氮杂冠醚研究Ⅶ、双仲胺型氮杂冠醚对过渡金属离子的选择性萃取作用

合成了五种新型双仲胺型氦杂冠醚，研究了它们对过渡金属离子进行液—液萃取，并用原子吸收法测定其浓度。实验结果表明：这类冠醚对Ａｇ￣＋、Ｐｄ￣（２＋）、和Ｐｔ￣（４＋）等贵金属离子有较强的选择配位性能，对选择性分离这些金属离子有重要的意义。     

Micellar core-shell-type acrylic-polyurethane hybrid materials with self-polishing property

Abstract

Marine fouling can be a serious problem in the shipping industry, since it increases the surface roughness of the hull and hence its frictional resistance to its movement through water. Antifouling paint can be defined as preventing the attachment of marine organisms onto surfaces. However, the most commonly used antifouling coating which is the tributyltin-based self-polishing copolymer causes the severe pollution of marine environment. Ammonium salt-based paints include tertiary amines as biocides which have effective biocidal and biodegradable properties without accumulation in the sea environment. However, ammonium salt-based coatings were too sensitive to seawater and became swollen. In this study, polyurethane-acrylic copolymers were synthesized by radical polymerization. These hybrid materials were found to form core–shell structures in aqueous media. Synthesis and properties of copolymers were investigated by Fourier transform-infrared spectrometer, proton-nuclear magnetic resonance, transmission electron microscopy, and dynamic light scattering. The polishing rate of self-polishing copolymer was determined from the reduction in dry film thickness after artificial seawater immersion under a dynamic condition.     

Controlled synthesis of stable poly(vinyl formamide-co-vinyl amine)/silica hybrid particles by interfacial post-cross-linking reactions

 The chemical synthesis and the physicochemical properties of stable poly(vinyl formamide-co-vinyl amine)/silica hybrid particles are presented. Copolymers of poly(vinyl formamide) (PVFA) and poly(vinyl amine) (PVAm) and their protonated forms were adsorbed onto silica from aqueous solutions. The influences of the pH strength and the ion concentration of the aqueous solution as well as the copolymer composition (degree of hydrolyzation of PVFA), and the molecular mass on the adsorption process were investigated by electrokinetic measurements, potentiometric titration, and quantitative elemental analyses. Silica surface-charge neutralization is achieved at a pH strength above 10 for highly hydrolyzed (95%) PVFA polymers. Decreasing the amino content in the PVAm chain shifts successively both the point of zero charge and the isoelectric point to lower pH values. PVFA-co-PVAm layers onto silica are adsorbed weakly. To fix these layers irreversibly, cross-linking reactions with (4,4′-diisocyanate)diphenyl methane were carried out on the surface of solid PVFA-co-PVAm/silica hybrid particles suspended in acetone. The cross-linking reaction, which is connected with the conversion of amino groups, is also a tool to control the surface charge of the PVFA-co-PVAm/silica hybrids. X-ray photoelectron spectroscopy and solid-state ¹³C cross-polarization magic-angle spinning NMR spectroscopy were used to obtain information on the number of and the structure of the functionalized polyelectrolyte layers on silica. The success of cross-linking was also shown by the results of these spectroscopic methods. Received: 28 June 1999 /Accepted: 27 August 1999     

Zur Reaktion eines Bis(amino)germylens mit Germaniumaziden: Abfangreaktionen von instabilen Germa-Iminen

Reaction of a Cyclic Bis(amino)germylene with Germaniumazides: Trapping-Reactions of Unstable Germa-Imines . The cyclic bis(amino)germylene 1 reacts with different germaniumazides of the type Me₂Si(NtBu)₂Ge(R)N₃ (R = Me ( 2 ), tBu ( 3 ), N(SiMe₃)₂ ( 4 ), R = N₃ ( 5 )). With the exception of 4 all azides lose dinitrogen when treated with 1 and the Ge^II center coordinates the α-nitrogen of the azide group. It seems to be reasonable to assume a transient germaimine (nitride) which is trapped by further reaction with the azide molecules 2 and 5 or by reaction with the solvent pyridine ( 3 ). In the case of 2 the germatetrazole [Me₂Si(NtBu)₂]GeN₄[Ge(NtBu)₂SiMe₂]₂ ( 6 ) is formed, the tetrazole nitrogens being exclusively substituted by germanium atoms (point symmetry of the molecule C_s(m)). When 1 is treated with 5 a tris(germa)amine [Me₂Si(NtBu)₂Ge(N₃)]₃N ( 8 ) is formed, which has an azide group attached to each Ge-atom. X-ray analysis reveals that the nine nitrogen atoms of the azide groups are coplanar with the trigonal planar Ge₃N moiety (crystallographic symmetry: 3/m). The reaction of 1 with 3 is very surprising: the pyridine in the product Me₂Si(NtBu)₂Ge(C₅H₄N)? N(H)Ge(tBu)(NtBu)₂SiMe₂ ( 7 ) is bonded via an α-carbon atom while the remaining hydrogen has added to the nitride-nitrogen. 6 crystallizes in the monoclinic system space group C2/m, a = 24.306(9), b = 10.933(6), c = 19.420(9) Å, β = 91.81(2)° and Z = 4. 7 crystallizes in the hexagonal system space group P6₃/m with a = b = 16.73(1), c = 11.006(8) Å, γ = 120° and Z = 2, and 8 crystallizes in the monoclinic system space group P2₁/n, a = 11.341(6), b = 26.086(9), c = 13.244(7) Å, β = 98. I2(2)° mit Z = 4.     

氮杂冠醚的研究：Ⅳ.大环仲胺型氮杂冠醚的合成

在高度稀释条件下芳香族二胺与相应的二酰氯起环化缩合反应,合成了5种大环酰胺型氮杂冠醚,接着用 LiAlH_4-THF 还原生成大环仲胺型氮杂冠醚;这两类冠醚的结构均经元素分析、IR、~1HNMR 和 MS 所证实。     

一水合高氯酸三（2—苯并咪唑亚甲基）胺合钴（Ⅱ）配合物的合成 …

合成了一水合高氯酸三(2-苯并咪唑亚甲基)胺合钴(Ⅱ)配合物,用单晶X- 射线衍射方法测定了它们的晶体结构.测定结果表明,该配合物属正交晶系,Pbcn(No.60) 空间群.晶胞参数a=19.393(9),b=18.232(8),c=17.052(8),α=β=γ=90.000(1)°,V=602 9.33,Z=8,最终偏离因子R1=0.156.配合物中的金属Co(Ⅱ)原子与配体NTB分子中的四个氮原子和高氯酸根中的一个氧原子形成扭曲三角双锥构型.     

叔胺弱碱树脂的强度研究

研究了影响苯乙烯系叔胺弱碱性阴离子交换树脂性能的诸因素．提出了经二甲胺胺化 后所形成的胺基桥是影响树脂强度的主要原因的观点．用磷酸一渗磨圆球率方法对树脂进行强 度检验,使强度数据更为可靠．     

Thermal characterization and solid‐state 13C‐NMR investigation of blends of poly(N‐phenyl‐2‐hydroxytrimethylene amine) and poly(N‐vinyl pyrrolidone)

The miscibility and thermal properties of poly(N‐phenyl‐2‐hydroxytrimethylene amine)/poly(N‐vinyl pyrrolidone) (PHA/PVP) blends were examined by using differential scanning calorimetry (DSC), high‐resolution solid‐state nuclear magnetic resonance (NMR) techniques, and thermogravimetric analysis (TGA). It was found that PHA is miscible with PVP, as shown by the existence of a single composition‐dependent glass transition temperature (T_g) in the whole composition range. The DSC results, together with the ¹³C crosspolarization (CP)/magic angle spinning (MAS)/high‐power dipolar decoupling (DD) spectra of the blends, revealed that there exist rather strong intermolecular interactions between PHA and PVP. The increase in hydrogen bonding and in T_g of the blends was found to broaden the line width of CH—OH carbon resonance of PHA. The measurement of the relaxation time showed that the PHA/PVP blends are homogeneous at least on the scale of 1–2 nm. The proton spin‐lattice relaxation in both the laboratory frame and the rotating frame were studied as a function of the blend composition, and it was found that blending did not appreciably affect the spectral densities of motion (sub‐T_g relaxation) in the mid‐MHz and mid‐KHz frequency ranges. Thermogravimetric analysis showed that PHA has rather good thermal stability, and the thermal stability of the blend can be further improved with increasing PVP content. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 237–245, 1999     

Spherical Particles of Zirconia-Titania of Hexagonal Structure from a Neutral Amine Route

Through the sol–gel process, using the so-called neutral amine route, spherical particles of 1:1 zirconia–titania were synthesized from zirconium(IV) and titanium(IV) butoxides as well as 1,12-diaminododecane as precursor species. The obtained product exhibited a hexagonal structure, as determinated by X-ray diffraction data. The obtained material was also characterized by thermogravimetry, differential scanning calorimetry, infrared spectroscopy, scanning electron microscopy, and surface area measurements. Despite the release of template molecules on heating, the spherical morphology was retained up to about 1200°C, at which the disruption of the spheres took place.