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

Abstract

The reaction of poly(dichlorophosphazene) [NPCl 2] n with 2,2′-dihydroxybiphenyl, 2,2′-(OH)C 6H 4–C 6H 4(OH), and then with p-anisidine, p-NH 2C 6H 4OMe, in the presence of K 2CO 3 led to the formation of the chlorine containing phosphazene copolymer {[NP(O 2C 12H 8)] 0.75[NP(NHC 6H 4OMe) 2] 0.15[NP(NHC 6H 4OMe)Cl] 0.05[NPCl 2] 0.05} n ( 1), which could be isolated and fully characterised. When using cyclic secondary amines instead of aromatic primary amines, namely, HNC 5H 10 (piperidine), HNC 4H 8O (morpholine), HNC 4H 8S (thiomorpholine), the reaction gave the functionalized copolymers {[NP(O 2C 12H 8)] 0.6[NP(NC 5H 10) 2] 0.4} n ( 2), {[NP(O 2C 12H 8)] 0.65[NP(NC 4H 8O) 2] 0.35} n ( 3) and {[NP(O 2C 12H 8)] 0.75[NP(NC 4H 8S) 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.