Hansen solubility parameters polymer

Hansen solubility parameters. A convenient scheme for the evaluation of solvency is the use of the Hansen plot, a 3D diagram positioning 8, 5p and of polymer and solvent. 

Hansen CM, Smith AL (2004) Using Hansen solubility parameters to correlate solubility of C60 fullerene in organic solvents and in polymers. Carbon 42 1591-1597. 

Belmares, M., M. Blanco, W. A. Goddard, R. B. Ross, G. Caldwell, S.-H. Chou, J. Pham, P. M. Olofson, and C. Thomas. 2004. Hildebrand and Hansen solubility parameters from molecular dynamics with applications to electronic nose polymer sensd>.r omputat. Chen25 1814-1826. 

Hansen, C.M., Hansen Solubility Parameters A User s Handbook, CRC Press, Boca Raton, FL, 1999. Blanks, R.F. and Prausnitz, J.M., Thermodynamics of polymer solubility in polar and nonpolar systems, Ind. Eng. Chem. Fund., 3(1), 1-8, 1964. 

A three-dimensional model is used to plot polymer solubilities by giving the coordinates of the centre of a solubility sphere based on dispersion force components, hydrogen bonding and polar components, and by plotting a radius of interaction of around 2 SI units. A sphere of solution is plotted from the coordinates and radius. Liquids whose parameters lie within the sphere for a particular polymer are likely to be suitable solvents for it (Hansen, 1971). While extensive data has been published for liquids, the number of Hansen solubility parameters for polymers is more limited (Barton, 1983). From tbe selected solubility parameters for liquids and polymers in Table 4.1, it is clear tbat the high value for water excludes it as a solvent for polymers and that polystyrene and poly (methyl methacrylate) should be soluble in acetone. 

If Rab lies below a certain threshold Ro, the substances are predicted to be miscible, i. e.the polymer is predicted to be soluble in the solvent. On the other hand, the solvent will neither dissolve nor swell the solute in case of Rab Ro- Furthermore, the Hansen solubility parameters can be used for estimating the Flory-Huggins interaction parameter of two polymers... 

Table 7.1 Experimentally determined and theoretically calculated Hansen solubility parameters for selected polymers and solvents...

With one exception, the solubility predictions based on the Hansen solubility parameters were fairly consistent with the experimental findings of this study. The results together with the calculated Rab values for several solvents are listed in Table 7.2. Note that the Hansen sphere radius Ro = 12.7 of poly(styrene) is expected to be considerably larger than that of conjugated polymers. 

Latnikova, A. Grigoriev, D. O. Moehwald, H. Shchukin, D. G. Capsules made of cross-linked polymers and liquid core Possible morphologies and their estimation on the basis of Hansen solubility parameters. Journal of Physical Chemistry C (2012), 116(14), 8181-8187. 

Table 6.2. Hansen solubility parameters of selected polymers...

Champagne M F Prud homme R E, J. Polym. Sci. Polym. Phys. Ed., 32, No.4, March 1994, p.615-24. Hansen C M, Hansen Solubility Parameters, CRC Press, Boca Raton, 2000. 

SOLVENT ACTION AND MEASUREMENT Table 2.16 Hansen s solubility parameters—polymers... 

Buckley-Smith (2006) discussed the use of solubility parameters to select man-brane materials for PV of organic mixtures. His research showed that Hansen solubility parameters (HSP) are a good screening method for PV manbranes, especially where the molecules being separated are of comparable size. Polymers that have HSP close to the desired component and not to other components tend to have the best selectivity and flux characteristics. However, diffusion is an important factor and is not completely accounted for by HSP. 

Table 2.19 Hansen solubility parameters for selected polymers at 25 °C. All values are in (J/mL). For some polymers, more than one set of 5 values are provided (a, b, etc.), indicating variability in experiments/fittings or polymer structure effects (comonomer, M-, additives, etc.). A much more comprehensive collection of such values can be found in the relevant handbook (Hansen 2000)...

The total solubility parameter, 5, corresponds to the overall Hildebrand solubility parameter, and the Hansen solubility parameters, 5p, and h, are contributions from non-polar interaction, polar interaction, and hydrogen bonding, respectively [15]. The end point of the radius vector represents the solubility parameter. This means that each solvent and each polymer can be located in a three-dimensional space. 

The present study aims to understand the influence of solvent quality on the molecular-level friction mechanism of tethered, brushlike polymers. It involves complementary adsorption studies of PLL-,g-PEG by means of optical waveguide lightmode spectroscopy (OWLS) and quartz crystal microbalance with dissipation (QCM-D) as well as friction studies performed on the nanoscale using colloidal-probe lateral force microscopy (LFM). The adsorbed mass measured by QGM-D includes a contribution from solvent molecules absorbed within the surface-bound polymer fllm. This is in contrast to optical techniques, such as OWLS, which are sensitive only to the dry mass of a polymer adsorbed onto the surface of the waveguide.By subtracting the dry mass , derived from OWLS measurements, from the wet mass , derived from QCM-D measurements, it is therefore possible to determine the mass of the solvent per unit substrate area absorbed in the brushlike structure of PLL- -PEG, expressed as areal solvation, P. Areal solvation was varied by choosing solvents (aqueous buffer solution, methanol, ethanol, and 2-propanol) of different quality with respect to the PEG brush. The solvents were characterized in terms of the three-component Hansen solubility parameters, and these values were compared with measured areal solvation of the PEG brush. 

Solvent Characteristics. In an attempt to rationalize the effect of solvent characteristics on solvation, we make use of the three-component Hansen solubility parameter model.3043 These solubility parameters are commonly used in polymer chemistry to predict the solubility of a polymer in a solvent. The Hansen solubility parameters are defined in terms of the cohesive energy density that relates to the amount of energy required to vaporize 1 mol of the solvent. 

A special feature in this book is the inclusion of the Hansen solubility parameter theory that can be used to classify solvents in terms of their nonpolar, polar and hydrogen bonding characteristics. Use of the Hansen solubility parameter theory will allow the worker to systematically search for a solvent substitute or determine the solubility of a resin/polymer in a certain solvent or solvent blend. The files necessary to construct computer spreadsheets that can utilize the Hansen solubility parameter theory are included with this book. The useful spreadsheet files on a computer disk are included in a plastic pocket on the back inside cover of the book. These files can be used on an IBM-compatible computer with Lotus 123 (or Excel) software. These computer spreadsheets were developed in the Lotus 123. WKl file format. The data files can be used with the Lotus 123 Version 5.0 for Windows, the Microsoft Excel Version 5.0 for Windows or any earlier version of the spreadsheet software. The files can also be translated into the Macintosh Excel format if the correct version of Excel is available. The coating industry will find the information on solvent substitution using the Hansen solubility parameter theory of particular interest. The use of computer spreadsheets to compare the solubility envelope of the polymer with likely solvent candidates has been very helpful to the author in past work and others in the coating in selecting substitute solvents or solvent blends. The Hansen solubility parameter values for 166 resins and polymers and 289 solvents are listed. 

Selection of a suitable solvent or blend for an industrial process or for determination of a resin or polymer solubility characteristics can make use of the Hansen solubility parameter theory. The solvent selection rules are applied by calculating the solubility parameters of the solvent or solvent blend to be replaced and then selecting new solvents that have similar solubility parameters. The concept is that the total solubility parameter value can be represented as a dispersion (nonpolar) 6, a polar 6, and a hydrogen-bonding 6 component. The total solubility parameter can be mathematically expressed as the square root of the sum of the squares of the nonpolar, polar, and hydrogen-bonding components as shown in Equation 1.1. 

Other uses of the solubility parameter theory include pigment-solvent interactions in terms of suspension behavior, the compatibility of plasticizers and polymers, the critical strain behavior of commercial plastics in the presence of solvents, the effects of solvents on other mechanical properties of the polymers and the affinities of organic solvents in biological systems. Equation 1.3, which uses the three partial Hansen solubility parameters, can be used to estimate the surface tension of a liquid. 

Figure 4.1 The idealized spherical solubility envelope for a polymer. The total solubility parameter 5f of a material is a point in three dimensional space where the three partial Hansen solubility parameter vectors meet. The Hansen parameters are the nonpolar bd, polar bp and hydrogen bonding 5 components. Source [4].

A separate list of resin and polymer solubility parameters are available from another Barton publication [5] and are discussed in Chapter 5. Archer [6] discussed the use of the Hansen solubility parameter theory to reformulate a solvent-based coating. The following example demonstrates the usefulness of the Hansen method. Neither xylene nor methanol are good solvents for a D.E.N. epoxy novolac 438 resin. However, calculations suggested that a 50 50 (by volume) solvent blend should be able to dissolve the epoxy resin. Using the Hansen parameters for xylene and methanol from Table 4.1 the solubility parameters for the 50 50 blend were calculated as follows ... 

Using Hansen Solubility Parameters to Categorize Resins and Polymers... 

Coating and paint formulations, adhesives, polymer-plasticizer compatibility and solvent effects on plastic surfaces are only a few of the areas that can benefit from the Hansen solubility parameter theory. Hansen [1] extended the solubility concepts discussed in Chapter 4 to include resin and polymeric materials. The total solubility parameter of a polymer is the point in three-dimensional space where the three partial solubility parameter vectors meet as the center point of the idealized spherical envelope. The distance in space between the two sets of parameters (solvent and polymer) can be represented by the term, radius of interaction or R. The radius of interaction term is used to express the degree of mutual solubility. All of these solubility comparisons can be made by using computer spreadsheets that are described in Chapters 4, 19, and this chapter. 

---