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 (oTh), 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 N-2 greater than 444 degrees 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. (C) 2013 Elsevier Ltd. All rights reserved.