ORGANOSILOXYPHOSPHAZENE POLYMERS - SYNTHESIS VIA AMINOSILOXANE REAGENTS

Cyclic and high polymeric phosphazenes have been synthesized with aminosiloxane side groups either as the sole substituent or with cosubstituents such as OCH2CF3, OCH2CH2OCH2CH2OCH3, or OC6H5. Small-molecule model compound reactions were first carried out between N3P3(OPh)5Cl and H2N(CH2)3SiMe2OSiMe3 or H2N(CH2)3Si(OSiMe3)3 to yield the pentaphenoxymonoaminosiloxy derivatives N3P3(OPh)5NH(CH2)3SiMe2OSiMe3 and N3P3(OPh)5NH(CH2)3Si(OSiMe3)3. Following the structural identification of these species, similar reactions were carried out between the high polymeric phosphazenes [NP(R)xCly]n, where R = OCH2CF3, OPh, or OCH2CH2OCH2CH2OCH3> χ = 0, 0.5, or 1.5, y = 2 -χ, and η = 15 000, and the same two aminosiloxanes. The molecular structures of the final polymers were deduced from a combination of elemental analysis and1H NMR integration. The substituent distribution and thermal-, surface-, and solid-state properties of the aminosiloxyphosphazene polymers are described. © 1990, American Chemical Society. All rights reserved.