CN106317383A - Organic monomer containing 8-hydroxyquinoline boron, conjugated polymer based on monomer, preparation method and application - Google Patents
Organic monomer containing 8-hydroxyquinoline boron, conjugated polymer based on monomer, preparation method and application Download PDFInfo
- Publication number
- CN106317383A CN106317383A CN201610669251.8A CN201610669251A CN106317383A CN 106317383 A CN106317383 A CN 106317383A CN 201610669251 A CN201610669251 A CN 201610669251A CN 106317383 A CN106317383 A CN 106317383A
- Authority
- CN
- China
- Prior art keywords
- compound
- solution
- hydroxyquinoline
- boron
- organic monomer
- 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
- 239000000178 monomer Substances 0.000 title claims abstract description 80
- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 59
- GSEFVFUHICERMB-UHFFFAOYSA-N boron;quinolin-8-ol Chemical compound [B].C1=CN=C2C(O)=CC=CC2=C1 GSEFVFUHICERMB-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 91
- 150000001875 compounds Chemical class 0.000 claims abstract description 78
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 126
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 117
- 239000000243 solution Substances 0.000 claims description 110
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 98
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 90
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 87
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 84
- 238000003756 stirring Methods 0.000 claims description 74
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 67
- 229910052786 argon Inorganic materials 0.000 claims description 49
- 208000035126 Facies Diseases 0.000 claims description 45
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 42
- 229940043279 diisopropylamine Drugs 0.000 claims description 42
- 239000002904 solvent Substances 0.000 claims description 40
- 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 37
- 238000002390 rotary evaporation Methods 0.000 claims description 37
- 239000007787 solid Substances 0.000 claims description 35
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 32
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 30
- 229940126214 compound 3 Drugs 0.000 claims description 30
- 239000000047 product Substances 0.000 claims description 29
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 28
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 28
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 28
- 125000000217 alkyl group Chemical group 0.000 claims description 26
- 229940125782 compound 2 Drugs 0.000 claims description 26
- 239000002027 dichloromethane extract Substances 0.000 claims description 25
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 25
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 24
- 239000000706 filtrate Substances 0.000 claims description 24
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 24
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 239000012065 filter cake Substances 0.000 claims description 19
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 18
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 17
- 239000012528 membrane Substances 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 16
- -1 alkyl 2,5-dibromo thiophene Chemical compound 0.000 claims description 16
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 16
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000000376 reactant Substances 0.000 claims description 15
- 239000008346 aqueous phase Substances 0.000 claims description 14
- 229940125904 compound 1 Drugs 0.000 claims description 14
- 229940125898 compound 5 Drugs 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 13
- 239000011777 magnesium Substances 0.000 claims description 13
- 229910052749 magnesium Inorganic materials 0.000 claims description 13
- KBVDUUXRXJTAJC-UHFFFAOYSA-N 2,5-dibromothiophene Chemical class BrC1=CC=C(Br)S1 KBVDUUXRXJTAJC-UHFFFAOYSA-N 0.000 claims description 12
- 239000005725 8-Hydroxyquinoline Substances 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 229960003540 oxyquinoline Drugs 0.000 claims description 12
- SKOWZLGOFVSKLB-UHFFFAOYSA-N hypodiboric acid Chemical compound OB(O)B(O)O SKOWZLGOFVSKLB-UHFFFAOYSA-N 0.000 claims description 11
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 11
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 10
- 238000010790 dilution Methods 0.000 claims description 10
- 239000012895 dilution Substances 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 9
- 229910052796 boron Inorganic materials 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 8
- 229910000085 borane Inorganic materials 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- CWMFRHBXRUITQE-UHFFFAOYSA-N trimethylsilylacetylene Chemical compound C[Si](C)(C)C#C CWMFRHBXRUITQE-UHFFFAOYSA-N 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- KWTSZCJMWHGPOS-UHFFFAOYSA-M chloro(trimethyl)stannane Chemical compound C[Sn](C)(C)Cl KWTSZCJMWHGPOS-UHFFFAOYSA-M 0.000 claims description 5
- 238000001514 detection method Methods 0.000 claims description 5
- 229910000474 mercury oxide Inorganic materials 0.000 claims description 5
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 claims description 5
- 238000001953 recrystallisation Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 238000001548 drop coating Methods 0.000 claims description 4
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- MCQRPQCQMGVWIQ-UHFFFAOYSA-N boron;methylsulfanylmethane Chemical compound [B].CSC MCQRPQCQMGVWIQ-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- RKFFUJHJOUYEKT-UHFFFAOYSA-N boron;quinoline Chemical compound [B].N1=CC=CC2=CC=CC=C21 RKFFUJHJOUYEKT-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- SZYJELPVAFJOGJ-UHFFFAOYSA-N trimethylamine hydrochloride Chemical compound Cl.CN(C)C SZYJELPVAFJOGJ-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 17
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000006862 quantum yield reaction Methods 0.000 abstract description 4
- 238000004440 column chromatography Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 description 43
- 238000003786 synthesis reaction Methods 0.000 description 43
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Divinylene sulfide Natural products C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 229930192474 thiophene Natural products 0.000 description 8
- FXDUXBIZVCPXPZ-UHFFFAOYSA-N 2-iodoquinolin-8-ol Chemical compound C1=C(I)N=C2C(O)=CC=CC2=C1 FXDUXBIZVCPXPZ-UHFFFAOYSA-N 0.000 description 7
- 239000010409 thin film Substances 0.000 description 7
- MXHOLIARBWJKCR-UHFFFAOYSA-N 1-bromo-4-hexylbenzene Chemical compound CCCCCCC1=CC=C(Br)C=C1 MXHOLIARBWJKCR-UHFFFAOYSA-N 0.000 description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 230000021615 conjugation Effects 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004020 luminiscence type Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 230000003381 solubilizing effect Effects 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- GZZMPRDPYFYDLW-UHFFFAOYSA-M O1CCCC1.C[Sn](C)(C)Cl Chemical compound O1CCCC1.C[Sn](C)(C)Cl GZZMPRDPYFYDLW-UHFFFAOYSA-M 0.000 description 3
- 229930040373 Paraformaldehyde Natural products 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 238000005401 electroluminescence Methods 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229920002866 paraformaldehyde Polymers 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- CMQCNTNASCDNGR-UHFFFAOYSA-N toluene;hydrate Chemical compound O.CC1=CC=CC=C1 CMQCNTNASCDNGR-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 0 Cc1c[s]c(-c2c(*)cc[s]2)c1* Chemical compound Cc1c[s]c(-c2c(*)cc[s]2)c1* 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 description 2
- 238000004847 absorption spectroscopy Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical group C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- BRGVKVZXDWGJBX-UHFFFAOYSA-N 1-bromo-4-butylbenzene Chemical compound CCCCC1=CC=C(Br)C=C1 BRGVKVZXDWGJBX-UHFFFAOYSA-N 0.000 description 1
- RFFMRBISTZHCNY-UHFFFAOYSA-N 1-bromo-4-dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=C(Br)C=C1 RFFMRBISTZHCNY-UHFFFAOYSA-N 0.000 description 1
- UWZYHHMSEIANER-UHFFFAOYSA-N 1-bromo-4-hexadecylbenzene Chemical compound CCCCCCCCCCCCCCCCC1=CC=C(Br)C=C1 UWZYHHMSEIANER-UHFFFAOYSA-N 0.000 description 1
- OOZQSVXPBCINJF-UHFFFAOYSA-N 1-bromo-4-octylbenzene Chemical compound CCCCCCCCC1=CC=C(Br)C=C1 OOZQSVXPBCINJF-UHFFFAOYSA-N 0.000 description 1
- TUCRZHGAIRVWTI-UHFFFAOYSA-N 2-bromothiophene Chemical compound BrC1=CC=CS1 TUCRZHGAIRVWTI-UHFFFAOYSA-N 0.000 description 1
- 206010049244 Ankyloglossia congenital Diseases 0.000 description 1
- 241000040710 Chela Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 238000005700 Stille cross coupling reaction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- RZWZDIVNLQZHGB-UHFFFAOYSA-N chloroform;methylsulfinylmethane Chemical compound CS(C)=O.ClC(Cl)Cl RZWZDIVNLQZHGB-UHFFFAOYSA-N 0.000 description 1
- NWSBNVVOFKKFNV-UHFFFAOYSA-N chloroform;oxolane Chemical compound ClC(Cl)Cl.C1CCOC1 NWSBNVVOFKKFNV-UHFFFAOYSA-N 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 235000012000 cholesterol Nutrition 0.000 description 1
- 125000003716 cholic acid group Chemical group 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- FZGRPBJBMUNMQH-UHFFFAOYSA-N trimethyl-$l^{3}-chlorane Chemical compound CCl(C)C FZGRPBJBMUNMQH-UHFFFAOYSA-N 0.000 description 1
- HYUFXBPAIGJHRY-UHFFFAOYSA-N triphenylphosphane;dihydrochloride Chemical compound Cl.Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 HYUFXBPAIGJHRY-UHFFFAOYSA-N 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention discloses an organic monomer containing 8-hydroxyquinoline boron, a conjugated polymer based on the monomer, a preparation method and application, and belongs to the technical field of preparation of the conjugated polymer containing a main group element and application of photoelectrical properties of the conjugated polymer. The preparation method of the compound has the outstanding advantages of being easy and convenient to operate, mild in reaction condition, capable of conducting large-scale production, high in adaptability to substrate, free of column chromatography purification and the like; the prepared monomer and the polymer are good in photochemical stability, high in fluorescence quantum yield and excellent in solubility, and a firm foundation is laid for sensing application and photoelectric property application of the monomer and the polymer.
Description
Technical field
The invention belongs to the preparation containing major element conjugated polymer and photoelectric property applied technical field thereof, be specifically related to
One class is containing the organic monomer of 8-hydroxyquinoline boron and conjugated polymer based on this monomer and preparation method and application.
Background technology
Organic optoelectronic as an emerging research field, be across chemistry, material, physics, one of information novel
Cross discipline, the most received the extensive concern of academia and industrial quarters.At present, organic electroluminescent LED, have
Field effect transistors, organic photovoltaic battery, organic sensor and have sending out rapidly of the organic electro-optic devices such as machine information storage
Exhibition has embodied the advantage that inorganic semiconductor device is incomparable.Organic photoelectrical material is attached most importance to most as organic electro-optic device
The ingredient wanted, directly affects the development of these photoelectric devices.Compared with inorganic material, organic photoelectrical material can pass through
Solwution method realizes large area preparation and prepared by flexible device.Meanwhile, organic material has diversified structure composition and broadness
Property regulation space, can obtain required performance by MOLECULE DESIGN, it is possible to carry out the device from bottom to top such as self assembly
Part assembling mode prepares nano-device and molecular device.From structure, organic photoelectrical material is typically rich in carbon atom, tool
There is the most pi-conjugated organic molecule, be broadly divided into the little molecule of conjugation and the big class of conjugated polymer two.Either organic molecule,
Or conjugatd polymers, its photoelectric property by changing the structure of molecule itself or can introduce the sense of specific function
Group carries out improving and regulating, thus realizes the regulation and control to device performance.
Organic conjugate system is from full carbon system to other heteroatomic introducings, prepared organic conjugate heterocyclic arene, nothing
Have by the performance the most finally preparing device from material nature and significantly promoted.From the electronic structure of atom,
Compared with common carbon atom, either the 14th other Elements Atom of main group (silicon, germanium and stannum etc.) or other adjacent main groups (
13,15 and 16 main group) Elements Atom introduces in conjugated system electron energy level and the structure that all can greatly change system, and tie
The change of structure itself often will carry out the biggest impact by donor frenulum；Corresponding, 8-hydroxyquinoline is a kind of typical chela
Mixture, has prominent luminescence generated by light, Electroluminescence Properties, obtains wide in Coordinative Chemistry and photoelectric activity organic solid are formulated
General application.
Although before the organic conjugate heterocyclic arene containing major element has shown performance and the huge development of excellence
Scape, but realize that this compounds is designed synthesis efficiently, easily and still there is a lot of difficulties.
At present, this compounds is mainly by the halogenide EX of major element2(E: major element, X: halogen atom) and phase
Synthesis is prepared in the metal double lithium reagent reaction answering organic backbone, and often these synthetic routes are the longest, reaction condition is more severe
Carve, synthesis difficulty the biggest.Obviously, develop the little molecule of the new organic conjugate containing major element and the synthetic method of polymer, preparation
The a series of conjugatd polymers material containing major element is always a focus of concern, otherwise will day of one's doom greatly
Make the extensive application of such material.Therefore, simple efficient synthesis strategy, the preparation little point of the organic conjugate containing major element are set up
Son and polymer are the outstanding problems of this area research at present.
Summary of the invention
It is an object of the invention to provide the class organic monomer containing 8-hydroxyquinoline boron and conjugation based on this monomer is gathered
Compound and preparation method and application, it is short that the method has synthesis cycle, and method is simple, it is possible to carries out extensive synthesis etc. and highlights
Advantage, the organic monomer prepared and conjugated polymer all show the photoelectric properties of excellence, are expected at selectivity efficient, high
Fluorescence sense and organic photoelectrical material obtain application.
The present invention is to be achieved through the following technical solutions:
The invention discloses the class organic monomer containing 8-hydroxyquinoline boron, the structural formula of this organic monomer is as follows:
Wherein, R represents Br or I；M=0,1,2,3,4,6,8,12 or 16.
The invention also discloses conjugated polymer based on the above-mentioned organic monomer containing 8-hydroxyquinoline boron, including 4 kinds
Conjugated polymer, respectively P1, P2, P3 and P4, its structural formula is respectively as follows:
Wherein, m=0,1,2,3,4,6,8,12 or 16；N is the integer between 1-100；K=0,4 or 6；H=0,1,2,3,
4,5,6,8,10,12,14 or 16；Q=0,4,6 or 12；T=0,4 or 6.
The invention also discloses the method preparing the above-mentioned organic monomer containing 8-hydroxyquinoline boron, comprise the following steps:
1) compound 1 is prepared
Under argon shield atmosphere, diisopropylamine is joined in anhydrous tetrahydrofuran solution, stir, at ice bath bar
Under part, dropwise dropping borane dimethylsulfide ethereal solution, after dropping, continues reaction 1-3 hour under condition of ice bath；The most again to instead
Answer the solution being added dropwise over n-BuLi in system, under condition of ice bath, continue stirring 1-3 hour；Finally, in reaction system by
It is added dropwise to trim,ethylchlorosilane, produces substantial amounts of white precipitate, after treating all to drip, after being stirred at room temperature 1-3 hour, reaction
Liquid stands 0.5-2 hour, filters, obtain water white filtrate and be compound 1 under argon shield, and by it in argon shield
Under save backup；
2) compound 2 is prepared
Under argon shield atmosphere, in the anhydrous tetrahydrofuran solution of 1-(4-alkyl) bromobenzene, it is separately added into magnesium chips and change
Compound 1, stirring reaction 20-24 hour at 70-85 DEG C, after reaction terminates, ice bath downhill reaction liquid adds hydrochloric acid, room temperature
Stirring 45-60 minute, then add water and ether, extraction in reaction system, collect organic facies, aqueous phase dichloromethane extracts
Taking, merge organic facies, be dried, filter, rotary evaporation removes solvent, prepares compound 2；
Wherein, described 1-(4-alkyl) bromobenzene structural formula such as following formula:
Wherein m=0,1,2,3,4,6,8,12 or 16；
3) compound 3 is prepared
Being dissolved in ether by compound 2, in solution, addition 5,7-dihalo-8-hydroxyquinoline, be stirred at room temperature reaction
After 15-20 hour, in solution, add pentane, separate out precipitation, filter, collect filter cake, prepare compound 3, the i.e. hydroxyl Han 8-
The organic monomer of quinoline boron.
Step 1) in, diisopropylamine, borane dimethylsulf iotade, n-BuLi, trim,ethylchlorosilane and oxolane mole
Ratio is 1:1:1:1:(4-5)；
Step 2) in, the mol ratio of compound 1,1-(4-alkyl) bromobenzene, magnesium, hydrochloric acid and oxolane is 1:(2-3):
(2-4): (15-24): the volume ratio of (90-120), water and ether is 1:1；
Step 3) in, compound 2,5, the mol ratio of 7-dihalo-8-hydroxyquinoline and ether is 1:1:(50-70)；Institute
Stating 5,7-dihalo-8-hydroxyquinoline, wherein halogen is bromine or iodine.
The method that the invention also discloses the conjugated polymer preparing the above-mentioned organic monomer containing 8-hydroxyquinoline boron, including
Following steps:
Step 1: prepare conjugated polymer P1
Under argon shield, the organic monomer containing 8-hydroxyquinoline boron is dissolved in anhydrous tetrahydro furan, in solution
Add tetrakis triphenylphosphine palladium, the wet chemical of anaerobic and the substituted Isosorbide-5-Nitrae of alkyl-benzene hypoboric acid, anti-in 70-80 DEG C of stirring
After answering 24-30 hour, being extracted by reactant liquor dichloromethane, organic facies anhydrous magnesium sulfate is dried, and rotary evaporation removes solvent；
Being dissolved by product with dichloromethane, drop to, in the methanol of strong stirring, obtain yellow mercury oxide, filter, collect filter cake, vacuum is done
Dry, obtaining yellow solid is conjugated polymer P1；
Step 2: prepare conjugated polymer P2
Under argon shield, the organic monomer containing 8-hydroxyquinoline boron is dissolved in dry toluene and diisopropylamine, to
Solution adds Hydro-Giene (Water Science)., tetrakis triphenylphosphine palladium and the substituted Isosorbide-5-Nitrae-diacetylene-benzene of alkoxyl, anti-in 70-80 DEG C of stirring
After answering 22-30 hour, add toluene and be diluted, filter, filtrate priority water and saturated common salt washing, dichloromethane extracts,
Organic facies anhydrous magnesium sulfate is dried, and rotary evaporation removes solvent, is dissolved by product with dichloromethane, drops to strong stirring
In methanol, filtering, be dried, prepared orange solids is conjugated polymer P2；
Step 3: prepare compound 4
Under argon shield, by substituted for alkyl 2,5-dibromo thiophene is dissolved in anhydrous diisopropylamine, adds in solution
Hydro-Giene (Water Science)., double (triphenylphosphine) palladium chloride, stir 30-40 minute, adds trimethyl acetenyl silicon in solution, and ice bath stirs
Mix 60-80 minute, be then stirred at room temperature 60-80 minute, be finally warming up to 75-85 DEG C of stirring reaction 20-24 hour；Reaction terminates
Backward solution adds dichloromethane be diluted, filter, filtrate rotary evaporation is removed, use silica gel-normal hexane system to enter
Row pillar layer separation, prepares compound 4；
Step 4: prepare compound 5
Compound 4 is dissolved in methanol, is subsequently adding potassium hydroxide aqueous solution, lucifuge, be stirred at room temperature reaction 6-
10 hours, after reaction terminates, adding water in solution, with n-hexane extraction, be dried, filter, rotary evaporation removes solvent, and vacuum is done
Dry, prepare compound 5；
Step 5: prepare compound 6
Under argon shield, by substituted for alkyl chain 2,2 '-di-thiophene is dissolved in anhydrous tetrahydro furan, and-78
Under the conditions of DEG C, in solution, drip n-butyllithium solution, after dropping, stir 1-2 hour at-78 DEG C；Then, at 0 DEG C
Under the conditions of, in solution, drip trimethyl ammonia chloride solution of tin, after dropping, after being stirred at room temperature 12-15 hour, add acetic acid second
Ester is diluted, washing, and separatory collects organic facies, and aqueous phase dichloromethane extracts, and merges organic facies, is dried, and filters, and rotates
Evaporation of solvent；Finally with ethyl alcohol recrystallization, prepare compound 6；
Step 6: prepare conjugated polymer P3
Under argon shield, the organic monomer containing 8-hydroxyquinoline boron is dissolved in dry toluene and diisopropylamine, to
Solution adds Hydro-Giene (Water Science)., tetrakis triphenylphosphine palladium and compound 5, after 70-80 DEG C of stirring reaction 22-30 hour, adds
Toluene is diluted, and filters, and filtrate priority water and saturated common salt washing, dichloromethane extracts, organic facies anhydrous magnesium sulfate
Being dried, rotary evaporation removes solvent；With dichloromethane, product is dissolved, drops in the methanol of strong stirring, filter, be dried,
Prepare dark red solid P3；
Step 7: prepare conjugated polymer P4
Under argon shield, the organic monomer containing 8-hydroxyquinoline boron is dissolved in dry toluene, adds in solution
Tetrakis triphenylphosphine palladium and compound 6, after 110-120 DEG C of stirring reaction 22-30 hour, filter, and filtrate uses water with full respectively
Washing with Sal, collect organic facies, aqueous phase dichloromethane extracts, and organic facies anhydrous magnesium sulfate is dried, and filters, rotary evaporation
Remove solvent, with dichloromethane, product is dissolved, drop in the methanol of strong stirring, filter, be dried, prepare red solid altogether
Conjugated polymer P4.
In step 1, organic monomer containing 8-hydroxyquinoline boron, alkyl replace Isosorbide-5-Nitrae-benzene hypoboric acid, tetrakis triphenylphosphine palladium,
The mol ratio of potassium carbonate and oxolane is 1:1:(0.05-0.15): (10-20): (350-400)；
In step 2, the substituted Isosorbide-5-Nitrae-diacetylene-benzene of the organic monomer containing 8-hydroxyquinoline boron, alkoxyl, four (triphenyls
Phosphine) palladium, Hydro-Giene (Water Science)., the mol ratio of toluene and diisopropylamine be 1:1:(0.05-0.15): (0.05-0.15): (250-400):
(80-130)；
In step 3, alkyl substituted 2,5-dibromo thiophene, Hydro-Giene (Water Science)., double (triphenylphosphine) palladium chloride, trimethyl second
The mol ratio of alkynyl silicon and diisopropylamine is 1:(0.05-0.15): (0.05-0.15): (4-6): (50-60)；
In step 4, the mol ratio of compound 4, potassium hydroxide and methanol is 1:(0.3-0.5): (320-350)；
In step 5, alkyl chain substituted 2, rubbing of 2 '-di-thiophene, n-BuLi, trimethyltin chloride and oxolane
That ratio is 1:(2-3): (2-3): (50-80)；
In step 6, the organic monomer containing 8-hydroxyquinoline boron, compound 5, Hydro-Giene (Water Science)., tetrakis triphenylphosphine palladium, toluene
It is 1:1:(0.05-0.15 with the mol ratio of diisopropylamine): (0.05-0.15): (250-400): (80-130)；
Organic monomer, compound 6, tetrakis triphenylphosphine palladium and the mol ratio of toluene in step 7, containing 8-hydroxyquinoline boron
For 1:1:(0.05-0.15): (360-400).
In step 3, described alkyl substituted 2,5-dibromo thiophene structural formula such as following formula:
Wherein, q=0,4,6 or 12；
In step 5, described alkyl chain substituted 2, the structural formula of 2 '-di-thiophene such as following formula:
Wherein, t=0,4 or 6.
Preferably, involved solvent is at least one in benzene, toluene, oxolane, DMF.Institute
Relating to catalyst is coupling reaction custom catalysts, such as tetrakis triphenylphosphine palladium, double (triphenylphosphine) palladium chloride etc..Involved
Solubilizing group-CkH2k+1、-CqH2q+1、-ChH2h+1、-CtH2t+1、-CmH2m+1Being not limited to long chain alkane, other solubilizing group is still
Try out in patent of the present invention, such as cholesterol fragment, cholic acid fragment, polyhydroxy substituent group etc..
The invention also discloses the organic monomer used containing 8-hydroxyquinoline boron or the organic list containing 8-hydroxyquinoline boron
The conjugated polymer of body prepares the method for fluorescence membrane, is dissolved in chloroform by described conjugated polymer, is prepared as 1-
The storing solution of 10mg/mL；Take 20-50 μ L storing solution drop coating every time and prepare fluorescence membrane in glass matrix surface.
The invention discloses the application in detection formalin and formaldehyde gas of the above-mentioned prepared fluorescence membrane.
Compared with prior art, the present invention has a following useful technique effect:
The invention discloses the class organic monomer containing 8-hydroxyquinoline boron and four kinds of conjugated polymers based on this monomer,
These several compounds all contain major element boron and 8-hydroxyquinoline fragment, the electron deficiency (Lewis is acid) that boron atom is intrinsic
The organic conjugated molecule making boracic is the most all preferable electron acceptor material, thus in the side such as organic photoelectric and fluorescence sense
Face all has boundless application prospect；And 8-hydroxyquinoline is a kind of typical chelating agen, have prominent luminescence generated by light,
Electroluminescence Properties；And by introducing solubilizing group, such as chain alkyl, improve dissolubility and the film property of polymeric material,
And its assembly behavior can be regulated, and then produce abundant optics behavior.
It is little that the major element boron and 8-hydroxyquinoline unit with excellent photoelectric properties are simultaneously introduced into conjugation by the present invention
In molecule, and using long alkyl chain as solubilizing group, the method having developed efficient, the pervasive synthesis of conjugate polymer of a class, system
For having gone out the little molecule of the organic conjugate containing major element of a series of high reaction activity functional groups functionalization, and then pass through
Sonogashira cross-coupling reaction, Suzuki cross-coupling reaction, Stille cross-coupling reaction etc. are efficiently, make easily
For having obtained four kinds of boron polymers Han 8-hydroxyquinoline, preparation technology is simple, and equipment requirements is low, and monomer adaptability is relatively strong, equally
It is suitable for other polyreaction type.Obtained by monomer and polymer be respectively provided with excellent dissolubility, high fluorescence quantum yield,
Abundant photophy-sical behavior, and photochemical stability performance is prominent, for realizing its sensitive, selectivity sensing detection and enriching
Photoelectric characteristic established solid foundation.The preparation method of compound disclosed in this invention has easy and simple to handle, reaction bar
Part is gentle, can carry out large-scale production, to substrate strong adaptability, it is not necessary to carry out the outstanding advantages such as column chromatography purification；Made
Standby monomer and polymer photochemistry good stability, fluorescence quantum yield is high, dissolubility is excellent, special for its Application in Sensing and photoelectricity
Property application established solid foundation.
Accompanying drawing explanation
Fig. 1 is the organic monomer obtained by the present invention and the four kinds of boracic conjugated polymers ultraviolet in chloroform-can
See abosrption spectrogram；
Fig. 2 is the organic monomer obtained by the present invention and four kinds of boracic conjugated polymers fluorescent emission in chloroform
Spectrogram；
Fig. 3 is the organic monomer obtained by the present invention and the four kinds of boracic conjugated polymers fluorescence emission spectrum in thin-film state
Figure；
Fig. 4 is photochemical in chloroform soln of the organic monomer obtained by the present invention and four kinds of boracic conjugated polymers
Learn stability emission spectrum figure；
Fig. 5 is the organic monomer obtained by the present invention and the four kinds of boracic conjugated polymers photochemical stability in thin-film state
Emission spectrum figure；
Fig. 6 is that the organic monomer obtained by the present invention and four kinds of boracic conjugated polymer sense films are in daylight lamp and ultraviolet
Photo under lamp；
Fig. 7 is the conjugated polymer P4 for preparing of present invention fluorescence sense figure in the presence of variable concentrations formaldehyde；
Fig. 8 is the visualization photo of the conjugated polymer P4 PARA FORMALDEHYDE PRILLS(91,95) sensing that the present invention prepares；
Fig. 9 is boracic monomer and the synthetic route schematic diagram of conjugated polymer of the present invention.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail, described in be explanation of the invention and
It not to limit.
See Fig. 9, the organic monomer containing 8-hydroxyquinoline boron disclosed by the invention and four kinds of conjugated polymers can pass through
Prepared by following steps:
1, a kind of organic monomer containing 8-hydroxyquinoline boron and the preparation of four kinds of conjugated polymers
1) compound 1 is prepared
Under argon shield atmosphere, diisopropylamine joined in anhydrous tetrahydrofuran solution and be sufficiently stirred for, and at ice
Under the conditions of bath, dropwise borane dimethylsulfide ethereal solution is joined in above-mentioned reactant liquor, after dropping, continue anti-under condition of ice bath
Answer 1-3 hour；In reaction system, it is added dropwise over the solution of n-BuLi the most again, under condition of ice bath, continues stirring 1-3 hour；
Finally, in reaction system, it is added dropwise over trim,ethylchlorosilane, produces substantial amounts of white precipitate, after all adding, room immediately
Temperature stirring 1-3 hour.After reaction terminates, reactant liquor stands 0.5-2 hour, filters, obtain water white filter under argon shield
Liquid is compound 1, and it is saved backup under argon shield.Wherein diisopropylamine, borane dimethylsulf iotade, n-BuLi,
The mol ratio of trim,ethylchlorosilane and oxolane is: 1:1:1:1:(4-5).Its reaction equation is as follows:
2) compound 2 is prepared
Under argon shield atmosphere, in the anhydrous tetrahydrofuran solution of 1-(4-alkyl) bromobenzene, it is separately added into magnesium chips and change
Compound 1, stirring reaction 20-24 hour at 70-85 DEG C.After reaction terminates, in ice bath downhill reaction liquid, add 3-6mol/L's
Hydrochloric acid, is stirred at room temperature 45-90 minute, then adds water and ether, separatory in reactant liquor, collect organic facies, aqueous phase dichloro
Methane extracts 3-5 time, merges organic facies, and anhydrous magnesium sulfate is dried, and filters, and rotary evaporation removes solvent, obtains faint yellow oily
Thing.Wherein the mol ratio of compound 1,1-(4-alkyl) bromobenzene, magnesium, hydrochloric acid and oxolane is: 1:(2-3): (2-4): (15-
24): the volume ratio of (90-120), water and ether is 1:(1-3).Its reaction equation is as follows:
M=0,1,2,3,4,6,8,12 or 16；
3) compound 3 is prepared
Being dissolved in ether by compound 2, in solution, addition 5, the iodo-8-hydroxyquinoline of 7-bis-, be stirred at room temperature 15-30 little
Time.After reaction terminates, in solution, add a large amount of pentane, separate out a large amount of yellow-green precipitate, filter, collect filter cake, obtain Huang
Green solid.Wherein the mol ratio of compound 2, the iodo-8-hydroxyquinoline of 5,7-bis-and ether is 1:1:(50-70).Its reaction side
Formula is as follows:
4) compound 4 is prepared
Under argon shield, by substituted for alkyl chain 2,5-dibromo thiophene is dissolved in anhydrous diisopropylamine, adds in solution
Enter Hydro-Giene (Water Science)., double (triphenylphosphine) palladium chloride, stir 30-40 minute, in solution, be added dropwise over trimethyl acetenyl silicon,
Ice bath stirs 60-80 minute, is then stirred at room temperature 60-80 minute, is finally warming up to 75-85 DEG C of stirring reaction 20-24 hour.Instead
After should terminating, in solution, add q. s. methylene chloride dilution, filter, filtrate rotary evaporation is removed solvent, recycle silicon glue/just
Hexane carries out pillar layer separation, obtains yellow crystalline solid.Wherein alkyl substituted 2,5-dibromo thiophene, Hydro-Giene (Water Science)., double (three
Phenylphosphine) palladium chloride, the mol ratio of trimethyl acetenyl silicon and diisopropylamine be 1:(0.05-0.15): (0.05-0.15):
(4-6): (50-60).Its reaction equation is as follows:
Q=0,4,6 or 12；
5) compound 5 is prepared
Compound 4 is dissolved in methanol, in solution, adds the potassium hydroxide aqueous solution of 0.5-1mol/L, lucifuge,
Under room temperature, stirring reaction 6-10 hour, after reaction terminates, adds appropriate water in solution, with n-hexane extraction 3-5 time, collection
Organic facies, anhydrous magnesium sulfate is dried, and filters, and rotary evaporation removes solvent, obtains yellow oil.Wherein compound 4, hydroxide
The mol ratio of potassium and methanol is 1:(0.3-0.5): (320-350).Its reaction equation is as follows:
6) compound 6 is prepared
Under argon shield, by substituted for alkyl chain 2,2 '-di-thiophene is dissolved in anhydrous tetrahydro furan, and-78
Under the conditions of DEG C, in solution, drip the n-butyllithium solution of 1.6-2.5mol/L.After dropping, at-78 DEG C, stir 1-3 little
Time.Then, warm naturally to 0 DEG C and under this condition, in solution, drip trimethyltin chloride tetrahydrofuran solution, drip
Bi Hou, is stirred at room temperature 12-15 hour.After reaction terminates, add appropriate diluted ethyl acetate, successively with water and saturated aqueous common salt
Washing, separatory, collect organic facies, aqueous phase dichloromethane extracts 3-5 time, merges organic facies, and anhydrous magnesium sulfate is dried, and filters, rotation
Turn evaporation of solvent, finally with ethyl alcohol recrystallization, obtain gray solid.Wherein alkyl chain substituted 2,2 '-di-thiophene, just
The mol ratio of butyl lithium, trimethyltin chloride and oxolane is 1:(2-3): (2-3): (50-80).Reaction equation is:
T=0,4 or 6；
7) target product P1 is prepared
Under argon shield, compound 3 is dissolved in anhydrous tetrahydro furan, in solution, adds four (triphenylphosphines)
Palladium, the anaerobic wet chemical of 1-2mol/L and alkyl replace 1,4-benzene hypoboric acid.70-80 DEG C of stirring is reacted 24-30 hour.
After reaction terminates, reactant liquor dichloromethane extracts 3-5 time, merges organic facies, and anhydrous magnesium sulfate is dried, and rotary evaporation removes molten
Agent.With trace dichloromethane, product is dissolved, drop to, in a large amount of methanol of strong stirring, obtain yellow mercury oxide, filter, collect
Filter cake, vacuum drying, obtain yellow solid.Wherein compound 3, alkyl replace 1,4-benzene hypoboric acid, tetrakis triphenylphosphine palladium, carbon
The mol ratio of acid potassium and oxolane is 1:1:(0.05-0.15): (10-20): (350-400).Reaction equation is:
8) target product P2 is prepared
Under argon shield, compound 3 is dissolved in dry toluene and anhydrous diisopropylamine, in solution, adds iodate
Cuprous, tetrakis triphenylphosphine palladium and alkoxyl substituted 1,4-diacetylene-benzene.70-80 DEG C of stirring is reacted 22-30 hour.Reaction
After end, adding q. s. toluene dilution, filter, filtrate priority water and saturated common salt are washed, dichloromethane extracts, organic facies
Being dried with anhydrous magnesium sulfate, rotary evaporation removes solvent.With trace dichloromethane, product is dissolved, drop to the big of strong stirring
In amount methanol, obtain orange precipitation, filter, collect filter cake, vacuum drying, obtain orange solids.Wherein compound 3, alkoxyl
The mol ratio of substituted 1,4-diacetylene-benzene, tetrakis triphenylphosphine palladium, Hydro-Giene (Water Science)., toluene and diisopropylamine is: 1:1:
(0.05-0.15): (0.05-0.15): (250-400): (80-130).Reaction equation is:
9) target product P3 is prepared
Under argon shield, compound 3 is dissolved in dry toluene and anhydrous diisopropylamine, in solution, adds iodate
Cuprous, tetrakis triphenylphosphine palladium and compound 5.70-80 DEG C of stirring is reacted 22-30 hour.After reaction terminates, add q. s. toluene
Dilution, filters, and filtrate priority water and saturated common salt washing, dichloromethane extracts, and organic facies anhydrous magnesium sulfate is dried, and rotates
Evaporation of solvent.Then with trace dichloromethane, product is dissolved, drop to, in a large amount of methanol of strong stirring, obtain dark red
Color precipitates, and filters, and collects filter cake, vacuum drying, obtains dark red solid.Wherein compound 3, compound 5, Hydro-Giene (Water Science)., four
The mol ratio of (triphenylphosphine) palladium, toluene and diisopropylamine is: 1:1:(0.05-0.15): (0.05-0.15): (250-400):
(80-130).Reaction equation is:
10) target product P4 is prepared
Under argon shield, compound 3 is dissolved in dry toluene, in solution, adds tetrakis triphenylphosphine palladium and change
Compound 6.110-120 DEG C of stirring is reacted 22-30 hour.After reaction terminates, filtering, filtrate is washed with water and saturated common salt respectively,
Collecting organic facies, aqueous phase dichloromethane extracts 3-5 time, merges organic facies, and anhydrous magnesium sulfate is dried, and filters, and rotary evaporation removes
Remove solvent.With trace dichloromethane, product is dissolved, drop to, in a large amount of methanol of strong stirring, obtain red precipitate.Filter,
Collect filter cake, vacuum drying, obtain red solid.Wherein compound 3, compound 6, tetrakis triphenylphosphine palladium and toluene mole
Ratio is: 1:1:(0.05-0.15): (360-400).Reaction equation is:
Wherein, m=0,1,2,3,4,6,8,12 or 16；N is the integer between 1-100；K=0,4 or 6；H=0,1,2,3,
4,5,6,8,10,12,14 or 16；Q=0,4,6 or 12；T=0,4 or 6.
2, the preparation of fluorescence membrane
By gained compound dissolution in chloroform, it is prepared as the storing solution of 1-10mg/mL.Take 20-50 μ L storage every time
The glass matrix surface that standby drop is applied to special handling prepares fluorescence membrane.
Preferably, in the step that the present invention prepares monomer and polymer:
The step 1 of synthesis compound 1) in, described diisopropylamine, borane dimethylsulf iotade, n-BuLi, trimethylchloro-silicane
The optimum mole ratio of alkane and oxolane is: 1:1:1:1:4.4；
The step 2 of synthesis compound 2) in, described compound 1,1-(4-alkyl) bromobenzene, magnesium, hydrochloric acid and oxolane
Optimum mole ratio is: 1:3:3.3:15:98.5；
The step 3 of synthesis compound 3) in, described compound 2,5, most preferably rubbing of the iodo-8-hydroxyquinoline of 7-bis-and ether
That ratio is 1:1:57.8；
The step 4 of synthesis compound 4) in, described alkyl substituted 2,5-dibromo thiophene, Hydro-Giene (Water Science)., double (triphenyl
Phosphine) palladium chloride, the optimum mole ratio of trimethyl acetenyl silicon and diisopropylamine be 1:0.12:0.06:4:52；
The step 5 of synthesis compound 5) in, the optimum mole ratio of described compound 4, potassium hydroxide and methanol is 1:
0.35:340.5；
The step 6 of synthesis compound 6) in, described alkyl chain substituted 2,2 '-di-thiophene, n-BuLi, trimethyl chlorine
The optimum mole ratio changing stannum and oxolane is 1:2.1:2.2:60；
The step 7 of synthesis compound P1) in, described compound 3, alkyl replace Isosorbide-5-Nitrae-benzene hypoboric acid, four (triphenylphosphines)
The optimum mole ratio of palladium, potassium carbonate and oxolane is 1:1:0.1:10:370；
The step 8 of synthesis compound P2) in, the substituted Isosorbide-5-Nitrae-diacetylene-benzene of described compound 3, alkoxyl, four (triphens
Base phosphine) palladium, Hydro-Giene (Water Science)., the optimum mole ratio of toluene and diisopropylamine be: 1:1:0.1:0.1:265:86；
The step 9 of synthesis compound P3) in, described compound 3, compound 5, Hydro-Giene (Water Science)., tetrakis triphenylphosphine palladium, first
The optimum mole ratio of benzene and diisopropylamine is: 1:1:0.1:0.1:265:86；
The step 10 of synthesis compound P4) in, described compound 3, compound 6, tetrakis triphenylphosphine palladium and toluene are
Good mol ratio is: 1:1:0.1:378.
During preparing fluorescence membrane, by gained compound dissolution in chloroform, it is prepared as the storage of 1mg/mL
Standby liquid.Take 30 μ L storing solution drop coatings every time and prepare fluorescence membrane in the glass matrix surface of special handling.
Embodiment 1
A kind of organic monomer and the preparation of four kinds of conjugated polymers
1. synthesis compound 1
Under argon shield atmosphere, 7mL diisopropylamine is joined in 18mL anhydrous tetrahydrofuran solution and is sufficiently stirred for,
And under condition of ice bath, dropwise the tetrahydrofuran solution (10mol/L) of 5mL borane dimethylsulf iotade is joined above-mentioned reactant liquor
In, after dropping, under condition of ice bath, continue reaction 1.5 hours；20mL normal-butyl it is added dropwise over the most again in reaction system
The hexane solution (2.5mol/L) of lithium, continues stirring 2 hours under condition of ice bath；Finally, it is added dropwise in reaction system
6.4mL trim,ethylchlorosilane, produces substantial amounts of white precipitate immediately, after all adding, is stirred at room temperature 2 hours.Reaction terminates
After, reactant liquor stands 1 hour, filters, obtain water white filtrate and be compound 1 under argon shield, and by it at argon
Save backup under protection, productivity about 99%.Wherein diisopropylamine, borane dimethylsulf iotade, n-BuLi, trim,ethylchlorosilane and four
The mol ratio of hydrogen furan is: 1:1:1:1:4.4.
2. synthesis compound 2
Under argon shield atmosphere, in 40ml anhydrous tetrahydrofuran solution, it is separately added into 0.4g magnesium chips, 3.3ml 1-(4-
Alkyl) bromobenzene and 5ml compound 1.Stirring reaction 20 hours at 80 DEG C.After reaction terminates, add in ice bath downhill reaction liquid
The hydrochloric acid of 25ml 3mol/L, is stirred at room temperature 45 minutes.Wherein compound 1,1-(4-bromophenyl) hexane, magnesium, hydrochloric acid and tetrahydrochysene furan
The mol ratio muttered is: 1:3:3.3:18:98.5.In reactant liquor, add 20ml water and 20ml ether, separatory again, collect organic
Phase, aqueous phase uses 30mL dichloromethane to extract every time 3 times, merges organic facies, be dried with anhydrous magnesium sulfate, filters, rotary evaporation
Remove solvent, obtain pale yellow oil, productivity about 98%.Wherein the volume ratio of water and ether is 1:1.
3. synthesis compound 3
5mmol compound 2 is dissolved in 30ml ether, in solution, adds 1.9848g 5,7-bis-iodo-8-hydroxyl quinoline
Quinoline.Wherein the mol ratio of compound 2, the iodo-8-hydroxyquinoline of 5,7-bis-and ether is 1:1:57.8.It is stirred at room temperature 15 hours.Instead
After should terminating, in solution, add a large amount of pentane, separate out precipitation.Filter, collect filter cake, obtain greenish yellow solid, productivity
92%.
4. synthesis compound 4
Under argon shield, by 0.93ml 2,5-dibromo thiophene is dissolved in the anhydrous diisopropylamine of 60ml, adds in solution
Double (triphenylphosphine) palladium chloride of 0.19g Hydro-Giene (Water Science)., 0.345g, stirs 30 minutes, adds 4.7ml trimethyl second in solution
Alkynyl silicon, ice bath stirs 60 minutes, is then stirred at room temperature 60 minutes, is finally warming up to 75 DEG C and stirs 20 hours.Wherein 2,5-bis-
The mol ratio of bromothiophene, Hydro-Giene (Water Science)., double (triphenylphosphine) palladium chloride, trimethyl acetenyl silicon and diisopropylamine is 1:
0.12:0.06:4:52.After reaction terminates, in solution, add q. s. methylene chloride dilution, filter, filtrate rotary evaporation is removed
Remove solvent, use silica gel/normal hexane to carry out pillar layer separation, obtain yellow crystalline solid, productivity 56%.
5. synthesis compound 5
Being dissolved in 20ml methanol by 0.4g compound 4, the potassium hydroxide adding 1ml 0.5mol/L in solution is water-soluble
Liquid, lucifuge, it is stirred at room temperature reaction 7 hours.Wherein the mol ratio of compound 4, potassium hydroxide and methanol is 1:0.35:
340.5.After reaction terminates, adding 50ml water in solution, with n-hexane extraction 4 times, collect organic facies, anhydrous magnesium sulfate is done
Dry, filter, rotary evaporation removes solvent, obtains yellow oil, productivity 75%.
6. synthesis compound 6
Under argon shield, by 0.3174g 2,2 '-di-thiophene is dissolved in 10ml anhydrous tetrahydro furan, and-78
Under the conditions of DEG C, in solution, drip the n-BuLi hexane solution of 1.8ml 2.5mol/L.After dropping, at-78 DEG C
Stir 1 hour.Then, under the conditions of 0 DEG C, in solution, drip 4.4ml 1mol/L trimethyltin chloride tetrahydrofuran solution,
After dropping, it is stirred at room temperature 12 hours.Wherein 2,2 '-di-thiophene, n-BuLi, trimethyltin chloride and oxolane
Mol ratio is 1:2.1:2.2:60.After reaction terminates, add appropriate diluted ethyl acetate, successively with water and saturated common salt washing,
Separatory, collects organic facies, and aqueous phase dichloromethane extracts 4 times, merges organic facies, and anhydrous magnesium sulfate is dried, and filters, rotary evaporation
Remove solvent, with ethyl alcohol recrystallization, obtain gray solid, productivity 85%.
7. target product P1 is prepared
Under argon shield, 0.3641g compound 3 is dissolved in 15ml anhydrous tetrahydro furan, adds in solution
0.0578g tetrakis triphenylphosphine palladium, the anaerobic wet chemical of 10ml 1mol/L and 0.0829g 1,4-benzene hypoboric acid.80
DEG C stirring reaction 24 hours.Wherein the rubbing of compound 3,1,4-benzene hypoboric acid, tetrakis triphenylphosphine palladium, potassium carbonate and oxolane
That ratio is 1:1:0.1:10:370.After reaction terminates, reactant liquor dichloromethane extracts 4 times, merges organic facies, anhydrous magnesium sulfate
Being dried, rotary evaporation removes solvent.With trace dichloromethane, product is dissolved, drop in a large amount of methanol of strong stirring,
To yellow mercury oxide, filter, collect filter cake, vacuum drying, obtain yellow solid, productivity 56%.
8. target product P2 is prepared
Under argon shield, 0.3641g compound 3 is dissolved in 14ml dry toluene and the anhydrous diisopropylamine of 6ml, to
Solution adds 0.0095g Hydro-Giene (Water Science)., 0.0578g tetrakis triphenylphosphine palladium and 0.0631g 1,4-diacetylene-benzene.Wherein
The mol ratio of compound 3,1,4-diacetylene-benzene, tetrakis triphenylphosphine palladium, Hydro-Giene (Water Science)., toluene and diisopropylamine is: 1:1:
0.1:0.1:265:86.80 DEG C of stirrings are reacted 24 hours.After reaction terminates, add q. s. toluene dilution, filter, by filtrate successively
Washing with water and saturated common salt, dichloromethane extracts, and organic facies anhydrous magnesium sulfate is dried, and rotary evaporation removes solvent.With micro-
Product is dissolved by amount dichloromethane, drops to, in a large amount of methanol of strong stirring, obtain orange precipitation, filters, and collects filter cake, very
Empty dry, obtain orange solids, productivity 73%.
9. target product P3 is prepared
Under argon shield, 0.3641g compound 3 is dissolved in 14mL dry toluene and the anhydrous diisopropylamine of 6mL, to
Solution adds 0.0095g Hydro-Giene (Water Science)., 0.0578g tetrakis triphenylphosphine palladium and 80ul 2,5-diacetylene thiophene.80 DEG C are stirred
Mix reaction 24 hours.Wherein compound 3,2,5-diacetylene thiophene, Hydro-Giene (Water Science)., tetrakis triphenylphosphine palladium, toluene and two are different
The mol ratio of propylamine is: 1:1:0.1:0.1:265:86.After reaction terminates, adding q. s. toluene dilution, filter, filtrate is successively used
Water and saturated common salt washing, dichloromethane extracts, and organic facies anhydrous magnesium sulfate is dried, and rotary evaporation removes solvent.Then use
Product is dissolved by trace dichloromethane, drops in a large amount of methanol of strong stirring, obtains kermesinus precipitation, filters, collects filter
Cake, vacuum drying, obtain dark red solid, productivity 51%.
10. target product P4 is prepared
Under argon shield, 0.3641g compound 3 is dissolved in 20ml dry toluene, in solution, adds 0.0578g
Tetrakis triphenylphosphine palladium and 0.2459g 4,4 '-two tin trimethyl connect thiophene.Wherein compound 3,4,4 '-two tin trimethyl connects thiophene
The mol ratio of fen, tetrakis triphenylphosphine palladium and toluene is: 1:1:0.1:378.110 DEG C of stirrings are reacted 24 hours.After reaction terminates,
Filtering, filtrate with water and saturated common salt washing, collects organic facies respectively, and aqueous phase dichloromethane extracts 5 times, merges organic facies,
Anhydrous magnesium sulfate is dried, and filters, and rotary evaporation removes solvent.With trace dichloromethane, product is dissolved, drop to strong stirring
A large amount of methanol in, obtain red precipitate.Filter, collect filter cake, vacuum drying, obtain red solid, productivity 76%.
2, the preparation of fluorescence membrane
By gained compound dissolution in chloroform, it is prepared as the storing solution of 1mg/mL.Take 30 μ L every time and lay in drop
The glass matrix surface being applied to special handling prepares fluorescence membrane.
Embodiment 2
In the present embodiment, synthesis compound 1 step 1. in, under argon shield atmosphere, by 7mL diisopropylamine add
In 32.5mL anhydrous tetrahydrofuran solution and be sufficiently stirred for, and under condition of ice bath, dropwise by the four of 5mL borane dimethylsulf iotade
Hydrogen tetrahydrofuran solution (10mol/L) joins in above-mentioned reactant liquor, after dropping, continues reaction 1.5 hours under condition of ice bath；So
After in reaction system, be added dropwise over the hexane solution (2.5mol/L) of 20mL n-BuLi again, continue stirring under condition of ice bath
2 hours；Finally, in reaction system, it is added dropwise over 6.4mL trim,ethylchlorosilane, produces substantial amounts of white precipitate immediately, treat complete
After portion adds, it is stirred at room temperature 2 hours.Wherein diisopropylamine, borane dimethylsulf iotade, n-BuLi, trim,ethylchlorosilane and tetrahydrochysene
The mol ratio of furan is: 1:1:1:1:5.5.After reaction terminates, reactant liquor stands 1 hour, filters, obtain colourless under argon shield
Transparent filtrate is compound 1, and it is saved backup under argon shield, productivity about 99%.
In the present embodiment, synthesis compound 2 step 2. in, be separately added in 40ml anhydrous tetrahydrofuran solution
0.48g magnesium chips, 3.3ml 1-(4-alkyl) bromobenzene and 6.25ml compound 1.Stirring reaction 20 hours at 80 DEG C.Reaction terminates
After, ice bath downhill reaction liquid adds the hydrochloric acid of 30ml 3mol/L, is stirred at room temperature 45 minutes.Wherein compound 1,1-(4-bromine
Phenyl) hexane, magnesium, the mol ratio of hydrochloric acid and oxolane be: 1:3:4:22.5:98.5.20ml water is added again in reactant liquor
With 20ml ether, separatory, collecting organic facies, aqueous phase uses 30mL dichloromethane to extract 3 times every time, merges organic facies, with anhydrous
Magnesium sulfate is dried, and filters, and rotary evaporation removes solvent, obtains pale yellow oil, productivity about 98%.Wherein water and the body of ether
Long-pending ratio is 1:1.
In the present embodiment, synthesis compound 3 step 3. in, 5mmol compound 2 is dissolved in 39ml ether, to
Solution adds the iodo-8-hydroxyquinoline of 1.9848g 5,7-bis-.Wherein compound 2, the iodo-8-hydroxyquinoline of 5,7-bis-and ether
Mol ratio is 1:1:75.1.It is stirred at room temperature 15 hours.After reaction terminates, in solution, add a large amount of pentane, separate out precipitation.Cross
Filter, collects filter cake, obtains greenish yellow solid, productivity about 90%.
Synthesis compound 4 step 4. in, under argon shield, by 0.93ml 2,5-dibromo thiophene be dissolved in 60ml without
In water diisopropylamine, in solution, add 0.19g Hydro-Giene (Water Science)., double (triphenylphosphine) palladium chloride of 0.345g, stir 30 minutes,
5.9ml trimethyl acetenyl silicon is added in solution.Wherein 2,5-dibromo thiophene, Hydro-Giene (Water Science)., double (triphenylphosphine) dichloride
The mol ratio of palladium, trimethyl acetenyl silicon and diisopropylamine is 1:0.12:0.06:5:52.Ice bath stirs 60 minutes, then room temperature
Stir 60 minutes, be finally warming up to 75 DEG C and stir 20 hours.After reaction terminates, in solution, add q. s. methylene chloride dilution,
Filter, filtrate rotary evaporation is removed solvent, use silica gel/normal hexane to carry out pillar layer separation, obtain yellow crystalline solid, produce
Rate about 55%.
Synthesis compound 5 step 5. in, 0.4g compound 4 is dissolved in 20ml methanol, in solution add 1ml
The potassium hydroxide aqueous solution of 0.7mol/L, lucifuge, it is stirred at room temperature reaction 7 hours.Wherein compound 4, potassium hydroxide and first
The mol ratio of alcohol is 1:0.5:340.5.After reaction terminates, adding 50ml water in solution, with n-hexane extraction 4 times, collection has
Machine phase, anhydrous magnesium sulfate is dried, and filters, and rotary evaporation removes solvent, obtains yellow oil, productivity about 70%.
Synthesis compound 6 step 6. in, under argon shield, by 0.3174g 2,2 '-di-thiophene is dissolved in
In 10ml anhydrous tetrahydro furan, and under the conditions of-78 DEG C, in solution, drip the n-BuLi normal hexane of 2.2ml 2.5mol/L
Solution.After dropping, stir 1 hour at-78 DEG C.Then, under the conditions of 0 DEG C, in solution, drip 4.4ml 1mol/L
Trimethyltin chloride tetrahydrofuran solution, after dropping, is stirred at room temperature 12 hours.Wherein 2,2 '-di-thiophene, normal-butyl
The mol ratio of lithium, trimethyltin chloride and oxolane is 1:2.5:2.2:60.After reaction terminates, add appropriate ethyl acetate dilute
Releasing, successively with water and saturated common salt washing, separatory, collect organic facies, aqueous phase dichloromethane extracts 4 times, merges organic facies, nothing
Water magnesium sulfate is dried, and filters, and rotary evaporation removes solvent, with ethyl alcohol recrystallization, obtains gray solid, productivity about 86%.
Synthesis target product P1 step 7. in, under argon shield, 0.3641g compound 3 is dissolved in 15ml without
In water oxolane, in solution, add 0.0578g tetrakis triphenylphosphine palladium, the anaerobic wet chemical of 10ml 2mol/L
With 0.0829g 1,4-benzene hypoboric acid.80 DEG C of stirrings are reacted 24 hours.Wherein compound 3,1,4-benzene hypoboric acid, four (triphenyls
Phosphine) palladium, the mol ratio of potassium carbonate and oxolane be 1:1:0.1:20:370.After reaction terminates, reactant liquor dichloromethane extracts
Taking 4 times, merge organic facies, anhydrous magnesium sulfate is dried, and rotary evaporation removes solvent.With trace dichloromethane, product is dissolved, drip
Add to, in a large amount of methanol of strong stirring, obtain yellow mercury oxide, filter, collect filter cake, vacuum drying, obtain yellow solid, produce
Rate about 61%.
Synthesis target product P2 step 8. in, under argon shield, 0.3641g compound 3 is dissolved in 21ml without
In water-toluene and the anhydrous diisopropylamine of 9ml, in solution add 0.0095g Hydro-Giene (Water Science)., 0.0578g tetrakis triphenylphosphine palladium and
0.0631g 1,4-diacetylene-benzene.Wherein compound 3,1,4-diacetylene-benzene, tetrakis triphenylphosphine palladium, Hydro-Giene (Water Science)., first
The mol ratio of benzene and diisopropylamine is: 1:1:0.1:0.1:397.5:129.80 DEG C of stirrings are reacted 24 hours.After reaction terminates, add
Entering q. s. toluene dilution, filter, filtrate priority water and saturated common salt are washed, dichloromethane extracts, the anhydrous sulfur of organic facies
Acid magnesium is dried, and rotary evaporation removes solvent.With trace dichloromethane, product is dissolved, drop to a large amount of methanol of strong stirring
In, obtain orange precipitation, filter, collect filter cake, vacuum drying, obtain orange solids, productivity about 65%.
Synthesis target product P3 step 9. in, under argon shield, 0.3641g compound 3 is dissolved in 14mL without
In water-toluene and the anhydrous diisopropylamine of 6mL, in solution add 0.0095g Hydro-Giene (Water Science)., 0.0578g tetrakis triphenylphosphine palladium and
80ul 2,5-diacetylene thiophene.80 DEG C of stirrings are reacted 24 hours.Wherein compound 3,2,5-diacetylene thiophene, iodate Asia
The mol ratio of copper, tetrakis triphenylphosphine palladium, toluene and diisopropylamine is: 1:1:0.1:0.1:397.5:129.After reaction terminates,
Adding q. s. toluene dilution, filter, filtrate priority water and saturated common salt washing, dichloromethane extracts, the anhydrous sulfur of organic facies
Acid magnesium is dried, and rotary evaporation removes solvent.Then with trace dichloromethane, product is dissolved, drop to a large amount of first of strong stirring
In alcohol, obtain kermesinus precipitation, filter, collect filter cake, vacuum drying, obtain dark red solid, productivity about 48%.
Synthesis target product P4 step 10. in, under argon shield, 0.3641g compound 3 is dissolved in 22ml without
In water-toluene, in solution, add 0.0578g tetrakis triphenylphosphine palladium and 0.2459g 4,4 '-two tin trimethyl connects thiophene.Its
The mol ratio that middle compound 3,4,4 '-two tin trimethyl connects thiophene, tetrakis triphenylphosphine palladium and toluene is: 1:1:0.1:400.
110 DEG C of stirrings are reacted 24 hours.After reaction terminates, filtering, filtrate with water and saturated common salt washing, collects organic facies, water respectively
Extracting 4 times with dichloromethane, merge organic facies, anhydrous magnesium sulfate is dried, and filters, and rotary evaporation removes solvent.With trace two
Product is dissolved by chloromethanes, drops to, in a large amount of methanol of strong stirring, obtain red precipitate.Filtering, collect filter cake, vacuum is done
Dry, obtain red solid, productivity 73%.
During preparing fluorescence membrane, by gained compound dissolution in chloroform, it is prepared as the storage of 5mg/mL
Standby liquid.Take 30 μ L storing solution drop coatings every time and prepare fluorescence membrane in the glass matrix surface of special handling.
Embodiment 3
Embodiment 1～2 synthesis compound 2 step preparing monomer and four kinds of conjugated polymer steps 1 2. in, used
1-(4-bromophenyl) hexane replace with equimolar 1-(4-bromophenyl) butane, other steps of this step and corresponding embodiment
Identical, prepare compound 2, in formula, the value of m is 4.
Other steps are identical with embodiment 1～2.
Embodiment 4
Embodiment 1～2 synthesis compound 2 step preparing monomer and four kinds of conjugated polymer steps 1 2. in, used
1-(4-bromophenyl) hexane replace with equimolar 1-(4-bromophenyl) octane, other steps of this step and corresponding embodiment
Identical, prepare compound 2, in formula, the value of m is 8.
Other steps are identical with embodiment 1～2.
Embodiment 5
Embodiment 1～2 synthesis compound 2 step preparing monomer and four kinds of conjugated polymer steps 1 2. in, used
1-(4-bromophenyl) hexane replace with equimolar 1-(4-bromophenyl) dodecane, other steps of this step are implemented with corresponding
Example is identical, prepares compound 2, and in formula, the value of m is 12.
Other steps are identical with embodiment 1～2.
Embodiment 6
Embodiment 1～2 synthesis compound 2 step preparing monomer and four kinds of conjugated polymer steps 1 2. in, used
1-(4-bromophenyl) hexane replace with equimolar 1-(4-bromophenyl) hexadecane, other steps of this step are implemented with corresponding
Example is identical, prepares compound 2, and in formula, the value of m is 16.
Other steps are identical with embodiment 1～2.
Embodiment 7
Embodiment 1～2 synthesis compound 2 step preparing monomer and four kinds of conjugated polymer steps 1 2. in, used
1-(4-bromophenyl) hexane replace with equimolar bromobenzene, other steps of this step are identical with corresponding embodiment, preparationization
Compound 2, in formula, the value of m is 0.
Other steps are identical with embodiment 1～2.
Embodiment 8
Embodiment 1～2 synthesis compound 3 step preparing monomer and four kinds of conjugated polymer steps 1 3. in, used
5, the iodo-8-hydroxyquinoline of 7-bis-is replaced with equimolar 5,7-D-Br-8-HQ, and other steps of this step are with corresponding
Embodiment is identical, prepares compound 3.
Other steps are identical with embodiment 1～2.
Embodiment 9
In the step preparing fluorescence membrane of embodiment 1～8, by storing solution solvent for use chloroform oxolane
Replace.Other steps are identical with embodiment 1～2.
Embodiment 10
In the step preparing fluorescence membrane of embodiment 1～8, by storing solution solvent for use chloroform N, N-diformazan
Base Methanamide is replaced.Other steps are identical with embodiment 1～2.
Embodiment 11
In the step preparing fluorescence membrane of embodiment 1～8, by storing solution solvent for use chloroform dimethyl sulfoxide
Replace.Other steps are identical with embodiment 1～2.
Embodiment 12
Embodiment 1～2 synthesis compound 4 step preparing monomer and four kinds of conjugated polymer steps 1 4. in, used
2,5-dibromo thiophene equimolar alkyl substituted 2,5-dibromo thiophene replaces, and other steps of this step are implemented with corresponding
Example is identical, prepares compound 4, and in formula, the value of q is 4.
Other steps are identical with embodiment 1～2.
Embodiment 13
Embodiment 1～2 the synthesis compound P2 step preparing monomer and four kinds of conjugated polymer steps 1 8. in, institute
Isosorbide-5-Nitrae-diacetylene-benzene substituted Isosorbide-5-Nitrae of equimolar alkoxyl-diacetylene-benzene replace, other steps of this step with
Corresponding embodiment is identical, prepares compound P2, and in formula, the value of h is 8.
Other steps are identical with embodiment 1～2.
Embodiment 14
Embodiment 1～2 the synthesis compound P2 step preparing monomer and four kinds of conjugated polymer steps 1 8. in, institute
Isosorbide-5-Nitrae-diacetylene-benzene substituted Isosorbide-5-Nitrae of equimolar alkoxyl-diacetylene-benzene replace, other steps of this step with
Corresponding embodiment is identical, prepares compound P2, and in formula, the value of h is 16, and other steps are identical with embodiment 1～2.
Embodiment described above only have expressed the several embodiments of the present invention, and it describes more concrete and detailed, but also
Therefore the restriction to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that, for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, it is also possible to make some deformation and improvement, these broadly fall into the guarantor of the present invention
Protect scope.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
In order to verify this patent benefit to society, inventor is poly-to monomer synthesized in embodiment 1 and boracic conjugation
The Fluorescence behaviour of compound and the detection of PARA FORMALDEHYDE PRILLS(91,95) have carried out desk study.
Seeing Fig. 1, for the ultraviolet-visible absorption spectroscopy figure of synthesized compound, wherein a is blank CHCl3Absorption, b,
C, d, e, f are respectively synthesized monomer and the absorption spectrum of four kinds of polymer.By ultraviolet-visible absorption spectroscopy this it appears that
Increase along with conjugated degree and the enhancing for receptor relationship, the absworption peak of compound presents the trend gradually broadened；
Fig. 2 and Fig. 3 is respectively the synthesized compound emission spectrum figure in chloroform soln and thin-film state, and interior figure is
Fluorescence photo under 365nm ultra violet lamp, as can be seen from the figure monomer 3 there occurs relatively to the transmitted wave length of polymer P 4
For obvious red shift, solution state maximum emission wavelength is from 520nm red shift to 625nm, and fluorescence color is also become red from green；Thin
Film state maximum emission wavelength is from 500nm red shift to 670nm, and fluorescence color is also become red from green, and the luminescence in this region is relatively
Easily arrived by eye-observation, established certain basis for its optical application.
Fig. 4 and Fig. 5 is respectively the gained compound photochemical stability spectrogram in chloroform soln and thin-film state, from
Figure can be seen that, the compound of gained either still all shows excellent photochemical stability in thin-film state in solution state,
Successfully evade " photobleaching " phenomenon, establish solid foundation for the application of its fluorescence sense and photovoltaic applications.
Fig. 6 be gained monomer and polymer at the thin-film state optical photograph under daylight lamp and 365nm uviol lamp respectively, can
To find out that solid color and fluorescence are all to be become red from green, the structure for its sensor array provides possibility.
Fig. 7 is resulting polymers P4 fluorescence sense figure of PARA FORMALDEHYDE PRILLS(91,95) aqueous solution in tetrahydrofuran solution.The first detected
Aldehyde solution concentration is 5 μMs.Shown by figure, along with the increase of scanning times, the fluorescence intensity of P4 by notable quencher, and along with
The movement of maximum emission wavelength.Fig. 8 is the fluorescence photo before and after addition formaldehyde, can be clearly observed fluorescence color and there occurs
Significantly change, can lay a good foundation for it in actual application.
In sum, a kind of organic monomer related in the present invention and four kinds of conjugated polymers all contain major element boron and
8-hydroxyquinoline fragment, the intrinsic electron deficiency of boron atom (Lewis is acid) makes the organic conjugated molecule of boracic to be the most all
Preferably electron acceptor material, thus at the aspect such as organic photoelectric and fluorescence sense, all there is boundless application prospect；And
8-hydroxyquinoline is a kind of typical chelating agen, has prominent luminescence generated by light, Electroluminescence Properties；And by introducing hydrotropy base
Group, such as chain alkyl, improves dissolubility and the film property of polymeric material, and can regulate its assembly behavior, and then produces
Raw abundant optics behavior.The major element boron and 8-hydroxyquinoline unit with excellent photoelectric properties are simultaneously introduced by the present invention
To being conjugated in little molecule, simply and efficiently synthesize polymerisable monomer, and it is efficient, pervasive to have developed a class based on this
The method of synthesis boracic conjugated polymer, has prepared the having containing major element of a series of high reaction activity functional groups functionalization
Machine is conjugated little molecule, and then intersects even by Sonogashira cross-coupling reaction, Suzuki cross-coupling reaction, Stille
Connection reaction etc. has prepared four kinds of boron polymers Han 8-hydroxyquinoline efficiently, easily, and preparation technology is simple, equipment requirements
Low, the most also explanation monomer adaptability is relatively strong, other polyreaction type similarly suitable.Obtained monomer and polymer all have
There are excellent dissolubility, high fluorescence quantum yield, abundant photophy-sical behavior, and photochemical stability performance prominent, for
It is sensitive, selectivity sensing detection and abundant photoelectric characteristic have established solid foundation.
Claims (9)
1. the class organic monomer containing 8-hydroxyquinoline boron, it is characterised in that the structural formula of this organic monomer is as follows:
Wherein, R represents Br or I；M=0,1,2,3,4,6,8,12 or 16.
2. conjugated polymer based on the organic monomer containing 8-hydroxyquinoline boron described in claim 1, it is characterised in that include
4 kinds of conjugated polymers, respectively P1, P2, P3 and P4, its structural formula is respectively as follows:
Wherein, m=0,1,2,3,4,6,8,12 or 16；N is the integer between 1-100；K=0,4 or 6；H=0,1,2,3,4,5,
6,8,10,12,14 or 16；Q=0,4,6 or 12；T=0,4 or 6.
3. the method for the preparation organic monomer containing 8-hydroxyquinoline boron described in claim 1, it is characterised in that include following step
Rapid:
1) compound 1 is prepared
Under argon shield atmosphere, diisopropylamine is joined in anhydrous tetrahydrofuran solution, stir, in condition of ice bath
Under, dropwise dropping borane dimethylsulfide ethereal solution, after dropping, continues reaction 1-3 hour under condition of ice bath；The most again to reaction
System is added dropwise over the solution of n-BuLi, under condition of ice bath, continues stirring 1-3 hour；Finally, in reaction system dropwise
Add trim,ethylchlorosilane, produce substantial amounts of white precipitate, after treating all to drip, after being stirred at room temperature 1-3 hour, reactant liquor
Stand 0.5-2 hour, filter under argon shield, obtain water white filtrate and be compound 1, and by it under argon shield
Save backup；
2) compound 2 is prepared
Under argon shield atmosphere, in the anhydrous tetrahydrofuran solution of 1-(4-alkyl) bromobenzene, it is separately added into magnesium chips and compound
1, stirring reaction 20-24 hour at 70-85 DEG C, after reaction terminates, ice bath downhill reaction liquid adds hydrochloric acid, is stirred at room temperature
45-60 minute, then adding water and ether, extraction in reaction system, collect organic facies, aqueous phase dichloromethane extracts, and closes
And organic facies, it being dried, filter, rotary evaporation removes solvent, prepares compound 2；
Wherein, described 1-(4-alkyl) bromobenzene structural formula such as following formula:
Wherein m=0,1,2,3,4,6,8,12 or 16；
3) compound 3 is prepared
Compound 2 is dissolved in ether, addition 5,7-dihalo-8-hydroxyquinoline in solution, reaction 15-20 is stirred at room temperature
After hour, in solution, add pentane, separate out precipitation, filter, collect filter cake, prepare compound 3, the i.e. boron Han 8-hydroxyquinoline
Organic monomer.
The method of the organic monomer containing 8-hydroxyquinoline boron the most according to claim 3, it is characterised in that:
Step 1) in, the mol ratio of diisopropylamine, borane dimethylsulf iotade, n-BuLi, trim,ethylchlorosilane and oxolane is
1:1:1:1:(4-5)；
Step 2) in, the mol ratio of compound 1,1-(4-alkyl) bromobenzene, magnesium, hydrochloric acid and oxolane is 1:(2-3): (2-4):
(15-24): the volume ratio of (90-120), water and ether is 1:1；
Step 3) in, compound 2,5, the mol ratio of 7-dihalo-8-hydroxyquinoline and ether is 1:1:(50-70)；Described 5,
7-dihalo-8-hydroxyquinoline, wherein halogen is bromine or iodine.
5. the method for the conjugated polymer of the preparation organic monomer containing 8-hydroxyquinoline boron described in claim 2, its feature exists
In, comprise the following steps:
Step 1: prepare conjugated polymer P1
Under argon shield, the organic monomer containing 8-hydroxyquinoline boron is dissolved in anhydrous tetrahydro furan, adds in solution
Tetrakis triphenylphosphine palladium, the wet chemical of anaerobic and alkyl substituted Isosorbide-5-Nitrae-benzene hypoboric acid, in 70-80 DEG C of stirring reaction
After 24-30 hour, being extracted by reactant liquor dichloromethane, organic facies anhydrous magnesium sulfate is dried, and rotary evaporation removes solvent；With
Product is dissolved by dichloromethane, drops to, in the methanol of strong stirring, obtain yellow mercury oxide, filters, and collects filter cake, and vacuum is done
Dry, obtaining yellow solid is conjugated polymer P1；
Step 2: prepare conjugated polymer P2
Under argon shield, the organic monomer containing 8-hydroxyquinoline boron is dissolved in dry toluene and diisopropylamine, to solution
Substituted Isosorbide-5-Nitrae-the diacetylene-benzene of middle addition Hydro-Giene (Water Science)., tetrakis triphenylphosphine palladium and alkoxyl, in 70-80 DEG C of stirring reaction
After 22-30 hour, adding toluene and be diluted, filter, filtrate priority water and saturated common salt washing, dichloromethane extracts, has
Machine anhydrous magnesium sulfate is dried, and rotary evaporation removes solvent, is dissolved by product with dichloromethane, drops to the first of strong stirring
In alcohol, filtering, be dried, prepared orange solids is conjugated polymer P2；
Step 3: prepare compound 4
Under argon shield, by substituted for alkyl 2,5-dibromo thiophene is dissolved in anhydrous diisopropylamine, adds iodate in solution
Cuprous, double (triphenylphosphine) palladium chloride, stirs 30-40 minute, adds trimethyl acetenyl silicon in solution, and ice bath stirs
60-80 minute, then it is stirred at room temperature 60-80 minute, is finally warming up to 75-85 DEG C of stirring reaction 20-24 hour；After reaction terminates
In solution, add dichloromethane be diluted, filter, filtrate rotary evaporation is removed, use silica gel-normal hexane system to carry out
Pillar layer separation, prepares compound 4；
Step 4: prepare compound 5
Compound 4 is dissolved in methanol, is subsequently adding potassium hydroxide aqueous solution, lucifuge, be stirred at room temperature reaction 6-10 little
Time, after reaction terminates, adding water in solution, with n-hexane extraction, be dried, filter, rotary evaporation removes solvent, is vacuum dried,
Prepare compound 5；
Step 5: prepare compound 6
Under argon shield, by substituted for alkyl chain 2,2 '-di-thiophene is dissolved in anhydrous tetrahydro furan, and at-78 DEG C of bars
Under part, in solution, drip n-butyllithium solution, after dropping, stir 1-2 hour at-78 DEG C；Then, 0 DEG C of condition
Under, in solution, drip trimethyl ammonia chloride solution of tin, after dropping, after being stirred at room temperature 12-15 hour, add ethyl acetate and enter
Row dilution, washing, separatory, collect organic facies, aqueous phase dichloromethane extracts, and merges organic facies, is dried, and filters, rotary evaporation
Remove solvent；Finally with ethyl alcohol recrystallization, prepare compound 6；
Step 6: prepare conjugated polymer P3
Under argon shield, the organic monomer containing 8-hydroxyquinoline boron is dissolved in dry toluene and diisopropylamine, to solution
Middle addition Hydro-Giene (Water Science)., tetrakis triphenylphosphine palladium and compound 5, after 70-80 DEG C of stirring reaction 22-30 hour, add toluene
It is diluted, filters, filtrate priority water and saturated common salt washing, dichloromethane extracts, and organic facies anhydrous magnesium sulfate is dried,
Rotary evaporation removes solvent；With dichloromethane, product is dissolved, drop in the methanol of strong stirring, filter, be dried, prepare dark
Red solid P3；
Step 7: prepare conjugated polymer P4
Under argon shield, the organic monomer containing 8-hydroxyquinoline boron is dissolved in dry toluene, in solution, adds four (three
Phenylphosphine) palladium and compound 6, after 110-120 DEG C of stirring reaction 22-30 hour, to filter, filtrate is respectively with water and saturated common salt
Washing, collects organic facies, and aqueous phase dichloromethane extracts, and organic facies anhydrous magnesium sulfate is dried, and filters, and rotary evaporation removes molten
Agent, dissolves product with dichloromethane, drops in the methanol of strong stirring, filters, and is dried, and prepares red solid conjugated polymers
Thing P4.
The method of the conjugated polymer of the preparation the most according to claim 5 organic monomer containing 8-hydroxyquinoline boron, it is special
Levy and be:
In step 1, organic monomer, alkyl containing 8-hydroxyquinoline boron replace Isosorbide-5-Nitrae-benzene hypoboric acid, tetrakis triphenylphosphine palladium, carbonic acid
The mol ratio of potassium and oxolane is 1:1:(0.05-0.15): (10-20): (350-400)；
In step 2, the substituted Isosorbide-5-Nitrae-diacetylene-benzene of the organic monomer containing 8-hydroxyquinoline boron, alkoxyl, four (triphenylphosphines)
The mol ratio of palladium, Hydro-Giene (Water Science)., toluene and diisopropylamine is 1:1:(0.05-0.15): (0.05-0.15): (250-400):
(80-130)；
In step 3, alkyl substituted 2,5-dibromo thiophene, Hydro-Giene (Water Science)., double (triphenylphosphine) palladium chloride, trimethyl acetenyl
The mol ratio of silicon and diisopropylamine is 1:(0.05-0.15): (0.05-0.15): (4-6): (50-60)；
In step 4, the mol ratio of compound 4, potassium hydroxide and methanol is 1:(0.3-0.5): (320-350)；
In step 5, alkyl chain substituted 2, the mol ratio of 2 '-di-thiophene, n-BuLi, trimethyltin chloride and oxolane
For 1:(2-3): (2-3): (50-80)；
In step 6, the organic monomer containing 8-hydroxyquinoline boron, compound 5, Hydro-Giene (Water Science)., tetrakis triphenylphosphine palladium, toluene and two
The mol ratio of 2-aminopropane. is 1:1:(0.05-0.15): (0.05-0.15): (250-400): (80-130)；
In step 7, the mol ratio of organic monomer, compound 6, tetrakis triphenylphosphine palladium and toluene containing 8-hydroxyquinoline boron is 1:
1:(0.05-0.15): (360-400).
The method of the conjugated polymer of the preparation the most according to claim 5 organic monomer containing 8-hydroxyquinoline boron, it is special
Levy and be:
In step 3, described alkyl substituted 2,5-dibromo thiophene structural formula such as following formula:
Wherein, q=0,4,6 or 12；
In step 5, described alkyl chain substituted 2, the structural formula of 2 '-di-thiophene such as following formula:
Wherein, t=0,4 or 6.
8. use described in the organic monomer containing 8-hydroxyquinoline boron described in claim 1 or claim 2 containing 8-hydroxyl
The conjugated polymer of the organic monomer of quinoline boron prepares the method for fluorescence membrane, it is characterised in that: by molten for described conjugated polymer
Solution, in chloroform, is prepared as the storing solution of 1-10mg/mL；Take 20-50 μ L storing solution drop coating in glass matrix surface every time
Prepare fluorescence membrane.
9. the application in detection formalin and formaldehyde gas of the fluorescence membrane described in claim 8.
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| CN107607477A (en) * | 2017-09-22 | 2018-01-19 | 青海大学 | A kind of construction method of polymer sensor array of 8 oxyquinoline boronation lithium modification and application |
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| CN108774255A (en) * | 2018-08-08 | 2018-11-09 | 陕西师范大学 | One kind boron compound of 8-hydroxy-quinoline containing four-coordination and its preparation method and application |
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