CN111154075A - 氟代喹喔啉-噻吩共聚物及其制备方法 - Google Patents
氟代喹喔啉-噻吩共聚物及其制备方法 Download PDFInfo
- Publication number
- CN111154075A CN111154075A CN201910364271.8A CN201910364271A CN111154075A CN 111154075 A CN111154075 A CN 111154075A CN 201910364271 A CN201910364271 A CN 201910364271A CN 111154075 A CN111154075 A CN 111154075A
- Authority
- CN
- China
- Prior art keywords
- fluoroquinoxaline
- derivative monomer
- thiophene
- preparation
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 69
- 239000000178 monomer Substances 0.000 claims abstract description 60
- RWYDWNBCELWNLD-UHFFFAOYSA-N 2-fluoroquinoxaline Chemical class C1=CC=CC2=NC(F)=CN=C21 RWYDWNBCELWNLD-UHFFFAOYSA-N 0.000 claims abstract description 46
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000001816 cooling Methods 0.000 claims abstract description 22
- 150000003577 thiophenes Chemical class 0.000 claims abstract description 15
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000007800 oxidant agent Substances 0.000 claims abstract description 11
- 230000001590 oxidative effect Effects 0.000 claims abstract description 10
- 239000000654 additive Substances 0.000 claims abstract description 9
- 230000000996 additive effect Effects 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 31
- -1 hexadecyloxy, phenyl Chemical group 0.000 claims description 24
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 22
- 238000000967 suction filtration Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 17
- 238000000944 Soxhlet extraction Methods 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 13
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 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 12
- 239000000203 mixture Substances 0.000 claims description 12
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 11
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-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
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 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 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 8
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 7
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 claims description 7
- 239000012043 crude product Substances 0.000 claims description 6
- 125000004185 ester group Chemical group 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N Pd(PPh3)4 Substances [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
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 4
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 claims description 4
- 238000004062 sedimentation Methods 0.000 claims description 4
- KQTXIZHBFFWWFW-UHFFFAOYSA-L silver(I) carbonate Inorganic materials [Ag]OC(=O)O[Ag] KQTXIZHBFFWWFW-UHFFFAOYSA-L 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical group C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 239000002026 chloroform extract Substances 0.000 claims description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 3
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 3
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 2
- 229910004039 HBF4 Inorganic materials 0.000 claims description 2
- 229910004373 HOAc Inorganic materials 0.000 claims description 2
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 2
- YNHIGQDRGKUECZ-UHFFFAOYSA-L PdCl2(PPh3)2 Substances [Cl-].[Cl-].[Pd+2].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 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 claims description 2
- WIKQEUJFZPCFNJ-UHFFFAOYSA-N carbonic acid;silver Chemical group [Ag].[Ag].OC(O)=O WIKQEUJFZPCFNJ-UHFFFAOYSA-N 0.000 claims description 2
- SBTSVTLGWRLWOD-UHFFFAOYSA-L copper(ii) triflate Chemical compound [Cu+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F SBTSVTLGWRLWOD-UHFFFAOYSA-L 0.000 claims description 2
- 229940078552 o-xylene Drugs 0.000 claims description 2
- 125000005447 octyloxy 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])O* 0.000 claims description 2
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 15
- 230000008878 coupling Effects 0.000 abstract description 6
- 238000010168 coupling process Methods 0.000 abstract description 6
- 238000005859 coupling reaction Methods 0.000 abstract description 6
- 238000009826 distribution Methods 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 58
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 48
- 239000007787 solid Substances 0.000 description 40
- 238000003760 magnetic stirring Methods 0.000 description 23
- 238000005160 1H NMR spectroscopy Methods 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 15
- 239000002994 raw material Substances 0.000 description 14
- 238000010992 reflux Methods 0.000 description 14
- 239000012295 chemical reaction liquid Substances 0.000 description 12
- 238000001291 vacuum drying Methods 0.000 description 12
- 239000012074 organic phase Substances 0.000 description 11
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 10
- PPWRHKISAQTCCG-UHFFFAOYSA-N 4,5-difluorobenzene-1,2-diamine Chemical compound NC1=CC(F)=C(F)C=C1N PPWRHKISAQTCCG-UHFFFAOYSA-N 0.000 description 10
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 230000002194 synthesizing effect Effects 0.000 description 9
- QICRFTDHNHLHBP-UHFFFAOYSA-N 6,7-difluoro-2-hexadecoxy-3-methylquinoxaline Chemical compound CCCCCCCCCCCCCCCCOC1=NC2=CC(=C(C=C2N=C1C)F)F QICRFTDHNHLHBP-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 7
- QMDWWTUQHWXOCR-UHFFFAOYSA-N 6,7-difluoro-2,3-diphenylquinoxaline Chemical compound C=1C=CC=CC=1C=1N=C2C=C(F)C(F)=CC2=NC=1C1=CC=CC=C1 QMDWWTUQHWXOCR-UHFFFAOYSA-N 0.000 description 6
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 6
- 229930192474 thiophene Natural products 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 5
- 235000019341 magnesium sulphate Nutrition 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- RWEKWRQKAHQYNE-UHFFFAOYSA-N 7-(bromomethyl)pentadecane Chemical compound CCCCCCCCC(CBr)CCCCCC RWEKWRQKAHQYNE-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- CWKLZLBVOJRSOM-UHFFFAOYSA-N methyl pyruvate Chemical compound COC(=O)C(C)=O CWKLZLBVOJRSOM-UHFFFAOYSA-N 0.000 description 4
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical group C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 3
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical class [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 description 3
- 150000002641 lithium Chemical class 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 229920000307 polymer substrate Polymers 0.000 description 3
- 235000011056 potassium acetate Nutrition 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 229910001958 silver carbonate Inorganic materials 0.000 description 3
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 2
- FHHYBPFAKBJDHJ-UHFFFAOYSA-N 6,7-difluoro-2,3-dimethylquinoxaline Chemical compound FC1=C(F)C=C2N=C(C)C(C)=NC2=C1 FHHYBPFAKBJDHJ-UHFFFAOYSA-N 0.000 description 2
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical compound CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229920000547 conjugated polymer Polymers 0.000 description 2
- NXQGGXCHGDYOHB-UHFFFAOYSA-L cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;dichloropalladium;iron(2+) Chemical compound [Fe+2].Cl[Pd]Cl.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 NXQGGXCHGDYOHB-UHFFFAOYSA-L 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 239000011698 potassium fluoride Substances 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 1
- FLDPALRHDMQIKK-UHFFFAOYSA-N 2,3-bis(4-octoxyphenyl)quinoxaline Chemical compound C(CCCCCCC)OC1=CC=C(C=C1)C1=NC2=CC=CC=C2N=C1C1=CC=C(C=C1)OCCCCCCCC FLDPALRHDMQIKK-UHFFFAOYSA-N 0.000 description 1
- JEDHEMYZURJGRQ-UHFFFAOYSA-N 3-hexylthiophene Chemical compound CCCCCCC=1C=CSC=1 JEDHEMYZURJGRQ-UHFFFAOYSA-N 0.000 description 1
- YOYGBPLAFUOTCP-UHFFFAOYSA-N 6,7-difluoro-2,3-bis(4-octoxyphenyl)quinoxaline Chemical compound FC=1C=C2N=C(C(=NC2=CC=1F)C1=CC=C(C=C1)OCCCCCCCC)C1=CC=C(C=C1)OCCCCCCCC YOYGBPLAFUOTCP-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000006254 arylation reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- ZOAIGCHJWKDIPJ-UHFFFAOYSA-M caesium acetate Chemical compound [Cs+].CC([O-])=O ZOAIGCHJWKDIPJ-UHFFFAOYSA-M 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000000732 glass refractive index measurement Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 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
- C08G61/121—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from organic halides
-
- 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
-
- 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
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Abstract
本发明公开了氟代喹喔啉‑噻吩共聚物及其制备方法，制备方法，包括以下步骤：将氟代喹喔啉衍生物单体、噻吩衍生物单体、溶剂、氧化剂、碱、添加剂和钯催化剂混合，在90～130℃下搅拌反应24～48h，冷却至室温，得到含有氟代喹喔啉‑噻吩共聚物的反应液，本发明采用C‑H/C‑H直接偶联，比传统的C‑X/C‑M和C‑X/C‑H等制备技术缩短一到两步有机合成步骤，提高了反应总产率，降低了生产成本；该制备方法原子经济性高，合成的氟代喹喔啉聚合物分子量相对稳定，能控制不同批次的聚合物分子量及其分布相对稳定。
Description
技术领域
本发明属于共轭聚合物技术领域，具体来说涉及一种氟代喹喔啉-噻吩共聚物及其制备方法。
背景技术
含有氟代喹喔啉结构单元的共轭聚合物在光伏材料中具有广泛的应用，这些共轭聚合物通常具有给体(D)-受体(A)交替的结构特征。目前报道的合成方法主要有Suzuki法、Stille法、McCullough法、Rieke法、GRIM法以及直接芳基化法等偶联聚合方法。这些合成方法需要对单体进行预修饰，制备其相应的有机金属化合物或卤代物，而这些有机金属化合物通常极不稳定，并且合成方法严苛，如需要极低的温度，无氧等，反应步骤多，耗时，成本高，且在光伏器件应用中还需要对聚合物进行封端的处理。
发明内容
针对现有技术的不足，本发明的目的在于提供一种氟代喹喔啉-噻吩共聚物的制备方法，该制备方法以氟代喹喔啉衍生物单体为受体结构单元，噻吩衍生物单体为给体结构单元，利用钯催化剂氧化C-H/C-H偶联缩聚法直接制备了氟代喹喔啉-噻吩共聚物，本发明较传统方法合成步骤少，避免了有机金属化合物、卤化物的制备环节，减少了反应步骤，节约了成本。另外，本发明原料简单易得，不需要对单体进行预处理，原子经济性高，且不同批次合成的共聚物分子量及其分布相对稳定。
本发明的另一目的是提供上述制备方法获得的氟代喹喔啉-噻吩共聚物。
本发明的目的是通过下述技术方案予以实现的。
一种氟代喹喔啉-噻吩共聚物的制备方法，包括以下步骤：
将氟代喹喔啉衍生物单体、噻吩衍生物单体、溶剂、氧化剂、碱、添加剂和钯催化剂混合，在90～130℃下搅拌反应24～48h，冷却至室温20～25℃，得到含有氟代喹喔啉-噻吩共聚物的反应液，其中，按物质的量份数计，所述氟代喹喔啉衍生物单体、噻吩衍生物单体、钯催化剂、氧化剂、碱和添加剂的比为1：1：(0.005～0.2)：(0～10)：(0～10)：(0～10)；
所述氟代喹喔啉衍生物单体的结构通式为：
所述噻吩衍生物单体为：
在上述技术方案中，所述溶剂为甲苯、1,4-二氧六环、邻二甲苯、四氢呋喃、N,N-二甲基乙酰胺、甲苯和二甲基亚砜中的一种或几种的混合物；
所述氧化剂为Ag2CO3、AgF、AgOAc、Ag2O、Cu(OAc)2、Cu(OTf)2、CuCl2和AgNO3中的一种；
所述碱为Na2CO3、K2CO3、Cs2CO3、NaHCO3、NaOAc、KOAc、CsOAc和KF中的一种；
所述添加剂为PPh3、PCy3HBF4、P(t-Bu)3、PivOH(新戊酸)和HOAc中的一种；
所述钯催化剂为Pd(dppf)Cl2、Pd(OAc)2、PdCl2、Pd2(dba)3、Pd(TFA)2、PdCl2(PPh3)2、Pd(OH)2、Pd(PPh3)4和钯碳中的一种。
在上述技术方案中，按物质的量份数计，所述氟代喹喔啉衍生物单体、噻吩衍生物单体、钯催化剂、氧化剂、碱和添加剂的比为1：1：(0.05～0.2)：(1～4)：(1～4)：(0～4)。
在上述技术方案中，所述碱为K2CO3、Cs2CO3或KOAc，所述氧化剂为Ag2CO3或Cu(OAc)2，所述钯催化剂为Pd(OAc)2或Pd(PPh3)4，所述溶剂为四氢呋喃或N,N-二甲基乙酰胺。
在上述技术方案中，搅拌反应的温度为100～120℃。
在上述技术方案中，所述氟代喹喔啉衍生物单体和噻吩衍生物单体在所述溶剂中的浓度各为0.01～1mol/L，优选为0.1～0.5mol/L。
在上述技术方案中，将所述反应液逐滴加入至甲醇中进行沉降，抽滤，得到粗产品，将所述粗产品先后依次用甲醇和正己烷索氏抽提，再用氯仿索氏抽提，收集氯仿提取液，浓缩后加入甲醇进行沉降，抽滤，干燥后得到氟代喹喔啉-噻吩共聚物。
上述制备方法获得的氟代喹喔啉-噻吩共聚物。
与现有技术路线相比，本发明具有合成步骤少、原料简单易得、原子经济性高、聚合物分子量及其分布相对稳定的特点，具体表现在：
1.本发明采用C-H/C-H直接偶联，比传统的C-X/C-M和C-X/C-H等制备技术缩短一到两步有机合成步骤，提高了反应总产率，降低了生产成本；
2.所需原料简单易得，所涉及的C-H/C-H偶联缩聚方法不需要预处理，直接可以进行聚合，不需要预先制备相应的有机金属化合物或卤代烃单体，避免了后续聚合物的封端等问题；
3.该制备方法原子经济性高，合成的氟代喹喔啉聚合物分子量相对稳定，能控制不同批次的聚合物分子量及其分布相对稳定，为氟代喹喔啉衍生物单体和噻吩衍生物单体的共聚物。
具体实施方式
当噻吩衍生物单体为
时，本发明的制备方法的反应式如下：
下面结合具体实施例进一步说明本发明的技术方案。下述实施例中所涉及药品的购买源如下：
下述实施例中所涉及仪器的型号如下：
采用索式提取方法对下述实施例所得反应液进行提取，索式提取方法的步骤为：将1mL反应液以每秒钟2滴(每滴的体积为1mL)的速度滴入100mL甲醇中进行沉降，沉降24h，抽滤，得到粗产品。将粗产品分别先后用甲醇和正己烷索氏提取24小时，用于除去杂质和低分子量聚合物，最后用氯仿索氏抽提至索氏提取管中氯仿无色，停止抽提，收集氯仿提取液，浓缩至2mL，滴入60mL甲醇中进行沉降，沉降24h，抽滤，得到固体为氟代喹喔啉-噻吩共聚物。
下述实施例中涉及原料如下：
实施例1
一种氟代喹喔啉-噻吩共聚物的制备方法，包括以下步骤：
将6,7-二氟-3-甲基-2-十六烷氧基喹喔啉(0.095mmol)、2,2'-二噻吩(0.095mmol)、碳酸银(0.38mmol)、醋酸钾(0.38mmol)、三环己基膦氟硼酸盐(0.038mmol)和醋酸钯(0.0095mmol)依次加入到反应器中，取1mL N,N-二甲基乙酰胺将上述原料溶解，升温至110℃，在磁力搅拌条件下反应48h后，停止反应，冷却至室温20～25℃，得到含有氟代喹喔啉-噻吩共聚物的反应液。采用索式提取方法对所得反应液进行提取，将提取所得固体在60℃真空干燥箱中干燥12h，即得共聚物P1为6,7-二氟-3-甲基-2-十六烷氧基喹喔啉-2,2'-二噻吩(36.8mg,产率63％,Mn 4.6kDa,PDI 1.2)。1H NMR(400MHz,CDCl3)δ:7.08(d,4H),4.39(d,2H),3.04(dd,3H),1.90(s,1H),1.33-0.91(d,30H).
再重复实施例1中制备方法3次，采用索式提取方法对所得反应液进行提取。所得氟代喹喔啉-噻吩共聚物分别标记为P2(35.1mg,产率60％,4.3kDa,PDI 1.4)、P3(38mg,产率65％,4.5kDa PDI 1.3)和P4(35.6mg,产率61％,4.0kDa,PDI 1.3)。
上述氟代喹喔啉衍生物单体(6,7-二氟-3-甲基-2-十六烷氧基喹喔啉)的结构式为：
上述制备方法的反应过程为：
合成氟代喹喔啉衍生物单体的步骤为(Sun,C.；Pan,F.；Bin,H.；Zhang,J.；Xue,L.；Qiu,B.；Wei,Z.；Zhang,Z.G.；Li,Y.,A low cost and high performance polymerdonor material for polymer solar cells.Nature communications 2018,9(1),743.)：将4,5-二氟苯-1,2-二胺(27.75mmol)溶于100mL乙醇中，冰水浴中将2.5mL丙酮酸甲酯以每秒钟2滴的速度滴入，滴加完后升温至40℃，磁力搅拌下冷凝回流6h后，停止反应，冷却至室温。抽滤得到白色固体(3.25g,60％)。将白色固体(16.57mmol)溶于100mL N,N-二甲基乙酰胺中，依次加入碳酸钾(19.9mmol)和1-溴-2-己基癸烷(16.57mmol)，升温至80℃，磁力搅拌下冷凝回流24h后，停止反应，冷却至室温。用150mL饱和氯化铵水溶液洗涤，再用50mL二氯甲烷萃取，得到有机相，再将有机相用500mL去离子水水洗后，将水相用50mL二氯甲烷萃取3次，合并二氯甲烷萃取所得有机相，用无水硫酸镁干燥，抽滤除去硫酸镁，减压蒸馏浓缩至2mL，通过柱层析，即得无色液体为氟代喹喔啉衍生物单体(3.2g,46％)。1H NMR(400MHz,CDCl3)δ:7.67(dd,1H),7.55-7.47(m,1H),4.34(d,2H),2.61(s,3H),1.91-1.81(m,1H),1.49-1.19(m,27H),0.87(dd,7H).13C NMR(100MHz,CDCl3)δ:179.0,157.43,148.94,139.14,135.6,114.21,113.51,70.27,37.85,32.36,32.30,32.00,30.44,30.17,30.11,30.04,29.80,27.30,27.27,23.14,20.48,14.59.
实施例2
一种氟代喹喔啉-噻吩共聚物的制备方法，包括以下步骤：
将6,7-二氟-2,3-双(4-辛氧苯基)喹喔啉(0.1mmol)、3,3'-二辛基-2,2'-二噻吩(0.1mmol)、醋酸铜(0.2mmol)、碳酸钾(0.4mmol)、(1,1'-双(二苯基膦基)二茂铁)二氯化钯(0.01mmol)依次加入到反应瓶中，取0.25mL N,N-二甲基乙酰胺将原料溶解，升温至110℃，在磁力搅拌条件下反应48h后，停止反应，冷却至室温20～25℃，得到含有氟代喹喔啉-噻吩共聚物的反应液。采用索式提取方法对所得反应液进行提取，将提取所得固体在60℃真空干燥箱中干燥12h，即得共聚物P5为6,7-二氟-2,3-双(4-辛氧苯基)喹喔啉-3,3'-二辛基-2,2'-二噻吩(51.2mg,产率54％,Mn 5.0kDa,PDI 1.3)。1H NMR(400MHz,CDCl3)δ:7.34(s,4H),6.83(s,4H)6.40(s,2H),3.94(t,4H),2.72(d,4H),1.78-0.96(m,60H)
上述氟代喹喔啉衍生物单体(6,7-二氟-2,3-双(4-辛氧苯基)喹喔啉)的结构式为：
上述制备方法的反应过程为：
合成氟代喹喔啉衍生物单体的步骤为(Xu,X.；Wu,Y.；Fang,J.；Li,Z.；Wang,Z.；Li,Y.；Peng,Q.,Side-Chain Engineering of Benzodithiophene-FluorinatedQuinoxaline Low-Band-Gap Co-polymers for High-Performance Polymer SolarCells.Chemistry–A European Journal 2014,20(41),13259-13271.)：将4,5-二氟苯-1,2-二胺(10mmol)溶于60mL乙酸中，再加入1,2-双(4-辛氧苯基)乙烷-1,2-二酮(10mmol)，升温至50℃，磁力搅拌10min，冷凝回流反应2h后，停止反应，冷却至室温。抽滤，将抽滤所得固体用150mL乙醇洗涤后，抽滤，将抽滤所得固体在50℃真空干燥箱中干燥12h，即得白色固体为氟代喹喔啉衍生物单体(4.14g,82.4％)。1H NMR(500MHz,CDCl3)δ:7.8(d,2H),7.23(d,2H),7.21(m,2H),7.16(d,2H),6.94(dd,2H),3.86(t,4H),1.73(m,4H),1.42(m,4H),1.33-1.29(m,16H),0.89(t,6H).13C NMR(CDCl3,125MHz)δ:159.11,153.99,151.60,149.61,138.81,136.07,129.39,122.46,116.63,115.76,68.14,31.85,29.35,29.28,29.12,26.03,22.68,14.12.
实施例3
一种氟代喹喔啉-噻吩共聚物的制备方法，包括以下步骤：
将6,7-二氟-2,3-二甲基喹喔啉(0.1mmol)、3,6-二辛氧基苯并[1,2-b；4,5-b]噻吩(0.1mmol)、氧化银(0.3mmol)、醋酸钠(0.3mmol)和三(二亚苄基丙酮)二钯(0.005mmol)依次加入到反应瓶中，取1mL溶剂将原料溶解，升温至100℃，在磁力搅拌条件下反应48h后，停止反应，冷却至室温20～25℃，得到含有氟代喹喔啉-噻吩共聚物的反应液，其中，溶剂为体积比为20:1的N,N-二甲基甲酰胺和二甲基亚砜的混合物。采用索式提取方法对所得反应液进行提取，将提取所得固体在真空干燥箱中60℃干燥12h，即得共聚物P6为6,7-二氟-2,3-二甲基喹喔啉-3,6-二辛氧基苯并[1,2-b；4,5-b]噻吩(31.8mg,产率50％,Mn 3.4kDa,PDI 1.5)。1H NMR(400MHz,CDCl3)δ:7.30(t,2H),3.94(t,4H),3.04(dd,6H),1.71-0.96(m,30H).
上述氟代喹喔啉衍生物单体(6,7-二氟-2,3-二甲基喹喔啉)的结构式为：
上述制备方法的反应过程为：
合成氟代喹喔啉衍生物单体的步骤为(Iyer,A.；Bjorgaard,J.；Anderson,T.；
M.E.,Quinoxaline-Based Semiconducting Polymers:Effect of Fluorination onthe Photophysical,Thermal,and Charge Transport Properties.Macromolecules2012,45(16),6380-6389.)：将4,5-二氟苯-1,2-二胺.(7.3mmol)、丁二酮(8.6mmol)溶于60mL乙醇，升温至80℃，磁力搅拌下冷凝回流24h后，停止反应，冷却至室温，待析出固体后，进行抽滤。将固体用100mL甲醇进行洗涤，抽滤，再在60℃真空干燥箱中干燥12h，即得氟代喹喔啉衍生物单体(1.0g,70.2％)。1H NMR(400MHz,CDCl3)δ:7.76(t,2H),2.73(t,6H).13CNMR(100MHz,CDCl3)δ:156.5,153.4,137.9,113.9,18.7.
实例例4
一种氟代喹喔啉-噻吩共聚物的制备方法，包括以下步骤：
将6,7-二氟-1,3-二己基噻吩喹喔啉(0.1mmol)、3,3'-二己基并噻吩(0.1mmol)、醋酸银(0.4mmol)、碳酸铯(0.4mmol)、特戊酸(0.2mmol)和双三苯基磷二氯化钯(0.01mmol)依次加入到反应瓶中，取0.5mL四氢呋喃将原料溶解，升温至120℃，在磁力搅拌条件下反应48h后，停止反应，冷却至室温20～25℃，得到含有氟代喹喔啉-噻吩共聚物的反应液。
采用索式提取方法对所得反应液进行提取，将提取所得固体在60℃真空干燥箱中干燥12h，即得共聚物P7为6,7-二氟-1,3-二己基噻吩喹喔啉-3,3'-二己基并噻吩共聚物(57.8mg,产率72％,Mn 5.1kDa,PDI 1.3)。1H NMR(400MHz,CDCl3)δ:6.70(d,4H),2.55(dd,8H),1.62-0.96(d,44H)
上述氟代喹喔啉衍生物单体(6,7-二氟-1,3-二己基噻吩喹喔啉)的结构式为：
上述制备方法的反应过程为：
合成氟代喹喔啉衍生物单体的步骤为(Chen H C,Chen Y H,Liu C H,etal.Fluorinated thienyl-quinoxaline-based D-p-A-type copolymer towardefficient polymer solar cells:synthesis,characterization,and photovoltaicproperties[J].Polymer Chemistry,2013,4(11):3411-3418.)：将4,5-二氟苯-1,2-二胺(10mmol)溶于60mL乙酸，升温至50℃，磁力搅拌4h后，再加入1,2-二((5-己基)噻吩基)-2,2'-二噻吩二酮(10mmol)，继续于50℃加热，磁力搅拌下冷凝回流反应8h，停止反应，冷却至室温。加入50mL二氯甲烷进行萃取。再将二氯甲烷萃取所得有机相用500mL去离子水水洗后，将水相用50mL二氯甲烷萃取3次，合并二氯甲烷萃取所得有机相，用无水硫酸镁干燥后，抽滤除去硫酸镁，减压蒸馏浓缩至2mL，通过柱层析，得到固体为氟代喹喔啉衍生物单体(3.40g,68％)。1H NMR(400MHz,CDCl3)δ:7.8(d,2H),7.38(d,2H),6.70(d,2H),2.85(t,4H),1.76-1.68(m,4H),1.53-1.36(m,4H),1.33-1.29(m,8H),0.88(t,6H).13C NMR(100MHz,CDCl3)δ:152.32,151.59,149.03,147.20,137.91,135.12,130.43,125.00,31.52,31.45,30.44,28.83,22.55,14.04.
实施例5
一种氟代喹喔啉-噻吩共聚物的制备方法，包括以下步骤：
将6,7-二氟-3-甲基-2-十六烷氧基喹喔啉(0.1mmol)、3,6-二辛氧基苯并[1,2-b；4,5-b]噻吩(0.1mmol)、硝酸银(0.4mmol)、醋酸铯(0.4mmol)和四(三苯基磷)钯(0.01mmol)依次加入到反应瓶中，取1.0mL二甲基亚砜将原料溶解，升温至110℃，在磁力搅拌条件下反应48h后，停止反应，冷却至室温20～25℃，得到含有氟代喹喔啉-噻吩共聚物的反应液。
采用索式提取方法对所得反应液进行提取，将提取所得固体在60℃真空干燥箱中干燥12h，即得共聚物P8为6,7-二氟-3-甲基-2-十六烷氧基喹喔啉-3,6-二辛氧基苯并[1,2-b；4,5-b]噻吩共聚物(48.3mg,产率56％,Mn 5.2kDa,PDI 1.3)。1H NMR(400MHz,CDCl3)δ:7.53(t,2H),4.24(t,6H),3.04(dd,3H),1.90(s,1H),1.70-0.82(m,60H).
上述氟代喹喔啉衍生物单体(6,7-二氟-3-甲基-2-十六烷氧基喹喔啉)的结构式为：
上述制备方法的反应过程为：
合成氟代喹喔啉衍生物单体的步骤为(Sun,C.；Pan,F.；Bin,H.；Zhang,J.；Xue,L.；Qiu,B.；Wei,Z.；Zhang,Z.G.；Li,Y.,A low cost and high performance polymerdonor material for polymer solar cells.Nature communications 2018,9(1),743.)：将4,5-二氟苯-1,2-二胺(27.75mmol)溶于100mL乙醇中，冰水浴中将2.5mL丙酮酸甲酯以每秒钟2滴的速度滴入，滴加完后升温至40℃，磁力搅拌下冷凝回流6h后，停止反应，冷却至室温。抽滤得到白色固体(3.25g,60％)。将白色固体(16.57mmol)溶于100mL N,N-二甲基乙酰胺中，依次加入碳酸钾(19.9mmol)、1-溴-2-己基癸烷(16.57mmol)，升温至80℃，磁力搅拌下冷凝回流24h后，停止反应，冷却至室温。用150mL饱和氯化铵水溶液洗后，用50mL二氯甲烷萃取。再将二氯甲烷萃取所得有机相用500mL去离子水水洗后，将水相用50mL二氯甲烷萃取3次，合并二氯甲烷萃取所得有机相，用无水硫酸镁干燥后，抽滤除去硫酸镁，减压蒸馏浓缩至2mL，通过柱层析，即得无色液体(3.2g,46％)为氟代喹喔啉衍生物单体。1H NMR(400MHz,CDCl3)δ:7.67(dd,1H),7.55-7.47(m,1H),4.34(d,2H),2.61(s,3H),1.91-1.81(m,1H),1.49-1.19(m,27H),0.87(dd,7H).13C NMR(100MHz,CDCl3)δ:179.0,157.43,148.94,139.14,135.6,114.21,113.51,70.27,37.85,32.36,32.30,32.00,30.44,30.17,30.11,30.04,29.80,27.30,27.27,23.14,20.48,14.59.
实施例6
一种氟代喹喔啉-噻吩共聚物的制备方法，包括以下步骤：
将6,7-二氟-3-甲基-2-十六烷氧基喹喔啉(0.1mmol)、3-己基噻吩(0.1mmol)、氯化铜(0.4mmol)、氟化钾(0.4mmol)和氯化钯(0.02mmol)依次加入到反应瓶中，取1mL甲苯将原料溶解，升温至100℃，在磁力搅拌条件下反应48h后，停止反应，冷却至室温20～25℃，得到含有氟代喹喔啉-噻吩共聚物的反应液。
采用索式提取方法对所得反应液进行提取，将提取所得固体在60℃真空干燥箱中干燥12h，得共聚物P9为6,7-二氟-3-甲基-2-十六烷氧基喹喔啉-3-己基噻吩共聚物(32.5mg,产率57％,Mn 3.1kDa,PDI 1.3)。1H NMR(400MHz,CDCl3)δ:7.08(d,2H),4.39(d,2H),3.04(dd,15.9,3H),1.90(s,1H),1.55-0.81(d,30H).
上述氟代喹喔啉衍生物单体(6,7-二氟-3-甲基-2-十六烷氧基喹喔啉)的结构式为：
上述制备方法的反应过程为：
合成氟代喹喔啉衍生物单体的步骤为(Sun,C.；Pan,F.；Bin,H.；Zhang,J.；Xue,L.；Qiu,B.；Wei,Z.；Zhang,Z.G.；Li,Y.,A low cost and high performance polymerdonor material for polymer solar cells.Nature communications 2018,9(1),743.)：将4,5-二氟苯-1,2-二胺(27.75mmol)溶于100mL乙醇中，冰水浴中将2.5mL丙酮酸甲酯以每秒钟2滴的速度滴入，滴加完后升温至40℃，磁力搅拌下冷凝回流6h后，停止反应，冷却至室温。抽滤得到白色固体(3.25g,60％)。将白色固体(16.57mmol)溶于100mL N,N-二甲基乙酰胺中，依次加入碳酸钾(19.9mmol)、1-溴-2-己基癸烷(16.57mmol)，升温至80℃，磁力搅拌下冷凝回流24h后，停止反应，冷却至室温。用150mL饱和氯化铵水溶液洗后，用50mL二氯甲烷萃取。再将二氯甲烷萃取所得有机相用500mL去离子水水洗后，将水相用50mL二氯甲烷萃取3次，合并二氯甲烷萃取所得有机相，用无水硫酸镁干燥后，抽滤除去硫酸镁，减压蒸馏浓缩至2mL，通过柱层析，即得无色液体为氟代喹喔啉-噻吩共聚物(3.2g,46％)。1H NMR(400MHz,CDCl3)δ:7.67(dd,1H),7.55-7.47(m,1H),4.34(d,2H),2.61(s,3H),1.91-1.81(m,1H),1.49-1.19(m,27H),0.87(dd,7H).13C NMR(100MHz,CDCl3)δ:179.0,157.43,148.94,139.14,135.6,114.21,113.51,70.27,37.85,32.36,32.30,32.00,30.44,30.17,30.11,30.04,29.80,27.30,27.27,23.14,20.48,14.59.
实施例7
一种氟代喹喔啉-噻吩共聚物的制备方法，包括以下步骤：
将6,7-二氟-2,3-二苯基喹喔啉(0.1mmol)、3,3'-二辛基-2,2'-二噻吩(0.1mmol)、碳酸银(0.4mmol)、醋酸钾(0.4mmol)和醋酸钯(0.01mmol)依次加入到反应瓶中，取1.0mL N,N-二甲基乙酰胺将原料溶解，升温至110℃，在磁力搅拌条件下反应48h后，停止反应，冷却至室温20～25℃，得到含有氟代喹喔啉-噻吩共聚物的反应液。
采用索式提取方法对所得反应液进行提取，将提取所得固体在60℃真空干燥箱中干燥12h，即得共聚物P10为6,7-二氟-2,3-二苯基喹喔啉-3,3'-二辛基-2,2'-二噻吩共聚物(49.3mg,产率70％,Mn 3.3kDa,PDI 1.7)。1H NMR(400MHz,CDCl3)δ:7.48(s,4H),7.32,7.22(s,6H),6.70(s,2),2.72(d,4H),1.78-0.53(m,30H).
上述氟代喹喔啉衍生物单体(6,7-二氟-2,3-二苯基喹喔啉)的结构式为：
上述制备方法的反应过程为：
合成氟代喹喔啉衍生物单体的步骤为(Jing Y M,Wang F Z,Zheng Y X,etal.Efficient deep red electroluminescence of iridium(Ⅲ)complexes with2,3-diphenylquinoxaline derivatives and tetraphenylimidodiphosphinate[J].J.Mater.Chem.C,2017,5(15):3714-3724.)：将4,5-二氟苯-1,2-二胺(6.94mmol)、联苯甲酰(6.94mmol)溶于60mL乙醇中，升温至80℃，磁力搅拌下冷凝回流24h后，停止反应，冷却至室温，待析出固体后，进行抽滤。将固体用100mL甲醇进行洗涤，抽滤，得到固体。将固体在60℃真空干燥箱中干燥12h，即得固体为氟代喹喔啉衍生物单体(1.89g，85.9％)。1H NMR(400MHz,CDCl3)δ:7.95,7.93,7.91(t，2H),7.51(d,2H),7.49(d,2H),7.41-7.32(m,6H).13CNMR(100MHz,CDCl3)δ:155.153.5,140,133.1,129.3,128.8,127.5,115.
实施例8
一种氟代喹喔啉-噻吩共聚物的制备方法，包括以下步骤：
将6,7-二氟-3-甲基-2-十六烷氧基喹喔啉(0.1mmol)、3,3'-双十二烷基磺酰基并噻吩(0.1mmol)、碳酸银(0.4mmol)、碳酸钾(0.4mmol)和醋酸钯(0.01mmol)依次加入到反应瓶中，取1.0mL N,N-二甲基乙酰胺将原料溶解，升温至110℃，在磁力搅拌下反应48h后，停止反应，冷却至室温20～25℃，得到含有氟代喹喔啉-噻吩共聚物的反应液。采用索式提取方法对所得反应液进行提取，将提取所得固体在60℃真空干燥箱中干燥12h，即得共聚物P11为6,7-二氟-3-甲基-2-十六烷氧基喹喔啉-3,3'-双十二烷基磺酰基并噻吩共聚物(57.2mg,产率56％,Mn 3.5kDa,PDI 1.5)。1H NMR(400MHz,CDCl3)δ:4.39(d,2H),3.41(d,4H),3.04(dd,3H),1.90(s,1H),1.33-0.96(d,76H).
上述氟代喹喔啉衍生物单(6,7-二氟-3-甲基-2-十六烷氧基喹喔啉)体的结构式为：
上述制备方法的反应过程为：
合成氟代喹喔啉衍生物单体的步骤为(Sun,C.；Pan,F.；Bin,H.；Zhang,J.；Xue,L.；Qiu,B.；Wei,Z.；Zhang,Z.G.；Li,Y.,A low cost and high performance polymerdonor material for polymer solar cells.Nature communications 2018,9(1),743.)：将4,5-二氟苯-1,2-二胺(27.75mmol)溶于100mL乙醇中，冰水浴中将2.5mL丙酮酸甲酯以每秒钟2滴的速度滴入，滴加完后升温至40℃，磁力搅拌下冷凝回流6h后，停止反应，冷却至室温。抽滤得到白色固体(3.25g,60％)。将白色固体(16.57mmol)溶于100mL N,N-二甲基乙酰胺中，依次加入碳酸钾(19.9mmol)、1-溴-2-己基癸烷(16.57mmol)，升温至80℃，磁力搅拌下冷凝回流24h后，停止反应，冷却至室温。用150mL饱和氯化铵水溶液洗后，用50mL二氯甲烷萃取。再将二氯甲烷萃取有机相用500mL去离子水水洗后，将水相用50mL二氯甲烷萃取3次，合并二氯甲烷萃取有机相，用无水硫酸镁干燥后，抽滤除去硫酸镁，减压蒸馏浓缩至2mL，通过柱层析，即得无色液体为氟代喹喔啉衍生物单体(3.2g,46％)。1H NMR(400MHz,CDCl3)δ:7.67(dd,1H),7.55-7.47(m,1H),4.34(d,2H),2.61(s,3H),1.91-1.81(m,1H),1.49-1.19(m,27H),0.87(dd,7H).13C NMR(100MHz,CDCl3)δ:179.0,157.43,148.94,139.14,135.6,114.21,113.51,70.27,37.85,32.36,32.30,32.00,30.44,30.17,30.11,30.04,29.80,27.30,27.27,23.14,20.48,14.59.
实施例9
一种氟代喹喔啉-噻吩共聚物的制备方法，包括以下步骤：
将6,7-二氟-2,3-二苯基喹喔啉(0.1mmol)、3-甲基噻吩(0.1mmol)、醋酸铜(0.2mmol)、碳酸钾(0.4mmol)和(1,1'-双(二苯基膦基)二茂铁)二氯化钯(0.02mmol)依次加入到反应瓶中，取1mL四氢呋喃将原料溶解，升温至120℃，在磁力搅拌条件下反应48h后，停止反应，冷却至室温20～25℃，得到含有氟代喹喔啉-噻吩共聚物的反应液。
采用索式提取方法对所得反应液进行提取，将提取所得固体在60℃真空干燥箱中干燥12h，得共聚物P12为6,7-二氟-2,3-二苯基喹喔啉-3-甲基噻吩共聚物(27.6mg,产率67％,Mn 4.0kDa,PDI 1.7)。1H NMR(400MHz,CDCl3)δ:7.48(s,4H),7.32,7.22(s,6H),6.50(s,1H),2.21(s,3H).
上述氟代喹喔啉衍生物单体(6,7-二氟-2,3-二苯基喹喔啉)的结构式为：
上述制备方法的反应过程为：
合成氟代喹喔啉衍生物单体的步骤为(Jing Y M,Wang F Z,Zheng Y X,etal.Efficient deep red electroluminescence of iridium(Ⅲ)complexes with2,3-diphenylquinoxaline derivatives and tetraphenylimidodiphosphinate[J].J.Mater.Chem.C,2017,5(15):3714-3724.)：将4,5-二氟苯-1,2-二胺(6.94mmol)、联苯甲酰(6.94mmol)溶于60mL乙醇中，升温至80℃，磁力搅拌下冷凝回流24h后，停止反应，冷却至室温，待析出固体后，进行抽滤。将固体用100mL甲醇进行洗涤，抽滤，得到固体。将固体在60℃真空干燥箱中干燥12h，即得固体为氟代喹喔啉衍生物单体(1.89g，85.9％)。1H NMR(400MHz,CDCl3)δ:7.95,7.93,7.91(t，2H),7.51(d,2H),7.49(d,2H),7.41-7.32(m,6H).13CNMR(100MHz,CDCl3)δ:155.153.5,140,133.1,129.3,128.8,127.5,115.
实施例10
一种氟代喹喔啉-噻吩共聚物的制备方法，包括以下步骤：
将6,7-二氟-2,3-二苯基喹喔啉(0.1mmol)、3,6-二辛氧基苯并[1,2-b；4,5-b]噻吩(0.1mmol)、硝酸银(0.4mmol)、醋酸钾(0.4mmol)和醋酸钯(0.01mmol)依次加入到反应瓶中，取1.0mL N,N-二甲基乙酰胺将原料溶解，升温至110℃，在磁力搅拌条件下反应48h后，停止反应，冷却至室温20～25℃，得到含有氟代喹喔啉-噻吩共聚物的反应液。
采用索式提取方法对所得反应液进行提取，将提取所得固体在60℃真空干燥箱中干燥12h，即得共聚物P13为6,7-二氟-2,3-二苯基喹喔啉-3,6-二辛氧基苯并[1,2-b；4,5-b]噻吩共聚物(57.1mg,产率75％,Mn 5.0kDa,PDI 1.4)。1H NMR(400MHz,CDCl3)δ:7.48(s,4H),7.32,7.22(s,6H),7.30(s,2H),3.94(t,4H),1.71-0.96(m,30H).
上述氟代喹喔啉衍生物单体(6,7-二氟-2,3-二苯基喹喔啉)的结构式为：
上述制备方法的反应过程为：
合成氟代喹喔啉衍生物单体的步骤为(Jing Y M,Wang F Z,Zheng Y X,etal.Efficient deep red electroluminescence of iridium(Ⅲ)complexes with2,3-diphenylquinoxaline derivatives and tetraphenylimidodiphosphinate[J].J.Mater.Chem.C,2017,5(15):3714-3724.)：将4,5-二氟苯-1,2-二胺(6.94mmol)、联苯甲酰(6.94mmol)溶于60mL乙醇中，升温至80℃，磁力搅拌下冷凝回流24h后，停止反应，冷却至室温，待析出固体后，进行抽滤。将固体用100mL甲醇进行洗涤，抽滤，得到固体。将固体在60℃真空干燥箱中干燥12h，即得固体为氟代喹喔啉衍生物单体(1.89g，85.9％)。1H NMR(400MHz,CDCl3)δ:7.95,7.93,7.91(t，2H),7.51(d,2H),7.49(d,2H),7.41-7.32(m,6H).13CNMR(100MHz,CDCl3)δ:155.153.5,140,133.1,129.3,128.8,127.5,115.
以上通过钯催化氧化C-H/C-H偶联缩聚法直接制备的氟代喹喔啉-噻吩共聚物，其分子量Mn大致都在3～5kDa左右，多分散系数PDI在1.5左右，聚合物的分子量及其分布相对稳定。
以上对本发明做了示例性的描述，应该说明的是，在不脱离本发明的核心的情况下，任何简单的变形、修改或者其他本领域技术人员能够不花费创造性劳动的等同替换均落入本发明的保护范围。
Claims (10)
1.一种氟代喹喔啉-噻吩共聚物的制备方法，其特征在于，包括以下步骤：
将氟代喹喔啉衍生物单体、噻吩衍生物单体、溶剂、氧化剂、碱、添加剂和钯催化剂混合，在90～130℃下搅拌反应24～48h，冷却至室温20～25℃，得到含有氟代喹喔啉-噻吩共聚物的反应液，其中，按物质的量份数计，所述氟代喹喔啉衍生物单体、噻吩衍生物单体、钯催化剂、氧化剂、碱和添加剂的比为1：1：(0.005～0.2)：(0～10)：(0～10)：(0～10)；
所述氟代喹喔啉衍生物单体的结构通式为：
所述噻吩衍生物单体为：
2.根据权利要求1所述的制备方法，其特征在于，所述溶剂为甲苯、1,4-二氧六环、邻二甲苯、四氢呋喃、N,N-二甲基乙酰胺、甲苯和二甲基亚砜中的一种或几种的混合物；
所述氧化剂为Ag2CO3、AgF、AgOAc、Ag2O、Cu(OAc)2、Cu(OTf)2、CuCl2和AgNO3中的一种或几种的混合物；
所述碱为Na2CO3、K2CO3、Cs2CO3、NaHCO3、NaOAc、KOAc、CsOAc和KF中的一种或几种的混合物。
3.根据权利要求2所述的制备方法，其特征在于，所述添加剂为PPh3、PCy3-HBF4、P(t-Bu)3、PivOH和HOAc中的一种或几种的混合物；
所述钯催化剂为Pd(dppf)Cl2、Pd(OAc)2、PdCl2、Pd2(dba)3、Pd(TFA)2、PdCl2(PPh3)2、Pd(OH)2、Pd(PPh3)4和Pd/C中的一种或几种的混合物。
4.根据权利要求3所述的制备方法，其特征在于，按物质的量份数计，所述氟代喹喔啉衍生物单体、噻吩衍生物单体、钯催化剂、氧化剂、碱和添加剂的比为1：1：(0.05～0.2)：(1～4)：(1～4)：(0～4)。
5.根据权利要求4所述的制备方法，其特征在于，所述碱为K2CO3、Cs2CO3或KOAc，所述氧化剂为Ag2CO3或Cu(OAc)2，所述钯催化剂为Pd(OAc)2或Pd(PPh3)4，所述溶剂为四氢呋喃或N,N-二甲基乙酰胺。
6.根据权利要求5所述的制备方法，其特征在于，搅拌反应的温度为100～120℃。
7.根据权利要求6所述的制备方法，其特征在于，所述氟代喹喔啉衍生物单体和噻吩衍生物单体在所述溶剂中的浓度各为0.01～1mol/L。
8.根据权利要求6所述的制备方法，其特征在于，所述氟代喹喔啉衍生物单体和噻吩衍生物单体在所述溶剂中的浓度各为0.1～0.5mol/L。
9.根据权利要求7或8所述的制备方法，其特征在于，将所述反应液逐滴加入至甲醇中进行沉降，抽滤，得到粗产品，将所述粗产品先后依次用甲醇和正己烷索氏抽提，再用氯仿索氏抽提，收集氯仿提取液，浓缩后加入甲醇进行沉降，抽滤，干燥后得到氟代喹喔啉-噻吩共聚物。
10.如权利要求1～9中任意一项所述制备方法获得的氟代喹喔啉-噻吩共聚物。
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011143825A1 (zh) * | 2010-05-21 | 2011-11-24 | 海洋王照明科技股份有限公司 | 含二噻吩并吡咯喹喔啉类共轭聚合物及其制备方法和应用 |
| CN102276802A (zh) * | 2010-06-10 | 2011-12-14 | 海洋王照明科技股份有限公司 | 含噻吩-喹喔啉单元芴类共聚物及其制备方法和应用 |
| CN102295753A (zh) * | 2010-06-25 | 2011-12-28 | 海洋王照明科技股份有限公司 | 含环戊二烯二噻吩-喹喔啉-噻吩共轭聚合物及其制备方法和应用 |
| CN102816306A (zh) * | 2012-08-30 | 2012-12-12 | 西安近代化学研究所 | 氟代喹喔啉与噻吩的共轭聚合物 |
| CN102816303A (zh) * | 2012-08-30 | 2012-12-12 | 西安近代化学研究所 | 双噻吩并环硅戊二烯-氟代喹喔啉共轭聚合物 |
| CN102838733A (zh) * | 2012-08-30 | 2012-12-26 | 西安近代化学研究所 | 9,9-二辛基芴与氟代喹喔啉的共轭聚合物 |
| CN102906151A (zh) * | 2010-06-25 | 2013-01-30 | 海洋王照明科技股份有限公司 | 基于苯唑二噻吩和噻吩并吡嗪的共轭聚合物及其制备方法和应用 |
| WO2015154190A1 (en) * | 2014-04-11 | 2015-10-15 | The Governing Council Of The University Of Toronto | Conjugated polymers, and synthesis and use thereof |
-
2019
- 2019-04-30 CN CN201910364271.8A patent/CN111154075B/zh not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011143825A1 (zh) * | 2010-05-21 | 2011-11-24 | 海洋王照明科技股份有限公司 | 含二噻吩并吡咯喹喔啉类共轭聚合物及其制备方法和应用 |
| CN102276802A (zh) * | 2010-06-10 | 2011-12-14 | 海洋王照明科技股份有限公司 | 含噻吩-喹喔啉单元芴类共聚物及其制备方法和应用 |
| CN102295753A (zh) * | 2010-06-25 | 2011-12-28 | 海洋王照明科技股份有限公司 | 含环戊二烯二噻吩-喹喔啉-噻吩共轭聚合物及其制备方法和应用 |
| CN102906151A (zh) * | 2010-06-25 | 2013-01-30 | 海洋王照明科技股份有限公司 | 基于苯唑二噻吩和噻吩并吡嗪的共轭聚合物及其制备方法和应用 |
| CN102816306A (zh) * | 2012-08-30 | 2012-12-12 | 西安近代化学研究所 | 氟代喹喔啉与噻吩的共轭聚合物 |
| CN102816303A (zh) * | 2012-08-30 | 2012-12-12 | 西安近代化学研究所 | 双噻吩并环硅戊二烯-氟代喹喔啉共轭聚合物 |
| CN102838733A (zh) * | 2012-08-30 | 2012-12-26 | 西安近代化学研究所 | 9,9-二辛基芴与氟代喹喔啉的共轭聚合物 |
| WO2015154190A1 (en) * | 2014-04-11 | 2015-10-15 | The Governing Council Of The University Of Toronto | Conjugated polymers, and synthesis and use thereof |
Non-Patent Citations (1)
| Title |
|---|
| QIANG ZHANG ET AL: "A Direct C-H Coupling Method for Preparing π‑Conjugated Functional Polymers with High Regioregularity", 《MACROMOLECULES》 * |
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