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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 ( k  p ) and termination rate coefficients ( k  t ) 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 ( k  β1 , k  β2 ) and to polymeric RAFT agent ( k  β ) 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 ( k  tr ) to cyanoisopropyl dithiobenzoate is found to be close to 9.0 × 10³ L·mol -1 ·s -1 and the chain-transfer constant ( C  tr ) for CPDB-mediated RAFT polymerization of TBDMSMA is about 9.3.

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