Titration microcalorimetry of poly(vinylpyrrolidone) and sodium dodecylbenzenesulphonate in aqueous solutions

Microcalorimetric titrations are carried out on solutions containing the anionic surfactant sodium dodecylbenzenesulphonate (SDBS), and mixtures of SDBS and the uncharged polymer poly(vinylpyrrolidone) (PVP). Measurements are taken at different temperatures. Micellisation of SDBS is driven by hydrophobic bonding. The interaction enthalpy of mixed PVP/SDBS systems shows clearly a consecutive endothermic and exothermic region with increasing surfactant concentration. The endothermic part can be looked upon as an incremental binding isotherm and reflects the number of surfactant molecules involved in the association process. The exothermic region features inverse hydrophobic bonding behaviour. This is related to the flexible nature of the adsorbent, i.e. the polymer. Electrostatic repulsion between neighbouring surfactant molecules causes at increased surfactant concentrations structural rearrangements of the polymer-surfactant complexes. This is accompanied by losing inter- and intrachain linking and entropy gain since the expanded complexes can move more freely. Additional surfactants continue to adsorb on the vacant hydrophobic adsorption sites. The influence of the initial amount of polymer and the electrolyte concentration support our proposals.     

Mixed adsorption of poly(vinylpyrrolidone) and sodium dodecylbenzenesulfonate on kaolinite

The mixed adsorption of the nonionic polymer poly(vinylpyrrolidone) (PVP) and the anionic surfactant sodium dodecylbenzenesulfonate (SDBS) on kaolinite has been studied. Both components adsorb from their mixture onto the clay mineral. The overall adsorption process is sensitive to the pH, the electrolyte concentration, and the amounts of polymer and surfactant. Interpretation of the experimental data addresses also the patchwise heterogeneous nature of the clay surface. In the absence of PVP, SDBS adsorbs on kaolinite by electrostatic and hydrophobic interactions. However, when PVP is present, surfactant adsorption at 10(-2) M NaCl is mainly driven by charge compensation of the edges. The adsorption of PVP from the mixture shows similar behavior under different conditions. Three regions can be distinguished based on the changing charge of polymer-surfactant complexes in solutions with increasing SDBS concentration. At low surfactant content, PVP adsorbs by hydrogen bonding and hydrophobic interactions, whereas electrostatic interactions dominate at higher surfactant concentrations. Over the entire surfactant concentration range, polymer-surfactant aggregates are present at the edges. The composition of these surface complexes differs from that in solution and is controlled by the surface charge.     

Preparation and properties of hyperbranched polymer containing functionalized Nano-SiO<Subscript>2</Subscript> for low-moderate permeability reservoirs

A novel water-soluble hyperbranched polymer (AA/AM/SMNS) consisting of functionalized Nano-SiO₂ as the core was synthesized by free-radical polymerization for low-moderate permeability reservoirs. The AA/AM/SMNS was carefully characterized by spectroscopic and electronic technologies. It was found that the microscopic structures of AA/AM/SMNS was denser and more regular in comparison to the linear polymer HPAM. The hydrodynamic radius of AA/AM/SMNS was 197 nm, less than the HPAM radius of 244 nm with similar molecular weight, so that the AA/AM/SMNS had a good matching relationship with pore throat in midpermeability reservoirs (100–500 mD). Besides, the introduction of Nano-SiO₂ endowed the AA/AM/SMNS remarkable thermal stability, shear resistance and viscoelasticity. Based on core flooding experiments, the AA/AM/SMNS could build high resistance factor and residual resistance factor in the corresponding porous medium. Furthermore, the sheared AA/AM/SMNS solution of 1500 mg L–1 performed excellent oil recovery of 15.47% in the 300 mD porous medium, which suggested the hyperbranched polymer based on modified Nano-SiO₂ have a valuable prospect for enhancing oil recovery in low-moderate permeability reservoirs.     

RADICAL GRAFTING REACTIONS ONTO STARCH AND OTHER WATER-SOLUBLE COPOLYMERS IN ISOLATED GEL DROPLETS

A novel radical grafting copolymerization process has been designed for water-soluble polymers which avoids the problems of conducting grafting reactions in highly viscous polymerization media. A variety of water-soluble graft copolymers having starch or dextran as the backbone chain with grafted side chains of polyacrylamide (—AM—), poly (acrylic acid ) (—AA—), poly (acrylamide-co-acrylic acid) (—AM—NH_4AA—) or poly ( acrylamide-co-2-acryiamido-2-methyl-l-propanesulphinic acid) (—AM—AMPS—) have been synthesized in gel droplets using aceric sulphate redox initiator, and their properties compared. The reaction conditions were optimized taking into account reaction kinetic data and the observed properties of the products produced under different reaction conditions. The effects of the ratios of [backbone]/[graft monomer], [ AM]/[ AA]/[AMPS] , [Ce~(4+)]/[ S_2O_8=] and pH value on the reaction rate , conversion, grafting degree, grafted chain length and the product molecular weight have been investigated.     

粘度和光谱方法研究二元阴离子型丙烯酰胺共聚物(P3A)在不同pH水溶液中的构象变化

采用粘度和光谱方法,研究了强酸性和弱酸性2种阴离子型单体与丙烯酰胺的三元共聚物(P3A)在稀水溶液中pH诱发的构象变化,P3A聚合物由丙烯酰胺(AM)和强酸性离子单体(AMPS)及弱酸性离子单体(AA)组成.试验结果表明P3A聚合物溶液的粘度随pH呈现非单调的增长关系,在pH为4～5范围内产生急剧的升高,这现象归因于聚合物链团从紧密状态向膨胀状态迅速的转变.这两种状态的溶液粘度变化幅度和聚合物P3A中AMPS和AA组合比例紧密相关,芘探针在聚合物P3A溶液中的荧光强度和pH的关系呈现类似粘度变化的结果.在低pH值时,发现单一弱酸离子共聚物(P2AA)溶液发生相分离,然而在含有强酸单元(AMPS)的P3A聚合物情况下,这种现象不再产生.     

Polymeric Fluorosurfactant‐Mediated Perfluorocarbon Emulsions

Polymeric fluorosurfactants, using poly(N,N‐dimethylacrylamide) (PDMA) or PDMA copolymers containing acrylic acid (AA) or 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid (AMPS) comonomers were synthesized by copolymerization of DMA, DMA/AA, or DMA/AMPS and methacrylates composed of 1,1‐dihydroperfluorodecanoyl groups separated from the methacrylate by polyethylene glycol (PEG) groups with molecular weights ranging from 1 to 6 kD. The stability of aqueous perfluorocarbon (PFC) emulsions mediated by these polymeric fluorosurfactants was found to be affected by polymer concentration, ionic comonomer content, perfluoroalkyl (R_F) comonomer content, and PEG spacer length. Thus, emulsion stability characterized by average particle size and morphology was improved by increased AA or AMPS content (up to 30 weight percent), increased PEG chain length and R_F comonomer content, and greater polymer concentration.     

二元阴离子型丙烯酰胺共聚物在二价金属离子存在下相分离行为的研究

水溶性丙烯酰胺类共聚物 ,作为粘度改性剂 ,在工业上已得到广泛应用 .特别近年来 ,它们大量应用于石油工业强化采油技术 ,引起了人们很大的重视[1] .目前 ,这类用途的聚合物 ,主要在聚丙烯酰胺结构中 ,引入阴离子组分和不断增高产物分子量的方法 ,以提高聚合物溶液粘度和增粘效果 ,然而 ,在二价金属离子 (如Ｃａ2 + ,Ｍｇ2 + 等 )存在下 ,羧酸阴离子型丙烯酰胺类共聚物很容易络合发生沉淀 ,从而失去增粘作用[2 ] .同时这类聚合物中酰胺基不稳定 ,易发生水解反应转化为羧酸基 ,并随温度升高而加剧[3 ] ,因此在温度较高的应用条件下 ,二价金属…     

Synthesis of water-soluble hyperbranched polymer and its application in acrylic latex

A water-soluble hyperbranched polymer (WHBP), obtained from a second generation of hyperbranched polyester and maleic anhydride, was studied. Its effects on the properties of acrylic latexes, which were based on emulsion polymerization of butyl acrylate (BA), methyl methacrylate (MMA), acrylic acid (AA) and WHBP, and latex film were discussed. The characteristics of WHBP were determined by nuclear magnetic resonance spectroscopy (NMR), Fourier transform infrared (FTIR) and gel permeation chromatography (GPC). Particle size and morphology of latex particles were confirmed by dynamic light scattering (DLS) and transmission electron microscope (TEM). The investigation showed that WHBP could be used in emulsion polymerization, and that latex of poly(BA-MMA-WHBP) was more stable than that of poly(BA-MMA-AA). The hardness of latex film increased from 2B to HB when WHBP was used.     

DSC研究高吸水树脂吸水性能与分子结构的关系

以丙烯酸(AA)、丙烯酰胺(AM)和2-丙烯酰胺基-2-甲基丙磺酸(AMPS)为共聚单体合成了聚丙烯酸-丙烯酰胺-2-丙烯酰胺基-2-甲基丙磺酸(PAA-AM-AMPS)三元共聚物高吸水树脂.利用茶叶袋法测定了其最大吸水倍率,通过差示扫描量热仪(DSC)测定并比较了含水量为50%,75%和91%的各种水凝胶的自由水和结合水含量.结果表明在蒸馏水和生理盐水中高吸水树脂的最大吸水倍率分别为1900g/g和185g/g,共聚物的结合水含量随着AMPS和AA含量增加及AM含量的减少而增大;在0.9%生理盐水中,结合水含量随着AMPS和AM含量增加及AA含量的减少而增大,共聚物和均聚物高吸水树脂的最大吸水倍率呈现出与结合水含量相同的变化规律.     

Study of surfactant-polymer system containing a novel ternary sulfonated polyacrylamide on the oil-water interface properties

A novel ternary sulfonated polyacrylamide was synthesized using 2,2′-azobis[2- methylpropionamidine] dihydrochloride and redox initiation system as initiator, respectively. The competitive adsorption of the ternary sulfonated polyacrylamide (TSPAM) and sodium dodecyl benzene sulfonate (SDBS) on the oil-water interface was investigated by equilibrium interfacial tension, interfacial viscoelasticity, zeta potendial and interfacial film strength. The SDBS molecules in the surfactant-polymer (SP) system preferentially adsorb on the oil-water interface due to the amphiphilic structure of the SDBS molecules. Electrostatic force between the charged groups of the polyacrylamide and the head groups of surfactant adsorbed on the interface in the SP system leads to the formation of the complex interface film, which is helpful to enhance the stability of the oil-water interface. The ternary sulfonated polyacrylamide (TSPAM) has a similar influence on the other interface properties with SDBS except the interfacial tension. The interfacial tension decreases and then increases with increasing of the TSPAM concentration due to the competitive adsorption of the TSPAM molecules and the SDBS molecules on the oil-water interface. Moreover, TSPAM has the more influence on the stability of oil-water interface than partially hydrolyzed polyacrylamide (HPAM) in the SP system, and the addition of TSPAM is better to improve the stability of emulsion in the SP flooding.     

Effect of Polycarboxylic Acid Used as High-Performance Dispersant on Low-Rank Coal-Water Slurry

A new polycarboxylic (PC) acid was prepared from copolymerization of 2-methyl-1-butylene alcohol polyoxyethylene ether (HPEG), acrylic acid (AA), and 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and used as a high-performance dispersant in low-rank coal-water slurry (CWS). The optimized conditions are as follows: the reaction temperature is 80°C, the mole ratio of HPEG, AA, and AMPS is 1:3:0.3, and the inherent viscosity of PC polymer is 49.26 ml/g. The molecule structure of PC polymer was characterized by means of FTIR. Moreover, the apparent viscosity, static stability, and rheological property of CWS with the concentration of 63.0 and 65.0 wt% were all determined by adding PC hyper-dispersant or naphthalene sulfonate-formaldehyde (NSF) condensate dispersant at 0.5 wt% dosage. The result shows that PC dispersant has better properties than commercial NSF product in low-rank CWS. The effect was well rationalized by a combination of electrostatic repulsion force, wetting property, and steric hindrance provided by PC polymer.     

Interaction forces between particles stabilized by a hydrophobically modified inulin surfactant

The adsorption isotherm of a hydrophobically modified inulin (INUTEC SP1) on polystyrene (PS) and poly(methyl methacrylate) (PMMA) particles was determined. The results show a high affinity isotherm for both particles as expected for a polymeric surfactant adsorption. The interactions forces between two layers of the hydrophobically modified inulin surfactant adsorbed onto a glass sphere and plate was determined using a modified atomic force microscope (AFM) apparatus. In the absence of any polymer, the interaction was attractive although the energy of interaction was lower than predicted by the van der Waals forces. The results between two layers of the adsorbed polymer confirms the adsorption isotherms results and provides an explanation to the high stability of the particles covered by INUTEC SP1 at high electrolyte concentration. Stability of dispersions against strong flocculation could be attributed to the conformation of the polymeric surfactant at the solid/liquid interface (multipoint attachment with several loops) which remains efficient at Na(2)SO(4) concentration reaching 1.5 mol dm(-3). The thickness of the adsorbed polymer layer in water determined both by AFM and rheology measurements, was found to be about 9 nm.     

表面活性剂与高分子链混合体系的模拟

计算机模拟了高分子链对表面活性剂胶束形成过程的影响，以及高分子链构象性质随胶束化过程的变化.结果表明,当高分子链与表面活性剂之间的相互作用强度超过临界值后，高分子链的存在有利于表面活性剂胶束的形成.临界聚集浓度（CAC）与临界胶束浓度（CMC）的比值CAC/CMC随高分子链长的增大和相互吸引作用的增强而减小.在CAC之前，高分子链与表面活性剂分子只有动态的聚集；但在CAC之后，表面活性剂胶束随表面活性剂浓度X的增加而增大，并静态地吸附在高分子链上，形成表面活性剂/高分子聚集体.随着表面活性剂分子的加入，高分子链的均方末端距和平均非球形因子先保持恒定；从X略小于CAC开始， 和快速减小，至极小值后又逐渐增大.模拟结果支持高分子链包裹在胶束表面的实验模型.     

Dynamic adsorption of weakly interacting polymer/surfactant mixtures at the air/water interface

The dynamic adsorption of polymer/surfactant mixtures containing poly(ethylene oxide) (PEO) with either tetradecyltrimethylammonium bromide (C(14)TAB) or sodium dodecyl sulfate (SDS) has been studied at the expanding air/water interface created by an overflowing cylinder, which has a surface age of 0.1-1 s. The composition of the adsorption layer is obtained by a new approach that co-models data obtained from ellipsometry and only one isotopic contrast from neutron reflectometry (NR) without the need for any deuterated polymer. The precision and accuracy of the polymer surface excess obtained matches the levels achieved from NR measurements of different isotopic contrasts involving deuterated polymer, and requires much less neutron beamtime. The PEO concentration was fixed at 100 ppm and the electrolyte concentration at 0.1 M while the surfactant concentration was varied over three orders of magnitude. For both systems, at low bulk surfactant concentrations, adsorption of the polymer is diffusion-controlled while surfactant adsorption is under mixed kinetic/diffusion control. Adsorption of PEO is inhibited once the surfactant coverage exceeds 2 μmol m(-2). For PEO/C(14)TAB, polymer adsorption drops abruptly to zero over a narrow range of surfactant concentration. For PEO/SDS, inhibition of polymer adsorption is much more gradual, and a small amount remains adsorbed even at bulk surfactant concentrations above the cmc. The difference in behavior of the two mixtures is ascribed to favorable interactions between the PEO and SDS in the bulk solution and at the surface.     

丙烯酸/2-丙烯酰胺基-2-甲基丙磺酸高吸水树脂的反相悬浮聚合及其性能

采用反相悬浮聚合法,通过均匀实验设计,制备了聚(丙烯酸(AA)/2-丙烯酰胺基-2-甲基丙磺酸(AMPS)）(PAAMPS)高吸水树脂,探讨了单体摩尔分数及其中和度、引发剂及交联剂摩尔分数（相对于单体总量）对蒸馏水、质量分数0.9%NaCl水溶液中吸液性能的影响,并经实验数据拟合,得到了二次回归方程,比较了优化配方、单因素实验的模拟值和实验值,结果表明,模拟值与优化值基本接近,其优化工艺参数为：AMPS占单体的摩尔分数8%,中和度为75%,交联剂、引发剂用量与单体的摩尔分数分别为0.035%和0.17%,单体总质量浓度为30%,分散剂用量为单体质量分数的0.5%,反应温度70 ℃,反应时间1.5 h。 此条件下合成的PAAMPS在蒸馏水、0.9%NaCl水溶液中的吸液倍率分别为1.600和130 g/g。     

AM/AMPS共聚物光化学改性

水溶性高分子AM/AMPS系由丙烯酰胺(AM)和2-丙烯酰胺基-2-甲基丙磺酸(AMPS)组成.本文应用光化学方法对AM/AMPS共聚物进行改性,得到活性可聚合产物.应用这种方法,在高分子链上生成的过氧化物含量随UV光照时间有明显变化,照射5-10 min过氧化物含量最高.值得指出,较高的过氧化物生成量仅在采用二苯酮作为光敏剂和保持低温的条件下才能得到.这种活性改性AM/AMPS共聚物,可用光聚合或热聚合方法引发不同烯类单体共聚合,得到不同用途的接枝/交联共聚物产品.     

Polychlorinated Biphenyls-contaminated Soil Washing with Mixed Surfactants Enhanced by Electrokinetics

On the basis of comparing the adsorption loss of different surfactants[single nonionic surfactant sorbitanmonooleatepolyoxyethylene ether(Tween 80), anionic surfactant sodium dodecyl benzene sulfonate(SDBS), and mixed surfactants Tween 80/SDBS(3:2), Tween 80/SDBS(4:1)] and their performance in the enhancement of polychlorinated biphenyls(PCBs) desorption from soil, the impact of electric field intensity on the desorption of PCBs and the transport of surfactants in washing resulted solution were investigated in this study. With regard to the remediation cost, 1000 mg/L mixed Tween 80/SDBS(3:2) was recognized as an optimum concentration in the remediation of PCBs-contaminated soil, because Tween 80/SDBS(3:2) had the highest washing capacity and relatively low adsorption loss onto soil. Electrokinetics can enhance the washing efficiency of PCBs-contaminated soil by Tween 80/SDBS(3:2) effectively and safely at an electric field intensity of 1.5 V/cm for 10 d, for the desorption of PCBs was 1.57 times more than that without electrokinetics, and the most of organic residue in washing resulted solution was removed in an electrical field to avoid the possible secondary contamination risk.     

Dynamics of adsorption of an oppositely charged polymer-surfactant mixture at the air-water interface: poly(dimethyldiallylammonium chloride) and sodium dodecyl sulfate

The dynamic adsorption behavior of mixtures of the cationic polymer poly(dimethyldiallylammonium chloride) [poly(dmdaac)] and the anionic surfactant sodium dodecyl sulfate (SDS) has been studied at the expanding liquid surface of an overflowing cylinder. A combination of ellipsometry and external reflection Fourier transform infrared spectroscopy was used to measure the adsorbed amounts of poly(dmdaac) and SDS as a function of the bulk surfactant concentration for various polymer concentrations in the range 0-0.2 g dm-3. Laser Doppler velocimetry was used to determine the surface age, which was approximately 1 s for solutions where the polymer adsorbed. The interfacial behavior is rationalized in terms of competition between surface activity and mass transport to the expanding surface. At low surfactant concentrations, adsorption of both poly(dmdaac) and SDS is enhanced as a result of the formation in solution of polymer-surfactant complexes that are more surface active than either component alone. The rate of adsorption of these complexes is diffusion-controlled, and their interfacial composition remains constant at three dmdaac units per SDS molecule over a 5-fold change in the surfactant concentration. For the higher polymer concentrations studied, the complexes saturate the air-water interface: the adsorbed amount is independent of the polymer concentration and remains constant also over a factor of 5 in the surfactant concentration. Once the number of bound surfactant molecules per dmdaac monomer exceeds 0.3, the complexes begin to form large aggregates, which are not surface active due to their slower mass transport. The adsorbed amount decreases rapidly on approach to the equivalence point (one SDS molecule per dmdaac monomer), and when it is reached, only a very small amount of material remains at the interface. At still higher surfactant concentrations, the free SDS adsorbs but there is no adsorbed poly(dmdaac). The dynamic adsorption data are compared with equilibrium measurements of the same system by Staples et al. (Langmuir 2002, 18, 5147), which show very different surface compositions and no significant change in surface coverage at the equivalence point.     

聚(丙烯酰胺-丙烯酸)/聚(丙烯酰胺-二甲基二烯丙基氯化铵)聚电解质复合溶液动态光散射研究

通过动态光散射、粘度和透光率测定，研究了聚（丙烯酰胺 丙烯酸）［Ｐ（ＡＭ ＡＡ）］／聚（丙烯酰胺 二甲基二烯丙基氯化铵）［Ｐ（ＡＭ ＤＭＤＡＡＣ）］聚电解质复合溶液的结构和性能．结果表明，Ｐ（ＡＭ ＡＡ）与Ｐ（ＡＭ ＤＭＤＡＡＣ）复合比、溶液浓度和氯化钠用量影响溶液中复合物的构象和流体力学半径．Ｐ（ＡＭ ＡＡ）与Ｐ（ＡＭ ＤＭＤＡＡＣ）分子链间适度的库仑相互作用，可形成均相Ｐ（ＡＭ ＡＡ）／Ｐ（ＡＭ ＤＭＤＡＡＣ）聚电解质复合溶液，复合物具有较伸展的构象和较大的流体力学半径，因而溶液粘度较高．Ｐ（ＡＭ ＡＡ）与Ｐ（ＡＭ ＤＭＤＡＡＣ）分子链间过强的库仑相互作用或小分子电解质的屏蔽作用，可使复合物构象卷曲，结构紧缩，流体力学半径减小，甚至产生相分离，导致溶液粘度降低．     

Adsorption of sodium dodecyl sulfate at the hydrophobic solid/aqueous solution interface in the presence of poly(ethylene glycol): dependence upon polymer molecular weight

The polar orientation and degree of conformational order of sodium dodecyl sulfate (SDS) adsorbed at the hydrophobic octadecanethiol/aqueous solution interface in the presence of poly(ethylene glycol) (PEG) has been investigated as a function of the surfactant concentration and the molecular weight of the polymer. Sum frequency generation (SFG) vibrational spectroscopy was employed to obtain spectra of interfacial surfactant; weak SFG signals from interfacial polymer were also detected for polymer molecular weights of 900 and above. The phase of the SFG spectra indicated that both the surfactant and polymer had a net orientation of their CH2 and/or CH3 groups toward the hydrophobic surface. Spectra of SDS in the presence of mixed polymer/surfactant solutions showed increasing conformational order as the surfactant concentration was raised. At the lowest surfactant concentrations, the spectra of SDS were weaker in the presence of the polymer than in its absence. All PEG molecular weights investigated, with the exception of PEG 400, gave rise to significant inhibition of ordered surfactant adsorption below the critical micelle concentration. The greatest inhibitory effect was noted for PEG 900. Probing interfacial PEG specifically through the use of perdeuterated SDS revealed that the polymer spectral intensity decreased monotonically as the surfactant concentration was increased for all polymer molecular weights where a PEG spectrum was apparent. These findings are interpreted in terms of the displacement of preadsorbed polymer as the surfactant concentration increases. This result is compatible with observations of adsorption from SDS/PEG solutions at solid/solution and solution/air interfaces made using other techniques.