Kinetics and mechanisms of emulsion polymerization of vinylidene chloride. I. Effects of operating variables on the rate of polymerization and the number of polymer particles produced

Emulsion polymerization of vinylidene chloride was carried out at 50°C using sodium lauryl sulfate as emulsifier and potassium persulfate as initiator, respectively. Contrary to the results so far reported, the stirring rate did not affect the progress of the polymerization and such an abnormal kinetic behavior as the rate of polymerization suddenly drops in the course of polymerization was not observed. The number of polymer particles produced was proportional to the 0.7 power of the concentration of emulsifier forming micelles and to the 0.3 power of the initial initiator concentration, respectively, and was independent of the initial monomer concentration. The rate of polymerization was in proportion to the 0.3 power of the concentration of emulsifier forming micelles, to the 0.5 power of the initial initiator concentration, to the 0.2 power of the initial monomer concentration, and to the 0.45 power of the number of polymer particles, respectively. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1919–1928, 1998     

Influence of Electrolytes on Foaming of Sodium Lauryl Sulfate

The influence of various electrolytes on the foamability of an anionic surfactant, sodium lauryl sulfate was studied. Foamability was measured by using a recently designed method for foam testing of surfactant solutions. The results are discussed in terms of foaming efficiency and foaming effectiveness. The addition of NaCl increases foaming efficiency whereas foaming effectiveness increased only marginally. The effect of cations on foaming efficiency and foaming effectiveness increased in the order, Li⁺< Na⁺<Cs⁺. This observation is explained in terms of the hydrated size of cations which decreases as Li⁺> Na⁺> Cs⁺.     

月桂醇聚氧乙烯醚与十二烷基硫酸钠聚集行为的介观模拟

采用MesoDyn密度泛函方法研究了月桂醇聚氧乙烯醚(C12E10)与十二烷基硫酸钠体系(SDS)之间的相互作用, 模拟了它们的聚集体形成的微观动态过程以及聚集形貌的演变, 研究了剪切作用对相行为的影响. 通过二维密度切片图, 探讨了C12E10/SDS复配体系中珠子间的聚集方式. 在此基础上, 以苯、正辛醇为油污代表, 直观地比较了C12E10/SDS对这两种油污的去除机理的差异. 结果表明: 非离子表面活性剂C12E10与阴离子表面活性剂SDS之间存在很强的协同作用, 在各自浓度很低时就会有聚集行为发生. 剪切作用对体系相行为的影响在一定程度上解释了真实实验与模拟的差别原因所在. 对密度切片图的观察可得出由于所选油污结构的差异导致了复配体系对其增溶方式的差异.     

胶束反相高效液相色谱最佳化研究

本文介绍以YWG-C_(18)为固定相,十二烷基硫酸钠(SDS)胶束溶液为移动相,探讨了SDS浓度和柱温对胶束反相高效液相色谱分离最佳化的影响。测定了胶束体系中苯胺的热力学函数ΔH~0值及SDS的临界胶束浓度(C.M.C.),还讨论了非极性和极性溶质的保留机理。     

Investigations of the Effects of Salt and Biopolymer Ratio on Sodium Caseinate-Xanthan Interactions in Aqueous Solution and Emulsions

The aim of this work was to investigate interactions that can take place between, proteins and polysaccharides, in the presence of electrolytes. Thus, our objective was to study the influence of NaCl addition on the associative and/or segregative interactions in the case of biopolymer mixtures and fine emulsions stabilized by sodium caseinate, by analysis of the rheological properties and zeta potential. From the experimental results, it was shown that the presence of salt affects the rheological and physicochemical properties of the aqueous phase and consequently the emulsion stability. Indeed, the electrolytes can modify the conformation of proteins and polysaccharides, by electric neutralization of their charge, as they can generate a complex coacervation or increase their incompatibility.     

Rheological characterization of the dilatant flow behavior of highly substituted hydroxypropylmethyl- cellulose solutions in the presence of sodium lauryl sulfate

 The flow behavior of aqueous solutions of three highly substituted, hydrophobic hydroxypropylmethylcelluloses (HPMC) in mixtures containing the anionic surfactant sodium lauryl sulfate (SLS) was investigated both rheo-mechanically and rheo-optically. For the first time it was possible to demonstrate dilatant flow in these systems, a phenomenon which is otherwise only known of some suspensions and associative thickening solutions. Without addition of SLS, the aqueous HPMC solutions showed the predicted flow behavior of polymer solutions, and the Cox–Merz rule was fulfilled. With the addition of SLS to these HPMC solutions, the least hydrophobic HPMC displayed no dilatancy. The solutions of a more hydrophobic HPMC with SLS exhibited on the one hand an increase in viscosity, and on the other hand shear thinning as well as shear thickening. The most hydrophobic HPMC displayed more clearly the effects of an SLS-dependent viscosity increase and the appearance of dilatant flow. At constant HPMC concentration (0.5% w/w), a maximum increase in viscosity (factor 15) was observed in the critical micelle concentration range for SLS. By rheo-optical measurements it was possible to detect an unusually pronounced alignment of the polymer segments as well as a sharp increase in the birefringence values, even before the macroscopic occurrence of dilatant flow. According to the existing network theories, this behavior of the aqueous solutions of highly substituted HPMCs in mixture with SLS has been interpreted as a shear-induced transition from intra-molecular to intermolecular interactions. Received: 4 February 1998 Accepted: 13 March 1998     

粘度对聚合物共混物相分离动力学的影响研究

模拟了粘度反差二元流体混合物的相分离,考察了粘度对相分离动力学的影响,发现相区域的增长主要由粘度较大的组分所控制,合理地解释了粘度效应所导致的一些实验现象.证明了即使组分间的粘度比很大,也没有出现反转相结构,说明在不施加剪切流场情况下,粘度反差不是形成反转相的原因.     

基于莫高窟成盐元素相关系探究壁画盐害作用机理

壁画盐害与壁画的成盐元素种类、盐分迁徙活动以及环境气象条件等密切相关.莫高窟壁画酥碱病变的可溶盐主要为NaCl和Na2SO4,盐的结晶是破坏力的重要来源.本文运用经典溶液化学的研究方法,界定了三元体系NaCl-Na2SO4-H2O于308K,298K,288K,278K,268K的相关系,以此为基础阐释了壁画盐害的发生和发展规律,计算得到了安全含盐量和环境条件的临界数值.研究表明:NaCl的饱和溶解度对温度敏感度不大,它的结晶析出更多的是伴随着水分的蒸发而发生;Na2SO4的饱和溶解度对温度表现较为敏感,它的结晶析出,除了因溶剂水分的蒸发而发生发展之外,还将因温度的降低而产生,他们各自在壁画盐害的发生发展过程中有一定的行为差异,其主导作用的交替点大致在wNa2SO4 /w NaCl=1:3～6左右,即当该体系中Na2SO4的质量比约达30%～15%时,Na2SO4将成为壁画盐害随洞窟温度变化而发生的主导诱因.三元体系NaCl-Na2SO4-H2O中NaCl和Na2SO4在5～35℃的介稳饱和溶解度的测定,取得了与相图相一致的结果.NaCl结晶物质地坚硬、粒度均匀,在壁画盐害表现形式上应以点状疱疹为主;Na2SO4结晶物主要以十水硫酸钠Na2SO4·10H2O的形式析出,质地疏松,易风化,易返潮,所导致的壁画酥碱病变有一定的反复性.Na2SO4的过饱和溶解度大,易富集,易浓缩,结晶区域较大,相应破坏面也较大,在壁画盐害的表现形式应以粉状酥碱为主,如壁画较大面积的空鼓、地仗层酥松等.     

刚果红-溴化十六烷基吡啶光度法测定阴离子表面活性剂

日常生活中常用的表面活性剂多数是阴离子洗涤剂.洗涤剂进入水环境后,其分子聚集在水和其它介质的表面,产生泡沫、乳化和微粒悬浮等现象,隔绝水中氧与空气中氧的交换,影响水体净化,导致水质恶化,由此对水体的环境污染问题越来越严重,引起了人们的重视.因此, 准确快速地测定阴离子表面活性剂的含量, 对于研究其在环境中的转化、迁移及对生理过程的影响, 均具有重要意义.     

混合表面活性剂的表面活性及加溶能力

阴阳离子混合表面活性剂具有很高的表面活性［1］，但该类表面活性剂的浓度超过临界胶团浓度（cmc）以后，就将沉淀而失去表面活性［2］．因此，对该类体系的研究，主要在cmc以下．曾作过许多努力，希望解决阴阳离子混合表面活性剂的沉淀（或分层）问题，但效果均不理想［3，4］．直到最近，在这方面的研究才取得明显的进展，找到了在水溶液中，任何浓度和混合比之下，都不沉淀或分层的一类阴阳离子混合表面活性剂［4］．本文在此基础上，研究了该类表面活性剂的表面活性及其对戊醇和乙烷的加溶，该方面的研究工作，在国内外尚属首次，这对…     

微乳体系相图及其在液相色谱分离多组分药物应用的研究

采用滴加法和电导率法绘制了十二烷基硫酸钠(SDS)/正丁醇/油相(正辛醇、正辛烷、正庚烷、正己烷)/水四组分微乳体系的拟三元相图。以O/W型微乳区域大小为指标,考察不同油相、表面活性剂与助表面活性剂的质量比对微乳形成的影响,并通过测定电导率、相对粘度以及表面张力等物理化学参数,考察了微乳体系的相行为及特性。根据得到的微乳体系相图,进行色谱条件优化,建立了快速、稳定的测定阿莫西林舒巴坦匹酯片剂中阿莫西林与舒巴坦匹酯二组分含量的方法,结果显示此微乳分离系统有较好的色谱适用性及方法可行性。     

Salt influence in the polymer-surfactant interaction in solution. A fluorescence probe investigation of the EHEC/SDS/ water system

 The effect of small amounts of salt on the interaction between two fractions of ethyl(hydroxy)ethyl cellulose, EHEC, and sodium dodecyl sulfate, SDS, has been investigated by means of steady-state fluorescence measurements. The two polymer fractions display different properties in hydrophobicity expressed as different cloud points. The results are discussed in relation to hydrodynamic (viscosity) and thermodynamic (equilibrium dialysis) properties. The micropolarity as sensed by the probe pyrene shows that the polymers begin to interact with SDS at a lower concentration in the presence of salt. The average aggregation numbers of polymer-bound clusters, N _p, were obtained by fluorescence-quenching data in combination with equilibrium dialysis experiments. N _p was found to increase in the presence of salt for the EHEC fraction with a high cloud point (CP). The polymer with a low CP displays higher N _p in the presence of salt at low SDS concentrations, but exhibit lower N _p at higher SDS concentrations than in the salt-free system. The microviscosity index as determined by intramolecular excimer formation of 1, 3-di(1-pyrenyl)propane (P3P) is highest for the lowest N _p and there is a corre-lation with N _p in the presence as well as absence of salt for both EHEC fractions. It is found that when the same fractional amount of SDS is bound to the polymers, 10–20% of the value of saturation, the increase in macroviscosity occurs and the microviscosity shows high rigidity. Received: 3 March 1997 Accepted: 23 May 1997     

脂肪酸盐-烷基吡啶盐混合体系的双水相

研究了脂肪酸盐和烷基吡啶盐混合水溶液中双水相的形成规律和性质．考察了形成双水相的组成范围和烷基碳链长的影响。测定了两相的密度及化学组成．应用电子显微镜观察了两相的微观结构．结果表明,两相均存在囊泡结构．两相含水均在95％以上．上相为表面活性剂富集的囊泡絮凝相,浓度远远大干下相,相差均在二十倍以上．下相为含有分散的囊泡的表面活性剂稀溶液．     

Thermodynamics of electrolytes. Binary mixtures formed from aqueous NaCl,Na2SO4, CuCl2, and CuSO4, at 25°C

Osmotic coefficients to high ionic strengths are reported for five of the binary mixtures formed from NaCl, Na₂SO₄, CuCl₂, and CuSO₄; the sixth system studied, NaCl–Na₂SO₄, is one studied by Wu, Rush, and Scatchard. The equations recently developed by Pitzer are used successfully in the interpretation of the experimental results. Revised values are given for the activity and osmotic coefficients for pure CuSO₄ and CuCl₂ solutions.     

A novel RP-HPLC refractive index detector method development and validation for determination of trace-level alcohols (un-sulfated) in sodium lauryl sulfate raw material

The main aim of the study is to develop and validate a simple and rapid liquid chromatographic analytical method for simultaneous determination of trace level of un-sulfated alcohol impurities in sodium lauryl sulfate using high-performance liquid chromatography with a refractive index detector. The chromatographic separation was achieved using flow rate of 3.0 ml/min with a Waters Symmetry C₁₈ (150 × 4.6 mm, 5 μm) column and 50°C as a column temperature. The mobile phase comprised milliQ water and acetonitrile in the ratio of 30:70 v/v respectively. The detection was performed using a refractive index detector at a sensitivity of 64. The resolutions among n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, and n-heptadecanol were found to be >4. Regression analysis showed a correlation coefficient for the stated compounds of >0.999. The validated HPLC method was utilized effectively for the estimation of un-sulfated alcohols in quality control labs for commercial release of sodium lauryl sulfate.     

乙基曙红-溴化十六烷基吡啶光度法测定水样中阴离子表面活性剂

在弱酸性的HAC-NaAC缓冲介质中,将溴化十六烷基吡啶(CPB)与乙基曙红(EE)染料溶液混合,加入阴离子表面活性剂(AS),溶液颜色加深,最大吸收波长都在516nm处,且阴离子表面活性剂的浓度与溶液的增色程度呈良好线性关系。在最大吸收波长处,3种阴离子表面活性剂——十二烷基苯磺酸钠(SDBS)、十二烷基磺酸钠(SLS)及十二烷基硫酸钠(SDS)的浓度分别在0~2.05×10-5mol/L、0~2.08×10-5mol/L、0~2.04×10-5mol/L范围内遵守比尔定律,表观摩尔吸光系数分别为2.38×104、2.82×104和2.98×104L/(mol.cm),检出限分别为8.42×10-7、4.56×10-7和7.95×10-7mol/L。方法具有较高的灵敏度和良好的选择性,用于不同水样中AS的测定,结果满意。     

30%亚硫酸氢钠溶液样品中Cl~-和SO_4~(2-)的同时测定

建立了采用离子色谱测定 30%亚硫酸氢钠溶液样品中的氯化钠和硫酸钠含量的新方法。采用IonPacAS14分析柱,选择三乙醇胺为亚硫酸氢钠的稳定剂,以丙酮为有机改进剂,淋洗液组成为 1 5mol/LNa2CO3 3 5mol/LNaHCO3 10% (体积分数) (CH3 )2CO,流速为 1 0mL/min,抑制电导检测。实验结果表明,氯离子、硫酸根离子分别在 0.05~1.5mg/L,0.20~15mg/L时,其峰面积与质量浓度呈线性关系,相关系数均大于 0.999,检出限分别为0 01mg/L和 0 03mg/L。该法用于实际样品分析,操作便捷,结果可靠。     

Kinetics of the acid hydrolysis of isoproturon in the absence and presence of sodium lauryl sulfate micelles

Kinetics of the hydrolysis of isoproturon by hydrochloric acid has been studied spectrophotometrically in the absence and the presence of anionic sodium lauryl sulfate (NaLS) micelles. The anionic micelle was found to increase the rate of reaction. The reaction followed first-order kinetics with respect to isoproturon and was linearly dependent upon [HCl]. In both aqueous and micellar pseudophases, the reaction was started with the protonation of the amino group of isoproturon followed by attack of water to yield phenylcarbamic acid and the corresponding amine, thus obeying the addition–elimination mechanism. The surfactant decreased the activation entropy. The binding constant in consistence with the rate constants was evaluated on the basis of pseudophase ion-exchange model. The added salts (NaCl and KCl) decreased the rate of reaction due to the exclusion of H⁺ from micellar surfaces.     

以粗盐为原料提纯氯化钠的问题探讨

为培养学生的创新性思维和实验探究能力,师生共同探讨“以粗盐为原料提纯氯化钠”实验的几个问题。分离和提纯物质都是除掉杂质吗?煅炒粗盐时,为什么会发生轻微的爆炸现象?沉淀法除去SO42-、Ca2+等杂质时,盐水一定要煮沸吗?为除去过量的Na2CO3,溶液的pH应该控制在什么范围?