Composition and plasticizing effect of poly(carboxylic acid) complexes with amino compounds

Poly(carboxylic acid)-dimethylalkylamine complexes were prepared and examined by various methods including infrared spectrometry and chemical titrations. FTIR measurements provided some of the most complete and detailed insights into the type and the stoichiometry of the acid-base complexes. A (1:1) stoichiometric complexation of the poly(carboxylic acid) with tertiary amines was involved in protic solvents. A threshold degree of complexation of 42% was obtained in such a macromolecular system. The equilibrium constant of the proton transfer reaction K was estimated to be independent on the alkyl chain length of the base reagent. Besides the formation of the acid-base complexes, a plasticizing effect of the amine derivatives was demonstrated by differential calorimetry. A T_g depression could be both attributed to the amine molecules linked to the polymer backbone via ionic bonds and to the free molecules dissolved within the free volume of the polymer.