Synthesis and Electrical Conductivity of Phosphorus-Nitrogen Compounds. V. Synthesis and Electrical Resistivity of Poly[bis(amino)phosphazenes]

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Abstract
Three new poly [bis(amino)phosphazenes] of formulas [NP(NHC6H13)2]n, [NP(NHCH2CHCH2)2]n, and [NP(NHCH2C6H5)2]n have been synthesized by direct aminolysis of (NPCl2)n. The electrical resistivity and thermal stability of a series of poly[bis(amino)phoshazenes], (NPR2) (R: amino group), have been examined. Most polymers showed an increase in resistance with time to an equilibrium value, possibly due to space charge effects, allowance for this conductivity being ohmic up to 500(V/cm). The aliphatic amino derivatives have a lower resistivity and a lower ΔE value than the aromatic amino derivatives. The resistivity of the poly [bis(amino)phosphazenes] was found to decrease in the order, R : NHC2H5>NHC3H7>NHC4H9>NHC6H13>>N(CH3)2. This seems to be predominantly due to the nature of an inductive electron supply of amino side groups. In some polymers the change of energy gap, ΔE, was observed in the range 70–90 °C. The ΔE value was usually lower in the low temperature region than in the high temperature region. All the polymers were found to decompose at about 200 °C, losing the amino side group.