Carborane‐containing cardo polyphosphazenes

Abstract

The reactions of poly(dich1orophosphazenes) and hexachlorocyclophosphazene with bis-(hydroxymethy1)-o-carborane has been studied. By this reactions carborane-containing cardo polyphosphazenes and spiro-o-carboranylene cyclophosphazenes were obtained which had been not described until now. The compounds were characterized. Curboranhultige CardopolyphosphazeneDie Reaktion von Poly(dich1orphosphazenen) und Hexachlorcyclophosphazenen mit Bis-(oxymethy1)-o-carboran wurde untersucht. Hierbei werden bisher nicht bekannte carboranhaltige Cardopolyphosphazene und Spiro-o-carboranylen-cyclophosphazene erhalten. Die Verbindungen werden charakterisiert. €Capdome icap6opa~codepxau+ue nom~oc@a3enb& B p e s y n b~a~e KoToporo nonysem H o x a p a~~e p~3 0 s a~~ Heonmamare paHee KapnosbIe Kap6OpaHCO~epXaIqHe H3YYeHO B3aHMOAefiCTBHe IIOJIHAliXJIOp@OC@l3eHa H r e K C a X n O p q H K J r O~O C~a 3 e H a C ~H C -(OKCHMeTHJI)-O-Kap6OpaIiOM,

Open-chain poly(organophosphazenes). Synthesis and properties

“…The reaction of bis(hydroxymethyl)-o-carborane with PDCP was carried out in THF in the presence of triethylamine at 20 ± 50 8C or by the alkoxide method at 20 ± 22 8C. 109,110,112 The results obtained indicate that the two chlorine atoms at the same phosphorus atom in PDCP can, in principle, be replaced by a carborane-containing group yielding cardo-type polymers; this is accomplished using bis(hydroxymethyl)-o-carborane as the nucleophilic agent.…”

“…Replacement of the remaining chlorine atoms in these polymers by tetrafluoropropoxy groups (without isolation of the product formed in the first stage) has given poly(organophosphazenes) in which the surrounding groups are represented by fluoroalkoxy groups in addition to the cardo carborane groups. 110 Poly(dichlorophosphazene) is a highly reactive initial compound for the synthesis of insoluble polymeric catalysts containing oligooxyethylene fragments. 14, 113 ± 115 The reaction is carried out with stirring in a mixture of anhydrous THF with toluene.…”

“…Mono-( 16), bis- (17), and tris-( 18) o-carboranyl-substituted cyclotriphosphazenes have been prepared in order to synthesise carborane-containing polyphosphazenes. 110,141,142 This polymer is formed under milder conditions than those resulting from polymerisation of hexachlorocyclotriphosphazene and previously known carboranecyclophosphazenes. 143 To increase the hydrolytic stability of this carborane-containing polymer, the remaining chlorine atoms were substituted by tetrafluoropropoxy groups.…”

Thermal-Oxidation-Resistant Poly(Carborane-Silane) for Protective Coatings Under Harsh Environments

“…Carborane and its derivatives are highly sought after due to their 3D-aromatic structure and have been investigated to improve the heat stability of organic polymers. Carborane is soluble in commonly used organic solvents and can be easily introduced into polymer systems such as polyester, , polysiloxane, , polyamides/polyimides, − polyphosphazenes, − heteroelement-substituted polymers, , and so on. − Among the polymers discussed above, polysiloxane stands out because the introduction of carborane segments substantially improves its heat resistance. The addition of carborane segments significantly improved the modified polymers’ thermal resistance.…”

Carborane–Siloxanes: Synthesis and Properties. New Possibilities for Structure Control

“…carborane-containing polyarylenes [2][3][4][5][6][7]; carborane-containing polyesters [8,9]; carborane-containing polyamides and polyimides [10,11]; heteroelement-substituted carborane polymers [12,13]; carborane-containing polyphosphazenes [14][15][16][17];…”