疏水缔合聚合物P(AM-AMPS-SA)的合成与性能研究

采用2-丙烯酰胺基-2-甲基丙磺酸(AMPS)与丙烯酸十八酯(SA)、丙烯酰胺(AM)通过自由基胶束共聚法合成疏水缔合聚合物P(AM-AMPS-SA)。经红外和核磁共振表征聚合物结构,并测定在不同剪切速率、NaCl、CaCl2浓度及温度条件下的聚合物溶液表观黏度的变化以及聚合物溶液的临界缔合浓度。结果表明,所制备的疏水缔合聚合物P(AM-AMPS-SA),它的临界缔合浓度在0.25~0.3g/dL,具有一定的抗温、抗盐性以及抗剪切性,且对二价盐的抗盐性比一价盐要好。     

二元醇混合物汽液相平衡的GEMC模拟与微观结构分析

采用Gibbs蒙特卡罗模拟方法和OPLS-AA力场计算了乙二醇（EG）/1,2-丁二醇（1,2-BDO）、乙二醇/1,3-丁二醇（1,3-BDO）、乙二醇/1,4-丁二醇（1,4-BDO）三组二元醇混合物的汽液相平衡数据,通过与实验数据及Wilson状态方程计算数据的比较验证了方法和力场对体系汽液相平衡预测的适用性。对混合体系饱和液相的径向分布函数分析可知,各二醇间存在与羟基官能团位置近似无关的强氢键作用和作用范围不同的范德华作用。经体系O-O平均数目的统计及氢键缔合比例分析发现,随乙二醇组成增大,3种体系的微观结构由主要包含较大的BDO-BDO、BDO-EG缔合结构（>6）向包含较小的EG-BDO、EG-EG缔合结构（2～4）转变,且缔合比例下降。Molclus+Gaussian09对小分子EG、1,2-BDO缔合结构进行能量优化与构型搜索,由此提出了二醇缔合比例随EG组成变化的可能原因：1,2-BDO间缔合结构稳定于其他缔合结构,随缔合分子数增大,各缔合结构稳定性增加,但EG自缔成大分子结构的稳定性与其和BDO缔合成小分子结构稳定性差异减小。     

微乳液聚合法AM-SMA疏水缔合聚合物的研究

通过甲基丙烯酸十八酯(SMA)与丙烯酰胺(AM)微乳液聚合合成了疏水缔合聚合物,采用红外光谱(FTIR)表征了疏水缔合聚合物的结构,考察了SMA含量、AM含量、聚合物浓度、NaCl浓度以及剪切速率对疏水缔合聚合物溶液表观粘度的影响。结果表明聚合物水溶液临界缔合浓度为0.6g/dL,疏水缔合聚合物表现出较强的盐增粘效应和抗盐性;12%SMA的疏水缔合聚合物水溶液表现出剪切增粘和假塑性流体行为,FTIR谱图初步证实疏水缔合聚合物的结构。     

油井酚醛树脂封堵剂封堵固化机理研究

为了保证酚醛树脂堵剂的注入性和封堵效果,设计了将热塑性的树脂预聚体注入地层后在地层中再固化而形成连续的高强度树脂封堵带的段塞封堵材料工艺。水溶性酚醛树脂固化效果是封堵剂能否成功的关键。利用红外光谱与DSC,测定酚醛树脂固化过程分子结构变化趋势,获得了树脂预聚体固化机理,结果表明,树脂预聚体固化后形成的羟基缔合结构是树脂具有高强度的主要原因,随着温度升高,当温度达到70℃后,固化时间7 h以后,酚醛树脂完全固化后,3 414.5 cm^(-1)处发现了缔合羟基峰,在1 400 cm(-1)处发现了缔合羟基峰,在1 400 cm^(-1)出现对-对位连接方式产生的亚甲基桥吸收峰,出现了酚醛树脂固化后网状缔合结构,使得酚醛树脂材料具有较高强度。     

系列尼古丁PVC膜选择性电极的研制

以尼古丁为研究对象 ,研制了一系列含有不同增塑剂 (苯二甲酸二辛酯、苯二甲酸二壬酯和癸二酸二辛酯 )和电活性物质 (尼古丁 四苯硼缔合物、尼古丁 硅钨酸缔合物、尼古丁 磷钨酸缔合物和尼古丁 雷氏盐缔合物 )的PVC膜电极。所有的 8支电极均对尼古丁盐酸溶液有Nernst响应。所制备的电极中 ,以尼古丁 四苯硼缔合物、尼古丁 硅钨酸缔合物、尼古丁 磷钨酸缔合物或尼古丁 雷氏盐缔合物为活性物的电极 ,其线性范围达到 10 - 4～ 10 - 1 mol/L ,以尼古丁 硅钨酸缔合物为活性物的电极线性范围达到 10 - 5～ 10 - 1 mol/L。电极响应的均匀性还在进一步的研究和改善中     

水体系中含卟啉基团的两亲高分子的自组装行为和性质的研究

在文中合成了两种不同的卟啉单体5-(4-acryloyloxyphenyl)-10,15,20-tris(4-carboxylphenyl)porphyrinate zinc(II)(ZnAOTCPP)和5-(4-acrylo-yloxyphenyl)-10,15,20-tris(4-methoxycarboxylphenyl)porphyrinate zinc(II)(ZnMeAOTCPP),它们分别与丙烯酰胺(Acrylamide,AM)聚合得到含有卟啉基团的两亲高分子.与对应的单体相比,含有三羧酸卟啉基团的高分子在水中形成了一个新的紫外吸收峰和一个新的荧光发射峰,而含有三羧酸甲酯卟啉基团的高分子除此之外在更长波的方向上还另外出现了一个新的紫外吸收峰和一个新的荧光发射峰.随着高分子水溶液浓度的提高,高分子中卟啉基团的光谱性质的变化趋势显示高分子在水中的自组装行为可以分为分子间缔合和分子内缔合的两种情况.此外,实验结果显示含有三羧酸甲酯卟啉基团的高分子相对于含有三羧酸卟啉基团的高分子更加有利于卟啉缔合物的形成.     

环戊酮-甲醇氢键复合物的热力学性质

测定了常压下环戊酮(CPN)与CH3OH二元混合体系在283.15—333.15 K之间全摩尔分数范围的密度,并基于密度数据计算了该混合体系的超额摩尔体积。其超额摩尔体积在所测定的温度和全摩尔分数范围内均呈负偏差。表明该二元混合体系中分子间的交叉缔合作用强于分子间的自缔合作用。同时采用B3LYP/6-311++G(d,p)方法研究了CPN与CH3OH氢键复合物的氢键结构和性质。经几何优化和振动分析获得了2种稳定的氢键复合物。基于统计热力学方法计算了200.00—800.00 K之间从单体形成氢键复合物的热力学性质变化,结果表明CPN和CH3OH分子间氢键交叉缔合是一个放热、熵减的热力学非自发过程。     

疏水缔合型聚合物P(AM/TA)溶液性质的研究

采用沉淀聚合法制备了疏水缔合型聚合物丙烯酰胺 /丙烯酸十四酯共聚物P(AM/TA)。研究了在链结构中引入不同疏水基团摩尔分数的共聚物的溶液性质。结果表明该共聚物在w(NaCl) =1 5 %的溶液中的黏度较之水溶液有较大提高 ,表现出明显的抗盐性质 ,而临界缔合质量分数和特性黏度均出现下降趋势。该聚合物是一种性能优异的疏水缔合型增稠剂。作者对共聚物溶液的黏度 -温度性质和剪切速度对溶液黏度的影响也进行了研究。     

油井酚醛树脂封堵剂封堵固化机理研究

为了保证酚醛树脂堵剂的注入性和封堵效果,设计了将热塑性的树脂预聚体注入地层后在地层中再固化而形成连续的高强度树脂封堵带的段塞封堵材料工艺。水溶性酚醛树脂固化效果是封堵剂能否成功的关键。利用红外光谱与DSC,测定酚醛树脂固化过程分子结构变化趋势,获得了树脂预聚体固化机理,结果表明,树脂预聚体固化后形成的羟基缔合结构是树脂具有高强度的主要原因,随着温度升高,当温度达到70℃后,固化时间7 h以后,酚醛树脂完全固化后,3 414.5 cm~(-1)处发现了缔合羟基峰,在1 400 cm~(-1)出现对-对位连接方式产生的亚甲基桥吸收峰,出现了酚醛树脂固化后网状缔合结构,使得酚醛树脂材料具有较高强度。     

藏红T萃取-浮选光度法测定痕量钯

研究了Pd(Ⅱ)-Br~--藏红T(ST)萃取-浮选体系的最佳条件。在pH 1.5～0.2M盐酸介质中,Pd(Ⅱ)-Br~--ST离子缔合物可被苯定量浮选。浮选物溶于丙酮,在520 nm进行光度测定,ε_(520mm)=2.2×10~5l·mol~(-1).cm~(-1)。测得Pd:Br:ST=1:5:3,推测生成了[PdBr_4~(2-)·2 ST~+]·EBr~-·ST~+]复杂离子缔合物。选择性也较好,可用于矿石和有色冶炼渣中痕量钯的测定。提出了生成复杂离子缔合物是缔合物能萃取浮选的主要原因,也是萃取-浮选光度法灵敏度普遍高于相应萃取光度法的根本原因。     

Hydrotropic properties of a novel alkylnaphthalene sulfonate

Alkylbenzenesulfonates based on toluene, xylene, as well as cumene, and alkylnaphthalenesulfonates, act as hydrotropes in surfactant systems. A novel sodium diisopropyl-naphthalene sulfonate (SDIPNS) has been devepoped that contains about 92% diisopropylnaphthalene sulfonate, compared to other diisopropylnaphthalene sulfonate preparations that contain less than 50% diisopropylnaphthalene sulfonate. This material is both a hydrotrope and a surfactant. The color of a 35% solution is light yellow, Gardner 3, significantly lighter than comparable materials. Draves wetting time for a 0.5% solution is about 30 s. The Ross-Miles foam test (1% solution) indicates a significant level of initial foam, but the foam is unstable. The solubilites of toluene and limonene in SDIPNS are much higher than in other hydrotropes tested. Hydrotropes raise the cloud point of nonionic surfactants; SDIPNS is the most efficient hydrotrope found for this application. Another measure of hydrotropicity is the amount of hydrotrope required to clear a cloudy detergent formulation; this hydrotrope is quite effective. Another measure is the modification of surfactant formulation viscosity; SDIPNS is quite effective. Additionally, SDIPNS changes the solubility of nonionic surfactants in water. SDIPNS is a surfactant as well as a hydrotrope, demonstrating a critical micelle concentration at about 1%. Presented as a poster session at the American Oil Chemists' Society Annual Meeting & Expo, May 11–13, 1998, Chicago, IL.     

Aqueous Hydrotropic Solution as an Efficient Solubilizing Agent for Andrographolide from Andrographis paniculata Leaves

Abstract

An aqueous solution based extraction process for andrographolide from Andrographis paniculata leaves has been developed using alkyl benzene sulfonates and carboxylates as hydrotropes. The plant cells are permeabilized by the hydrotrope solutions followed by solubilization of andrographolide into the solutions. The extraction and solubilization of andrographolide is affected by structure and concentration of hydrotrope, temperature and particle size. Sodium cumene sulfonate (Na‐CS) shows the most efficient solubilization of andrographolide amongst the hydrotropes studied. The solubility of andrographolide increased by two orders of magnitude in Na‐CS aqueous solutions and ～96% andrographolide extraction was achieved in just 20 min.     

Extraction of Piperine from Piper Nigrum (Black Pepper) by Aqueous Solutions of Surfactant and Surfactant + Hydrotrope Mixtures

Abstract

The effect of combining butyl benzene sulfonate as hydrotrope with a surfactant in aqueous solutions is investigated for isolation of piperine, an alkaloid, from black pepper. The standard free energy change associated with piperine solubilization in the aqueous solutions of surfactant and hydrotrope individually and in their mixtures is determined from the solubility of piperine in these solutions. A combination of sodium dodecyl sulfate (SDS) and the hydrotrope gives increased percentage extraction of piperine as compared to the hydrotrope alone. The piperine purity recovered from aqueous solutions was higher as compared to the purity of piperine recovered using organic solvents. The piperine crystallized from aqueous solutions of surfactants and hydrotrope also showed cleaner surfaces and uniform structures with sharp edges, unlike the particles crystallized from organic solvents.     

Alkyl polyglucosides as hydrotropes

The hydrotropic effect of different alkyl polyglucosides (APG) has been studied and compared with a model hydrotrope, toluol-4-sulfonic acid. The effect has been assessed by two different methods: (i) as the cloud point elevation of a solution containing different nonionic surfactants upon addition of the hydrotrope and (ii) the destabilization of liquid crystaline phases in a ternary system. The effect of the hydrophobic alkyl group length was found to be opposite in the two methods. APG with intermediate alkyl chain lengths (octyl and decyl) was shown to be very effective in elevating the cloud point, while APG with a short (butyl) group was the most efficient in destabilizing liquid crystalline phases in the system of water, sodium dodecyl sulfate and pentanol. Effects on phase behavior and cloud point elevation with addition of an APG are highly dependent on its structure. However, the correlation between structural effects, as observed in the two methods requires further study.     

Effective Separation of Petro Products through Hydrotropy

This paper presents a comprehensive study on the effect of hydrotropes such as sodium salicylate, sodium benzoate, and nicotinamide on the separation of a near boiling mixture, o‐/p‐xylene. The influence of a wide range of hydrotrope concentrations (0 to 3.0 mol/L) and different system temperatures (303 to 333 K) on the separation of o‐/p‐xylene were studied. All hydrotropes used in this work showed an enhancement in the percentage extraction of p‐xylene to different degrees. The percentage extraction of p‐xylene from the o‐/p‐xylene mixture increases with an increase in hydrotrope concentration and also with system temperature. A minimum hydrotrope concentration (MHC) was found essential to initiate significant extraction of p‐xylene from the o‐/p‐xylene mixture. The maximum enhancement factor, which is the ratio of the value in the presence and absence of a hydrotrope, was determined for both cases. The Setschenow constant, k_s, a measure of the effectiveness of a hydrotrope, was determined for each case.     

Hydrotropic effect and thermodynamic analysis on the solubility and mass transfer coefficient enhancement of ethylbenzene

Concentrated aqueous solutions of a large number of hydrotropic agents, urea, nicotinamide, and sodium salicylate, have been employed to enhance the aqueous solubilities of poorly water soluble organic compounds. The influence of a wide range of hydrotrope concentrations (0–3.0mol·L^?1) and different system temperatures (303–333 K) on the solubility of ethylbenzene has been studied. The solubility of ethylbenzene increases with increase in hydrotrope concentration and also with system temperature. Consequent to the increase in the solubility of ethylbenzene, the mass transfer coefficient was also found to increase with increase in hydrotrope concentration at 303 K. The enhancement factor, which is the ratio of the value in the presence and absence of a hydrotrope, is reported for both solubility and mass transfer coefficient of ethylbenzene. The Setschenow constant, K _s , a measure of the effectiveness of a hydrotrope, was determined for each case. To ascertain the hydrotropic aggregation behavior of ethylbenzene, thermodynamic parameters such as Gibb’s free energy, enthalpy, and entropy of ethylbenzene were determined.     

Effect of hydrotropes on the aqueous solution behavior of surfactants

Aqueous solutions of surfactants—cationic: tetradecyltrimethylammonium bromide (C₁₄TABr); anionic: sodium dodecyl sulfate (SDS); and nonionic: polyoxyethylene t-octylphenol (trade name Triton X-102, also called OPE-8)— in the presence of three hydrotropes, viz., sodium xylene sulfonate, sodium p-toluene sulfonate, and sodium chlorobenzene sulfonate, were examined by measuring surface tension, viscosity, and cloud points for the nonionic surfactant. The results show a marked decrease in the critical micelle concentration with increase in hydrotrope concentration for C₁₄TABr, a marginal decrease for SDS, and very little change for OPE-8 up to 0.1 M hydrotrope. The viscosity of cationic surfactant solutions showed a remarkable increase in the presence of trace amounts of hydrotropes (up to 15 mM). In contrast, the SDS solution showed only a slight increase in viscosity at high hydrotrope concentration (150 mM), and the viscosity of the OPE-8 solution remained constant. The cloud point of OPE-8 increased in the presence of hydrotropes, unlike its behavior with the simple salt NaCl. The strong dependence of the solution behavior of cationic surfactants on the presence of hydrotropes is discussed in terms of electrostatic interaction.     

ENHANCEMENT OF SOLUBILITY AND MASS-TRANSFER COEFFICIENT OF 1,2-DIHYDROXY-9,10-ANTHRAQUINONE (ALIZARIN) THROUGH HYDROTROPY

The effect of hydrotropes potassium p-toluene sulfonate (KPTS), citric acid, and nicotinamide on the solubility and mass-transfer coefficient of 1,2-dihydroxy-9,10-anthraquinone (alizarin) was studied. Solubility studies were carried out under a wide range of hydrotrope concentrations (0 to 3.0 mol·L^?1) and different system temperatures (303 to 333 K). It was observed that the solubility and mass-transfer coefficient of alizarin increases with an increase in hydrotrope concentration and system temperature. The maximum enhancement factor, the ratio of the value of solubility in the presence and absence of a hydrotrope, was determined for all experiments under study. The effectivity of hydrotropes was measured by the determination of the Setschenow constant, K_s. The order of effectiveness of various hydrotropes based on K_s values is potassium p-toluene sulfonate > citric acid > nicotinamide.     

水溶助长剂的效果研究

介绍了碱性洗涤剂配方的助溶剂计算与选择，以及一种特殊的磷酸酯两性表而活性剂，该表面活性剂可以提供助溶性、增强清洗能力，同时还能保护铝表面等材质免受腐蚀，与聚碳酸酯和聚乙烯材质亦相容性很好。     

添加剂的浓度对非离子表面活性剂AEO9浊点的影响

各类添加剂都能对非离子表面活性剂的浊点产生影响.今研究了离子型表面活性剂、增溶物和电解质类添加剂在不同浓度下对非离子表面活性剂AEO9浊点的影响.其中离子型表面活性剂和增溶物类添加剂可在极低的浓度上改变AEO9的浊点,且随着添加剂加入浓度的增加,AEO9的浊点也逐渐增加,当添加剂浓度达到离子型表面活性剂或增溶物的临界胶束浓度时,AEO9的浊点将出现急剧上升.而电解质类添加剂对AEO9浊点的影响表现出具有临界浓度现象,只有当添加剂的浓度达到相应的临界浓度之后,具有盐析效应的电解质将使AEO9浊点线性下降,而具有盐溶效应的电解质则使AEO9浊点线性升高,且不同电解质相应的临界浓度随着其阴离子的感胶离子数的增大而线性增加,同时其对AEO9浊点的改变程度则随着阴离子的感胶离子数的增大而线性下降.