Synthesis of polyesters containing disiloxane subunits: Structural characterization, kinetics, and an examination of the thermal tolerance of Novozym-435

This paper reports the Novozym-435 mediated polymerization of disiloxane-containing polyester monomers under solvent-free conditions. The thermal tolerance of the immobilized enzyme was examined by conducting polymerization cycles over a temperature range of 35–150 °C. Increasing the temperature up to 100 °C afforded an increase in the apparent second order rate constant. Residual activity was measured using the production of octyl palmitate. The enzyme was shown to retain on average greater than 90% of its residual activity regardless of the polymerization temperature. This prompted a study of the long term thermal tolerance of the biocatalyst in which it was determined that over ten reaction cycles there was a significant decrease in the initial polymerization rate, but no change in the degree of monomer conversion after 24 h. The disiloxane containing polyesters were characterized using nuclear magnetic resonance spectroscopy and Fourier-transform infrared spectroscopy. Differential scanning calorimetry was used to determine the thermal properties of the disiloxane-containing polyesters.

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► Enzymatic catalysis of siloxane-containing materials.
► N435 shows good thermal tolerance when polymerizing siloxane-materials.
► N435 can be used over multiple reaction cycles at high temperatures.