Synthesis of metal‐free poly(p‐dioxanone) by phosphazene base catalyzed ring‐opening polymerization

Abstract

ABSTRACTPoly(p‐dioxanone) (PPDO) has received significant attention due to its good biocompatibility and fast biodegradation profiles. In addition, PPDO is a polymer with high potential in biomedical applications. However, the conventional syntheses of PPDO via the ring‐opening polymerization (ROP) of p‐dioxanone (PDO) often use a metallic catalyst, which significantly limits its biorelated applications. This investigation was focused on the synthesis of metal‐free PPDO by using phosphazene base t‐BuP4 as the catalyst. The effects of the reaction conditions including temperature, reaction time, initiators, and feed molar ratios were studied in detail by nuclear magnetic resonance spectroscopy, viscosimetry, differential scanning calorimetry, and thermogravimetric analysis. The results showed that t‐BuP4 exhibited especially high activity in catalyzing alcohol or aniline to initiate the ROP of PDO, consequently resulting in metal‐free PPDOs. The polymerization was optimum at a reaction temperature of approximately 100°C and 88.7% of PDO was consumed. The viscosity–average molecular weights of the resulting polymer reached as high as 2.09 × 104 g/mol. The molar ratios of [PDO]/[t‐BuP4] also had an obvious effect on both the polymerization and the resulting polymer. Increasing [PDO]/[t‐BuP4] ratios facilitated the molecular weight growth, whereas the conversions of PDO significantly decreased. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43030.