疏水化水溶性两性纤维素接枝共聚物与粘土的相互作用

运用紫外光谱法研究了疏水化水溶性两性纤维素接枝共聚物(羧甲基纤维素接枝丙烯酰胺及N,N 二甲基辛基(2 甲基丙烯酰氧乙基)溴化铵的共聚物, CGAO)在粘土上的吸附,考察了聚合物浓度、无机盐浓度、温度、 pH、 表面活性剂和粘土浓度等因素对CGAO在粘土上吸附量的影响,以及通过X射线衍射分析了CGAO在粘土上的吸附位置.结果表明， CGAO在粘土上的吸附规律与一般聚合物有很大差别,而且CGAO未深入到粘土晶层间,只在其表面吸附. 粘土与CGAO作用前后的粒度分析表明CGAO对粘土粒子有很好的桥接聚集作用. 扫描电镜分析显示粘土与CGAO作用后,其颗粒形态发生了显著变化.     

表面活性剂对海藻酸钠稀水溶液剪切粘度的影响

通过粘度法考察了不同pH值时, 阴离子聚电解质海藻酸钠(NaAlg)与阴离子表面活性剂十二烷基硫酸钠(SDS)、阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)、非离子表面活性剂辛基酚聚氧乙烯醚(TritonX-100)以及它们的复配体系的相互作用. 研究表明, 在酸性条件下, SDS和TritonX-100与NaAlg之间主要是疏水作用, 随着表面活性剂浓度的增加, 体系粘度下降直到基本不变, CTAB与NaAlg主要发生静电作用和疏水作用, 体系粘度随CTAB浓度的增加呈现先上升后下降的趋势. 在实验条件下, TritonX-100浓度为0.05 mmol·L-1时, SDS的加入, 使得NaAlg/TritonX-100体系的零剪切粘度下降, 而CTAB的加入, 在pH=3.0和5.0时, NaAlg/TritonX-100体系的零剪切粘度出现上升, 在pH=6.4时, 该体系零剪切粘度下降.     

新型疏水缔合聚合物P(AM/POEA)与表面活性剂的相互作用

采用粘度法、荧光探针和透射电镜研究了新型疏水缔合聚合物P(AM/POEA)和表面活性剂SDS和CTAB在水溶液中的相互作用. 聚合物P(AM/POEA)结构中, 疏水体(2-苯氧乙基丙烯酸酯)呈嵌段状无序地分布在聚丙烯酰胺主链上. 这类聚合物很容易和表面活性剂相互作用, 通过疏水缔合, 形成混合胶束状聚集体, 导致溶液粘度剧增. 随聚合物溶液中SDS的加入, 溶液粘度发生大幅度起伏变化, 出现最大值. 粘度最大值对应的表面活性剂浓度c_S,max位于表面活性剂CMC附近, 并发现它的位置不随聚合物微结构而变化. 然而它们缔合作用的增粘程度却与聚合物疏水体含量X_H及疏水嵌段尺寸N_H有关. 在实验浓度范围内, X_H和N_H愈大, 溶液的粘度越高. 此外用透射电镜直接观察到聚合物/表面活性剂体系中聚集体的交联结构形貌.     

树枝聚醚改性聚丙烯酰胺和阴离子表面活性剂的缔合行为

采用粘度法、荧光探针技术和^1H NMR驰豫和自扩散方法，研究了树枝聚醚疏 水改性丙烯酰胺共聚物(PDAM)和十二烷基硫酸钠(SDS)在水溶液中的相互作用．这 种共聚物含有少量的树枝聚醚，具有疏水性，容易和SDS发生相互作用，在表面活 性剂浓度远低于临界胶束浓度(cmc)的情况下，生成混合胶束状聚集体．它们的缔 合行为和溶液性质明显地取决于表面活性剂的浓度，随着聚合物溶液中加入SDS， 溶液粘度发生急剧变化，并在较低的表面活性剂浓度处出现很大的最高点．荧光和 ^1H NMR测定结果表明，这是由于在不同SDS浓度范围内，PDAM/SDS形成的聚集体结 构不同的缘故．     

磺酸基丙烯酸酯三元无规共聚物胶束的聚集行为

采用自由基溶液共聚合法,合成了系列磺酸基丙烯酸酯三元无规共聚物表面活性剂(APSA).利用FTIR、1H-NMR、13C-NMR、GPC及元素分析证实了APSA的结构及组成.APSA胶束为核壳结构,随磺酸基含量增加,亲水层增厚.低剪切速率下,APSA溶液的黏度随磺酸基含量的增加而增加,胶束间的相互作用增强,假塑行为增强;高剪切速率下,黏度基本保持一致.DLS和表面张力表明,APSA1可将水溶液的表面张力降至43.26 m N/m.随亲水基团增加,表面张力增加,临界胶束浓度(cmc)增加.溶液浓度在cmc以下时,光散射强度较低且变化缓慢,高于cmc后,光散射强度呈现急剧的线性增长趋势,胶束聚集数急剧增加.随溶液浓度和亲水基团增加,胶束尺寸和分布系数增加.荧光光谱表明,随APSA浓度增加,I1/I3值从1.8降低到约1.2,芘的(0,0)吸收峰从334 nm迁移到338 nm,I338/I334值从0.7增大到1.45,表明疏水基团聚集形成疏水微区,芘分子从水相极性环境转移到胶束疏水内核.随亲水基团含量增加,分子聚集形成胶束的难度增加,速率降低.     

孪尾疏水缔合三元共聚物的粘度行为:水解度的影响

以十二烷基硫酸钠(SDS)为表面活性剂,利用氧化还原体系、采用前加碱共聚-共水解的方法制备了孪尾疏水缔合水溶性三元共聚物聚(丙烯酰胺／丙烯酸钠／N,N-二己基丙烯酰胺)[P(AM/NaAA／DiC6AM)],研究了P(AM／NaAA／DiC6AM)稀溶液及亚浓溶液的性能。随理论水解度的增加,P(AM／NaAA／DiC6AM)水溶液的特性粘数[η]增加,Huggins常数KH减小。P(AM／NaAA／DiC6AM)水溶液的表现粘度随理论水解度的增加而增加,随温度、剪切速率的增加而降低,随剪切速率的增加开始时降低较快而后变化较小。P(AM／NaAA/DiC6AM)在盐溶液中随NaCl、CaCl2质量浓度的增加,出现盐增粘现象;理论水解度不同的P(AM／NaAA／DiC6AM)与SDS水溶液的表现粘度在wSDS=0．050～0．400g／L范围内随SDS质量浓度的变化差别不大。     

青霉素钾对CTAB胶束性质的影响

研究了青霉素钾对十六烷基三甲基溴化铵（CTAB）的cmc、CTAB胶束聚集数和扩散系数的影响.研究结果表明，青霉素钾(Pen K)的加入使得CTAB胶束的第一cmc、第二cmc上升；CTAB球形胶束的聚集数下降,扩散系数增加；CTAB棒状胶束的聚集数增加,扩散系数降低.     

聚丙烯酰胺/聚L-谷氨酸苄酯接枝共聚物的合成及其胶束制备

以聚丙烯酰胺(PAM)为大分子引发剂, 采用开环聚合方法, 在N,N-二甲基甲酰胺(DMF)中引发L-谷氨酸苄酯环内酸酐(BLG-NCA)聚合合成了两亲性聚丙烯酰胺/聚L-谷氨酸苄酯接枝共聚物(PAM-g-BLG), 采用IR, 1H NMR和GPC方法对共聚物结构进行了表征; 用芘作荧光探针, 研究了共聚物胶束的形成及其临界胶束浓度(cmc), 利用动态光散射(DLS)和透射电镜(TEM)研究了胶束的粒径分布和形态. 结果表明, PAM能够引发BLG-NCA开环聚合得到接枝共聚物, 在一定条件下接枝共聚物能够形成球形的稳定胶束, cmc值和胶束粒径随着共聚物中疏水性聚L-谷氨酸苄酯(PBLG)链段含量的增加而减小.     

疏水基改性聚丙烯酰胺的合成及溶液性质

利用自由基胶束聚合法,由丙烯酰胺和甲基丙烯酸十八酯共聚合成了疏水缔合型水溶性聚合物.通过红外光谱表征了共聚物的结构,考察了共聚物浓度、盐浓度、剪切速率以及温度对共聚物溶液性能的影响.试验结果表明,聚合物质量分数大于临界缔合浓度(2%)时,溶液的粘度急剧增大;疏水缔合聚合物溶液的表观粘度随着溶液中NaCl质量分数的增加而增大.     

丙烯酰胺与二(烯丙基)十二胺在羧甲基纤维素上的接枝共聚物合成与表征

以十二胺与 3 氯丙烯的反应物二 (烯丙基 )十二胺 (DALA)、丙烯酰胺 (AM)和羧甲基纤维素 (CMC)为原料 ,合成了疏水化水溶性两性纤维素接枝共聚物 (CGAL) .利用FTIR、1 H NMR、MS和元素分析 (EA)等方法确证了DALA的结构 .考察了CMC的取代度与浓度 ,AM、DALA与引发剂浓度 ,温度及pH等因素对接枝共聚的影响 .通过FTIR对CGAL进行了分析 .借助比色滴定、EA和GPC等手段测定了CGAL的组成与分子量 .TG分析和粘度法研究了CGAL及其溶液的热稳定性 .纤维素酶降解试验说明CGAL具有生物降解性     

NaCMC与甲基丙烯酰氧乙基二甲基辛基溴化铵及AM接枝共聚物的性能

水溶性增粘剂;增粘性能;协同增效作用;疏水缔合作用;剪切作用;NaCMC与甲基丙烯酰氧乙基二甲基辛基溴化铵及AM接枝共聚物的性能     

Synergistic effect of mixed anionic and cationic surfactant systems on the interfacial tension of crude oil-water and enhanced oil recovery

Surfactant based enhanced oil recovery (EOR) is an interesting area of research for several petroleum researchers. In the present work, individual and mixed systems of anionic and cationic surfactants consisting of sodium dodecyl sulphate (SDS) and cetyltrimethylammonium bromide (CTAB) in different molar ratios were tested for their synergistic effect on the crude oil-water interfacial tension (IFT) and enhanced oil recovery performance. The combination of these two surfactant systems showed a higher surface activity as compared to individual surfactants. The effect of mixed surfactant systems on the IFT and critical micellar concentration (CMC) is strongly depends on molar ratios of the two surfactant. Much lower CMC values were observed in case of mixed surfactant systems prepared at different molar ratios as compared to individual surfactant systems. The lowest CMC value was found when the molar concentration of SDS was higher than the CTAB. When the individual and mixed surfacant systems were tested for EOR performance through flooding experiments, higher ultimate oil recovery was obtained from mixed surfactant flooding compared to individual surfactants. Combination of SDS and CTAB or probably other anionic-cationic surfactants show synergism with substantial ability to reduce crude oil water IFT and can be a promising EOR method.     

Polymethylmethacrylate derivatives Eudragit E100 and L100: Interactions and complexation with surfactants

Precipitation or coprecipitation of polyelectrolytes has been largely investigated. However, the precipitation of polyelectrolytes via addition of charged and non‐charged surfactants has not been systematically studied and reported. Consequently, the aim of this work is to investigate the effect of different surfactants (anionic, cationic, non‐charged and zwitterionic) on the precipitation of cationic and anionic polymethylmethacrylate polymers (Eudragit). The surfactants effect has been investigated as a function of their concentration. Special attention has been dedicated to the CMC range and to the colloidal characterization of the formed dispersions. Moreover, the effect of salt (NaCl) and pH was also addressed. It is pointed out that non‐ionic and zwitterionic surfactants do not interact with charged Eudragit E100 and L100. For oppositely charged Eudragit E100/SDS and Eudragit L100/CTAB, precipitation occurs, and the obtained dispersions have been characterized in terms of particle size distribution and zeta potential. It was established that the binding of SDS molecules to Eudragit E100 polymer chains is made through the negative charges of the surfactant heads under the CMC value whereas binding of CTAB to Eudragit L100 chains is made at a CTAB concentration 5 times above its CMC. For Eudragit E100/SDS system, a more acidic medium induces aggregation. A same result was observed for the Eudragit L100/CTAB at a more basic pH. Moreover, it was observed that increasing salt concentration (higher than 100 mM) led to aggregation as generally observed for polycations/anionic surfactant systems.     

疏水缔合共聚物与表面活性剂的界面相互作用

采用界面张力弛豫法研究了疏水缔合聚合物聚丙烯酰胺/2-乙基己基丙烯酸酯[P(AM/2-EHA)]在正辛烷-水界面上的扩张粘弹性质, 考察了不同类型表面活性剂十二烷基硫酸钠(SDS)、聚环氧乙烯醚(Tx-100)和十六烷基三甲基溴化铵(CTAB)对其界面扩张性质的影响. 研究发现, 界面上的表面活性剂分子可以与聚合物的疏水嵌段形成类似混合胶束的聚集体, 表面活性剂分子与聚集体之间存在快速交换. 这种弛豫过程的特征时间远比分子在体相与界面间的扩散交换时短. 当界面面积增大时, 上述混合胶束中的表面活性剂分子能快速释放, 在界面层内原位快速消除界面张力梯度, 从而大大降低界面扩张弹性. 界面上的CTAB分子与聚合物链节上的负电中心通过较强的电荷吸引作用形成复合物. 当界面面积增大时, 上述混合胶束中的CTAB分子释放较慢, 界面张力梯度较大. 非离子表面活性剂Tx-100分子量较大, 扩散速率较慢, 它在界面上与聚集体间的交换比阴离子表面活性剂SDS慢, 其特征时间约为0.9 s.     

Effects of Metal Ions on the Micellization of Ionic Surfactants

The effect of metal ions (Cu(II), Zn(II), Co(II), Ni(II), La(III), Fe(III)) on the critical micelle concentration (CMC) of ionic surfactants (sodium dodecyl sulfate (SDS) and hexadecyltrimethylammonium bromide (CTAB)) were investigated at 25±0.1°C, μ = 0.1 M (KNO₃), using conductivity method in this paper. A series of general empirical expressions about the relationship between the CMC values for SDS and CTAB and the concentrations of metal ions have been derived. The results showed that the CMC values for both SDS and CTAB decreased with increasing the concentrations of metal ions. This can be interpreted by the counterion effect and the entropy driving effect.     

Effect of Sodium Barbital on the Physico‐chemical Properties of Surfactants with Different Charges

The effects of sodium barbital (SB) on the solubility of different kinds of surfactants viz., CTAB (cationic head group), SDS (anionic head group) and Triton X‐100 (non ionic head group) in solution phase as well as their first and second critical micelle concentrations (CMC1 and CMC2), the change in Kraft temperatures (T_K) and cloud points (CP) have been studied. Furthermore, the article reports SB‐surfactant interaction study, which is application oriented and highlights the underlying physico‐chemical aspects of the system through florescence and conductivity measurements. The results show that the solubility of CTAB and Triton X‐100 increases with the addition of SB, and that of SDS increases in the presence of small amounts of SB and decreases in the presence of large amounts of SB. With the increasing SB concentration, the CMC of CTAB and CMC1 of Triton X‐100 both increase, while the CMC of SDS decreases, and the CMC2 of Triton X‐100 has no obvious change. The addition of SB decreases the T_K of CTAB sharply, but it increases the T_K of SDS and the CP of Triton X‐100. The different effects of SB on the physico‐chemical properties of differently charged surfactants may be related to its different interactions with the surfactants.     

The Viscous Properties of Anionic/Cationic and Cationic/Nonionic Mixed Surfactant Systems

The behavior of mixed cationic/anionic and cationic/nonionic surfactants solutions have been studied by viscosimetry. The systems studied were sodium dodecyl sulfate (SDS)/cetyltrimethylammonium bromide (CTAB) and CTAB/Brij (polyoxyethylene lauryl ether, n = 10 and 23) in aqueous and sodium chloride solutions. The relative viscosity of single nonionic surfactant solutions is larger than that of SDS or CTAB solutions. It increases with the number of ethylene oxide groups. In the mixed systems, viscosity deviates from ideal behavior. The deviation results from electrostatic interactions. The surfactant mixture composition affects the self-assembled microstructure and rheology. A new mixed system that forms clear micellar solution above CMC was detected. In CTAB/Brij systems, the experimental data also deviate from ideal behavior due to mixed micelle formation and electroviscous effect. This effect is less pronounced than that of SDS/CTAB system and could be suppressed by adding an electrolyte (NaCl).     

Investigation of SDS, DTAB and CTAB micelle microviscosities by electron spin resonance

Electron spin resonance spectroscopy (ESR) of the nitroxide labelled fatty acid probes (5-, 16-doxyl stearic acid) was used to monitor the micelle microviscosity of three surfactants at various concentrations in aqueous solution: sodium dodecyl sulphate (SDS), dodecyltrimethylammonium bromide (DTAB) and cetyltrimethylammonium bromide (CTAB). At low surfactant concentration, there is no micelle, the ESR probe is dissolved in water/surfactant homogeneous phase and gives his microviscosity. At higher surfactant concentration, an abrupt increase in microviscosity indicates the apparition of micelles and, the solubilization of the probes in micelles. The microviscosity of the three surfactants, in a large surfactant range, was obtained as well as the critical micelle concentration (CMC). The microviscosity increased slightly with the increase in surfactant concentration. Phosphate buffer lowered the CMC value and generally increased the microviscosity.