Melts of aromatic carboxylic acids are found to be excellent reaction
media for 1-pot high molecular weight polyimide synthesis from diamine
s and tetracarboxylic acid dianhydrides. No reversible reaction of pol
yamic acids (PAA) formation was observed. The effect of the reactivity
equalization was observed for low-and high reactive diamines in acid
media. The intrinsic acid catalysis of the imidization reaction was sh
own to take place also in polycyclization of PAA in concentrated solut
ions in amic solvents. It is found that the dependence of relative imi
dization rate (% conv./min) vs. AA/N-MP ratio for model low molecular
and oligomeric amic acids (AA) in N-MP at 140-150 degrees C possesses
a sharp maximum near the molar ratio 1:1, the imidization rate at the
point of the maximum being an order of magnitude higher than that for
diluted solutions. A scheme is proposed which includes the opportunity
of two reaction channels to occur: a usual one (I) and a catalytic on
e (II). In diluted solutions and in solid phase experiments with easy
evacuation of volatile products, the role of catalytic channel II is l
ow. To the contrary, in high concentrated solutions or in solid phase
experiments under the conditions exluding volatile products evacuation
, the catalytic channel becomes the key one. It is proposed that the c
atalytic reaction proceeds via the common acid catalysis mechanism, th
e solvent and water playing the role of co-catalysts, probably through
the mechanism of ionic dissociation of AA or hydrogen-bound complex A
A-solvent. It is shown that the water released in the course of solid
phase imidization of phtalamic acid at 140 degrees C under the conditi
ons where vaporization is impossible causes a sharp autocatalytic effe
ct after initial 20%-conversion period to obtain entirely imidizied pr
oduct.