正丁胺对苯膦酸铜的插层反应研究

分别采用溶液搅拌和超声的方法,研究了有机正丁胺分子对苯膦酸铜的插层反应.对插层复合物进行了红外光谱(IR)、X射线粉末衍射(XRD)和热重分析等测试及结构分析.结果表明,有机正丁胺的插入使得苯膦酸铜的层间距增大.     

Thermochemical data for n-alkylmonoamine intercalation into crystalline lamellar zirconium phenylphosphonate

Layered crystalline zirconium phenylphosphonate, Zr(O₃PC₆H₅)₂, changed its interlamellar distance of 1481 pm after intercalation of n-alkylmonoamines, CH₃---(CH₂)_n---NH₂ (n=0–6). The infrared spectra of the precursor host and the corresponding intercalated compounds presented vibrations associated with PO₃ groups in the 1163–1039 cm⁻¹ range and additional bands related to C---H stretching bands in the 2950–2850 cm⁻¹ interval were observed after amine insertion. The thermogravimetric curves showed a mass loss assigned to the phenyl group; however, the amine intercalated fraction was not quantitatively determined. A peak in the ³¹P NMR spectrum centered at −6 ppm for the host was observed. The surface area was 42.0±0.2 m² g⁻¹ and the scanning electron micrograph gave images consistent with lamellar structural features. The layered compound was calorimetrically titrated with amine in ethanol, requiring three independent operations: (i) titration of matrix with amine, (ii) matrix salvation, and (iii) dilution of the amine solution. From those thermal effects the variation in enthalpy was calculated as: −41±1.00,−33.28±0.50,−34.40±0.80,−10.40±0.40,−12.40±0.42,−16.10±0.08 and −7.0±0.04 kJ mol⁻¹, for n=0–6, respectively. The exothermic enthalpic values reflected a favorable energetic process of amine–host intercalation in ethanol. The negative Gibbs free energy results supported the spontaneity of all these intercalation reactions. The positive favorable entropic values, as carbon chain size increased, are in agreement with the free solvent molecules in the medium, as the amines are progressively bonded to the crystalline lamellar inorganic matrix at the solid/liquid interface.     

Host hydrated barium phenylphosphonate/guest heterocyclic amine intercalation energetics by calorimetric titration

The heterocyclic amines 2,6-lutidine, pyrazine, piperazine and piperidine were intercalated into layered crystalline hydrated barium phenylphosphonate, Ba(HO₃PC₆H₅)₂·H₂O, through a batch method in ethanolic solution, to give the maximum amounts 0.39, 0.82, 2.80 and 5.50 mmol g⁻¹, respectively. The original host interlayer distance (d) of 1532 pm increased after intercalation for piperazine (1752 pm) and piperidine (2112 pm) molecules, while for 2,6-lutidine and pyrazine molecules d values were maintained. The enthalpy of intercalation gave −5.60 ± 0.10, −1.00 ± 0.02, −9.55 ± 1.00 and −30.70 ± 0.68 kJ mol⁻¹ for the sequence of heterocyclic amines. The Gibbs free energies are negative and entropies are positive for intercalation.     

Full factorial design applied to intercalation of amines in lamellar titanium phenylphosphonate and titanium phenylarsonate

The intercalation of amines into titanium phenylphosphonate M(O₃PC₆H₅)₂ and titanium phenylarsonate M(O₃AsC₆H₅)₂ was investigated through batch and back-titration processes. Amine insertion in both layered lamellar inorganic matrices, measured by the number of moles of intercalated agent, was optimized using a complete factorial design based on two levels and four factors. The effects of solvent, ethanol and acetonitrile, neutral organic base, ethyl and propylamines, H₃C(CH₂)_nNH₂ (n=1, 2), and material mass, 30 and 40 mg, on amine insertion in both lamellar inorganic matrices was optimized using a full factorial design. Important positive effect values, 0.40×10⁻³ and 0.69×10⁻³ mol g⁻¹ were observed for inorganic material and solvent whereas a negative effect, −0.33×10⁻³ mol g⁻¹ was observed for material mass. Two significant but less important binary interactions were also observed. The use of either ethyl or propylamine does not appear to affect the quantity of amine insertion. Recommended experimental conditions for maximum amine insertion obtained from this factorial design are 30 mg of titanium phenylarsonate in acetonitrile solvent using either of the studied amines.     

氧化铬层柱苯膦酸锆的合成与选择氧化性能

采用乙胺预胶体化方法合成了一系列氧化铬层柱苯膦酸锆和氧化铬层柱磷酸锆催化剂,其铬含量达到22.5%-36.5%,比表面为316-462m^2/g,中孔孔容占总孔容的70%以上,孔径集中在2nm左右。氧化铬层柱苯膦酸锆的热稳定性较高。以30%H~2O~2为氧化剂时,这类催化剂对苯、甲苯、乙苯、环己烷、环己烯、正庚烷和正丁醇等有机化合物具有比CrAPO-11和CrMCM-41更高的选择氧化活性。     

Solubility parameters of poly(sulfonyldiphenylene phenylphosphonate) and its miscibility with poly(ethylene terephthalate)

The solubility behaviors of poly(sulfonyldiphenylene phenylphosphonate) (PSPPP), a very efficient flame retardant for poly(ethylene terephthalate) (PET), in more than 50 solvents were examined. Its solubility parameters (δ) were determined by the intrinsic viscosity and turbidic titration methods. The two methods obtained consistent results, δ = 21.0–21.6 J^1/2/cm^3/2 and δ = 21.0 J^1/2/cm^3/2, and the three‐dimensional solubility parameters were δ_d = 18.9 J^1/2/cm^3/2, δ_p = 8.8 J^1/2/cm^3/2, and δ_h = 5.9 J^1/2/cm^3/2. The miscibility of PSPPP with PET was estimated by the calculation of the heats of mixing, which were related to the difference between the solubility parameters of PSPPP and PET. Fourier transform infrared was used to examine the interactions between PSPPP and PET macromolecules, which were the internal factors of polymer–polymer miscibility. The results showed that PSPPP and PET were miscible within a very wide composition range, especially with less than 15 wt % PSPPP, a composition of interest for the preparation of flame‐retardant PET. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2296–2301, 2003     

Thermal Intercalation of Alkali Halides into Kaolinite

Solid state intercalation of alkali halides into kaolinite takes place by heating pressed disks of dimethylsulfoxide (DMSO)-kaolinite complex ground in different alkali halides. This reaction involves diffusion of the DMSO outside the interlayer space and the alkali halide into the interlayer space. IR and Raman spectroscopy reveal two types of intercalation complexes: (i) almost non-hydrous, obtained during thermal treatment of the DMSO complex; and (ii) hydrated, obtained by regrinding the disk in air. The strength of the hydrogen bonds between intercalated water or halide anions and the inner surface hydroxyls decreases in the order Cl⁻>Br⁻>I⁻. Chlorides penetrate the ditrigonal holes and form hydrogen bonds with the inner OH groups. This revised version was published online in August 2006 with corrections to the Cover Date.     

芳香胺对微孔层状磷酸铝材料的剥离与嵌入

用XRD和SEM研究了芳香胺对微孔层状磷酸铝 [Al3P4O16][CH3CH2NH3]3和[Al2P3O10(OH)2]•[C6NH8]的剥离和嵌入过程, 结果发现, 芳香胺本身的碱性大小是形成新的柱撑物的关键. 卞胺是碱性较强的芳香胺, 可以很好地将磷酸铝剥离并嵌入到层间形成新的层状化合物; 而碱性较弱的苯胺却无法做到. 新柱撑物形成的速度除与介质的介电常数和芳香胺的加入量有关外, 还取决于原有磷酸铝层板间相互作用的强弱.     

Excess enthalpies of alcohol + amine mixtures. Experimental results and theoretical description using the ERAS-model

New experimental data of the molar excess enthalpy H^E of mixtures containing eight liquids - propylamine + methanol, ethanol, propan-1-ol, butan-1-ol, butylamine + methanol, ethanol, propan-1-ol, butan-1-ol - are presented using a quasi-isothermal flow calorimeter. The results are used for testing the ERAS-model which provides a theoretical concept accounting for the self-association and cross-association of alcohol and amine molecules, as well as for non-associative intermolecular interactions. Excess molar volumes V^E are also successfully described by the model. It turns out that the strong cross-association occurring between alcohol and amine molecules is the predominant reason for the remarkably low exothermic values of H^E observed for the mixtures studied.     

三聚磷酸二氢铝与有机胺的插层反应特征

采用IR、XRD、SEM、EDS、DT-TG和滴定实验等技术手段研究主体三聚磷酸二氢铝(ATP)与客体甲胺、乙胺、正丙胺和正丁胺等有机胺的插层反应特性。 实验结果表明,ATP与甲胺、乙胺、正丙胺、正丁胺发生了化学反应,有机胺中的N与ATP层间-OH上的H形成配位键。 这些有机胺通过插层反应改变了ATP的酸性、层间距和热分解温度,但没有改变颗粒的层状形貌。 层间距从0.795 nm增大至1.71 nm,层间距d与有机胺的碳原子数Cn呈线性关系：d=0.229Cn+0.811,R2=0.9986。 有机胺分子链越长则越具有剥离倾向。     

Construction of lamellar morphology by side-chain crystalline comb-like polymers for gas barrier

A comb-like polymer containing crystallized alkyl side chains and the intermolecular hydrogen bonds between the linking groups was fabricated by grafting long-chain fatty amine onto poly(styrene-co-acrylic acid)_n (P(S-AA)_n, wherein “n” denoted AA feed ratio). The chemical structures and crystallization behaviors of the comb-like polymer P(S-AA)_n-g(p) (wherein “p” denoted the number of side-chain carbon atoms) were analyzed by Fourier transform infrared, gel permeation chromatography, X-ray photoelectron spectroscopy, and X-ray diffractometer, differential scanning calorimetry, atomic force microscopy, respectively. It was found that the lamellar morphology could be generated by controlling the grafting density and side chain length of P(S-AA)_n-g(p). Moreover, it was identified that the hydrogen bonds between amide groups could enhance the crystallinity and then adjust the interlamellar spacing of lamellar phase. As a result, P(S-AA)₇₀-g(18) with the highest degree of crystallinity and closely packed lamellar morphology showed a good gas-barrier performance, and the nitrogen permeability reached 1.78 × 10^?14 cm³·cm/cm²·s·Pa. Furthermore, the permeation switch of the obtained comb-like polymer could reach 500 times traversing the melting point.     

高氯酸根阴离子在HOPG中嵌入行为的EC-STM研究

运用电化学扫描隧道显微镜（EC-STM）和循环伏安（CV）技术对高氯酸根阴离子ClO₄^-在高序热解石墨（HOPG）中的电化学嵌入行为进行了研究. 通过观察嵌入前后石墨台阶处高度的变化,比较了不同高度的台阶对嵌入的影响,讨论了ClO₄^-离子嵌入石墨的可行性、可逆性和嵌入速率. 研究表明,3层以上的台阶位才有可能观察到由四阶和三阶嵌入引起的台阶高度变化,4 ~ 8个原子层高度的石墨台阶可以实现ClO₄^-在台阶处较为可逆的四阶嵌入,但1 ~ 2层台阶处无法观察到嵌入引起的台阶高度变化,嵌入反应通常会伴随台阶的剥离和脱落现象. 四阶的嵌入反应较三阶可逆,二阶和一阶时,嵌入所需反应电势较高,此时氧化反应较为剧烈,嵌入反应被掩盖,很难观察到台阶高度的变化,更多的形貌变化是台面和台阶处不可逆的损坏如剥落、断层、黑坑等.     

Asymmetric azomethine amines with azobenzene moieties – liquid crystalline and optical properties

ABSTRACT

Three asymmetric azomethine-azobenzene intermediates (M1-M3), having internal reactive amine functional group, and both n-butoxy and p-chloro, p-methyl, o-methyl terminal moieties, have been synthesised by reacting asymmetric substituted azobenzene diamines with 4-butoxybenzaldehyde. Their proposed chemical structures were confirmed by FTIR and 2D-NMR spectroscopy. The mesomorphic behaviour was investigated by polarised optical microscopy (POM), differential scanning calorimetry (DSC) and room temperature powder X-ray diffraction techniques. Characteristic textures of smectic A and nematic phases have been observed for samples M1 and M2, while only unsolved texture was revealed for sample M3 at room temperature, showing sharp reflections in the medium-wide angle region. From X-ray diffraction measurements, a layered ordered structure of all compounds was established by analyzing successive scattering vectors ratios (q_i/q₁). The dependence of thermal behaviour on molecular parameters like: interdigitation parameter γ, dipole moment, molecular polarisability, halogen radius, was commented. The UV-Vis spectral investigations of the intermediates, performed in six solvents, revealed that the absorption bands were influenced by the substituent nature.     

正烷基单胺对层状甘氨酸-N，N-双甲基膦酸锆的插层

The layered zirconium glycine-N,N-dimethylphosphonate (ZGDMP) was prepared and the intercalation behavior of n-alkylmonoamines was investigated. The X-ray diffraction powder patterns demonstrated that the n-alkylmonoamines were taken up in one step and there were no other intermediate phases. The interlayer distance correlated with the number of carbon atoms of the n-alkylmonoamine chains. The n-alkylmonoamines were intercalated into ZGDMP in such a way that the protons of the interlayer -CO₂H groups were replaced by the terminal -NH₃⁺ of the protonated n-alkylmonoamines. The intercalated n-alkylmonoamines were released from the lamellar ZGDMP at temperature of 150 to 250 ℃.     

层状水滑石对吡啶二甲酸异构阴离子的选择性插层行为

本文采用焙烧复原法研究了镁铝水滑石与吡啶二甲酸异构阴离子单体及其混合体的插层反应，实验发现镁铝水滑石对吡啶二甲酸异构阴离子存在着明显的选择性，有机酸异构体优先进入层间的顺序是：2,3-吡啶二甲酸>2,5-吡啶二甲酸>2,4-吡啶二甲酸>3,5-吡啶二甲酸>3,4-吡啶二甲酸>2,6-吡啶二甲酸。利用XRD、IR和TG测试技术对样品进行了表征，同时采用Gaussian-98软件包中ab initio 分子轨道法（HF/6-31G）计算了吡啶二甲酸异构阴离子的分子结构，理论结合实验探讨了阴离子在水滑石层间可能的空间构型，分析了其结构与插层行为的关系。研究表明镁铝水滑石层状材料插层过程中具有分子识别能力，可用于分离有机异构阴离子。     

The effect of temperature on lithium intercalation into carbon materials

The effects of temperature on lithium intercalation into non-graphitized carbonized cloth from various electrolytes have been studied. The open-circuit potential (o.c.p.) of the intercalates shifts in the negative direction as the temperature is raised. The average temperature coefficient of the o.c.p. is equal to −0.04 mV·K⁻¹ in the range from −35 to +45 °C. Intercalation-deintercalation kinetics was studied by the galvanostatic technique. It was shown that this process is quasi-ohmic at room and higher temperatures and has activation-ohmic control at lower temperatures. The effective activation energy of intercalation-deintercalation is about 20kJ·mol⁻¹. Intercalates are corroded in all electrolytes, the corrosion rate being drastically increased as the temperature is raised. The apparent activation energy of corrosion is 120–150 kJ·mol⁻¹. The corrosion rate is suggested to be controlled by cathodic reduction of electrolyte components. Received: 11 April 1997 / Accepted: 8 September 1997     

Electrochemical lithium and sodium intercalation into TaFe1.25Te3

Lithium and sodium have been topotactically inserted in the lattice of TaFe_1.25Te₃ by electrochemical procedures. The existence of electronically unequivalent sites occupied by tellurium atoms conditions a two-step insertion process. In each step, the alkali metal ions occupy empty sites in the structure which are coordinated by tellurium atoms of a different set of sites. The␣thermodynamic and kinetic parameters of Li _x TaFe_1.25Te₃ and Na _x TaFe_1.25Te₃ have been determined and compared with other inserted binary and ternary chalcogenides. The values of the free energy of intercalation are less negative than those previously reported for TaTe₂ and close to those found for the misfit layer compound (PbS)_1.13TaS₂. The values of alkali metal ion diffusivity are closer to those reported for the binary telluride, due to the similarities in the atoms exposed to the interlayer space. Received: 14 October 1997 / Accepted: 14 November 1997     

Phase diagrams of new lamellar liquid crystalline systems based on 2H NMR spectroscopy data

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Structural characterization and in vivo evaluation of retinyl palmitate in non-ionic lamellar liquid crystalline system

Carrier systems for lipophilic drugs, such as the liquid crystalline systems (LCS) have been extensively studied to improve effect and selectivity. Retinyl palmitate (RP) is widely used in pharmaceutical and cosmetics products to improve the skin elasticity. The aim of this study was the development, characterization and the in vivo effectiveness of RP in non-ionic LCS structures. LCS containing polyether functional siloxane as oil phase, silicon glycol copolymer as surfactant and water in the ratio 30:10:60, with and without RP were studied. The results of the polarized light microscopy, small-angle X-ray scattering and rheology analysis indicated the presence of typical LCS structures with lamellar arrangement. Regardless of the presence of RP, the rheological studies showed the pseudo plastic behavior of the systems. However, highest hysteresis area was verified when comparing the system in the presence and in the absence of RP. Stability study SAXS monitored, carried out up to 30 days in various storage temperature conditions (25±2 °C, 37±2 °C and 5±2 °C) demonstrated the great structural stability of the LCS systems. The in vivo effectiveness analysis suggests that the RP-loaded LCS provided a significant reduction of the orbicular wrinkles in human volunteers (P=0.048).     

Intercalation of 1,2-alkanediols into Vanadyl and Niobyl Phosphate

Intercalation compounds of VOPO₄and NbOPO₄ with 1,2-alkanediols (from C3 to C16)have been prepared. The diol molecules are placedbetween host layers in a bimolecular way with theiraliphatic chains tilted at an angle of 70°. Itwas found that the intercalates contain 1.5 moleculesof diol per formula unit. Three ways of bonding of thediol molecules to the host layers are proposed. Twomolecules of diol are coordinated to the metal atomsby their first and second oxygen, respectively. Thethird diol molecule is anchored in the interlayerspace by H-bonds.