叠氮二异丁基铝及其配合物的制备与表征

通过三异丁基铝和四氯化碳反应制得氯化二异丁基铝。在芳烃溶液中，氯化二异丁基铝进一步和叠氮化钠反应合成了新化合物叠氮二异丁基铝（DBAA），以四氢呋喃为溶剂，合成DBAA时则得到了新化合物叠氮二异丁基铝和四氢呋喃的配合物（DBAA．THF）。用红外光谱、核磁共振谱等技术对这两个化合物的结构进行了表征；研究讨论了这些化合物的性质。     

Enhancement of methane hydrate formation using a mixture of tetrahydrofuran and oxidized multi‐wall carbon nanotubes

Methane hydrate is a kind of gas hydrate formed by physical binding between water molecules and methane gas, which is captured in the cavities of water molecules under a specific temperature and pressure. Pure methane hydrate of 1 m³ can be decomposed into methane gas of 172 m³ and water of 0.8 m³ at standard conditions. Methane hydrate has many practical applications such as separation processes, natural gas storage transportation, and carbon dioxide sequestration. For the industrial utilization of this substance, it is essential to find a rapid method of manufacturing it. This work studies the formation of methane hydrates by using tetrahydrofuran (THF) and oxidized carbon nanotubes (OMWCNTs) by testing different fluid mixtures of THF and carbon nanotubes. The results show that when the mixed fluid contained THF, the OMWCNTs showed the gas consumption 5.2 times that of distilled water at 3.4 K subcooling. Also, THF's effects as a thermodynamic phase equilibrium promoter were preserved when it was used with OMWCNTs. Therefore, it can be expected that when OMWCNTs are used with an aqueous mixture of THF, both the favorable phase equilibrium of THF and the high gas consumption of the carbon nanotubes can be obtained. Copyright © 2013 John Wiley & Sons, Ltd.     

用于深水钻井的水合物抑制剂HBH的研制及评价

在深水钻井过程中如钻遇含气地层,地层气窜入井眼或在环空的钻井液中,形成水合物,堵塞井眼、环空或防喷器,严重影响钻井工作的正常进行.介绍了水合物抑制剂HBH的合成工艺,对其水合物抑制性及与其它处理剂的配伍性进行了室内评价.结果表明,加入少量水合物抑制剂HBH于钻井液(约为0.5%)中即能有效地抑制水合物的生成;低分子量的聚乙二醇具有一定的润滑性和防塌性,同时对天然气水合物有较好的抑制性;HBH与低分子量的聚乙二醇PEG600按一定比例(1∶3)复配使用,抑制性能更佳,复配使用时的BST值比二者单独加入时的BST值要大几倍.     

废纸脱墨浆生产线典型部位的浆料中细小组分所含黏性物质的分布调查和特性研究

对于脱墨浆生产线典型部位（热分散后、后浮选后和成浆池）取样分离的细小组分,采用四氢呋喃（THF）进行抽提。研究结果表明：从卸料塔到流浆箱,浆料中细小组分的THF抽出物降低了约35%。THF抽出物的傅里叶变换红外光谱（FTIR）分析表明：黏性物质中存在的成分包括饱和脂肪酸酯、聚醋酸乙烯类物质、丙烯酸类物质、含有Si—O键的有机硅化合物,以及少量的苯环邻位二取代物。将上述试样及成纸的THF抽出物进行气相色谱-质谱（GC-MS）分析,检测出的物质亦可归类于合成黏合剂成分、木材抽出物成分和木质素降解产物。可以看出,黏合剂类物质是细小组分THF抽出物的主要成分。     

Oxidation reactions of steryl esters in a saturated lipid matrix

In the present study, the formation and further reactions of intact steryl ester hydroperoxides were followed in a tripalmitin matrix maintained at 100 °C. The effects of the acyl moiety and its unsaturation degree, and of the sterol structure were investigated. Intact steryl ester hydroperoxides were isolated from the lipid matrix by a developed solid-phase extraction (SPE) method and were determined by HPLC–ELSD. Further reactions of hydroperoxides were followed by determining secondary oxidation products of sterol by GC-FID/MS and oligomers by HPSEC-RI. The oxidation of sterol decreased when its solubility in the lipid medium was increased by introduction of acyl moiety. Increased unsaturation of the acyl or steryl moiety of steryl ester shortened the induction period and increased the oxidation of both steryl and acyl moieties. Thus, by changing the chemical and physical properties of sterols, their oxidation may be greatly affected.     

水逸度模型预测THF添加剂体系下气体水合物相平衡

加入添加剂降低水合物生成压力是当前水合物法分离混合气体研究热点。本研究以水的逸度模型为基础, 结合PRSV2 状态方程研究了CH₄、O₂、N₂ 及其混合气体水合物在纯水体系下的相平衡条件;通过UNIFAC 基团 贡献法对添加剂四氢呋喃(THF)水溶液进行基团划分,计算该体系下液相各组分的活度,理论研究了添加剂 THF 对气体水合物相平衡条件的影响;结果表明在相应的温度范围内,与其他模型相比,在纯水体系下该模型 预测精度较高,在THF 水溶液体系下该模型对单组分和双组分气体的预测精度平均相对误差在7%左右,随着 THF 浓度增加,气体水合物相平衡压力的降低幅度减小;当THF 摩尔分数达到6%时,对气体水合物相平衡影 响达到最大。相关研究结果为混合气体的大规模工业提纯分离提供了理论基础。     

从废四氢呋喃制备环丙基甲酸

在格氏反应生产过程中，会产生大量的回收四氢呋喃，因含水量高不能再用。该四氢呋喃通过用氯化氢气体开环（以无水氯化锌作催化剂）得到4－氯丁醇－1，经浓硝酸氧化得到4－Chlorobutyric acid，与sec-butanol缩合得到sec-Butyl-4-chlorobutyric，该酯在强碱条件下用CH2Cl2作溶剂环合得到sec-Butylcyclopanecarboxxylate，该酯在甲醇溶液中碱性水解得到环丙基甲酸，总收率49％（以THF计）。     

四氢呋喃生产工艺技术比较

四氢呋喃（THF）是一种重要的有机化工及精细化工原料,用途十分广泛。目前其生产工艺技术主要包括糠醛法、Reppe法、丁二烯法、顺酐加氢法。介绍了THF性质、用途和主要生产工艺技术,并对4种主要生产工艺技术进行了比较。     

四丁基溴化铵-四氢呋喃系蓄冷水合物

基于二元工质水合物相对单一工质水合物在蓄冷特性方面的优越性,在水合物客体组分总质量分数为31.4%的条件下,实验研究了四丁基溴化铵(TBAB)-四氢呋喃(THF)混合水合物蓄冷特性. 通过改变TBAB-THF组分配比,考察了水合物的诱导时间、近似相变温度、蓄冷面积及释冷面积的变化. 结果表明,TBAB-THF系中TBAB浓度减少使诱导时间增长、温度突变点降低、近似相变温度降低,从而减小了水合物在生长阶段的蓄冷面积,缩短了分解阶段的分解完成时间;TBAB浓度在25.7%~27.4%时,相变温度在6.3~8.0℃之间,与空调冷冻水相近,且释冷面积相对其他浓度较高,可作为蓄冷空调的良好介质.     

Electrosynthesis and properties of poly(3,4-ethylenedioxythiophene) films functionalized with titanocene dichloride complex

Synthesis of a titanocene dichloride derivative functionalized with 3,4-etylenedioxythiophene group, Tc1EDOT (Cl₂TiCpC₅H₄(CH₂) (3,4-ethylenedioxythiophene)) has been described. Redox behavior of the monomer in tetrahydrofuran (THF), dichloromethane (DCM) and acetonitrile (AN) at different scan rates has been discussed in terms of different ability of these solvents to coordination with the reduced titanocene (Tc) complex and the solvation of Cl⁻ anions. Electrooxidation of Tc1EDOT to get a conducting polymer film with immobilized titanocene dichloride centers and electrochemical properties of its polymer matrix in background acetonitrile solution have been compared with those of non-substituted PEDOT and PEDOT-methanol derivative (PEDOTMet), to elucidate the effect of substituents both on polymerization and redox potentials of the matrix. STM and AFM images of p(Tc1EDOT) films obtained with potentiodynamic and potentiostatic regimes are compared to illustrate that the films deposited at constant potential are better ordered and more compact than those obtained by cyclic voltammetry. A comparison of the cyclic voltammograms of p(Tc1EDOT) and poly(titanocene-propyl-pyrrole) (p(Tc3Py)) films in 0.1 TBAPF₆ in THF has shown that the electroactivity of the polymer matrix of p(Tc1EDOT) is extended to more negative potentials in comparison to that of p(Tc3Py). This results in the anodic shift of redox potential of Tc centers immobilized in p(Tc1EDOT) film with respect to that of the centers fixed in p(Tc3Py).