阳离子无皂含氟丙烯酸酯的合成与表面性能

在合成甲基丙烯酸全氟辛酰氧基乙酯(FA)基础上,用半连续法制备了无皂阳离子含氟丙烯酸酯乳液。当乳液的粒径在100~200 nm、ζ电位大于40 mV时,乳液较稳定。阳离子亲水单体甲基丙烯酰氧乙基三甲基氯化铵(DMC)在含氟丙烯酸酯中质量分数为0.10~0.18、固含量小于20%时乳液的稳定性好,且随DMC含量的增加稳定性提高;含氟丙烯酸酯乳胶膜的附着力与耐磨性好,乳胶膜的透湿率随DMC的增加而增加。随热处理温度的提高,膜表面自由能下降;经160℃热处理后膜发生了交联,表面自由能为18 mN/m,与聚四氟乙烯(PTFE)的表面能相近,DMC含量对膜表面自由能影响不大。XPS分析也表明膜表面氟含量随热处理温度的提高而增加。     

Crystal Structure, Thermal Stability and Luminescence of Coordination Polymer [Cd（BBP）（p-PDOA）]n

Hydrothermal reaction of Cd（NO3）2·4H2O with bbp and p-PDOAH2 at 140 ℃ yielded a novel 1D cadmium（Ⅱ） coordination polymer, [Cd（bbp）（p-PDOA）]n （bbp=2,6-bis（benzimidazol-2-yl）pyridine, p-PDOA=p-phenylenedioxydiacetate dianion）, in which CdN3O4 pentagonal bipyramids were linked by p-PDOA ligands in a bis-bidentate mode to construct a zigzag chain with the adjacent Cd…Cd distance of 1.14（1） nm, There exists a 2D supramolecular network linked by π-π stacking with a face-to-face distance of 0.35（1） nm between the 2,6-bis（benzimidazol-2-yl） pyridine ligands and hydrogen-bonding interactions （0.27（4） nm）. A 3D supramolecular network was further constructed by these non-covalent interactions between the zippers. The TG/DTG showed that its chain skeleton was thermally stable up to 389 ℃ and the blue fluorescent emission of the complex was determined at 428 nm in a solid state with its long decay lifetime of 7.24 ns.     

Design of organic semiconductors: tuning the electronic properties of pi-conjugated oligothiophenes with the 3,4-ethylenedioxythiophene (EDOT) building block

Hybrid oligothiophenes based on a various combinations of thiophene and 3,4-ethylenedioxythiophene (EDOT) groups have been synthesized. UV/Vis absorption spectra show that the number and relative positions of the EDOT groups considerably affect the width of the HOMO-LUMO gap and the rigidity of the conjugated system. Analysis of the crystallographic structure of two hybrid quaterthiophenes confirms that insertion of two adjacent EDOT units in the middle of the molecule leads to a self-rigidification of the conjugated systems by intramolecular SO interactions. Cyclic voltammetry data shows that the first oxidation potential of the oligomers decreases with increasing chain length and increasing number of EDOT groups for a given chain length. Electrochemical studies and theoretical calculations show that the positions of the EDOT units in the conjugated chain control the potential difference (DeltaE(p)) between the first and second oxidation steps. Moving the EDOT groups from the outer to the inner positions of the conjugated system increases DeltaE(p). Theoretical calculations confirm that this phenomenon reflects an increase of the intramolecular coulombic repulsion between positive charges in the dication. A thin-film field-effect transistor was fabricated by vacuum sublimation of a pentamer with alternating thiophene-EDOT structure, and the hole mobility was determined.     

Systematic high-pressure synthesis of new filled skutterudites with heavy lanthanide, LnFe4P12 (Ln=heavy lanthanide, including Y)

New filled skutterudites with heavy lanthanide, LnFe₄P₁₂ (Ln=Tb, Dy, Ho, Er, Tm, Yb, Lu and Y) have systematically been prepared for the first time by the high-pressure technique. The relationship between lattice constants and atomic numbers of lanthanide (including Y) is established for LnFe₄P₁₂. Electrical and magnetic properties of several new filled skutterudites with heavy lanthanide have been studied at low temperatures; YFe₄P₁₂ shows a superconducting transition at around 7 K, and DyFe₄P₁₂ behaves as a ferromagnet below 10 K. Electrical and magnetic anomalies in DyFe₄P₁₂ and YFe₄P₁₂ are mainly discussed.     

四唑及其衍生物的理论研究Ⅷ: 硝氨四唑衍生物的从头算

运用从头计算法,在HF/6-31G^*水平下,全优化计算了7种硝氨四唑衍生物的分子几何和电子结构。结果表明,标题物的四唑环近似为平面构型;2H式中性分子的芳香性大于相应的1H式异构体。5-硝氨-1H四唑分子内氢键使硝氨基与环共面;其余标题物中硝氨基与环垂直。不同水平下的总能量计算表明,标题物中电子相关效应显著;1H式中性分子较2H式的能量高,5-硝氨四唑负离子在三个负离子中最稳定。根据电荷分布阐明了四唑环质子化位置和标题物与金属的配位方式。此外还计算了各标题物的红外光谱及热力学性质。     

Construction of a Novel 2D Polymer [Co（dmpzm）（dca）2]∞ from Reaction of a Mononuclear Complex [Co（dmpzm）Cl2] with Sodium Dicyanamide （dca） [dmpzm=bis（3,5-dimethylpyrazolyl）methane]

Reaction of COC12.6H20 with equimolar bis（3,5-dimethylpyrazolyl）methane （dmpzm） produced a mononuclear adduct [Co（dmpzm）Cl2] （1）. Treatment of 1 with sodium dicyanamide （dca） afforded a polymeric complex [Co（dmpzm）（μ-dca）2]∞ （2）. 1 and 2 were characterized by elemental analysis, IR spectra, thermogravimetric analysis and single-crystal X-ray diffraction. The cobalt atom in 1 adopts a distorted tetrahedral coordination geometry, bound to two N atoms of one dmpzm and two Cl atoms. Complex 2 has a 2D brick-wall network （extended along the bc plane） in which the { [Co（dmpzm）（μ-dca）]2} n^2n＋ chains are interconnected by pairs of μ-dca anions along the c axis. The magnetic properties of 1 and 2 were also investigated.     

Studies on tetra-amine phthalocyanines

Metal(II) tetranitro phthalocyanines of cobalt, nickel and copper are synthesized in pure state by a novel modified method. The complexes are characterized using elemental, electronic and IR spectral studies. Pure metal(II) tetra-amino phthalocyanines of cobalt, nickel and copper are synthesized by reducing the nitro groups of the above complexes using sodium sulphide. These complexes are also characterized by elemental, electronic, IR spectral and magnetic susceptibility measurements. The nature of the electrical conductivities of the above three metal(II) tetra-amino phthalocyanine derivatives are studied in the temperature range 303-473 K and the data are presented. Among the effect of various substituent groups on the electrical conducting property of phthalocyanine, amine group substituent on the peripheral benzene ring of the phthalocyanine molecule has been found to increase electrical conductivity to a greatest extent. These complexes showed about 10⁵-10⁶ times higher electrical conductivities compared to their parent phthalocyanine compounds.     

Synthesis and property of soluble poly(1,1′-dialkyl-3,3′-ferrocenylenevinylene)s via titanium-induced dicarbonyl-coupling reaction of 1,1′-dialkylferrocene-3,3′-dicarbaldehydes

1,1′-Dialkylferrocene-3,3′-dicarbaldehydes ( 1a–c ) with long alkyl chains such as ethyl, hexyl, and dodecyl groups were prepared in 13–25% yield via three-step reactions. The titanium-induced dicarbonyl-coupling reaction of 1a–c gave poly(1,1′-dialkyl-3,3′-ferrocenylenevi-nylene)s ( 2a–c ) in quantitative yields, which were the molecular weights of 3000–10,000 and highly soluble in chloroform, benzene, and hexane. The electrical conductivity and the third-order nonlinear optical susceptibility for poly(1,1′-dihexyl-3,3′-ferrocenylenevinylene) ( 2b ) were estimated to be 1 × 10^?2 S/cm on doping with iodine and 1–4 × 10^?12 esu at a wavelength of 1–2.4 μm, respectively. © 1995 John Wiley & Sons, Inc.     

Electrochemical Characteristics of Mg0.9Ti0.1-xZrxNi （x=0.02, 0.04, 0.06） Alloys

Mg-based hydrogen storage alloys Mg0.9Ti0.1-xZrxNi (x=0.02, 0.04, 0.06) were successfully prepared by means of mechanical alloying (MA). The effects of Zr addition on the discharge capacity and the cycle performance of the Mg-based electrodes were also studied. It was found that the discharge capacities were improved with addition of a small amount of Zr and the cycle performances of the alloy were stabilized with the addition of Ti. The effects of surface modification or coating on the properties of Mg0.9Ti0.06Zr0.04Ni were also studied. The results indicated that coating with graphite improved both the discharge capacity and cycle life of the amorphous Mg0.9Ti0.06Zr0.04Ni electrode.     

Bola型阴离子表面活性剂与溴化十二烷基三乙铵混合体系的表面性质与聚集行为

研究了具有简单结构的bola型阴离子表面活性剂二十酸二钠（C_(20)Na_2)与 阳离子型普通表面活性剂溴化十二烷基三乙铵（C_(12)Et_3）混合体系的表面性质 ，发现混合体系的cmc和γ_(cmc)比C_(12)Et_3单一体系未有显著降低。以负染色 ，FF-TEM，动态光散射（DLS）及粘度方法研究了混合体系的聚集行为，发现混合 体系中同时形成球形囊泡和管状聚集体，提出了产生这种聚集行为的机制。