Chemical transformation of polymers. XVII. Amination of poly(oxy(2,2‐bis‐chloromethyl‐trimethylene)) (penton)

Abstract

AbstractPoly(oxy(2,2‐bis‐chloromethyl‐trimethylene)) reacts with methylamine, dimethylamine, and ethylenediamine in N‐methylpyrrolidone at 115–190°C forming corresponding amino derivatives; trimethylamine does not react under these conditions. The aminations are accompanied by a decrease in molecular weight. The dimethylamino derivative was quaternized with methyl iodide in dimethylformamide, and from the iodide the corresponding quaternary ammonium polybase was prepared using a strongly basic anion exchanger. This base, in an approximately 10% aqueous solution, was thermally degraded at 120°C for 70 hr. Under these conditions, the quaternary ammonium base was completely degraded, viz., about 63 %, to the polymeric dimethylamino derivative and methanol and about 37 % to the polymeric alcohol and trimethylamine. The unexpected splitting off of trimethylamine during the degradation is explained by the proximity of the ammonium groups in geminal CH2N+(CH3)3OK−.