High molecular weight poly-biphenoxyphosphazene copolymers with cyclic secondary amino groups

The reaction of poly(dichlorophosphazene) [NPCl2]n with 2,2′-dihydroxybiphenyl, 2,2′-(OH)C6H4–C6H4(OH), and then with p-anisidine, p-NH2C6H4OMe, in the presence of K2CO3 led to the formation of the chlorine containing phosphazene copolymer {[NP(O2C12H8)]0.75[NP(NHC6H4OMe)2]0.15[NP(NHC6H4OMe)Cl]0.05[NPCl2]0.05}n (1), which could be isolated and fully characterised. When using cyclic secondary amines instead of aromatic primary amines, namely, HNC5H10 (piperidine), HNC4H8O (morpholine), HNC4H8S (thiomorpholine), the reaction gave the functionalized copolymers {[NP(O2C12H8)]0.6[NP(NC5H10)2]0.4}n (2), {[NP(O2C12H8)]0.65[NP(NC4H8O)2]0.35}n (3) and {[NP(O2C12H8)]0.75[NP(NC4H8S)2]0.25}n (4), respectively. The broad bands in their 31P NMR spectra and the bimodal aspect of their GPC chromatograms suggested they could be forming aggregates in solution.