Autocatalytic one-step high-temperature synthesis of carboxylated polyimides for in-situ high performance applications

Carboxylated polyimides (CxPIs) represent a great potential for gas separation membranes, highly thermostable coatings and fibers, ion-conducting materials, aerogels, (nano)composites, etc. However a prolonged and expensive two-stage method proceeding through the formation of an unstable poly(amic acid) and subsequent thermal or chemical imidization is traditionally used for the synthesis of CxPIs. Herein a new strategy consisting in one-step high-temperature synthesis of CxPIs based on 3,5-diaminobenzoic acid (DABA), the carboxyl groups of which provide an autocatalytic effect, in N-methyl-2-pyrrolidone (NMP) is presented. The effect of DABA content on the formation and properties of CxPIs is studied. It is established that high-molecular-weight CxPIs (Mw = 158–356 kDa) with five- and more stable six-membered imide rings from various dianhydrides of aromatic tetracarboxylic acids and diamines as comonomers are synthesized within 1–4 h of the reaction even with 25 mol% of DABA content. Additional catalyst-free synthesis of CxPIs in NMP allows to use the solutions obtained in situ for the production of various materials. In particular, CxPI-varnishes form the primary protective coating of the optical fiber superior to the commercial analogue in terms of its manufacturing technology, thermal and hydrolytic stability, which provides more reliable and long-term operation.