The preparation and acid‐catalyzed hydrolysis of polyoxymethylene isopropyl methyl ethers

Abstract

SynopsisThe first four members of the polyoxymethylene ether series (CH&CHO(CHZO),CH~ were prepared, separated by fractional distillation and GLC, and characterized by NMR.Rate constants for the aqueous acid hydrolysis of the compounds were determined at 25", 30°, and 35OC. Although the polyformals (n > 1) in this series hydrolyzed a t essentidy the same rate, they all hydrolyzed three times faster than the formal (n = 1). It is proposed that a mixed polyformal, (CH&CHO(CHZO),>~CH,, undergoes two concurrent fissions to yield (1) the stem (CH3)zCHOCHz with ChO(CHz0).-1 as the leaving group and (2) the stem CHsOCHz with (CH~)&HO(CHZO),-I as the leaving group. Most of the fissions occur by the first path. An equation that can aid in predicting the rate of hydrolysis of a mixed polyformal was developed and tested.