Solvent systems weight polymers

For high molecular-weight polymer-solvent systems, the polymer critical concentration is close to zero and the interaction parameter has a value close to 0.5. Thus, a good solvent (polymer soluble in the solvent at all proportions) is obtained if < 0.5, whereas values greater than 0.5 indicate poor solvency. Since we mentioned that the model is only an approximate representation of the physical picture and that the FH parameter is often not a constant at all, this empirical rule is certainly subject to some uncertainty. Nevertheless, it has found widespread use and its conclusions are often in good agreement with experiment. 

An alternative polymerization process utilizes a slurry of calcium chloride in NMP as the polymerization medium. The solubiHty of calcium chloride is only 6% at 20°C however, the salt continues to dissolve as conversion of monomers to polymer proceeds and calcium chloride/polyamide complexes are formed. Polymer molecular weight is further increased by the addition of /V, /V- dim ethyl a n i1 in e as an acid acceptor. This solvent system produces fiber-forming polymer of molecular weights comparable to that formed in HMPA/NMP. 

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). 

Membrane stmcture is a function of the materials used (polymer composition, molecular weight distribution, solvent system, etc) and the mode of preparation (solution viscosity, evaporation time, humidity, etc). Commonly used polymers include cellulose acetates, polyamides, polysulfones, dynels (vinyl chloride-acrylonitrile copolymers) and poly(vinyhdene fluoride). 

Eor low molecular weight polymers the separation of the system peaks from the low molecular weight end of the polymer peak is very critical in obtaining accurate MWD and the percentage of low molecular weight materials in the polymer. The water/methanol mixture is a better solvent for PVP than water. PVP K-15 and K-30 should be better separated from the system peaks in the water/methanol mixture than in water because the difference in hydrodynamic volumes between PVP K-15 or K-30 and system peaks is larger in... 

This polymer can be prepared from p-phenylenediamine and terephthaloyl chloride. The polymer is highly crystalline and, thus, difficult to keep in solution. Sufficiently high molecular weight polymers can be obtained by solution polymerization using a special solvent system. This ridged rod polymer can form a liquid crystalline solutions.7,9 14... 

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. 

Table XXX.—Dependence of Intrinsic Viscosity on Molecular Weight FOR Various Polymer-Solvent Systems...

The composition of the nonsolvent-solvent mixture representing the critical composition of the ternary system with polymer of infinite molecular weight (see Fig. 123,a) possesses unique significance. Scott and Tompa have shown that the composition at the critical point in the limit of infinite molecular weight is specified by... 

We have reported the first example of a ring-opening metathesis polymerization in C02 [144,145]. In this work, bicyclo[2.2.1]hept-2-ene (norbornene) was polymerized in C02 and C02/methanol mixtures using a Ru(H20)6(tos)2 initiator (see Scheme 6). These reactions were carried out at 65 °C and pressure was varied from 60 to 345 bar they resulted in poly(norbornene) with similar conversions and molecular weights as those obtained in other solvent systems. JH NMR spectroscopy of the poly(norbornene) showed that the product from a polymerization in pure methanol had the same structure as the product from the polymerization in pure C02. More interestingly, it was shown that the cis/trans ratio of the polymer microstructure can be controlled by the addition of a methanol cosolvent to the polymerization medium (see Fig. 12). The poly(norbornene) prepared in pure methanol or in methanol/C02 mixtures had a very high trans-vinylene content, while the polymer prepared in pure C02 had very high ds-vinylene content. These results can be explained by the solvent effects on relative populations of the two different possible metal... 

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