Incorporation of Cyclic Phosphazene Trimers into Saturated and Unsaturated Ethylene-like Polymer Backbones

Abstract

The synthesis of well-defined cyclolinear phosphazene polymers via acyclic diene metathesis (ADMET) has been demonstrated. This work extends the range of properties achievable in cyclolinear phosphazenes synthesized via ADMET and provides an assessment of the synthetic limitations. A series of tetraphenoxy and tetramethoxyethoxyethoxy functionalized phosphazene trimers have been synthesized that bear two alkene side chains, which together form the diene structure necessary for ADMET. The alkene chains vary in length from three carbons to 11 carbons. This has allowed the influence of the negative neighboring group effect to be examined as well as steric factors as they apply to the metathesis of phosphazene monomers. Moreover, the role of different catalysts is discussed together with the influence of the nonolefinic phosphazene substituents on the reactivity of the monomers. The influence on bulk polymer properties of the incorporation of different amounts of cyclic phosphazene per average polymer chain, through copolymerization studies with decadiene, is also discussed.

Synthesis of hexa‐allylamino‐cyclotriphosphazene as a reactive fire retardant for unsaturated polyesters

“…Hexa‐chloro‐cyclotriphosphazene, (NPCl 2 ) 3 , has been synthesized by Rose since 1834 1. Up to now, extensive studies on its derivatives and applications are still active 2–10. Their potential applications included solid polymer electrolytes,3, 8 flame retardants,4, 6 nonlinear optics,7 biodegradable materials,9, 10 et al In this study, we prepared the hexa‐allylamino‐cyclotriphosphazene (HACTP) by substituting the chloro groups of (NPCl 2 ) 3 with allylamines and employed it as a reactive non‐halogen flame retardant for unsaturated polyesters (UP).…”

Towards Cyclophosphazene Based Dendrimers For Energetic Binders

“…It has also been used in the construction of more complicated polymeric architectures such as cyclo linear [3] and dendritic [4] as well as being incorporated into linear carbon based polymers as pendant groups [5]. In each of these cases however the synthesis of the desired phosphazene based A x B y monomer is hindered by the ability to control the substitution pattern during desymmetrisation of the trimer.…”

Synthesis and characterization of novel thermoplastic poly(oligophosphazene‐urethane)s

“…Bis‐chlorinetetraphenoxycyclotriphosphazene (HCPPZ) was synthesized following a procedure described in the literature 20. A solution of BPS (8.75 g, 35 mmol) and TEA (6.06 g, 60 mmol) in 100 mL of THF was added dropwise to a solution of HCPPZ (17.34 g, 30 mmol) in 100 mL of THF at room temperature.…”