高强度高电导率聚乙炔的合成——醚类溶剂的结构对性能的影响

通过选用不同醚类结构做溶剂加热回流Ti(OBu)_4-AIEt_3催化剂,并采用非溶剂聚合方法进行乙炔聚合发现,所得HPPA膜的强度和电导率都有了较大提高。其中直链醚制得的PA膜强度(抗张强度大于100MPa)和空气稳定性比用环醚得到的PA膜高得多,但用前者时的乙炔聚合速率远低于后者。两体系得到的HPPA膜的碘掺杂电导率值相近(～10~3S/cm),拉伸后可达10~4S/cm量级。SEM、TEM及IR光谱的结果表明,不同醚制得的PA膜的纤维束直径及顺式含量有较大差别。     

INFLUENCE OF BACKBONE RIGIDITY ON THE LIQUID CRYSTALLINITY OF MESOGEN-CONTAINING POLYACETYLENES

Two acetylene polymers containing cyanobiphenyl-based mesogens,poly { 10-[ ((4'- cyano-4-biphenylyl ) oxy ) carbonyl] - 1 -decyne } (PA8CN ), which has a relativelyfiexible polyalkyne backbone, and poly {[4-(((12-((4'-cyano-4-biphenylyl)oxy)dodecyl)oxy)carbonyl) phenyl]-acetylene} (PB12CN), which has a fairly rigid poly (phenylacetylene )backbone, were synthesized using respectively WCl_6 and [Rh(nbd)Cl]_2 as the catalysts.PA8CN exhibits enantiotropic interdigitated smectic A phase (S_(Ad)) over a temperaturerange as wide as ca. 100℃, whereas PB12CN is non-mesomorphic, demonstrating thatthe backbone rigidity plays an important role in determining the liquid crystallinity of thepolyacetylenes.     

Cytotoxic Components from the Leaves of Schefflera Taiwaniana

The isolation and identification of eighteen components from the leaves of Schefflera taiwaniana are presented. Their structures were determined on the basis of spectral data as well as direct comparison with authentic samples. These compounds include two polyacetylenes, one carotenoid‐like, three sesquiterpenes, one diterpene, four triterpenes, two tocopherols, and five alkyl 4‐hydroxycinnamate mixtures. Among these, 4‐hydroxy‐trans‐cinnamic acid docosyl ester and 4‐hydroxy‐cis‐cinnamic acid tetracosyl ester are new compounds. Some of these components exhibit cytotoxic activity.     

POLYMERIZATION OF 1-BUTYL-2-TRIMETHYLSILYLACETYLENE BY TRANSITION METAL CATALYSTS

New silicon-containing disubstituted polyacetylene was prepared by the polymerization of BTMSA having two bulky substituents (n-butyl and trimethylsilyl) using transition metal catalysts. The polymerization proceeded in a mild manner and the final polymer yield was generally lower than those of silicon-containing monosubstituted acetylenes by the similar catalyst system. The characterization on the polymer structure revealed that the resulting poly(BTMSA) have a conjugated backbone system, but the polymers have peculiar copolymer composition of poly-(BTMSA) and poly(1-hexyne) due to the spontaneous desilylation during the polymerization. The fluoride-ion induced desilylation of poly(BTMSA) using n-Bu₄N⁺F^? in THF yielded a completely desilylated product, pure poly(1-hexyne).     

SYNTHESIS AND PROPERTIES OF COPOLYMERS FROM 1-[3,5-BIS(TRIMETHYLSILYL)PHENYL]-2-PHENYLACETYLENE

Copolymerization of 1-[3,5-bis(trimethylsilyl)phenyl]-2-phenylacetylene (m,m-(Me₃Si)₂DPA) with other diphenylacetylene derivatives and their copolymer properties were investigated. Homopolymerization of m,m-(Me₃Si)₂DPA by TaCl₅─n-Bu₄Sn (1:2) did not give the polymer due to steric hindrance. However, m,m-(Me₃Si)2DPA copolymerized with diphenylacetylene (DPA), 1-phenyl-2-[p-(trimethylsilyl)phenyl]acetylene (p-Me₃Si DPA), and 1-phenyl-2-[m-(trimethylsilyl)phenyl]acety-lene (m-Me₃SiDPA) in the presence of TaCl₅─n-Bu₄Sn at various feed ratios to give copolymers in moderate yields. The formed copolymers were yellow to orange solids, which were soluble in common organic solvents such as toluene and CHCl₃. The highest weight-average molecular weights (M_w) of these copolymers reached ca. 6 × 105 and tough films could be obtained by solution casting. Their onset temperatures of weight loss in air were observed around 400°C, indicating high thermal stability. The oxygen permeability coefficients at 25°C of copoly(m,m-(Me₃Si)₂ DPA/DPA) (feed ratio 1:1) and copoly(m,m-(Me₃Si)₂DPA/p-Me₃SiDPA) (feed ratio 1:2) were 21 and 100 barrers, respectively, medium in magnitude among polymers from substituted acetylenes.     

膦手性丙炔胺脯氨酸磷酸酯螺旋聚合物的合成与表征

通过添加对映体拆分剂,合成了4种含膦手性的丙炔胺磷酸酯单体[HC帒CC H2NH(PO)R1R2].单体1,R1=OPh,R2=NC4H7COOCH3;单体2,R1=OPh,R2=NC4H7COOCH2CH3;单体3,R1=OPh,R2=NC4H7-COOC(CH3)3;单体4,R1=Ph,R2=NC4H7COOC(CH3)3].1H-NMR和31P-NMR表征可知对映体(单体1)不能被拆分剂拆分,而单体2、单体3、单体4通过拆分剂可以制得单一手性的磷化合物.以(nbd)Rh+[η6-C6H5B--(C6H5)3]为催化剂,以三氯甲烷为溶剂成功得到聚合物分子量范围在0.4×10-4～0.7×10-4,分子量分布在1.26～1.98范围的3种含手性膦侧基的丙炔胺类聚合物.比旋光度([α]D)、圆二色谱(CD)对聚合物的不同侧基及温度对光学活性的影响表明,聚合物具有良好的光学活性且能够形成单一方向的螺旋构象,说明膦手性在构建螺旋聚合物具有重要作用.     

Synthesis,chiroptical properties of a helical polyacetylene derivative carrying urea moieties

A novel phenylacetylene derivative containing urea groups was synthesized and polymerized with a Rh catalyst to give the corresponding polymer, poly（1） with moderate number-average molecular weights. The poly（1） was soluble in toluene, CHCI3, CH2C12, THF, DMF, and DMSO, but insoluble in hexane, diethyl ether and MeOH. The specific rotation and circular dichroism （CD） spectroscopic studies revealed that poly（1） took predominantly one-handed helical structures. The presence of intramolecular hydrogen bonding was confirmed by liquid-state IR spectroscopy. The helicity of poly（1） could be tuned by temperature and anion. The helical conformation of the polymer was stable against Br but susceptible to F.     

A multichannel Raman spectrometry study of polyacetylene isomerization induced by laser irradiation

The multichannel Raman spectrometry has been used in the study of the isomerization reaction of an 80% cis PA film into a trans PA, using a laser beam for a double purpose. It is employed simultaneously as an activation agent inducing the isomerization reaction and the Raman diffusion. In each experience, the power of the laser beam Pⁱ(λ) was equivalent to the temperature. Twelve spectra have been recorded at different time periods tj = j·dt. The integrations of the Raman intensities related to two selected bands were numerically calculated.We also proposed an original method for the determination of the isomeric composition. A quantitative relationship between the equilibrium temperature and the laser beam power (in the range of laser power: 30 < Pⁱ(λ) < 300 mW) has been found. An estimate number of isomerized molecules N₀ and then a correction factors f_cis and f_trans were also obtained.