Polymer-solvent systems

We concluded the last section with the observation that a polymer solution is expected to be nonideal on the grounds of entropy considerations alone. A nonzero value for AH would exacerbate the situation even further. We therefore begin our discussion of this problem by assuming a polymer-solvent system which shows athermal mixing. In the next section we shall extend the theory to include systems for which AH 9 0. The theory we shall examine in the next few sections was developed independently by Flory and Huggins and is known as the Flory-Huggins theory. 

Figure 8.2 Schematic illustrations of AGm versus X2 showing how jUj -may be determined by the tangent drawn at any point, (a) The polymer-solvent system forms a single solution at all compositions, (b) Compositions between the two minima separate into equilibrium phases P and Q.

Table 8.3 Theta Temperatures for a Few Polymer-Solvent Systems...

Table 9.2 Values for the Mark-Houwink Coefficients for a Selection of Polymer-Solvent Systems at the Temperatures Noted...

Experimental values of X have been tabulated for a number of polymer-solvent systems (4,12). Unfortunately, they often turn out to be concentration and molecular weight dependent, reducing their practical utility. The Flory-Huggins theory quahtatively predicts several phenomena observed in solutions of polymers, including molecular weight effects, but it rarely provides a good quantitative fit of data. Considerable work has been done subsequentiy to modify and improve the theory (15,16). 

Polyisobutylene is readily soluble in nonpolar Hquids. The polymer—solvent interaction parameter Xis a. good indication of solubiHty. Values of 0.5 or less for a polymer—solvent system indicate good solubiHty values above 0.5 indicate poor solubiHty. Values of X foi several solvents are shown in Table 2 (78). The solution properties of polyisobutylene, butyl mbber, and halogenated butyl mbber are very similar. Cyclohexane is an exceUent solvent, benzene a moderate solvent, and dioxane a nonsolvent for polyisobutylene polymers. 

The formation mechanism of structure of the crosslinked copolymer in the presence of solvents described on the basis of the Flory-Huggins theory of polymer solutions has been considered by Dusek [1,2]. In accordance with the proposed thermodynamic model [3], the main factors affecting phase separation in the course of heterophase crosslinking polymerization are the thermodynamic quality of the solvent determined by Huggins constant x for the polymer-solvent system and the quantity of the crosslinking agent introduced (polyvinyl comonomers). The theory makes it possible to determine the critical degree of copolymerization at which phase separation takes place. The study of this phenomenon is complex also because the comonomers act as diluents. 

This stipulation of the interaction parameter to be equal to 0.5 at the theta temperature is found to hold with values of Xh and Xs equal to 0.5 - x < 2.7 x lO-s, and this value tends to decrease with increasing temperature. The values of = 308.6 K were found from the temperature dependence of the interaction parameter for gelatin B. Naturally, determination of the correct theta temperature of a chosen polymer/solvent system has a great physic-chemical importance for polymer solutions thermodynamically. It is quite well known that the second viiial coefficient can also be evaluated from osmometry and light scattering measurements which consequently exhibits temperature dependence, finally yielding the theta temperature for the system under study. However, the evaluation of second virial... 

Vrentas, JS Duda, JL, Diffusion in Polymer-Solvent Systems. I. Reexamination of the Free-Volume Theory, Journal of Polymer Science Polymer Physics Edition 15, 403, 1977. Vrentas, JS Duda, JL, Diffusion in Polymer-Solvent Systems. II. A Predictive Theory for the Dependence of Diffusion Coefficients on Temperature, Concentration, and Molecnlar Weight, Journal of Polymer Science Polymer Physics Edition 15, 417, 1977. 

The results of determinations of heats of dilution for several polymer-solvent systems over wide ranges in concentration are shown in Fig. 

Reciprocals of the critical temperatures, i.e., the maxima in curves such as those in Fig. 121, are plotted in Fig. 122 against the function l/x +l/2x, which is very nearly 1/x when x is large. The upper line represents polystyrene in cyclohexane and the lower one polyisobutylene in diisobutyl ketone. Both are accurately linear within experimental error. This is typical of polymer-solvent systems exhibiting limited miscibility. The intercepts represent 0. Values obtained in this manner agree within experimental error (<1°) with those derived from osmotic measurements, taking 0 to be the temperature at which A2 is zero (see Chap. XII). Precipitation measurements carried out on a series of fractions offer a relatively simple method for accurate determination of this critical temperature, which occupies an important role in the treatment of various polymer solution properties. 

The results of intrinsic viscosity measurements for four polymer-solvent systems made at the -temperature of each are shown in Fig. 141. The four systems and their -temperatures are polyisobutylene in benzene at 24°C, polystyrene in cyclohexane at 34°C, poly-(di-methylsiloxane) in methyl ethyl ketone at 20°C, and cellulose tricapry-late in 7-phenylpropyl alcohol at 48°C. In each case a series of poly-... 

For polymer-solvent systems with known Mark-Houwink coefficients, K and a, the polymer intrinsic viscosity value [n] can be estimated from the SEC-MW data using the following equation ... 

An added benefit of the direct SEC-[n] calibration approach is that a new independent way of determining K and a values, using only broad MW standards, has also resulted. As few as three standards (or four, if all are narrow MWD) are needed to obtain both MW and [x]] calibration curves for a particular polymer-solvent system by using the broad-standard, linear calibration approach. From the experimental calibration constants of the two calibration curves, one can calculate K and a directly as described later. 

Equation 7 shows that linear calibration using bimodal colximns can be applied to simplify the SEC-In I calibration procedure as has been done for the SEC-MW calibration. The objective of this [n] calibration then is to determine E and E2 values of the SEC column set for the particular polymer-solvent system of interest. The approach is the same as that for SEC-MW calibration. The similarities between the and the [n] formulations are summarized in Table... 

D. SEC Measurement of Mark-Houwink Constants Using Only Polydispersed Standards. If the SEC-MW calibration curve of the polymer-solvent system is known in addition to the [n] calibration, the Mark-Houwink constants of the polymer-solvent system are... 

Table 4. ri0-M-c relationships for some polymer/solvent systems... 

Solvency is the interacting force (strength) of a solvent (or additive) for a designated polymer. The free energy of mixing for a polymer-solvent system can be expressed as ... 

The choice of vx is a matter of convenience for the system of interest. Table 1 summarizes the various definitions of vx and corresponding, /Y, commonly in use [3], The various diffusion coefficients listed in Table 1 are interconvertible, and formulas have been derived. For polymer-solvent systems, the volume average velocity, vv, is generally used, resulting in the simplest form of Jx,i- Assuming that this vv = 0, implying that the volume of the system does not change, the equation of continuity reduces to the common form of Fick s second law. In one dimension, this is... 

JS Vrentas, JL Duda. Diffusion in polymer-solvent systems. I. Reexamination of the free volume theory. J Polym Sci, Polym Phys Ed 15 403-416, 1977. 

JL Duda, YC Ni, JS Vrentas. An equation relating self-diffusion and mutual diffusion coefficients in polymer-solvent systems. Macromolecules 12 459-462, 1979. 

JS Vrentas, CM Jarzebski, JL Duda. Deborah number for diffusion in polymer-solvent systems. AIChE J 21 894-902, 1975. 

If the crossover points Q (x) are determined from Fig. 45, taking the x-values at half-step height, Q (x) = 1/1 (x) = (0.7 + 0.2)x is obtained in the case of the PS system. This has to be compared with static value Qs (x) = 1.6x, derived from the same polymer solvent system by elastic neutron scattering [103], As long as no corresponding data from other polymer solvent systems are available, the final decision as to whether static and dynamic scaling lengths coincide or not, is still open. 

Binder, K., Muller, M., Virnau, P. and Gonzalez MacDowell, L. Polymer+Solvent Systems Phase Diagrams, Interface Free Energies, and Nucleation. Vol. 173, pp. 1-104. 

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