Phosphonitrilic Compounds. XV.¹ High Molecular Weight Poly [bis (amino)phosphazenes] and Mixed-Substituent Poly(aminophósphazenes)2

The synthesis of four new poly[bis(amino)phosphazenes] of formulas [NP(NHCH3)2]n, [NP(NHC3H7)2]n, [NP(NHC4H9)2]n, and [NP(NHCH2CFs)2]n by direct aminolysis of (NPCl2)n is described. The replacement of chlorine in high molecular weight (NPCl2)n is incomplete when bulky primary ámines, such as isopropylamine, isobutylamine, or see-butylamine, or secondary amines, such as diisopropylamine, diphenylamine, N-methylamline, or diethylamine, are used as nucleophiles. With diethylamine, approximately half of the chlorine atoms are replaced nongeminally to yield [NP(Cl)N(C2H5)2]n. Treatment of this derivative with primary amines yields mixed substituent polymers, [NP(NHCH3)N(C2H5)2]n. [NP(NHC2H5)-N(C2H5)2ln, [NP(NHC3H7)N(C2H5)2]n, and [NP(NHC4H9)N(C2H5)2]n. Terpolymers which contain dietliylamino, piperi-dino, and methylamino substituents or diethylamino, methylamino, and trifluoroethoxy groups have also been prepared.