高分子表面活性剂对超声辐照下苯乙烯乳液聚合的影响

在超声辐照引发苯乙烯乳液聚合中加入一种新型的以羧甲基纤维素为基础的高分子表面活性剂(CMC—A9)，讨论了高分子表面活性剂对反应动力学的影响。实验表明，超声辐照下初级自由基并非由通常认为的高分子表面活性剂产生，而是十二烷基硫酸钠在超声辐照下断裂，产生自由基。通过对反应动力学的研究，发现超声辐照下乳液聚合机理不同于常规乳液聚合，聚合反应过程只有两个阶段，即加速期和减速期，不存在恒速期。加入CMC—A9高分子表面活性剂，可以在较短的时间内和较低的超声功率下达到较高的单体转化率。     

十二酰胺丙基二甲基羟乙基氯化铵与十二烷基硫酸钠水溶液的表面吸附和胶束形成

利用十二酰胺丙基二甲胺和氯乙醇反应 ,合成了十二酰胺丙基二甲基羟乙基氯化铵 (DDHA)阳离子表面活性剂 ,将其与十二烷基硫酸钠 (SDS)以不同摩尔比进行混合 ,测定了混合系统的表面张力 ,计算了单一系统和混合系统的饱和吸附量、分子最小截面积 ,表面层和胶束中 DDHA的摩尔分率及分子间相互作用参数 ,目视观察了混合系统的浑浊情况。结果表明 :在降低γcmc和 cmc方面 ,DDHA SDS混合系统有协同效应 ,表面层和胶束的组成与二组分配比有关 ,但是非对称的 ,等物质的量混合物中 ,DDHA在胶束和表面层中具有较大的摩尔分数。DDHA与 SDS在实验测定的各混合系统中都不出现混浊     

Preparation of BaMgAl10O17∶Eu2+ and Its Phase Behavior in Microemulsion System

BaMgAl10O17∶Eu2 (BAM) was prepared in the microemulsion system and its phase behavior was studied. There exists a small region in the reverse microemulsion system where the dispersed particles are of spherical form. In this way, BAM blue phosphor with good dispersion can be synthesized. The microemulsion phase diagrams of the pseudo-ternary system (Triton X-100/cosurfactant-oil-BAM brine) were first established intuitively by the dilution method. The microstructure of microemulsions was determined through eyeballing, conductance technique, and polar optical microscopy. Its phase behavior is affected by various factors, such as temperature (room temperature, 30, 40 ℃), oil, surfactants, and cosurfactants in microemulsions. According to the phase diagrams, the microemulsion system of Triton X-100/1-hexanol-hexane-BAM brine was chosen to prepare the precursor. The BAM phosphor can be obtained via sintering the precursor at a comparatively low temperature. The phosphors were characterized by XRD and vacuum ultraviolet (VUV) spectra.     

Effect of surfactants and liquid hydrocarbons on gas hydrate formation rate and storage capacity

Hydrate formation rate plays an important role in making hydrates for the storage and transport of natural gas. Micellar surfactant solutions were found to increase gas hydrate formation rate and storage capacity. With the presence of surfactant, hydrate could form quickly in a quiescent system and the energy costs of hydrate formation reduced. Surfactants (an anionic surfactant, a non‐ionic surfactant and their mixtures) and liquid hydrocarbons (cyclopentane and methylcyclohexane) were used to improve hydrate formation. The experiments of hydrate formation were carried out in the pressure range 3.69–6.82 MPa and the temperature range 274.05–277.55 K. The experimental pressures were kept constant during hydrate formation in each experimental run. The effect of anionic surfactant (sodium dodecyl sulphate (SDS)) on natural gas storage in hydrates is more pronounced compared to a non‐ionic surfactant (dodecyl polysaccharide glycoside (DPG)). The induction time of hydrate formation was reduced with the presence of cyclopentane (CP). Cyclopentane and methylcyclohexane (MCH) could increase hydrate formation rate, but reduced hydrate storage capacity The higher methylcyclohexane concentration, the lower the hydrate storage capacity. Copyright © 2003 John Wiley & Sons, Ltd.     

Photoresponsive peptide and polypeptide systems: part II. Photochromism of poly(l-ornithine) containing various azo-contents in side chains

Poly(L-ornithine)s having various azo-contents in the side chains were synthesized by the water-soluble carbodiimide procedure. The photochemical properties of the polypeptides poly[N^δ-p-(phenylazo)benzoyl-L-ornithine] (PPABLO) containing 3–77 mol% azobenzene were investigated by absorption and circular dichroism spectroscopy in hexafluoro-2-propanol (HFIP) or water, and in HFIP-water or methanol-water solvent mixtures. The photochromism of the dichroic bands of the PPABLOs containing 20–77 mol% azobenzene in the visible and ultraviolet wavelength regions was found to be mostly reversible as a function of irradiation time at different wavelengths due to the photostationary state (above 80% trans-cis photoisomerization) of the azo aromatic moieties. The PPABLO containing 3.2 mol% azobenzene in water exhibited conformational changes from random coil to helix by the addition of methanol or sodium dodecyl sulphate (SDS). The photo-induced conformational change was observed in HFIP-water-SDS solvent mixtures, while no conformational change was seen in water and HFIP-water solvent mixtures.     

Micellar polymerisation of ionic surfactants studied by conductimetry

The micellar polymerisation of ionic surfactants such as allyldodecyl-dimethylammonium bromide and 3-dodecyl-1-vinyl imidazolium iodide has been studied by conductimetry in aqueous solution. The polymerisation was carried out using two different sources of γ rays directed into solutions of surfactant above the critical micellar concentration. Conductimetry is shown to be a very good physicochemical method for analysis of these solutions. The results showed different behaviour for the two surfactants, which has highlighted a change in the structure of their aggregates which led to the assumption of an interaction between the polymers of high mass and different products of the polymerisation (oligomers, products of degradation, monomers etc.). Ultrafiltration experiments coupled with ¹H-NMR and conductivity analysis confirm these assumptions.     

降凝剂对高蜡稠油的改性效果及机理研究

实验研究了工业品原油降凝剂WHP改善含蜡56.9%、其中96.6%为正构烷烃的胜利郑王庄稠油流动性的效果。WHP含乙烯/醋酸乙烯/乙烯醇嵌段聚醚三元共聚物30%-35%。在60℃将WHP加入稠油中,测定其凝点和32℃、0-42.6 s^-1范围5个剪切速率下的黏度,均随WHP加量的增加（50-300 mg/L）而降低,200 mg/L为最佳加量,在该加量下0.32 s^-1黏度由34.16 Pa·s降至79.2 mPa·s,凝点（℃）、屈服值（Pa）、稠度系数（Pa·s^n）分别由49.0、32.42、31.57降至39.5、0.1297、0.02142,流型指数由0.1176升至0.9790。由黏温曲线求出,加入200mg/L WHP使该稠油析蜡点由65℃降至58℃,反常点由70℃降至50℃。根据空白和加剂原油扫描电镜照片显示的蜡晶形态,利用共晶机理分析讨论了WHP这种高分子表面活性剂的降凝、降黏、改善流动性的作用。图3表3参5。     

硝酸铵的膨化机理研究

膨化硝酸铵是一种自敏化改性硝酸铵,由硝酸铵溶液在专用表面活性剂作用下,经真空强制析晶工艺制得.文中研究了膨化硝酸铵制备的膨化过程和专用表面活性剂的作用,结果表明:在真空和表面活性剂作用下,硝酸铵溶液由不饱和状态至饱和状态,进而达到过饱和状态,最终导致硝酸铵的快速结晶和体系的膨胀.在真空干燥过程中,形成中心空穴、微细孔道和裂缝,它们使膨化硝酸铵的起爆感度提高;专用表面活性剂具有降低硝酸铵溶液表面张力、发泡剂和加快结晶成核的作用.     

Liquid–liquid extraction of a recombinant protein with reverse micelles

Recombinant cytochrome b₅ was extracted into the reversed micelle phase of an anionic surfactant (AOT) in octane and back-extracted to a final aqueous phase. The extraction of the protein was controlled by an electrostatic mechanism, since it was dependent on the global charge of the protein. This was directly demonstrated by experiments with native and mutant cytochromes obtained by site directed mutagenesis. The back-extraction of cytochrome b₅ to a fresh aqueous phase was decreased by factors that reduced the size of the water pool of the organic phase, such as high salt concentrations (1–2 mol dm^?3 NaCl) and low temperatures (4°C), probably because of an increase in a favourable interaction of this protein with the surfactant at closer distances.     

N,N′-二(β-十八酰氧基)乙基乙二胺二乙酸钠的合成及性能研究

用 N,N′-二羟乙基乙二胺、氯乙酸钠合成了 N,N′-二羟乙基乙二胺二乙酸钠(中间体),中间体再与硬脂酰氯反应制备了一种新型 Gemini 两性表面活性剂 N,N′-二(β-十八酰氧基)乙基乙二胺二乙酸钠。对产物合成条件进行了考察,优化的反应条件为:n(硬脂酰氯):n(中间体)=2.5,溶剂 V(水):V(氯仿)=1:2,pH=9.0～10.0,反应温度15～20℃,反应时间5 h。通过红外光谱和质谱分析确定了产物结构,并测试了产物的表面性能。结果表明,在25℃时,该产物的临界胶束浓度为0.24 mmol/L,临界胶束浓度下的表面张力为35.7 mN/m;即时泡沫高度为250 mm,5 min 后泡沫高度为220 mm;乳化时间为22.48 min(甲苯-水物系)和4.65 min(正己烷-水物系),亲水-亲油平衡值为5.4,等电点为 pH 3.3～6.5。