Facile and Efficient Synthesis of Fluorosilicone Polymers by Using an Optimized Gradient Ring‐Opening Reaction

Abstract Fluorosilicone rubber is essential for sealing in extreme temperatures and non‐polar environments due to its exceptional adaptability. However, achieving a high yield of fluorosilicone polymers with medium and high fluorine content remains a challenge. Herein, a facile gradient strategy is developed that involves modifying the method of cyclic monomer addition based on the rate of ring‐opening polymerization (ROP), to improve yield and adjust fluorine content precisely. The polymerization process is designed and tailored based on the reaction rates of anionic ring‐opening polymerization (AROP) and cationic ring‐opening polymerization (CROP) via an efficient gradient strategy. The effects of the polymerization process on the viscosity and yield of vinyl fluorosilicone polymers and hydrofluorosilicone polymers are investigated and optimized. Notably, the as‐prepared vinyl‐terminated fluoromethylsilane with 60% fluorine content (FMS‐Vi‐60F) has a high yield (86.6%) and high viscosity (150 000 mPa·s) in a short reaction time, which is superior to previous methods. Clearly, the gradient ring‐opening method developed in this work provides a facile and efficient synthesis for fabricating fluorosilicone polymers with a high yield and tunable fluorine content.