Synthesis and thermal stability of silicon-containing esters of phosphorus acids

A number of trialkylsilylmethyl diphenyl phosphates MeRR′SiCH₂OP(O)(OPh)₂ (1a-e: R=Et (a), Pr (b), CF₃CH₂CH₂ (c, e), Me₃SiCH₂ (d); R′=Me (a-d), Et (e)) were synthesized and their thermal rearrangement, of the 1,2-shift type, was studied. The rearrangement consists of the migration of an alkyl group from Si atom to the methylene carbon atom and gives the corresponding silyl esters. The rate of the rearrangement was found to increase in the order1d<1b<1a<1 (R=R′=Me)<1c corresponding to the enhancement of the total inductive effect (−I) of the substituents at the Si atom. The relative migration ability of the substituents at the Si atom, determined by GC/MS analysis of the disiloxane fraction resulting from hydrolysis of pyrolyzed phosphates1a-e, increases in the order R=Pr<Et<CF₃CH₂CH₂<Me≪Me₃SiCH₂, which differs substantially from the order in which the rate of the rearrangement of phosphates1a-d changes. The electronegativity of the migrating group affects noticeably the relative ability to migrate. For Part 4, see Ref. 1. Deceased. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 9, pp. 1767–1772, September, 1998.     

羧甲基纤维素系列高分子表面活性剂超声合成的研究

研究了在超声波作用下羧甲基纤维素的降解反应及ＣＭＣ与具有不同亲水亲油比值的活性大单体「烷基醇（酚）聚氧乙烯醚丙烯酸酯及第三单体」的超声共聚反应。经萃取提纯的共聚产物用ＩＲ，＾１３Ｃ ＮＭＲ和ＵＶ等方法进行表证，证实通过超声反应制得了二元和三元共聚物。     

Ce(III)在辣根体中的迁移

应用放射性同位素示踪法, 即结合放射自显影和液体闪烁器检测及电镜放射自显影技术, 首次定性、定量地研究Ce(III)离子在辣根植物中的迁移. 结果表明: (1) Ce(III)离子能被辣根植物吸收并随时间发生迁移; (2)电镜放射自显影结果显示, Ce(III)离子迁移是通过质外体至共质体进入细胞的. Ce(III)离子在辣根植物体中的行为, 为稀土离子植物环境效应机理及辣根植物安全防护提供借鉴.     

光敏型季铵盐类阳离子表面活性剂的合成及表面活性和泡沫性质

本文报道了一种光敏型的阳离子表面活性剂（AZO），其分子结构中含有偶氮苯基团，并研究了光照对表面活性和泡沫性能的影响。经紫外光照射后，表面活性剂的饱和吸附量（Г_max）减小，临界胶束浓度（cmc）、最低表面张力（γ_cmc）和分子极限占有面积（A_min）增大；气泡数目增多，直径变小，发泡能力和泡沫稳定性降低。实验结果证实，该表面活性剂的表面活性和泡沫稳定性可以用光照进行调控。     

Mixed micelles of cetyltrimethylammonium bromide and poly(ethylene glycol)-600 monolaurate as catalysts of polyethylenimine phosphorylation in chloroform

Micelle formation in a cetyltrimethylammonium bromide-poly(ethylene glycol)-600 monolaurate-chloroform system in the absence and presence of hydroxybenzylated polyethylenimines (PEI) was studied by dielcometric titration, NMR self-diffusion, light scattering, and kinetic methods. A catalytic effect of mixed micelles on the reaction of 4-nitrophenylbis(chloromethyl)phosphinate with PEI was shown. The catalytic effect depends on the degree of substitution of PEI and composition of a surfactant mixture. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1359–1365, August, 2006.     

Investigation of the interactions in emulsions stabilized by a polymeric surfactant and its mixtures with an anionic surfactant

 The interaction of a nonionic polymeric surfactant with an anionic surfactant at the oil–water interface has been studied by its effects on the droplet size, stability and rheology of emulsions. Oil-in-water (o/w) emulsions were prepared using isoparaffinic oil and mixtures of a nonionic polymeric surfactant with an anionic surfactant. The macro-molecular surfactant was a graft copolymer with a backbone of polymethyl methacrylate and grafted polyethylene oxide (a graft copolymer with PEO chains of MW=750). The anionic surfactant was sodium dodecyl sulfate (SDS). The stabiliza-tion of the emulsion droplets was found to be different when using one or the other surfactant. The mechanism of stabilization of emulsion droplets by the macro-molecular surfactant is of the steric type while the stabilization by anionic surfactant is of the electrostatic repulsion type. Emulsions stabilized with mixtures present both types of stabilization. Other effects on the preparation and stabilization of emulsions were found to be dependent on properties associated with the surfactant molecular weight such as the Marangoni effect and Gibbs elasticity. The initial droplet size of the emulsions showed a synergistic effect of the surfactant combination, showing a minimum for the mixtures compared to the pure components. Emulsion stability also shows a synergistic interaction of both surfactants. Rheological measurements allow for the estimation of the interparticle interaction when measured as a function of volume fraction. Most of the effects observed can be attributed to the differences in interfacial tension and droplet radius produced by both surfactants and their mixtures. The elastic moduli are well explained on the basis of droplet deformation. Ionic versus steric stabilization produce little difference in the observed rheology, the only important differences observed concerned the extent of the linear viscoelasticity region. Received: 22 November 1996 Accepted: 24 March 1997     

Formation at low surfactant concentrations and characterization of mesoporous MCM-41

At low concentrations of cetyltrimethylammonium bromide,all silica-based mesoporous materials with hexagonal phase have been synthesized via interactions between self-assembled surfactant molecule aggregates and aniomc silicate polymers.The resulting materials are characterized by XRD,FT-IR,solid state 29Si MAS NMR,thermal analysis and N2 adsorption-desorption measurements.After soluble ions are removed,the interactors between surfactant micelles and silicate polymers are reorganized and then form mesostructures 1 he hexagonal framework is sonsistent with amorphous silica gel.The structures of materials depend on the synthesis conditions Hydrothermal process improves the interactions between molecules and increases the degree of framework silicon atom polymerization The.surface area and the mesopore volume of the material prepared at 100℃ increase by 87% and 71 %,respectively,compared with those obtained at room temperature.     

Highly hydrophobically modified polyelectrolytes: Field variables to control emulsion type

Highly hydrophobically modified (with n-dodecylamide chain) linear poly(acrylic acid)s (HHMPAAH) and poly(sodium acrylate)s (HHMPAANa) with various degrees of grafting (τ) were synthesized and used as emulsifiers of the n-dodecane/water system. The type of emulsion, oil in water (O/W) or water in oil (W/O), was investigated as a function of the polymer chemical structure (τ, salt or acid form of the copolymer) and aqueous phase electrolyte concentration (NaNO₃). Increasing τ and/or salt concentration was found to favor the formation of inverse emulsions. Direct liquid–liquid dispersions are more likely to form with poly(sodium acrylate)s than with poly(acrylic acid)s. Hence, field variables such as τ, pH and ionic strength are relevant parameters to control emulsion type. Moreover, a balanced polyelectrolyte neither soluble in oil nor in water was synthesized for the first time. With this original emulsifier, the dispersion type was found to change from O/W to W/O with polymer salting out. The work provides convenient model system for fundamental studies of polymer conformation at liquid–liquid interfaces. Received: 31 March 1998 Accepted: 30 April 1998     

介孔分子筛MSU-1的合成

MSU X介孔分子筛具有三维立体交叉排列的蠕虫状孔道结构,有利于客体分子在其孔道内扩散[1]。目前合成MSU X的原料[2 4]TEOS水解速度慢,合成过程较易控制,但价高、易燃、有刺激性。本文采用文献[5 7]法,以水玻璃、A(EO)9为原料,在酸性至近中性的范围里合成了MSU 1介孔分子筛,与TEOS为原料的MSU 1合成进行了比较,考察了pH值和不同类型表面活性剂(脂肪醇聚氧乙烯醚和烷基酚聚氧乙烯醚)对产物结构性质的影响。1　实验部分1 1　试剂和仪器水玻璃(SiO2%≈26、Na2O%≈8),工业级,青岛海洋化工厂生产;脂肪醇聚氧乙烯醚非离子表面活性…     

Crystal Structures of Double Vanadates LiCoVO4 and Li0.5Co1.25VO4

The crystal structures of vanadates Li_1-2xCo_1+xVO₄ with x = 0 and 0.25 have been studied by a full pattern analysis. It has been shown that in cubic spinel LiCoVO₄ (space group Fd3m), the 8a tetrahedral sites contain a majority of vanadium and a small amount of lithium; all cobalt, lithium, and a small amount of vanadium occupy the 16d octahedral sites. Li_0.5Co_1.25VO₄ crystals belong to the rhombic system (Imma space group) with unit cell parameters a = 5.939(1), b = 5.810(1), and c = 8.303(1). On substitution of lithium by cobalt according to the scheme 2Li⁺ Co²⁺ + , half of the lithium and 70% of the vacancies formed are in the 4a octahedral sites, and onethird of lithium and most of cobalt occupy the 4d octahedral sites. The 4e tetrahedral sites are completely occupied by vanadium and lithium in a ratio of 0.92/0.08. The interatomic distances in LiCoVO₄ and Li_0.5Co_1.25VO₄ are calculated, and the sizes of lithium ion transport channels are evaluated.