EFFECT OF POLYMER ON ELECTRON-DONATING CHARACTER OF POLYMER DONOR .2. FORMATION OF CHARGE-TRANSFER COMPLEX BETWEEN POLYMERS CONTAINING N-DIMETHYLANILINE GROUP AND TRINITROTOLUENE

Formation of charge-transfer complexes with trinitrotoluene (TNT) as a common acceptor was studied in detail by using dimethyltoluidine (DMT), poly-N-dimethyl-p-aminostyrene (poly-ASt), and also copolymers of aminostyrene (ASt) and styrene (St) as donors. A smooth bathochromic shift in lambda //m//a//x was observed with increasing ASt unit content in copolymers. Values of the constant for charge transfer complex formation K//C//T were found to increase smoothly with ASt unit content. However, the K//C//T value with DMT did not coincide with the value extrapolated from the plot of K//C//T value versus ASt unit content to zero ASt unit content, but was found to be much higher than the limiting value, in contradiction to the results obtained with maleic anhydride. The entropy of complex formation with DMT was found to be exceptionally small; this small value may be responsible for the high K//C//T value with DMT.