利用溶解度参数选择有机溶剂提取土壤中多种有机氯农药

采用基团贡献法计算了提取溶剂（正己烷、二氯甲烷、正己烷—甲醇（体积比4：1)、正己烷—丙酮（体积比1：1)、正己烷—二氯甲烷(体积比1：1))和有机氯农药（o,p′—DDT,o．p′—DDE,o,p′—DDD,α—endosubn,endrin,HCB)的色散溶解度参数(δd)、极性溶解度参数(δp)和氢键溶解度参数(δh),运用溶解度参数的理论筛选有机溶剂提取江西红壤中多种有机氯农药：研究表明正己烷—甲醇（体积比4：1)和正己烷—丙酮（体积比1：1)是提取江西红壤中o,p′—DDT,o,p′—DDE,o,p′—DDD多种有机氯农药的最佳提取溶剂（回收率大于82％),对α—endosulfan,endrin,HCB的提取也能满足检测需要（回收率大于75％)。超声波提取的结果验证了溶解度参数预测的合理性。     

反气相色谱法对八异辛基倍半硅氧烷热力学性质的表征

采用反气相色谱技术,以23种溶剂为探针分子,表征了八异辛基倍半硅氧烷(octaisooctyl-POSS)的热力学性质,包括摩尔溶解焓、分子间相互作用参数、质量活度系数、Hansen溶度参数,并有效判断了溶剂探针分子与共聚物分子间的相互作用以及共聚物在这些溶剂中的溶解性.结果表明,在实验温度范围内(343 ～393 K),烷烃、芳香烃、卤代烃类、乙醚以及乙酸甲酯是octaisooctyl-POSS的良溶剂,乙酸乙酯、乙酸正丙酯、乙酸正丁酯与乙酸正戊酯是中等溶剂,醇类、丙酮以及四氢呋喃是不良溶剂;Hansen溶度参数表明,octaisooctyl-POSS与烷烃分子强烈的色散作用使其在烷烃溶剂中具有优良的溶解性能.     

加速溶剂萃取法提取海洋沉积物中正构烷烃的方法研究

采用加速溶剂萃取法(ASE)提取了海洋沉积物中的正构烷烃,并对ASE的萃取剂比例、萃取温度、静态萃取时间以及循环次数等实验条件进行优化。结果表明,当样品长碳链正构烷烃含量较高或需要检测长碳链正构烷烃含量时,可使用甲醇-二氯甲烷(1∶3)作为萃取剂;而甲醇-二氯甲烷(1∶9)适用于短碳链正构烷烃含量较高或需要检测短碳链正构烷烃含量的样品。加速溶剂萃取提取沉积物中正构烷烃的最佳条件为:萃取温度150℃,静态提取时间15 min,循环3次。在优化条件下,测定沉积物样品中正构烷烃的精密度除C15为20%外,其余为3%~14%,替代物回收率为84%~114%。相比于传统的索氏提取法,该方法的工作效率高、回收率高、精密度良好,适用于沉积物样品中正构烷烃的定量分析。     

加速溶剂萃取-气相色谱法测定岩石中痕量正构烷烃(C21~C40)

建立了气相色谱法结合加速溶剂萃取技术测定岩石中痕量正构烷烃(C21~C40)的方法,对比了超声波萃取、加速溶剂萃取及索氏萃取3种提取方式,研究了提取溶剂及净化方式对正构烷烃测定的影响。实验结果表明:以丙酮-二氯甲烷(1∶1,V/V)为萃取剂,使用硅胶和中性氧化铝进行净化,各物质标准曲线相关系数均大于0.999,检出限为0.01~0.09μg/kg,对3个浓度的空白加标样进行回收实验和精密度实验,回收率在70.7%~91.7%之间,相对标准偏差(RSD)为1.8%~13%。方法可用于实际岩石样品中痕量正构烷烃的测定。     

聚合物-溶剂的相互作用参数

在溶解度参数理论中,聚合物-溶剂的相互作用参数X_1计算式为: X_1=V_1/RT(δ_1-δ_2)~2+β (1)式中V_1为溶剂的摩尔体积,δ_1和δ_2分别为溶剂和聚合物的溶解度参数。经验常数β是作为对Flory组合熵的改进而计入X_1中的。     

含密胺基团新型酰胺类凝胶因子的合成、性能及Hansen溶度参数对凝胶行为的预估

设计合成了一种含有密胺基团的新型酰胺类凝胶因子AMOG,其在多种常用有机溶剂中均能形成凝胶,且在甲苯和二甲苯中形成凝胶的临界凝胶浓度(CGC)约为1 mmol/L.采用"试管倒转法"确定了凝胶的溶剂-凝胶转变温度(Tgel),利用SEM表征了凝胶的微观结构,发现AMOG具有明显的溶剂效应.运用溶剂的Hansen溶度参数探索溶剂对凝胶行为的作用机制,发现溶剂的氢键作用参数(δh)对凝胶的微观结构和凝胶性质有显著影响:AMOG在1.0 MPa~(1/2)δh4.1 MPa~(1/2)的溶剂中形成透明凝胶,在4.1 MPa~(1/2)δh8.0MPa~(1/2)的溶剂中为不透明凝胶,在δh8.0 MPa~(1/2)的溶剂中为沉淀或溶液状态.进一步将溶剂的Hansen溶度参数以三维坐标(δ_d,δ_p和δ_h)表示,发现能使AMOG形成凝胶的溶剂主要集中在Hansen空间的特定区域内.实验结果表明,凝胶体系的溶液-凝胶转变温度主要受色散参数δ_d与极性参数δ_p的影响,氢键参数δh对其有微调的作用.     

基于Hansen溶度参数的煤直接液化残渣超临界萃取

以丙酮、 异丙醇和苯为溶剂在超临界状态下对煤直接液化残渣进行萃取, 应用溶度参数分析了超临界萃取环境中溶剂和萃取原料的变化; 基于Hansen拓展方法建立了关联Hansen溶度参数和萃取收率的理论方程. 结果表明, 临界温度较高. 以色散力溶度参数为主的苯的萃取收率明显高于其它2种溶剂; 液化残渣中可萃出组分的理想溶解度随温度的升高而增大, 该效应也是超临界溶剂萃取重质组分时萃取收率提高的重要原因; 萃取收率与Hansen溶度参数之间的回归模型与实验结果具有较好的一致性, 证明Hansen溶度参数理论和Hansen拓展方法适用于描述煤直接液化残渣的超临界萃取过程.     

液-液溶解度法与气-液色谱法研究溶剂-溶剂的相互作用

测量了角鲨烷(B)+邻苯二甲酸二丁酯(C)的溶解度相图, 应用HSFH二元系公式推算得相互作用参数Abc; 用气-液色谱测量了若干正构烷烃、环烷烃用作探测溶质(A)在(B+C)混合溶剂中的无限稀活度系数, 应用HSFH三元系公式推算得相互作用参数Abc, 两者符合热力学一致性。     

基于溶解度参数模拟的耐溶剂型PI膜材料的筛选

运用分子动力学模拟(MD)对典型的二元聚酰亚胺(PI)结构(BTDA-MDA)的溶解度参数(δ)进行模拟,考察了力场、分子间作用力、重复单元数和链根数对模拟结果的影响,确定了计算溶解度参数的最佳模拟参数。在二元PI溶解度参数模拟的基础上,对12种不同三元PI结构的溶解度参数进行模拟,基于与酰胺溶剂分子(DMF、DMAc)溶解度参数差值(|Δδ|)≥2(J/cm3)1/2的原则对三元PI结构进行筛选,制备耐溶剂的PI膜,并测试其在酰胺溶剂中的溶胀度。结果表明,制备的几种PI膜具有较好的耐溶剂性,说明分子动力学模拟对膜材料的筛选具有一定的指导意义。     

反气相色谱法测定离子液体1-己基-3-甲基咪唑三氟甲磺酸盐的热力学参数

采用反气相色谱法研究了343.15~373.15 K温度范围内离子液体1-己基-3-甲基咪唑三氟甲磺酸盐([HMIM]OTF)的热力学参数。根据18种探针溶剂的保留时间计算出探针溶剂与[HMIM]OTF之间的摩尔吸附焓、无限稀释的摩尔混合焓、摩尔蒸发焓、质量部分活度系数、Flory-Huggins相互作用参数及[HMIM]OTF的溶解度参数。结果表明,所选溶剂中正构烷烃、四氢呋喃、乙醚、环己烷和苯为[HMIM]OTF的不良溶剂;二氯甲烷、丙酮、氯仿、乙酸乙酯、四氯化碳、乙酸甲酯、甲苯和甲醇为[HMIM]OTF的良溶剂;运用外推法得到了室温(298.15 K)时[HMIM]OTF的溶解度参数为20.74 (J/cm³)^0.5。本研究为离子液体的应用及相关工作提供了参考。     

Effect of sulfonic group on solubility parameters and solubility behavior of poly(2,6‐dimethyl‐1,4‐phenylene oxide)

An investigation on the effect of sulfonic group on solubility parameters and solubility behavior of poly(2,6‐dimethyl‐1,4‐phenylene oxide) (PPO) is presented. Sulfonated PPO (SPPO) was prepared using chlorosulfonic acid as a sulfonating agent. The structure of SPPO was confirmed by FT‐IR, and the ion exchange capacity (IEC) of SPPO was accurately determined by conductometric titration and ¹H‐NMR. The three‐dimensional solubility parameters of SPPO defined by Hansen were estimated by group contribution, and this approach was used to obtain the three coordinates of a solubility parameter in terms of: a dispersion part δ_d, a polar part δ_p and a hydrogen bonding part δ_h. The theoretical predications of solubility behavior were characterized using “soluble sphere” in three‐dimensional space. The estimated results were in accordance with the solubility experiments in different solvents. Copyright © 2006 John Wiley & Sons, Ltd.     

Prediction of solvents extraction-the organochlorine pesticides in soil using solubility parameter

Prediction of the optimal extraction solvent based on the solubility parameter to extract the typical organochlorine pesticides from Jiangxi red soil was reported in this paper. Hildebrand solubility parameters, including dispersion coefficient (δ_d), polarity (δ_p) and hydrogen bonding (δ_h), of extraction solvents (including hexane, dichloromethane, hexane/methanol (4:1, v/v), hexane/acetone (1:1, v/v), hexane/dichloromethane (1:1, v/v) and organochlorine pesticides were calculated using group contribution method. The solvents, such as hexane/methanol (4:1, v/v) and hexane/acetone (1:1, v/v) were selected as ideal extraction solvents to extract o,p′-DDT o,p′-DDE and o,p′-DDD with high recoveries (>82%), furthermore, these solvents can be used to extract α-endosulfan, Endrin and HCB with the reliable recoveries (>75%). The estimated finding by solubility parameters was supported by the results of soxhlet extraction.     

Solubility parameters of poly(vinylidene fluoride)

The solubility behavior of poly(vinylidene fluoride) (PVDF) in about 50 liquids was investigated. The results were input to a computer program to obtain a three-dimensional representation of the polymer solubility region in the Hansen space; the values of dispersion, hydrogen bonding, and polar components of the total solubility parameter δ_t,P were evaluated. The latter was also estimated from limiting viscosity number data in the eight solvents found. Both experimental methods gave δ_t,P values in very good agreement. Comparisons among our findings, the literature, and calculated results are discussed.     

Thermodynamic interactions and characterisation of naphthenic oil by inverse gas chromatography

The thermodynamic properties of naphthenic oil, a plasticiser, were investigated by means of inverse gas chromatography (IGC) using 10 different kinds of solvents as probes. Some thermodynamic parameters, such as specific retention volume, weight fraction activity coefficient, Flory–Huggins interaction parameter, partial molar heats of mixing and solubility parameter were obtained to judge the interactions between oil and solvents and the solubility of oil in these solvents. The results indicated that n-heptane, n-hexane, cyclohexane, chloroform, benzene and diethyl ether are good solvents for oil at experimental temperatures. The solubility parameters of oil varied from 13.94 to 13.21?(J?cm^?3)^1/2 at temperature range 323–353?K. The solubility parameter of oil was calculated to be 14.38?(J?cm^?3)^1/2 at room temperature, which is consistent with that obtained using surface tension–solubility parameter relation method.     

紫草中活性成分的非极性溶剂动态微波提取及高效液相色谱法测定

用非极性溶剂动态微波辅助提取,高效液相色谱法测定紫草中的紫草素和β,β′-二甲基丙烯酰紫草素.考察了微波吸收介质类型、提取溶剂种类、提取溶剂流速、微波功率和样品粒度对提取产率的影响,优化提取参数.在优化条件下,将所建立的方法与超声提取和索氏提取相比,所得紫草素和β,β′-二甲基丙烯酰紫草素的产率相差不大,但本文所建立的方法所需提取时间短(5min)、溶剂消耗少(10mL).与极性溶剂动态微波辅助提取相比,提取产率大幅度提高.结果说明,所建立的方法是一种有效的提取中草药中一些活性成分的方法,特别是对于一些在非极性溶剂中有更高溶解度的化合物,此方法更具优势.     

反气相色谱法测定环氧树脂的表面张力和溶解度参数

采用反气相色谱(IGC)测定了环氧E51树脂在30、40、50和60 ℃下的表面张力和溶解度参数。采用Schultz法,以正癸烷、正壬烷、正辛烷和正庚烷为非极性溶剂探针,计算了不同温度下环氧E51树脂的色散表面张力。根据Good-van Oss方程,以甲苯为碱性探针,二氯甲烷为酸性探针,计算得到环氧E51树脂的极性表面张力。结果表明,环氧E51树脂的色散表面张力和极性表面张力均随着温度的升高而线性降低。根据不同溶剂探针与树脂间的Flory-Huggins相互作用参数,采用DiPaola-Baranyi和Guillet方法计算得到环氧E51树脂在不同温度下的溶解度参数,其在30、40、50和60 ℃下分别为11.78、11.57、11.48和11.14 MPa1/2。根据表面张力、内聚能和溶解度参数的相互关系,计算得到不同温度下溶解度参数的色散和极性分量。结果发现,环氧E51树脂的溶解度参数的色散分量大于极性分量,且均随着温度的升高而降低。     

A new way to determine the three-dimensional solubility parameters of hydrogenated nitrile rubber and the predictive power

In order to understand the swelling behavior of hydrogenated nitrile rubber (HNBR) more fully, the total solubility parameters (δ_t) of HNBR (Therban 2568) were determined by equilibrium swelling tests. Then, the swelling responses were analysed by a computer program to determine the Hansen three-dimensional solubility parameter (HSP). The HSP values – determined from lightly cured rubber samples – were estimated as δ_d = 18.4 (J/cm³)^1/2, δ_p = 6.0 (J/cm³)^1/2, δ_h = 4.5 (J/cm³)^1/2 and δ_t = 19.9 (J/cm³)^1/2. The energy difference (Ra) between HNBR and solvents or solvent mixtures have been calculated by their HSP values and proven to be useful for predicting the swelling behaviour of HNBR. The swelling volume decreases with increasing Ra values. Using blended solvents, a clear correlation between Ra values and the rubber swelling response was established. Thus, it may be possible to use the Hansen three-dimensional solubility parameters to predict swelling phenomena of cured rubber articles in mixed fluids such as bio-fuels or lubricants. Also, the HSP values may be used to predict the response of rubber seals or gaskets when replacing toxic or expensive fluids with more favorable environmentally friendly or inexpensive ones.     

Solubility parameters of poly(sulfonyldiphenylene phenylphosphonate) and its miscibility with poly(ethylene terephthalate)

The solubility behaviors of poly(sulfonyldiphenylene phenylphosphonate) (PSPPP), a very efficient flame retardant for poly(ethylene terephthalate) (PET), in more than 50 solvents were examined. Its solubility parameters (δ) were determined by the intrinsic viscosity and turbidic titration methods. The two methods obtained consistent results, δ = 21.0–21.6 J^1/2/cm^3/2 and δ = 21.0 J^1/2/cm^3/2, and the three‐dimensional solubility parameters were δ_d = 18.9 J^1/2/cm^3/2, δ_p = 8.8 J^1/2/cm^3/2, and δ_h = 5.9 J^1/2/cm^3/2. The miscibility of PSPPP with PET was estimated by the calculation of the heats of mixing, which were related to the difference between the solubility parameters of PSPPP and PET. Fourier transform infrared was used to examine the interactions between PSPPP and PET macromolecules, which were the internal factors of polymer–polymer miscibility. The results showed that PSPPP and PET were miscible within a very wide composition range, especially with less than 15 wt % PSPPP, a composition of interest for the preparation of flame‐retardant PET. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2296–2301, 2003     

Determination of gossypol solubility

To improve the extraction of gossypol from the cotton seeds, the solubility of gossypol in different solvents and at different concentrations of micelles was studied. Petroleum ether, hexane, and extraction benzol were used as solvents. Model micelles were prepared from the cotton oil free of gossypol; concentration of micelles ranged from 0 to 50%. Pure gossypol was added to the micelles in the amount sufficient for formation of saturated solution. The solution was then heated to a temperature close to the boiling point of the respective solvent for 10 minutes. The undissolved gossypol was then filtered off, washed and degreased with petroleum ether, dried and weighed. The amount of dissolved gossypol was determined by the difference between the initial and remaining amounts. Solubility of gossypol in the micelles was found to rise with the increase in the oil content. The solubility grew with the increase in the boiling point of a solvent. At micelles concentrations of 0-25%, solubility of gossypol increased in proportion to the increase in oil concentration. Further increase in the concentration resulted in marked rise in solubility, which reached 2.83% in the pure oil.