取代二吡咯甲烷的合成及其光学性能

以吡咯和硝基苯甲醛为原料,二氯甲烷为溶剂,采用碘催化水浴法于35℃反应5 min合成了5-(4-硝基苯基)二吡咯甲烷(2a)和5-(3-硝基苯基)二吡咯甲烷(2b),其中2b为新化合物,收率分别为82%和84%,其结构经1H NMR,IR,MS和元素分析表征。并利用UV-Vis和FL研究了2a和2b的光学性能。结果表明:2a和2b的λmax分别位于212 nm,264 nm和206 nm,258 nm;最大发射波长分别位于528 nm(λex=264 nm)和525nm(λex=258 nm)。     

不同形貌聚吡咯的制备及其电化学性能研究

以吡咯为单体,用化学氧化法和电化学沉积法分别制备聚吡咯(PPy)纳米粒子和微球。实验表明,PPy-ED微球的比电容要优于PPy-CS纳米粒子,并且PPy微球表现出理想的赝电容行为,可以进行快速可逆的法拉第反应,其原因在于PPy微球分子链规整,具有较大的共轭程度,从而表现出优异的电化学储能性。     

含氯化锌的聚吡咯微胶囊的制备与性能表征

以油包水(W/O)乳液作为软模板,十二烷基苯磺酸钠(DBSNa)和对甲苯磺酸(Ts OH)作为掺杂剂,过氧化苯甲酰(BPO)作为氧化剂,采用原位聚合法制备了聚吡咯微胶囊,形成以氯化锌水溶液为芯材,聚吡咯为壁材的核-壳结构的微米材料.表征结果发现,当包覆氯化锌水溶液浓度为20%(质量分数),十二烷基苯磺酸钠、对甲苯磺酸和过氧化苯甲酰含量占单体的质量分数分别为1.27%,4.12%和123.71%时,形成的聚吡咯微胶囊大小均一,粒径在50μm左右,微胶囊表面形貌饱满光滑.有望拓展水性药物和全固态离子选择电极的应用领域.     

可溶性聚吡咯复合导电薄膜的研制

聚吡咯具有容易合成、导电率较高、稳定性较好等优点,已经对其进行了广泛而深入的研究,并且逐渐向工业应用方向发展^[1].但其不溶不熔性使得难于对其进行分子结构表征和加工.     

电流型聚吡咯碘离子化学修饰电极的制备与性能研究

在玻碳电极(GCE)表面上修饰了一层导电聚合物 聚吡咯(Ppy)薄膜,用循环伏安法制备了新型的基于电流响应的掺杂碘离子的聚吡咯修饰电极;研究了电极的电化学特性。此修饰电极对碘离子的响应是基于碘离子在Ppy膜与电解质溶液中的掺杂平衡以及Ppy膜中的碘离子在修饰电极表面的氧化还原过程;制成的电流型电极对5 0×10-2mol/L～1 0×10-5mol/L的碘离子呈良好的线性响应关系,检出限为6 0×10-6mol/L。     

聚吡咯修饰烟酸电位型生物传感器的制备与性能研究

用循环伏安法制备了对烟酸有良好Ｎｅｒｎｓｔ电位响应的聚吡咯修饰烟酸化学传感器。传感器的响应是基于烟酸根离子在掺杂了烟酸的聚吡咯膜中掺杂＝释放平衡。研究了聚合条件对传感器电化学性能的影响,表征了传感器的电化学特性。     

电聚吡咯固定化酪氨酸酶电极的制备及性能

在应用恒电位法电化学聚合吡咯的同时 ,将酪氨酸酶固定在导电聚吡咯膜内 ,制成一种灵敏、稳定的酪氨酸电极 .讨论了溶液 pH值和聚合电位对酶固定化的影响 ,对酶分子嵌入吡咯膜前后的SEM图和CV曲线进行了分析、比较 .该电极对甲苯酚响应的线性范围为 5 .0× 10 -8～ 1.0× 10 -6mol/L ,最适 pH值为 6 .6 ,酶反应表观上遵循Michaelis_Menten动力学 ,表观米氏常数为 2 .2× 10 -5mol/L .     

聚ε-己内酯/聚吡咯电纺膜的制备与性能

以吡咯(Py)和聚ε-己内酯(PCL)为原料、氯仿为溶剂,并掺杂一定量的十二烷基硫酸钠制备电纺膜,利用三氯化铁的氧化作用原位生成聚吡咯(PPy).对所得到的PCL/PPy电纺膜用红外光谱进行表征,在扫描电镜和透射电镜下观察纤维形貌,并测定力学性能和体积电阻率.结果表明,所生成的PPy以纳米粒子形式附着在电纺纤维表面,随着Py相对于PCL的质量百分含量由0增加到20%,PCL/PPy电纺膜的纤维直径从(730±341)nm逐渐下降至(325±84)nm;膜的拉伸模量和拉伸强度由不含Py的(25.7±0.8)MPa和(2.48±0.14)MPa分别增加至含有20%Py的(48.4±7.6)MPa和(5.05±0.59)MPa,断裂伸长率由(129±27)%下降至(86.2±9.1)%;体积电阻率降低了2～3个数量级.该PCL/PPy电纺纤维膜以期可作为电活性材料用于功能或生物医用领域.     

聚吡咯敏化磁载TiO_2光催化剂的制备及性能研究

以自制锰锌铁氧体为磁基体,采用乳液分散和原位聚合相结合的方法成功制得了聚吡咯(PPy)敏化磁载TiO2光催化剂(PPy-TiO2/M-Mn0.4Zn0.6Fe2O4),运用傅里叶变换红外光谱(FT-IR)、X射线衍射(XRD)对催化剂的结构进行分析表征,以甲基橙为模拟降解物,对比了不同光照条件下PPy敏化前后TiO2的光响应特性及催化性能,应用重量分析法考察了催化剂的磁回收特性。结果表明:经PPy敏化处理后,PPy-TiO2/M-Mn0.4Zn0.6Fe2O4的光催化响应范围拓宽到435nm,在自然光照射90min后,经PPy敏化的PPy-TiO2/M-Mn0.4Zn0.6Fe2O4对甲基橙的降解率较纯TiO2高29.0%。催化剂经5次使用后,回收率仍可达97%以上,具有良好的回收特性。     

Synthesis and optical properties of novel soluble and optically transparent semifluorinated poly (ether imide)s

A fluorinated diamine monomer containing flexible ether linkage and bulky trifluoromethyl substituents, namely, bis(4‐amino‐2‐trifluoromethylphenyl) ether (a), is employed to react with nonfluorinated 1,4‐bis(3,4‐dicarboxyphenoxy) benzene dianhydride (3) and CF₃‐free 2,2‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl] propane dianhydride (4), respectively, to prepare 2 novel soluble and optically transparent semi‐fluorinated poly (ether imide)s (PEIs; 3a and 4a). Compared with the corresponding PEIs based on nonfluorinated 4,4′‐diaminodiphenyl ether (b) and CF₃‐free pyromellitic dianhydride (5), the novel semifluorinated PEIs 3a and 4a not only display better solubility in some organic solvents and higher optical transparency with cutoff absorption wavelength (λ₀) below 370 nm but also maintain outstanding mechanical properties and thermal stability. 3a and 4a have tensile strength beyond 80 MPa and possess glass‐transition temperatures (T_g) beyond 210°C, coupled with the temperatures of 5% weight loss (T_5%) exceeding 500°C. It is also found that 3a and 4a exhibit contact angles against water beyond 110° and water absorptions below 0.8% together with dielectric constants less than 3.2.     

Preparation and properties of poly(phosphonatoalanes)

Two general types of poly(phosphonatoalanes), [? Al(X)O? P(O)(R)O? ]_n (X = Cl or F, R = alkyl or aryl) and [? Al(OP(O)R₂)O? P(O)(R′)O? ]_n, were prepared and studied. Poly[chloro(phosphonato)alanes] are influsible and have low molecular weights (n = 4–11). Polyfluoro(phosphonato)alanes are fusible and also have low molecular weights, but under certain conditions grow to higher polymers (n = 30–45). Poly[phosphinato(phosphonato)alanes] are fusible and are prepared with high molecular weights (n = 83–340).     

Novel soluble aromatic poly(amideimide)s containing 9,9-diphenylfluorene moieties: characterization and optical properties

A series of aromatic poly(amideimide)s containing 9,9-diphenylfluorene moieties and the amide units in the main chain have been synthesized by solution polycondensation reaction of newly prepared diamidedianhydride with several aromatic diamines: 1,3-phenylenediamine, 3,3′-dimethoxy-biphenyl-4,4′-diamine, 4,4′-oxydianiline, 4,4′-(1,3-phenylenedioxy)dianiline, 4,4′-(9-fluorenylidene)dianiline and 1,5-diaminonaphthalene. Molecular structures of the polymers obtained have been characterized using ¹³C NMR, ¹H NMR and FTIR spectroscopies. The polymers prepared are readily soluble in aprotic polar solvents, and form optically transparent films by solution casting. The resultant poly(amideimide)s have been analyzed by differential scanning calorimetry (DSC), thermogravimetry (TG) and wide-angle X-ray diffraction measurements. They exhibited high levels of thermal stability, with decomposition temperatures in the range 452–494 °C, and high glass transition temperatures (181–278 °C). The optical behavior of these polymers has been investigated in NMP solution as well as in the films. The photoluminescence (PL) spectra of the free-standing films prepared from the poly(amideimide)s exhibited maximum emission bands around 506–525 nm in the green region.     

Preparation and properties of novel soluble poly(aryl ether)s bearing covalently bound tetrapyrazinoporphyrazine units

Thermooxidatively stable amorphous poly(dicyanopyrazine ether)s with high glass transition temperatures are synthesized and converted into poly(aryl ether)s bearing covalently bound zinc(II) 2,3,9,10,16,17,23,24-octaphenyltetrapyrazinoporphyrazine units. They are soluble in common organic solvents and can be cast into strong and flexible films. The maximum absorption wavelength of the poly(aryl ether)s bearing zinc (II) 2,3,9,10,16,17,23,24-octaphenyltetrapyrazinoporphyrazine units in chloroform is 654 nm. © 1995 John Wiley & Sons, Inc.     

Preparation and properties of poly(imide-oxoisoindolobenzothiadiazine dioxides)

New thermally stable poly(imide-oxoisoindolobenzothiadiazine dioxides) (PIOD) have been prepared by the three-step cyclopolycondensation reaction of diaminobenzenesulfonamides with aromatic tetracarboxylic dianhydrides. The polymerization proceeded through the formation of poly(amic acid-sulfonamides) (PAAS), followed by cyclodehydration to yield polyimide-sulfonamides (PIS), which were subsequently converted to PIOD at 300°C. PAAS having inherent viscosities in the range of 0.1–0.5 in N-methyl-2-pyrrolidone (NMP) were obtained in approximately quantitative yield. PIOD were insoluble in most organic solvents, whereas PAAS and PIS were soluble in NMP and dimethyl sulfoxide. Differential thermal analysis and thermogravimetric analysis indicated that PIOD began to decompose at 460°C in air. The cyclodehydration of the model compounds was also investigated.     

Preparation of soluble and fusible poly(2,5-dimethoxy-1,4-phenylene)

Poly(2,5-dimethoxy-1,4-phenylene) was prepared by oxidative polymerization of p-dimethoxybenzene with aluminum chloride and copper(II) chloride in nitrobenzene under reduced pressure. The polymers obtained were soluble in sulfuric acid and fusible at 320°C. The intrinsic viscosity of the polymer was ca. 0.07 in sulfuric acid. Demethylation of methoxy groups did not occur during the polymerization.     

Preparation and properties of poly(methylene terephthalates)

A systematic study of poly(methylene terephthalates) has been made. Melting points, second-order transition temperatures, and solubility temperatures are presented for the homologous series of terephthalate polyesters of ethylene glycol through 1,10-dodecanediol, and for terephthalate copolyesters of: (1) ethylene glycol/1,3-propanediol and (2) ethylene glycol/1,4-butanediol. Fiber properties of the terephthalate polyesters and the 70/30 ethylene glycol/1,3-propanediol copolyterephthalate ester are presented. Only the first three members of the poly(methylene terephthalate) series show promise for use in textile fibers.     

Nonlinear optical properties of poly(arylenevinylene) polymers

This paper concerns investigations of the third order nonlinear optical response of poly(arylene vinylene) polymers and in particular precursor route poly(p-phenylene vinylene) [PPV]. Results for photoexcitation measurements provide information on the response time and the nature of the nonlinearity in the single-photon resonant excitation regime. Transmission third harmonic generation [THG] measurements yield complimentary information on the single-photon non-resonant regime.     

界面聚合法合成聚吡咯甲烷微球及其影响因素研究

采用吡咯和对二甲氨基苯甲醛通过酸催化静态界面聚合的方法得到了聚[吡咯-2,5-二(对二甲氨基苯甲烷)]微球。通过扫描电镜分析．研究了酸催化剂种类、浓度和反应温度对成球的影响。红外光谱分析表明得到的聚合物具有类似开环卟啉的结构。