Effects of aliphatic esters, aldehydes and some impurities, as monovinyl and divinyl acetylene which exist normally in vinyl acetate, on the polymerization of vinyl acetate were studied. Esters and saturated aldehydes such as methyl acetate, ethyl acetate, isopropyl acetate and dimethyl oxalate etc., and acetaldehyde and butyraldehyde act only as transfer agent and the values of the transfer constants on these substances were determined. Unsaturated aldehyde such as crotonaldehyde and also benzaldehyde, and monovinyl and divinyl acetylene act as retarder. The several reaction constants relating the retarding effect were obtained.
ZUSAMMENFASSUNG:Es wurde der EinfluB von aliphatischen Estern, Aldehyden und Verunreinigungen, die imvinylacetat iiblicherweise vorhanden sindwie Monovinylacetylen und Divinylacetylen a d die Polymerisation von Vinylacetat untersucht. Ester und gesattigte aliphatische Aldehyde, wie z. B. Methylacetat, Athylacetat, Isopropylacetat, Dimethyloxalat usw., Acetaldehyd und Butyraldehyd, wirken nur als ubertrager. Ihre tfbertragungskonstanten wurden bestimmt. Ungesattigte Aldehyde, wie Crotonaldehyd, aber auch Benzaldehyd, ferner Mono-und Divinylacetylen wirken als Verzogerer. Die Polymerisationsgeschwindigkeit von Vinylacetat in Gegenwdrt solcher Verzogerer wurde nach der Gleichung von KICE analysicrt, und die verschiedenen Geschwindigkeitskonstanten wprden bestimmt. *) This report is a summarization of several of the author' papers which appear in the 1) I. SAKURADA and R. INOUE, Chem. High Polymers (Japan) 7 (1950) 211. Industrially pure vinyl acetate, made by the KURASAIKI RAYON COMPANY, was used in all tests. The monomer was washed with aqueous NaHSO, and water. It was then dried and rectified. The fraction boiling at 72.5"C. was partially polymerized, and the unpoly-5) A. J. BUSELLI, M. K. LINDEMANN, and C. E. BLADES, J. Polymer Sci. 28 (1958) 485. 6) T. OHSUGI, Chem. High Polymers [Japan] 6 (1949) 460. 7) 0. L. WHEELER, S. L. ERNST, and R. N. CROZIER, J. Polymer Sci. 8 (1952) 409. 8 ) 0. L. WHEELER, E. LAVIN, and R. N. CROZIER, J. Polymer Sci. 9 (1952) 157. 9) M. YANO and M. MATSUMOTO, J. chem. SOC. Japan; Ind. Chem. Sect. (Kogyo Kagaku