全氟辛酸钠与三甲胺及三乙胺盐酸盐混合体系的表面活性

测定了全氟辛酸钠－三甲胺盐酸盐及三乙胺盐酸盐混合水溶液的表面张力,自表面张力曲线研究了混合体系的表面活性。结果表明,无表面活性的有机铵盐的加入,可大大提高全氟酸钠的表面活性,对此类混合体系的表面吸附计算及胶团形成结果进行了分析、讨论。     

电喷雾质谱法研究不同碳链长度的全氟羧酸与肌红蛋白的相互作用

采用电喷雾质谱法(ESI-MS)检测了全氟丁酸、全氟己酸、全氟辛酸和全氟癸酸分别与肌红蛋白的相互作用,通过直接计算法测定了4种全氟羧酸与肌红蛋白的结合常数,并研究了碳链长度对全氟羧酸类化合物与肌红蛋白相互作用的影响。结果表明,不同碳链长度的全氟羧酸类化合物与肌红蛋白相互作用的能力有差别,碳链越长,其结合能力越强,且与蛋白质结合的配体数目越多。     

废水中全氟辛酸及全氟辛磺酰基化合物的气相色谱法

建立操作简便、快速测定废水中全氟辛酸及全氟辛磺酰基化合物的气相色谱法。样品经液液萃取、衍生,μ-ECD检测器检测、外标法定量。结果表明,用本法测定废水中的PFOA和PFOS的残留量,加标回收率都在80%以上,其相对标准偏差在7.9%以下,PFOA的定量限为0.25μg/L,PFOS的定量限为0.12μg/L。由此可见本法准确可行、前处理简便、适用于工厂批量废水的测定。     

对全氟壬烯氧基苯磺酸钠的合成与表面活性

以全氟壬烯、苯酚和氯磺酸为主要原料,经醚化、磺化和中和反应制备对全氟壬烯氧基苯磺酸表面活性剂,用红外光谱和19FNMR,1HNMR对分子结构进行了表征。研究了醚化反应投料方式对全氟壬烯基苯酚醚收率的影响,氯磺酸和全氟壬烯基苯酚醚的配比以及反应时间对磺化反应收率的影响。结果显示,向苯酚、三乙胺和二甲基甲酰胺(DMF)的混合物中滴加全氟壬烯,比向全氟壬烯、苯酚和二甲基甲酰胺的混合物中滴加三乙胺,醚化反应收率高17%。氯磺酸和全氟壬烯基苯酚醚的摩尔比为3∶1,40℃反应2h,磺化反应收率67.6%。表面活性的测定结果表明,对全氟壬烯氧基苯磺酸钠表面活性剂的临界胶束浓度为1.28×10-3mol/L,γcmc为19.23mN/m(20℃)。对全氟壬烯氧基苯磺酸钠表面活性剂性能优良。     

全氟辛烷磺酸/全氟辛酸替代物——新型含氟表面活性剂的研究进展

全氟辛烷磺酸/全氟辛酸(PFOA/PFOS)由于存在有争议的环境污染和生物蓄积等问题,已经成为全世界关注的焦点之一,寻找能够替代PFOA/PFOS的新型含氟表面活性剂具有重要的意义.本文综述了可能替代PFOA/PFOS新型含氟表面活性剂的合成路线和方法,并按照分子结构进行了分类,着重介绍了以下4类:①端基为CF₃O或(CF₃)₂N系列表面活性剂;②短氟链系列表面活性剂;③基于VDF或TFP系列表面活性剂;④全氟聚醚系列表面活性剂;同时对4类新型替代物的表面活性、生物降解性及在乳液聚合中的应用进行了归纳总结.目前PFOA/PFOS替代物的研究趋势,主要朝着降低含氟表面活性剂中氟元素比例、含减少氟链“有效长度”及插入N、O等杂原子等方向发展,使得新型含氟表活性剂更易降解、更环保、更安全.     

全氟辛酸的工业化环保及利用

对氟化工行业的PFOA环保问题、工业化消除及替代品开发进行详细的综述,并对PFOA解决方案进行了综合评估。     

全氟化合物改性分子印迹TiO2纳米管对全氟辛酸光催化性能研究

以全氟化合物的增效和选择性去除为目标,制备了全氟化合物改性分子印迹TiO2纳米管,通过降解实验研究了材料对全氟辛酸的光催化降解性能、脱氟性能和选择性,结果表明材料具有出色的催化性能、脱氟性能和选择性.     

全氟碳涂料树脂四元共聚物的研究

介绍合成全氟碳涂料树脂用单体 ;讨论了合成单体的最佳工艺条件 ,并探索了聚合工艺。     

全氟羧酸酯乙烯基醚的合成研究

全氟羧酸酯乙烯基醚用于多种含氟聚合物的改性,合成全氟羧酸离子交换树脂等高性能含氟聚合物,也可以合成含氟醚类的绿色可降解表面活性剂。采用3-羧酸甲酯全氟丙酰氟与六氟环氧丙烷进行加成反应,然后脱羧制备全氟羧酸酯乙烯基醚。     

光氧化法制备全氟聚醚酸工艺研究

以四氟乙烯为原料,通过紫外光引发,氧气氧化并聚合制备全氟聚醚化合物,然后经过KOH水溶液中和、分解过氧化物、酸析、精馏得到全氟聚醚酸,分析了光氧化制备全氟聚醚化合物的工艺条件和参数对收率和化合物组分分布的影响,检测了全氟聚醚酸的主要性质。结果表明,选择-40℃光化反应温度,紫外灯功率50 W、紫外光波长254 nm,精馏压力-98 kPa,并加入少量的CF2O,可以将主要产物相对分子质量控制在2 000以下,并保持较高的TFE转化率;在加热至100℃和150 W、254 nm紫外灯照射条件下,分解过氧化物得到稳定的全氟聚醚酸;所得全氟聚醚酸具有较低的粘度,其铵盐水溶液表面张力可以降低至17～18 nm/m2,具有很好的表面性能。     

Synthesis and surface activity of sodium salts of branched perfluorocarboxylic acids and their analogs containing one chlorine atom

Individual sodium salts of branched perfluorocarboxylic acids, (CF₃)₂CF(CF₂CF₂)_nCOONa, and their analogs containing one chlorine atom, CF₃CF(CF₂CI)(CF₂CF₂)_nCOONa, were synthesized by telomerization of 2-iodoheptafluoropropane and l-chloro-2-iodohexafluoropropane with tetrafluoroethene, the addition of ethylene to both types of iodides considered, HI elimination and the oxidation of perfluoroalkylethylenes with potassium bichromate. The surface tension measurements demonstrated the high surface activity of sodium salts containing 9 and 11 carbon atoms in the hydrophobe. Perfluorocompounds were more surface active than their analogs having one chlorine atom but the differences were not great.     

The effect of carboxylic acids and phosphate salts additives on the properties of chondroitin sulfate calcium phosphate cements

The use of liquid phase additives is a strategy to improve the physicochemical, mechanical, and biological properties of calcium phosphate cements. In this study, TTCP and α-TCP particles were synthesized using the solid-state reaction method. Apatite cements were prepared by mixing TTCP/DCPD/α-TCP powders and liquid phases containing chondroitin sulfate with various additives of carboxylic acids and phosphate salts. The formation of hydroxyapatite and consumption of raw materials as well as the acceleration and deceleration periods through cementation process were investigated by XRD and DSC experiments, respectively. In addition, the morphology, setting time, porosity, compressive strength, degradation, in-vitro bioactivity and cytotoxicity were studied. The results showed that the approximate amount of hydroxyapatite resulting from the cementation process was divergent in the presence of liquid phase additives. The use of phosphate salt additives presented better results compared to carboxylic acid ones regarding hydroxyapatite cement product formation, compressive strength, hardening, setting, and cytotoxicity. All cements showed, generally a similar tendency to form dense hydroxyapatite on their outer surfaces through immersion in the simulated body fluid. The cement containing Na₂HPO₄ salt exhibited the lowest cytotoxicity and highest strength. The ALP assay and the morphological behavior of MG63 cells indicated the good activity and proper cell adhesion of this cement.     

Studies on polyurethanes and polyurethane–ureas derived from divalent metal salts of mono(hydroxybutyl) hexolate

Divalent metal salts of mono(hydroxybutyl)hexolate [M(HBH)₂), M=Ca²⁺, Mn²⁺or Pb²⁺] were synthesized by the reaction of 1,4‐butanediol, 5,6,7,8,10,10‐hexachloro‐3a,4,4a,5,8,8a,9,9a‐octahydro‐5,8‐methanonaphtho‐[2,3‐C]‐furan‐1,3‐dione and divalent metal acetates. Hexamethylene bis [N′‐(1‐hydroxy‐2‐methyl‐prop‐2‐yl)urea] (HBHMPU) and tolylene 2,4‐bis[N ′‐(1‐hydroxy‐2‐methyl‐prop‐2‐yl)urea] (TBHMPU) were synthesized by reacting 2‐amino‐2‐methyl‐propan‐1‐ol with hexamethylene diisocyanate (HMDI) and tolylene 2,4‐diisocyanate (TDI), respectively, in toluene solvent. Flame‐retardant metal‐containing polyurethanes were synthesized by the solution polymerization of HMDI with M(HBH)₂ and the polyurethane–ureas by reacting HMDI with 1:1 mixture of M(HBH)₂ and HBHMPU or TBHMPU, respectively, in DMSO as solvent. The polymers have been characterized by elemental analysis, solubility, viscosity and IR and ¹H NMR spectroscopy. The thermal stability of the polymers has been studied by thermogravimetry. The flame‐retardant property of the polymers has been investigated by measuring limiting oxygen index values. © 2000 Society of Chemical Industry     

Rate and mechanism of divalent metal transport through supported liquid membrane containing di(2-ethylhexyl) phosphoric acid as a mobile carrier

The rate and mechanism of copper, cobalt, nickel and zinc transport through a supported liquid membrane containing di(2-ethylhexyl) phosphoric acid as a mobile carrier were studied, respectively. The permeation rate equations have been derived taking into account aqueous film diffusion, interfacial chemical reaction and membrane diffusion as simultaneous controlling steps. The possible rate-controlling steps were estimated by comparing the relative values of the three successive resistances. The measured permeation rates of zinc agreed well with the proposed mechanism in this study.     

Dehydration of carboxylic acids on the MgO(100) surface

The interaction of formic and acetic acids with the MgO(100) surface has been studied under UHV conditions using XPS and TPD. Both acids dissociated heterolytically on the MgO surface, forming surface formate and acetate species respectively. The carboxylates decomposed at 520 K into dehydration products H₂O + CO from HCOO, and H₂O+CH₂CO from CH₃COOH.     

烷基苯磺酸盐Gemini的合成与性能

以十二烷基苯、二氯甲烷、1,2-二氯乙烷、三乙醇胺、NaOH等为原料,经傅-克烷基化反应、磺化及中和反应,合成出4种不同结构的烷基苯磺酸盐Gemini表面活性剂异构体,用FTIR和 1H NMR鉴定了中间产品的结构,用滴体积法测定表面活性剂水溶液25℃时的表面张力,确定了临界胶束浓度（CMC）,并对其在乳液聚合中的应用做了研究。结果表明增加侧链烷基或桥链基碳原子的个数,表面活性剂的CMC和γCMC减小,三乙醇胺中和形成的烷基苯磺酸盐表面张力值最小;随着乳化剂浓度增加,乳胶粒子平均粒径减小,平衡时间缩短,转化率提高。     

Densities and surface tensions of ionic liquids/sulfuric acid binary mixtures

The densities and surface tensions of [Bmim][TFO]/H_2SO_4, [Hmim][TFO]/H_2SO_4 and [Omim][TFO]/H_2SO_4 binary mixtures were measured by pycnometer and Wilhelmy plate method respectively. The results show that densities and surface tensions of the mixtures decreased monotonously with increasing temperatures and increasing ionic liquid(IL) molar fraction. IL with longer alkyl side-chain length brings a lower density and a smaller surface tension to the ILs/H_2SO_4 binary mixtures. The densities and surface tensions of the mixtures are fitted well by Jouyban–Acree(JAM) model and LWW model respectively. Redlich-Kister(R–K) equation and modified Redlich-Kister(R–K) equation describe the excess molar volumes and excess surface tensions of the mixtures well respectively. Adding a small amount of ILs(xILb 0.1) into sulfuric acid brings an obvious decrease to the density and the surface tension. The results imply that the densities and surface tensions of ILs/H_2SO_4 binary mixtures can be modulated by changing the IL dosage or tailoring the IL structure.     

On the prediction of surface tension for multicomponent mixtures

A prediction method for surface tension of real mixtures was developed based on the Davis theory, and tested with the molecular dynamics simulation results of Mecke et al. (1997) for surface tension of the Lennard‐Jones fluid. An effective Lennard‐Jones potential was introduced for correlating surface tension for real pure liquids and binary liquid mixtures, leading to prediction of surface tension of multicomponent systems, including aqueous mixtures. The overall average absolute percentage deviations (AAPD) obtained in the correlated results for 62 pure liquids, 91 non‐aqueous and 11 aqueous binaries are 0.66, 0.80, and 1.75, respectively. In the prediction of the surface tension for 9 ternary and 4 quaternary systems, using the molecular parameters of pure liquids and the adjustable binary parameters, the overall AAPDs are 1.75 and 1.03, respectively.     

Adhesives from divalent metal salts of mono(hydroxyethyl)phthalate,anhydrides, and bisepoxides

Systems of divalent metal salts of mono(ydroxyethyl)phthalate-anhydride-bisepoxide were evaluated as adhesives. The bisepoxides, bisphenol A diglycidyl ether (BADG) and hexahydrophthalic acid diglycidyl ester and the anhydrides, maleic anhydride and hexahydrophthalic anhydride (HPA) were used. The adhesive properties of the above metal-containing systems were generally superior to those of the systems not containing metal, due to the polarity effect of metal carboxylate groups. The effect of introducing metal (ionic links) on tensile shear and peel strenghths clearly appeared, especially in the metal salt-HPA-BADG systems.     

Surface activity of mixtures of oxyethylated methyl dodecanoate and sodium dodecylbenzenesulfonate

Surface and interfacial tension and detergency of mixtures containing oxyethylated methyl dodecanoate and sodium dodecylbenzenesulfonate were determined. Synergism in the surface tension reduction was not observed. The competition for adsorption at the air/water interface between oxyethylated methyl dodecanoate and sodium dodecylbenzenesulfonate depended on the considered surface tension, the weight ratio of surfactants in the aqueous phase, and the hydrophile-lipophile balance of the nonionic surfactant. Generally, coverage of the interface with oxyethylated methyl dodecanoate increased when surface tension decreased. Nonionics were the dominant species at the interface in the important region of surface activity, i.e., for surface tensions below 40 mN m⁻¹. The mole fraction of the hydrophobic nonionic at the interface was higher than the contribution of hydrophilic oxyethylates. An increase of the surfactant ratio in the bulk phase affects the interfacial ratio of surfactants in the same way. The lowest interfacial tension (1.5 mN m⁻¹) at the hexadecane/water interface was observed for oxyethylated methyl dodecanoate having an average degree of oxyethylation equal to 8 and 10. Nearly 5 min was needed to achieve equilibrium value. Mixtures with sodium dodecylbenzenesulfonate decreased the interfacial tension somewhat less efficiently but the equilibrium was rapidly established. The standard washing powders containing oxyethylated methyl dodecanoates exhibited washing ability similar to that obtained for the powder with traditional alcohol oxyethylate.