Abstract The aim of this work was to functionalize substituted cyclotriphosphazenes to increase their flame retardant properties.

The inorganic rings, similar to benzene in structure and aromaticity can be modified similarly by nucleophilic aromatic substitution. Substitution of chlorines on the cyclotriphosphaziene by nirtophenol groups lead to the product, hexakis(4nitrophenoxy)cyclotriphosphazene, which exhibited flame retardant properties. Introduction Flame retardants have been around for ages. In the fifth century, Greek historian Herodotus recorded that the Egyptians were soaking wood in an alum solution for the purpose of fire retardance.1 The idea never died, and over time has evolved into a well-documented science that has recently become the subject of controversy. Flame retardants decrease the flammability of materials, working by physical or chemical action, or both. Some of the ways they work are by providing a protective layer, releasing inert gases to dilute oxygen, releasing water, or forming a char barrier that is difficult to burn.2 Polymeric flame retardants are commonplace and extensively used in industry. Hexacyclotriphosphazenes are similar to benzene in structure, and may be functionalized by a nucleophilic aromatic substitution. These inorganic molecules exhibit aromaticity and consist of alternating nitrogen and phosphorous atoms. They have been shown to exhibit characteristics desired in a flame retardant, such as high chemical and thermal stability.4-5 The goal of this study is to develop a flame retardant by an accelerated method of functionalizing a hexacyclotriphosphazene derivative with the use of a phase transfer catalyst by nucleophilic aromatic substitution. Results and discussion Substitution of the chlorine atoms by nitrophenol groups in hexachlorotriphosphazene proceeds by a nucleophilic aromatic substitution (NAS). Hexachlorotriphosphazene consists of -P=Nunits in which both atoms are in group 15. Unlike carbon, phosphorous is capable of making five bonds. The NAS reaction creates an anionic intermediate in which the electronegative nitrogen atoms in the ring help stabilize the molecule by resonance. Addition of the nucleophile, 4nitrophenoxide, takes place at the phosphorous atom bearing the leaving group. The structure of hexachlorotriphosphazene is what makes this reaction so useful. This is due to the fact that in respect to any nitrogen atom in the ring, the phosphorous atoms bearing the leaving groups are in either the 2 or 4 positions, in which addition to these leads to a resonance stabilized intermediate. Elimination of the leaving group occurs with restoration of the aromatic bond. The reaction proceeded as expected, but the final percent yield was rather low, and seemed as if the final product had slightly undergone decomposition. The use of reaction tubes for this synthetic procedure may have contributed to this due to evaporation of the solvent, THF. Employment of a reaction flask fitted with a condenser should prevent this from occurring. The final product did show flame retardant properties. Paper towels treated with hexakis(4nitrophenoxy)cyclotriphosphazene exhibited a lesser degree of flammability when compared to an untreated paper towel control. Experimental

Potassium 4-Nitrophenoxide. Potassium hydroxide (0.3072 g, 5.5 mmol, 1 equiv) dissolved in ethanol (2.5 mL) was added dropwise over 1 min to a solution of 4-nitrophenol (0.6164 g, 4.43 mmol, 1 equiv) dissolved in ethanol (2.0 mL). The solution was allowed to cool in an ice water bath for 10 min, in which a micro-crystalline precipitate formed. The precipitate was filtered by vacuum filtration and washed with two aliquots of chilled ethanol (5.0 mL). The precipitate was recovered on the filter paper which was subsequently folded in half and placed between two paper towels. The paper towel was compressed by hand to wick away moisture and left to dry. The dried product, potassium 4-nitrophenoxide, was a yellow crystalline solid (0.5631 g, 72% yield). Hexakis(4-nitrophenoxy)cyclotriphosphazene. Hexachlorotriphosphazene (0.2140 g, 0.6 mmol, 1 equiv), potassium 4-nitrophenoxide (0.5631 g, 3.2 mmol, 6 equiv), tetra-nbutylammonium bromide (0.0252 g, 0.08 mmol), and THF (6 mL) were added to a loosely capped reaction tube and refluxed in a hot water bath for 1 hr with occasional stirring. THF (0.06 mL) was added after 30 min due to evaporation of solvent. The contents of the reaction tube were poured into a beaker of ice cold water to precipitate the desired product. The precipitate was filtered by vacuum filtration, washed with three aliquots of water (10 mL) followed by three aliquots of ethanol (10 mL) and left to dry. The crude product, hexakis(4nitrophenoxy)cyclotriphosphazene, was an off-white solid (0.2030 g, 38% yield): IR v 1613, 1588, 1487 cm-1 (aromatic); 1522, 1348 cm1 (asymmetrical and symmetrical nitro group stretching); 1204, 1182, 1162 cm1 (cyclotriphosphazene ring PN), 949 cm1 (POC).3 Conclusion The functionalization of cyclotriphosphazenes proceeded by nucleophilic aromatic substitution as expected. Substitution of chlorines on the cyclotriphosphaziene by nirtophenol groups lead to the product, hexakis(4-nitrophenoxy)cyclotriphosphazene, which exhibited flame retardant properties. The aromatic properties of benzene are indeed similar to cyclotriphosphazenes, and their structure allows us to utilize some of the same reactions.