The incorporation of phosphazenes into organic polymers.

摘要

The work described in this thesis involves novel synthetic approaches towards the incorporation of phosphazene materials into organic polymers. The successful integration of phosphazenes into organic polymer systems may yield hybrid polymers with properties previously unattainable with organic polymers.; The synthesis of phosphazene cyclic trimers with the basic structure N₃P₃(R)_x(N₃)_6–x where R represents phenoxy, trifluoroethoxy, dimethylamino, or diethylamino groups and x = 3–5 was accomplished. Experiments were conducted to determine the ability of these materials to undergo nitrene insertion reactions. The aryloxy derivative, N₃P₃(OC₆H₅) ₅(N₃), underwent thermal nitrene insertion. The alkoxy derivative, N₃P₃(OCH₂CF₃)₅(N ₃), underwent photolytic nitrene insertion. The dialkylamino derivatives did not undergo nitrene insertion. The ability to undergo nitrene insertion reactions make these molecules attractive candidates for use as polymer cross-linking agents.; A new, facile means for incorporating phosphorus-containing components into organic polymers is reported. This approach uses the Staudinger reaction to attach cyclic phosphazene trimers bearing azide groups to phosphorus(III) atoms pendent to the organic polymer backbone. Experiments were first conducted to examine the factors affecting the reactivity of phosphazene azides towards phosphorus(III) compounds. Poly(diphenyl-p-styrylphosphine) was then reacted with a variety of azido compounds such as N₃P ₃(OCH₂CF₃)₅(N₃), N ₃P₃(OC₆H₅)(N₃), and (C ₆H₅O)₂P(=O)(N₃) in near quantitative yields. This approach should be applicable to a wide variety of organic polymer systems.; A series of phosphazene containing copolymers was synthesized using the phosphinimine coupling process described above. Copolymers of diphenyl- p-styrylphosphine were synthesized with styrene and with methyl methacrylate. Cyclic azidophosphazenes were then linked to the phosphine-containing copolymers via the Staudinger reaction. The thermal stability and fire resistance of these phosphazene-modified copolymers were examined using thermo gravimetric analysis and oxygen index methods.; The synthesis of a phosphazene-organic block copolymers is reported by the use of poly(ethylene oxide) macroinitiators. An excess of Cl₃P=NSiMe ₃ was polymerized from a difunctional macroinitiator. The resultant block copolymer was exposed to an excess of a sodium alkoxide (Na+− OR) solution to replace the chlorine atoms by the alkoxy groups and generate a hydrolytically stable triblock copolymer. Diblock poly(phosphazene-ethylene oxide) copolymers were synthesized using a monofunctional macroinitiator. Copolymers with ethyleneoxy substituted polyphosphazene blocks were analyzed as for use as solid polymer electrolytes.