Kinetics and thermal properties of polydiethylsiloxane initiated by potassium trimethylsilanolate

Abstract

This work reports the kinetics of anionic ring‐opening polymerization of hexaethylcyclotrisiloxane (D3Et) with potassium trimethylsilanolate as initiator and diglyme and N,N‐dimethylformamide (DMF) as promoters. The polymerization rate of D3Et is influenced by the nature of promoters and the reaction temperatures. With the use of DMF as a promoter, the polymerization activation energy is 107.89 kJ/mol, and the polymerization rate constant at 110°C is 0.08466 min−1 with [P]/[I] = 3.0. Gel permeation chromatography and 29Si NMR spectra showed that the intermolecular redistribution occurred during the late stage of polymerization, which facilitated the synthesis of high‐molecular‐weight polydiethylsiloxane (PDES). Differential scanning calorimetry analysis showed that PDES exhibited a glass transition temperature of −142°C and complex crystallization phenomena. Thermogravimetric analysis illustrated that the PDES that was prepared using this method had good thermal stability with onset decomposition temperatures of 483 and 452°C under nitrogen and air conditions, respectively. This work presents innovative approaches for achieving a more energy‐efficient synthesis of PDES to meet the demands of industrial‐scale production.