萘在三氟化硼乙醚溶液中的电化学聚合

电化学聚合是制备许多电子型导电高分子的有效方法,如合成聚吡咯、聚噻吩、聚呋喃、聚苯等,但对聚萘的报道甚少,并且几乎都采用氯化亚铜的复合催化剂作为电解质。近来我们发现强路易斯酸BF_3的乙醚溶液既是萘的良好溶剂,又是其电化学聚合反应的良好催化剂。将萘溶解于三氯化硼乙醚溶液后,在2V(υs.Ag/AgCl)的外加电压作用下     

9,9-二乙基芴在三氟化硼乙醚中的电化学聚合

在三氟化硼乙醚(BFEE)中,9,9-二乙基芴(DEF)直接阳极氧化聚合可以获得高质量聚(9,9-二乙基芴)膜(PDEF,电导率2×10-2S.cm-1).DEF在BFEE中的起始氧化电位为1.20 VvsSCE,远低于单体在0.1 mol.L-1Bu4NBF4的CH3CN溶液中的起始氧化电位(1.70 V).在BFEE中获得的PDEF膜具有良好的电化学性质.红外光谱和1H NMR结果表明聚合反应主要发生在2,7位.     

9,10-二氢化菲在三氟化硼乙醚-浓硫酸混酸中的电化学聚合

在三氟化硼乙醚(BFEE)-浓硫酸混合电解质体系中直接氧化9,10-二氢化菲获得了高质量聚(9,10-二氢化菲)膜, 其电导率为3.8×10－1 S/cm. 9,10-二氢化菲在BFEE＋10%浓硫酸体系中的起始氧化电位为0.93 V vs. SCE, 远低于其在乙腈＋0.1 mol/L Bu4NBF4溶液中的起始氧化电位(1.75 V vs. SCE). 在BFEE＋10%浓硫酸体系中获得的聚(9,10-二氢化菲)膜具有良好的电化学性质. 聚合物部分溶于二甲基亚砜、四氢呋喃、氯仿等极性溶剂. FT-IR和量化计算表明聚合反应主要发生在2, 7位或者3, 6位. 荧光光谱和热重分析表明聚合物是一种良好的蓝色荧光材料且具有良好的热稳定性.     

三氟化硼乙醚溶液中卤代芴的电化学聚合

在三氟化硼乙醚(BFEE)溶液中9-溴芴和9,9-二氯芴可以直接阳极氧化制备聚(9-溴芴)和聚(9,9-二氯芴).单体在BFEE中的起始氧化电位远低于在乙腈体系中的起始氧化电位.聚(9-溴芴)和聚(9,9-二氯芴)均可溶于强极性有机溶剂,如二甲基亚砜、四氢呋喃等,并分别表现出良好的蓝色和黄绿色发光性能,其电导率测定为10-1S/cm.红外光谱和核磁共振波谱表明聚合反应主要发生在2,7位.     

四氢呋喃/三氟化硼乙醚混合电解质中咔唑的电化学聚合

在四氢呋喃/三氟化硼乙醚混合电解质中直接阳极氧化咔唑制备聚咔唑.单体的起始氧化电位为0.92 Vversus SCE,远低于单体在含0.1 mol.L-1Bu4NBF4的乙腈溶液中的起始氧化电位(1.36 Vversus SCE).在此体系中获得的聚咔唑膜具有良好的电化学活性和稳定性,其电导率为7.0×10-3S.cm-1.聚合物可部分溶解于二甲基亚砜等强极性有机溶剂.UV-Vis,FT-IR,1H-NMR证明聚合物共轭长链的形成.该体系中获得的聚咔唑是一种蓝光发射材料,并具有良好的热稳定性.     

三氟化硼乙醚溶液中聚(二苯并呋喃)的电化学合成

在三氟化硼乙醚-硫酸混合电解质溶液中,二苯并呋喃直接阳极氧化聚合可以获得高质量聚(二苯并呋喃)膜.二苯并呋喃在纯三氟化硼乙醚中的起始氧化电位为1.30 VvsSCE,远低于单体在0.1 mol.L-1Bu4NBF4乙腈溶液中的起始氧化电位(2.14 V).硫酸的加入进一步降低了二苯并呋喃的氧化电位.在三氟化硼乙醚-硫酸混合电解质溶液中,二苯并呋喃的起始氧化电位可降低至1.0 V;同时在该体系中获得的聚(二苯并呋喃)膜具有良好的电化学性质和荧光性质.     

乙酸/三氟化硼乙醚混合电解质中咔唑的电化学聚合

在新型混合电解质——乙酸含体积比26%的三氟化硼乙醚和5%的分子量为400的聚乙二醇中直接氧化咔唑制得高质量的聚咔唑膜,导电率为10-2 S·cm-1。在该体系中,咔唑的起始氧化电位相对于饱和甘汞电极只有0.89 V,远低于在含0.1 mol·L-1四氟化硼四丁基铵的乙腈溶液中的1.36V（相对于饱和甘汞电极）。从该体系中获得的聚咔唑膜具有良好的电化学性质和热稳定性,可以部分溶于二甲基亚砜、四氢呋喃等强极性溶剂。荧光光谱表明该体系中获得的聚咔唑膜是一种良好的蓝光发射材料。红外、核磁波谱和理论量子化学计算结果表明,咔唑的电化学聚合主要发生在3,6位。据我们所知,这是利用乙酸三氟化硼乙醚混合电解质进行电化学聚合的首次报道。     

三氟化硼乙醚/乙酸混合电解质中芴的电化学聚合

在三氟化硼V(乙醚):V(乙酸)=4:5的混合电解质体系中直接氧化芴,获得芴聚合物膜,其电导率为0.5 S cm-1,高于在纯三氟化硼乙醚中制得的聚芴的电导率0.25 S cm-1.在三氟化硼乙醚:乙酸=4:5的混合电解质体系中获得的聚芴膜具有良好的电化学性质和化学稳定性.FTIR,1H-NMR和量化计算表明反应发生在...     

9,9-二辛基芴的电化学聚合

在三氟化硼乙醚(BFEE)中, 9,9-二辛基芴可以直接阳极氧化制备高质量聚(9,9-二辛基芴)膜, 其电导率为1×10^－2 S/cm. 9,9-二辛基芴在BFEE中的起始氧化电位为1.25 V vs. SCE, 低于单体在0.1 mol/L Bu₄NBF₄的乙腈溶液体系中的起始氧化电位(1.52 V vs. SCE). BFEE中获得的聚(9,9-二辛基芴)膜具有良好的电化学性质. 聚合物部分溶于氯仿、四氢呋喃、二甲基亚砜等极性溶剂. FTIR和¹H NMR表明聚合反应主要发生在2,7位. 荧光光谱表明聚合物是一种良好的蓝色荧光物质.     

三氟化硼乙醚中聚(N-甲基吲哚)的电化学合成

在三氟化硼乙醚(BFEE)溶液中N甲基吲哚可以阳极氧化聚合生成聚(N-甲基吲哚).单体在BFEE中的起始氧化电位为0.95V,远低于单体在CH3CN+0.1mol LBu4NBF4体系中的起始氧化电位(1.23V).BFEE中获得的聚(N-甲基吲哚)膜具有良好的电化学性质和荧光性质.红外光谱表明聚合反应发生在2,3位.     

ELECTROCHEMICAL COPOLYMERIZATION OF DIBENZOFURAN AND 3-METHYLTHIOPHENE IN BORON TRIFLUORIDE DIETHYL ETHERATE

The copolymerization of dibenzofuran(DBF)and 3-methylthiophene(MET)was successfully achieved electrochemically by direct anodic oxidation of the monomer mixtures in boron trifluoride diethyl etherate.The effects of applied polymerization potential and the monomer concentration ratios on the copolymerization were investigated by linear sweep voltammetry and cyclic voltammetry(CV).The structure of copolymer films were investigated by UV-Vis,infrared spectroscopy,thermal analysis.As-formed novel copolymers ...     

ELECTROCHEMICAL COPOLYMERIZATION OF 3-（4-FLUOROPHENYL）THIOPHENE AND 3-METHYLTHIOPHENE IN BORON TRIFLUORIDE DIETHYL ETHERATE

The copolymer poly（3-（4-fluorophenyl）thiophene-co-3-methylthiophene） was successfully prepared from mixtures of 3-（4-fluorophenyl）thiophene （FPT） and 3-methylthiophene （MET） via electrochemical oxidation in boron trifluoride diethyl etherate （BFEE） and its mixed electrolytes with acetonitrile （ACN）. The influence of monomer concentration ratios on the copolymerization was investigated by using linear sweep voltammetry and cyclic voltammetry. The structure and morphology of these copolymer films were elucidated by UV-Vis, infrared spectroscopy, elemental analysis, thermal analysis and scanning electron microscopy （SEM）, respectively. The results showed that the molar ratio of FPT and MeT units, when copolymer was electrodeposited from feed ratio of FPT：MeT = 1：2, was about 1.08：1. In addition, the introduction of ACN into BFEE has little effect on the properties of as-formed copolymers.     

Low-potential electrosynthesis of conducting and electroactive oligocatecholborane with blue light-emitting properties

Novel conducting oligocatecholborane (OCOB) with electrical conductivity of 3.73 × 10-2S cm-1 was successfully synthesized by low-potential electropolymerization of catecholborane (COB) in boron trifluoride diethyl etherate at 0.70 V versus Ag/AgCl. FT-IR and 1H-NMR spectra, together with the computational results, proved that COB was polymerized through the coupling at C(4) and C(5) positions and the reactive B―H bond was stable during the electrochemical polymerization. The resulting product was mainly composed of oligomers with short chain lengths by GPC and mass spectral results. The as-formed OCOB film showed good electrochemistry in monomer-free electrolytes with the electrochromic property from opaque blue to sap green. Fluorescence studies indicated that soluble OCOB can emit bright blue light under excitation of 365 nm UV light with the maximum emission at 396 nm and a fluorescence quantum yield of 0.21. The deposited OCOB also exhibited favorable thermal stability and smooth and compact morphology even at high magnifications.     

聚吲哚及其衍生物的荧光光谱

在三氟化硼乙醚及其混合电解质中,吲哚及其衍生物阳极氧化可以获得高质量的聚吲哚及其衍生物膜:聚吲哚、聚(5-甲基吲哚)、聚(5-硝基吲哚)、聚(5-氰基吲哚)、聚(5-溴吲哚).它们可溶于DMSO和THF中.聚吲哚及其衍生物具有良好的荧光性质;单体的发射光谱与取代基有关,而聚合物的发射光谱几乎不受取代基的影响.电子离域程度增大,使得聚合物的激发和发射光谱红移,宽的分子量分布则会使聚合物的激发和发射光谱变宽.     

Electrosynthesis of highly conducting poly(1,5-dihydroxynaphthalene) in BF3·Et2O

Direct anodic oxidation of 1,5-dihydroxynaphthalene (DHN), an important derivative of naphthalene, led to the formation of high-quality semiconducting poly(1,5-dihydroxynaphthalene) (PDHN) on stainless steel sheets in boron trifluoride diethyl etherate (BFEE). The onset oxidation potential of DHN in this medium was measured to be only 0.78 V vs. SCE, which was lower than that determined in traditional acetonitrile containing 0.1 mol/L tetrabutylammonium tetrafluoroborate (0.98 V vs. SCE). As-formed PDHN films showed good redox activity and stability, together with interesting electrochromic property from brown (doped) to yellow-green (dedoped). Structural characterization, including FTIR, ¹H NMR, and quantum chemistry calculations, indicated that the polymerization of DHN probably occurred at C₄ and C₈ positions. Moreover, thermal analysis revealed that PDHN displayed better thermal stability than that synthesized by chemical method. The fluorescence spectral studies, together with the electrical tests, showed that PDHN was a good blue light-emitter (fluorescence quantum yield higher than 0.1) with an electrical conductivity of as high as 0.46 S/cm.     

ELECTROCHEMICAL POLYMERIZATION OF 5-CYANOINDOLE IN MIXED ELECTROLYTES OF BORON TRIFLUORIDE DIETHYL ETHERATE AND DIETHYL ETHER

High quality poly（5-cyanoindole） （P5CI） films were electrosynthesized by direct anodic oxidation of 5-cyanoindole on stainless steel sheet in the mixed electrolytes of boron trifluoride diethyl etherate （BFEE） and diethyl ether （EE） （by volume 1：1） ＋ 0,05 mol L^-1 Bu4NBF4. The film formed can be peeled off the electrode into freestanding films, The addition of EE into BFEE can improve the solubility of monomer. P5CI films obtained from this medium showed excellent electrochemical behavior with conductivity of 10^-2 S cm^-1, Structural studies showed that the polymerization of 5-cyanoindole occurred at the 2,3 position. As-formed P5CI films were thoroughly soluble in strong polar organic solvent dimethyl sulfoxide （DMSO） while partly soluble in tetrahydrofuran （THF） or acetone. Fluorescence spectral studies indicated that P5CI was a good blue-ight emitter.