Measurement of the unperturbed dimensions of stereoregular poly(methyl methacrylate)

The results of measurements of unperturbed dimensions for a series of stereoregular poly(methyl methacrylates) are reported. The measurements were made by a recently developed method involving a gel permeation chromatograph coupled with an on-line low angle laser light scattering photometer. Measurements were performed in a thermodynamically good solvent, tetrahydrofuran at 25°C. The unperturbed dimensions were obtained by means of viscosity plots. Comparison of the results obtained by this method with those currently available in the literature, as well as with values predicted by statistical calculations, show good agreement. It was determined that a measurable difference occurs in the Mark-Houwink relationship between isotactic and syndiotactic poly(methyl methacrylate); isotactic poly(methyl methacrylate) is 30% more extended than syndiotactic poly(methyl methacrylate) in its unperturbed state; and isotactic poly(methyl methacrylate) exhibits a smaller degree of polymer solvent interaction than the syndiotactic form.