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.     

1,8-亚乙基萘在三氟化硼乙醚-聚乙二醇中的电化学聚合

在三氟化硼乙醚(BFEE)-聚乙二醇(分子量400,PEG400)混合电解质溶液中,1,8-亚乙基萘直接阳极氧化聚合可以获得自支撑聚(1,8-亚乙基萘)膜.单体在三氟化硼乙醚+10%PEG400中的起始氧化电位为0.95 Vversus SCE,远低于单体在0.1 mol.L-1四氟化硼四丁基胺-乙腈溶液中的起始氧化电位(1.38 VversusSCE).同时PEG400的加入可以有效改善单体在三氟化硼乙醚中的溶解性.UV-Vis,FTIR和1H-NMR确定了1,8-亚乙基萘在4,5位聚合,荧光光谱表明固态及可溶聚(1,8-亚乙基萘)膜是蓝色发光材料.     

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.     

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.     

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。     

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.     

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.     

烷基步长对聚丙烯酸修饰咔唑电聚合的影响

合成了含有不同烷基链取代的N-丙烯酰氧癸基咔唑(MACZ10)和N-丙烯酰氧十二烷基咔唑(MACZ12), 通过自由基聚合得到聚N-丙烯酰氧烷基咔唑(PMACZ). 分子量分析表明, 随着烷基链长度的增加, 聚合物分子量减小, 分布变宽. 荧光光谱表明, 随着烷基链长度的增加, 聚合物在353 nm处的发射峰逐渐减弱. 在四氢呋喃和体积分数为10%三氟化硼乙醚与四氟化硼四丁基胺的混合电解质溶液中, 直接阳极氧化PMACZ获得自支撑交联网状的聚(聚N-丙烯酰氧烷基咔唑)(PPMACZ)薄膜. PPMACZ薄膜具有良好的氧化还原活性、热稳定性和蓝色发光性能, 聚合物氧化还原可逆性随着烷基链长的增加而增加, 且发射峰变宽.     

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...     

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.     

Low potential electrosyntheses of free‐standing poly(dibenzofuran) films in mixed electrolytes of boron trifluoride diethyl etherate and trifluoroacetic acid

Free‐standing poly(dibenzofuran) (PDBF) films were synthesized electrochemically by direct anodic oxidation of dibenzofuran in mixed electrolytes of boron trifluoride diethyl etherate (BFEE) containing certain amount of trifluoroacetic acid (TFA). The oxidation potential of dibenzofuran in pure BFEE was measured to be only 1.31 V versus saturated calomel electrode (SCE). This value was much lower than that determined in acetonitrile + 0.1 mol L^?1 TBATFB (2.14 V vs. SCE). The addition of TFA to BFEE can further decrease the oxidation potential of the monomer to 1.07 V versus SCE in the mixed electrolyte of BFEE + 30% TFA. PDBF films obtained from this medium showed good electrochemical behavior, good electrochromic properties, and good thermal stability with conductivity of 10⁰ S cm^?1. FTIR and ¹H NMR spectra showed that the polymer was grown mainly via the coupling of the monomer at C₍₃₎ C₍₁₀₎ or C₍₄₎ C₍₉₎ positions (Scheme 1). As‐formed PDBF films were partly soluble in tetrahydrofuran (THF) or chloroform. Fluorescent spectral studies indicated that either soluble or PDBF in solid state was a good blue light PDBF emitter. To the best of our knowledge, this is the first report that free‐standing PDBF films can be electrodeposited. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1125–1135, 2006     

Low potential electrochemical polymerization of diphenyl ether and characterization of its polymers

High‐quality poly(diphenyl ether) (PDPE) films with electrical conductivity of 4.4 × 10^?1 S cm^?1 were synthesized electrochemically by direct anodic oxidation of diphenyl ether (DPE) in boron trifluoride diethyl etherate (BFEE) containing 5% concentrated sulfuric acid (SA) (by volume). The oxidation potential onset of DPE in pure BFEE was measured to be only 1.37 V versus a saturated calomel electrode (SCE), which was much lower than that determined in acetonitrile + 0.1 mol L^?1 tetrabutylammonium tetrafluoroborate (1.98 V vs. SCE). The addition of SA to BFEE can further decrease the oxidation potential onset of the monomer to 1.18 V versus SCE in the mixed electrolyte of BFEE + 5% SA. PDPE films obtained from this medium showed good redox activity and stability even in concentrated SA. Dedoped PDPE films were partly soluble in the strong polar organic solvent dimethyl sulfoxide. Fluorescent spectral studies indicated that soluble PDPE was a good blue‐light emitter with a quantum yield of 0.30. Infrared spectroscopy and quantum chemistry calculations indicated that the electropolymerization of DPE occurred mainly at C₄ and C_4′. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5932–5941, 2007