RAFT Polymerization of Tert-Butyldimethylsilyl Methacrylate: Kinetic Study and Determination of Rate Coefficients.

Well-defined poly(tert-butyldimethylsilyl methacrylate)s (TBDMSMA) were prepared by the reversible addition-fragmentation chain transfer (RAFT) process using cyanoisopropyl dithiobenzoate (CPDB) as chain-transfer agents (CTA). The experimentally obtained molecular weight distributions are narrow and shift linearly with monomer conversion. Propagation rate coefficients (kp) and termination rate coefficients (kt) for free radical polymerization of TBDMSMA have been determined for a range of temperature between 50 and 80 °C using the pulsed laser polymerization-size-exclusion chromatography (PLP-SEC) method and the kinetic method via steady-state rate measurement, respectively. The CPDB-mediated RAFT polymerization of TBDMSMA has been subjected to a combined experimental and PREDICI modeling study at 70 °C. The rate coefficient for the addition reaction to RAFT agent (kβ1, kβ2) and to polymeric RAFT agent (kβ) is estimated to be approximately 1.8 × 10⁴ L·mol-1·s-1 and for the fragmentation reaction of intermediate RAFT radicals in the pre-equilibrium (k-β1, k-β2) and main equilibrium (k-β) is close to 2.0 × 10-2 s-1. The transfer rate coefficient (ktr) to cyanoisopropyl dithiobenzoate is found to be close to 9.0 × 10³ L·mol-1·s-1 and the chain-transfer constant (Ctr) for CPDB-mediated RAFT polymerization of TBDMSMA is about 9.3.