Phosgen-free Synthesis of Oligoureas Having Amino End-groups: Their Application to the Synthesis of Poly(urea-imide)

The thermal reaction of acetoacetanilide in the presence of aniline or phenol yielded carbanilide in quantitative yields. This reaction was applied to the synthesis of polyurea. Bisacetoacetamides were prepared from diamines and diketene in DMF. They were thermally polymerized in the presence of phenol or a diamine (6FDA) to yield polyureas of low molecular weights. The polymers were soluble in DMSO and NMP. $^1{H-NMR}$ analysis showed that they had amino group terminated structures. Poly(urea-imide) was synthesized by the reaction of an oligourea diamine with pyromellitic dianhydride in NMP. The concentration of terminal amino groups was determined by an acid-base titration. The thermal property of poly(urea-imide) was evaluated by thermogravimetric analysis (TGA). Initial decompisition took place at 332-$350^{\circ}C$.