The reactions of chlorocyclophosphazenes N3P3Cl6 (1) and N4P4Cl8 (2) and polydichlorophosphazene (3) with
cyclohexylamine, cyclopentylamine, and cyclopropylamine have been studied. The major product with 1 is the
geminal tetrakis derivative N3P3Cl2(NHR)4, while 2 gives the completely substituted derivative, N4P4(NHR)8.
X-ray crystal structure determinations of N3P3Cl2(NHC6H11)4 (1a) and N4P4(NHC3H5)8 (2c) have been carried
out. 1a crystallizes in a triclinic space group, P1, with a = 11.2330(13) Å, b = 11.4269(16) Å, c = 13.4055(12)
Å, α = 72.211(10)°, β = 72.150(9)°, γ = 81.777(11)°, V = 1557.3(3) Å3, and Z = 2. 2c crystallizes in a
monclinic space group, P21/n, with a = 12.433(3) Å, b = 20.484(4) Å, c = 12.645(3) Å, β = 92.81(2)°, V =
1557.3(3) Å3, and Z = 4. The cycloalkylamino-substituted polyphosphazenes contain a small amount of residual
chlorine atoms. These have high glass transition temperatures.
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