New Polymer Syntheses. 13. Synthesis of Aromatic Polyphosphates from Silylated Bisphenol A or Tetrachlorohydroquinone

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Abstract
Bulk condensations of bissilylated Bisphenol A and tetrachloro-hydroquinone with various aryl phosphorodichloridates (phosphoric acid arylester dichlorides) were conducted at temperatures between 180 and about 300°C. Only when the pentachlorophenylester of phosphoric dichloride was condensed was partial crosslinking observed. Yields in the range of 80–95%, and [Mbar]n of ∼ 12 000 were obtained. DSC measurements above 25°C show T g in the range of 65–145°C, whereas melting endotherms were never found. Thermo-gravimetric analyses indicate that the thermal stability decreases with an increasing number of chlorines in the aryloxy group. Consequently, the fully chlorinated polyphosphate possesses the lowest thermal stability.