CN1594314A - Fluorene based water soluble conjugated polymer and process for preparing same - Google Patents
Fluorene based water soluble conjugated polymer and process for preparing same Download PDFInfo
- Publication number
- CN1594314A CN1594314A CN 200410025431 CN200410025431A CN1594314A CN 1594314 A CN1594314 A CN 1594314A CN 200410025431 CN200410025431 CN 200410025431 CN 200410025431 A CN200410025431 A CN 200410025431A CN 1594314 A CN1594314 A CN 1594314A
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- fluorene
- solution
- compound
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- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229920000547 conjugated polymer Polymers 0.000 title claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 title 1
- 239000000126 substance Substances 0.000 claims abstract description 47
- 238000001514 detection method Methods 0.000 claims abstract description 25
- -1 fluorene compound Chemical class 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 13
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 230000000171 quenching effect Effects 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 43
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 38
- 150000002220 fluorenes Chemical class 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 33
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 18
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 15
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000004327 boric acid Substances 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 9
- AVXFJPFSWLMKSG-UHFFFAOYSA-N 2,7-dibromo-9h-fluorene Chemical compound BrC1=CC=C2C3=CC=C(Br)C=C3CC2=C1 AVXFJPFSWLMKSG-UHFFFAOYSA-N 0.000 claims description 8
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 8
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 7
- 230000007062 hydrolysis Effects 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 238000002189 fluorescence spectrum Methods 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 238000000862 absorption spectrum Methods 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 229940043279 diisopropylamine Drugs 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 4
- 238000000502 dialysis Methods 0.000 claims description 4
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 claims description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 238000005815 base catalysis Methods 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 125000001246 bromo group Chemical group Br* 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 claims description 3
- 235000009518 sodium iodide Nutrition 0.000 claims description 3
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 3
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims description 3
- 102000004190 Enzymes Human genes 0.000 claims description 2
- 108090000790 Enzymes Proteins 0.000 claims description 2
- 238000007341 Heck reaction Methods 0.000 claims description 2
- 239000012359 Methanesulfonyl chloride Substances 0.000 claims description 2
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 claims description 2
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 150000001345 alkine derivatives Chemical class 0.000 claims description 2
- IYYIVELXUANFED-UHFFFAOYSA-N bromo(trimethyl)silane Chemical compound C[Si](C)(C)Br IYYIVELXUANFED-UHFFFAOYSA-N 0.000 claims description 2
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 2
- 150000003983 crown ethers Chemical class 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 229920002866 paraformaldehyde Polymers 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 239000003223 protective agent Substances 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 238000010791 quenching Methods 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- 229930192474 thiophene Natural products 0.000 claims description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000012491 analyte Substances 0.000 claims 4
- 125000000542 sulfonic acid group Chemical group 0.000 claims 4
- 239000002202 Polyethylene glycol Substances 0.000 claims 3
- 125000003545 alkoxy group Chemical group 0.000 claims 3
- 230000015572 biosynthetic process Effects 0.000 claims 3
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 claims 3
- 229920001223 polyethylene glycol Polymers 0.000 claims 3
- 238000003786 synthesis reaction Methods 0.000 claims 3
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims 2
- 125000003172 aldehyde group Chemical group 0.000 claims 2
- 238000005374 membrane filtration Methods 0.000 claims 2
- 150000004714 phosphonium salts Chemical group 0.000 claims 2
- 238000001556 precipitation Methods 0.000 claims 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims 2
- 238000010992 reflux Methods 0.000 claims 2
- LCKDOHRDONNZTG-UHFFFAOYSA-N 1,2-dibromo-9h-fluorene Chemical compound C1=CC=C2CC3=C(Br)C(Br)=CC=C3C2=C1 LCKDOHRDONNZTG-UHFFFAOYSA-N 0.000 claims 1
- 150000003990 18-crown-6 derivatives Chemical group 0.000 claims 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 229940126062 Compound A Drugs 0.000 claims 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 1
- 239000003513 alkali Substances 0.000 claims 1
- 150000001642 boronic acid derivatives Chemical class 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- PRAHCKGOTFKWKD-UHFFFAOYSA-N dimethyl(propyl)azanium;chloride Chemical compound Cl.CCCN(C)C PRAHCKGOTFKWKD-UHFFFAOYSA-N 0.000 claims 1
- 125000003827 glycol group Chemical group 0.000 claims 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 claims 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 238000005956 quaternization reaction Methods 0.000 claims 1
- 235000010265 sodium sulphite Nutrition 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- NHDIQVFFNDKAQU-UHFFFAOYSA-N tripropan-2-yl borate Chemical compound CC(C)OB(OC(C)C)OC(C)C NHDIQVFFNDKAQU-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 11
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 238000006053 organic reaction Methods 0.000 abstract 1
- 125000001424 substituent group Chemical group 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000004440 column chromatography Methods 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- GQZMENWHQDYTNK-UHFFFAOYSA-N 3-[2,7-dibromo-9-(3-hydroxypropyl)fluoren-9-yl]propan-1-ol Chemical compound C1=C(Br)C=C2C(CCCO)(CCCO)C3=CC(Br)=CC=C3C2=C1 GQZMENWHQDYTNK-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- VHHWAUKXFGPSRM-UHFFFAOYSA-N 1-bromo-9h-fluorene Chemical class C12=CC=CC=C2CC2=C1C=CC=C2Br VHHWAUKXFGPSRM-UHFFFAOYSA-N 0.000 description 2
- XHHZIFBFFGIFNI-UHFFFAOYSA-N 20-bromo-2,5,8,11,14,17-hexaoxabicyclo[16.4.0]docosa-1(18),19,21-triene Chemical compound O1CCOCCOCCOCCOCCOC2=CC(Br)=CC=C21 XHHZIFBFFGIFNI-UHFFFAOYSA-N 0.000 description 2
- BFIFBPKRZALASC-UHFFFAOYSA-N 3-[2,7-dibromo-9-(3-sulfopropyl)fluoren-9-yl]propane-1-sulfonic acid Chemical compound OS(=O)(=O)CCCC1(CCCS(O)(=O)=O)c2cc(Br)ccc2-c2ccc(Br)cc12 BFIFBPKRZALASC-UHFFFAOYSA-N 0.000 description 2
- JNWPRPLNUUMYCM-UHFFFAOYSA-N 5-bromo-2-(5-bromopyridin-2-yl)pyridine Chemical compound N1=CC(Br)=CC=C1C1=CC=C(Br)C=N1 JNWPRPLNUUMYCM-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 150000001412 amines Chemical group 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
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- 238000002156 mixing Methods 0.000 description 2
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- 239000003960 organic solvent Substances 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
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- 238000010189 synthetic method Methods 0.000 description 2
- RQFUZUMFPRMVDX-UHFFFAOYSA-N 3-Bromo-1-propanol Chemical compound OCCCBr RQFUZUMFPRMVDX-UHFFFAOYSA-N 0.000 description 1
- RJIWYGUYDXBQCJ-UHFFFAOYSA-N 3-[2,7-dibromo-9-[3-(dimethylamino)propyl]fluoren-9-yl]-n,n-dimethylpropan-1-amine Chemical compound C1=C(Br)C=C2C(CCCN(C)C)(CCCN(C)C)C3=CC(Br)=CC=C3C2=C1 RJIWYGUYDXBQCJ-UHFFFAOYSA-N 0.000 description 1
- LJQNMDZRCXJETK-UHFFFAOYSA-N 3-chloro-n,n-dimethylpropan-1-amine;hydron;chloride Chemical compound Cl.CN(C)CCCCl LJQNMDZRCXJETK-UHFFFAOYSA-N 0.000 description 1
- WHWUWIBHXHJDHB-UHFFFAOYSA-N 5-ethynyl-2-(5-ethynylpyridin-2-yl)pyridine Chemical compound N1=CC(C#C)=CC=C1C1=CC=C(C#C)C=N1 WHWUWIBHXHJDHB-UHFFFAOYSA-N 0.000 description 1
- CYSPWCARDHRYJX-UHFFFAOYSA-N 9h-fluoren-1-amine Chemical class C12=CC=CC=C2CC2=C1C=CC=C2N CYSPWCARDHRYJX-UHFFFAOYSA-N 0.000 description 1
- KLYCPFXDDDMZNQ-UHFFFAOYSA-N Benzyne Chemical compound C1=CC#CC=C1 KLYCPFXDDDMZNQ-UHFFFAOYSA-N 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 description 1
- BPOFERVZWUJYOW-UHFFFAOYSA-N [Cl-].[NH4+].CC(=CC)C Chemical compound [Cl-].[NH4+].CC(=CC)C BPOFERVZWUJYOW-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
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- YNHIGQDRGKUECZ-UHFFFAOYSA-L bis(triphenylphosphine)palladium(ii) dichloride Chemical compound [Cl-].[Cl-].[Pd+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
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- 230000026045 iodination Effects 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229960004249 sodium acetate Drugs 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- RPVMXPBNLPRCSD-UHFFFAOYSA-N trimethyl-[2-[6-[5-(2-trimethylsilylethynyl)pyridin-2-yl]pyridin-3-yl]ethynyl]silane Chemical compound N1=CC(C#C[Si](C)(C)C)=CC=C1C1=CC=C(C#C[Si](C)(C)C)C=N1 RPVMXPBNLPRCSD-UHFFFAOYSA-N 0.000 description 1
- CWMFRHBXRUITQE-UHFFFAOYSA-N trimethylsilylacetylene Chemical group C[Si](C)(C)C#C CWMFRHBXRUITQE-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
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- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
本发明为一种基于芴的水溶性共轭聚合物及其制备方法以及在化学/生物检测方面的应用。本发明以9位含有取代基团的芴化合物为原料，通过金属催化等一系列有机反应，合成了一系列以芴为共轭主链主要结构的水溶性共轭聚合物。合成所得聚合物具有良好的发光性能，是一类高效稳定的高分子发光材料。同时，能溶解于水中，对某些特定的基团或化合物具有很好的荧光淬灭效应。在聚合物的主链及侧链中引入检测基团，就能实现在水溶液中的化学/生物检测，这将是一种新型的化学/生物检测材料。The invention is a fluorene-based water-soluble conjugated polymer, its preparation method and its application in chemical/biological detection. The invention uses the fluorene compound containing a substituent group at the 9-position as a raw material, and synthesizes a series of water-soluble conjugated polymers with fluorene as the main structure of the conjugated main chain through a series of organic reactions such as metal catalysis. The synthesized polymer has good luminescent performance, and is a kind of high-efficiency and stable polymer luminescent material. At the same time, it can be dissolved in water and has a good fluorescence quenching effect on some specific groups or compounds. By introducing detection groups into the main chain and side chain of the polymer, chemical/biological detection in aqueous solution can be realized, which will be a new type of chemical/biological detection material.
Description
Technical field
The invention belongs to the photoelectric material technical field, be specifically related to a kind of ionic soluble conjugated polymer based on fluorenes and preparation method thereof, and in the application of chemical/biological context of detection.
Technical background
Conjugatd polymers has been widely used in aspects such as flexible flat demonstration and polymer battery and light emitting electrochemical cell, photodiode as a kind of good electroluminescent material.In recent years, scientist finds that the existence of some micro substance can make the photoelectric property of conjugated polymers take place to change greatly.The variation of this photoelectric property makes conjugated polymers have good prospect as the high sensor material.
Conjugated polymers is applied to chemical/biological at first and detects, and mainly is to introduce cyclodextrin or cyclic crown ether on the conjugated polymers side chain, realizes the detection to metal ion.This class experiment generally can only be carried out in organic solvent, and the more solubleness of detected material in organic solvent is unsatisfactory, therefore develops the emphasis that water miscible detection architecture becomes research.Side chain contains the neutral soluble conjugated polymer of polyol, alcoxyl long-chain, side chain contains the ionic soluble conjugated polymer of cationic quaternary amine group, anion sulfoacid base, phosphate, carboxyl etc., has begun to be studied and to be applied to the chemical/biological detection range.The system of research mainly concentrates on poly-to vinylbenzene support (PPV) system (ruddiness, green glow) and p-phenylene vinylene's support (PPP) (more weak blue light) system at present.Under study for action, exist many problems to need to be resolved hurrily simultaneously, for example polymkeric substance is stable bad, and a little less than the luminous intensity, the sensitivity of detection is low, detects the exploitation of the bad and more detection architecture of selectivity etc.
Poly-fluorenes is the high molecule electroluminescent material that a class has the efficient stable of development prospect.No matter be at solution state, still at the solid film state, poly-fluorenes family macromolecule has all demonstrated outstanding thermostability and good illumination efficiency, and its light stability and thermostability are better than being all the poly-to vinylbenzene support (PPV), p-phenylene vinylene's support (PPP) etc. of high molecule electroluminescent material greatly.Main chain is based on the conjugated polymers of fluorenes, and good conjugacy own makes it become a kind of very outstanding blue light material.9 introducings of going up substituted radical, can reduce by macromolecular chain on the one hand and assemble caused fluorescent quenching effect, on the other hand, substituted radical can improve the luminescent properties of polymkeric substance, simultaneously, the introducing of functional group also will be given new character of polymkeric substance and function.Because main chain has good luminous property based on the polymkeric substance of fluorenes, therefore, studies the fluorescent quenching and the recovery process of this base polymer, and be applied to chemical/biological and detect very fine development prospect will be arranged.Powerful luminous efficiency will greatly improve the sensitivity that detects, and provides the foundation for detecting trace substance; The water miscible realization of polymkeric substance can make and widen sensing range widely, from micromolecular inorganic metal ion, to macromolecular protein dna segment, can realize testing goal in the aqueous solution.Base-base in the applied biology, enzyme-substrate and antibody-antigen pair principle inserts side chain with special groups, can realize detecting the unicity of target.Therefore, research will have boundless application prospect based on the soluble conjugated polymer of fluorenes aspect biology/chemical detection
Summary of the invention
The objective of the invention is to propose a kind of have the good light electrical property based on soluble conjugated polymer of fluorenes and preparation method thereof, the application of this polymkeric substance aspect biology/chemical detection proposed.
The present invention adopts the organo-metallic catalyzed reaction to synthesize the soluble conjugated polymer of a class based on fluorenes, and characterizes its structure and measure its luminescent properties.Carried out the research aspect biology/chemical detection simultaneously.With respect to the existing conjugated polymers that can be used for biology/chemical detection, the material of being contained among the present invention has better luminescent properties, chemical stability, thermostability and better water-solubility, simultaneously, side chain can articulate multiple detection moiety, provides precondition for carry out biology/chemical detection extensive, single-mindedly.
The employing organo-metallic catalyzed reaction synthetic that the present invention proposes is based on the soluble conjugated polymer of fluorenes, and its molecular structure is as follows:
Wherein, R is that chain length is the alkyl of random length, and alkyl chain can contain N, O atom and amido linkage;
X is a water soluble group, specifically can be a kind of in carboxyl, sulfonic group, phosphate, quaternary amines, the alcoxyl long-chain;
Ar is an aryl, specifically can be pyridine, 9, and 9-two replaces fluorenyls, phenyl, thiophene, pyrroles, a kind of in vinylbenzene support, the benzyne;
Ar and fluorenyl junction can be singly-bound, two key or three key on the main chain.
The polymkeric substance that the present invention proposes has the good characteristics of luminescence, chemical stability, thermostability and water-soluble.
In the polymkeric substance of the present invention, also can articulate radicals R with biological or chemical measuring ability at the Ar side chain
1, R
2, for example crown ether, alcoxyl long-chain, base, antibody, enzyme etc. then obtain having the test material of chemistry or biological detection function.
Above-claimed cpd of the present invention, comparatively the typical case has following several:
R is a propyl group, and X is a sulfonic group, and Ar is dipyridyl-alkynes, and its structural formula is:
R is a propyl group, and X is a sulfonic group, and Ar is a phenyl, R
1Be 18-hat-6, its structural formula is:
R is a polyethylene group, and X is a hydroxyl, and Ar is a phenyl, R
1, R
2Be the alcoxyl long-chain, for two keys are connected, its structural formula is between fluorenes and the Ar group:
R is a propyl group, and X is a quaternary amines, and Ar is dipyridyl-alkynes, and its structural formula is:
The synthetic method of the compound that the present invention proposes is as follows:
(1) fluorenes is monomeric synthetic
(1) anionic monomer
With 2,7-dibromo fluorenes is a masterplate, adds 1.5 times and measure synthetic 9 the fluorenes A that two alkyl replace of bromo alkyl that end groups are hydroxyl under the base catalysis condition.
A is directly carried out oxidation with potassium permanganate to hydroxyl, and can get end group is the fluorenes A of two alkyl replacements of carboxyl
1
In A, add the hydroxy-protecting agent methane sulfonyl chloride, and the iodination reagent sodium iodide, obtaining end group through the S-WAT reaction with 3 times of amounts again is the fluorenes A that sulfonic pair of alkyl replaces
2
A is placed carbon tetrabromide and triphenyl phosphorus mixing solutions, and with the tributyl phosphate reaction, products therefrom reacts with bromotrimethylsilane in lutidine, souring soln, and promptly obtaining end group is the fluorenes A of two alkyl replacements of phosphate
3
(2) cationic monomer
With the fluorenes is raw material, and in dimethyl sulfoxide solution, sodium hydroxide catalysis obtains two alkyl substituted fluorene B that end group is a dimethyl amine with the reaction of dimethyl propylene ammonium chloride down, further reacts in acetum with Paraformaldehyde 96, and obtaining 2,7 is the monomers B of aldehyde radical
1
With 2,7-dibromo fluorenes is a raw material, the samely obtains two alkyl substituted fluorene B that end group is a dimethyl amine
2B
2Trimethyl borate with 3 times of amounts under the catalysis of n-Butyl Lithium reacts, and it is 9 two substituted fluorene B of boric acid that hydrolysis can get 2,7
3, adding toluene, propylene glycol backflow again, it is 9 two substituted fluorene B of boric acid ester that reaction makes 2,7
4
(3) neutral monomer
With two sections polyoxyethylene glycol and phosphorus tribromide reactions that have hydroxyl, obtain two sections polyoxyethylene glycol that have bromine.Then under the base catalysis condition with 2,7-dibromo fluorenes reaction obtains neutral monomer, 9 fluorenes C that two alcoxyl long-chains replace
1
A under the catalysis of n-Butyl Lithium with the reaction of the trimethyl borate of 3 times of amounts, obtaining 2,7 through hydrolysis be 9 couples of alkyl substituted fluorene C of boric acid
2
(2) Ar is monomeric synthetic
The Ar of two bromos with the reaction of triisopropyl boric acid ester, obtains the Ar group of two sections band boric acid through hydrolysis under the catalysis of n-Butyl Lithium from two ends; Further in toluene solution with the propylene glycol back flow reaction, obtain the Ar group of two ends band boric acid ester;
With the Ar group of the two bromos in two ends under the catalysis of triphenyl phosphorus palladium and cuprous iodide with the trimethyl silicane alkyne reaction, products therefrom carries out basic hydrolysis in methanol solution, obtaining two ends is the Ar group of alkynes;
Two ends are that Ar group methyl under acetic acid and sodium-acetate effect that dimethyl replaces becomes methylol, continuation and thionyl chloride and triphenyl phosphorus reaction again, and obtaining two ends is the Ar group that two quaternary alkylphosphonium salts replace.
(3) polymkeric substance is synthetic
With above-mentioned 2,7 two bromo fluorenes monomers and equimolar amount have the Ar group of unsaturated triple bond acetylene bond in the mixed solvent of Diisopropylamine and dimethyl formamide, carry out the Heck reaction with the triphenyl phosphorus palladium as catalyzer, products therefrom through acetone precipitate step by step filter with aqueous solution dialysis membrane after, obtain connecting the conjugated polymers of fluorenes and Ar group with conjugation three key.
With 2,7 two bromo fluorenes monomers and two sections Ar groups that have boric acid or boric acid ester of equimolar amount are in toluene, carry out the Suzuki reaction with yellow soda ash and triphenyl phosphorus palladium as catalyzer, products therefrom precipitates step by step with aqueous solution dialysis membrane through acetone and filters, and obtains connecting with singly-bound the conjugated polymers of fluorenes and Ar group.
With 2,7 for the fluorenes monomer of aldehyde radical and two ends be the Ar group that replaces of two quaternary alkylphosphonium salts in the solution of ethanol and sodium ethylate, through the catalysis of triphenylphosphine palladium chloride, obtain connecting the conjugated polymers of fluorenes and Ar group with conjugated double bond
, need again and the bromic ether reaction for after the amino fluorenes synthetic polymer from 9 end groups, carry out quaternary ammoniatedly, just can obtain the positively charged ion conjugated polymers.
Above-mentioned resulting polymers molecular weight is between 5000 to 300000, and molecular weight distribution is below 2
In the synthetic method of the present invention, water miscible fluorenes is an important monomer, takes into account good luminescent properties and good water-solubility simultaneously.The aryl of main chain can carry out various modifications, and different groups can improve the luminescent properties of polymkeric substance and water-soluble.Side chain articulates the different groups with biology/chemical detection function simultaneously, can further realize its measuring ability.Concrete testing process is as follows:
With deionized water compound and test substance are made into 5 * 10 respectively
-6M and 10
-5The M dilute solution;
The solution of test substance is joined in the compound solution by the micropipette rifle, and wherein the ratio of test substance liquor capacity and polymers soln volume is less than 0.1%, greater than 0.001%;
Be determined at different test substances and have down the ultra-violet absorption spectrum of compound solution and fluorescence emission spectrum.According to the attenuation of determinand fluorescence intensity, think to add behind the determinand fluorescence and former compound fluorescence ratio 0.1 when following, can detect determinand;
Measure under the test substance different concns state, the ultra-violet absorption spectrum of compound solution and fluorescence emission spectrum, by fluorescence intensity and testing concentration graph of a relation, the cancellation constant K of computerized compound
Sv, wherein transverse axis is for adding the concentration of determinand, and the longitudinal axis is for adding the ratio of determinand front and back fluorescence intensity, K
SvBe slope, think K
SvValue reaches 10
5It is respond well to be detection when above.
Description of drawings
Fig. 1 is that there is fluorescence emission spectrum under the situation in the synthetic polymkeric substance at different transition metal ions among the present invention.
Embodiment
Further specify technical scheme of the present invention below by embodiment, so that understand content of the present invention better.
Embodiment carries out according to the following steps:
1. anionic water-soluble polymers:
2,7-dibromofluorene and 3-bromopropanol, 50%NaOH and catalyzer back flow reaction in DMSO was used CH after 12 hours
2Cl
2Extraction is spin-dried for solvent and gets thick product.Thick product gets yellow powder shape solid 2,7-dibromo-9,9-di (3-hydroxyl-propyl)-fluorene (1) through column chromatography for separation.Intermediate (1) and MsCl react filtration in 3 hours in THF and triethylamine mixing solutions, filtrate be spin-dried for the yellow solid crude product.Crude product gets yellow powder shape solid 2,7-dibromo-9,9-di (3-methane-sulfonatopropyl)-fluorene (2) through column chromatography for separation.Intermediate (2) reacts filtration in 24 hours with NaI in acetone soln, filtrate is spin-dried for the thick product in back and gets pale yellow crystals 2 by column chromatography for separation, 7-dibromo-9,9-di (3-iodipropyl)-fluorene (3).Intermediate (3) and Na
2SO
3Aqueous solution reaction 48 hours, reaction solution is through CHCl
3Impurity is removed in extraction, again with the acetone washing, obtains pale solid 2,7-dibromo-9,9-di (3-sulfonatopropyl)-fluorene (4) after being spin-dried for.
Toward 2, feed HBr gas in the methanol solution of 2 '-dipyridyl, will in tube sealing, be heated to 180 ℃ of reactions 72 hours with pure bromine after the drying precipitate, in the gained mixture and after use CH
2Cl
2Extraction, the head product that removing desolvates obtains obtains white solid 5,5 '-dibromo-2,2 '-bipyridine (5) through recrystallization.Intermediate (5) CuI and catalyst mix are dissolved in the piperidines, in reaction system, slowly add Trimethylsilyl acetylene, intensification stirring reaction 6 hours.Underpressure distillation removes and desolvates, and crude product obtains white solid through column chromatography for separation and recrystallization
5，5’-Bis[(trimethylsilyl)ethynyl]-2，2’-bipyridine(6)。The KOH solution that in the THF solution that is dissolved with intermediate (6), slowly adds methanol and 20%, normal-temperature reaction 10 hours, gained solution extracted with diethyl ether, drying.Remove the crude product that obtains behind the ether and pass through column chromatography and recrystallization again, obtain jonquilleous crystal 5,5 '-diethynyl-2,2 '-bipyridine (7).
In being 5: 2 mixed solvent, diisopropylamine and dry toluene ratio add intermediate (4), (7) and catalyzer [Pd (PPh successively
3)
4], CuI.Reaction system is heated to 70 ℃, keeps reaction 24 hours.After reaction was finished, cool to room temperature splashed into reaction solution in the methyl alcohol, collected the throw out of gained.With throw out with methanol wash after, in apparatus,Soxhlet's, removed oligomer and unnecessary catalyzer in 24 hours with washing with acetone reaction, through after the vacuum-drying, obtain jonquilleous solid Poly[9,9-di (3-sulfonatopropyl)
fluorene-2，7-yleneethylene-co-alt-5，5’-(2，2’-bipyridylethylene)]。1H?NMR(D
2O，400MHz，ppm)：δ8.75(br，2H)，δ8.47(br，2H)，δ7.82(br，2H)，δ7.73(br，2H)，δ7.35(br，2H)，δ7.18(br，2H)，δ3.41(m，4H)，δ1.87(m，4H)，δ1.85(m，4H).
Embodiment 2, Poly[(9,9-di (3-sulfonatopropylfluorene-col-alt-(and 1,4-benzo-18-crown-6)] synthetic
In being 5: 2 mixed solvent, diisopropylamine and dry toluene ratio add compound 4,1 in the example 1 successively, 4-bromo-benzo-18-crown-6 and catalyzer [Pd (PPh
3)
4], CuI.Reaction system is heated to 70 ℃, keeps reaction 24 hours.After reaction was finished, cool to room temperature splashed into reaction solution in the methyl alcohol, collected the throw out of gained.With throw out with methanol wash after, in apparatus,Soxhlet's, removed oligomer and unnecessary catalyzer in 24 hours with washing with acetone reaction, through after the vacuum-drying, obtain jonquilleous solid
Poly[(9，9-di(3-sulfonatopropylfluorene-col-alt-(1，4-benzo-18-crown-6))].
2. cation type water-soluble polymkeric substance:
Embodiment 3, Poly[(9,9-bis (3 '-((N, N-dimethyl)-N-ethylammonium)-propyl)-2,7-fluorene)-co-alt-5,5 '-(2,2 '-bipyridylethylene)] Dibromide synthetic
2,7-dibromofluorene and 3-dimethylaminopropylchloride hydrochloride, 50%NaOH and catalyzer back flow reaction in DMSO was used CH after 12 hours
2Cl
2Extraction is spin-dried for solvent and gets thick product.Thick product gets white crystal 2,7-dibromo-9,9-bis (3 '-(N, N-dimethylamino) propyl)-fluorene (1 ') through recrystallization
With compound 7, catalyzer [Pd (PPh among intermediate (1 '), the embodiment 1
3)
4], the CuI mixed dissolution is in toluene.Under protection of inert gas, reaction system is heated to 70 ℃, keeps reaction 72 hours.After reaction was finished, cool to room temperature splashed into reaction solution in the methyl alcohol, collected the throw out of gained.With throw out with methanol wash after, in apparatus,Soxhlet's, removed oligomer and unnecessary catalyzer in 24 hours with the washing with acetone reaction, through after the vacuum-drying, obtain jonquilleous solid Poly[(9,9-bis (3 '-((N, N-dimethyl)-N-ethylammonium)-propyl)-2,7-fluorene)-co-alt-5,5 '-(2,2 '-bipyridylethylene)]. (2 ')
Embodiment 4, Poly[(9,9-bis (3 '-((N, N-dimethyl)-N-ethylammonium)-propyl)-2,7-fluorene)-co-alt-(1,4-benzo-18-crown-6)] synthetic
In being 5: 2 mixed solvent, diisopropylamine and dry toluene ratio add the compound 1 ', 1 among the embodiment 3 successively, 4-bromo-benzo-18-crown-6 and catalyzer [Pd (PPh3) 4], CuI.Reaction system is heated to 70 ℃, keeps reaction 24 hours.After reaction was finished, cool to room temperature splashed into reaction solution in the methyl alcohol, collected the throw out of gained.With throw out with methanol wash after, in apparatus,Soxhlet's, removed oligomer and unnecessary catalyzer in 24 hours with washing with acetone reaction, through after the vacuum-drying, obtain jonquilleous solid
Poly[(9，9-bis(3’-((N，N-dimethyl)-N-ethylammonium)-propyl)-2，7-fluorene)-co-alt-(1，4-benzo-18-crown-6)]。
3, the detection of metal ion in the aqueous solution (with Poly[9,9-di (3-sulfonatopropyl) fluorene-2,7-yleneethylene-co-alt-5,5 '-(2,2 '-bipyridylethylene)] to Ni
2+Detection be example)
Polymkeric substance is made into 5 * 10
-6The aqueous solution of M adds the metal ion aqueous solution of 1.0M therein, and the volume percent of adding is no more than 0.1%.Can be observed the polymers soln color by the colourless deep yellow that becomes this moment.Measure polymers soln and get ultra-violet absorption spectrum, the phenomenon of red shift occurs absorbing, shift value reaches 26nm.Adopt titrating method to measure the fluorescence emission spectrum of polymers soln under the different metal ionic concn situation simultaneously, find that the fluorescence of polymkeric substance just can be by complete cancellation under the situation of concentration of metal ions less than 0.1ppm.Therefore, prove that polymkeric substance can detect Ni effectively in the aqueous solution
2+
Claims (5)
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