α-Sulfonated fatty acid esters: I. Structural effects of sodium α-sulfonated fatty acid higher alcohol esters on surface-active properties and emulsification ability

The surface-active properties and emulsification ability of sodium α-sulfonated fatty acid esters, C_mH_2m+1CH-(SO₃Na)COOC_nH_2n+1, were studied as a function of the hydrophobic alkyl chainlength in the fatty acid (m=8−16) and the alcohol (n=8−18). As a result, it was discovered that sodium α-sulfonated fatty acid esters have a structural effect on the Krafft point different from that of amphiphiles with short alkyl chains. Moreover, some of the α-sulfonated fatty acid esters have quite low interfacial tensions, as well as non-foaming properties, which depend upon the total (m+n) number of carbon atoms in the alkyl chains.     

石油羧酸盐/重烷基苯磺酸盐/碱复配体系的界面活性及吸附特性

实验考察了石油羧酸盐(POS-2和POS-4)/重烷基苯磺酸盐(ORS-41)/碱(NaOH)复配体系与大庆脱气原油(45℃粘度18.7 mPa·s)间的界面张力IFT(45℃)及2种表面活性剂在大庆去油油砂上的吸附特性.实验复配体系用矿化度4.3 g/L的模拟注入水配制.在复配体系中加入C2～C5正构脂肪醇使实验油水体系IFT达到平衡的时间由～70 min缩短至～50 min,使IFT稳定值(～5.8×10-3 mN/m)有所降低,各种醇的影响力相差不大,C3醇略好.当POS-2、ORS-41、C2、C3混合醇(1∶1)质量比为24∶8∶1时,在POS-2浓度0.6～6.0 g/L、NaOH浓度2.5～12 g/L范围出现超低IFT.POS-4/CTMAB或CPC/NaOH复配体系只在很窄的阳离子表面活性剂浓度范围出现超低IFT.OP类和Tween类非离子表面活性剂使POS-2/NaOH体系的IFT升高,升高幅度随加入量和乙氧基数增大而增大.POS-4和ORS-41在油砂上的吸附符合Langmuir定律,从POS-4/ORS-41/NaOH(2.5/0.83/12 g/L)复配体系中的吸附量(饱和吸附量为1.444和6.741 mg/g油砂),低于从POS-4/NaOH(2.5/12 g/L)和ORS-41/NaOH(0.83/12 g/L)体系中的相应吸附量(分别为2.925和7.581 mg/g油砂).图6表1参9.     

Viscosities of Nonelectrolyte Liquid Mixtures Containing Acrylonitrile

The measurements of viscosity are reported for seven binary mixtures of acrylonitrile (AN) with ethanenitrile (EN), methyl acetate (MA), ethyl acetate (EA), n-butyl acetate (BA), dimethylformamide (DMF), dimethylacetamide (DMA), and dimethyl sulphoxide (DMSO) at 303.15 K temperature. The viscosity data have been correlated with the equations of Grunberg and Nissan; Hind, McLaughlin, and Ubbelohde; Tamura and Kurata; Katti and Chaudhri; McAllister; Heric and Brewer; and of Auslaender. The relations between the viscosity deviations , excess Gibbs energy of activation G*^E of viscous flow, and the intermolecular interaction in these mixtures are discussed.     

烷基糖苷的制备与性能

介绍了以对甲基苯磺酸为催化剂 ,以葡萄糖和醇为原料合成APG的方法。确定了较佳工艺条件为 :正丁醇与高碳醇之比为 1∶1(mol/mol) ,醇糖比为 3∶1(mol/mol) ,用H2 O2 脱色 ,反应温度为 110～ 115℃ ,反应时间为 1 5h ,葡萄糖的转化率达到 98% ,合成出的产品性能好 ,特别适用于餐具洗涤剂和洗发香波     

脂肪胺氧化物的生产及应用前景

论述以α－烯烃为原料经氢溴化、胺化及氧化和回收溴等步骤生产氧化胺的工艺过程、设计基础及技术－经济指标；α－烯烃路线生产氧化胺的生产、应用前景。     

NMR study of the role of isopropylsulfates in the two-step “conjunct oligomerization” of propylene and isopentane–propylene alkylation catalyzed by 95% sulfuric acid

“Conjunct oligomerization” of propylene or the isopentane–propylene alkylation catalyzed by an excess of 95% sulfuric acid was performed in two consecutive steps. First di-isopropylsulfate was prepared by interaction of sulfuric acid with propylene. The ester was then either decomposed at room temperature in the presence of the 5–10 molar excess of 95% acid or was used in the acid-catalyzed alkylation of isopentane. In situ ¹H and ¹³C NMR study of the reaction mixture of “conjunct oligomerization” indicated that the diester participates in two equilibria with sulfuric acid. The first one transforms the diester into a monoester. The second equilibrium corresponds to protonation of the monoester with an excess of sulfuric acid. This converts a minor fraction of the mono-alkylsulfate into isopropyl carbenium ions that are only weakly solvated with sulfuric acid: C₃H₇HSO₄ + H₂SO₄ ⇄ C₃H₇ ⁺ H₂SO₄ + HSO₄ ⁻. The subsequent reactions of alkyl carbenium ions with the non-protonated alkylsulfate result in final products of “conjunct oligomerization” while in the presence in the reaction mixture of isopentane, alkylation with the predominant formation of C₈ branched paraffins takes place. A very low yield of propane indicates a minor role of hydride transfer in alkylation. Another unexpected result is the absence in both reaction mixtures of propylene. These findings are in contradiction with the classical mechanism of isoparaffin–olefin alkylation by Schmerling. Therefore, an alternative mechanism of this reaction is suggested via a direct alkylation of isopentane with the mono-alkylsulfate. This revised version was published online in July 2006 with corrections to the Cover Date.     

高密度高热安定烷基金刚烃燃料的合成及性质研究进展

烷基金刚烃具有高密度和高热安定性等特点,可为航空航天飞行器提供充足的推进能量和冷却能力。综述了烷基金刚烃燃料的合成进展,包括多环烷烃重排反应和金刚烷基化合物烷基化反应。分析了重排反应受热力学控制的特性,结合量子化学计算与实验产物分布推测重排反应路径;讨论了以金刚烷基化合物为原料烷基化反应具有区域选择性,能够实现定向合成指定烷基结构(甲基、乙基、丙基、丁基等)的金刚烃。同时,总结了烷基金刚烃燃料性质,归纳了针对烷基金刚烃燃料热安定性的评价方法和结果,分析了构效关系。其中,烷基金刚烃的密度和分子结构的紧凑程度有关,取代烷基链越长,密度越低,黏度越大;烷基金刚烃碳环数越多,密度越大。燃料的冰点和分子结构对称性有关,对称度越低,冰点越低。碳氢燃料热安定性主要由分子结构中包含的碳原子的种类及数量决定,其中各种碳原子稳定性顺序为季碳原子>伯碳原子>仲碳原子>叔碳原子。因此,未来有望采用具有区域选择性的高效合成方法,将烷基定向取代于金刚烃母体的叔碳原子上,实现从叔碳原子到季碳原子的转变,提升热安定性的同时保持烷基金刚烃较高的密度,这为未来定向高通量合成高密度、高热安定烷基金刚烃燃料提供了新的思路。     

C_(10)~C_(14)烷基糖苷的合成及其作为乳化剂的应用

采用直接法合成了碳链长度为C10~C14的烷基糖苷(APG),用红外光谱对产品结构进行了表征,研究了烷基糖苷浓度及碳链长度对产品表、界面性质的影响。结果表明:随烷基糖苷浓度增大,水溶液表面张力、柴油-水界面张力降逐渐降低,而起泡性、泡沫稳定性逐渐增强。烷基糖苷碳链越长,临界胶束浓度(cmc)值越低;水溶液表面张力、柴油-水界面张力越低,起泡性、泡沫稳定性越强。基于烷基糖苷良好的表、界面性质,将其作为乳化剂制备成乳液,并与常见非离子表面活性剂OP-10制备的乳液进行了对比。烷基糖苷乳化性随浓度增大、碳链长度增长而增强;乳液微观形态表明不同碳链烷基糖苷形成乳状液稳定性、液滴均一性、填充性均优于OP-10稳定的乳液;稳定时间对乳液微观形态影响不大。所合成烷基糖苷中性能最优的为C14APG。     

Increased Emulsion Stability for Reverse Y‐Shaped Sugar‐Based Surfactants

A series of reverse Y‐shaped surfactants containing aromatic and aliphatic linkers to combine two short hydrocarbon chains and one carbohydrate head group was prepared. Liquid crystalline behavior, air–water interfacial properties, and efficiency as an emulsifier was investigated for each reverse Y‐shaped surfactant. All reverse Y‐shaped surfactants mediated higher emulsion stabilities for water‐in‐oil compared to common typical reference surfactants, reflecting an improved ability to cope with a curvature towards water. The introduction of a benzene ring into the linker substantially increased the affinity of the surfactant for hydrophobic media, resulting in improved emulsion stability for both water‐in‐oil and oil‐in‐water.     

Visible Light‐Initiated C(sp3)?Br/C(sp3)?H Functionalization of α‐Carbonyl Alkyl Bromides through Hydride Radical Shift

A new visible light‐initiated 1,5‐hydride radical shift strategy has been developed to enable the one‐step functionalization of both a C(sp³) Br bond and a C(sp³) H bond adjacent to the same carbon atom. This visible light photoredox catalysis offers a mild and straightforward access to diverse five‐membered carbocyclic ring‐fused polycyclic hydrocarbons with high turnover numbers (TONs; up to 4.93×10³) and broad substrate scope.