Heterogeneous surface saponification of suspension-polymerized monodisperse poly(vinyl acetate) microspheres using various ions

• Published in: Journal of polymer science. Part A, Polymer chemistry Polymer chemistry, 2006-06, Vol.44 (11), p.3567-3576
• Main Authors: Lee, Se Geun, Kim, Jae Pil, Chan Kwon, Ick, Park, Ki Hong, Noh, Seok Kyun, Han, Sung Soo, Lyoo, Won Seok
• Format: Article
• Language: English
• Subjects: Applied sciences; Chemical modifications; Chemical reactions and properties; Exact sciences and technology; Heterogeneous saponification; ion-specificity; Organic polymers; Physicochemistry of polymers; PVA/PVAc microspheres
• ISSN: 0887-624X; 1099-0518
• DOI: 10.1002/pola.21406

Poly(vinyl alcohol) (PVA)/poly(vinyl acetate) (PVAc) microspheres with a skin/core structure were prepared through the heterogeneous surface saponification of PVAc microspheres suspension‐polymerized. The PVA skin formed through the heterogeneous saponification was hydrogel swellable in water. In addition, to obtain monodisperse PVA/PVAc microspheres having various skin/core ratios and morphologies, the ion‐specificities to the heterogeneous saponification were investigated using SO 42−, Cl−, NO 3−, Br−, and I− for anions and Li+, Na+, and K+ for cations, respectively. The ions were not specific significantly to the rate of the heterogeneous saponification, while were related to the degree of saponification (DS). DSs had different values between by weight loss (DSw) and by proton nuclear magnetic resonance spectroscopy (DSNMR) measurements. The order of DSws was SO 42− < Cl− < NO 3− < Br− < I− for anions and K+ < Na+ < Li+ for cations, and that of DSNMRs, I− < Br− < NO 3− < Cl− < SO 42− for anions and Li+ < Na+ < K+ for cations. The differences in values between DSws and DSNMRs were caused by the dissolution of PVA skin and were significantly decreased for SO 42−. The peaks at melting temperature of PVA were sharp and their areas were large for ions deswelling PVA skins. The ion‐specificities to the heterogeneous saponification of monodisperse poly(vinyl acetate) (PVAc) were investigated using SO 42−, Cl−, NO 3−, Br−, and I− for anions and Li+, Na+, and K+ for cations, respectively. The ions affected significantly on the degree of saponification (DS). DSs had different values between by weight loss (DSw) and by 1H NMR (DSNMR) measurements. The order of DSws was SO 42− < Cl− < NO3 − < Br− < I− for anions and K+ < Na+ < Li+ for cations, and for DSNMRs, the order was reverse. The differences between DSws and DSNMRs were caused by the dissolution of PVA skin.