CN117384356A - 一种含苯硼酸侧基的荧光共轭聚电解质及其制备方法 - Google Patents
一种含苯硼酸侧基的荧光共轭聚电解质及其制备方法 Download PDFInfo
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- CN117384356A CN117384356A CN202311275913.XA CN202311275913A CN117384356A CN 117384356 A CN117384356 A CN 117384356A CN 202311275913 A CN202311275913 A CN 202311275913A CN 117384356 A CN117384356 A CN 117384356A
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- Prior art keywords
- phenylboronic acid
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- monomer
- side groups
- conjugated polyelectrolyte
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- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229920000867 polyelectrolyte Polymers 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 16
- -1 dibromo aromatic hydrocarbon Chemical class 0.000 claims abstract description 6
- LLCSWKVOHICRDD-UHFFFAOYSA-N buta-1,3-diyne Chemical group C#CC#C LLCSWKVOHICRDD-UHFFFAOYSA-N 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- CBUOGMOTDGNEAW-UHFFFAOYSA-N 2-[4-(bromomethyl)phenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=C(CBr)C=C1 CBUOGMOTDGNEAW-UHFFFAOYSA-N 0.000 claims description 3
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 3
- PDNOURKEZJZJNZ-UHFFFAOYSA-N [4-(bromomethyl)phenyl]boronic acid Chemical compound OB(O)C1=CC=C(CBr)C=C1 PDNOURKEZJZJNZ-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000004440 column chromatography Methods 0.000 claims description 3
- 229940043279 diisopropylamine Drugs 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 2
- 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 2
- 238000010025 steaming Methods 0.000 claims description 2
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- 229920000642 polymer Polymers 0.000 abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- 229920000547 conjugated polymer Polymers 0.000 abstract description 14
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 abstract description 10
- 238000001514 detection method Methods 0.000 abstract description 9
- 150000001720 carbohydrates Chemical class 0.000 abstract description 6
- 238000005956 quaternization reaction Methods 0.000 abstract description 6
- 238000012984 biological imaging Methods 0.000 abstract description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract 2
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 abstract 1
- 125000006239 protecting group Chemical group 0.000 abstract 1
- 238000006467 substitution reaction Methods 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
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- VALXCIRMSIFPFN-UHFFFAOYSA-N 2,5-dibromobenzene-1,4-diol Chemical compound OC1=CC(Br)=C(O)C=C1Br VALXCIRMSIFPFN-UHFFFAOYSA-N 0.000 description 2
- LJQNMDZRCXJETK-UHFFFAOYSA-N 3-chloro-n,n-dimethylpropan-1-amine;hydron;chloride Chemical compound Cl.CN(C)CCCCl LJQNMDZRCXJETK-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 101150003085 Pdcl gene Proteins 0.000 description 2
- 238000007112 amidation reaction Methods 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
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- AVXFJPFSWLMKSG-UHFFFAOYSA-N 2,7-dibromo-9h-fluorene Chemical compound BrC1=CC=C2C3=CC=C(Br)C=C3CC2=C1 AVXFJPFSWLMKSG-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
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 102100032373 Coiled-coil domain-containing protein 85B Human genes 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 101000868814 Homo sapiens Coiled-coil domain-containing protein 85B Proteins 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 108091005461 Nucleic proteins Proteins 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 238000004220 aggregation Methods 0.000 description 1
- 150000001347 alkyl bromides Chemical class 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
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- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 125000005619 boric acid group Chemical group 0.000 description 1
- PWYPGEFOZYBWDP-UHFFFAOYSA-N boric acid;pyridine Chemical compound OB(O)O.C1=CC=NC=C1 PWYPGEFOZYBWDP-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical group 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
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- 230000006872 improvement Effects 0.000 description 1
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
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- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 229920001223 polyethylene glycol Polymers 0.000 description 1
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- 102000004169 proteins and genes Human genes 0.000 description 1
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- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- CWMFRHBXRUITQE-UHFFFAOYSA-N trimethylsilylacetylene Chemical compound C[Si](C)(C)C#C CWMFRHBXRUITQE-UHFFFAOYSA-N 0.000 description 1
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- C08G2261/1424—Side-chains containing oxygen containing ether groups, including alkoxy
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- C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
- C08G2261/3142—Condensed aromatic systems, e.g. perylene, anthracene or pyrene fluorene-based, e.g. fluorene, indenofluorene, or spirobifluorene
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- C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
- C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
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Abstract
本发明公开了一种含苯硼酸侧基的荧光共轭聚电解质及其制备方法。分别合成含二甲氨基侧基的二乙炔基单体、二溴芳烃单体，再通过Sonogashira偶联反应合成含二甲氨基侧基的共轭聚电解质前驱体；经季铵化反应并脱除保护基团，得到含苯硼酸侧基的荧光共轭聚电解质。本发明将含有苯硼酸基团的卞溴化合物和二甲氨基基团通过取代反应形成稳定季铵盐的形式引入到共轭聚合物的侧基，在赋予聚合物水溶性的同时引入大量能够与具有邻二醇结构的分子可逆共价结合的苯硼酸基团，从而改变其性能，在化学、生物成像、碳水化合物检测等领域具有应用前景。
Description
技术领域
本发明涉及一种荧光共轭聚电解质，特别涉及一种含高密度苯硼酸侧基的聚芴苯类荧光共轭聚电解质及其制备方法。
背景技术
共轭聚合物的分子骨架具有大的离域电子结构，使得信号能够在整个共轭长链中传递，从一定程度上可以起到增强信号的作用。（参见文献：Chem Rev. 2007, 107, 1339-1386），因此在荧光信号形式、量子效率等方面具有更多优势。共轭聚合物作为荧光材料与其他材料相比具有许多优点，如合成简便、化学结构和发射颜色可调、成本相对较低、毒性低、抗光漂白性强、稳定性好等（参见文献：Chem. Rev. 2000, 100, 1605-1644），因此被广泛地应用于生物成像、传感检测等领域中。
近年来，荧光共轭高分子在生物检测领域的发展十分迅速，这是由于这类高分子在侧基离子化后变成共轭聚电解质，它们既具有我们所提到的共轭高分子的优异性能，同时也具有良好的水溶性，因其侧链一般含有带电荷的季铵盐或者羧酸盐结构。越来越多的共轭聚电解质被选择用于水介质中的分子研究，例如生物体内核酸、蛋白质或细胞的检测与成像等等（参见文献：Adv. Mater. 2008, 20, 2959-2964; Angew. Chem. Int. Ed.2009, 48, 4300-4316）。
硼酸作为有机化学领域的重要中间体，参与了化学合成、药物研究和分子识别等多种过程。（参见文献：Biomol. Chem. 2019, 17, 683-691）。硼酸可与路易斯碱和多元醇进行可逆共价结合，因此已被用作检测碳水化合物的受体以及相关的细胞和组织成像。（参见文献：Analyst. 2020, 145, 719-744.）。目前，关于将苯硼酸基团引入到聚合物的侧基鲜有报道。只有极个别研究通过吡啶硼酸与烷基溴的季铵化反应将硼酸基团引入到聚噻吩的侧基，将其制备成亲水性聚合物并应用于葡萄糖、果糖等碳水化合物检测（参见文献：Chem. Eur. J. 2008, 14, 1648-1653）。也有文献报道了一种含苯硼酸侧基的共轭聚合物纳米粒子，（参见文献：ACS Appl. Polym. Mater, 2021, 3, 4543-4553），首先合成主链为聚芴-苯并噻唑，重复单元含有两个末端带氨基的侧基，接着利用氨基与羧基间的酰胺化反应在侧基修饰聚三乙二醇和苯硼酸两种基团。此聚合物本身不溶于水，需要制备成纳米粒子才能稳定分散在水中；且酰胺化后每个重复单元中只含有一个苯硼酸侧基。综上，目前已报道的含苯硼酸侧基的荧光共轭聚合物在化学、生物成像、痕迹检验方面的应用具有局限性。
据文献报导，二甲氨基能够在温和的反应条件下与末端溴化合物进行高效的季铵化反应，生成水溶性盐（参见文献：J. Am. Chem. Soc. 2004, 126, 9845-9853），但目前还未见通过偶联法制备含高密度二甲氨基侧基共轭聚合物的报道。由于二甲氨基团会对偶联反应中的催化过程产生部分影响，因此，制备含高密度二甲氨基的聚合物前驱体，需要对聚合过程使用的催化剂及其用量进行选择和优化。通过聚合物前驱体中高密度的二甲氨基与卞溴间的季铵化反应不仅能在共轭聚合物侧基引入苯硼酸基团，并且反应同时能够在侧基生成季铵盐赋予其良好的水溶性。在碱性条件下苯硼酸基团与水环境中的分子产生共价结合等相互作用，有望在化学、生物等领域实现各种应用性能的提升，具有重要的实际意义。
发明内容
本发明针对现有技术存在的不足，提供一种合成工艺简便高效，得到的产物水溶性好且荧光明亮的含高密度苯硼酸侧基的聚芴苯类荧光共轭聚电解质及其制备方法。
实现本发明的技术方案是提供一种含苯硼酸侧基的荧光共轭聚电解质， 它的结构式为：
,
其中，n为重复单元数，n=8～21。
本发明技术方案还提供一种含苯硼酸侧基的荧光共轭聚电解质的制备方法，包括如下步骤：
（1）按物质的量计，将1份2,5-双（3'-（N,N-二甲基氨基）丙基）-1,4-二（三甲基硅基乙炔）苯，2~2.5 份n-Bu4NF与1100~1200份四氢呋喃的混合物，搅拌至固体溶解，再在室温下搅拌0.5~1小时后，经萃取、旋蒸、中性氧化铝柱层析分离提纯、干燥处理，得到一种二乙炔基单体，记作M1；
所述单体M1的结构式为：
；
（2）在无水无氧条件下，按物质的量计，将1份二溴芳烃单体M2和1份步骤（1）得到的单体M1，0.015～0.05份四（三苯基膦）二氯化钯，0.015～0.05份碘化亚铜，100～200份二异丙胺，200～300份甲苯加入到反应器中混合搅拌，在氩气保护、温度为70～75℃的条件下反应30～50小时，再经过滤、重结晶、离心、干燥处理，得到一种共轭聚电解质前驱体，记作PFPE-NMe2；
所述单体M2的结构式为：
；
所述前驱体PFPE-NMe2的结构式为：
，
其中，n为重复单元数，n=8~21；
（3）按物质的量计，将1份步骤（2）制备的前驱体PFPE-NMe2与3500~3600份四氢呋喃混合，在温度为60~66℃的油浴条件下加入35~55份4-溴甲基苯硼酸频哪醇酯进行反应，反应时间为48~72小时，反应期间分2~3次共加入400~900份甲醇；反应结束后，冷却至室温，加入35~55份4-溴甲基苯硼酸和80~100份盐酸，搅拌20~40分钟后，置于丙酮/乙醚体积比为1:9~1:7的混合溶剂中沉淀，再经离心、干燥处理，得到一种含苯硼酸侧基的荧光共轭聚电解质。
本发明提供的含苯硼酸侧基的荧光共轭聚电解质溶液，其苯硼酸侧基在碱性条件下与邻二醇类物质存在可逆共价结合，因此，在化学、生物成像、碳水化合物检测等领域有着极大的应用前景。
与现有技术相比，本发明的有益效果在于：
1. 本发明通过选择合适的催化剂种类及优化其用量提供了一种新型含高密度二甲氨基侧基的聚电解质前驱体合成策略，以便于在后续季铵化反应引入更高密度的苯硼酸基团，合成简便且具有经济效益。
2. 本发明提供的含苯硼酸侧基的聚芴苯类荧光共轭聚电解质，聚合物在极性良溶剂中有明亮的蓝色荧光，且具有优异的光稳定性；聚电解质的侧基为非规整结构，能够在一定程度上避免聚合物链间聚集，具有重要的应用价值和实际意义。
3. 本发明制备的含苯硼酸侧基的荧光共轭聚电解质是通过二甲氨基与卞溴间的季铵化反应引入到共轭聚合物侧基，在反应同时使侧基形成季铵盐结构，成为共轭聚电解质赋予其良好的水溶性，以适应水环境中的各种应用，尤其是在化学、生物成像、碳水化合物检测等领域有极大的应用潜力。具有重要的应用价值和实际意义。
4. 本发明制备的荧光共轭聚电解质与现有报道相比含有更高密度的苯硼酸侧基，能够提供更多位点在碱性条件下与邻二醇类物质可逆共价结合，有望在生物成像、碳水化合物检测等领域中提供更优异的性能。
附图说明
图1是本发明实施例1提供的含苯基的二乙炔基单体M1的合成路线图；
图2是本发明实施例1制备的二溴芳烃单体M2的合成路线图；
图3是本发明实施例1提供的前驱体聚合物PFPE-NMe2和含苯硼酸侧基的荧光共轭聚电解质PFPE-PBA的合成路线图；
图4、5、6、7分别是本发明实施例1制备的单体M1、单体M2、聚合物前驱体PFPE-NMe2和共轭聚电解质PFPE-PBA的核磁谱图；
图8是本发明实施例1制备的M1、单体M2、聚合物前驱体PFPE-NMe2和共轭聚电解质PFPE-PBA的红外谱图；
图9是本发明实施例2制备的含苯硼酸侧基的荧光共轭聚电解质PFPE-PBA的光物理性能数据图。
实施方式
下面结合附图和实施例对本发明技术方案作进一步的阐述。
实施例1
1.单体M1和M2的合成
（1）参见附图1，它是制备荧光共轭聚合物所需单体M1的合成路线图。
图1中，化合物1（2,5-二溴对苯二酚）的制备：将对苯二酚（4.26 g，0.039 mol）加入到烧瓶中，加入20 mL 乙酸搅拌至微溶解，然后在3小时内逐滴滴加4 mL溴（溶于18 mL乙酸），通过冰水浴维持混合物在10 ℃以下反应过夜。用布氏漏斗抽滤以除去溶剂，过滤后的固体在甲醇/去离子水中重结晶，得到纯白色晶体，并在真空中干燥过夜（3.52 g，产率32.9%）。
图1中，化合物2（1,4-双（3'-（N,N-二甲基氨基）丙基）-2,5-二溴苯）的制备：将2,5-二溴对苯二酚（2.67 g，10 mmol）和3-（二甲基氨基）氯丙烷盐酸盐（3.16 g，20 mmol）放入100 mL的圆底烧瓶中，然后添加DMSO（30 mL）以溶解固体颗粒。随后加入研磨成细粉的KOH（8.40 g，0.15 mol）。反应混合物在20℃下搅拌过夜。反应完成后，将反应液倒入冰水中，静置12小时。混合物在减压下通过布氏漏斗过滤。固体用冰水洗涤三次，得到白色固体（3.75 g，产率42.8%）
图1中，化合物3（2,5-双（3'-（N,N-二甲基氨基）丙基）-1,4-二（三甲基硅基乙炔）苯）的制备：在氩气环境下，将化合物2（2.18 g，5 mmol）、CuI（0.026 g，0.14 mmol）、(PPh3)2PdCl2（0.145 g，0.20 mmol）和二异丙胺（20 mL）加入100 mL圆底烧瓶中。搅拌底物直至溶解，并向混合物中滴加三甲基乙炔硅（1.5 mL）。该混合物在室温下搅拌1小时，然后回流12小时。终止反应并冷却至室温。过滤后，收集滤液并在减压下除去溶剂，得到黑色固体。粗品通过硅胶柱色谱法（二氯甲烷/乙酸乙酯/三乙胺，100∶50∶1，v/v）提纯。去除溶剂后，得到棕色固体（2.05 g，产率86.9%）。
图1中，M1单体的制备：将化合物3（1.42 g，3 mmol）置于100 mL的烧瓶中，加入 20mL的四氢呋喃搅拌至固体溶解，然后加入6 mL溶于四氢呋喃的n-Bu4NF (1 M)。将该混合物在室温下搅拌0.5小时。结束反应后，向反应混合物中加入30 mL去离子水，并用3 ´ 100 mL的二氯甲烷萃取。合并有机相，加入无水硫酸钠以除去水分。在减压下旋转蒸发除去多余的溶剂，得到粗品，在中性氧化铝柱上以二氯甲烷/石油醚（2∶1，v/v）为淋洗剂纯化，得到浅棕色固体（0.82 g，产率83.1%）。1H NMR (400 MHz, CDCl3, ppm): δ 6.98 (s, 2H), 4.03(t, J = 8.5 Hz, 4H), 3.33 (s, 2H), 2.48 (t, J = 9.6 Hz, 4H), 2.25 (s, 12H),1.95 (t, 4H). 13C NMR (100 MHz, CDCl3, ppm): δ 153.93, 117.80, 113.27, 82.50,79.68, 77.30, 77.04, 76.72, 67.84, 56.23, 45.52, 27.41. FTIR (cm-1): 3160,2966, 2938, 2854, 2817, 2775, 1492, 1459, 1386, 1226, 1033, 964, 873, 730.Elemental Anal. Calcd for C20H28N2O2 (%): C, 73.14; H, 8.95; N, 8.53. found: C,67.71; H, 8.32; N, 8.18.
参见附图4，它是本实施例提供的单体M1的核磁谱图，由图4可以看出，单体M1的结构正确。
（2）参见附图2，它是本实施例制备荧光共轭高分子所需单体M2的合成路线图。本实施例中，单体M2为2,7-二溴-9,9-双（3'-（N,N-二甲基氨基）丙基）芴。
图2中，单体M2的制备：在氩气下，向烧瓶中加入2,7-二溴芴（3.05 g，9.4 mmol）和60 mL DMSO并搅拌至溶解，再加入四丁基溴化铵（60 mg）和8 mL质量分数为50%的氢氧化钠水溶液。在氩气氛围下向该混合物中滴加20 mL的3-二甲基氨基氯丙烷盐酸盐（3.51 g，22mmol）的DMSO溶液。反应混合物在室温下搅拌6小时。停止反应，然后用50 mL水稀释以溶解所有的盐。用乙醚（3 ´ 100 mL）萃取产物，并用去离子水（3 ´ 100 mL）和饱和氯化钠（100mL）洗涤。合并有机层，经MgSO4干燥，过滤，减压除去溶剂，得到的粗产物为绿色固体。将粗产物在MeOH/H2O中重结晶，得到白色晶体（2.15 g，产率47.8%）。1H NMR (400 MHz, CDCl3,ppm): δ 7.52 (d, 2H), 7.47 (s, 3H), 7.44 (s, 1H), 1.99 (m, 14H), 1.69 (s,4H), 0.75 (m, 4H). 13C NMR (100 MHz, CDCl3, ppm): δ 152.19, 139.31, 130.61,126.38, 121.84, 121.45, 77.56, 77.24, 76.93, 59.77, 55.50, 45.53, 37.78,22.22. FTIR (cm-1): 2965, 2937, 2856, 2822, 2776, 1454, 1403, 1371, 1272,1130, 1052, 1016, 673. Elemental Anal. Calcd for C23H30Br2N2 (%): C, 55.89; H,6.12; N, 5.67. found: C, 55.31; H, 6.04; N, 5.91。
参见附图5，它是本实施例提供的单体M2的核磁谱图，由图5可以看出，单体M2的结构正确。
2. 重复单元中含有高密度苯硼酸侧基的荧光共轭聚电解质的制备
参见附图3，它是本实施例制备荧光共轭高分子聚合物的合成路线图。
（1）前驱体聚合物PFPE-NMe2的制备：实验装置抽真空三次。在氩气的保护下，将M1（0.082 g，0.25 mmol）、M2（0.12 g，0.25 mmol）、(PPh3)2PdCl2（0.0142 g，0.02 mmol）和CuI（0.0042 g，0.02 mmol）加入烧瓶中。然后，在氩气下向烧瓶中加入干DIPA（3 mL）和甲苯（8mL）。该混合物在氩气下回流48小时，然后冷却至室温。用孔径为0.22 μm的滤头过滤该混合物。滤液经减压浓缩并滴入100 mL的正己烷中，置于冰箱上层过夜。离心（3分钟，3000 rpm）后，收集沉淀物，然后在真空下干燥24小时，得到暗红色固体（0.16 g，产率83.5%）。1H NMR(400 MHz, CDCl3, ppm): δ 7.8 – 7.3 (m, 6H), 7.09 (s, 1H), 4.10 (s, 4H), 2.52(d, 4H), 2.28 (s, 12H), 2.00 (s, 16H), 1.74 (s, 8H), 0.79 (s, 4H). FTIR (cm-1): 2954, 2856, 2817, 2773, 1498, 1460, 1205, 1052, 840, 723, 694. ElementalAnal. Calcd for C43H57BrN4O2 (%): C, 69.62; H, 7.74; N, 7.55. found: C, 65.24;H, 6.35; N, 6.12. GPC: M̅ w = 14.0 kDa; M̅ n = 6.2 kDa; Đ = 2.26，重复单元数n约为10。
参见附图6，它是本实施例提供的前驱体聚合物PFPE-NMe2的核磁谱图，由图6可以看出，前驱体聚合物PFPE-NMe2的结构正确。
（2）共轭聚电解质PFPE-PBA的制备：将PFPE-NMe2（0.075 g，0.1 mmol）和四氢呋喃（10 mL）放入100 mL的烧瓶中，搅拌至聚合物溶解，并在60 ℃的油浴条件下向烧瓶中加入4-溴甲基苯硼酸频哪醇酯（1.20 g，4 mmol）。在此期间，一旦烧瓶中出现固体，就加入约3mL的甲醇，共消耗9 mL的甲醇。反应48小时后，停止加热并冷却至室温，加入4-溴甲基苯硼酸（0.85 g，4 mmol）和盐酸（0.5 mL），在室温下搅拌30分钟后停止反应。反应混合液通过减压蒸馏除去大部分溶剂，并在100 mL的混合溶剂（丙酮/乙醚，1∶9，v/v）中沉淀，于冰箱上层放置过夜。离心（3分钟，3000 rpm）收集沉淀物，然后在真空下干燥24小时，得到暗红色固体。（0.12 g，产率79.3%）。1H NMR (400 MHz, CD3OD, ppm): δ 8.25 – 7.0 (m, 22H), 4.6(s, 4H), 4.25 (s, 4H), 3.75 (s, 4H), 3.12 (s, 8H), 2.70 (s, 6H), 2.50 (s,4H), 1.20 (s, 16H), 1.30 (s, 10H). FTIR (cm-1): 3384, 2785, 1654, 1467, 1438,1369, 1207, 1049, 1024, 848, 761. Elemental Anal. Calcd for C71H89B4Br5N4O10(%): C, 53.26; H, 5.60; N, 3.50. found: C, 56.15; H, 6.50; N, 2.09.
参见附图7，它是本实施例提供的聚电解质PFPE-PBA的核磁谱图，由图7可以看出，聚电解质PFPE-PBA的结构正确。
参见附图8，它是本实施例中单体M1、M2和聚合物PFPE-NMe2、PFPE-PBA的红外谱图，由图8可以进一步证实单体M1、M2和聚合物PFPE-NMe2、PFPE-PBA的结构正确。
实施例2
本实施例对实施例1中合成的聚合物PFPE-PBA进行光物理性能的测定。参见附图9，聚合物PFPE-PBA易溶于甲醇、水等常见极性溶剂，最大吸收波长在400 nm左右，最大发射波长在460 nm附近。
Claims (3)
1.一种含苯硼酸侧基的荧光共轭聚电解质，其特征在于它的结构式为：
2.其中，n为重复单元数，n=8～21。
3.一种含苯硼酸侧基的荧光共轭聚电解质的制备方法，其特征在于包括如下步骤：
（1）按物质的量计，将1份2,5-双（3'-（N,N-二甲基氨基）丙基）-1,4-二（三甲基硅基乙炔）苯，2~2.5 份n-Bu4NF与1100~1200份四氢呋喃的混合物，搅拌至固体溶解，再在室温下搅拌0.5~1小时后，经萃取、旋蒸、中性氧化铝柱层析分离提纯、干燥处理，得到一种二乙炔基单体，记作M1；
所述单体M1的结构式为：
；
（2）在无水无氧条件下，按物质的量计，将1份二溴芳烃单体M2和1份步骤（1）得到的单体M1，0.015～0.05份四（三苯基膦）二氯化钯，0.015～0.05份碘化亚铜，100～200份二异丙胺，200～300份甲苯加入到反应器中混合搅拌，在氩气保护、温度为70～75℃的条件下反应30～50小时，再经过滤、重结晶、离心、干燥处理，得到一种共轭聚电解质前驱体，记作PFPE-NMe2；
所述单体M2的结构式为：
；
所述前驱体PFPE-NMe2的结构式为：
，
其中，n为重复单元数，n=8~21；
（3）按物质的量计，将1份步骤（2）制备的前驱体PFPE-NMe2与3500~3600份四氢呋喃混合，在温度为60~66℃的油浴条件下加入35~55份4-溴甲基苯硼酸频哪醇酯进行反应，反应时间为48~72小时，反应期间分2~3次共加入400~900份甲醇；反应结束后，冷却至室温，加入35~55份4-溴甲基苯硼酸和80~100份盐酸，搅拌20~40分钟后，置于丙酮/乙醚体积比为1:9~1:7的混合溶剂中沉淀，再经离心、干燥处理，得到一种含苯硼酸侧基的荧光共轭聚电解质。
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