一种有机电致发光共聚物的制备和性能

采用Suzuki方法合成了9，9-二辛基芴与萘并硒二唑的两种无规共聚物并研究了其紫外光谱、光致发光和电致发光性能。两种聚合物的电致发光波长为650～666nm，均为发饱和红光的LED材料，其电致发光外量子效率最高达到了1．05％。随着共聚物中萘并硒二唑含量的增加，共聚物的光致发光和电致发光的发射波长均有少量红移。证明了根据共轭高聚物链内能量转移原理，在聚芴链中引入不同含量的窄带隙杂环单元可实现对聚芴发光颜色的调节。     

Vanadium(III) chloride catalyzed Biginelli condensation: solution phase library generation of dihydropyrimidin-(2H)-ones

The three component condensation of an aldehyde, a β-keto ester and urea (thiourea) in the presence of a catalytic amount of VCl₃ is disclosed for the solution phase synthesis of dihydropyrimidinones. The ease of synthesis and work-up allowed the parallel synthesis of a 48-membered library of dihydropyrimidinones quickly and efficiently in good yields.     

Photorefractive Four-Wave Mixing Switches Utilizing Pockels Effect -Longitudinal and Lateral Switches-

We carried out detailed calculations for photorefractive wave-mixing switches based on one of three crystals with high electro-optic coefficients, namely, BaTiO₃, Strontium Barium Niobate (SBN (0.75)), and Potasium Sodium Strontium Barium Niobate (KNSBN). A comparison of results for the three crystals shows that a 0_-cut BaTiO³ crystal is suitable for a longitudinal switch and requires a voltage of about 80 for a 2-mm-thick crystal to induce sufficient phase mismatch. The electrodes must be transparent for the incident and diffracted beams. A 45_-cut SBN (0.75) crystal, however, is suitable for a lateral switch and requires a voltage of about 150 for a 1-mm-wide crystal. The electrodes do not need to be transparent.     

Rare earth photoionization study by the resonant microwave cavity technique

Photoconductivity spectra of rare earth-doped insulating materials are measured using the resonant microwave cavity method. This technique is based on the detection of the cavity Q-factor changes induced by irradiation of the sample (inserted in the cavity) by a pulsed tunable laser. Results obtained with Lu₂(SiO₄)O:Ce³⁺ and BaF₂:Eu²⁺ are presented and discussed. Photoionization thresholds at 400 nm (3.1 eV) and 310 nm (4.0 eV) are measured for Lu₂(SiO₄)O:Ce³⁺ and BaF₂:Eu²⁺, respectively.     

One step synthesis of 2-substituted 3-tri-(or di-)fluoromethyl-2-propenals in an ionic liquid

Investigation of one step synthesis of 2-substituted 3-tri-(or di-)fluoromethyl-2-propenals has been carried out using versatile aldehydes, tri- or di-fluoroacetaldehyde ethyl hemiacetal in the presence of diethylaminotrimethylsilane (DEATMS) in an ionic liquid, and it was demonstrated that this route enabled us to successfully construct 2-substituted 3-tri-(or di-)fluoromethyl-2-propenals with the high level selectivity of geometric isomers.     

Polymerization of 1,3‐dienes with functional groups. III. Free‐radical polymerization of N,N‐diethyl‐2‐methylene‐3‐butenamide

Free‐radical homo‐ and copolymerization behavior of N,N‐diethyl‐2‐methylene‐3‐butenamide (DEA) was investigated. When the monomer was heated in bulk at 60 °C for 25 h without initiator, rubbery, solid gel was formed by the thermal polymerization. No such reaction was observed when the polymerization was carried out in 2 mol/L of benzene solution with with 1 mol % of azobisisobutyronitrile (AIBN) as an initiator. The polymerization rate (R_p) equation was R_p ∝ [DEA]^1.1[AIBN]^0.51, and the overall activation energy of polymerization was calculated 84.1 kJ/mol. The microstructure of the resulting polymer was exclusively a 1,4‐structure where both 1,4‐E and 1,4‐Z structures were included. From the product analysis of the telomerization with tert‐butylmercaptan as a telogen, the modes of monomer addition were estimated to be both 1,4‐ and 4,1‐addition. The copolymerizations of this monomer with styrene and/or chloroprene as comonomers were also carried out in benzene solution at 60 °C. In the copolymerization with styrene, the monomer reactivity ratios obtained were r₁ = 5.83 and r₂ = 0.05, and the Q and e values were Q = 8.4 and e = 0.33, respectively. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 999–1007, 2004     

Structure and properties of the mesophase of syndiotactic polystyrene. VIII. Solvent sorption behavior of syndiotactic polystyrene/p‐chlorotoluene mesophase membranes

A crystalline δ form of a syndiotactic polystyrene (sPS) membrane was prepared from a solution of sPS (1 wt %) and p‐chlorotoluene (p‐CT) by a solution‐casting method. The mesophase (δ empty form) of sPS was obtained by the extraction of the guest solvent from the δ form of sPS by a stepwise solvent‐extraction method. The sPS/p‐CT mesophase membrane [p‐CT (A‐M)] was used for the sorption of 1 mol % p‐CT for different times and for the sorption of different concentrations of p‐CT, chlorobenzene (CB), p‐xylene (p‐X), toluene, and chloroform for 48 h. The presence of solvents in the sPS membrane was confirmed by IR analysis. A thermal study revealed that the sorption amount of 1 mol % p‐CT increased with increasing immersion time, and the sorption amounts of different solvents increased with increasing solvent concentration. Differential scanning calorimetry results showed that the desorption peak temperature increased as the amount of the solvent increased in the clathrated sPS membrane. Wide‐angle X‐ray diffraction results showed that 2θ at 8.25° was slightly shifted toward 8°, and there was no change in the peak position at 10° for p‐CT (A‐M), which was immersed in different solvents (1 mol %); however, the intensity of 2θ at 10° was not similar for all the samples. Among the solvents used for the sorption studies at 1 mol %, p‐CT (A‐M) could sorb more p‐CT and CB than p‐X, toluene, and chloroform. The solvent sorption isotherm was the Langmuir sorption mechanism. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3439–3446, 2004     

Toughness mechanism in polypropylene composites: Polypropylene toughened with elastomer and calcium carbonate

Polypropylene (PP) was modified with elastomer or CaCO₃ particles of two different sizes (1 μm and 50 nm) in various volume fractions. The dispersion morphology and mechanical properties of the two systems were investigated as functions of the particle size and volume fraction of the modifier. The brittle‐to‐tough transition occurred when the matrix ligament thickness was less than the critical ligament thickness, which was about 0.1 μm for the PP used here, being independent of the type of modifier. At the same matrix ligament thickness, the improvement of the toughness was obviously higher with the elastomer rather than with CaCO₃, but adding CaCO₃ increased the modulus of PP. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1656–1662, 2004     

类钙钛矿化合物Ca(Mn2 Cu1)Mn4 O12的磁性与磁电阻效应

利用固相反应法制备了名义成分为Ca(Mn2 Cu1 )Mn4 O1 2 的类钙钛矿锰氧化物 .x射线衍射表明 ,为了获得较为致密的样品和减小杂相含量 ,可以采用高温烧结再在 10 73K长时间空气中退火的制备方法 .样品在低温下同时存在铁磁相和反铁磁相 ,由于反铁磁相的存在导致样品在 4 5K时的磁化强度显著降低 ,并在 8T的高磁场下仍未达到饱和 .样品呈半导体导电性质 ,在 85K和 6T磁场下磁电阻比的最大值可达 - 4 6 % .