Synthesis, properties and electropolymerization of starshaped oligothiophenes with hexakis(fluoren-2-yl)benzene as core

Star-shaped oligothiophenes with hexakis(fluoren-2-yl)benzene (HFB) as cores were designed and synthesized. Grafting thiophene units to HFB results in a bond flattening of the core, and makes the molecules a flipping-twist shape. Their thermal, photophysical and electrochemical properties were studied. Highly cross-linked conjugated polymers can be produced by electropolymerization of T1-T3.     

Influence of clay on the morphology and phase separation behavior of poly(methyl methacrylate)/poly(styrene-co-acrylonitrile) blends

The effect of clay on the morphology and phase-separation behavior of poly(methyl methacrylate)/poly(styreneco-acrylonitrile)(PMMA/SAN) blends and the variation of clay dispersion have been investigated. With the evolution of phase separation in PMMA/SAN, most of the clays are first located at the boundaries between PMMA and SAN, and then gradually move to the PMMA-rich domain, owing to the affinity of clay to PMMA. The introduction of clay causes the increase of binodal and spinodal temperatures of PMMA/SAN and enlarges their metastable region, indicating the phase stabilizing effect of clay on the matrix. But the influence of clay on the cloud points obviously depends on the composition of PMMA/SAN. The selective adsorption of PMMA on the clay results in the difference between the composition of surface layer and that of polymer matrix. Hence, the clay plays the role of an agent changing the conditions of phase structure formation.     

Crystal orientation and melting behavior of poly(ɛ-Caprolactone) under one-dimensionally “hard” confined microenvironment

Crystal orientation and melting behavior of poly(ε-caprolactone) in a diblock copolymer of poly(ε-caprolactone)-block-poly(2,5-bis[4-methoxyphenyl]oxycarbonyl)styrene) (PCL-b-PMPCS) was investigated. The degrees of polymerization of the PCL and PMPCS block are 200 and 98, respectively. With the PMPCS in a columnar liquid crystalline phase, the diblock is rod-coil one, which exhibits a lamellar phase morphology with the PCL layer thickness of 15.2 nm. Since the glass transition temperature of PMPCS block is much higher than the melting temperature of PCL, the crystallization of PCL is in a one-dimensionally "hard" confinement environment. Mainly on the basis of two-dimensional wide-angle X-ray diffraction experiments, we identified the orientation of PCL isothermally crystallized at various crystallization temperatures (Tcs). At high Tcs (Tc≥10℃), the c-axis of the PCL crystal is along the layer normal of the microphase-separated sturcture. Decreasing Tc can result in the tilting of PCL c-axis with respect to the layer normal. The lower the Tc is, the more the c-axis inclines. Meanwhile, the b-axis of PCL remains perpendicular to the layer normal. At a very low Tc of -78℃, the orientation of the PCL crystals is completely random. For the samples isothermally crystallized at Tc≤10℃, double melting behavior can be observed. While the low temperature endotherm reflects the melting of the crystals originally formed at the Tc applied, the high temperature one is associated with the crystals subjected to the process of recrystallization/reorganization upon heating due to the annealing effect.     

Preparation of single-hole hollow polymer nanospheres by raspberry-like template method

Single-hole hollow polymer nanospheres were fabricated by raspberry-like template method using "graft-from" strategy through atom transfer radical polymerization (ATRP). Nanometer-sized silica spheres were covalently attached onto the surfaces of micrometer-sized silica spheres. Crosslinked polymer shells on the nano-sized spheres outside the attached area were formed by "graft-from" strategy through ATRP. After removal of the silica cores, single-hole hollow crosslinked polymer nanospheres were obtained. In this strategy, most of ATRP monomers may be used and thus many functional groups can be easily incorporated into the single-hole hollow crosslinked polymer nanospheres.     

基于i.MX35的工程机械显示终端设计

工程机械显示终端是重要的人机交互界面,随着工程机械控制系统信息化和智能化水平的不断提高,对车载显示终端也提出了越来越高的要求。为了满足需求,研制了基于i.MX35的工程机械显示终端,该显示终端以i.MX35多媒体应用处理器为核心,采用CODESYS作为应用编程平台,实现了人机界面显示、CAN总线通信、摄像头视频采集、大容量数据存储等功能,具有显示性能强大、启动速度快、应用编程灵活、易于扩展等特点,可以广泛应用于各种工程机械控制系统中。     

运载火箭试验数据管理及可视化系统设计

针对现有运载火箭试验数据管理及可视化系统依赖于第三方功能插件,未实现纯浏览器端三维模型渲染及交互,系统对运行环境依赖性强、部署和维护成本高等问题,设计了基于JavaScript框架ExtJS和WebGL框架three.js的运载火箭试验数据管理及可视化系统。首先基于B/S架构设计了系统总体框架,然后针对二维图形数据传输延迟问题设计了基于Web Worker的数据读取方案,最后针对浏览器端三维模型渲染需求提出了基于VTK模型的转换算法,设计了三维模型渲染及交互方案。试验结果显示,本系统不依赖于运行环境和功能插件,能实现浏览器端二维图形和三维模型渲染及流畅交互,为兼容国产化操作系统、降低部署和维护成本创造了条件。     

螺桨烷型分子BX[(CH_2)_n]_3和BX(CH_2)[CH(CH_2)_nCH](X=N,P)的结构和性质

采用密度泛函理论(DFT)研究了螺桨烷型分子BX[(CH2)n]3和BX(CH2)[CH(CH2)n CH](X=N,P;n=1-6)的结构、稳定性、化学键和电子光谱性质.计算结果表明这些分子都是稳定的.BX[(CH2)n]3(X=N,P;n=1-6)的最高占据分子轨道(HOMO)和最低空分子轨道(LUMO)之间的能隙均大于5.20 eV,其中BN[CH2]3和BP[CH2]3的能隙超过7.0 eV,与C5H6的能隙(7.27 eV)很接近,BX(CH2)[CH(CH2)n CH](X=N,P;n=1-6)的能隙在6.80 eV左右.所研究分子能量的二阶差分表明BN[(CH2)3]3、BP[(CH2)4]3及BX(CH2)[CH(CH2)2CH](X=N,P)是最稳定的.BX[(CH2)n]3的Wiberg键级表明除了BN[(CH2)n]3(n=2和6)中不存在B―N键,其它化合物中B和N均形成了化学键,BP[(CH2)n]3中除了BP[(CH2)2]3不存在B―P键,其它的均存在.电子密度的拓扑分析表明N―B键属于离子键,而P―B键具有共价键特征.BX[(CH2)n]3(X=N,P)的第一垂直激发能分别在191.1-284.8 nm和191.8-270.1 nm之间,BX(CH2)[CH(CH2)n CH](X=N,P)的第一垂直激发能分别在190.5-199.7 nm和209.0-221.3 nm之间.     

卟啉化聚合物纤维膜负载TiO_2光催化剂的制备及其光催化性能研究

通过烯基铁卟啉分别和苯乙烯、丙烯腈及甲基丙烯酸甲酯共聚制备三种卟啉化聚合物,然后利用静电纺丝技术将这三种卟啉共聚物与TiO2颗粒共纺制备卟啉共聚物纤维膜负载TiO2光催化剂。扫描电子显微镜(SEM)表征结果显示卟啉共聚物纤维负载TiO2催化剂都具有良好的纤维结构,纤维直径约为1.0-2.0μm。X-射线衍射仪(XRD)则表明TiO2的晶型在纺丝前后都没有受到明显影响。对甲基橙溶液的催化降解实验结果显示:铁卟啉-丙烯腈共聚物负载TiO2催化剂的光催化活性最高,而且铁卟啉的含量对催化剂催化活性起着非常重要的作用。优化后的铁卟啉-丙烯腈共聚物纤维膜负载TiO2光催化剂对甲基橙溶液的脱色率达到76.3%,同时纤维膜结构有利于催化剂的回收和重复使用。     

C.I.颜料红177中间体的制备工艺改进

本文较为系统地研究了铜粉催化剂加入方式对C.I.颜料红177中间体4,4'-二氨基-1,1'-二蒽醌-3,3'-二磺酸(DAS)合成过程中的乌尔曼偶联反应速率的影响规律。 研究结果表明,在55 ℃较佳反应温度下,先加入与溴氨酸钠质量比为2:5的铜粉,反应一段时间后再加入与溴氨酸钠的质量比为1:5的铜粉,与一次性加入与溴氨酸钠的质量比为3:5的铜粉相比较,综合反应时间可节省2~3 h。 另外,对于DAS中混有的铜盐,采取在制备过程中加入柠檬酸的方法予以去除,此举可提高DAS的纯度。 当铜粉与柠檬酸的质量比为6:1时,可使DAS中铜盐的含量小于0.001%。 此外还探究了蒸馏后滤液的剩余量对DAS收率的影响,结果表明,滤液的剩余量在20 mL时,DAS的收率在95%以上。 基于本文的研究结果提出,欲进一步提高该反应的收率,需要寻找更高效的催化剂。     

A biomass carbon material with microtubule bundling and natural O-doping derived from goldenberry calyx and its electrochemical performance in supercapacitor

A promising biomass carbon material,manufactured by the carbonation of Physalis peruviana L.calyx at 700℃,is presented in this wo rk.Morphology characterization shows that the carbon material possesses long microtubule bundling and above 30%natural O-atom component on the surface.After KOH chemical etching,the materials maintain the oxygen content but exhibit more micropores and higher specific surface area up to 1732.6 m^2/g.Using as an electrode material for supercapacitor,the active carbon material exhibits high specific capacitance up to 339.7 F/g at 0.5 A/g in 3 mol/L KOH aqueous solution through three-electrode system.The active carbon material also exhibits excellent cycling stability(97%retention)by 10,000 cycles at 10 A/g.The outstanding electrochemical performances are attributing to the unique long microtubule bundling with much more pores and the abundant Oelement on the surface.This biomass carbon material with excellent electrochemical properties could be a useful material for multiple applications.