新型对称性两亲含硅聚合物的合成与界面性能

基于原子转移自由基聚合(ATRP)机理,以二甲基一氯硅烷封端的烯丙基-聚乙二醇为起始剂,甲基丙烯酸乙酯(EMA)为单体,通过控制反应温度,合成了一系列聚合度(DP_(NMR))分别为0. 74,1. 67和3. 07的新型对称性两亲含硅共聚物(PEMA-b-Si-PEG-Si-b-PEMA),并评价了该共聚物在氯仿/水界面的界面活性和吸附行为。结果表明:该类聚合物可以有效降低氯仿/水界面张力,具有最短PEMA链的聚合物可将氯仿/水界面张力从32 m N/m降低至约23 m N/m。动态界面张力分析表明:低浓度的共聚物在吸附的初始阶段符合扩散控制,且较短的PEMA链段有利于产生较快的扩散速率。平衡界面张力分析表明:随着界面浓度的增加,共聚物将表现出多种吸附状态,其吸附状态的数量以及聚合物在界面的偏摩尔面积将随着PEMA链长度的增加而增加。     

无机盐对新疆油田三元复合驱界面性能影响研究

界面性能对复合驱提高采收率有重大的影响,界面张力越低,洗油效率越高;Zeta电位越高,油水乳状液越稳定。研究了各类无机盐对新疆油田复合驱界面性能的影响。结果显示,Zeta电位的绝对值随着无机盐浓度的增高而增大;无机碱中,碳酸根离子降低界面张力效果最好,氢氧根次之,碳酸氢根最差;阳离子中,钾离子降低界面张力效果最好,其次是钠离子,镁离子会略微提高界面张力,钙离子则会大幅度提高界面张力;阴离子中,与硫酸根相比,氯离子能更好地降低界面张力。通过以上研究,确定了Q站污水处理站外排水更适合三元复合驱配液。     

The effect of the embedded interface dynamics on mass transport in immiscible polymer blends

Mass transport of solvents into immiscible blends may exhibit a non-Fickian behavior due to the deformation of the embedded interface that couples with diffusion. We introduce an interface area covariant tensor N as a structural state variable and derive a set of thermodynamically-consistent PDEs and ODEs transport equations for the bulk and time-dependent boundaries. The proposed model, which is a reformulation of that derived by El Afif (2008) and El Afif et al. (2003), improves both mathematically and numerically the investigation of the diffusion-interface coupling and provides reasonable predictions of the sorption-permeation one dimensional treatment affording good agreement with experimental data. The tensor N englobes, into a single morphological quantity, all information regarding diffusion-induced changes in the size and shape anisotropy of the interface area. Predicted results include concentration, components of N , residual stresses, mass-uptake, and swelling. Scaling leads to three relevant dimensionless parameters: a mixing-interface coupling constant and bulk and boundary diffusion Deborah numbers.     

羧酸盐表面活性剂与两亲聚合物相互作用研究

根据黏度和表面张力的测定数据研究了羧酸盐表面活性剂(HF-E)与两亲聚合物的相互作用,结果表明,HF-E/两亲聚合物混合溶液的表观黏度随HF-E质量浓度的增加先升高后下降;两亲聚合物的质量浓度越大,HF-E/两亲聚合物混合溶液表面张力越高;随着水的矿化度的升高,HF-E/两亲聚合物混合溶液的表观黏度先略有增加,到一定值后反而降低,而表面张力则随矿化度的增加而降低;温度升高,HF-E/两亲聚合物混合溶液的表观黏度随之降低而其与大庆模拟油间的界面张力则升高。优化后的高黏度低界面张力二元体系配方为HF-E和两亲聚合物的质量浓度分别为3和1.5 g·L-1;此外,还加入质量浓度为1 g·L-1的烷基醇酰胺(NS)。     

Enthalpic effects on interfacial adhesion of immiscible polymers compatibilized with block copolymers

The influence of enthalpic interactions on interfacial adhesion between immiscible polymer matrices and reinforcing block copolymer segments has been studied using the transmission electron microscopic (TEM) methodology of Creton et al. We examined the behaviour of four statistical styrene-acrylonitrile (SAN) copolymers, each having different acrylonitrile (AN) content, blended with polystyrene (PS) as the minor component, and reinforced by three poly(methyl methacrylate-b-styrene) (PMMA-b-PS) block copolymers of differing molar masses, viz. 20000, 65000 and 680000 g mol⁻¹. These observations were compared with similar experiments on poly(methyl methacrylate) (PMMA) blended with PS and reinforced by PMMA-b-PS. Emulsification was observed with all three PMMA-b-PS copolymers. Crazes were formed in the SAN matrices and a statistical evaluation of interfacial failures was performed on the discrete PS domains that lay within the crazes. For the two block copolymers of higher molar mass, optimal reinforcement of the interfaces was observed independent of the SAN composition. With the 20000 block copolymer, however, the pattern of the interfacial failure depended strongly on the SAN composition. Specifically, it was observed that the fraction of the discrete particles that suffered interfacial failure, and led to the creation of large voids in the crazes in these blends, increased with increased AN content of the SAN matrix. Thus, we found that the fraction of discrete PS particles that produce large voids in crazes of blends containing SAN33 is always higher than in blends containing SAN15, when reinforced with the 20000 PMMA-b-PS. We infer that the critical molar mass required of a mechanically reinforcing copolymer depends on the short-range (attractive and repulsive) interactions between the blend components in the interfacial region. The TEM method could not, however, distinguish between reinforced and neat PMMA/PS blends, all of which showed strong adhesion. This is attributed to the comparatively diffuse interface in the PMMA/PS system, a consequence of the relatively weak repulsion between these two polymers.     

Local rates of heat and mass transfer during condensation of non-eutectic vapours of binary immiscible liquids

Heat and mass transfer data are reported for the condensation of vapours of immiscible liquids. Condensation occurred on the outside of 0.0254 m diameter horizontal copper tube. Mixtures of organic vapours in steam have been studied, such mixtures being rich in steam and removed from the eutectic composition.

The condensate flow pattern has been determined experimentally. In systems where the density ratio of the organic to water liquids is less than one, a standing-drop pattern is observed; when the ratio is greater than one, channeling flow is the main feature.

For systems removed from the eutectic composition, diffusional resistance through the vapour phase adjacent to the vapour—liquid interface has a major effect on the transfer rates.     

两种驱油用两亲聚合物复配对其乳化性能的影响

利用稳定性分析仪和光学显微镜研究了B型和海博Ⅲ型2种驱油用两亲聚合物复配对其乳状液稳定性和乳化效果的影响;采用流变仪、界面张力仪和电位分析仪研究了该2种驱油用两亲聚合物及其复配体系的流变性能和界面特性。结果表明:2种驱油用两亲聚合物及其复配体系均能形成O/W型乳状液,随着B型两亲聚合物复配量的增加,复配体系乳状液粒径介于2种两亲聚合物单独形成的乳状液粒径之间,且逐渐减小,分布变窄;其外相体系的黏度、油/水界面张力和Zeta电位的绝对值均呈现先降低后升高的趋势;综合作用下,复配体系乳状液液滴的迁移速率降低,絮凝、聚并程度先升高后降低;相比于2种驱油用两亲聚合物单独使用时,复配体系乳状液的稳定性呈现先降低后升高的趋势,并最终将其超越。     

The viscosity of immiscible polymer blends: influences of the interphase and deformability

The viscosity of immiscible polymer blends has been studied via application of certain aspects of rheology. A symmetric mixture rule was derived, and the deviations from the ‘additivity rule’ have been associated, essentially, with the properties of the interphase, with its influence on the effective volumes of the two polymers constituting the blend and with the deformability of both the interphase and the disperse phase. The rule predicts a positive deviation for a mixture with a disperse-phase viscosity (η_d) greater than that (η_m) of the continuous medium, and a much higher-viscosity interphase, i.e. η_i å η_d ≥ η_m. Negative deviation is to be expected when the interphase has a much lower viscosity than those of the two pure polymers (η_d, η_m å η_i) in the blend. The viscosity and strength of the interphase depend mostly on the specific thermodynamic interactions that led to its creation.     

Influences of compatibilization and compounding process on electrical conduction and thermal stabilities of carbon black‐filled immiscible polypropylene/polystyrene blends

The influences of styrene–butadiene–styrene (SBS) copolymer compatibilizer and compounding process on the electrical conduction and thermal stabilities of carbon black (CB)‐filled immiscible polypropylene (PP)/polystyrene (PS) (1/1) blends were investigated. The immiscible CB/PP/PS composite with CB homogeneously located in the PS phase exhibited the highest resistivity and the fastest variation amplitudes of electrical resistivity (ρ) and rheological parameters upon annealing. An optimal content of 5 vol% SBS could significantly lower ρ of the composites by partially trapping CB particles in the PP/PS interfacial region and by reducing the phase size. The compatibilizer markedly slowed down the variation amplitudes of ρ and rheological parameters and the phase coalescence of the composites submitted to thermal annealing. The (SBS/CB)/PP/PS composite with CB located at the PP/PS interface and in the PP phase prepared by blending a (SBS/CB) masterbatch with PP and PS exhibited lower ρ and better thermal stability in comparison with the CB/SBS/PP/PS composite with CB mainly within the PS phase and partially at the PP/PS interface prepared by direct blending. Spreading and wetting coefficients were used to explain the CB distribution and the phase morphology of the composites. © 2012 Society of Chemical Industry     

含氟季铵盐的动态界面张力性能和润湿铺展性能的研究

含氟季铵盐表面活性剂是一类具有高表面活性、高耐热稳定性、高化学稳定性和憎水、憎油等特殊性能的表面活性剂。该文通过测定不同时间、不同种类的油相、不同质量分数的表面活性剂以及不同无机盐添加比例对油水界面张力的影响以及不同浓度的含氟季铵盐表面活性剂水溶液在石蜡、金属铁等不同固体表面上的接触角,对其动态界面张力以及润湿铺展性能进行了研究。结果表明：界面张力值通常在10min后基本达到平衡,且用渤61#油做油相时,界面张力值较低,效果比较好;随着表面活性剂质量分数的增加,界面张力先减小,达到一个最低值后渐渐趋于平缓;无机盐的加入使得界面张力先降后升,在NaCl质量浓度为50~80g/L内均降至低界面张力,最低值达到0.0531mN/m;同时,在典型的具有强疏水性的低能表面石蜡上的铺展性能优良。该研究为其在水溶性场合的应用提供了实验数据。     

熔融盐对合成气成分影响模型

气化粗合成气主要成分为CO、CO2、H2,经过变换和重整后在催化剂作用下可以合成不同的化学品。熔融盐可吸收粗合成气中的CO2,并实现H2/CO在1.5～2.9之间调整。熔融盐合成气成份调整过程是一个传质与化学反应同时进行的非平衡、耦合过程。从球体扰流方程和反应动力学方程出发,通过量纲分析推导出合成气组分与操作条件的关系,对固定床内熔融盐对合成气成份调整过程进行了分析。熔融盐合成气成份调整的限制过程为气体从气泡表面向熔融盐内部的传质过程。温度升高、气泡直径减小、停留时间增加有利于合成气中H2百分比增加;然后对模型进行了实验验证,实验结果与理论结果吻合良好。     

Synergistic effect of salt ions and water-soluble amphiphilic compounds of acidic crude oil on surface and interfacial tension

This study investigated the effect of solubility of amphiphilic compounds of acidic crude oil in water on the surface and interfacial tension (IFT) with NaCl, MgCl₂, CaCl₂, and Na₂SO₄ salts. Accordingly, distilled water, along with the salts mentioned in zero ionic strength up to 2 mol were put in contact with crude oil to become saturated with amphiphilic compounds. The effects of these compounds were investigated on the properties of contact water by pH, total organic carbon (TOC), FTIR (Fourier transform infrared spectroscopy), water-air surface tension (ST), and water-n-decane IFT tests. The results showed that some of the organic components of crude oil, especially acidic and basic compounds, are present or soluble in water, which have a significant effect on reducing the surface and IFT. The IFT reduction of water-n-decane was greater than the water-air ST system. Also, the observations showed that for both NaCl and Na₂SO₄ salt water, with increasing ionic strength of water, there was an optimum salinity within the range of 0.1-0.25 mol/L for both salts with the amount of surface and IFT minimized at this point. In the other two salts, this point was delayed upon elevation of ionic strength and was observed at high salinity. In this case, divalent cations reduce tension rate compared to monovalent cations. Due to solubility of acidic and basic groups in water, pH of salt water illustrates an acidic trend. Results of the FTIR test confirmed solubility of these compounds as well.     

Interpretation of ion transfer reactions across the interface between two immiscible electrolyte solutions by the model of “elastic” inner layer

The model assuming that the elastic force of interfacial tension counteracts introduction of ions into adjacent electrolyte solution is discussed. The main electrochemical properties of ITIES are analyzed on the basis of this model. It is shown that many of experimental results of study of double-layer capacitance, potential drop across the inner layer, kinetics of simple and facilitated ion transfer as well as resolvation energy of hydrophobic ions are in good agreement with predictions drawn from the model. It is concluded that ITIES acquire the property of polarizability although heterogeneous step of simple ion transfer is reversible. The performed theoretical analysis of transfer of ions of supporting electrolytes has offered a simple equation to describe experimental voltammetric curves and to obtain a quantitative criterion of the polarizability.     

Quaternary ammonium salts ionic liquids for immobilization of chiral Ru-BINAP complexes in asymmetric hydrogenation of β-ketoesters

Chiral catalytic complex (R)—[RuCl(binap)(p-cymene)]Cl was used in asymmetric hydrogenation of methyl acetoacetate to methyl-3-hydroxybutyrate in the mixed methanol-ionic liquid phase. Quaternary ammonium salts ionic liquids, namely n-alkyl-triethylammonium bis(trifluoromethane sulfonyl) imides (N_R222Tf₂N, R = 6, 7, 8, 10, 12, 14), were prepared and employed in this transformation. Enough evidence was provided that only a small amount of this type of IL in a conventional solvent was necessary to accommodate the catalytic complex and that the reaction could be carried out with very high enantioselectivity. Similarly it was proved that under optimized conditions the catalytic complex immobilized in this manner could be used repeatedly. A part of the work was focused on the role of the alkyl chain length in the N_R222Tf₂N ionic liquid which was found as very essential. Role of the reaction impurities with origin in the synthesis of the employed ILs was also investigated.     

Modification of the air–water interface by a chitosan adsorption process. Effect on an amphiphilic polymer monolayer

Monolayer formation by poly[(maleic anhydride)‐alt‐(stearyl methacrylate)] (MA‐alt‐StM) on aqueous subphases, with and without chitosan, was studied by the Langmuir technique. Chitosan (CS) modified considerably the shape of the MA‐alt‐StM isotherms on water. To explain this behavior, the surface activity properties of chitosan at the air–solution interface were studied. The variations of the interfacial tension, γ_int, with chitosan concentration and temperature, were also determined. The results were discussed in terms of the modification of the air–water interface owing to the presence of chitosan in the subphase and the surface activity. It was found that the standard free energy of adsorption, , values were dependent on the degree of acetylation (DA) over the DA range being studied. Copyright © 2004 Society of Chemical Industry     

The marangoni effect and enhanced oil recovery Part 2. Interfacial tension and drop instability

A computer-based method is described for the determination of the interfacial tension between pendant and sessile drops in a surrounding continuous phase. This has been used to determine the effect on interfacial tension of increasing amounts of aliphatic alcohols, from methanol up to n-octanol, equilibrated between a hydrocarbon solvent (Shellsol) and water. The results indicated large decreases in interfacial tension, with n-butanol, followed by n-propanol giving the greatest reduction. Measurements were also made of the rate of change of interfacial tension during the mass transfer of 2.5% of the alcohols between phases. Changes were observed for all alcohols from ethanol to n-pentanol, the effect being greatest for transfer into water drops and out of solvent drops. Application of the linear stability theory of Sørensen to these results failed to predict the observed instability for transfer into solvent drops.     

有机物在离子液体中无限稀释活度因子及液液界面张力的定量机构-性质关系

用PM3半经验量子化学方法计算了烷烃、烯烃和芳烃等的疏水性参数lgP、偶极矩、前线分子轨道能隙和水合能等结构描述符,与实验测定的烃类在1-丁基-3-甲基咪唑六氟磷酸盐（［C₄MIM］［PF₆］）、1-烯丙基-3-甲基咪唑四氟硼酸盐（［AMIM］［BF₄］）、1-异丁烯基-3-甲基咪唑四氟硼酸盐（［MPMIM］［BF₄］）和［MPMIM］［BF₄］-AgBF₄ 4种离子液体中的无限稀释活度因子进行定量结构-性质关系（QSPR）研究,建立的QSPR模型具有良好的关联和预测能力.同时测定了烃类等溶质与离子液体［C₄MIM］［PF₆］的液液界面张力,发现其与无限稀释活度因子有相似的变化趋势,据此采用同样的结构描述符,建立了溶质与［C₄MIM］［PF₆］界面张力的QSPR模型,模型的关联能力良好.     

The effect of gas injection on the flow of immiscible liquids in horizontal pipes

The flow of two immiscible liquids and the influence of an additional inserted gas phase in horizontal pipes is investigated. The experiments are carried out in a transparent horizontal pipe with an inner diameter of 59 mm and a total length of 48 m. Experimental results are presented for the flow regimes of the two phase and three phase flow of oil, water and gas mixtures. The effect of phase inversion on the pressure drop is measured. The experimental results obtained for the three phase flow of oil, water and air indicate that drag reduction is possible by injecting gas in laminar flowing mixtures of oil and water. In the aerated slug flow regime of oil, water and air a water dominated and an oil dominated flow system can be distinguished. The pressure drop of the three phase flow system is of the magnitude as the pressure drop of the two phase flow of gas and the dominating liquid phase.     

Molecular insight into the effect of ion structure and interface behavior on the ammonia absorption by ionic liquids

Molecular dynamics simulations were performed to elucidate the roles of ion structure and interface behavior in absorption of gases (NH₃, N₂, H₂) by ILs (protic IL [Bim][Tf₂N] and conventional IL [Bmim][Tf₂N]). The results indicated that NH₃ compete with [Tf₂N]⁻ to interact with N3-H site of [Bim]⁺ cation, forming a strong N3 H∙∙∙N(NH₃) hydrogen bond with the energy of −79 kJ/mol, which is twice as much as the energy of the hydrogen bond between C2 H of [Bmim]⁺ and NH₃ (−33.2 kJ/mol). Moreover, there is a dramatic increase in the number density of cations near the IL-gas interface, resulting in the NH₃ molecules permeate into the bulk rapidly and effectively and achieving the high selective absorption of NH₃ to H₂ and N₂. Considering the inevitable trace water in the raw gases, the influence of water was studied and it was shown that trace water can enhance the absorption of NH₃ by [Bim][Tf₂N].