CN102918033B - 衍生自甘油单元的芳族单体,制备它们的方法以及它们用于制备水溶性共轭聚合物的用途 - Google Patents
衍生自甘油单元的芳族单体,制备它们的方法以及它们用于制备水溶性共轭聚合物的用途 Download PDFInfo
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- CN102918033B CN102918033B CN201180021941.8A CN201180021941A CN102918033B CN 102918033 B CN102918033 B CN 102918033B CN 201180021941 A CN201180021941 A CN 201180021941A CN 102918033 B CN102918033 B CN 102918033B
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- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000000178 monomer Substances 0.000 title claims abstract description 21
- 229920000547 conjugated polymer Polymers 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title claims description 4
- 125000003118 aryl group Chemical group 0.000 title description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title description 6
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 20
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 19
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 11
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 9
- 238000006266 etherification reaction Methods 0.000 claims abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 3
- -1 2-ethylhexyl Chemical group 0.000 claims description 51
- 238000006243 chemical reaction Methods 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 150000001875 compounds Chemical class 0.000 claims description 24
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 8
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 150000003254 radicals Chemical group 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- 238000006482 condensation reaction Methods 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- 238000007099 Yamamoto allylation reaction Methods 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 229950000688 phenothiazine Drugs 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 4
- 229930192474 thiophene Natural products 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- 238000006619 Stille reaction Methods 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- 238000007341 Heck reaction Methods 0.000 claims description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- VJYJJHQEVLEOFL-UHFFFAOYSA-N thieno[3,2-b]thiophene Chemical compound S1C=CC2=C1C=CS2 VJYJJHQEVLEOFL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 150000002314 glycerols Chemical class 0.000 abstract description 3
- HSDAJNMJOMSNEV-UHFFFAOYSA-N benzyl chloroformate Chemical compound ClC(=O)OCC1=CC=CC=C1 HSDAJNMJOMSNEV-UHFFFAOYSA-N 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 17
- 239000002904 solvent Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 238000004821 distillation Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 239000012074 organic phase Substances 0.000 description 11
- 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 description 9
- 239000000047 product Substances 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 7
- 238000010828 elution Methods 0.000 description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 description 7
- 235000011152 sodium sulphate Nutrition 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 6
- 238000004770 highest occupied molecular orbital Methods 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000002940 palladium Chemical class 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- KYLUAQBYONVMCP-UHFFFAOYSA-N (2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P KYLUAQBYONVMCP-UHFFFAOYSA-N 0.000 description 3
- VEFLKXRACNJHOV-UHFFFAOYSA-N 1,3-dibromopropane Chemical compound BrCCCBr VEFLKXRACNJHOV-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- LVENUGJGJBXIGS-UHFFFAOYSA-N 2,7-dibromo-9,9-bis(3-bromopropyl)fluorene Chemical compound C1=C(Br)C=C2C(CCCBr)(CCCBr)C3=CC(Br)=CC=C3C2=C1 LVENUGJGJBXIGS-UHFFFAOYSA-N 0.000 description 3
- ZVWBNQIFWBNRRV-UHFFFAOYSA-N 3,6-dibromo-9-(3-bromopropyl)carbazole Chemical compound BrC1=CC=C2N(CCCBr)C3=CC=C(Br)C=C3C2=C1 ZVWBNQIFWBNRRV-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QWOJMRHUQHTCJG-UHFFFAOYSA-N CC([CH2-])=O Chemical compound CC([CH2-])=O QWOJMRHUQHTCJG-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000001246 bromo group Chemical group Br* 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 238000013087 polymer photovoltaic Methods 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- PDQRQJVPEFGVRK-UHFFFAOYSA-N 2,1,3-benzothiadiazole Chemical compound C1=CC=CC2=NSN=C21 PDQRQJVPEFGVRK-UHFFFAOYSA-N 0.000 description 2
- FULQGNHFNHTPIU-UHFFFAOYSA-N 2,5-dibromo-3-(bromomethyl)thiophene Chemical compound BrCC=1C=C(Br)SC=1Br FULQGNHFNHTPIU-UHFFFAOYSA-N 0.000 description 2
- IHFXZROPBCBLLG-UHFFFAOYSA-N 2,5-dibromo-3-methylthiophene Chemical compound CC=1C=C(Br)SC=1Br IHFXZROPBCBLLG-UHFFFAOYSA-N 0.000 description 2
- XQQBUAPQHNYYRS-UHFFFAOYSA-N 2-methylthiophene Chemical compound CC1=CC=CS1 XQQBUAPQHNYYRS-UHFFFAOYSA-N 0.000 description 2
- FIHILUSWISKVSR-UHFFFAOYSA-N 3,6-dibromo-9h-carbazole Chemical compound C1=C(Br)C=C2C3=CC(Br)=CC=C3NC2=C1 FIHILUSWISKVSR-UHFFFAOYSA-N 0.000 description 2
- OQTXENMKMAORGK-UHFFFAOYSA-N 3-(bromomethyl)-2,5-dimethylthiophene Chemical compound CC1=CC(CBr)=C(C)S1 OQTXENMKMAORGK-UHFFFAOYSA-N 0.000 description 2
- SODVBWGBCSYZGR-UHFFFAOYSA-N 4-[(2,5-dibromothiophen-3-yl)methoxymethyl]-2,2-dimethyl-1,3-dioxolane Chemical compound O1C(C)(C)OCC1COCC1=C(Br)SC(Br)=C1 SODVBWGBCSYZGR-UHFFFAOYSA-N 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- 150000002009 diols Chemical group 0.000 description 2
- 125000005879 dioxolanyl group Chemical group 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 230000026030 halogenation Effects 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
- 238000003306 harvesting Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 238000013086 organic photovoltaic Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 1
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Abstract
具有通式(I)的单体和用于合成它们的方法,该方法包括根据下列方案的具有通式(Ш)的卤素衍生物(Z=Cl,Br,I)与甘油衍生物(Ⅳ)的羟基的醚化反应:(通式Ш,Ⅳ和I)(Ш)(Ⅳ)(I)。
Description
技术领域
本发明涉及衍生自甘油单元的芳族单体和制备它们的方法以及它们用于制备在水或含水混合物中可溶解的共轭聚合物/共聚物的用途。
背景技术
已知光伏器件是能够将光辐射能量转换为电能的器件。目前,可用于实际应用的大多数光伏器件开发的是无机类型光活性材料的物理化学性能,特别是高纯晶体硅。然而由于硅的高生产成本,科学研究长期以来致力于替代的有机材料的研发,该有机材料具有共轭的、低聚物或聚合物结构。与高纯晶体硅不同,事实上,除了允许在其中使用所述聚合物的器件的生命周期结束时将其回收外,共轭有机材料的特征在于相对合成容易、调整物理化学性能的可能性、低生产成本、相对光伏器件的减少的重量。
有机和聚合物光伏电池的功能基于电子受体化合物和电子给体化合物的结合使用。在技术现状中,在科学和专利文献中指出的器件中最广泛使用的电子给体和受体化合物是π-共轭共聚物,特别是分别属于聚对-亚苯基-亚乙烯基和聚噻吩类和富勒烯衍生物的那些。
在聚合物光伏电池中光成为电流的基本转换方法通过以下步骤发生:
1:给体化合物局部吸收光子从而形成激发子,即:一对“电子空穴”电荷传输体;
2.激发子在其解离可发生的给体化合物区域内扩散;
3.激发子在分离的两个电荷传输体(电子(-)和空穴(+))中解离;
4.将由此形成的电荷传输到阴极(电子,通过受体化合物)和阳极(电子空穴,通过给体化合物)从而在器件的电路中产生电流。
形成激发子和随后的对受体化合物产生电子的光吸收方法导致将来自给体的HOMO(最高占有分子轨道)的电子传输到LUMO(最低占有分子轨道)以及之后自此传输到受体的LUMO。
由于有机或聚合物光伏电池的效率取决于由激发子解离产生的自由电子的数目,因此最影响所述效率的给体化合物结构特征之一是给体化合物的HOMO和LUMO轨道之间存在能量差异(所谓的带隙)。给体化合物能够收集和有效地转换为电能(所谓的“光子收获”或“光收获”方法)的光子波长尤其取决于这种差异。
电池的效率也与在器件中可获得的电压成正比。已经证明电压与给体的HOMO和受体化合物的LUMO之间的能量差异相关。因此显然也在这种情况下,所选材料的能级具有根本的重要性。
另一重要特征是受体化合物中电子的移动性和给体化合物中的电子间隙,这决定了一旦光生成,电荷到达电极的容易程度。除了是分子固有特征外,光活性层形态对此影响也很大,而光活性层形态进而取决于组分的相互混溶性和它们的溶解度。最后,另一基本特征是材料的抗热氧化和光氧化降解性,该材料在器件的操作条件下必须是稳定的。
为了获得可接受的电流,HOMO和LUMO之间的带隙不能过高,但是同时不能过低,因为过低的间隙将会危害在器件的电极处可获得的电压。
在最简单的操作方法中,通过在两个电极之间引入受体化合物和给体化合物的混合物薄层(约100nm)而生产电池。为了生产这种类型的层,制备该两种组分的溶液。从溶液开始,采取适宜的沉积方法例如“旋转涂覆”、“喷涂”、“喷墨打印”等随后在第一电极上产生光活性膜。最后在干燥的膜上沉积对电极。
给体材料由共轭芳族聚合物组成。在聚合物太阳能电池的构建中最经常使用的那些中的一种是区域规则(regioregular)聚(3-己基噻吩)。这种聚合物具有适宜的电学和光学特征(HOMO和LUMO轨道值;吸收系数),在用于构建电池的有机溶剂中良好的溶解度和电子间隙的合理的移动性。
用于生产聚合物电池的当前技术采取自溶液的薄光活性层的沉积方法,加上用于生产电极(或同样的光活性层,假设电池基于低分子量的有机分子)的高真空方法。自聚合物溶液的沉积采取滴铸、旋转涂覆、浸涂、喷涂、喷墨打印、丝网印刷、卷对卷式沉积方法等,并且使用适宜的溶剂。给体聚合物通常溶解在有机溶剂例如甲苯、二甲苯、三氯甲烷、氯代苯等中以保证完全的溶解。然而这些溶剂是剧毒的,因此在工业过程中希望消除它们。使用在含水溶剂、醇类溶剂或在水-醇混合物或水/丙酮、水/二噁烷、水/四氢呋喃混合物等中可溶解的聚合物将是非常有益的。除了毒性外,由于在空气和有机溶剂的蒸气或精细分开的有机溶剂滴之间形成爆炸性混合物导致潜在发生爆炸的危险在这种方式中也显著地降低。
然而,由于所使用的聚合物的化学结构,这些在水中或含水混合物中的溶解度实际上为零。
申请人现已发现一组新型的官能化芳族单体,其可产生在水中或含水混合物中可溶解的共轭聚合物/共聚物。
发明内容
因此,本发明的目的涉及具有下列一般结构(I)的单体:
其中,
-Ar是C6-C12芳族基,C12-C18多环芳族基,或Ar是包含一个或多个杂原子例如S、N、Se、O的杂芳族基,任选为缩聚的,
-X是通过选自Suzuki、Stille、Heck或Yamamoto反应的反应方法可聚合的基团,选自-Br、-Cl、-I、-O-(SO2)-CF3、-B(OH)2、-B(OR')2、-SnR'3、-B(OR"O)和乙烯基,R'为C1-C6烷基和R"为亚乙基,任选用C1-C2烷基取代;
-R1和R2,彼此相同或不同,可为氢原子或C1-C6烷基;
-R为二价C1-C12,优选C1-C6亚烷基;
-n为1-4,且优选1或2。
根据本发明的优选单体是其中Ar是衍生自苯、芴、噻吩、咔唑、二噻吩并环戊二烯或吩噻嗪的基团的那些。
具有下列一般结构(П)的单体表示本发明的另一目的:
其中,R、R1、R2、Ar、X、n具有如上所示的相同意思;和
-Ar'表示包含杂原子例如S、N、Se的杂芳族基;
-m=1或2,m优选为1。
根据本发明的优选单体是其中Ar'是衍生自噻吩、噻吩并-噻吩、噻唑、咔唑、二噻吩并环戊二烯或吩噻嗪的基团的那些。
通过常规的化学合成方法可制备具有通式(I)和(П)的单体。(I)的合成,例如,通过根据下列方案1的具有通式(Ш)的卤素衍生物(Z=Cl、Br、I,优选溴)与甘油衍生物(Ⅳ)的羟基的醚化反应(Williamson反应)而发生:
在文献中已知这种类型的反应,例如在美国专利3,960,902中有描述。
这些反应通常在碱例如碱金属(钠、钾、铯、优选叔丁醇钾)醇盐(甲醇盐、乙醇盐、丁醇盐、叔醇盐)存在时发生。在选自醚(例如四氢呋喃、二甲氧基乙烷等)、烃(苯、甲苯、二甲苯等)、偶极非质子溶剂(N-二甲基甲酰胺、N-甲基吡咯烷酮等)的有机溶剂中进行该反应。使用的Ш:Ⅳ:碱的摩尔比范围为1:1.1:1.15-1:3:3.3。在15℃-150℃,优选20℃-80℃的温度范围进行该反应。该反应也可在相转移条件下进行。
通过常规的有机合成方法合成卤素衍生物(Ш),例如根据下列方案2包含酸式氢(通过碱处理可轻易除去)的芳族体系(Ⅴ)用二卤素衍生物(Ⅵ)(Z=Cl,Br,I)的烷基化。
在本领域已知卤素衍生物(Ш)的合成,存在于文献中的一些实例为:Macromol.Rapid Commun.2008,29,390;JACS 2003,125,6705;Synthetic Metals 2007,157,813;Journal Polymer Science:Part A:Polymer Chemistry 2008,46,4407。
通过使用常规的合成方法制备甘油衍生物(Ⅳ),通过甘油(Ⅶ)与包含羰基官能团(Ⅷ)的衍生物的酸催化反应,R1和R2具有之前在通式(I)中定义的含义。方案3描述了该反应:
在本领域中已知这些化合物的合成,在Synthesis 1981,501中全面地描述了该反应。
从具有通式(I)的化合物开始,通过金属辅助缩合反应和得到的衍生物的随后卤化制备具有通式(П)的化合物。通式(I)的化合物与具有通式(Ⅸ)(W=-SnR'3、-B(OH)2、-B(OR)2)的芳族化合物反应以得到缩合产物,该缩合产物具有通式X,如在下列方案4中所描述:
文献中存在这些缩合反应的各种实例(Chem.Mater.2006,18,3151-3161;Chem.Eur.Journal 2009,15,4906)。Suzuki反应(W=-B(OH)2、-B(OR)2)和Stille反应(W=-SnR'3)通过钯络合物(例如Pd(PPh3)4、PdCl2(PPh3)2)催化,也可从PdCl2或Pd(OAc)2和合适的膦(例如三苯基膦PPh3、三-邻-甲苯基膦、三-对-甲苯基膦)开始在原位制备该催化剂。反应物之间的摩尔比(I):(Ⅸ)范围为1:2-1:4。使用的催化剂摩尔比范围为(I):催化剂为1:0.008-1:0.02。
反应可在醚溶剂(例如二甲氧基乙烷、四氢呋喃)、偶极非质子溶剂(例如N,N-二甲基甲酰胺、N-甲基吡咯烷酮)或烃溶剂例如甲苯、二甲苯等中进行。在Suzuki反应的情况下,当W=-B(OH)2、-B(OR)2时,碱(例如碳酸氢钠或碳酸氢钾、碳酸钠或碳酸钾)的存在是必须的,使用的摩尔比范围I:碱为1:1-1:20。碱通常溶解于脱气水中。含水溶液可具有1M-3M,优选2M的浓度范围。在10-200℃,优选30-150℃的温度范围进行该反应。在反应结束时,将缩合产物(X)分离并且通过在中性氧化铝的色谱柱上洗脱而纯化。
随后通过芳族体系的常规卤化方法将由此获得的产物X卤化,如在方案5中所述:
通常使用的反应物是溴(Synth.Met.2010,160-354);N-卤代丁二酰亚胺例如N-溴丁二酰亚胺、N-碘丁二酰亚胺(Chem.Mater.2006,18,3151-3161;Tele 2010,51,205)。在反应结束时,将产物分离并且通过在中性氧化铝的色谱柱上洗脱而纯化。
作为本发明的目的,用于获得共轭水溶性聚合物/共聚物的方法提供了至少一种化合物(I)或(П)的与选自以下描述的那些的一种或多种共聚单体的反应:
其中,
-R3-R10,彼此相同或不同,为氢原子;C1-C37烷基,可能支化的,例如,比如甲基、乙基、丙基、丁基、己基、辛基、癸基、十二烷基、十四烷基、十六烷基、十八烷基、二十烷基、2-乙基己基、2-乙基辛基、2-乙基癸基、2-乙基十二烷基、4-丁基己基、4-丁基辛基、4-丁基癸基、4-丁基十二烷基、2-己基辛基、2-己基癸基、4-己基癸基、异丙基、1-乙基丙基、1-丁基戊基、1-己基庚基、1-辛基壬基、1-十二烷基十三烷基、1-十六烷基十七烷基、1-十八烷基十九烷基;如果该基与碳原子连接,R3-R10可以为-OC1-OC16烷氧基。
-Y是通过选自Suzuki、Stille、Heck或Yamamoto的这些反应的方法的可聚合的基团,选自-Br、-Cl、-I、-O-(SO2)-CF3、-B(OH)2、-B(OR')2、-SnR'3、-B(OR"O)、乙烯基,R'为C1-C6烷基和R"为亚乙基,任选用C1-C2烷基取代。
通过采取由过渡金属衍生物催化的缩合反应发生该聚合反应,该过渡金属在Suzuki、Stille和Heck反应的情况下可为钯,或在Yamamoto反应的情况下可为镍。
本领域技术人员已知Suzuki、Stille、Heck和Yamamoto反应并且描述于Chem.Rev.,1995,95,2457;J.Am.Chem.Soc.,1995,117,12426;J.Poly.Sci.,Polym.Lett.Ed.,1980.18,9;Makromol.Chem.,1988,189,119中。
Suzuki聚合以其最通用的形式提供了具有硼官能(酸或酯)的单体和携带卤素例如溴或碘或三氟甲磺酸根的单体之间的反应。可在均相溶液(溶剂选自,例如四氢呋喃、二噁烷、二甲基甲酰胺、甲苯等)中或在有机溶剂与水的混合物中进行该反应。在该第二种情况下,通常使用相转移试剂,例如四-烷基铵盐。
反应在碱例如碳酸钠、碳酸氢钠、四-烷基氢氧化铵、氟化铯存在下发生,并且该反应通过钯配位络合物,例如四-(三苯基膦)钯、四(邻-甲苯基膦)钯催化,从钯盐例如乙酸钯或氯化钯和膦开始也可在原位获得该钯配位络合物。
Stille聚合以其最通用的形式提供了具有三烷基甲锡烷基官能的单体和携带卤素例如溴或碘的单体之间的反应。可在均相溶液(例如四氢呋喃、二噁烷、二甲基甲酰胺、甲苯等)中进行该反应。该反应通过钯配位络合物,例如四-(三苯基膦)钯或四(邻-甲苯基膦)钯催化,从钯盐例如乙酸钯或氯化钯和膦开始也可在原位获得该钯配位络合物。
Yamamoto聚合以其最通用的形式提供了携带卤素例如溴或碘的单体的反应。该反应在有机溶剂中进行,并且通过镍配位络合物,例如环辛二烯基镍催化。
Heck聚合以其最通用的形式提供了具有乙烯基功能的单体和携带卤素例如溴或碘的单体之间的反应。该反应在有机溶剂中进行,并且该反应通过钯配位络合物,例如四-(三苯基膦)钯、四(邻-甲苯基膦)钯催化,从钯盐例如乙酸钯或氯化钯和膦开始也可在原位获得该钯配位络合物。
一旦已经得到共聚物并且使用对本领域技术人员已知的方法将其分离之后,对得到的产品在酸水解条件下进行处理,例如在醇例如甲醇、乙醇、丁醇等;或酮例如丙酮等和水或这些溶剂的混合物存在下。在通过盐酸或对-甲苯磺酸,通常HCl的酸性环境中进行该反应以将沿着链存在的二氧戊环基转换为对应的二元醇基。
缩酮/缩醛的水解是有机合成的已知技术的一部分(ProtectiveGroups in Organic Synthesis-T.W.Greene 1981,73页)。
证明最终共聚物在水、醇或水/醇、水/丙酮、水/THF混合物中是溶解的,并且可与在相同溶剂中可溶的受体化合物例如官能化的富勒烯结合使用以形成用于太阳能电池的薄层。
为较好地理解本发明和其应用的实施方案,提供了一些示例性的和非限制性的实施例。
具体实施方式
实施例1
2,7-二溴-9,9-双-(3'-溴丙基)芴的合成
(中间体)
在惰性气氛中,将下列产品添加到在2,7-二溴芴(10.0g,31.06mmole)的40ml 1,3-二溴丙烷的溶液中:首先溶解在60ml水中的氢氧化钠(30.0g,750.0mmole)且最终0.2g的四丁基溴化铵。将温度调至100℃。6小时后,在添加水后,用二氯甲烷实施萃取。在用水洗涤有机相直至中性后,将所述有机相在硫酸钠上脱水。在降低的压力下通过蒸馏将过量的二氯甲烷和1,3-二溴丙烷除去。通过在硅胶色谱柱(洗脱液:庚烷/乙酸乙酯=99/1)上的洗脱纯化之后,得到5.2g的2,7-二溴-9,9-双-(3'-溴丙基)芴(收率=30%)。
2,7-二溴-9,9-双{3-[(2,2-二甲基-1,3-二噁烷-4-基)甲氧基]丙基}芴的合成
在惰性气氛中,将叔丁醇钾(3.0g,26.7mmole)添加到在丙酮缩甘油(3.5g,26.7mmole)的50.0ml 1,2-二甲氧基乙烷溶液中。在20分钟后,添加在15.0ml 1,2-二甲氧基乙烷中溶解的2,7-二溴-9,9-双-(3'-溴丙基)芴(5.0g,8.9mmole)。
在8小时后,在降低的压力下通过蒸馏将1,2-二甲氧基乙烷除去后,使用乙酸乙酯将残余物回收并且使用水洗涤直至中性。在将有机相在硫酸钠上脱水后,在降低的压力下通过蒸馏将溶剂除去。通过在氧化铝色谱柱(庚烷/乙酸乙酯=95/5)上的洗脱纯化之后,得到4.0g的2,7-二溴-9,9-双{3-[(2,2-二甲基-1,3-二噁烷-4-基)甲氧基]丙基}芴(收率=74%)。
实施例2
2,5-二溴-3-甲基噻吩的合成
(第一中间体)
在惰性气氛中,将N-溴丁二酰亚胺(20.0g,113.0mmole)添加到在40ml四氢呋喃和40ml乙酸中溶解的3-甲基噻吩(5.0g,51.0mmole)中。在1小时后,添加水并使用乙醚实施萃取。
在将有机相先用水和然后用碳酸氢钠饱和水溶液洗涤至中性后,将所述有机相在硫酸钠上脱水。在降低的压力下将溶剂蒸馏。得到9.7g的2,5-二溴-3-甲基噻吩(收率=75%)。
2,5-二溴-3-溴甲基噻吩的合成
(第二中间体)
在惰性气氛中,将下列产品N-溴丁二酰亚胺(4.4g,24.9mmole)和最终50mg过氧化二苯酰添加到在2,5-二溴-3-溴甲基噻吩(5.6g,22.0mmole)的50ml四氯化碳溶液中。在7小时后,添加水并使用乙酸乙酯实施萃取。在使用水将有机相涤至中性后,将所述有机相在硫酸钠上脱水。在降低的压力下通过蒸馏将溶剂除去,得到5.0g 2,5-二甲基-3-溴甲基噻吩(收率=70%)。
4-{[(2,5-二溴-3-噻吩基)甲氧基]甲基}-2,2-二甲基-1,3-二氧戊环的合成
在惰性气氛中,将叔丁醇钾(2.6g,23.2mmole)添加到在丙酮缩甘油(3.1g,23.5mmole)的35.5ml 1,2-二甲氧基乙烷溶液中。在15分钟后,逐滴加入在15ml 1,2-二甲氧基乙烷中溶解的2,5-二甲基-3-溴甲基噻吩(5.0g,15.0mmole)。
在3小时后,在降低的压力下通过蒸馏将1,2-二甲氧基乙烷除去,使用水将残余物回收并且使用乙酸乙酯将残余物萃取。在使用水将有机相涤至中性后,将所述有机相在硫酸钠上脱水。在降低的压力下通过蒸馏将溶剂除去,通过在氧化铝柱(庚烷/乙酸乙酯=95/5)上的洗脱纯化之后,得到4.0g的4-{[(2,5-二溴-3-噻吩基)甲氧基]甲基}-2,2-二甲基-1,3-二氧戊环(收率=70%)。
实施例3
3,6-二溴-9-(3'-溴丙基)咔唑的合成
(中间体)
在惰性气氛中,将下列产品:溶解在13ml水中的氢氧化钾(6.5g,98mmole)、四丁基溴化铵和最终1,3-二溴丙烷(9.9g,49.2mmole)添加到在3,6-二溴咔唑(2.5g,7.74mmole)的13ml甲苯溶液中。
将温度调至70℃。3小时后,添加水并且用乙酸乙酯实施洗提。在用水将有机相洗涤至中性后,将所述有机相在硫酸钠上脱水。在降低的压力下通过蒸馏将溶剂除去后,得到2.5g的3,6-二溴-9-(3'-溴丙基)咔唑(收率=75%)。
3,6-二溴-9-{3-[(2,2-二甲基-1,3-二噁烷-4-基)甲氧基]丙基}-9H-咔唑的合成
在惰性气氛中,将叔丁醇钾(0.8g,7.1mmole)添加到在丙酮缩甘油(0.9g,7.1mmole)的10ml1,2-二甲氧基乙烷溶液中。15分钟后,逐滴加入在10.0ml 1,2-二甲氧基乙烷中溶解的3,6-二溴-9-(3'-溴丙基)咔唑(2.1g,4.7mmole)。3小时后,在降低的压力下通过蒸馏将1,2-二甲氧基乙烷除去,使用水将残余物回收并且使用乙酸乙酯将残余物萃取。在使用水将有机相洗涤直至中性后,将所述有机相在硫酸钠上脱水。在降低的压力下通过蒸馏将溶剂除去。通过在氧化铝柱(庚烷/乙酸乙酯=9/1)上的洗脱纯化之后,得到1.6g的3,6-二溴-9-{3-[(2,2-二甲基-1,3-二噁烷-4-基)甲氧基]丙基}-9H-咔唑(收率=70%)。
实施例4
无规共聚物聚{(2,1,3-苯并噻二唑)-交替-[(3-(4-钠磺基丁氧基)甲基-噻吩)-共-(9,9-双-(3-((2,2-二甲基-1,3-二噁烷-4-基)甲氧基)丙基芴)]}的合成
在惰性气氛中,将下列产品引入至配置有磁搅拌器和回流冷却器的50ml双颈烧瓶中:
-324.3mg(0.485mmole)2,7-二溴-9,9-双-{(3-[(2,2-二甲基-1,3-二噁烷-4-基)甲氧基]丙基}芴;
-373.80mg(0.963mmole)4,7-双-频哪醇硼-2,1,3-苯并噻二唑)酯;
-200.6mg(0.482mmole)[(2,5-二溴-3-噻吩基)甲氧基]丁磺酸钠;
-10ml蒸馏的THF(四氢呋喃)
-1ml 4M的K2CO3的水溶液;
-几滴Aliquat334。
将反应混合物加热至70℃,持续15分钟,和然后加入下列产品:
-12mg(0.01mmole)Pd(0)四(三苯基膦);
将反应混合物在此温度下停留40小时。5小时后该反应基本上无水,并且进一步添加5ml THF。在40小时后将混合物冷却和通过蒸馏将溶剂除去。
聚{(2,1,3-苯并噻二唑)-交替-[(3-(4-钠磺基丁氧基)甲基噻吩)-共-(9,9-双-(3-((2,2-二甲基-1,3-二噁烷-4-基)甲氧基)丙基)芴)]}的合成
将下列产品引入至250ml双颈烧瓶中:
-600mg之前制备的2,7-二溴-9,9-双-{3-[(2,2-二甲基-1,3-二噁烷-4-基)甲氧基]丙基}芴,4,7-双-频哪醇硼-2,1,3-苯并噻二唑)酯和[(2,5-二溴-3-噻吩基)甲氧基]丁磺酸钠之间的无规共聚物;
-45ml丙酮;
-35ml水;
-5ml 37%的HCl。
在18小时后,将混合物冷却至室温。从石蕊试纸测试结果得到该溶液处于中性pH。然后通过蒸馏将溶剂除去。将该聚合物再溶解到由45ml丙酮和5ml蒸馏水组成的溶液中。
将含聚合物的溶液转移到截留值为1,200Da的渗析膜并且在1升的圆筒中渗析两天,该圆筒含有重量比为9:1的丙酮/水溶液。
通过蒸馏将溶剂从含聚合物的溶液中除去。得到375mg暗红色聚合物。
核磁共振波谱表明由于二氧戊环基的甲基的信号消失且它们向二醇基的转变。
Claims (13)
1.具有下列一般结构(I)的单体:
其中,
-Ar是选自苯、芴、噻吩、咔唑、二噻吩并环戊二烯或选自吩噻嗪的基团,
-X是通过选自Suzuki、Stille、Heck或Yamamoto反应的反应可聚合的基团,选自-Br、-Cl、-I、-O-(SO2)-CF3、-B(OH)2、-B(OR')2、-SnR'3、-B(OR"O)和乙烯基,R'为C1-C6烷基和R"为亚乙基,任选用C1-C2烷基取代;R1和R2,彼此相同或不同,可为氢原子或C1-C6烷基;
-R为二价C1-C12亚烷基;
-n为1-4。
2.具有下列一般结构(П)的单体:
其中,R、R1、R2、Ar、X、n具有如权利要求1中所定义的相同含义;和
-Ar'是选自噻吩、噻吩并-噻吩、噻唑、咔唑、二噻吩并环戊二烯或选自吩噻嗪的基团;
-m=1或2。
3.用于合成权利要求1的具有通式(I)的单体的方法,所述方法包括根据下列方案的具有通式(Ш)的卤素衍生物,其中Z=Cl,Br,I,与甘油衍生物(Ⅳ)的羟基的醚化反应:
4.权利要求3的方法,其中使用的Ш:Ⅳ:碱的摩尔比范围为1:1.1:1.15-1:3:3.3。
5.权利要求3或4的方法,其中在15℃-150℃的温度范围进行所述反应。
6.权利要求5的方法,其中在20℃-80℃的温度范围进行所述反应。
7.用于合成权利要求2的具有通式(П)的单体的方法,所述方法包括根据下列方案的缩合反应:
其中W=SnR'3、-B(OH)2、-B(OR)2,接着使得到的衍生物用选自Br、Cl或I的卤素卤化。
8.权利要求7的方法,其中使用的摩尔比(I):(Ⅸ)范围为1:2-1:4。
9.权利要求7或8的方法,其中在10-200℃的温度范围进行所述反应。
10.权利要求9的方法,其中在30-150℃的温度范围进行所述反应。
11.用于制备在水中可溶解的共轭聚合物或共聚物的方法,所述方法包括至少一种权利要求1的化合物(I)或权利要求2的化合物(П)与选自以下描述的那些的一种或多种共聚单体反应:
其中R3-R10,彼此相同或不同,为氢原子或任选支化的C1-C37烷基;如果该基与碳原子连接,R3-R10为-OC1-OC16烷氧基,和
Y是通过选自Suzuki、Stille、Heck或Yamamoto的这些反应的反应可聚合的基团,选自-Br、-Cl、-I、-O-(SO2)-CF3、-B(OH)2、-B(OR')2、-SnR'3、-B(OR"O)、乙烯基,R'为C1-C6烷基和R"为亚乙基,任选用C1-C2烷基取代,
以及随后使得到的聚合物或共聚物酸水解。
12.权利要求11的方法,其中所述任选支化的C1-C37烷基选自甲基、乙基、丙基、丁基、己基、辛基、癸基、十二烷基、十四烷基、十六烷基、十八烷基、二十烷基、2-乙基己基、2-乙基辛基、2-乙基癸基、2-乙基十二烷基、4-丁基己基、4-丁基辛基、4-丁基癸基、4-丁基十二烷基、2-己基辛基、2-己基癸基、4-己基癸基、异丙基、1-乙基丙基、1-丁基戊基、1-己基庚基、1-辛基壬基、1-十二烷基十三烷基、1-十六烷基十七烷基或1-十八烷基十九烷基。
13.权利要求11的方法,其中所述反应为由过渡金属衍生物催化的缩合反应,所述过渡金属在Suzuki、Stille和Heck反应的情况下选自钯,或在Yamamoto反应的情况下选自镍。
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