severely detrimental effects on the properties of the conductive polymer, including, for example, charge localization or trapping, exciton quenching, charge mobility reduction, Interface morphological effects such as phase separation, and oxidation or reduction of the polymer to atypical conductive states that may not be suitable for a particular application. There are several types of self-conjugated polymers that remove impurities. Most of these methods can be facilitated by the ability of the polymer to be dissolved in common organic and polar solvents. The positionally oriented conductive block copolymers are prepared by the methods described herein. Polymerization of other types of non-excimer polymers is described, for example, in Yokozawa et al., Po/ywer >/〇Μ" «α/, 36(2), 65 (2004). The materials are well known to those skilled in the art. For example, see Yang (Editor), The Chemistry of Nanostructured Materials * pp. 317-327 ("Block Copolymers in Nanotechnology") (2003). The copolymer is also described (for example, Copo). /ywer·?, Overview awcf CWi/cfl/, Noshay and McGrath, Academic Press, 1977. For example, this article describes AB diblock copolymers (Chapter 5), ABA triblock copolymers (6th) And (-) AB-n-multiblock copolymers (Chapter 7), which form base block copolymer types in the present invention. Other block copolymers including, for example, polythiophene In (for example) the following documents: Francois et al, "ίΛ. Mei., 69, 463-466 (1995); Yang et al, 26, 1188-1190, (1993); Widawski et al, iWziwre, 369, 387-389 (1994); Jenekhe et al, 135320. Doc-39-200930743 279, 1903-1907 (1998); Wang et al., for example, ~C., 122, 6855-6861 (2000); Li et al., 32, 3034-3044 (1999); and Hempenius et al. , j 5〇c·, 120, 2798-2804 (1998). The derivative of the positionally regular conductive block copolymer may be a modified polymer such as poly(3-substituted thiophene) which retains the basic backbone structure of the base polymer but structurally modifies the base polymer. The derivative can be combined with the base polymer to form a family of related polymers. Derivatives ® retain the properties of the base polymer such as conductivity. Further, the positionally regular conductive block copolymer may comprise a conductive block having a conjugated structure that is doped or undoped, and one or more other non-conductive blocks. Non-conductive blocks can include various synthetic polymers including, for example, condensation polymers, addition polymers, and ring-opening polymers such as urethanes, polyamines, polyesters, polyethers, vinyl polymerizations. , aromatic polymers, aliphatic polymers, heteroatom polymers, decane, acrylate, methacrylate, phosphazene, decane, and the like. Inorganic and organic polymers can be used as the non-conductive portion. If desired, the positional regular conductive block copolymer can be blended with other components. These other components include, for example, inorganic glass and metals and other poly-[objects] such as inorganic polymers and organic polymers and the same type. (for example, two polythiophene types) or other conductive polymers of different types (for example, polythiophene and non-polythiophene). Block copolymers can be used as compatibilizers. Positionally regular poly(3-substituted porphin) block copolymers in a preferred embodiment 'position regular conductive block copolymer system position gauge 135320.doc 200930743 then poly(3-substituted thiophene) block copolymer . Materials having excellent π-conjugated, electrotransport, and solid state forms can be prepared by using position-specific chemical coupling methods that produce poly(s) having greater than 95% 2,5,-coupled alkyl substituents ( 3-substituted thiophene) block copolymer. Similar to the positional random poly(3-substituted thiophene) having a decyl group, an aryl group, and a decyl/aryl substituent, a positional regular poly(alkyl) group having an alkyl group, an aryl group, and an alkyl/aryl group 3-substituted thiophene) block copolymers are soluble in common organic solvents and by deposition methods (eg, spin coating, drop casting, dip coating, spray coating, and printing techniques (eg, inkjet printing, offset printing, and Transfer coating printing)) Enhanced workability when applied. Therefore, these materials have better processability in the large-area mode compared to the positionally random poly(3-substituted thiophene) block copolymers. In addition, due to their 2,5,-ring-ring coupling, uniformity 'Therefore it shows a clear π-common sign and a high extinction coefficient corresponding to the absorption of visible light by π-π* absorption in these materials. The quality of the absorption band structure is 'when the positional poly(3-substituted thiophene) block copolymer having a burnt group, an aryl group, or a aryl/aryl substituent is used in an organic electronic device, This structure is used and thus determines the efficiency and performance of the device. Another advantage of the positional regularity of poly(3-substituted thiophene) block copolymers is that they are self-assemblable and form highly ordered structures in the solid state. These structures tend to juxtapose the thiophene ring system via a π-stacking unit and allow for improved interchain charge transport via the bonding arrangement between the individual polymers, thereby enhancing the conductive properties compared to the positionally random polymer. Therefore, the morphological advantages of these materials can be understood. 135320.doc -41 · 200930743 As in the case of polybenzazole, it is shown that various poly(3.substituent) block copolymers having a pendant group, an aryl group, and an alkyl-aryl substituent are soluble in, for example, toluene. And common organic solvents such as xylene. These materials all share a common electron-band structure similar to polyphene, making it a P-type conductor suitable for use in electronic applications' but due to its solubility it is much easier than polythiophene. & Processing & Purification. These materials are made into oligomeric chains such as (3-alkylthiophene) n, (3-arylthiophene). Or (3_alkyl/arylthiophene)n, wherein the n-coefficient value is a repeating unit number of 2-10, or it is made into a polymer having η of 1 1-350 or higher, but such materials In terms of η, the most common value is η 50-200. Substituent effect Since the electronic properties of the conductive polymer are derived from the common band structure of the polymer backbone, any factor that increases or decreases the electron density in the main chain can directly affect the band gap and energy of the conductive polymer. Therefore, a substituent bonded to the main chain and containing an electron-withdrawing substituent can lower the electron density of the conjugated backbone and lower the HOMO of the polymer. The substituent bonded to the main chain and containing the electron-releasing functional group can have the opposite The nature of the substitution effect is known to those skilled in the art and is described in detail in the general text on organic chemistry (see, for example, March, J., Advanced Organic Chemistry, Second Edition 'John Wiley & Sons, New- York, 1985, and references cited therein. In both cases, the magnitude of the polymer energy level depends on the specific functional group of the substituent, the length or nature of the functional group to the conjugated backbone linkage, and the polymer. The presence of other functional features. In the case of poly(3-alkylthiophene), it usually includes a hospital that can improve solubility. 135320.doc •42- 200930743 base substituent , which has an electron-releasing effect, thereby increasing the HOMO of the polymer relative to the polythiophene. For example, it has been shown that the fluorine substituent as a 3-substituent or a 4-substituent component of the polythiophene is adsorbed from the polythiophene homopolymer. The electrons thereby reduce the H〇M〇 of the conductive polymer. It can be seen that the alkoxy substituent at the 3-position can be used to reduce the band gap of the positionally regular poly(3-substituted thiophene). In each of these cases The manipulation of the 'energy level' is achieved by modifying the homopolymer backbone. In many cases, it is desirable to incorporate specific functional groups into the conductive polymer to impart specific properties. For example, the introduction of poly(3-hexyl) • The thiophene-based substituents to render the polymer soluble in common organic solvents. However, for applications where low HOMO is required, this electron-releasing functional group actually imparts an opposite effect to the desired electronic effect. The flexible synthesis method that balances and adjusts the electronic, optical, and physical properties of conductive polymers to provide materials that meet different performance requirements provides practical benefits for organic device development. The modified positionally regular conductive block copolymers disclosed in the disclosed methods can include various combinations of different block linkages including, for example, unsubstituted polythiophenes, 3-substituted polythiophenes, and 3,4 a disubstituted polyporphin. The substituents may be any of the groups listed in the definition of the substituents above. In one embodiment, the 'thiophene 3-substituted thiophene, wherein the substituent is an alkyl group, sulfur-burning a substituent, a methoxy group, or a methoxy group. The substituent may be substituted with other functional groups, such as, but not limited to, from about 1 to about 5 esters, ketones, nitriles, amines, hydroxyls, aryl groups, a heterocyclic group, and a heteroaryl group. One or more carbon atoms of an alkyl chain in an alkyl group, an alkylthio group, a pyrenylalkyl group or an alkoxy group are also 135,320.doc •43- 200930743 may be one or more Atomic substitutions, such as deuterium, s, Np groups (wherein a p-substituent or a nitrogen protecting group), or a combination thereof. Substituents which improve the solubility of the polybenzazole copolymer are generally preferred. Preferably, the substituents include those having at least about 5 or 6 carbon atoms. For example, hexyl, hexyloxy, hexylthio, and hexylmethylcarbazide. In one embodiment, the substituent directly bonded to the 3 position may preferably be a hetero atom such as sulfur, helium, oxygen, or a nitrogen atom. The heteroatoms can be substituted with other suitable bases, such as those described above in the definition of substitution. The hetero atom at the 3-position of the porphin can further enhance the conductivity of the polythiophene block copolymer by, for example, the following, such that the aromatic electrons of the porphin ring system can delocalize and/or cause the encapsulation of the polymer. Improvements can be made and the microstructure can be optimized to improve charge carrier mobility. In another aspect of the invention, one or more (e.g., 丨 to 〇, 丨 to 5 or 丨 to ^) methylene groups (which are optionally composed of one or more heteroatoms) may be used. Alternatively, the aryl, heteroaryl, or heterocyclyl substituent is separated from the thiophene ring (e.g., polyethylene or polyethylenimine, wherein the oxime comprises from about 2 to about 1 repeat units). The substituent at the 3-position of the thiophene monomer can improve the positional regularity of the product polythiophene block copolymer by providing a space volume to influence the chemical orientation of the polymerization reaction. - The terminal group on the product polythiophene block copolymer (the group at the 2 or 5-position of the thiophene at the end of the polymer) may be hydrogen or halogen. The terminal group of the polythiophene block copolymer may also be a pendant or functionalized alkyl group which can be obtained by terminating the polymerization reaction with an organometallic substance such as an organic-zinc reagent. The polythiophene block copolymer prepared by the methods described herein has an average weight of 135,320.doc • 44 - 200930743 and may have a molecular weight of from about 5,000 to about 2, preferably from about 2 to about 80,000. More preferably, it is about 4 Å, _ to about 6 Å, _, as determined by Gpc using a polystyrene standard stored in tetra-furan. The degree of polymerization distribution index (PDI) may range from about 丨 to about 25, or preferably from about 丨 to about 24, or more preferably from about 1.2 to about 2.2. The polythiophene block copolymer prepared by the process of the present invention typically has a positional regularity of at least about 87% without any purification after treatment. Simple purification techniques such as performing Soxhlet extraction with hexane can improve the positionality to greater than about 94%, preferably greater than about 95%, more preferably greater than about 97%, still more preferably greater than about 98%, or even More preferably greater than about 99 〇 / 〇. The crude polyphenanthrene block copolymer can be isolated after polymerization by precipitation in methanol and subsequent simple filtration of the precipitated polymer. The crude polythiophene block copolymer has excellent properties relative to the prior art crude product. The crude polythiophene block copolymer has a higher positional regularity than known preparation methods, which reduces the amount of purification work required to provide usable materials for electronic applications. The higher position regularity gives the polythiophene block copolymer a higher conductivity. The conductivity of the regular 3 _ substituted poly porphin at the time of the "hetero" can be about 1'000 Siemens/cm, +/- about 400 Siemens/cm. Positional randomness 3_substitution The polystimulus copolymer is typically conductive at about 5-1 〇 Siemens/cm. In addition, the undoped positional 3-substituted polythiophene block copolymer is a conductive polythiophene block copolymer which is electrically conductive and undoped at a position of from about 1 〇 to about 5 6 Siemens/cm (semiconductor range). Conductive at approximately 10.9 Siemens/cm. Doping In a preferred embodiment, the positionally oriented conductive block copolymer can be doped by oxidation in the manner of 135,320.doc 45.200930743 or in a reducing manner. The addition of dopants can result in a range extension of the conjugated π system in individual polymer molecules. There is no need to extend the range of the conjugated enthalpy system over the entire molecular range. The range of the π-conjugated system in a single molecule must be sufficiently extended such that the π-conjugated moiety in the individual molecule is adjacent to a portion of the π-conjugated moiety in the adjacent molecule after removal of the solvent. In the π-conjugated system, electrons are delocalized substantially within the entire π conjugate bond. These electrons are more loosely bonded and can be used in electrical conduction. When an electric field is applied, electrons can flow along individual molecules and can jump from one molecule to an adjacent molecule in a region where π conjugated portions of adjacent molecules overlap. It is also possible to electrochemically achieve doping by limiting the positionally-regular conductive block copolymer to the surface of the electrode in an electrochemical cell and placing it at an oxidation potential. A positionally-regular conductive block copolymer matrix can be introduced. The dopants include, for example, angstroms (Id, bromo(2), iron hydride, and various kundamates or salt salts. Other dopants may include, for example, various known rust salts, iodonium a salt, a borate, a toluenesulfonate, a triflate, and a sulfoximine. The positionally regular conductive block copolymer can be doped by, for example, the following method: dissolving the polymer Suitable organic solvents and dopants are added to the solution, followed by evaporation of the solvent. A variety of variations of this technique can be used and are well known to those skilled in the art. For example, see U.S. Patent No. 5, 〖98,丨53, which is incorporated herein by reference. In conductive film applications, the conductivity can be between about lxl 〇-ss/cm to about 104 s/cm, but more typically it is about s/s/ From cm to about 5 〇〇s/cm. In the polythiophene block copolymer system Regular poly(3_substituted thiophene) embedded 135320.doc -46· 200930743 segment copolymer (wherein the 3-substituent is an alkyl, aryl, or alkyl/aryl moiety and a* in the 3-substituent. Where the position has an oxygen substitution or in the case where the α or the position of the 3 substituent has a hetero atom), the desired characteristic of the (4) film is that its conductivity retains thousands of hours under normal use conditions and at higher temperatures and/or humidity. The following can meet the requirements of the device stress test. This is beneficial to stabilize the range of charge mobility and allows the characteristics to be adjusted by controlling the amount and type of dopants and to adjust the characteristics by adjusting the primary structure. There are many types of oxidizing agents that can be used to adjust the conductive properties as described above. By controlling the amount of dopants exposed to the polythiophene block copolymer, the resulting conductive ruthenium film can be controlled due to its high vapor pressure and in organic High solubility in the solvent, the halogen can be applied to the gas phase or in the solution. Compared with the material of the neutral state, the oxidation of the polythiophene block copolymer can greatly reduce the solubility of the material. The solution is applied to the device. Suitable dopants may also include, for example, ferric chloride, tri-gas gold, pentafluorination, metal hypochlorites, proton acids (eg, benzoic acid). And its derivatives, propionic acid, and other organic carboxylic acids and sulfonic acids), nitrosonium salts (such as NOPF6 or NOBF4), or organic oxidants (such as tetracyanate, di-cyanide), and high-valent iodine oxidants ( For example, iodonium benzene and diethyl ethoxy phenoxy epoxide block copolymers can also be oxidized by adding a polymer containing an acid or an oxidizing functional group such as poly(styrenesulfonic acid). The solvent to be used for the addition of the dopant is not particularly limited. One or more solvent compounds or mixtures may be used. An organic solvent may also be used. For example, _, an ester, and an alcohol may be used. Water may be used. A polar solvent can be used. Can be used 135320.doc •47· 200930743 aprotic solvent. A solvent having a molecular weight of less than 2 Å or less than 1 〇〇 g/m 〇 i can be used. Suitable solvents for the addition of dopants include, for example, dimethylformamide (DMF), dioxolane, methyl ethyl ketone, mibk, ethylene glycol diterpene (tetra) butyronitrile, cyclopentamidine, rings. _, bite, chloroform, nitromethane, 2-nitromethane, diethylene, tetraethylene, propylene carbonate, quinoline, cyclohexane, 1,4-dioxolane, dimethyl argan DMS 〇), nitrobenzene, gas benzene, and methyl-2-" than bite _. ® Other Components In a preferred embodiment, the positionally-regular conductive block copolymer may also comprise or comprise a plurality of other suitable components, such as sensitizers, stabilizers, inhibitors, bond transfer agents, co-reacting monomers or A polymer, a surface active compound, a smoothing agent, a dispersing agent, a hydrophobic agent, a binder, a flow improver, a diluent colorant, a dye, a pigment, or a dopant. The optional components can be added to the polymer composition by dissolving the positionally regular e-block copolymer in a suitable organic solvent and adding the component to the solution, followed by evaporation of the solvent. . In certain embodiments of the invention, positionally oriented conductive block copolymers such as polythiophene block copolymers are readily useful as substantially pure polymers or doped polymers. Film In the preferred embodiment, the bit 4 regular conductive block copolymer may be in the form of a film. Highly conductive films of soluble positionally regular conductive block copolymers can be used in a variety of applications, including, for example, multiple types of diodes. In its neutral or undoped form, the soluble position regular conductive block copolymer 135320.doc -48· 200930743 provides the ability to be applied by the following techniques: spin casting, droplet casting screen printing, Inkjet, and standard printing techniques such as transfer coating or roll coating. Depending on the amount of dopant added, the conductivity can be adjusted from a neutral or semiconducting state to a highly conductive state, making the material specific for a given application. In general, the conductive film of the doped-site regular conductive block copolymer can be made to pass through the visible region for 3 months. This makes it suitable for transparent conductors. This combination of features makes it suitable for use in electronic devices such as diodes and light-emitting diodes. ° It has been shown in diodes and in luminescent diodes and solid-state illumination t-position regular conductive block copolymers (especially blended The hetero-position regular conductive block copolymer) is suitable for use as a positive charge carrier, also known as a hole injection layer. This depends on how easily it is oxidized and its stability in the mixed state. The properties of the conductive film were measured by evaluating its high conductivity value, good electronic properties, and high thermal stability. Conductivity is usually measured by the following method: σ = Ι / (4.53 VW), where the conductivity 〇 is measured by s / coffee, ❹ ❹ flow (10) P), electricity (V), and film thickness (cm). This value is usually measured by a standard four-point probe method in which a current flows between the two electrodes and is measured by another electrode. The thickness can be measured by different methods such as s belly and rim. The use of a soluble positional regular conductive block copolymer to construct a conductive layer or film provides several advantages in the polar body, such as ease of processing of materials and components during device fabrication. In a neutral or undoped form, the positionally oriented conductive block copolymer provides the ability to apply a poly(tetra) block copolymer layer using the following techniques: spin flooding, droplet washing, screen printing, spraying 135320.doc -49- 200930743 Ink, and standard printing techniques such as transfer coating or roll coating. These methods allow for in-situ gentle processing and precise control of the volume of conductive material applied. In general, methods for printable or printed electronic devices can be used. The lithography and nano silver engraving methods can be used. The use of positionally regular conductive block copolymers provides several advantages in this application. The most important of these advantages is the ability to adjust the conductivity of the device by controlling the morphology of the film, selecting the oxidant used, and the amount of oxidant used. When the materials are formed in a neutral or undoped state, the conductivity can be carefully adjusted by the amount of oxidation. Another key benefit of using such materials is the oxidation or "doped" conductivity stability of the positionally oriented conductive block copolymer compared to the use of other conductive polymers. The selective dissolution of such materials also permits the selective application and removal of films of such materials in the device. In addition, conductive polymers are described in The Encyclopedia of P〇丨ymer
Science and Engineering,Wiley,1990,第 298-300 頁中,其包 括(例如)聚乙炔、聚(對伸苯基)、聚(對苯硫醚)、聚吡咯、 及聚嚷吩。此參考文獻亦闡述聚合物之摻合及共聚,包括 嵌段共聚物形成。 藉由本文所述方法製備之高純度位置規則性導電嵌段共 聚物可用於形成薄膜。可藉由熟習此項技術者已知之標準 方法使用溶於溶劑中之位置規則性導電嵌段共聚物溶液來 形成薄臈,該等方法例如旋塗、澆注、浸塗、喷墨塗佈、 棒塗、輥塗、氣刀塗佈、幕塗、擠出式槽模塗佈、及諸如 此類。例如’關於製備薄膜及有機場效應電晶體之方法可 參見美國專利第5,892,244號、第6,337,102號、第7,049,631 135320.doc -50· 200930743 號、第 7,037,767號、第 7,025,277號、第 7,053,401 號、及第 7,〇57,339號,其係以引用方式併入本文中。 在一實施例中,可藉由(例如)以下方法來形成位置規則 性導電嵌·段共聚物薄膜:形成位置規則性導電嵌段共聚物 前體之蘭幕爾-布羅吉(Langmuir-Blodgett)薄膜,且將位置 規則性導電嵌段共聚物前鱧轉化為位置規則性導電嵌段共 聚物。類似地,可藉由(例如)以下方法來形成薄膜:氣相 沈積位置規則性導電嵌段共聚物前體,且將位置規則性導 電板段共聚物前體轉化為位置規則性導電嵌段共聚物。 在一實施例中,可藉由(例如)旋塗來形成位置規則性導 電嵌段共聚物薄膜。將位置規則性導電嵌段共聚物溶液置 於基材上,使其以高速旋轉以藉由離心力使流體鋪開。當 流體旋轉出基材邊緣時仍繼續旋轉基材,直至達成期望薄 膜厚度。所施加溶劑通常為揮發性,且同時蒸發。此外, 旋轉角速度愈高,所產生薄膜愈薄。薄膜厚度亦取決於溶 液濃度及溶劑。 在一實施例中,可藉由(例如)澆注來形成位置規則性導 電嵌段共聚物薄膜。將熔融位置規則性導電嵌段共聚物引 入模型中,使得可在模型中固化、冷卻,並拆卸該㈣以 提供薄膜。 在-實施例中,可藉由(例如)浸塗來形成位置規則 電嵌段共聚物薄臈,其中將基材浸潰於含有位置規 電喪段共聚物之罐中,自罐中移出基材並使其㈣。 經塗佈基材風乾或烤乾。 135320.doc •51 · 200930743 在一實施例中’可藉由(例如)喷墨塗佈來形成位置規則 性導電嵌段共聚物薄膜,其中將位置規則性導電嵌段共聚 物溶液自壓電噴墨機喷射至基材上。可將經塗佈基材風乾 或烤乾。 薄臈可具有多種厚度。典型薄膜係在約1 μιη至約丨mm 範圍内。薄膜可包括著色劑、增塑劑或摻雜劑。尤其在聚 合物基質中包括掺雜劑時,位置規則性導電嵌段共聚物可 導電。 應用 位置規則性導電嵌段共聚物之應用並未特別加以限制且 可包括光學、電子、能量、生物材料、半導體、電致發 光、光電伏打、LED、OLED、PLED、感測器、電晶體、 場效應電晶體、電池、平面屏幕顯示器、有機照明、經印 刷電子裝置、非線性光學材料、可調光窗口、RFID標記、 燃料電池、三極體、整流器、及其他應用。例如,參見 Kraft等人,如五乂,37, 402_428 (1998)。亦 可參見 Shinar,Orgam.c Zz.抑n丑Springer_ Verlag,(2004)。可製造電洞注入層。可製造多層結構且製 造薄膜裝置。可印刷薄膜。可實施圖案化。可在消費產品 上實施印刷。可製造小型電晶體。在多種應用中,調配組 合物以提供良好溶液加工及薄膜形成。可製備與包括導電 聚合物在内之其他聚合物之摻合物。可在奈米級製造中開 發嵌段共聚物之奈米線形態。下文係對位置規則性導電嵌 段共聚物之實例性應用之簡短說明。 135320.doc -52- 200930743 有機發光二極禮 在較佳實施例中,藉由本文所述方法製備之位置規則性 導電故段共聚物可用於(例如)有機發光二極體中。舉例而 言’位置規則性聚噻吩可用於有機發光二極體(OLED)製 造中。有機發光二極體(OLED)係用於電子應用十或用作 (例如)液晶顯示器之背光。一般有機發光二極體係使用多 層結構來製造。發射層通常夾在一或多個電子輸送層及/ 或電洞輸送層之間。藉由施加電壓可使作為電荷載流子之 電子及電洞向發射層移動’並在此處重新組合以激發含於 發射層中之發光團單元且使其發光。位置規則性導電嵌段 共聚物可用於一或多個電荷輸送層及/或發射層中,端視 其電子及/或光學特性而定。此外,若位置規則性導電嵌 段共聚物自身表現電致發光特性或包含電致發光基團或化 合物,則其在發射層中之應用尤其有利。在此情況下,可 藉由將電荷載流子僅注入導電聚合物中來達成發光。對用 於OLED中之適宜單體、寡聚及聚合化合物或材料之選 擇、表徵及加工一般為熟習此項技術者所知(例如參見And lei, pp. This reference also describes the blending and copolymerization of polymers, including the formation of block copolymers. High purity positionally regular conductive block copolymers prepared by the methods described herein can be used to form films. The crucible can be formed by using a conventionally-regulated conductive block copolymer solution dissolved in a solvent by standard methods known to those skilled in the art, such as spin coating, casting, dip coating, ink jet coating, and rods. Coating, roll coating, air knife coating, curtain coating, extrusion slot die coating, and the like. For example, 'for a method of preparing a film and an organic field-effect transistor, see U.S. Patent Nos. 5,892,244, 6,337,102, 7,049,631, 135,320, doc-50, 2009, 030, 743, 767, 767, 7,025, 277, 7, 053, 401, And 7, pp. 57,339, which is incorporated herein by reference. In one embodiment, the positionally regular conductive inlaid segment copolymer film can be formed by, for example, the following method: Langmuir-Blodgett forming a positionally regular conductive block copolymer precursor a film, and the positional regular conductive block copolymer front enthalpy is converted into a positionally regular conductive block copolymer. Similarly, a thin film can be formed by, for example, the following method: vapor deposition of a regular conductive block copolymer precursor, and conversion of a positionally regular conductive plate segment copolymer precursor to a positionally regular conductive block copolymer Things. In one embodiment, the positionally regular conductive block copolymer film can be formed by, for example, spin coating. The positionally regular conductive block copolymer solution is placed on the substrate and rotated at a high speed to spread the fluid by centrifugal force. The substrate continues to rotate as the fluid rotates out of the edge of the substrate until the desired film thickness is achieved. The solvent applied is generally volatile and simultaneously evaporates. In addition, the higher the angular velocity of rotation, the thinner the resulting film. The film thickness also depends on the solution concentration and solvent. In one embodiment, the positionally oriented conductive block copolymer film can be formed by, for example, casting. The molten position regular conductive block copolymer is introduced into the mold so that it can be solidified, cooled, and disassembled in the mold to provide a film. In an embodiment, the positional regular block copolymer thinner may be formed by, for example, dip coating, wherein the substrate is impregnated into a can containing a positionally regulated segment, and the substrate is removed from the can. Material and make it (four). The coated substrate is air dried or baked. 135320.doc • 51 · 200930743 In one embodiment, a positionally regular conductive block copolymer film can be formed by, for example, inkjet coating, wherein a positionally regular conductive block copolymer solution is self-piezoelectrically sprayed The ink is sprayed onto the substrate. The coated substrate can be air dried or baked. The tweezers can have a variety of thicknesses. Typical film systems range from about 1 μηη to about 丨mm. The film can include a colorant, a plasticizer, or a dopant. The positionally regular conductive block copolymer can be electrically conductive, especially when a dopant is included in the polymer matrix. The application of the positionally-regular conductive block copolymer is not particularly limited and may include optical, electronic, energy, biomaterials, semiconductors, electroluminescence, photovoltaic, LED, OLED, PLED, sensor, transistor , field effect transistors, batteries, flat panel displays, organic lighting, printed electronics, nonlinear optical materials, dimmable windows, RFID tags, fuel cells, triodes, rectifiers, and other applications. See, for example, Kraft et al., et al., 37, 402_428 (1998). See also Shinar, Orgam.c Zz. 丑 Spring Springer_ Verlag, (2004). A hole injection layer can be fabricated. A multilayer structure can be fabricated and a thin film device can be fabricated. Printable film. Patterning can be performed. Printing can be performed on consumer products. Small transistors can be fabricated. In a variety of applications, the compositions are formulated to provide good solution processing and film formation. Blends with other polymers including conductive polymers can be prepared. The nanowire morphology of the block copolymer can be developed in nanoscale manufacturing. The following is a brief description of an exemplary application of a positionally oriented electrically conductive block copolymer. 135320.doc -52- 200930743 Organic Light Emitting Diode In a preferred embodiment, a positionally oriented conductive segment copolymer prepared by the methods described herein can be used, for example, in an organic light emitting diode. For example, the positional regular polythiophene can be used in the fabrication of organic light emitting diodes (OLEDs). Organic light-emitting diodes (OLEDs) are used in electronic applications or as backlights for, for example, liquid crystal displays. Generally, organic light-emitting diode systems are fabricated using a multi-layer structure. The emissive layer is typically sandwiched between one or more electron transport layers and/or a hole transport layer. Electrons and holes as charge carriers are moved toward the emissive layer by application of a voltage and recombined therein to excite and illuminate the luminophore units contained in the emissive layer. The positionally oriented conductive block copolymer can be used in one or more charge transport layers and/or emissive layers depending on its electronic and/or optical properties. Furthermore, if the positionally regular conductive block copolymer itself exhibits electroluminescent properties or contains electroluminescent groups or compounds, its use in the emissive layer is particularly advantageous. In this case, luminescence can be achieved by injecting charge carriers only into the conductive polymer. The selection, characterization and processing of suitable monomers, oligomeric and polymeric compounds or materials for use in OLEDs are generally known to those skilled in the art (see, for example,
Meerholz,办31-34 (2000)及 Alcala,乂 却ρ/. 88,7124-7128 (2000)及其中所引用 文獻)。 在另一應用中,位置規則性導電嵌段共聚物(尤其表現 光致發光特性之彼等)可用作(例如)顯示器裝置之光源材 料’例如歐洲專利申請公開案第ΕΡ 〇 889 3 5〇 a丨號中所述 或由 C. Weder等人 ’ Science,279, 835-837 (1998)所述。 135320.doc -53- 200930743 場效應電晶髖 在較佳實施例中,位置規則性導電嵌段共聚物亦可用於 (例如)場效應電晶體(FET)中。在場效應電晶體中,可將有 機半導體材料佈置為位於閘極電介質、溝道與源電極之間 之薄膜(例如參見美國專利第5 892,244號、PCT專利申請公 開案第WO 00/79617號及美國專利第5 998 8〇4號)。由於該 等材料具有許多優勢(例如以低成本製作大型表面),故該 等場效應電晶體之較佳應用為(例如)積體電路、薄膜電晶 體(TFT)顯示器、及安全性應用。 在安全性應用中’場效應電晶體及具有半導體材料之其 他裝置(例如電晶體或二極體)可用於射頻識別(RFID)標記 或安全標記中以驗證並防止僞造有價憑證。有價憑證可包 括(例如)紙幣、信用卡、身份(ID)證、護照、執照、或具 有經濟價值之任何其他產品(例如郵票、車票、股份、債 券、支票、及諸如此類)。 先伏打電地 在較佳實施例中,位置規則性導電嵌段共聚物亦可用於 (例如)光伏打電池中。光伏打電池係將電磁輻射轉化為電 能之電化學裝置。儘管未受理論限制,可經由光子吸收後 所發生電荷分離事件來達成電磁輻射至電能之轉化。此導 致在與η-型半導體直接接觸之p_型半導體中形成可稱為激 子之激發態。通常半導體結構域夾在兩電極間之一或多個 活性層之間,其中至少一個電極充分透明以容許光子通 過。光伏打電池可用於充電電池中或用於運行電子裝置。 135320.doc •54- 200930743 其可為任何由配電網供電驅動的電應用提供諸多優點,無 論是作為電池之替代還是作為恢復裝置供電電池之電荷2 裝置。最後,其亦可用於補充配電網所提供之電力或替代 配電網所提供之電力。 光伏打電池通常包括至少四個組件,其中兩個為電極。 個組件為透明第一電極,例如塗佈於塑料或玻璃上之氧 化銦錫,其用作電荷載流子。此組件通常為負極,且使得 環境光可進入裝置中。第二電極可由金屬製成,例如鈣或 鋁。在某些情況下,可將此金屬塗佈至支撐表面上,例如 塑料、玻璃層、藍寶石、氣化㉖、石英、或金剛石。此第 二電極亦可運載電流。在該等電極之間存在離散層或p與 η-型半導體之混合物,即第三及第四組件。p型材料可稱 為主要捕光組件或層。此材料吸收具有特定能量之光子且 產生促使電子進入激發能態之狀態,從而在基態能級中留 下正電荷或"電洞"。此稱為激子形成。激子擴散至ρ型與 ❾ η-型材料之間之接面中,從而產生電荷分離或激子分離。 分別經由η-型及ρ-型材料將電子及"電洞”電荷導入電極 中。此導致電流自電池流出》除本文所述位置規則性導電 嵌段共聚物外,Ρ-型半導體亦可包含共軛聚合物,其包括 (例如)材料之混合物或摻合物’包括使用聚_伸苯基伸乙稀 基(PPV)或聚(3-己基)噻吩(Ρ3ΗΤ)。η-型組件可包含具有強 電子親和性之材料,包括(例如)碳富勒稀(carb〇n fuiierene)、 二氧化鈦、鎘硒、及經特殊設計可表現卜型行為之聚合物 及小分子。 135320.doc -55- 200930743 光伏打電池之性能可藉由4測光能向電化學能轉化之效 率來確定,該效率係如藉由量子效率(有效使用光子數除 以所吸收光子數)及藉由電池所產生峰值輸出功率(由乘積Meerholz, 31-34 (2000) and Alcala, 却 ρ/. 88, 7124-7128 (2000) and references cited therein). In another application, positionally regular conductive block copolymers (especially those exhibiting photoluminescence properties) can be used, for example, as light source materials for display devices. For example, European Patent Application Publication No. 〇 889 3 5 Said in a nickname or by C. Weder et al. 'Science, 279, 835-837 (1998). 135320.doc -53- 200930743 Field Effect Electron Crystal Hip In a preferred embodiment, the positionally oriented conductive block copolymer can also be used, for example, in field effect transistors (FETs). In a field effect transistor, the organic semiconductor material can be disposed as a thin film between the gate dielectric and the channel and the source electrode (see, for example, U.S. Patent No. 5,892,244, PCT Patent Application Publication No. WO 00/79617, U.S. Patent No. 5 998 8〇4). Preferred applications of such field effect transistors are, for example, integrated circuits, thin film electromorph (TFT) displays, and security applications due to the many advantages of such materials (e.g., fabrication of large surfaces at low cost). In safety applications, field effect transistors and other devices with semiconductor materials (such as transistors or diodes) can be used in radio frequency identification (RFID) tags or security tags to verify and prevent counterfeit voucher. Valuable documents may include, for example, banknotes, credit cards, identification (ID) certificates, passports, licenses, or any other product of economic value (such as stamps, tickets, shares, bonds, checks, and the like). First Placed Power In a preferred embodiment, the positionally oriented conductive block copolymer can also be used, for example, in photovoltaic cells. Photovoltaic cells are electrochemical devices that convert electromagnetic radiation into electrical energy. Although not limited by theory, the conversion of electromagnetic radiation to electrical energy can be achieved via a charge separation event that occurs after photon absorption. This results in the formation of an excited state called an exciton in a p-type semiconductor in direct contact with the n-type semiconductor. Typically the semiconductor domain is sandwiched between one or more of the active layers, at least one of which is sufficiently transparent to allow photons to pass. Photovoltaic cells can be used in rechargeable batteries or for running electronic devices. 135320.doc •54- 200930743 It offers many advantages for any electrical application powered by the distribution network, whether it is an alternative to a battery or a charge 2 device that supplies power to the recovery unit. Finally, it can also be used to supplement the electricity provided by the distribution network or to replace the electricity provided by the distribution network. Photovoltaic cells typically include at least four components, two of which are electrodes. The components are transparent first electrodes, such as indium tin oxide coated on plastic or glass, which acts as charge carriers. This component is typically a negative pole and allows ambient light to enter the device. The second electrode may be made of a metal such as calcium or aluminum. In some cases, the metal can be applied to a support surface such as plastic, glass, sapphire, gasification 26, quartz, or diamond. This second electrode can also carry current. There is a discrete layer or a mixture of p and η-type semiconductors, i.e., third and fourth components, between the electrodes. A p-type material can be referred to as a primary light-harvesting component or layer. This material absorbs photons of a specific energy and produces a state that causes electrons to enter an excited energy state, thereby leaving a positive charge or "hole" in the ground state level. This is called exciton formation. The excitons diffuse into the junction between the p-type and the η-type material, thereby generating charge separation or exciton separation. Electron and "holes" charge are introduced into the electrode via η-type and ρ-type materials, respectively. This causes current to flow out of the battery. In addition to the positionally-regular conductive block copolymer described herein, the Ρ-type semiconductor can also Containing a conjugated polymer comprising, for example, a mixture or blend of materials 'including the use of poly-phenylene vinylene (PPV) or poly(3-hexyl)thiophene (Ρ3ΗΤ). The η-type component can comprise Materials with strong electron affinity include, for example, carb〇n fuiierene, titanium dioxide, cadmium selenide, and polymers and small molecules that are specifically designed to exhibit budding behavior. 135320.doc -55- 200930743 The performance of photovoltaic cells can be determined by the efficiency of the 4 metering energy to the conversion of electrochemical energy, such as by quantum efficiency (the number of photons used effectively divided by the number of absorbed photons) and the peak output produced by the battery Power (by product
IppVpp給出’其中1叩係峰值功率下之電流且v叫係峰值功率 下之電壓)所量測。 零致發光裝置 在較佳實施例中’位置規則性導電嵌段共聚物亦可在有 機或聚°物電致發光裝置中用作(例如)電洞注人或電洞輸 &層。在電致發域置+使用位置規則性導錢段共聚物 可知:供若干期望特性,例如裝置發光性之提高、臨限電壓 之降低、壽命之延長、電子阻播材料及組件在裝置製造 期間之易加工性、可在電致發光裝置中使用旋轉洗注、液 滴澆庄噴墨、及其他印刷技術施加電洞注入或電洞輸送 層之能力、製備撓性更強電致發光裝置之能力、製備低重 量電致發光裝置之能力、及製備低成本電致發光裝置之能 © 力° 電致發光裝置係可將電流轉化為光子通量之裝置。此可 在電子與正電荷或"電洞"在電致發光材料中相遇產生激發 態物質或激子時完成,該激發態物質或激子在衰變至基態 時可發射光子。該裝置係以低電壓及最小輻射熱產生光之 有效方式。目前該等裝置可用於多種消費電子裝置中。 電致發光裝置之一實例包括四個組件。該等組件中兩個 係電極。第一組件可為塗佈於塑料或玻璃基材上之諸如氧 化銦錫等透明負極,其用作電荷載流子且容許自該裝置發 135320.doc -56- 200930743 射光子。第二電極或正極通常係由低功函數金屬(例如鈣 或鋁或二者)構成。在某些情況下,可將此金屬塗佈至支 撐表面上,例如塑料、玻璃層、藍寶石、氮化鋁、石英或 金剛石。此第二電極將電子導入或注入裝置中。在該兩個 電極之間存在電致發光層及電洞注入層或電洞輸送層。 第二組件係電致發光層材料。電致發光層可包含(例如) 基於位置規則性導電嵌段共聚物、其他導電聚合物、及有 機-過渡金屬小分子錯合物之材料。通常根據當激子經由 螢光或磷光衰變至基態時材料發射光子之效率且根據材料 穿過透明電極所發射光線之波長或顏色來選擇該等材料。 第四組件係電洞注入或電洞輸送層材料。電洞注入或電 洞輸送層係能將正電荷或"電洞"自透明負極轉移至電致發 光層以產生繼而導致發光之激子之導電材料。電洞注入或 電洞輸送層通常係P-經摻雜或經氧化導電材料,該等材料 一般係根據能將正電荷轉移至電致發光層之便利性及其總 效率來選擇。 有機及聚合物電致發光裝置可採用多種形式。倘若電致 發光層包括通常經真空沈積之小分子,則一般將裴置稱為 OLED(有機發光二極體p倘若電致發光層包括通常經溶 液加工及沈積之電致發光聚合物,則一般將裝置稱為 PLED(聚合物發光二極體)《»某些電致發光層可能不完全符 合上述任一描述,例如形成發光電化學電池之電致發光材 料與固體電解質之混合物。電致發光層可經設計而發射白 光(即各原色之均衡混合)以用於白光應用或可經濾色以用 135320.doc -57- 200930743 於全色顯示應用中。電致發光層亦可經設計以發射特定顏 色’例如紅色、綠色及藍色,可將其合併以產生全色譜。 可將各發光二極體(LED)組合以製造單色(單一顏色)或 全色(通常藉由合併紅色、綠色與藍色產生之大多數顏色) 平板顯示器。其可為被動式矩陣顯示器,其中以與兩電極 之間之電洞注入或電洞輸送層及電致發光層垂直之角度將 負極材料條沈積至正極材料條上,使得電流流經一負極及 一正極條而導致作為顯示器中單一像素之交點發光。其亦 可為主動式矩陣顯示器’其中每一像素處之電晶體控制單 獨像素是否發光及其亮度。主動式矩陣顯示器可為底發射 (其中光線經由或靠近電晶體電路射過)或頂發射(其中光線 沿含有電晶體電路之層之相反方向射出)。 其他二極艘 在較佳實施例中,位置規則性導電嵌段共聚物亦可用於 (例如)不發光或非光伏打二極體中。二極體闡述於(例 如)Ben G. Streetman,Siaie 五,第 4 版’ 1995(例如參見第5及6章)中。此書闞述(例如)接面及 二極體之製造。在一種二極體類型中,將p_型材料相對n_ 型材料置放。半導體接面類型二極體之實例包括正常p_n 二極體、金摻雜二極體、齊納(Zener)二極體、雪崩二極 體、瞬態電壓抑制(TVS)二極體、發光二極體(LED)、光電 一極體、肖特基(Schottky)二極體、急變二極體、江崎 (Esaki)或隧道二極體、impatt二極體、TRAPATT二極 體、BARITT二極體、及耿氏(Gunn)二極體。其他類型二 135320.doc -58- 200930743 極體包括點接觸型二極體、真空或真空管二極體、排氣二 極體及變容或變抗二極體。㉟習此項技術者可製備非發 光及非光伏打二極體。 該等非發光及非光伏打二極體可藉由業内已知之方法來 製造。舉例而f,ρ-η接面可藉由以下方法來製造:⑴提 供Ρ_型材料,(11)提供η_型材料,及(iii)藉由業内已知方 法組合p-型材料與n_型材料以使其彼此接觸。p_型材料可 為本文所述位置規則性導電嵌段共聚物。類似地,可提供 額外步驟以獲得額外P-型材料並將其與p_n接面組合以提供 Ρ_η·ρ夾心型結構。 位置規則性導電嵌段共聚物可另外用於(例如)液晶及/或 半導體材料、裝置或應用中。與習用合成相比,該等聚合 物之高電導使得可改良電導,且由此改良該等應用及裝置 之功能。 本文所述位置規則性導電嵌段共聚物亦可用於(例如)反 Q 射膜、電池中之電極材料、及類似應用中。因此,亦可使 用包括以本文所述聚合物(例如根據實例1中所述製備之聚 合物)構建之電路之電子裝置。 ' 位置規則性導電嵌段共聚物可為(例如)位置隨機性聚嚷 吩,其可用於不需要位置規則性聚噻吩所表現高電導率之 電子裝置應用中。舉例而言,位置隨機性聚噻吩之光學特 性明確取決於溶液之聚陽離子及pH,其在各總成之可見光 吸收最大值上表現介於435 nm與516 nm之間之顯著差異。 (例如參見 Myunghwan等人,《/. Macrowo/. 5W.,38(12) 135320.doc • 59- 200930743 1291 (2001))。位置隨機性聚噻吩對聚陽離子之此罕見敏 感性在感測器裝置中可具有潛在應用。 應瞭解,本發明中某些闡述已被簡化以僅闡釋彼等與清 楚地理解本發明有關之元件及限制,同時出於清晰性目的 未闞述其他元件。在考慮對本發明之說明後熟習此項技術 者可瞭解,可能需要其他元件及/或限制來實踐本發明。 然而’由於該等其他元件及/或限制可由熟習此項技術者 在慮及關於本發明之本說明後容易地確定,且對於完全理 解本發明而言並非必需’因此本文不提供關於該等元件及 限制之論述。舉例而言,可將本發明材料納入電子裝置 中,由於該等電子裝置已為熟習此項技術者所知,因此本 文中不再詳細闡述。 此外’本發明組合物可經概述並以各種形式具體化,且 將其施用至本文中未具體明確闡述之最終應用中。舉例而 言’熟習此項技術者可瞭解’可將本發明納入除本文中詳 細闡述之電子裝置以外之電子裝置中。其他可製造裝置 (端視本發明聚合物特性)包括(例如)單極電晶體(例如 FET、BJT、及JFET)、異質結電晶體(例如HEM1^HBT)、 檢測器(例如PIN、MSM、HPT、焦平面陣列、cCD、及主 動式像素感測器)、二極體(例如珀爾帖(peltier)及廢電)、 光學裝置(例如波導器、外部腔雷射及共振器、WGM雷 射、光學放大器、及可調發射器)、及量子結構(例如量子 線、量子點、及奈米線)。 製備组合物之方法 135320.doc 200930743 ❹IppVpp is measured as 'the voltage at which the peak current is 1 叩 and the voltage at the peak power is v. Photoluminescent Device In a preferred embodiment, the "positionally regular conductive block copolymer" can also be used, for example, as a hole injection or hole transport layer in an organic or polymeric electroluminescent device. In the electro-luminescence domain + use of the positional regular lead segment copolymer can be known for: a number of desired characteristics, such as improved device luminosity, reduced threshold voltage, extended life, electronic blocking materials and components during device manufacturing The ease of processing, the ability to apply hole injection or hole transport layers in electroluminescent devices using spin-on, drop-injection, and other printing techniques, and the ability to fabricate flexible, more electroluminescent devices The ability to prepare low-weight electroluminescent devices and the ability to produce low-cost electroluminescent devices. Electroluminescent devices are devices that convert current into photon flux. This can be done when electrons and positive charges or "holes" meet in an electroluminescent material to produce an excited species or excitons that emit photons when decaying to the ground state. The device is an efficient way to generate light with low voltage and minimal radiant heat. These devices are currently available in a variety of consumer electronic devices. An example of an electroluminescent device includes four components. Two tie electrodes in these components. The first component can be a transparent negative electrode such as indium tin oxide coated on a plastic or glass substrate that acts as a charge carrier and allows photons to be emitted from the device 135320.doc - 56 - 200930743. The second electrode or positive electrode is typically composed of a low work function metal such as calcium or aluminum or both. In some cases, the metal can be applied to a support surface such as plastic, glass, sapphire, aluminum nitride, quartz or diamond. This second electrode introduces electrons into or into the device. An electroluminescent layer and a hole injection layer or a hole transport layer are present between the two electrodes. The second component is an electroluminescent layer material. The electroluminescent layer can comprise, for example, materials based on positionally regular conductive block copolymers, other conductive polymers, and organic-transition metal small molecule complexes. The materials are typically selected based on the efficiency with which the material emits photons as it decays to the ground state via fluorescence or phosphorescence and depending on the wavelength or color of the light emitted by the material through the transparent electrode. The fourth component is a hole injection or hole transport layer material. The hole injection or hole transport layer is capable of transferring a positive charge or "hole" from the transparent negative electrode to the electroluminescent layer to produce a conductive material that in turn causes the excitons to emit light. The hole injection or hole transport layer is typically a P-doped or oxidized conductive material, which is generally selected based on the ease with which a positive charge can be transferred to the electroluminescent layer and its overall efficiency. Organic and polymeric electroluminescent devices can take a variety of forms. If the electroluminescent layer comprises a small molecule which is usually vacuum deposited, it is generally referred to as an OLED (organic light-emitting diode p. If the electroluminescent layer comprises an electroluminescent polymer which is usually solution processed and deposited, then generally The device is referred to as a PLED (Polymer Light Emitting Diode). » Some electroluminescent layers may not fully conform to any of the above descriptions, such as a mixture of electroluminescent materials and solid electrolytes that form a light-emitting electrochemical cell. The layer can be designed to emit white light (ie, a balanced blend of primary colors) for white light applications or can be filtered to use 135320.doc -57- 200930743 for full color display applications. The electroluminescent layer can also be designed to Emit specific colors 'eg red, green and blue, which can be combined to produce a full chromatogram. Each light emitting diode (LED) can be combined to make a single color (single color) or full color (usually by combining red, Most colors produced by green and blue) flat panel display. It can be a passive matrix display with a hole injection or hole transport layer and electroluminescent layer between the two electrodes. Straight angle deposits a strip of negative electrode material onto the strip of positive electrode material, causing current to flow through a negative electrode and a positive electrode strip to cause illumination at the intersection of a single pixel in the display. It can also be an active matrix display 'electricity at each pixel The crystal controls whether individual pixels emit light and their brightness. The active matrix display can be either bottom emission (where light passes through or near the transistor circuit) or top emission (where the light exits in the opposite direction of the layer containing the transistor circuit). In a preferred embodiment, the positionally oriented conductive block copolymer can also be used, for example, in non-luminescent or non-photovoltaic diodes. Diodes are described, for example, in Ben G. Streetman, Siaie V. , 4th edition '1995 (see, for example, Chapters 5 and 6). This book describes, for example, the fabrication of junctions and diodes. In a diode type, the p_type material is compared to the n_type material. Examples of semiconductor junction type diodes include a normal p_n diode, a gold doped diode, a Zener diode, an avalanche diode, and a transient voltage suppression (TVS) diode. Body, light-emitting diode (LED), photodiode, Schottky diode, urgency diode, Esaki or tunnel diode, impatt diode, TRAPATT diode, BARITT diodes, and Gunn diodes. Other types 2 135320.doc -58- 200930743 Polar bodies include point contact diodes, vacuum or vacuum tube diodes, exhaust diodes and variable capacitance Or a variable anti-diode. Those skilled in the art can prepare non-luminescent and non-photovoltaic diodes. The non-luminescent and non-photovoltaic diodes can be fabricated by methods known in the art. The ρ-η junction can be fabricated by (1) providing a Ρ-type material, (11) providing a η-type material, and (iii) combining a p-type material and an n-type by methods known in the art. The materials are brought into contact with each other. The p-type material can be a positionally oriented conductive block copolymer as described herein. Similarly, additional steps can be provided to obtain additional P-type materials and combine them with the p_n junction to provide a Ρ_η·ρ sandwich-type structure. The positionally regular conductive block copolymers can additionally be used, for example, in liquid crystal and/or semiconductor materials, devices or applications. The high conductance of such polymers allows for improved conductivity and thus improved functionality of such applications and devices as compared to conventional synthesis. The positionally oriented conductive block copolymers described herein can also be used, for example, in anti-Q films, electrode materials in batteries, and the like. Thus, electronic devices comprising circuits constructed with the polymers described herein (e.g., the polymers prepared as described in Example 1) can also be used. The positionally regular conductive block copolymer can be, for example, a positionally random polypene, which can be used in electronic device applications where high conductivity is not required for positional regular polythiophenes. For example, the optical properties of positionally random polythiophenes are clearly dependent on the polycation and pH of the solution, which represents a significant difference between 435 nm and 516 nm in the maximum visible light absorption of each assembly. (See, for example, Myunghwan et al., /. Macrowo/. 5W., 38(12) 135320.doc • 59-200930743 1291 (2001)). This rare sensitivity of positionally random polythiophenes to polycations can have potential applications in sensor devices. It is to be understood that the description of the invention has been inferred Other elements and/or limitations may be required to practice the invention in light of the teachings of the invention. However, as such other elements and/or limitations may be readily determined by those skilled in the art after having regard to the present description of the present invention, and are not necessary for a complete understanding of the present invention, therefore no such elements are provided herein. And the discussion of restrictions. For example, the materials of the present invention can be incorporated into electronic devices, and as such electronic devices are known to those skilled in the art, they are not described in detail herein. Further, the compositions of the present invention can be summarized and embodied in various forms and applied to the final application not specifically set forth herein. For example, those skilled in the art will appreciate that the invention can be incorporated into an electronic device other than the electronic devices detailed herein. Other manufacturable devices (respecting the polymer properties of the invention) include, for example, monopolar transistors (eg, FETs, BJTs, and JFETs), heterojunction transistors (eg, HEM1^HBT), detectors (eg, PIN, MSM, HPT, focal plane array, cCD, and active pixel sensors), diodes (such as peltier and waste), optical devices (such as waveguides, external cavity lasers and resonators, WGM Ray) Shots, optical amplifiers, and tunable emitters), and quantum structures (such as quantum wires, quantum dots, and nanowires). Method of preparing a composition 135320.doc 200930743 ❹
本文所述組合物可藉由有機合成中任一可用技術來製 備。許多該等技術為業内所熟知。然而,多種已知方法詳 述於以下文獻中:Compendium of Organic Synthetic Methods(John Wiley & Sons, New York)第 1卷,Ian T. Harrison 及 Shuyen Harrison (1971);第 2 卷,Ian T. Harrison 及 Shuyen Harrison (1974);第 3 卷,Louis S. Hegedus及 Leroy Wade (1977);第 4 卷,Leroy G. Wade Jr.,(1980);第 5 卷,Leroy G. Wade Jr. (1984);及第 6卷,Michael B. Smith ;以及March, J.,Advanced Organic Chemistry,第3 版,John Wiley & Sons,New York (1985) ; ComprehensiveThe compositions described herein can be prepared by any of the techniques available in organic synthesis. Many of these techniques are well known in the art. However, a variety of known methods are detailed in the following literature: Compendium of Organic Synthetic Methods (John Wiley & Sons, New York) Vol. 1, Ian T. Harrison and Shuyen Harrison (1971); Volume 2, Ian T. Harrison and Shuyen Harrison (1974); Vol. 3, Louis S. Hegedus and Leroy Wade (1977); Vol. 4, Leroy G. Wade Jr., (1980); Vol. 5, Leroy G. Wade Jr. (1984 And; Volume 6, Michael B. Smith; and March, J., Advanced Organic Chemistry, 3rd edition, John Wiley & Sons, New York (1985); Comprehensive
Organic Synthesis. Selectivity, Strategy & Efficiency in Modern Organic Chemistry,第 9 卷,Barry M. Trost 總編, Pergamon Press » New York (1993) ; Advanced Organic Chemistry,Part B: Reactions and Synthesis,第 4版;Carey及 Sundberg ; Kluwer Academic/Plenum Publishers: New York (2001) ; Advanced Organic Chemistry, Reactions, Mechanisms, and Structure,第 2版,March,McGraw Hill (1977) ; Protecting Groups in Organic Synthesis,第 2 版,Greene,T.W.及 Wutz, P.G.M.,John Wiley & Sons,New York (1991);及Comprehensive Organic Transformations,第 2版,Larock, R.C.,John Wiley & Sons,New York (1999)。 實例 以下實例闡釋本發明上文内容。熟習此項技術者可容易 地瞭解,實例中所述技術及試劑闡述實踐本發明之多種其 135320.doc -61 - 200930743 他方法。應瞭解,可做出諸多變化 本發明範圍内》 u時仍保持在 除操作實例中之情況外,4 #,, 次除非另外明確說明,即使詞 一約”未明確地與數值、數量 ^ ^ 置叉靶图起出現,所有數字 :、數值及百分比(例如關於材料數量、 :及溫度、數量比、及說明書以下部分中其他因素之彼 等)皆應理解為如同前面經詞語”約"修# —般。因此,除非 說明相反情況’否則以下說明書及隨附申請專利範圍中所 列不之數字參數均為可根據欲藉由本發明達成之期望性質 而變化的近似值。無論如何,且並非試圖限制申請專利範 圍等效項原則的應用,每一數字參數皆應至少根據所報道 有效位的數字且藉由使用普通舍入技術來解釋。 儘管本發明寬範圍中所列數值範圍及參數係近似值,但 在特定實例中盡可能準確地報告所列數值。然而,任一數 值固有地包含某些由其各自測試量測中所存在標準偏差引 起的必然誤差。此外,當在本文中列示各範疇之數字範圍 時,其涵蓋可使用包括所引用數值在内之該等數值之任一 組合。 通常可在雙接頭真空/氬或氮系統上實施反應。若需要 可在乾燥箱中於氬或氮氣下實施空氣敏感性材料之處理。 化學試劑主要構自Aldrich Chemical有限公司(Milwaukee, WI) ’且除非另外說明,否則係以未處理形式使用。 實例1 製備位置規則性HT聚(3-取代噻吩)嵌段共聚物 135320.doc •62· 200930743 有機鋅I及II係根據美國專利第5,756,653號中所述方法 (參見例如第54攔,第15-40列)使用裏克辞(Zn*)來製備。 將40毫升(mL)(20毫莫耳(mmol))有機鋅1(0.5莫耳(M),存 於四氫呋喃中)溶液置於燒瓶中且在室溫及惰性氣氛下攪 拌。以一份向此溶液中添加0.02克(0.2 mol%) Ni(dppe)Cl2 且將混合物授拌5分鐘。添加20 mL (1 0 mmol)有機鋅11(0.5 Μ,存於四氫呋喃中)且在室溫下將混合物攪拌過夜。將溶 液傾入曱醇中並授拌20分鐘(min)。經布氏漏斗(Buchner > funnel)過濾聚合物沈澱物並用甲醇洗滌。在高真空壓力下 乾燥聚合物,且在索克斯累特提取器(Soxhlet Extractor)中 用己烷萃取24小時而獲得4.4克聚合物。據1H NMR測定粗 聚合物具有約94:6位置規則性。粗聚合物含有約70% 3-己基-噻吩及約30% 3-乙基戊酸酯噻吩。此程序列示於方案3中。 方案3.Organic Synthesis. Selectivity, Strategy & Efficiency in Modern Organic Chemistry, Vol. 9, Barry M. Trost, ed., Pergamon Press » New York (1993); Advanced Organic Chemistry, Part B: Reactions and Synthesis, 4th edition; Carey And Sundberg; Kluwer Academic/Plenum Publishers: New York (2001); Advanced Organic Chemistry, Reactions, Mechanisms, and Structure, 2nd Edition, March, McGraw Hill (1977); Protecting Groups in Organic Synthesis, 2nd Edition, Greene, TW and Wutz, PGM, John Wiley & Sons, New York (1991); and Comprehensive Organic Transformations, 2nd Edition, Larock, RC, John Wiley & Sons, New York (1999). EXAMPLES The following examples illustrate the above aspects of the invention. Those skilled in the art will readily appreciate that the techniques and reagents described in the examples illustrate various methods of practicing the invention 135320.doc-61 - 200930743. It should be understood that many variations can be made within the scope of the invention, while still remaining in the operating example, 4 #,, unless otherwise explicitly stated, even if the word "about" is not explicitly related to the value, quantity ^ ^ The forked target image appears, all numbers:, values and percentages (eg, regarding the amount of material, : and temperature, the quantity ratio, and other factors in the following sections of the specification) should be understood as if the preceding words "about" Repair #-. Accordingly, the numerical parameters set forth in the following specification and the appended claims are intended to be an approximation that may vary depending on the desired properties to be achieved by the present invention. In any event, and without attempting to limit the application of the principles of the patented equivalents, each numerical parameter should be interpreted at least in accordance with the number of reported effective digits and by using ordinary rounding techniques. Although the numerical ranges and parameters set forth in the broad scope of the invention are approximations, the listed values are reported as accurately as possible in the particular examples. However, any value inherently contains certain inevitable errors caused by the standard deviations present in their respective test measurements. In addition, when a range of numbers for each category is recited herein, it is intended to encompass any combination of such values, including the recited values. The reaction can usually be carried out on a double joint vacuum/argon or nitrogen system. If desired, the treatment of air sensitive materials can be carried out in a dry box under argon or nitrogen. The chemical reagents were primarily constructed from Aldrich Chemical Co., Ltd. (Milwaukee, WI) and were used in untreated form unless otherwise stated. EXAMPLE 1 Preparation of a Positionally Regular HT Poly(3-Substituted Thiophene) Block Copolymer 135320.doc • 62· 200930743 Organic Zinc I and II are based on the method described in U.S. Patent No. 5,756,653 (see, for example, No. 54, No. 15 -40 columns) Prepared using Rick (Zn*). A solution of 40 ml (mL) (20 mmol (mmol)) of organozinc 1 (0.5 mol (M) in tetrahydrofuran) was placed in a flask and stirred at room temperature under an inert atmosphere. To this solution was added 0.02 g (0.2 mol%) of Ni(dppe)Cl2 in one portion and the mixture was stirred for 5 minutes. 20 mL (10 mmol) of organic zinc 11 (0.5 Torr in tetrahydrofuran) was added and the mixture was stirred at room temperature overnight. The solution was poured into methanol and stirred for 20 minutes (min). The polymer precipitate was filtered through a Buchner funnel (Buchner > funnel) and washed with methanol. The polymer was dried under high vacuum pressure and extracted with hexane for 24 hours in a Soxhlet Extractor to obtain 4.4 g of a polymer. The crude polymer was determined to have about 94:6 positional regularity by 1H NMR. The crude polymer contained about 70% 3-hexyl-thiophene and about 30% 3-ethylvalerate thiophene. This procedure is listed in scenario 3. Option 3.
135320.doc -63-135320.doc -63-
200930743 本文所述製備聚噻吩嵌段共聚物之方法之一優點在於, 嗟吩-鋅錯合物之形成容許在比多種已知方法低之溫度不 進行聚合。噻吩·鋅錯合物之聚合在環境溫度(例如約丨8〇c 至約2 5 C )下平穩進行且不需熱源或回流條件。更顯著優 點在於’本文所述方法產生具有更大位置規則度(更高頭_ 尾嗟吩連接百分比)之聚合物。此外,需要加載較少觸媒 由此降低程序之成本。 實例2 實例性位置規則性導電嵌段共聚物 方案4闡述可藉由本文所述方法製備之位置規則性導電 嵌段共聚物中若干種可能嵌段,其中n係使得位置規則性 導電被段共聚物之分子量可為約1〇〇〇〇至約2〇〇〇〇〇之數 值,"Hex"係己基但可為本文所述任一烷基;"Bn"係可視 需要如本文所述經取代之苄基;” Ar"係本文所述芳基; "Het"係本文所述雜芳基或雜環;至約2〇 ;且尺係本文 所述院基。 方案4·One of the advantages of the process for preparing polythiophene block copolymers described herein is that the formation of the porphin-zinc complex allows for polymerization to be carried out at temperatures lower than those of known methods. The polymerization of the thiophene-zinc complex is carried out smoothly at ambient temperature (e.g., about 8 〇c to about 2 5 C) without the need for heat or reflux conditions. A more significant advantage is that the method described herein produces a polymer having a greater degree of positional regularity (higher head-to-tail phenanthrene linkage percentage). In addition, less catalyst needs to be loaded, thereby reducing the cost of the program. EXAMPLE 2 Example Positioned Regular Conductive Block Copolymer Scheme 4 illustrates several possible blocks in a positionally regular conductive block copolymer that can be prepared by the methods described herein, wherein n is such that the positionally regular conductive is segmentally copolymerized The molecular weight of the substance may be from about 1 〇〇〇〇 to about 2 ,, "Hex" is a hexyl group but may be any of the alkyl groups described herein; "Bn" may be as described herein Substituted benzyl; "Ar" is an aryl group as described herein; "Het" is a heteroaryl or heterocyclic ring as described herein; to about 2 Å; and the ulnar is described herein.
HetHet
RR
135320.doc -64 - 200930743135320.doc -64 - 200930743
所有出版物、專利及專利文件皆係以引用方式併入本文 中,如同以引用方式單獨併入一般。上文已參照各具體實 施例及較佳實施例及技術闡述本發明。然而,應瞭解可作 出許多變化及修改 内。 同時仍保持處於本發明精神及範疇All publications, patents, and patent documents are hereby incorporated by reference in their entirety herein in their entirety herein The invention has been described above with reference to specific embodiments and preferred embodiments and techniques. However, it should be understood that many changes and modifications can be made. At the same time, it remains in the spirit and scope of the present invention.
135320.doc -65 -135320.doc -65 -
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