Phase Behavior and Physical Gelation of High Molecular Weight Syndiotactic Poly(vinyl alcohol) Solution

The physical gelation behavior of high molecular weight (HMW) syndiotactic poly(vinyl alcohol) (S-PVA) was investigated in consideration of stereoregularity of the polymer. To precisely identify the effect of stereoregularity, syndiotactic diad (S-diad) contents of PVAs with the similar molecular weights were controlled to 61.5, 58.2, and 55.7%, respectively. The gel point (GP) of HMW S-PVA solution was determined by observing the frequency-independent loss tangent and the crossover between the relaxation exponents from the oscillatory shear experiment. The gelation process of HMW S-PVA solution with S-diad content over 58.2% was divided into two types with respect to the concentration of solution. The first type is the gelation that took place directly from sol to gel with a clear GP which was well coincident with the macroscopic gelation temperature (Tgel). This is for the higher concentration regime. The second one is the gelation that occurred gradually accompanying the evolution of gel-like properties in sol state without a definite GP, which is for the lower concentration regime. The gel-like heterogeneity formed during the second type gelation might be related with the liquid−liquid phase separation. In contrast, HMW S-PVA solution with S-diad content of 55.7% followed only the first type gelation. The relaxation exponent of HMW S-PVA solution at GP decreased with concentration and had a lower value than the percolation value, 0.7. The higher fractal dimension indicates the structural compactness in the cross-linking system of HMW S-PVA. As compared with the other gelation system, lower gel stiffness was obtained, suggesting that the gelation of HMW S-PVA solution occurred without a serious crystallization.