WOBr_4催化聚苯乙炔的合成与表征

本文研究了苯乙炔在WOBr_4催化剂作用下的聚合行为,并对催化聚合机理进行了探讨。所得聚合物是可溶可熔的褐红色固体,其最高分子量为1830(M_n)。WOBr_4催化剂具有催化剂用量少(2/100),聚合反应时间短(10秒钟),产物收率高(80％以上)等特点。结构分析结果表明,WOBr_4催化聚苯乙炔具有顺-反式微观结构。     

Thermoanalytical characterization of polyphenylacetylene: III. Use of modulated differential scanning calorimetry (MDSC)

Four polyphenylacetylene samples, synthesized using different C₆H₅OH/Mo molar ratios, were investigated thermoanalytically by modulated temperature differential scanning calorimetry (MTDSC) in order to clarify a non-reversible exothermic event observed between 473 and 523 K on normal DSC. A stepwise, non-reversible change in heat capacity suggests the presence of internal reactions within the sample, that are followed by decomposition with loss of volatile products.     

UV LASER INITIATED STEREOSELECTIVE HOMOGENEOUS CATALYSIS POLYMERIZATION OF PHENYLACETYLENE

In this paper, the stereoselective homogeneous catalysis polymerization of phenylacetylene by using two kinds of catalysts W(CO)_5CH_3I and W(CO)_4I_2 produced from UV laser photolysis of W (CO)_6 in CH_3I, I_2—C_6H_6 and CHI_3—C_6H_6 respectively was studied. The effects of laser energy, laser irradiation time and lifetime of catalyst on the polymerization of phenylacetylene were discussed. The photoproducts of W (CO)_6 in CH_3I, I2—C_6H_6 and CHI_3—C_6I_6 were determined by IR spectra. The structures of polyphenylacetylene obtained by W (CO)_5CH_3I and W (CO)_4I_2 catalysts were characterized by IR spectra and ~1H NMR spectra.     

Cationic palladacycles as catalyst precursors for phenyl acetylene polymerization

Novel cationic palladacycles based on benzylidene-2,6-diisopropylphenylimines were prepared via C-H activation using Pd(CH₃CN)₂Cl₂ as metal precursor. The complexes were fully characterized by IR and NMR spectroscopy, mass spectrometry and elemental analysis. The cationic palladacycles were found to be active catalysts for the polymerization of phenylacetylene producing largely trans-cisoidal PPA.     

导电高聚物聚苯乙炔及其衍生物

聚苯乙炔(PPA)是一种具有半导体特性的高聚物。本文介绍了PPA及其衍生物的合成、化学结构与谱图及载流子的输运性质。     

稀土络合催化苯乙炔直接成膜聚合 Ⅴ.苯乙炔在钕、铁混合络合催化体系中的直接成膜聚合

乙酰丙酮(AA)、苯酰丙酮(BA)为配体的钕(Nd)、铁(Fe)混合催化剂与三异丁基铝[Al(i-Bu)_3]组成络合催化体系,能使苯乙炔在甲苯/己烷混合溶剂中直接聚合成膜。研究了其聚合反应规律及动力学行为,并对聚苯乙炔膜进行了全面表征,揭示了钕、铁两组分催化剂具有协同催化效应。     

聚苯乙炔立体结构与光致发光性能关系的研究

使用有机金属铑、金属钨 /四苯基锡催化剂体系聚合苯乙炔 ,分别获得了高产率和高分子量的聚苯乙炔 .使用UV ,IR ,NMR ,GPC等分别对聚合物结构进行了表征 .采用不同波长的激发光对聚合物荧光性能进行研究 ,详细分析了聚合物结构与荧光性能之间的关系 .研究结果发现 ,不同聚合物结构对聚合物荧光性能产生很大影响 ,规整性高的聚合物 ,将有较高的发光量子效率 ;聚合物规整性差 ,将可能导致多个荧光发光结构点 ,其荧光强度降低 .聚合物荧光光谱研究将对某些共轭聚合物结构的规整性分析提供一些有用的信息     

Probing the steric limits of rhodium catalyzed hydrophosphinylation. P-H addition vs. dimerization/oligomerization/polymerization

The reactivity of secondary phosphine oxides containing bulky organic fragments in hydrophosphinylation reactions has been investigated using several rhodium based catalysts. Upon heating in a focused microwave reactor, HP(O)(2-C₆H₄Me)₂ adds to prototypical terminal alkynes affording a complex mixture containing 1,2 and 1,1-addition products. Addition of a second ortho-substituent (HP(O)Mes₂) completely suppresses the hydrophosphinylation reaction for alkyl and aryl substituted alkynes. Variations in the temperature, catalyst loading, solvent, and microwave power were unable to induce an addition reaction in the case of HP(O)Mes₂. While this secondary phosphine oxide did not participate in the hydrophosphinylation reaction, it promoted the polymerization of phenylacetylene. HP(O)R₂ substrates are not commonly thought of as innocent ligands for rhodium complexes in reactions involving alkynes due to facile hydrophosphinylation. While this is certainly true for diphenylphosphine oxide, the chemistry presented herein suggests that HP(O)Mes₂ and related bulky secondary phosphine oxides have great potential as valuable ligands for rhodium catalyzed transformations involving alkynes due to their lack of reactivity towards the addition reaction.