WO2009007012A1 - Verfahren zur synthese von oligo/polythiophenen nach einem 'eintopf'-syntheseweg - Google Patents
Verfahren zur synthese von oligo/polythiophenen nach einem 'eintopf'-syntheseweg Download PDFInfo
- Publication number
- WO2009007012A1 WO2009007012A1 PCT/EP2008/005182 EP2008005182W WO2009007012A1 WO 2009007012 A1 WO2009007012 A1 WO 2009007012A1 EP 2008005182 W EP2008005182 W EP 2008005182W WO 2009007012 A1 WO2009007012 A1 WO 2009007012A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- thiophene
- group
- nickel
- catalyst
- ylene
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 61
- 230000008569 process Effects 0.000 title claims abstract description 29
- 229920000123 polythiophene Polymers 0.000 title claims description 12
- 238000005580 one pot reaction Methods 0.000 title abstract description 4
- 230000015572 biosynthetic process Effects 0.000 title description 3
- 238000003786 synthesis reaction Methods 0.000 title description 3
- 230000002194 synthesizing effect Effects 0.000 title 1
- -1 organometallic thiophene compound Chemical class 0.000 claims abstract description 63
- 150000003577 thiophenes Chemical class 0.000 claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 150000002902 organometallic compounds Chemical class 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- 239000011777 magnesium Substances 0.000 claims description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 13
- 229910052749 magnesium Inorganic materials 0.000 claims description 13
- 125000003545 alkoxy group Chemical group 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 125000001072 heteroaryl group Chemical group 0.000 claims description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 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 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 125000005549 heteroarylene group Chemical group 0.000 claims description 5
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 5
- 239000011135 tin Substances 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 125000000732 arylene group Chemical group 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 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 description 4
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 claims description 4
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 3
- 125000001188 haloalkyl group Chemical group 0.000 claims description 3
- 150000008282 halocarbons Chemical class 0.000 claims description 3
- 125000006588 heterocycloalkylene group Chemical group 0.000 claims description 3
- 235000021317 phosphate Nutrition 0.000 claims description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 3
- 125000002577 pseudohalo group Chemical group 0.000 claims description 3
- 125000001174 sulfone group Chemical group 0.000 claims description 3
- 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 2
- JTBOBRXTBCQEDC-UHFFFAOYSA-N 1,3-bis(1-adamantyl)imidazolidin-1-ium;chloride Chemical compound [Cl-].C1C(C2)CC(C3)CC2CC13[NH+]1CCN(C23CC4CC(CC(C4)C2)C3)C1 JTBOBRXTBCQEDC-UHFFFAOYSA-N 0.000 claims description 2
- NREOZXRFNFCTHM-UHFFFAOYSA-N 1,3-bis[2,6-di(propan-2-yl)phenyl]imidazolidin-1-ium;chloride Chemical compound [Cl-].CC(C)C1=CC=CC(C(C)C)=C1N1C[NH+](C=2C(=CC=CC=2C(C)C)C(C)C)CC1 NREOZXRFNFCTHM-UHFFFAOYSA-N 0.000 claims description 2
- VMSBCZLYJOAVIG-UHFFFAOYSA-N 3,4-dichloro-2-pyridin-2-ylpyridine;nickel Chemical compound [Ni].ClC1=CC=NC(C=2N=CC=CC=2)=C1Cl VMSBCZLYJOAVIG-UHFFFAOYSA-N 0.000 claims description 2
- 229930194542 Keto Natural products 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- WDQZIRSDNFWMAE-UHFFFAOYSA-L dichloronickel;1-diphenylphosphanylethyl(diphenyl)phosphane Chemical compound Cl[Ni]Cl.C=1C=CC=CC=1P(C=1C=CC=CC=1)C(C)P(C=1C=CC=CC=1)C1=CC=CC=C1 WDQZIRSDNFWMAE-UHFFFAOYSA-L 0.000 claims description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 2
- 125000000262 haloalkenyl group Chemical group 0.000 claims description 2
- 125000000232 haloalkynyl group Chemical group 0.000 claims description 2
- 125000003106 haloaryl group Chemical group 0.000 claims description 2
- 125000005216 haloheteroaryl group Chemical group 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000000468 ketone group Chemical group 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims description 2
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 2
- QEKXARSPUFVXIX-UHFFFAOYSA-L nickel(2+);triphenylphosphane;dibromide Chemical compound [Ni+2].[Br-].[Br-].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 QEKXARSPUFVXIX-UHFFFAOYSA-L 0.000 claims description 2
- KFBKRCXOTTUAFS-UHFFFAOYSA-N nickel;triphenylphosphane Chemical compound [Ni].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 KFBKRCXOTTUAFS-UHFFFAOYSA-N 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 125000005353 silylalkyl group Chemical group 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims 1
- GROYGRZSTCDMEM-UHFFFAOYSA-L dichloronickel 2-diphenylphosphanylpropan-2-yl(diphenyl)phosphane Chemical compound [Ni](Cl)Cl.C1(=CC=CC=C1)P(C1=CC=CC=C1)C(C)(C)P(C1=CC=CC=C1)C1=CC=CC=C1 GROYGRZSTCDMEM-UHFFFAOYSA-L 0.000 claims 1
- 150000002431 hydrogen Chemical group 0.000 claims 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 abstract description 21
- 229930192474 thiophene Natural products 0.000 abstract description 13
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 28
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- 238000009826 distribution Methods 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 238000005859 coupling reaction Methods 0.000 description 5
- 150000004795 grignard reagents Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 125000002524 organometallic group Chemical group 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000007818 Grignard reagent Substances 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 description 3
- 238000005442 molecular electronic Methods 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000010626 work up procedure Methods 0.000 description 3
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 0.000 description 2
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 2
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 2
- NSYFIAVPXHGRSH-UHFFFAOYSA-N 2,5-dibromo-3-hexylthiophene Chemical compound CCCCCCC=1C=C(Br)SC=1Br NSYFIAVPXHGRSH-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- 238000005577 Kumada cross-coupling reaction Methods 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000001347 alkyl bromides Chemical class 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- 150000004791 alkyl magnesium halides Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000000160 oxazolidinyl group Chemical group 0.000 description 2
- 125000003386 piperidinyl group Chemical group 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011877 solvent mixture Chemical group 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 description 1
- 125000003363 1,3,5-triazinyl group Chemical group N1=C(N=CN=C1)* 0.000 description 1
- HOOKQVAAJVEFHV-UHFFFAOYSA-N 1,3-bis(2,4,6-trimethylphenyl)imidazolidin-1-ium;chloride Chemical compound [Cl-].CC1=CC(C)=CC(C)=C1N1C[NH+](C=2C(=CC(C)=CC=2C)C)CC1 HOOKQVAAJVEFHV-UHFFFAOYSA-N 0.000 description 1
- KDCBVVQAMMXRFB-UHFFFAOYSA-N 1,4,7,10,13-pentazacyclopentadecane Chemical compound C1CNCCNCCNCCNCCN1 KDCBVVQAMMXRFB-UHFFFAOYSA-N 0.000 description 1
- QBPPRVHXOZRESW-UHFFFAOYSA-N 1,4,7,10-tetraazacyclododecane Chemical class C1CNCCNCCNCCN1 QBPPRVHXOZRESW-UHFFFAOYSA-N 0.000 description 1
- OZFOKTZBDJXZTE-UHFFFAOYSA-N 1,4,7-oxadiazonane Chemical class C1CNCCOCCN1 OZFOKTZBDJXZTE-UHFFFAOYSA-N 0.000 description 1
- CIBAIKDMTBNPNQ-UHFFFAOYSA-N 1,4,7-thiadiazonane Chemical compound C1CNCCSCCN1 CIBAIKDMTBNPNQ-UHFFFAOYSA-N 0.000 description 1
- ITWBWJFEJCHKSN-UHFFFAOYSA-N 1,4,7-triazonane Chemical class C1CNCCNCCN1 ITWBWJFEJCHKSN-UHFFFAOYSA-N 0.000 description 1
- PQNPKQVPJAHPSB-UHFFFAOYSA-N 1,4,7-trithionane Chemical compound C1CSCCSCCS1 PQNPKQVPJAHPSB-UHFFFAOYSA-N 0.000 description 1
- MDAXKAUIABOHTD-UHFFFAOYSA-N 1,4,8,11-tetraazacyclotetradecane Chemical compound C1CNCCNCCCNCCNC1 MDAXKAUIABOHTD-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical group C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 150000000094 1,4-dioxanes Chemical class 0.000 description 1
- 125000005940 1,4-dioxanyl group Chemical group 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical group CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- AOPDRZXCEAKHHW-UHFFFAOYSA-N 1-pentoxypentane Chemical group CCCCCOCCCCC AOPDRZXCEAKHHW-UHFFFAOYSA-N 0.000 description 1
- JEDHEMYZURJGRQ-UHFFFAOYSA-N 3-hexylthiophene Chemical compound CCCCCCC=1C=CSC=1 JEDHEMYZURJGRQ-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 125000004648 C2-C8 alkenyl group Chemical group 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical group COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 238000004639 Schlenk technique Methods 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical class CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- UORVGPXVDQYIDP-BJUDXGSMSA-N borane Chemical class [10BH3] UORVGPXVDQYIDP-BJUDXGSMSA-N 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- IZWRXCGNSVOSAT-UHFFFAOYSA-L dichloronickel;diphenyl(propyl)phosphane Chemical compound Cl[Ni]Cl.C=1C=CC=CC=1P(CCC)C1=CC=CC=C1 IZWRXCGNSVOSAT-UHFFFAOYSA-L 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229960005141 piperazine Drugs 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000010349 pulsation Effects 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 150000003235 pyrrolidines Chemical class 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 125000001422 pyrrolinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012713 reactive precursor Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- 125000003507 tetrahydrothiofenyl group Chemical group 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- VJYJJHQEVLEOFL-UHFFFAOYSA-N thieno[3,2-b]thiophene Chemical compound S1C=CC2=C1C=CS2 VJYJJHQEVLEOFL-UHFFFAOYSA-N 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- 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
Definitions
- the present invention relates to a process for the preparation of oligo / polythiophenes.
- OFETs Simple structuring and integration of OFETs into integrated organic semiconductor circuits makes possible low-cost solutions for smart cards or price tags, which hitherto can not be realized with the aid of silicon technology due to the price and lack of flexibility of the silicon components. Also, OFETs could be used as switching elements in large area flexible matrix displays.
- All compounds have continuous conjugated units and are subdivided into conjugated polymers and conjugated oligomers depending on their molecular weight and structure.
- a distinction is usually oligomers of polymers in that oligomers usually have a narrow molecular weight distribution and a molecular weight to about 10,000 g / mol (Da), whereas polymers usually have a correspondingly higher molecular weight and a broader molecular weight distribution.
- Da g / mol
- polymers usually have a correspondingly higher molecular weight and a broader molecular weight distribution.
- it makes more sense to differentiate on the basis of the number of repeating units since a monomer unit can certainly reach a molecular weight of 300 to 500 g / mol, as for example in (3,3 "-dihexyl) -quarterthiophene.
- the most important semiconducting poly- or oligomers include the poly / oligothiophenes whose monomer unit is e.g. 3-hexylthiophene.
- a distinction must in principle be made between two processes - the simple coupling reaction and the multiple coupling reaction in the sense of a polymerization mechanism.
- the polymerization in a catalytic cycle is started by the Kumada method (cross-coupling metathesis reaction) using a nickel catalyst (preferably Ni (dppp) Cl 2 ).
- the polymers are generally obtained via Soxhlet purifications of the necessary purity.
- alkylmagnesium halides as used in EP 1028136, are suitable as coupling reagents, as described in WO2006076150. Accordingly, a broad by-product spectrum would be expected in the reaction with alkyl magnesium halides or with magnesium in the presence of alkyl halides.
- the object of the present invention was therefore to provide a process which at least partially overcomes the disadvantages mentioned and enables the production of polythiophenes or oligothiophenes with defined average chain lengths and a narrow molecular weight distribution.
- a method for the polymerization of at least one thiophene derivative having at least two leaving groups is proposed, wherein the polymerization by means of a thiophene-organometallic compound and at least one catalyst, characterized in that a mixture containing the at least one thiophene derivative and the at least one Catalyst containing at least one metal and / or at least one organometallic compound is added.
- thiophene derivative is understood to mean both mono-, di- or polysubstituted and unsubstituted thiophene.
- thiophene derivatives which are alkyl-substituted, particularly preferably 3-alkyl-substituted thiophene derivatives.
- the term "leaving group” is understood in particular to mean any group which is capable of reacting by means of a metal or an organometallic compound to form a thiophene-organometallic compound.
- the at least one thiophene derivative contains at least two different leaving groups. This may be useful for achieving better regioselectivity of the polymer in many applications of the present invention.
- the leaving groups of the at least one thiophene derivative are identical.
- thiophene-organometallic compound is understood in particular to mean a compound in which at least one metal-carbon bond to one of the carbon atoms on the thiophene heterocycle is present.
- organometallic compound is understood in particular to mean an alkylmetalorganic compound.
- Preferred metals within the at least one thiophene-organometallic compound are tin, magnesium, zinc and boron. It should be understood that within the present invention, boron is also considered to be a metal. In the event that the process according to the invention proceeds with the participation of boron, the leaving group is preferably selected from the group comprising MgBr, MgI, MgCl, Li or mixtures thereof.
- organometallic compounds which are used in the process according to the invention are preferably organometallic Sn compounds, for example tributyltin chloride, or Zn compounds, for example activated zinc (Zn *) or borane compounds, for example B ( OMe) 3 or B (OH) 3 , or Mg compounds, particularly preferably organometallic Mg compounds, particularly preferably Grignard compounds of the formula R-Mg-X,
- R is alkyl, very particularly preferably C2-alkyl
- X is halogen, more preferably Cl, Br or I, and most preferably Br.
- the addition is preferably carried out by metering a solution of this compound, wherein the solvent does not have to correspond to that in the further process.
- At least one metal may be used in the process of the present invention, preferably selected from zinc, magnesium, tin and boron.
- metallic magnesium is used, catalytic amounts of at least one of the reaction mixture are added Organohalide added. It has been found, surprisingly and advantageously, that the by-products to be expected from the prior art do not occur and a polymer with a very high regioselectivity and narrow molecular weight distribution is obtained.
- the at least one metal can be added, for example, and preferably in the form of chips, grains, particles or feeds, and subsequently separated, for example by filtration, or made available to the reaction space in a rigid form z.
- the continuous reaction to the Grignard reagent also under high turbulence in equipped with static mixers tube reactors, wherein the liquid column is subjected to pulsations, as known from the patents DD260276, DD260277 and DD260278, to which hereby incorporated by reference
- the embodiments preferred therein for the preparation of the Grignard reagents are likewise preferred embodiments also for the method according to the invention described here.
- the reaction is preferably carried out with magnesium provided within the process and in the presence of catalytic amounts of at least one organohalide, preferably alkyl halide, more preferably alkyl bromide, most preferably ethyl bromide. Separation of unreacted magnesium is preferably accomplished by suitable retention means such as e.g. Metal or glass frits.
- organohalide preferably alkyl halide, more preferably alkyl bromide, most preferably ethyl bromide.
- catalyst is understood in particular to mean a catalytically active metal compound.
- the at least one catalyst contains nickel and / or palladium. This has been found to be favorable in many application examples of the present invention.
- the at least one catalyst particularly preferably contains at least one compound selected from the group of nickel and palladium catalysts with ligands selected from the group consisting of tri-tert-butylphosphine, triadamantylphosphine, 1,3-bis (2,4,6-trimethylphenyl) imidazolidinium chloride, 1,3-bis (2,6-diisopropylphenyl) imidazolidinium chloride or 1,3-diadamantyl imidazolidinium chloride or mixtures thereof; To- (triphenylphosphino) palladium dichloride (Pd (PPh 3 ) Cl 2 ), palladium (II) acetate (Pd (OAc) 2 ), tetrakis (triphenylphosphine) palladium (Pd (PPh 3 )), tetrakis (triphenylphosphine) nickel
- Ni (PPh 3 ) 4 nickel-ü-acetylacetonate Ni (acac) 2 , dichloro (2,2'-bipyridine) nickel, dibromobis (triphenylphosphine) nickel (Ni (PPh 3 ) 2 Br 2 ), (diphenylphosphino) propane nickel dichloride (Ni (dppp) Cl 2 ) or bis (diphenylphosphino) ethane nickel dichloride Ni (dppe) Cl 2 or mixtures thereof
- the amount of added catalyst is often dependent on the target molecular weight and is usually in the range of> 0.1 - ⁇ 20 mol%, preferably in the range of> 1- ⁇ 17.5 mol%, particularly preferably in the range of> 2- ⁇ 15 mol %, in each case based on the molar amount of the thiophene derivative used.
- alkyl linear and branched C 1 -C 8 -alkyls
- long-chain alkyls linear and branched C5-C20 alkyls
- alkenyl C2-C8 alkenyl
- cycloalkyl C3-C8-cycloalkyl
- alkoxy Cl-C6-alkoxy
- Alkylene selected from the group comprising:
- methylene 1, 1 -ethylene; 1,2-ethylene; 1, 1 -propylidenes; 1,2-propylene; 1,3-propylene; 2,2-propylidenes; butan-2-ol-1,4-diyl; propan-2-ol-1,3-diyl; 1, 4-butylenes; cyclohexane-l, l-diyl; cyclohexane-1,2-diyl; cyclohexane-1,3-diyl; cyclohexane-l, 4-diyl; cyclopentane-1, 1-diyl; cyclopentane-l, 2-diyl; and cyclopentane-1,3-diyl,
- aryl selected from aromatics having a molecular weight below 300Da.
- arylenes selected from the group comprising: 1, 2-phenylenes; 1,3-phenylenes; 1, 4-phenylene; 1,2-naphthalenylenes; 1, 3-naphthalenylenes; 1, 4-naphthalenylenes; 2,3-naphtalenylene; 1-hydroxy-2,3-phenylene; 1-hydroxy-2,4-phenylene; 1-hydroxy-2,5-phenylene; and 1-hydroxy-2,6-phenylene, heteroaryl: selected from the group comprising: pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl; 1,3,5-triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; oxazolidinyl; pyrrolyl; thiophenyl; carbazolyl; indolyl; and iso
- heteroarylenes selected from the group comprising: pyridinediyl; quinolindiyl; pyrazodiyl; pyrazoldiyl; triazolediyl; pyrazinediyl, thiophenediyl; and imidazolediyl, wherein the heteroarylene acts as a bridge in the compound via any atom in the ring of the selected heteroaryl, especially preferred are: pyridine-2,3-diyl; pyridin-2,4-diyl; pyridin-2,5-diyl; pyridine-2,6-diyl; pyridine-3,4-diyl; pyridine-3,5-diyl; quinolin-2,3-diyl; quinolin-2,4-diyl; quinoline-2, 8-diyl; isoquinoline-1, 3-diyl; isoquinoline-l, 4-diyl; pyrazole-1, 3-di
- heterocycloalkylenes selected from the group comprising: piperidin-1,2-ylenes; piperidin-2,6-ylene; piperidin-4,4-ylidene; l, 4-piperazine-1,4-ylene; 1,4-piperazine-2,3-ylene; 1, 4-piperazine-2,5-ylene; 1, 4-piperazine-2,6-ylene; 1, 4-piperazine-1,2-ylene; l, 4-piperazine-l, 3-ylene; 1, 4-piperazine-1, 4-ylene; tetrahydrothiophen-2,5-ylene; tetrahydrothiophen-3,4-ylene; tetrahydrothiophen-2,3-ylene; tetrahydrofuran-2,5-ylene; tetrahydrofuran-3,4-ylene; tetrahydrofuran-2,3-ylene; pyrrolidine-2,5-ylene; pyrrolidin-3,4-ylene; pyrrolidin
- heterocycloalkyl selected from the group comprising: pyrrolinyl; pyrrolidinyl; morpholinyl; piperidinyl; piperazinyl; hexamethylene imine; 1, 4-piperazinyl; tetrahydrothiophenyl; tetrahydrofuranyl; 1,4,7-triazacyclononanyl; 1, 4,8,1-tetraazacyclotetradecanyl; 1,4,7,10,13-pentaazacyclopentadecanyl; l, 4-diaza-7-thiacyclononanyl; 1,4-diaza-7-oxa-cyclononanyl; 1, 4,7,10-tetraazacyclododecanyl; 1,4-dioxanyl; 1,4,7-trithiacyclononanyl; tetrahydropyranyl; and oxazolidinyl, wherein the heterocycloalkyl may be linked to the compound via any atom in the
- halogen selected from the group comprising: F; Cl; Br and I,
- haloalkyl selected from the group consisting of mono, di, tri, poly and perhalogenated linear and branched C 1 -C 8 -alkyl
- pseudohalogen selected from the group consisting of -CN, -SCN, -OCN, N3, -CNO, -SeCN
- alkyl linear and branched C 1 -C 6 -alkyl
- long-chain alkyls linear and branched C5-C10 alkyl, preferably C6-C8 alkyl
- alkenyl C3-C6 alkenyl
- cycloalkyl C6-C8-cycloalkyl
- alkoxy Cl-C4-alkoxy
- long-chain alkoxy linear and branched C5-C10 alkoxy, preferably linear C6-C8 alkoxy
- Alkylene selected from the group comprising: methylenes; 1,2-ethylene; 1, 3-propylene; butan-2-ol-1,4-diyl; 1, 4-butylenes; cyclohexane-l, l-diyl; cyclohexane-l, 2-diyl; cyclohexane-1,4-diyl; cyclopentane-1, 1-diyl; and cyclopentane-1,2-diyl,
- Aryl selected from the group comprising: phenyl; biphenyl; naphthalenyl; anthracenyl; and phenanthrenyl,
- Arylene selected from the group comprising: 1, 2-phenylene; 1, 3-phenylene; 1, 4-phenylene; 1,2-naphthalenylenes; 1,4-naphthalenylene; 2,3-naphthalenylenes and 1-hydroxy-2,6-phenylenes,
- Heteroarylene thiophene, pyrrole, pyridine, pyridazine, pyrimidine, indole, thienothiophene
- Halogen selected from the group comprising: Br and Cl, more preferably Br
- the at least one thiophene derivative contains at least one compound of the general formula:
- R is selected from the group consisting of hydrogen, hydroxyl, halogen, pseudohalogen, formyl, carboxy and / or carbonyl derivatives, alkyl, long-chain alkyl, alkoxy, long-chain alkoxy, cycloalkyl, haloalkyl, aryl, arylenes, haloaryl, heteroaryl, heteroarylenes, Heterocycloalkylenes, heterocycloalkyl, halo-heteroaryl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, keto, ketoaryl, halo-ketoaryl, ketoheteroaryl, ketoalkyl, halo-ketoalkyl, ketoalkenyl, halo-ketoalkenyl, phosphoalkyl, phosphonates, phosphates, phosphine, phosphine oxide, phosphoryl, phosphoaryl, sulphonyl,
- X and X 'independently of one another are a leaving group, preferably halogen, particularly preferably Cl, Br or I and particularly preferably Br.
- the mixture of the thiophene derivative and the at least one catalyst and / or the metal or the organometallic compound contain a solvent.
- Suitable solvents include aliphatic hydrocarbons such as alkanes, especially pentane, hexane, cyclohexane or heptane, unsubstituted or substituted aromatic hydrocarbons such as benzene, toluene and xylenes, and compounds containing ether groups such as diethyl ether, tert-butyl methyl ether, dibutyl ether, amyl ether , Dioxane and tetrahydrofuran (THF) and solvent mixtures of the aforementioned groups, such as a mixture of THF and toluene.
- aliphatic hydrocarbons such as alkanes, especially pentane, hexane, cyclohexane or heptane, unsubstituted or substituted aromatic hydrocarbons
- Solvents containing ether groups are preferably used in the process according to the invention. Very particular preference is tetrahydrofuran. However, it is also possible and preferred for many embodiments of the present invention to use as solvent mixtures of two or more of these solvents. For example, mixtures of the solvent preferably used tetrahydrofuran and alkanes, for example hexane (eg, contained in commercially available solutions of starting materials such as organometallic compounds) can be used. It is important in the context of the invention that the solvent, the solvents or mixtures thereof are chosen such that the thiophene derivatives used or the polymerization-active monomers are present in dissolved form before the addition of the catalyst. Also suitable for the workup are halogenated aliphatic hydrocarbons such as methylene chloride and chloroform.
- a hydrolyzing solvent is added to the polymerization solution to terminate the reaction ("quenching"), preferably an alkyl alcohol, more preferably ethanol or methanol, most preferably methanol.
- the workup is preferably carried out so that the precipitated product is filtered off, washed with the precipitant and then taken up in a solvent.
- purification in the soxhlet can be carried out, preferably using nonpolar solvents, such as e.g. Hexane can be used as extractant.
- nonpolar solvents such as e.g. Hexane
- the process is used for the preparation of copolymers and / or block polymers.
- the mixture of the thiophene derivative and the at least one catalyst and / or the metal or the organometallic compound is first reacted according to a preferred embodiment of the invention, then carried out a metered addition of at least one further solution consisting of polymerization-active thiophene monomer and / or two solutions consisting of a) at least one thiophene monomer having two leaving groups and b) a metal or an organometallic compound for the purpose of chain extension based on the same thiophene derivative and / or at least one other thiophene derivative to produce block copolymers or copolymers.
- the method is carried out batchwise.
- the method is carried out continuously.
- a preferred embodiment of the process according to the invention for the continuous preparation of the polythiophenes succeeds in that in situ the polymerization-active monomers by mixing an organometallic reagent with the at least one thiophene derivative having two leaving groups or by reacting the thiophene derivative with two leaving groups with metal on one Column as described in DE 10304006 B3 or Reimschüssel, Journal of Organic Chemistry, 1960, 25, 2256-7, in a corresponding cartridge or in a static-equipped tubular reactor as described in DD260276, DD260277 and DD260278 in the presence of the polymerization-active catalyst in one polymerized first module.
- a second module at least once more - same or at least one different - monomer is added.
- the delivery of two metered streams, one for the solution consisting of the thiophene derivative with two leaving groups and a solution consisting of the organometallic compound is carried out.
- the educt streams are rapidly mixed by a mixer. After thorough mixing and polymerization in one module, it is preferable to replenish and polymerize in a further module at least once more - the same or at least one different monomer.
- Continuous reaction control is particularly advantageous in many embodiments of the present invention because it often allows for higher space-time yields compared to the prior art batchwise reaction regime and results in defined narrow molecular weight distribution poly- and oligothiophenes.
- Continuous reaction control is particularly advantageous in many embodiments of the present invention because it often allows for higher space-time yields compared to the prior art batchwise reaction regime and results in defined narrow molecular weight distribution poly- and oligothiophenes.
- inexpensive well-defined poly- and oligothiophenes are often accessible.
- the erf ⁇ ndungswashe process is used for the production of poly- and oligothiophenes. Preference is given to the preparation of degrees of polymerization or number of repeating units n in the chain of> 2 to ⁇ 5000, in particular from> 5 to ⁇ 2500, more preferably from> 100 to ⁇ 1000.
- the molecular weight is dependent on the molecular weight of the monomeric thiophene derivative from> 1000 to ⁇ 300,000, preferably from> 2000 to ⁇ 100,000, particularly preferably from> 5,000 to ⁇ 80,000, particularly preferably from> 10,000 to ⁇ 60,000.
- oligothiophenes preference is given to the preparation of chain lengths with n> 2 to ⁇ 20 monomer units, preferably from> 3 to ⁇ 10, particularly preferably from> 4 to ⁇ 8.
- a narrow molecular weight distribution with a polydispersity index PDI of> 1 to ⁇ 3, preferably PDI ⁇ 2, more preferably PDI> 1.1 to ⁇ 1.7.
- the present process is characterized in particular by the fact that in many applications, the average molecular weight or the average chain length can be set technically much easier and precisely defined by the amount of the catalyst by the single-stage implementation of thiophene derivative, catalyst and alkylmagnesium bromide.
- the present process is characterized in that the continuous conduct of the reaction leads to higher space-time yields than comparable prior art batch polymerizations.
- the poly- and oligomers prepared according to the method are also distinguished by the presence of one or two leaving groups at the chain end, which in the further course can serve as substitution sites for functionalizations or end-capping reactions.
- the thiophene derivative having only one leaving group has a further functionalizable radical, preferably in the 5-position, which is preferably selected from the group phosphoalkyl, phosphonates, phosphates, phosphine, Phosphine oxide, phosphoryl, phosphoaryl, sulphonyl, sulphoalkyl, sulphoarenyl, sulphonates, sulphates, sulphones or Mixtures thereof.
- a further functionalizable radical preferably in the 5-position, which is preferably selected from the group phosphoalkyl, phosphonates, phosphates, phosphine, Phosphine oxide, phosphoryl, phosphoaryl, sulphonyl, sulphoalkyl, sulphoarenyl, sulphonates, sulphates, sulphones or Mixtures thereof.
- suitable temperatures generally in the range of> +20 to ⁇ +200 0 C, preferably in the range of> +80 to ⁇ +160 0 C and especially at> +100 to ⁇ +140 ° C. Due to the low boiling temperatures of the solvents used, the reaction takes place at elevated pressures, preferably at> 1-30 bar, in particular at> 2-15 bar and more preferably in the range of> 4-10 bar.
- the metering rates depend primarily on the desired residence times or sales to be achieved.
- Typical residence times are in the range of> 5 min to ⁇ 120 min.
- the residence time is preferably between> 10 and ⁇ 40 min, preferably in the range of> 20- ⁇ 40 min.
- the reaction solutions are mixed together very quickly, whereby a broadening of the molecular weight distribution due to possible radial concentration gradients is avoided.
- the microreaction technique ( ⁇ -reaction technique) in a microreactor ( ⁇ -reactor) allows a usually much narrower residence time distribution than in conventional continuously guided apparatus, which also prevents broadening of the molecular weight distribution.
- the process according to the invention is carried out continuously using ⁇ -reaction apparatuses.
- the inventive method is characterized in particular in many applications by the possibility of targeted adjustment of a desired average chain length as well as the production of products with a narrow molecular weight distribution.
- a continuous conduct of the polymerization in many applications allows a significant increase in the space-time yield.
- the use according to the invention of a two-stage metering strategy for the polymerization of the organometallic thiophene derivative allows in many applications to significantly reduce the necessary amounts of the catalyst in terms of the desired average chain length or molecular weights or to significantly increase the average molecular weights for a given amount of catalyst humiliate.
- the invention also relates to the oligothiophenes obtainable by the process according to the invention.
- Example 1 shows the molecular weight distribution of a polythiophene according to Example 1 of the present invention
- Figures 1 to 3 relate to a polythiophene, which was prepared according to Example 1 of the present invention.
- Example 1 is to be understood as illustrative only and not as a limitation of the present invention, which is defined purely by the claims.
- Example 1 Preparation of poly-3-hexylthiophene:
- 2,5-Dibromo-3-hexylthiophene 90 ml of THF and nickel catalyst were initially introduced into the reaction flask under inert gas conditions and then the EtMgBr in hexane was added under Schlenk technique. The mixture is stirred for about 4 h at 5O 0 C.
- Fig. 1 shows the molecular weight distribution after Soxleth extraction in a GPC spectrum. It can be seen clearly a narrow molecular weight distribution with the peak at about 18500 Da (measured against polystyrene standards, THF as eluent).
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Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA 2692673 CA2692673A1 (en) | 2007-07-09 | 2008-06-26 | Process for the synthesis of oligo/polythiophenes by a "one-pot" synthesis route |
CN200880023744A CN101687982A (zh) | 2007-07-09 | 2008-06-26 | 通过“单釜”合成路线合成低聚/聚噻吩的方法 |
EP08773670A EP2167565A1 (de) | 2007-07-09 | 2008-06-26 | Verfahren zur synthese von oligo/polythiophenen nach einem "eintopf"-syntheseweg |
US12/602,660 US20100179301A1 (en) | 2007-07-09 | 2008-06-26 | Process for synthesizing oligo/polythiophenes by a "one-pot" synthesis route |
JP2010515371A JP2010532797A (ja) | 2007-07-09 | 2008-06-26 | 「ワンポット」合成法によるオリゴ/ポリチオフェンの合成方法 |
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DE102007031992 | 2007-07-09 | ||
DE102007031992.6 | 2007-07-09 | ||
DE102007033343A DE102007033343A1 (de) | 2007-07-09 | 2007-07-16 | Verfahren zur Synthese von Oligo/Polythiophenen nach einem "Eintopf"-Syntheseweg |
DE102007033343.0 | 2007-07-16 |
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PCT/EP2008/005182 WO2009007012A1 (de) | 2007-07-09 | 2008-06-26 | Verfahren zur synthese von oligo/polythiophenen nach einem 'eintopf'-syntheseweg |
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US (1) | US20100179301A1 (de) |
EP (1) | EP2167565A1 (de) |
JP (1) | JP2010532797A (de) |
KR (1) | KR20100032889A (de) |
CN (1) | CN101687982A (de) |
CA (1) | CA2692673A1 (de) |
DE (1) | DE102007033343A1 (de) |
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WO (1) | WO2009007012A1 (de) |
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WO2013010209A1 (en) * | 2011-07-15 | 2013-01-24 | The University Of Melbourne | Process for the synthesis of conjugated polymers |
US9859062B2 (en) | 2012-10-28 | 2018-01-02 | Polym Technology Corporation | Composition and method for forming electroactive polymer solution or coating comprising conjugated heteroaromatic polymer, electroactive polymer solution, capacitor and antistatic object comprising the electroactive coating, and solid electrolytic capacitor and method for fabricating the same |
US9627147B2 (en) | 2012-10-28 | 2017-04-18 | Polym Technology Corporation | Composition and method for forming electroactive coating comprising conjugated heteroaromatic polymer, capacitor and antistatic object comprising the electroactive coating, and solid electrolytic capacitor and method for fabricating the same |
US9790330B2 (en) | 2012-10-28 | 2017-10-17 | Polym Technology Corporation | Method for forming conjugated heteroaromatic homopolymer and copolymer, and products thereof |
US10519328B2 (en) | 2012-10-28 | 2019-12-31 | Polym Technology Corporation | Composition and method for forming electroactive polymer solution or coating comprising conjugated heteroaromatic polymer, electroactive polymer solution, objects comprising the electroactive coating, and solid electrolytic capacitor and method for fabricating the same |
EP3083491A1 (de) * | 2013-12-16 | 2016-10-26 | Council of Scientific and Industrial Research | Funktionalisierte zinkoxid-nanopartikel zur fotokatalytischen wasserspaltung |
US11690283B2 (en) | 2021-11-19 | 2023-06-27 | Phillips 66 Company | Fused dithieno benzothiadiazole polymers for organic photovoltaics |
US11332579B1 (en) | 2021-11-19 | 2022-05-17 | Phillips 66 Company | Fused dithieno benzothiadiazole polymers for organic photovoltaics |
US11849629B2 (en) | 2021-11-19 | 2023-12-19 | Phillips 66 Company | Fused dithieno benzothiadiazole polymers for organic photovolatics |
US11326019B1 (en) | 2021-11-19 | 2022-05-10 | Phillips 66 Company | Fused dithieno benzothiadiazole polymers for organic photovoltaics |
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JPS5647421A (en) * | 1979-09-28 | 1981-04-30 | Tokyo Inst Of Technol | Linear poly 2,5-thienylene polymer, its preparation, and semiconductor comprising it |
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EP0633614A1 (de) * | 1993-07-08 | 1995-01-11 | Rijksuniversiteit te Groningen | Abstimmbare lichtemittierende Diode auf Polymerbasis |
EP1520846A1 (de) * | 2003-09-30 | 2005-04-06 | JFE Chemical Corporation | Verfahren zur Herstellung polymerisierter Kohlenwasserstoffe |
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JPS5939447B2 (ja) * | 1982-02-26 | 1984-09-22 | 東京工業大学長 | 線状ポリ(3−アルキル2、5−チエニレン)重合体およびその製造方法 |
DD260277A1 (de) | 1987-04-29 | 1988-09-21 | Bitterfeld Chemie | Verfahren zur kontinuierlichen herstellung von alkylmagnesiumhalogeniden |
DD260278A1 (de) | 1987-04-29 | 1988-09-21 | Bitterfeld Chemie | Verfahren zur kontinuierlichen herstellung von cycloalkyl- oder arylmagnesiumhalogeniden |
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DE19904836C1 (de) | 1999-02-06 | 2000-08-31 | Krupp Uhde Gmbh | Verfahren zur Herstellung von 1,2-Dichlorethan |
US6166172A (en) | 1999-02-10 | 2000-12-26 | Carnegie Mellon University | Method of forming poly-(3-substituted) thiophenes |
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DE102006061966A1 (de) * | 2006-12-21 | 2008-06-26 | Bayer Technology Services Gmbh | Verfahren zur Darstellung von Thiophenen |
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2007
- 2007-07-16 DE DE102007033343A patent/DE102007033343A1/de not_active Withdrawn
-
2008
- 2008-06-26 JP JP2010515371A patent/JP2010532797A/ja active Pending
- 2008-06-26 WO PCT/EP2008/005182 patent/WO2009007012A1/de active Application Filing
- 2008-06-26 US US12/602,660 patent/US20100179301A1/en not_active Abandoned
- 2008-06-26 CA CA 2692673 patent/CA2692673A1/en not_active Abandoned
- 2008-06-26 EP EP08773670A patent/EP2167565A1/de not_active Withdrawn
- 2008-06-26 KR KR1020107000453A patent/KR20100032889A/ko not_active Application Discontinuation
- 2008-06-26 CN CN200880023744A patent/CN101687982A/zh active Pending
- 2008-07-08 TW TW097125631A patent/TW200918573A/zh unknown
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EP1520846A1 (de) * | 2003-09-30 | 2005-04-06 | JFE Chemical Corporation | Verfahren zur Herstellung polymerisierter Kohlenwasserstoffe |
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Also Published As
Publication number | Publication date |
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KR20100032889A (ko) | 2010-03-26 |
JP2010532797A (ja) | 2010-10-14 |
US20100179301A1 (en) | 2010-07-15 |
EP2167565A1 (de) | 2010-03-31 |
CN101687982A (zh) | 2010-03-31 |
TW200918573A (en) | 2009-05-01 |
CA2692673A1 (en) | 2009-01-15 |
DE102007033343A1 (de) | 2009-01-15 |
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