CN106317383B - The organic monomer of one kind boron containing 8-hydroxyquinoline and conjugated polymer and preparation method and application based on the monomer - Google Patents
The organic monomer of one kind boron containing 8-hydroxyquinoline and conjugated polymer and preparation method and application based on the monomer Download PDFInfo
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- CN106317383B CN106317383B CN201610669251.8A CN201610669251A CN106317383B CN 106317383 B CN106317383 B CN 106317383B CN 201610669251 A CN201610669251 A CN 201610669251A CN 106317383 B CN106317383 B CN 106317383B
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- Prior art keywords
- compound
- solution
- hydroxyquinoline
- added
- stirred
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- 239000000178 monomer Substances 0.000 title claims abstract description 76
- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 58
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 title claims abstract description 47
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 46
- 239000005725 8-Hydroxyquinoline Substances 0.000 title claims description 50
- 229960003540 oxyquinoline Drugs 0.000 title claims description 50
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 95
- 150000001875 compounds Chemical class 0.000 claims abstract description 94
- 239000007787 solid Substances 0.000 claims abstract description 36
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 156
- 239000000243 solution Substances 0.000 claims description 125
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 112
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 108
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 98
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 85
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 84
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 74
- 239000007789 gas Substances 0.000 claims description 51
- 229910052786 argon Inorganic materials 0.000 claims description 49
- 239000012074 organic phase Substances 0.000 claims description 46
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 45
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 43
- 238000003756 stirring Methods 0.000 claims description 42
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 40
- 239000002904 solvent Substances 0.000 claims description 40
- 238000001914 filtration Methods 0.000 claims description 38
- 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
- 229940043279 diisopropylamine Drugs 0.000 claims description 35
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 33
- 239000000047 product Substances 0.000 claims description 33
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 30
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 28
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 25
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 25
- 239000000706 filtrate Substances 0.000 claims description 24
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 23
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical group I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 23
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 22
- 229940126214 compound 3 Drugs 0.000 claims description 21
- 229930192474 thiophene Natural products 0.000 claims description 21
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- -1 bis- (triphenylphosphine) palladium chlorides Chemical class 0.000 claims description 19
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical class C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 19
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 18
- 229940125782 compound 2 Drugs 0.000 claims description 18
- 239000012065 filter cake Substances 0.000 claims description 18
- 239000012528 membrane Substances 0.000 claims description 17
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 16
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 16
- 238000000605 extraction Methods 0.000 claims description 16
- 239000012071 phase Substances 0.000 claims description 16
- 238000006467 substitution reaction Methods 0.000 claims description 16
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 15
- 229940125898 compound 5 Drugs 0.000 claims description 14
- 238000000034 method Methods 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
- 238000000926 separation method Methods 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000010790 dilution Methods 0.000 claims description 12
- 239000012895 dilution Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- KBVDUUXRXJTAJC-UHFFFAOYSA-N 2,5-dibromothiophene Chemical class BrC1=CC=C(Br)S1 KBVDUUXRXJTAJC-UHFFFAOYSA-N 0.000 claims description 11
- 229940125904 compound 1 Drugs 0.000 claims description 11
- SKOWZLGOFVSKLB-UHFFFAOYSA-N hypodiboric acid Chemical compound OB(O)B(O)O SKOWZLGOFVSKLB-UHFFFAOYSA-N 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 8
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 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
- 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
- 239000000126 substance Substances 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 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
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052740 iodine Inorganic materials 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
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application 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
- 239000002027 dichloromethane extract Substances 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 16
- 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
- 239000000758 substrate Substances 0.000 abstract description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 15
- 238000001035 drying Methods 0.000 description 11
- 230000002194 synthesizing effect Effects 0.000 description 11
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 10
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- PWPXLJCSWHZVBF-UHFFFAOYSA-N 2,3-diiodoquinolin-8-ol Chemical class IC1=C(I)N=C2C(O)=CC=CC2=C1 PWPXLJCSWHZVBF-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 229910052718 tin Inorganic materials 0.000 description 7
- 150000004694 iodide salts Chemical class 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 150000003384 small molecules Chemical class 0.000 description 5
- 230000021615 conjugation Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 230000003381 solubilizing effect Effects 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
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-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
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920002866 paraformaldehyde Polymers 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel 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
- 150000003613 toluenes Chemical class 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-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
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-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
- 239000005864 Sulphur Substances 0.000 description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004847 absorption spectroscopy Methods 0.000 description 2
- 239000002253 acid Substances 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
- 239000002738 chelating agent Substances 0.000 description 2
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound 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
- 230000002950 deficient Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- BHQCQFFYRZLCQQ-UHFFFAOYSA-N (3alpha,5alpha,7alpha,12alpha)-3,7,12-trihydroxy-cholan-24-oic acid Natural products OC1CC2CC(O)CCC2(C)C2C1C1CCC(C(CCC(O)=O)C)C1(C)C(O)C2 BHQCQFFYRZLCQQ-UHFFFAOYSA-N 0.000 description 1
- 206010049244 Ankyloglossia congenital Diseases 0.000 description 1
- 241000040710 Chela Species 0.000 description 1
- 239000004380 Cholic acid Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000005700 Stille cross coupling reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229940111121 antirheumatic drug quinolines Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RKFFUJHJOUYEKT-UHFFFAOYSA-N boron;quinoline Chemical compound [B].N1=CC=CC2=CC=CC=C21 RKFFUJHJOUYEKT-UHFFFAOYSA-N 0.000 description 1
- 150000004768 bromobenzenes Chemical class 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 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
- BHQCQFFYRZLCQQ-OELDTZBJSA-N cholic acid Chemical compound C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)[C@@H](O)C1 BHQCQFFYRZLCQQ-OELDTZBJSA-N 0.000 description 1
- 229960002471 cholic acid Drugs 0.000 description 1
- 235000019416 cholic acid Nutrition 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
- KXGVEGMKQFWNSR-UHFFFAOYSA-N deoxycholic acid Natural products C1CC2CC(O)CCC2(C)C2C1C1CCC(C(CCC(O)=O)C)C1(C)C(O)C2 KXGVEGMKQFWNSR-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000284 extract Substances 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
- 150000002240 furans Chemical class 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
- 150000004820 halides Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 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
- 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- BSCHIACBONPEOB-UHFFFAOYSA-N oxolane;hydrate Chemical compound O.C1CCOC1 BSCHIACBONPEOB-UHFFFAOYSA-N 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 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
- 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
- WIOADUFWOUUQCV-UHFFFAOYSA-N triphenylphosphanium dichloride Chemical class [Cl-].[Cl-].C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 WIOADUFWOUUQCV-UHFFFAOYSA-N 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
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- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
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- C08G2261/50—Physical properties
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
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- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
Abstract
The invention discloses a kind of organic monomers containing 8 oxyquinoline boron and the conjugated polymer based on the monomer and preparation method and application to belong to the preparation of the conjugated polymer containing major element and its photoelectric property applied technical field.The preparation method of compound disclosed in this invention has outstanding advantages of easy to operate, reaction condition is mild, can be mass produced, adaptable to substrate, does not need to carry out column chromatography purifying；Prepared monomer and polymer photochemistry stability is good, fluorescence quantum yield is high, dissolubility is excellent, and solid foundation has been established for its Application in Sensing and photoelectric characteristic application.
Description
Technical field
The invention belongs to the preparation of the conjugated polymer containing major element and its photoelectric property applied technical fields, and in particular to
The organic monomer of one kind boron containing 8-hydroxyquinoline and conjugated polymer and preparation method and application based on the monomer.
Background technology
The organic optoelectronic research field emerging as one, be across chemistry, material, physics, one of information it is novel
Cross discipline, received the extensive concern of academia and industrial quarters in recent years.At present, organic electroluminescent LED, have
Field effect transistors, organic photovoltaic battery, organic sensor and the rapid hair for having the organic electro-optic devices such as machine information storage
Exhibition has embodied the incomparable advantage of inorganic semiconductor device.Organic photoelectrical material is most attached most importance to as organic electro-optic device
The component part wanted directly affects the development of these photoelectric devices.Compared with inorganic material, organic photoelectrical material can pass through
Solwution method realizes that prepared by large area and prepared by flexible device.Meanwhile organic material has diversified structure composition and broadness
Property regulation space can obtain required performance by MOLECULE DESIGN, can 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 big pi-conjugated organic molecule, be broadly divided into conjugation two major class of small molecule and conjugated polymer.Either organic molecule,
Or conjugatd polymers, photoelectric property can be by changing molecule structure in itself or introducing the function of specific function
Group is improved and is adjusted, so as to fulfill 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 that device is still finally prepared from material nature and significantly promoted.From the electronic structure of atom,
Compared with common carbon atom, either the 14th main group other elements atom (silicon, germanium and tin etc.) or other adjacent main groups (
13rd, 15 and 16 main group) Elements Atom is introduced into conjugated system the electron energy level and structure that all can greatly change system, and tie
The change of structure in itself often will the next very big influence of donor frenulum；Correspondingly, 8-hydroxyquinoline is a kind of typical chela
Mixture has prominent luminescence generated by light, Electroluminescence Properties, is obtained in Coordinative Chemistry and the initiative of photoelectric activity organic solid wide
General application.
Before although the organic conjugate heterocyclic arene containing major element has shown excellent performance and huge development
Scape, however realize that efficiently, easily still there are many difficulties for design synthesis to such compound.
At present, such compound mainly passes through the halide EX of major element2(E：Major element, X：Halogen atom) with phase
The double lithium reagent reactions of metal of organic backbone is answered to prepare synthesis, often these synthetic routes are all longer, reaction condition is more severe
Carve, synthesize it is difficult.Obviously, develop the new small molecule of organic conjugate containing major element and the synthetic method of polymer, prepare
The a series of conjugatd polymers material containing major element is always a focus of concern, otherwise will the day of one's doom
Make the extensive use of such material.Therefore, the synthesis strategy being simple and efficient is established, prepares small point of the organic conjugate containing major element
Son and polymer are the outstanding problems of the current area research.
Invention content
The purpose of the present invention is to provide the organic monomers of one kind boron containing 8-hydroxyquinoline and the conjugation based on the monomer to gather
Object and preparation method and application are closed, this method is short with synthesis cycle, and method is simple, and it is prominent can to carry out synthesis etc. on a large scale
Advantage, the organic monomer and conjugated polymer being prepared all show excellent photoelectric properties, are expected to efficient, highly selective
It is applied in fluorescence sense and organic photoelectrical material.
The present invention is to be achieved through the following technical solutions：
The invention discloses the organic monomer of one kind boron containing 8-hydroxyquinoline, the structural formula of the 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 the conjugated polymer of the organic monomer based on the above-mentioned boron containing 8-hydroxyquinoline, including 4 kinds
Conjugated polymer, respectively P1, P2, P3 and P4, structural formula are respectively：
Wherein, m=0,1,2,3,4,6,8,12 or 16；Integers of the n 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 methods for the organic monomer for preparing the above-mentioned boron containing 8-hydroxyquinoline, include the following steps：
1) prepare compound 1
In the case where argon gas protects atmosphere, diisopropylamine is added in anhydrous tetrahydrofuran solution, is stirred evenly, in ice bath item
Under part, borane dimethylsulfide ethereal solution is added dropwise dropwise, the reaction was continued after being added dropwise, under condition of ice bath 1-3 hours；Then again to anti-
The solution that n-BuLi is added dropwise in system is answered, continues stirring 1-3 hours under condition of ice bath；Finally, into reaction system by
Trim,ethylchlorosilane is added dropwise to, generates a large amount of white precipitate, after being all added dropwise, after being stirred at room temperature 1-3 hours, reaction
Liquid stands 0.5-2 hours, and argon gas protection is lower to filter, and the filtrate for obtaining water white transparency is compound 1, and it is protected in argon gas
Under save backup；
2) prepare compound 2
In the case where argon gas protects atmosphere, magnesium chips and change are separately added into the anhydrous tetrahydrofuran solution of 1- (4- alkyl) bromobenzene
Object 1 is closed, is stirred to react at 70-85 DEG C 20-24 hours, after reaction, adds in hydrochloric acid, room temperature into reaction solution under ice bath
Then stirring 45-60 minutes adds in water and ether into reaction system, organic phase is collected in extraction, and water phase is extracted with dichloromethane
It takes, merges organic phase, dry, filtering, rotary evaporation removes solvent, and compound 2 is made；
Wherein, 1- (4- alkyl) the bromobenzene structural formulas such as following formula：
Wherein m=0,1,2,3,4,6,8,12 or 16；
3) prepare compound 3
Compound 2 is dissolved in ether, 5,7- dihalos -8-hydroxyquinoline is added in into solution, reaction is stirred at room temperature
After 15-20 hours, pentane is added in into solution, precipitation is precipitated, filter cake is collected in filtering, and compound 3, i.e. hydroxyl containing 8- is made
The organic monomer of quinoline boron.
In step 1), diisopropylamine, borane dimethylsulf iotade, n-BuLi, trim,ethylchlorosilane and tetrahydrofuran mole
Than being 1：1：1：1：(4-5)；
In step 2), compound 1,1- (4- alkyl) bromobenzene, magnesium, hydrochloric acid and tetrahydrofuran molar ratio be 1：(2-3)：
(2-4)：(15-24)：The volume ratio of (90-120), water and ether is 1：1；
In step 3), the molar ratio of compound 2,5,7- dihalos -8-hydroxyquinoline and ether is 1：1：(50-70)；Institute
5,7- dihalos -8-hydroxyquinoline is stated, wherein halogen is bromine or iodine.
The invention also discloses the method for the conjugated polymer for the organic monomer for preparing the above-mentioned boron containing 8-hydroxyquinoline, including
Following steps：
Step 1：Prepare conjugated polymer P1
Under protection of argon gas, the organic monomer of the boron containing 8-hydroxyquinoline is dissolved in anhydrous tetrahydro furan, into solution
Tetrakis triphenylphosphine palladium, the wet chemical of anaerobic and alkyl-substituted Isosorbide-5-Nitrae-benzene hypoboric acid are added in, it is anti-in 70-80 DEG C of stirring
After answering 24-30 hours, reaction solution is extracted with dichloromethane, organic phase is dried with anhydrous magnesium sulfate, and rotary evaporation removes solvent；
Product is dissolved with dichloromethane, is added dropwise in the methanol of strong stirring, obtains yellow mercury oxide, is filtered, collects filter cake, vacuum is done
It is dry, yellow solid is obtained as conjugated polymer P1；
Step 2：Prepare conjugated polymer P2
Under protection of argon gas, the organic monomer of the boron containing 8-hydroxyquinoline is dissolved in dry toluene and diisopropylamine, to
Isosorbide-5-Nitrae-diacetylene-benzene of cuprous iodide, tetrakis triphenylphosphine palladium and alkoxy substitution is added in solution, it is anti-in 70-80 DEG C of stirring
After answering 22-30 hours, add in toluene and be diluted, filter, filtrate priority water and saturated common salt washing, dichloromethane extraction,
Organic phase is dried with anhydrous magnesium sulfate, and rotary evaporation removes solvent, dissolves product with dichloromethane, is added dropwise to strong stirring
It in methanol, filters, dry, it is conjugated polymer P2 that orange solids, which are made,；
Step 3：Prepare compound 4
Under protection of argon gas, alkyl-substituted 2,5- dibromo thiophenes are dissolved in anhydrous diisopropylamine, are added in into solution
Cuprous iodide, bis- (triphenylphosphine) palladium chlorides stir 30-40 minutes, and trimethyl acetenyl silicon is added in into solution, and ice bath stirs
It mixes 60-80 minutes, is then stirred at room temperature 60-80 minutes, be finally warming up to 75-85 DEG C and be stirred to react 20-24 hours；Reaction terminates
Add in dichloromethane in backward solution to be diluted, filter, filtrate rotary evaporation is removed, using silica gel-n-hexane system into
Compound 4 is made in row pillar layer separation；
Step 4：Prepare compound 5
Compound 4 is dissolved in methanol, then adds in potassium hydroxide aqueous solution, is protected from light, reaction 6- is stirred at room temperature
10 hours, after reaction, into solution plus water, dry with n-hexane extraction, filtering, rotary evaporation removing solvent, vacuum were done
It is dry, compound 5 is made；
Step 5：Prepare compound 6
Under protection of argon gas, 2 alkyl chain replaced, 2 '-union II thiophene are dissolved in anhydrous tetrahydro furan, and -78
Under the conditions of DEG C, n-butyllithium solution is added dropwise into solution, after being added dropwise, is stirred 1-2 hours at -78 DEG C；Then, at 0 DEG C
Under the conditions of, trimethyl ammonia chloride solution of tin is added dropwise into solution, after being added dropwise, after being stirred at room temperature 12-15 hours, adds in acetic acid second
Ester is diluted, washing, and organic phase is collected in liquid separation, and water phase is extracted with dichloromethane, merges organic phase, dry, is filtered, rotation
Evaporation of solvent；Finally with ethyl alcohol recrystallization, compound 6 is made；
Step 6：Prepare conjugated polymer P3
Under protection of argon gas, the organic monomer of the boron containing 8-hydroxyquinoline is dissolved in dry toluene and diisopropylamine, to
Cuprous iodide, tetrakis triphenylphosphine palladium and compound 5 are added in solution, after 70-80 DEG C is stirred to react 22-30 hours, is added in
Toluene is diluted, filtering, filtrate priority water and saturated common salt washing, dichloromethane extraction, organic phase anhydrous magnesium sulfate
Dry, rotary evaporation removes solvent；Product is dissolved with dichloromethane, is added dropwise in the methanol of strong stirring, is filtered, it is dry,
Dark red solid P3 is made；
Step 7：Prepare conjugated polymer P4
Under protection of argon gas, the organic monomer of the boron containing 8-hydroxyquinoline is dissolved in dry toluene, is added in into solution
Tetrakis triphenylphosphine palladium and compound 6, after 110-120 DEG C is stirred to react 22-30 hours, filtering, filtrate with water and is satisfied respectively
It is washed with salt, collects organic phase, water phase is extracted with dichloromethane, and organic phase is dried with anhydrous magnesium sulfate, filtering, rotary evaporation
Solvent is removed, product is dissolved with dichloromethane, is added dropwise in the methanol of strong stirring, is filtered, dry, obtained red solid is total to
Conjugated polymer P4.
In step 1, the organic monomer of the boron containing 8-hydroxyquinoline, alkyl substitution Isosorbide-5-Nitrae-benzene hypoboric acid, tetrakis triphenylphosphine palladium,
The molar ratio of potassium carbonate and tetrahydrofuran is 1：1：(0.05-0.15)：(10-20)：(350-400)；
In step 2, the organic monomer of the boron containing 8-hydroxyquinoline, Isosorbide-5-Nitrae-diacetylene-benzene, the four (triphenyls of alkoxy substitution
Phosphine) palladium, cuprous iodide, toluene and diisopropylamine molar ratio be 1：1：(0.05-0.15)：(0.05-0.15)：(250-400)：
(80-130)；
In step 3, alkyl-substituted 2,5- dibromo thiophenes, cuprous iodide, bis- (triphenylphosphine) palladium chlorides, trimethyl second
The molar ratio of alkynyl silicon and diisopropylamine is 1：(0.05-0.15)：(0.05-0.15)：(4-6)：(50-60)；
In step 4, the molar ratio of compound 4, potassium hydroxide and methanol is 1：(0.3-0.5)：(320-350)；
In step 5, the 2 of alkyl chain substitution, 2 '-union II thiophene, n-BuLi, trimethyltin chloride and tetrahydrofuran rub
You are than being 1：(2-3)：(2-3)：(50-80)；
In step 6, organic monomer, compound 5, cuprous iodide, tetrakis triphenylphosphine palladium, the toluene of the boron containing 8-hydroxyquinoline
Molar ratio with diisopropylamine is 1：1：(0.05-0.15)：(0.05-0.15)：(250-400)：(80-130)；
In step 7, the organic monomer of the boron containing 8-hydroxyquinoline, compound 6, the molar ratio of tetrakis triphenylphosphine palladium and toluene
It is 1：1：(0.05-0.15)：(360-400).
In step 3, alkyl-substituted 2, the 5- dibromo thiophenes structural formula such as following formula：
Wherein, q=0,4,6 or 12；
In step 5, the 2 of the alkyl chain substitution, the structural formula such as following formula of 2 '-union II thiophene：
Wherein, t=0,4 or 6.
Preferably, involved solvent is at least one of benzene, toluene, tetrahydrofuran, n,N-Dimethylformamide.Institute
It is related to catalyst for coupling reaction custom catalysts, such as tetrakis triphenylphosphine palladium, bis- (triphenylphosphine) palladium chlorides etc..It is involved
Solubilizing group-CkH2k+1、-CqH2q+1、-ChH2h+1、-CtH2t+1、-CmH2m+1Long chain alkane is not limited to, other solubilizing groups are still
It tries out in patent of the present invention, such as cholesterol segment, cholic acid segment, polyhydroxy substituent group.
The invention also discloses use the organic monomer of the boron containing 8-hydroxyquinoline or organic list of the boron containing 8-hydroxyquinoline
The conjugated polymer is dissolved in chloroform, is prepared into 1- by the method that the conjugated polymer of body prepares fluorescence membrane
The storing solution of 10mg/mL；Take 20-50 μ L deposit drop-coateds that fluorescence membrane is made in glass matrix surface every time.
The invention discloses application of the fluorescence membrane obtained above in detection formalin and formaldehyde gas.
Compared with prior art, the present invention has technique effect beneficial below：
Four kinds of conjugated polymers the invention discloses the organic monomer of one kind boron containing 8-hydroxyquinoline and based on the monomer,
Several compounds are containing major element boron and 8-hydroxyquinoline segment, the intrinsic electron deficient of boron atom (Lewis is acid)
So that the organic conjugated molecule of boracic is all often ideal 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 agent, the luminescence generated by light with protrusion,
Electroluminescence Properties；And pass through introducing solubilizing group, such as chain alkyl, the dissolubility and film forming of polymer material are improved,
And its assembly behavior can be adjusted, and then generates abundant optics behavior.
It is small that major element boron with excellent photoelectric properties and 8-hydroxyquinoline unit are introduced into conjugation by the present invention simultaneously
In molecule, and using long alkyl chain as solubilizing group, the method for a kind of efficient, pervasive synthesis of conjugate polymer is developed, has made
It is standby gone out a series of organic conjugate small molecule containing major element of high reaction activity functional groups functionalization, and then pass through
Sonogashira cross-coupling reactions, Suzuki cross-coupling reactions, Stille cross-coupling reactions etc. are efficient, easily make
Standby to have obtained four kinds of boron polymers containing 8-hydroxyquinoline, preparation process is simple, and equipment requirement is low, and monomer adaptability is stronger, equally
It is suitble to other polymerisation types.Obtained monomer and polymer are respectively provided with excellent dissolubility, high fluorescence quantum yield,
Abundant photophy-sical behavior, and photochemical stability performance protrudes, to realize its sensitive, selective sensing detection and enriching
Photoelectric characteristic established solid foundation.The preparation method of compound disclosed in this invention has easy to operate, reaction item
Part is mild, can be mass produced, adaptable to substrate, outstanding advantages of not needing to carry out column chromatography purifying；It is made
Standby monomer and polymer photochemistry stability is good, fluorescence quantum yield is high, dissolubility is excellent, is that its Application in Sensing and photoelectricity are special
Solid foundation has been established in property application.
Description of the drawings
Fig. 1 be the present invention obtained by organic monomer and four kinds of boracic conjugated polymers in chloroform it is ultraviolet-can
See abosrption spectrogram；
Fig. 2 is the fluorescent emission of organic monomer and four kinds of boracic conjugated polymers in chloroform obtained by the present invention
Spectrogram；
Fig. 3 be the present invention obtained by organic monomer and four kinds of boracic conjugated polymers thin-film state fluorescence emission spectrum
Figure；
Fig. 4 is photochemical in chloroform soln for the organic monomer obtained by the present invention and four kinds of boracic conjugated polymers
Learn stability launching light spectrogram；
Fig. 5 be the present invention obtained by organic monomer and four kinds of boracic conjugated polymers thin-film state photochemical stability
Launching light spectrogram；
Fig. 6 is organic monomer obtained by the present invention and four kinds of boracic conjugated polymer sense films in fluorescent lamp and ultraviolet
Photo under lamp；
Fig. 7 is fluorescence sense figures of the conjugated polymer P4 produced by the present invention in the presence of various concentration formaldehyde；
Fig. 8 is the visualization photo of conjugated polymer P4 PARA FORMALDEHYDE PRILLS(91,95)s produced by the present invention sensing；
Fig. 9 is the boracic monomer of the present invention and the synthetic route schematic diagram of conjugated polymer.
Specific embodiment
With reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and
It is not to limit.
Referring to Fig. 9, the organic monomer of the boron disclosed by the invention containing 8-hydroxyquinoline and four kinds of conjugated polymers can pass through
It is prepared by following steps：
1st, the preparation of the organic monomer and four kinds of conjugated polymers of a kind of boron containing 8-hydroxyquinoline
1) prepare compound 1
In the case where argon gas protects atmosphere, diisopropylamine is added in anhydrous tetrahydrofuran solution and is sufficiently stirred, and in ice
Under the conditions of bath, borane dimethylsulfide ethereal solution is added in above-mentioned reaction solution dropwise, is continued after being added dropwise, under condition of ice bath anti-
It answers 1-3 hours；Then the solution of n-BuLi is added dropwise into reaction system again, continues stirring 1-3 hours under condition of ice bath；
Finally, trim,ethylchlorosilane is added dropwise into reaction system, generates a large amount of white precipitate immediately, after all adding in, room
Temperature stirring 1-3 hours.After reaction, reaction solution stands 0.5-2 hours, and argon gas protection is lower to filter, and obtains the filter of water white transparency
Liquid is compound 1, and it is saved backup under protection of argon gas.Wherein diisopropylamine, borane dimethylsulf iotade, n-BuLi,
The molar ratio of trim,ethylchlorosilane and tetrahydrofuran is：1：1：1：1：(4-5).Its reaction equation is as follows：
2) prepare compound 2
In the case where argon gas protects atmosphere, magnesium chips and change are separately added into the anhydrous tetrahydrofuran solution of 1- (4- alkyl) bromobenzene
Object 1 is closed, is stirred to react 20-24 hours at 70-85 DEG C.After reaction, add in 3-6mol/L's into reaction solution under ice bath
Hydrochloric acid is stirred at room temperature 45-90 minutes, and water and ether are then added in into reaction solution, and organic phase, water phase dichloro are collected in liquid separation
Methane extracts 3-5 times, merges organic phase, and anhydrous magnesium sulfate drying is filtered, and rotary evaporation removes solvent, obtains faint yellow oily
Object.The molar ratio of wherein compound 1,1- (4- alkyl) bromobenzene, magnesium, hydrochloric acid and tetrahydrofuran 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) prepare compound 3
Compound 2 is dissolved in ether, 5,7-, bis- iodo- 8-hydroxyquinolines are added in into solution, it is small that 15-30 is stirred at room temperature
When.After reaction, a large amount of pentanes are added in into solution, a large amount of yellow-green precipitates are precipitated, are filtered, filter cake is collected, obtains Huang
Green solid.Wherein the molar ratio of compound 2, bis- iodo- 8-hydroxyquinolines of 5,7- and ether is 1：1：(50-70).Its reaction side
Formula is as follows：
4) prepare compound 4
Under protection of argon gas, 2, the 5- dibromo thiophenes that alkyl chain replaces are dissolved in anhydrous diisopropylamine, added into solution
Enter cuprous iodide, bis- (triphenylphosphine) palladium chlorides, stir 30-40 minutes, trimethyl acetenyl silicon is added dropwise into solution,
Then ice bath stirring 60-80 minutes is stirred at room temperature 60-80 minutes, be finally warming up to 75-85 DEG C and be stirred to react 20-24 hours.Instead
Should after, add in q. s. methylene chloride dilution into solution, filtrate rotary evaporation is removed solvent by filtering, then with silica gel/just
Hexane carries out pillar layer separation, obtains yellow crystalline solid.Wherein alkyl-substituted 2,5- dibromo thiophenes, cuprous iodide, bis- (three
Phenylphosphine) palladium chloride, trimethyl acetenyl silicon and diisopropylamine molar ratio 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) prepare compound 5
Compound 4 is dissolved in methanol, the potassium hydroxide aqueous solution of 0.5-1mol/L is added in into solution, is protected from light,
It is stirred to react at room temperature 6-10 hours, after reaction, suitable water is added in into solution, with n-hexane extraction 3-5 times, collect
Organic phase, anhydrous magnesium sulfate drying, filtering, rotary evaporation remove solvent, obtain yellow oil.Wherein compound 4, hydroxide
The molar ratio of potassium and methanol is 1：(0.3-0.5)：(320-350).Its reaction equation is as follows：
6) prepare compound 6
Under protection of argon gas, 2 alkyl chain replaced, 2 '-union II thiophene are dissolved in anhydrous tetrahydro furan, and -78
Under the conditions of DEG C, the n-butyllithium solution of 1.6-2.5mol/L is added dropwise into solution.After being added dropwise, it is small that 1-3 is stirred at -78 DEG C
When.Then, 0 DEG C and under this condition is warmed naturally to, trimethyltin chloride tetrahydrofuran solution is added dropwise into solution, drips
Bi Hou is stirred at room temperature 12-15 hours.After reaction, appropriate ethyl acetate dilution is added in, successively with water and saturated salt solution
It washes, liquid separation, collects organic phase, water phase is extracted 3-5 times with dichloromethane, merges organic phase, and anhydrous magnesium sulfate drying is filtered, rotation
Turn evaporation of solvent, finally with ethyl alcohol recrystallization, obtain gray solid.Wherein 2,2 '-union II thiophene, just of alkyl chain substitution
The molar ratio of butyl lithium, trimethyltin chloride and tetrahydrofuran is 1：(2-3)：(2-3)：(50-80).Reaction equation is：
T=0,4 or 6；
7) target product P1 is prepared
Under protection of argon gas, compound 3 is dissolved in anhydrous tetrahydro furan, four (triphenylphosphines) is added in into solution
Palladium, the anaerobic wet chemical of 1-2mol/L and alkyl substitution 1,4- benzene hypoboric acid.70-80 DEG C is stirred to react 24-30 hours.
After reaction, reaction solution is extracted 3-5 times with dichloromethane, merges organic phase, anhydrous magnesium sulfate drying, rotary evaporation removes molten
Agent.Product is dissolved with micro dichloromethane, is added dropwise in a large amount of methanol of strong stirring, obtains yellow mercury oxide, is filtered, is collected
Filter cake, vacuum drying, obtains yellow solid.Wherein compound 3, alkyl substitution 1,4- benzene hypoboric acid, tetrakis triphenylphosphine palladium, carbon
The molar ratio of sour potassium and tetrahydrofuran is 1：1：(0.05-0.15)：(10-20)：(350-400).Reaction equation is：
8) target product P2 is prepared
Under protection of argon gas, compound 3 is dissolved in dry toluene and anhydrous diisopropylamine, iodate is added in into solution
Cuprous, tetrakis triphenylphosphine palladium and the 1,4- diacetylene-benzenes of alkoxy substitution.70-80 DEG C is stirred to react 22-30 hours.Reaction
After, q. s. toluene dilution is added in, filtrate priority water and saturated common salt are washed in filtering, dichloromethane extraction, organic phase
It is dried with anhydrous magnesium sulfate, rotary evaporation removes solvent.Product is dissolved with micro dichloromethane, is added dropwise to the big of strong stirring
It measures in methanol, obtains orange precipitation, filter, collect filter cake, vacuum drying obtains orange solids.Wherein compound 3, alkoxy
Substituted 1,4- diacetylene-benzenes, tetrakis triphenylphosphine palladium, cuprous iodide, toluene and diisopropylamine molar ratio be：1：1：
(0.05-0.15)：(0.05-0.15)：(250-400)：(80-130).Reaction equation is：
9) target product P3 is prepared
Under protection of argon gas, compound 3 is dissolved in dry toluene and anhydrous diisopropylamine, iodate is added in into solution
Cuprous, tetrakis triphenylphosphine palladium and compound 5.70-80 DEG C is stirred to react 22-30 hours.After reaction, q. s. toluene is added in
Dilution, filtering, filtrate priority water and saturated common salt washing, dichloromethane extraction, organic phase are dried with anhydrous magnesium sulfate, rotated
Evaporation of solvent.Then product is dissolved with micro dichloromethane, be added dropwise in a large amount of methanol of strong stirring, obtained dark red
Color precipitates, filtering, collects filter cake, and vacuum drying obtains dark red solid.Wherein compound 3, compound 5, cuprous iodide, four
The molar 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 protection of argon gas, compound 3 is dissolved in dry toluene, tetrakis triphenylphosphine palladium and change is added in into solution
Close object 6.110-120 DEG C is stirred to react 22-30 hours.After reaction, it filters, filtrate is washed respectively with water and saturated common salt,
Organic phase is collected, water phase is extracted 3-5 times with dichloromethane, merges organic phase, and anhydrous magnesium sulfate drying is filtered, and rotary evaporation removes
Remove solvent.Product is dissolved with micro dichloromethane, is added dropwise in a large amount of methanol of strong stirring, obtains red precipitate.Filtering,
Filter cake is collected, vacuum drying obtains red solid.Wherein mole of compound 3, compound 6, tetrakis triphenylphosphine palladium and toluene
Than for：1：1：(0.05-0.15)：(360-400).Reaction equation is：
Wherein, m=0,1,2,3,4,6,8,12 or 16；Integers of the n 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.
2nd, the preparation of fluorescence membrane
Gained compound is dissolved in chloroform, is prepared into the storing solution of 1-10mg/mL.20-50 μ L is taken to store up every time
Fluorescence membrane is made in the glass matrix surface that standby drop is applied to specially treated.
Preferably, in the step of present invention prepares monomer and polymer：
In the step 1) for synthesizing compound 1, the diisopropylamine, borane dimethylsulf iotade, n-BuLi, trimethylchloro-silicane
The optimum mole ratio of alkane and tetrahydrofuran is：1：1：1：1：4.4；
In the step 2) for synthesizing compound 2, the compound 1,1- (4- alkyl) bromobenzene, magnesium, hydrochloric acid and tetrahydrofuran
Optimum mole ratio is：1：3：3.3：15：98.5；
In the step 3) for synthesizing compound 3, the compound 2,5,7-, bis- iodo- 8-hydroxyquinolines and the best of ether rub
You are than being 1：1：57.8；
In the step 4) for synthesizing compound 4, alkyl-substituted 2, the 5- dibromo thiophenes, cuprous iodide, bis- (triphenyls
Phosphine) palladium chloride, trimethyl acetenyl silicon and diisopropylamine optimum mole ratio be 1：0.12：0.06：4：52；
In the step 5) for synthesizing compound 5, the optimum mole ratio of the compound 4, potassium hydroxide and methanol is 1：
0.35：340.5；
In the step 6) for synthesizing compound 6, the 2 of the alkyl chain substitution, 2 '-union II thiophene, n-BuLi, trimethyl chlorine
The optimum mole ratio for changing tin and tetrahydrofuran is 1：2.1：2.2：60；
In the step 7) for synthesizing compound P1, the compound 3, alkyl substitution Isosorbide-5-Nitrae-benzene hypoboric acid, four (triphenylphosphines)
The optimum mole ratio of palladium, potassium carbonate and tetrahydrofuran is 1：1：0.1：10：370；
In the step 8) for synthesizing compound P2, Isosorbide-5-Nitrae-diacetylene-benzene, four (triphens that the compound 3, alkoxy replace
Base phosphine) palladium, cuprous iodide, toluene and diisopropylamine optimum mole ratio be：1：1：0.1：0.1：265：86；
In the step 9) for synthesizing compound P3, the compound 3, compound 5, cuprous iodide, tetrakis triphenylphosphine palladium, first
The optimum mole ratio of benzene and diisopropylamine is：1：1：0.1：0.1：265：86；
In the step 10) for synthesizing compound P4, the compound 3, compound 6, tetrakis triphenylphosphine palladium and toluene are most
Good molar ratio is：1：1：0.1：378.
During fluorescence membrane is prepared, gained compound is dissolved in chloroform, is prepared into the storage of 1mg/mL
Standby liquid.Take 30 μ L deposit drop-coateds that fluorescence membrane is made in the glass matrix surface of specially treated every time.
Embodiment 1
A kind of preparation of organic monomer and four kinds of conjugated polymers
1. synthesize compound 1
In the case where argon gas protects atmosphere, 7mL diisopropylamines are added in 18mL anhydrous tetrahydrofuran solutions and are sufficiently stirred,
And under condition of ice bath, the tetrahydrofuran solution (10mol/L) of 5mL borane dimethylsulf iotades is added to above-mentioned reaction solution dropwise
In, the reaction was continued after being added dropwise, under condition of ice bath 1.5 hours；Then 20mL normal-butyls are added dropwise into reaction system again
The hexane solution (2.5mol/L) of lithium continues stirring 2 hours under condition of ice bath；Finally, it is added dropwise into reaction system
6.4mL trim,ethylchlorosilanes generate a large amount of white precipitate immediately, after all adding in, are stirred at room temperature 2 hours.Reaction terminates
Afterwards, reaction solution stands 1 hour, and argon gas protection is lower to filter, and the filtrate for obtaining water white transparency is compound 1, and by it in argon gas
It is saved backup under protection, yield about 99%.Wherein diisopropylamine, borane dimethylsulf iotade, n-BuLi, trim,ethylchlorosilane and four
The molar ratio of hydrogen furans is：1：1：1：1：4.4.
2. synthesize compound 2
In the case where argon gas protects atmosphere, 0.4g magnesium chips, 3.3ml 1- (4- are separately added into 40ml anhydrous tetrahydrofuran solutions
Alkyl) bromobenzene and 5ml compounds 1.It is stirred to react at 80 DEG C 20 hours.After reaction, it is added under ice bath into reaction solution
The hydrochloric acid of 25ml 3mol/L is stirred at room temperature 45 minutes.Wherein compound 1,1- (4- bromophenyls) hexane, magnesium, hydrochloric acid and tetrahydrochysene furan
The molar ratio muttered is：1：3：3.3：18：98.5.20ml water and 20ml ether are added in into reaction solution again, liquid separation is collected organic
Phase, water phase are extracted 3 times every time using 30mL dichloromethane, are merged organic phase, are dried with anhydrous magnesium sulfate, are filtered, rotary evaporation
Solvent is removed, obtains pale yellow oil, yield about 98%.Wherein the volume ratio of water and ether is 1：1.
3. synthesize compound 3
5mmol compounds 2 are dissolved in 30ml ether, 1.9848g 5, bis- iodo- 8- hydroxyls quinolines of 7- are added in into solution
Quinoline.Wherein the molar ratio of compound 2, bis- iodo- 8-hydroxyquinolines of 5,7- and ether is 1：1：57.8.It is stirred at room temperature 15 hours.Instead
After answering, a large amount of pentanes are added in into solution, precipitation is precipitated.Filtering collects filter cake, obtains greenish yellow solid, yield
92%.
4. synthesize compound 4
Under protection of argon gas, by 0.93ml 2,5- dibromo thiophenes are dissolved in the anhydrous diisopropylamines of 60ml, are added in into solution
Bis- (triphenylphosphine) palladium chlorides of 0.19g cuprous iodides, 0.345g stir 30 minutes, and 4.7ml trimethyl second is added in into solution
Then alkynyl silicon, ice bath stirring 60 minutes are stirred at room temperature 60 minutes, be finally warming up to 75 DEG C and stir 20 hours.Wherein 2,5- bis-
Bromothiophene, cuprous iodide, bis- (triphenylphosphine) palladium chlorides, trimethyl acetenyl silicon and diisopropylamine molar ratio be 1：
0.12：0.06：4：52.After reaction, q. s. methylene chloride dilution is added in into solution, filtering removes filtrate rotary evaporation
Solvent is removed, pillar layer separation is carried out using silica gel/n-hexane, obtains yellow crystalline solid, yield 56%.
5. synthesize compound 5
0.4g compounds 4 are dissolved in 20ml methanol, the potassium hydroxide that 1ml 0.5mol/L are added in into solution is water-soluble
Liquid is protected from light, and reaction 7 hours is stirred at room temperature.The molar ratio of wherein compound 4, potassium hydroxide and methanol is 1：0.35：
340.5.After reaction, 50ml water is added in into solution, with n-hexane extraction 4 times, collects organic phase, anhydrous magnesium sulfate is done
Dry, filtering, rotary evaporation removes solvent, obtains yellow oil, yield 75%.
6. synthesize compound 6
Under protection of argon gas, by 0.3174g 2,2 '-union II thiophene is dissolved in 10ml anhydrous tetrahydro furans, and -78
Under the conditions of DEG C, the n-BuLi hexane solution of 1.8ml 2.5mol/L is added dropwise into solution.After being added dropwise, at -78 DEG C
Stirring 1 hour.Then, under the conditions of 0 DEG C, 4.4ml 1mol/L trimethyltin chloride tetrahydrofuran solutions are added dropwise into solution,
After being added dropwise, it is stirred at room temperature 12 hours.Wherein 2,2 '-union II thiophene, n-BuLi, trimethyltin chloride and tetrahydrofuran
Molar ratio is 1：2.1：2.2：60.After reaction, appropriate ethyl acetate dilution is added in, is successively washed with water and saturated common salt,
Organic phase is collected in liquid separation, and water phase is extracted 4 times with dichloromethane, merges organic phase, anhydrous magnesium sulfate drying, filtering, rotary evaporation
Solvent is removed, with ethyl alcohol recrystallization, obtains gray solid, yield 85%.
7. prepare target product P1
Under protection of argon gas, 0.3641g compounds 3 are dissolved in 15ml anhydrous tetrahydro furans, are added in into solution
0.0578g tetrakis triphenylphosphine palladiums, the anaerobic wet chemical of 10ml 1mol/L and 0.0829g 1,4- benzene hypoboric acid.80
It DEG C is stirred to react 24 hours.Wherein compound 3,1,4- benzene hypoboric acid, tetrakis triphenylphosphine palladium, potassium carbonate and tetrahydrofuran rubs
You are than being 1：1：0.1：10：370.After reaction, reaction solution is extracted 4 times with dichloromethane, merges organic phase, anhydrous magnesium sulfate
Dry, rotary evaporation removes solvent.Product is dissolved with micro dichloromethane, is added dropwise in a large amount of methanol of strong stirring, obtains
To yellow mercury oxide, filter cake is collected in filtering, and vacuum drying obtains yellow solid, yield 56%.
8. prepare target product P2
Under protection of argon gas, 0.3641g compounds 3 are dissolved in 14ml dry toluenes and the anhydrous diisopropylamines of 6ml, to
0.0095g cuprous iodides, 0.0578g tetrakis triphenylphosphine palladiums and 0.0631g 1,4- diacetylene-benzenes are added in solution.Wherein
Compound 3,1,4- diacetylene-benzenes, tetrakis triphenylphosphine palladium, cuprous iodide, toluene and diisopropylamine molar ratio be：1：1：
0.1：0.1：265：86.80 DEG C are stirred to react 24 hours.After reaction, q. s. toluene dilution, filtering, by filtrate priority are added in
It is washed with water and saturated common salt, dichloromethane extraction, organic phase is dried with anhydrous magnesium sulfate, and rotary evaporation removes solvent.With micro-
Amount dichloromethane dissolves product, is added dropwise in a large amount of methanol of strong stirring, obtains orange precipitation, filters, and collects filter cake, very
Sky is dry, obtains orange solids, yield 73%.
9. prepare target product P3
Under protection of argon gas, 0.3641g compounds 3 are dissolved in 14mL dry toluenes and the anhydrous diisopropylamines of 6mL, to
0.0095g cuprous iodides, 0.0578g tetrakis triphenylphosphine palladiums and 80ul 2,5- diacetylene thiophene are added in solution.80 DEG C are stirred
Mix reaction 24 hours.Wherein compound 3,2,5- diacetylenes thiophene, cuprous iodide, tetrakis triphenylphosphine palladium, toluene and two are different
The molar ratio of propylamine is：1：1：0.1：0.1：265：86.After reaction, q. s. toluene dilution, filtering are added in, filtrate is successively used
Water and saturated common salt washing, dichloromethane extraction, organic phase are dried with anhydrous magnesium sulfate, and rotary evaporation removes solvent.Then it uses
Micro dichloromethane dissolves product, is added dropwise in a large amount of methanol of strong stirring, obtains kermesinus precipitation, and filter is collected in filtering
Cake, vacuum drying, obtains dark red solid, yield 51%.
10. prepare target product P4
Under protection of argon gas, 0.3641g compounds 3 are dissolved in 20ml dry toluenes, 0.0578g is added in into solution
Tetrakis triphenylphosphine palladium and 4,4 '-two tin trimethyls of 0.2459g connect thiophene.Wherein compound 3,4,4 '-two tin trimethyls connect thiophene
The molar ratio of fen, tetrakis triphenylphosphine palladium and toluene is：1：1：0.1：378.110 DEG C are stirred to react 24 hours.After reaction,
Filtering, filtrate are washed respectively with water and saturated common salt, collect organic phase, and water phase is extracted 5 times with dichloromethane, merges organic phase,
Anhydrous magnesium sulfate is dried, and filtering, rotary evaporation removes solvent.Product is dissolved with micro dichloromethane, is added dropwise to strong stirring
A large amount of methanol in, obtain red precipitate.Filtering, collects filter cake, and vacuum drying obtains red solid, yield 76%.
2nd, the preparation of fluorescence membrane
Gained compound is dissolved in chloroform, is prepared into the storing solution of 1mg/mL.30 μ L is taken to lay in drop every time
Fluorescence membrane is made in the glass matrix surface for being applied to specially treated.
Embodiment 2
In the present embodiment, synthesize compound 1 the step of 1. in, argon gas protect atmosphere under, 7mL diisopropylamines are added in
It into 32.5mL anhydrous tetrahydrofuran solutions and is sufficiently stirred, and under condition of ice bath, dropwise by the four of 5mL borane dimethylsulf iotades
Hydrogen tetrahydrofuran solution (10mol/L) is added in above-mentioned reaction solution, and the reaction was continued after being added dropwise, under condition of ice bath 1.5 hours；So
The hexane solution (2.5mol/L) of 20mL n-BuLis is added dropwise into reaction system again afterwards, continues to stir under condition of ice bath
2 hours；Finally, 6.4mL trim,ethylchlorosilanes are added dropwise into reaction system, generate a large amount of white precipitate immediately, treat complete
After portion adds in, it is stirred at room temperature 2 hours.Wherein diisopropylamine, borane dimethylsulf iotade, n-BuLi, trim,ethylchlorosilane and tetrahydrochysene
The molar ratio of furans is：1：1：1：1：5.5.After reaction, reaction solution stands 1 hour, and argon gas protection is lower to filter, and obtains colourless
Transparent filtrate is compound 1, and it is saved backup under protection of argon gas, yield about 99%.
In the present embodiment, synthesize compound 2 the step of 2. in, be separately added into 40ml anhydrous tetrahydrofuran solutions
0.48g magnesium chips, 3.3ml 1- (4- alkyl) bromobenzenes and 6.25ml compounds 1.It is stirred to react at 80 DEG C 20 hours.Reaction terminates
Afterwards, the hydrochloric acid of 30ml 3mol/L is added in into reaction solution under ice bath, is stirred at room temperature 45 minutes.Wherein compound 1,1- (4- bromines
Phenyl) hexane, magnesium, hydrochloric acid and tetrahydrofuran molar ratio be：1：3：4：22.5：98.5.20ml water is added in into reaction solution again
With 20ml ether, organic phase is collected in liquid separation, and water phase is extracted 3 times every time using 30mL dichloromethane, merges organic phase, and use is anhydrous
Magnesium sulfate is dried, and filtering, rotary evaporation removes solvent, obtains pale yellow oil, yield about 98%.The wherein body of water and ether
Product is than being 1：1.
In the present embodiment, synthesize compound 3 the step of 3. in, 5mmol compounds 2 are dissolved in 39ml ether, to
Bis- iodo- 8-hydroxyquinolines of 1.9848g 5,7- are added in solution.Wherein compound 2, bis- iodo- 8-hydroxyquinolines of 5,7- and ether
Molar ratio is 1：1：75.1.It is stirred at room temperature 15 hours.After reaction, a large amount of pentanes are added in into solution, precipitation is precipitated.It crosses
Filter collects filter cake, obtains greenish yellow solid, yield about 90%.
Synthesize compound 4 the step of 4. in, under protection of argon gas, by 0.93ml 2,5- dibromo thiophenes be dissolved in 60ml without
In water diisopropylamine, 0.19g cuprous iodides, bis- (triphenylphosphine) palladium chlorides of 0.345g are added in into solution, are stirred 30 minutes,
5.9ml trimethyl acetenyl silicon is added in into solution.Wherein 2,5- dibromo thiophenes, cuprous iodide, bis- (triphenylphosphine) dichlorides
The molar ratio of palladium, trimethyl acetenyl silicon and diisopropylamine is 1：0.12：0.06：5：52.Ice bath stirring 60 minutes, then room temperature
Stirring 60 minutes is finally warming up to 75 DEG C and stirs 20 hours.After reaction, q. s. methylene chloride dilution is added in into solution,
Filtering, solvent is removed by filtrate rotary evaporation, is carried out pillar layer separation using silica gel/n-hexane, is obtained yellow crystalline solid, produces
Rate about 55%.
Synthesize compound 5 the step of 5. in, 0.4g compounds 4 are dissolved in 20ml methanol, 1ml is added in into solution
The potassium hydroxide aqueous solution of 0.7mol/L, is protected from light, and reaction 7 hours is stirred at room temperature.Wherein compound 4, potassium hydroxide and first
The molar ratio of alcohol is 1：0.5：340.5.After reaction, 50ml water is added in into solution, with n-hexane extraction 4 times, collection has
Machine phase, anhydrous magnesium sulfate drying, filtering, rotary evaporation remove solvent, obtain yellow oil, yield about 70%.
Synthesize compound 6 the step of 6. in, under protection of argon gas, by 0.3174g 2,2 '-union II thiophene is dissolved in
In 10ml anhydrous tetrahydro furans, and under the conditions of -78 DEG C, the n-BuLi n-hexane of 2.2ml 2.5mol/L is added dropwise into solution
Solution.After being added dropwise, stirred 1 hour at -78 DEG C.Then, under the conditions of 0 DEG C, 4.4ml 1mol/L are added dropwise into solution
Trimethyltin chloride tetrahydrofuran solution after being added dropwise, is stirred at room temperature 12 hours.Wherein 2,2 '-union II thiophene, normal-butyl
The molar ratio of lithium, trimethyltin chloride and tetrahydrofuran is 1：2.5：2.2：60.After reaction, it is dilute to add in appropriate ethyl acetate
It releases, is successively washed with water and saturated common salt, liquid separation, collect organic phase, water phase is extracted 4 times with dichloromethane, merges organic phase, nothing
Water magnesium sulfate is dried, and filtering, rotary evaporation removes solvent, with ethyl alcohol recrystallization, obtains gray solid, yield about 86%.
Synthesize target product P1 the step of 7. in, under protection of argon gas, by 0.3641g compounds 3 be dissolved in 15ml without
In water tetrahydrofuran, the anaerobic wet chemical of 0.0578g tetrakis triphenylphosphine palladiums, 10ml 2mol/L are added in into solution
With 0.0829g 1,4- benzene hypoboric acid.80 DEG C are stirred to react 24 hours.Wherein compound 3,1,4- benzene hypoboric acid, four (triphenyls
Phosphine) palladium, potassium carbonate and tetrahydrofuran molar ratio be 1：1：0.1：20：370.After reaction, reaction solution is extracted with dichloromethane
It takes 4 times, merges organic phase, anhydrous magnesium sulfate drying, rotary evaporation removes solvent.Product is dissolved with micro dichloromethane, is dripped
It adds in a large amount of methanol of strong stirring, obtains yellow mercury oxide, filter, collect filter cake, vacuum drying obtains yellow solid, produces
Rate about 61%.
Synthesize target product P2 the step of 8. in, under protection of argon gas, by 0.3641g compounds 3 be dissolved in 21ml without
In water-toluene and the anhydrous diisopropylamines of 9ml, added in into solution 0.0095g cuprous iodides, 0.0578g tetrakis triphenylphosphine palladiums and
0.0631g 1,4- diacetylene-benzenes.Wherein compound 3,1,4- diacetylene-benzenes, tetrakis triphenylphosphine palladium, cuprous iodide, first
The molar ratio of benzene and diisopropylamine is：1：1：0.1：0.1：397.5：129.80 DEG C are stirred to react 24 hours.After reaction, add
Enter q. s. toluene dilution, filtrate priority water and saturated common salt are washed in filtering, dichloromethane extraction, the anhydrous sulphur of organic phase
Sour magnesium drying, rotary evaporation remove solvent.Product is dissolved with micro dichloromethane, is added dropwise to a large amount of methanol of strong stirring
In, orange precipitation is obtained, is filtered, collects filter cake, vacuum drying obtains orange solids, yield about 65%.
Synthesize target product P3 the step of 9. in, under protection of argon gas, by 0.3641g compounds 3 be dissolved in 14mL without
In water-toluene and the anhydrous diisopropylamines of 6mL, added in into solution 0.0095g cuprous iodides, 0.0578g tetrakis triphenylphosphine palladiums and
80ul 2,5- diacetylene thiophene.80 DEG C are stirred to react 24 hours.Wherein compound 3,2,5- diacetylenes thiophene, iodate are sub-
Copper, tetrakis triphenylphosphine palladium, toluene and diisopropylamine molar ratio be：1：1：0.1：0.1：397.5：129.After reaction,
Add in q. s. toluene dilution, filtering, filtrate priority water and saturated common salt washing, dichloromethane extraction, the anhydrous sulphur of organic phase
Sour magnesium drying, rotary evaporation remove solvent.Then product is dissolved with micro dichloromethane, is added dropwise to a large amount of first of strong stirring
In alcohol, kermesinus precipitation is obtained, filter cake is collected in filtering, and vacuum drying obtains dark red solid, yield about 48%.
Synthesize target product P4 the step of 10. in, under protection of argon gas, by 0.3641g compounds 3 be dissolved in 22ml without
In water-toluene, add in 0.0578g tetrakis triphenylphosphine palladiums into solution and 4,4 '-two tin trimethyls of 0.2459g connect thiophene.Its
The molar ratio that middle compound 3,4,4 '-two tin trimethyls connect thiophene, tetrakis triphenylphosphine palladium and toluene is：1：1：0.1：400.
110 DEG C are stirred to react 24 hours.After reaction, it filters, filtrate is washed respectively with water and saturated common salt, collects organic phase, water
It is mutually extracted 4 times with dichloromethane, merges organic phase, anhydrous magnesium sulfate drying is filtered, and rotary evaporation removes solvent.With micro two
Chloromethanes dissolves product, is added dropwise in a large amount of methanol of strong stirring, obtains red precipitate.Filtering, collects filter cake, and vacuum is done
It is dry, obtain red solid, yield 73%.
During fluorescence membrane is prepared, gained compound is dissolved in chloroform, is prepared into the storage of 5mg/mL
Standby liquid.Take 30 μ L deposit drop-coateds that fluorescence membrane is made in the glass matrix surface of specially treated every time.
Embodiment 3
Examples 1 to 22 step of synthesis compound for preparing monomer and four kinds of conjugated polymer steps 1 2. in, it is used
1- (4- bromophenyls) hexanes replaced with equimolar 1- (4- bromophenyls) butane, other steps of the step and corresponding embodiment
Identical, prepare compound 2, the value of m is 4 in formula.
Other steps are identical with Examples 1 to 2.
Embodiment 4
Examples 1 to 22 step of synthesis compound for preparing monomer and four kinds of conjugated polymer steps 1 2. in, it is used
1- (4- bromophenyls) hexanes replaced with equimolar 1- (4- bromophenyls) octane, other steps of the step and corresponding embodiment
Identical, prepare compound 2, the value of m is 8 in formula.
Other steps are identical with Examples 1 to 2.
Embodiment 5
Examples 1 to 22 step of synthesis compound for preparing monomer and four kinds of conjugated polymer steps 1 2. in, it is used
1- (4- bromophenyls) hexanes replaced with equimolar 1- (4- bromophenyls) dodecane, other steps of the step are implemented with corresponding
Identical, the prepare compound 2 of example, the value of m is 12 in formula.
Other steps are identical with Examples 1 to 2.
Embodiment 6
Examples 1 to 22 step of synthesis compound for preparing monomer and four kinds of conjugated polymer steps 1 2. in, it is used
1- (4- bromophenyls) hexanes replaced with equimolar 1- (4- bromophenyls) hexadecane, other steps of the step are implemented with corresponding
Identical, the prepare compound 2 of example, the value of m is 16 in formula.
Other steps are identical with Examples 1 to 2.
Embodiment 7
Examples 1 to 22 step of synthesis compound for preparing monomer and four kinds of conjugated polymer steps 1 2. in, it is used
1- (4- bromophenyls) hexane replaced with equimolar bromobenzene, other steps of the step are identical with corresponding embodiment, preparationization
Object 2 is closed, the value of m is 0 in formula.
Other steps are identical with Examples 1 to 2.
Embodiment 8
Examples 1 to 23 step of synthesis compound for preparing monomer and four kinds of conjugated polymer steps 1 3. in, it is used
5,7-, bis- iodo- 8-hydroxyquinolines replaced with equimolar 5,7-D-Br-8-HQ, other steps of the step with it is corresponding
Embodiment is identical, prepare compound 3.
Other steps are identical with Examples 1 to 2.
Embodiment 9
In Examples 1 to 8 is the step of preparing fluorescence membrane, by storing solution solvent for use chloroform tetrahydrofuran
It replaces.Other steps are identical with Examples 1 to 2.
Embodiment 10
In Examples 1 to 8 is the step of preparing fluorescence membrane, by storing solution solvent for use chloroform N, N- diformazan
Base formamide is replaced.Other steps are identical with Examples 1 to 2.
Embodiment 11
In Examples 1 to 8 is the step of preparing fluorescence membrane, by storing solution solvent for use chloroform dimethyl sulfoxide
It replaces.Other steps are identical with Examples 1 to 2.
Embodiment 12
Examples 1 to 24 step of synthesis compound for preparing monomer and four kinds of conjugated polymer steps 1 4. in, it is used
2,5- dibromo thiophenes replaced with equimolar alkyl-substituted 2,5- dibromo thiophenes, other steps of the step are implemented with corresponding
Identical, the prepare compound 4 of example, the value of q is 4 in formula.
Other steps are identical with Examples 1 to 2.
Embodiment 13
Examples 1 to 2 the synthesis compound P2 steps for preparing monomer and four kinds of conjugated polymer steps 1 8. in, institute
The Isosorbide-5-Nitrae that the equimolar alkoxy of Isosorbide-5-Nitrae-diacetylene-benzene replaces-diacetylene-benzene is replaced, other steps of the step with
Corresponding embodiment is identical, prepare compound P2, and the value of h is 8 in formula.
Other steps are identical with Examples 1 to 2.
Embodiment 14
Examples 1 to 2 the synthesis compound P2 steps for preparing monomer and four kinds of conjugated polymer steps 1 8. in, institute
The Isosorbide-5-Nitrae that the equimolar alkoxy of Isosorbide-5-Nitrae-diacetylene-benzene replaces-diacetylene-benzene is replaced, other steps of the step with
Corresponding embodiment is identical, prepare compound P2, and the value of h is 16 in formula, other steps are identical with Examples 1 to 2.
Embodiment described above only expresses the several embodiments of the present invention, and description is more specific and detailed, but simultaneously
Cannot the limitation to the scope of the claims of the present invention therefore 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, various modifications and improvements can be made, these belong to the guarantor of the present invention
Protect range.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
In order to verify benefit of this patent to society, inventor is conjugated monomer and boracic synthesized in embodiment 1 poly-
The detection for closing the Fluorescence behaviour and PARA FORMALDEHYDE PRILLS(91,95) of object has carried out desk study.
It is the ultraviolet-visible absorption spectroscopy figure of synthesized compound referring to Fig. 1, wherein a is blank CHCl3Absorption, b,
C, d, e, f are respectively the absorption spectrum of synthesized monomer and four kinds of polymer.By ultraviolet-visible absorption spectroscopy this it appears that
The trend gradually to broaden is presented in increase with conjugated degree and the enhancing for receptor relationship, the absorption peak of compound；
In chloroform soln and the launching light spectrogram of thin-film state, interior figure is the respectively synthesized compounds of Fig. 2 and Fig. 3
Fluorescence photo under 365nm ultra violet lamps, as can be seen from the figure the launch wavelength of monomer 3 to polymer P 4 have occurred compared with
For apparent red shift, for solution state maximum emission wavelength from 520nm red shifts to 625nm, fluorescence color also becomes red from green；It is thin
For film state maximum emission wavelength from 500nm red shifts to 670nm, fluorescence color also becomes red from green, and the region shine compared with
It is easily arrived by eye-observation, certain basis has been established for its optical application.
Fig. 4 and Fig. 5 be respectively gained compound in chloroform soln and the photochemical stability spectrogram of thin-film state, from
Compound obtained by it can be seen from the figure that either still shows excellent photochemical stability in solution state in thin-film state,
" photobleaching " phenomenon is successfully evaded, has been applied for its fluorescence sense and photovoltaic applications have established solid foundation.
Fig. 6 is gained monomer and polymer in the thin-film state optical photograph under fluorescent lamp and 365nm ultraviolet lamps respectively, can
To find out that solid color and fluorescence are all to become red from green, the structure for its sensor array provides possibility.
Fig. 7 is the fluorescence sense figure of resulting polymers P4 PARA FORMALDEHYDE PRILLS(91,95) aqueous solutions in tetrahydrofuran solution.The first detected
Aldehyde solution concentration is 5 μM.Bright by chart, with the increase of scanning times, the fluorescence intensity of P4 is significantly quenched, and along with
The movement of maximum emission wavelength.Fig. 8 is the fluorescence photo added in before and after formaldehyde, can be clearly observed fluorescence color and have occurred
Apparent variation, for its can practical application lay a good foundation.
In conclusion a kind of organic monomer and four kinds of conjugated polymers involved in the present invention containing major element boron and
8-hydroxyquinoline segment, the intrinsic electron deficient of boron atom (Lewis is acid) is so that the organic conjugated molecule of boracic is all often
Ideal electron acceptor material, thus all there is boundless application prospect in organic photoelectric and fluorescence sense etc.；And
8-hydroxyquinoline is a kind of typical chelating agent, has prominent luminescence generated by light, Electroluminescence Properties；And pass through and introduce hydrotropy base
Group, such as chain alkyl improves the dissolubility and film forming of polymer material, and can adjust its assembly behavior, and then produces
Raw abundant optics behavior.The present invention introduces the major element boron with excellent photoelectric properties and 8-hydroxyquinoline unit simultaneously
Into conjugation small molecule, polymerisable monomer is simply and efficiently synthesized, and developed based on this kind of efficient, pervasive
The method for synthesizing boracic conjugated polymer, has prepared a series of the having containing major element of high reaction activity functional groups functionalization
Machine is conjugated small molecule, and then is intersected occasionally by Sonogashira cross-coupling reactions, Suzuki cross-coupling reactions, Stille
Connection reaction etc. is efficient, four kinds of boron polymers containing 8-hydroxyquinoline have easily been prepared, and preparation process is simple, equipment requirement
It is low, while also illustrate that monomer adaptability is stronger, similarly suitable other polymerisation types.Obtained monomer and polymer have
There are excellent dissolubility, high fluorescence quantum yield, abundant photophy-sical behavior, and photochemical stability performance to protrude, be
Its sensitive, selective sensing detection and abundant photoelectric characteristic have established solid foundation.
Claims (7)
1. the conjugated polymer of the organic monomer of a kind of boron containing 8-hydroxyquinoline, which is characterized in that including 4 kinds of conjugated polymers,
Respectively P1, P2, P3 and P4, structural formula are respectively：
Wherein, m=1,2,3,4,6,8,12 or 16；Integers of the n 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 structural formula of the organic monomer of the boron containing 8-hydroxyquinoline is as follows：
Wherein, m=1,2,3,4,6,8,12 or 16.
2. prepare the method for the organic monomer of the boron containing 8-hydroxyquinoline described in claim 1, which is characterized in that including following
Step：
1) prepare compound 1
In the case where argon gas protects atmosphere, diisopropylamine is added in anhydrous tetrahydrofuran solution, is stirred evenly, in condition of ice bath
Under, borane dimethylsulfide ethereal solution is added dropwise dropwise, the reaction was continued after being added dropwise, under condition of ice bath 1-3 hours；Then again to reaction
The solution of n-BuLi is added dropwise in system, continues stirring 1-3 hours under condition of ice bath；Finally, into reaction system dropwise
Trim,ethylchlorosilane is added in, generates a large amount of white precipitate, after being all added dropwise, after being stirred at room temperature 1-3 hours, reaction solution
0.5-2 hours are stood, argon gas protection is lower to filter, and the filtrate for obtaining water white transparency is compound 1, and by it under protection of argon gas
It saves backup；
2) prepare compound 2
In the case where argon gas protects atmosphere, magnesium chips and compound are separately added into the anhydrous tetrahydrofuran solution of 1- (4- alkyl) bromobenzene
1, it is stirred to react at 70-85 DEG C 20-24 hours, after reaction, hydrochloric acid is added in into reaction solution under ice bath, is stirred at room temperature
45-60 minutes, water and ether are then added in into reaction system, organic phase is collected in extraction, and water phase is extracted with dichloromethane, is closed
And organic phase, dry, filtering, rotary evaporation removes solvent, and compound 2 is made；
Wherein, 1- (4- alkyl) the bromobenzene structural formulas such as following formula：
Wherein m=1,2,3,4,6,8,12 or 16；
3) prepare compound 3
Compound 2 is dissolved in ether, 5,7- dihalos -8-hydroxyquinoline is added in into solution, reaction 15-20 is stirred at room temperature
After hour, pentane is added in into solution, precipitation is precipitated, filter cake is collected in filtering, and compound 3, i.e. boron containing 8-hydroxyquinoline is made
Organic monomer；
Wherein, in step 1), diisopropylamine, borane dimethylsulf iotade, n-BuLi, trim,ethylchlorosilane and tetrahydrofuran mole
Than being 1：1：1：1：(4-5)；
In step 2), compound 1,1- (4- alkyl) bromobenzene, magnesium, hydrochloric acid and tetrahydrofuran molar ratio be 1：(2-3)：(2-4)：
(15-24)：The volume ratio of (90-120), water and ether is 1：1；
In step 3), the molar ratio of compound 2,5,7- dihalos -8-hydroxyquinoline and ether is 1：1：(50-70)；Described 5,
7- dihalos -8-hydroxyquinoline, wherein halogen are bromine or iodine.
3. prepare the method for the conjugated polymer of the organic monomer of the boron containing 8-hydroxyquinoline described in claim 1, feature
It is, includes the following steps：
Step 1：Prepare conjugated polymer P1
Under protection of argon gas, the organic monomer of the boron containing 8-hydroxyquinoline is dissolved in anhydrous tetrahydro furan, is added in into solution
Tetrakis triphenylphosphine palladium, the wet chemical of anaerobic and alkyl-substituted Isosorbide-5-Nitrae-benzene hypoboric acid, are stirred to react in 70-80 DEG C
After 24-30 hours, reaction solution is extracted with dichloromethane, organic phase is dried with anhydrous magnesium sulfate, and rotary evaporation removes solvent；With
Dichloromethane dissolves product, is added dropwise in the methanol of strong stirring, obtains yellow mercury oxide, filtering, collects filter cake, and vacuum is done
It is dry, yellow solid is obtained as conjugated polymer P1；
Step 2：Prepare conjugated polymer P2
Under protection of argon gas, the organic monomer of the boron containing 8-hydroxyquinoline is dissolved in dry toluene and diisopropylamine, to solution
Middle Isosorbide-5-Nitrae-the diacetylene-benzene for adding in cuprous iodide, tetrakis triphenylphosphine palladium and alkoxy substitution, is stirred to react in 70-80 DEG C
It after 22-30 hours, adds in toluene and is diluted, filter, filtrate priority water and saturated common salt washing, dichloromethane extraction have
Machine is mutually dried with anhydrous magnesium sulfate, and rotary evaporation removes solvent, dissolves product with dichloromethane, is added dropwise to the first of strong stirring
It in alcohol, filters, dry, it is conjugated polymer P2 that orange solids, which are made,；
Step 3：Prepare compound 4
Under protection of argon gas, alkyl-substituted 2,5- dibromo thiophenes are dissolved in anhydrous diisopropylamine, iodate is added in into solution
Cuprous, bis- (triphenylphosphine) palladium chlorides stir 30-40 minutes, and trimethyl acetenyl silicon, ice bath stirring are added in into solution
It 60-80 minutes, is then stirred at room temperature 60-80 minutes, is finally warming up to 75-85 DEG C and is stirred to react 20-24 hours；After reaction
Dichloromethane is added in into solution to be diluted, and filters, filtrate rotary evaporation is removed, carried out using silica gel-n-hexane system
Compound 4 is made in pillar layer separation；
Step 4：Prepare compound 5
Compound 4 is dissolved in methanol, then adds in potassium hydroxide aqueous solution, is protected from light, it is small that reaction 6-10 is stirred at room temperature
When, after reaction, into solution plus water, dry with n-hexane extraction, filtering, rotary evaporation removing solvent are dried in vacuo,
Compound 5 is made；
Step 5：Prepare compound 6
Under protection of argon gas, 2 alkyl chain replaced, 2 '-union II thiophene are dissolved in anhydrous tetrahydro furan, and in -78 DEG C of items
Under part, n-butyllithium solution is added dropwise into solution, after being added dropwise, is stirred 1-2 hours at -78 DEG C；Then, in 0 DEG C of condition
Under, into solution be added dropwise trimethyl ammonia chloride solution of tin, after being added dropwise, after being stirred at room temperature 12-15 hour, addition ethyl acetate into
Organic phase is collected in row dilution, washing, liquid separation, and water phase is extracted with dichloromethane, merges organic phase, dry, filtering, rotary evaporation
Remove solvent；Finally with ethyl alcohol recrystallization, compound 6 is made；
Step 6：Prepare conjugated polymer P3
Under protection of argon gas, the organic monomer of the boron containing 8-hydroxyquinoline is dissolved in dry toluene and diisopropylamine, to solution
Middle addition cuprous iodide, tetrakis triphenylphosphine palladium and compound 5, after 70-80 DEG C is stirred to react 22-30 hours, add in toluene
It being diluted, filters, filtrate priority water and saturated common salt washing, dichloromethane extract, and organic phase is dried with anhydrous magnesium sulfate,
Rotary evaporation removes solvent；Product is dissolved with dichloromethane, is added dropwise in the methanol of strong stirring, is filtered, it is dry, it is made dark
Red solid P3；
Step 7：Prepare conjugated polymer P4
Under protection of argon gas, the organic monomer of the boron containing 8-hydroxyquinoline is dissolved in dry toluene, four (three is added in into solution
Phenylphosphine) palladium and compound 6, after 110-120 DEG C is stirred to react 22-30 hours, filtering, filtrate uses water and saturated common salt respectively
Organic phase is collected in washing, and water phase is extracted with dichloromethane, and organic phase is dried with anhydrous magnesium sulfate, and filtering, rotary evaporation removes molten
Product with dichloromethane is dissolved, is added dropwise in the methanol of strong stirring by agent, is filtered, dry, and red solid conjugated polymers are made
Object P4.
4. the method for the conjugated polymer of the organic monomer according to claim 3 for preparing the boron containing 8-hydroxyquinoline, special
Sign is：
In step 1, organic monomer, alkyl substitution Isosorbide-5-Nitrae-benzene hypoboric acid, tetrakis triphenylphosphine palladium, the carbonic acid of the boron containing 8-hydroxyquinoline
The molar ratio of potassium and tetrahydrofuran is 1：1：(0.05-0.15)：(10-20)：(350-400)；
In step 2, the organic monomer of the boron containing 8-hydroxyquinoline, Isosorbide-5-Nitrae-diacetylene-benzene, four (triphenylphosphines) of alkoxy substitution
Palladium, cuprous iodide, toluene and diisopropylamine molar ratio be 1：1：(0.05-0.15)：(0.05-0.15)：(250-400)：
(80-130)；
In step 3, alkyl-substituted 2,5- dibromo thiophenes, cuprous iodide, bis- (triphenylphosphine) palladium chlorides, trimethyl acetenyl
The molar ratio of silicon and diisopropylamine is 1：(0.05-0.15)：(0.05-0.15)：(4-6)：(50-60)；
In step 4, the molar ratio of compound 4, potassium hydroxide and methanol is 1：(0.3-0.5)：(320-350)；
In step 5, the 2 of alkyl chain substitution, 2 '-union II thiophene, n-BuLi, trimethyltin chloride and tetrahydrofuran molar ratio
It is 1：(2-3)：(2-3)：(50-80)；
In step 6, organic monomer, compound 5, cuprous iodide, tetrakis triphenylphosphine palladium, the toluene and two of the boron containing 8-hydroxyquinoline
The molar ratio of isopropylamine is 1：1：(0.05-0.15)：(0.05-0.15)：(250-400)：(80-130)；
In step 7, the organic monomer of the boron containing 8-hydroxyquinoline, compound 6, the molar ratio of tetrakis triphenylphosphine palladium and toluene are 1：
1：(0.05-0.15)：(360-400).
5. the method for the conjugated polymer of the organic monomer according to claim 3 for preparing the boron containing 8-hydroxyquinoline, special
Sign is：
In step 3, alkyl-substituted 2, the 5- dibromo thiophenes structural formula such as following formula：
Wherein, q=4,6 or 12；
In step 5, the 2 of the alkyl chain substitution, the structural formula such as following formula of 2 '-union II thiophene：
Wherein, t=4 or 6.
6. the side of fluorescence membrane is prepared using the conjugated polymer of the organic monomer of the boron described in claim 1 containing 8-hydroxyquinoline
Method, it is characterised in that：The conjugated polymer is dissolved in chloroform, is prepared into the storing solution of 1-10mg/mL；It takes every time
Fluorescence membrane is made in glass matrix surface in 20-50 μ L deposit drop-coateds.
7. application of the fluorescence membrane in detection formalin and formaldehyde gas described in claim 6.
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| CN108774255B (en) * | 2018-08-08 | 2020-11-17 | 陕西师范大学 | Boron compound containing four-coordination octahydroxyquinoline and preparation method and application thereof |
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