Estimating Hansen solubility parameters of organic pigments by group contribution methods

The Hansen solubility parameters(HSP)are frequently used for solvent selection and characterization of polymers,and are directly related to the suspension behavior of pigments in solvent mixtures.The performance of currently available group contribution(GC)methods for HSP were evaluated and found to be insufficient for computer-aided product design(CAPD)of paints and coatings.A revised and,for this purpose,improved GC method is presented for estimating HSP of organic compounds,intended for organic pigments.Due to the significant limitations of GC methods,an uncertainty analysis and parameter confidence intervals are provided in order to better quantify the estimation accuracy of the proposed approach.Compared to other applicable GC methods,the prediction error is reduced significantly with average absolute errors of 0.45 MPa^(1/2),1.35 MPa^(1/2),and 1.09 MPa^(1/2) for the partial dispersion(δD),polar(δP)and hydrogen-bonding(δH)solubility parameters respectively for a database of 1106 compounds.The performance for organic pigments is comparable to the overall method performance,with higher average errors forδD and lower average errors forδP andδH.

A THEORETIC METHOD TO PREDICT POLYMER SOLUBILITY PARAMETERS

A partition function and a complete thermodynamic description for pure polymer fluids have been investigated based on a self-avoid-walk lattice model. Caused by the introduction of Gibbs distribution into the Flory-Huggins theory, the partition function and the thermodynamic description depicted their dependence on temperature well. In the present study, we applied the theory to calculate polymer solubility parameters. The polymer solubility parameters predicted by our theory are well consistent with the experiment values.

Selection of Extraction Solvents for Bitumen from Indonesian Oil Sands through Solubility Parameters

Indonesian oil sands were systematically separated to investigate their basic composition.The extraction effects of the solvents with different Hilderbrand solubility parameters(HSPs)on the bitumen of Indonesian oil sands were compared.Furthermore,the Hansen solubility combination parameter(HSCP)and Teas triangle were used to explore rules in the separation of oil sands bitumen via solvent extraction.Finally,the saturates,aromatics,resins,and asphaltenes(SARA)fractions of the bitumen from Indonesian oil sands were analyzed.The results showed that the Indonesian oil sands were oil-wet with a bitumen content of 24.93%.The solvent extraction for bitumen could be accurately and conveniently selected based on the solubility parameter.When the HSPs of the extraction solvent were around 18–19 and the HSCPs were closer to a certain range(δ_(d)=17.5–18.0,δ_(p)=1–3.5,and δ_(h)=2–6),the extraction effect of bitumen from Indonesian oil sands improved,and the primary component affecting the extraction rate of bitumen were asphaltenes.

Calculation of Hildebrand Solubility Parameters of Some Polymers Using QSPR Methods Based on LS-SVM Technique and Theoretical Molecular Descriptors

In this work, some chemometrics methods are applied for the modeling and prediction of the Hildebrand solubility parameter of some polymers. A genetic algorithm （GA） method is designed for the selection of variables to construct two models using the multiple linear regression （MLR） and least square-support vector machine （LS-SVM） methods in order to predict the Hildebrand solubility parameter. The MLR method is used to build a linear relationship between the molecular descriptors and the Hildebrand solubility parameter for these compounds. Then the LS-SVM method is utilized to construct the non-linear quantitative structure-activity relationship （QSAR） models. The results obtained using the LS-SVM method are then compared with those obtained for the MLR method; it was revealed that the LS-SVM model was much better than the MLR one. The root-mean-square errors of the training set and the test set for the LS-SVM model were 0.2912 and 0.2427, and the correlation coefficients were 0.9662 and 0.9518, respectively. This paper provides a new and effective method for predicting the Hildebrand solubility parameter for some polymers, and also reveals that the LS-SVM method can be used as a powerful chemometrics tool for the quantitative structure-property relationship （QSPR） studies.

Correlation between solubility parameters and recovery of phenolic compounds from fast pyrolysis bio-oil by diesel extraction

Fast pyrolysis bio-oils(fpBO)were extracted with two alternative commercial transportation fuels,hydrocarbon diesel and bio-diesel.The extraction of fpBO with commercial diesel fuel provided a yield of 4.3 wt%,but the yield increased significantly to 26.6 wt%when bio-diesel was the extractant.The molecular weight of fpBO before and after extraction were consistent with the loss of a more soluble,low molecular weight fraction from the crude fpBO.The relative energy difference(RED),based on the Hansen solubility parameter(HSP),is used to examine the extraction efficiency of specific compounds in the two different‘solvents’.Differences in the RED values could be used to rationalize differences in the partitioning of common fpBO phenolics.

Evaluation of Compatibilizers for Improving Compatibility between Waste Vegetable Oil and Aged Asphalt

Modifying agents 2,2-Bis(4-glycidyloxyphenyl)propane(2BPE)and dibutyl phthalate(DBP)were selected to enhance the compatibility.By using molecular simulation software(Materials Studio,MS),nine systems were constructed,including molecular models of aged asphalt and WVO monomers with 2BPE and/or DBP.The solubility parameters,Flory-Huggins parameters,and interaction energies of these systems were calculated to determine the impact of 2BPE and DBP on the compatibility of WVO and aged asphalt.Results showed that the addition of 2BPE and DBP reduced the difference in the solubility parameters between WVO and aged asphalt,thus improving the compatibility between WVO and aged asphalt.Additionally,using a combination of 2BPE and DBP in both aged asphalt and rejuvenator was found to be more effective than using either 2BPE or DBP alone.Finally,it was determined that evaluating the compatibility of WVO and aged asphalt using Van der Waals potential and non-bonding energy as evaluation indicators was more accurate than using electrostatic potential energy.

Effects of solubility parameter differences among PEG,PVP and CA on the preparation of ultrafiltration membranes:Impacts of solvents and additives on morphology,permeability and fouling performances

The effects of two different hydrophilic additives and two solvents on the membrane morphological structure,permeability property and anti-fouling performances of cellulose acetate(CA) ultrafiltration membranes were investigated. During the phase-inversion process, cellulose acetate was selected as a membrane forming polymer; polyethylene glycol(PEG) and polyvinyl pyrrolidone(PVP) were used as additives; acetone(Ac): N,N-Dimethylacetamide(DMAc) and N, N-Dimethylformamide(DMF) were used as solvents; and deionized(DI)water was used in the coagulation bath. All the prepared membranes were characterized in terms of hydraulic permeability(Pm), membrane resistance, average pore radius, and hydrophilicity. The top surface and crosssectional view of the prepared membranes were also observed by using field emission scanning electron microscopy. Membrane fouling and rejection experimentations were done using a stirred batch-cell filtration set-up.The experimental studies of fouling/rinsing cycles, rejection, and permeate fluxes were used to investigate the effect of PEG and PVP additives and effect of the two solvents on the fabricated membranes using bovine serum albumin(BSA) as a model protein.

Physicochemical Characterization and Solubility Enhancement Studies of Mebendazole Solid Dispersions in Solvent Mixtures

Abstract： The objective was to obtain solid dispersion to improve the dissolution rate, solubility and oral absorption of MB （mebendazole）, poor water-soluble drugs. The new formulation was characterized by DSC （differential scanning calorimetry）, PXRD （powder X-ray diffraction）, FT-1R （fourier transform infrared spectroscopy） and STEM （scanning transmission electron microscopy） methods. Solid dispersions of MB with polyvinylpyrrolidone K-30 （PVP K30） were prepared by solvent evaporation method. The solubility of MB （original powder） and that of the solid dispersions was measured at 25℃ in ethanol-water. The aqueous solubility of MB was favoured by the presence of the polymer in solvent mixtures. Combination of solid dispersions with co-solvents increased the water solubility of MB in a larger extent that each method separately. Solubility parameter （o） was used to relate to solubility profiles. MB and the solid dispersions show a solubility curve with a single peak at 51 = 30.78 MPav2. Solid state characterizations indicated that the solid dispersion exist an amorphous material entrapped in polymer matrix getting highest improvement in wettability and solubility.

Protic ionic liquids/poly(vinylidene fluoride) composite membranes for fuel cell application

Poly(vinylidene fluoride), PVDF, membranes have attracted considerable attention as polymer electrolytes for fuel cells. This study explores the effect of solvent on the spherulite size and the crystallinity of the polymeric membranes. Based on Hansen solubility parameters theory, the mixture of DMC and DMSO was selected among a dozen of solvents for the preparation of PVDF membranes by thermally induced phase separation. The addition of two protic ionic liquids(PILs), bis(2-ethyl hexyl) ammonium hydrogen phosphate [EHNH_2][H_2PO_4], and imidazolium hexanoate [Im][Hex] to PVDF membranes at concentrations(10% < wP IL< 50%) has been investigated by SEM, FTIR, DSC, TGA, EIS, and DMA. The inclusion of ionic liquids into the polymer matrix influences structural parameters(degree of crystallinity and electroactive phases), thermal stability, proton conductivity and mechanical properties of the membranes. The membranes become transparent regardless type of ionic liquid employed. A small amount of ionic liquids increases the degree of crystallinity and facilitates the production of polar β and γ crystals. The proton conductivity mechanism(Grotthuss) is dependent on the ionic liquid structure(due to its selforganization in water) and the content in the PVDF membrane, as well as the membrane water uptake.Different behavior has been observed for the two ionic liquids, which stresses the challenge on selecting an appropriate cation and anion combination. The obtained composite membranes exhibited excellent mechanical performance and reduced elastic modulus, with respect to the pure polymer matrix. These results indicate that PVDF/IL composite membranes have a high potential for PEMFC applications.

Tuning Intermolecular Interaction Between Lignin and Carbon Nanotubes in Fiber Composites–A Combined Experimental and Ab-Initio Modeling Study

Doping lignin with carbon nanotubes is a promising strategy for cost-effective high-performance carbon fibers.We investigate the intermolecular interaction potential of CNT and organosolv lignin with two main approaches.Experimentally,oxidized purified multiwalled carbon nanotubes(MWCNTs)and beech organosolv lignins and derivatives are analyzed with their Hansen solubility parameters(HSPs)to assess their mutual compatibility.Theoretically,dispersion-corrected density functional theory simulations of the interaction between model molecules and single-walled carbon nanotubes reveal the source of interactions.We find that oxidation enables and enhances the interaction between carbon nanotubes and organosolv lignin experimentally,which is in agreement with the enhanced polar interaction found in the simulations.

Preparation and Crystal Modification of Ibuprofen-Loaded Solid Lipid Microparticles

An emulsion-congealing technique is used to prepare solid lipid microparticles （SLM） containing ibuprofen with glyceryl behenate, tripalmitin and beewax as excipients. The difference of the solubility parameters between the excipients and ibuprofen are used to analyze their compatibility. Both the solubility parameter analysis and the experimental results show that glyceryl behenate is the best among the three excipients. The solid particles disperse well in aqueous phase when the drug loading reaches 10% （relative to lipid only）. Glycerides exhibit marked polymorphism and their rapid rates of crystallization accelerate the formation of metastable crystal modification. The metastable crystal modification characterizes high drug loading capacity but less stability. Increasing the content of lipophilic drug in a lipid matrix facilitates the transformation of excipients to more stable polymorphic forms.

STUDIES ON CRITICAL CONCENTRATION OF LIQUID CRYSTALLINE ETHYLCELLULOSE

Critical concentrations of lyotropic liquid crystalline ethylcellulose in more than ten solvents were determined using both Abbe refractometer and polarized microscopy. Critical concentration C-crit of forming Liquid crystal phase decreased with increasing solubility parameter delta of solvent until approaching the delta of polymer. Although the alcohols used as solvents had the same variation rule, the critical concentration values of their solutions were much higher, due to their excessive large hydrogen bond component of delta. The experiments of using mixed solvents which showed good linear relation between C-crit and delta also proved this rule. A technique of Transmission Optical Analysis was first used to estimate the concentration dependence of critical phase transition temperature T-crit of EC, and a T-C phase diagram could be drawn.

EFFECT OF SOLVENT COMPOSITION ON THE SULFONATION DEGREE OF POLY(PHENYLENE OXIDE) (PPO)

This paper investigates the possibility of attaining sulphonated poly(phenylene oxide) (SPPO) with a relativelyhigher sulfonation degree. To achieve this aim, the approach we adopt is to improve the solubility of the final product in themixed solvent so that the sulfonation may take place between the bulk solutions and PPO powders even at higher sulfonationdegree. It is shown that the addition of a proper amount of dimethyl formide (DMF) to the conventional PPO-chloroformsystem can actually enhance the sulfonation effect. The solvent composition is then correlated with the sulfonation degreebased on the solubility parameters. It is interesting to find that solubility parameters between the mixed solvent and theprecipitated products keep an approximately unchanged value at about 4.9, which is just equal to that when pure chloroformis used, though the solubility parameters of both solvents increase with the content of DMF in solution. This may be the mainreason why the addition of DMF can reduce the precipitation and improve the ion exchange capacity (IEC) of SPPOpolymer.

Prediction of Liquid-Liquid Equilibrium Using the Group Solubility Parameter Model

The group solubility parameter （GSP） model was used to analyze the liquid-liquid equilibrium （LLE） of ternary and quaternary systems. The GSP parameters are divided into four dimensions representing the four major intermolecular forces. The values of the parameters were determined by regression using the nonlinear SIMPLEX optimization method to fit the LLE data of 548 ternary and 26 quaternary systems selected from the literature. LLE predictions of 8 ternary systems were then made using the fit parameters. Comparison of the results with predictions using the modified UNIFAC model shows that the GSP model has less adjustable parameters to achieve a similar accuracy and that the parameter values are easily acquired by analysis of available data.

Calculation on phase diagrams of polyetherimide/ N,N-dimethylacetamide/H2O-BuOH casting system and their relevance to membrane performances

The ternary phase diagrams of polyetherimide （PEI）/N,N-dimethylacetamide （DMAc） with H2O and BuOH as non-solvent were simulated using solubility parameter and Flory-Huggins theory. The phase diagrams show that 5.5% H2O/BuOH system containing 5% BuOH and 0.5% H2O or 6.5% H2O/BuOH system containing 6.2% BuOH and 0.3% H2O is required to induce liquid- liquid demixing for 20 wt-% PEI/DMAc casting solution. Therefore, BuOH can enhance the phase separation of the PEI casting solution and hereby induce higher porosity of the membrane, and the diffusion of BuOH into the water coagulation bath causes larger pore size easily compared with DMAc. Our predictions that the membrane pure water flux first increases then decreases, and the rejection ratio of bovine serum albumin decreases with the increasing concentration of BuOH were validated by the experiments using the prepared membranes.