Study on ketalization reaction of poly(vinyl alcohol) by ketones. IV. Reaction between poly(vinyl alcohol) and aliphatic ketones and behavior of polyvinylketal in water

Abstract

AbstractKetalization reaction of poly(vinyl alcohol) (PVA) by aliphatic ketones, dimethylsulfoxide (DMSO) as solvent, under the presence of acidic catalyst, in homogeneous system was carried out and the synthesis of polyvinylketals were successfully performed. The equilibrium constant at 40°C is ca. 0.07 in the case of methyl n‐propyl ketone (nPK) and methyl n‐butyl ketone (nBK), but is ca. 0.05 in the case of methyl i‐propyl ketone (iPK) and ca. 0.01 in the case of methyl i‐butyl ketone (iBK) and methyl t‐butyl ketone (tBK), respectively. Moreover, the ketalization degree of polyvinylketal by iBK and tBK reached to only ca. 35 mol % as the maximum. It seems that these were due to steric hindrance of bulky side chain of ketones. But the heat of reaction is 7.5 kcal/mol in all aliphatic ketones, it seems to proceed the same ketalization reaction mechanism. Films prepared from the polyvinylketals were soaked in water and degree of swelling, solubility, and hydrolysis of films were measured. The reaction of film with water, in acidic side, at first the film swells, and then, as the deketalization reaction proceeds, the film dissolves in water. The dissolution time is controlled by the kind of ketones, ketalization degree, and pH of water which reveals that deketalization reaction proceeds proportional to proton concentration. It is more difficult to dissolve highly ketalized polyvinylketals obtained by propyl ketones and butyl ketones than that by acetone. The hydrolysis of polyvinylketal film proceeds in the order as follows: acetone > MEK > nPK > iPK ≒ nBK > iBK > tBK. This phenomenon seems to be affected by hydrophobicity of the film surface which depends upon the kind of the original ketones.