Polymers with inorganic backbones, such as polyphosphazenes [(–R2P=N–)n] and polysiloxanes [(–R2Si–O–)n], are known for their thermal and chemical stability. However, the chemistries of linear inorganic polymers are limited in scope compared to their organic counterparts. A new class of monomers, the aminocyanophosphines – (R2N)xR’yP(CN)z where x+y+z=3 – are presented to expand the scope of inorganic polymer chemistry. When suitably activated by pendant phosphines, cyano groups prove to be effective precursors to hydrogen-free polyimine backbones analogous to paracyanogen. Despite appearing exotic at first glance, many of the aminocyanophosphines can be conveniently synthesized in one-pot, multi-step reactions from commercially available components: a secondary amine; a chlorophosphine (or PCl3); and potassium cyanide. The syntheses of aminocyanophosphines with various R-groups and the polymerization behavior of the resulting monomers are reported. Ease of polymerization, mechanical properties, and thermal stability are shown to depend heavily on the selection of phosphine substituents. Bulky, sterically hindered aminocyanophosphines, such as bis(diphenylamino)cyanophosphine – (Ph2N)2PCN – are shown to form ductile, high thermal stability glasses when thermoset in a closed system. New aminocyanophosphine polymers have the potential to complement polyphosphazenes and polysiloxanes in applications where thermal and chemical stability are of the utmost importance.

Bulky aminocyanophosphine glasses: A new class of inorganic polymers

2019 Spring National Meeting

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