Synthesis of polyguanamines from 2-N,N-dibutylamino-4,6-dichloro-1,3,5-triazine with aromatic diamines

Solution polycondensation of 2-N,N-dibutylamino-4,6-dichloro-1,3,5-triazine (BDCT) with various aromatic diamines, including 4,4′-oxydianiline (ODA), p-phenylenediamine (pPDA), m-phenylenediamine (mPDA), o-tolidine (oTD), 4,4′-(9-fluorenylidene)dianiline (BAFL), and 2,4-diamino-6-(N,N-dibutylamino)-1,3,5-triazine (DABT), was investigated. High molecular weight (>10,000) polyguanamines (PGs) were obtained via the polymerization of BDCT with ODA, pPDA, oTD, and BAFL at 150-180 °C in N-methylpyrrolidone (NMP) for 6 h. The polymerizability with BDCT was determined on the basis of the molecular weights of the polymers and the chemical shifts of the NMR data as follows: ODA > oTD > BAFL > pPDA > mPDA ≫ DABT. PGs were obtained from the reaction of BDCT with ODA and mPDA in only 55-77% yield, which may be attributed to the formation of cyclic oligomers. All of the polymers showed high thermostability (5% weight-loss temperature in N2 greater than 444 °C), and the polymers generated from reaction of BDCT with ODA, mPDA, and BAFL exhibited good solubility in tetrahydrofuran and polar aprotic solvents such as NMP.