Abstract
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.
Highlights
Polymers containing hydrolysable bonds have been developed for many years in pharmaceutical, biomedical, and antifouling areas
Propagation and termination rate coefficients for free radical polymerization of tert-butyldimethylsilyl methacrylate (TBDMSMA) have been experimentally determined for various temperatures
In the present study we have demonstrated that the PREDICI® model can be a useful tool to describe in detail the cyanoisopropyl dithiobenzoate (CPDB)-mediated reversible addition-fragmentation chain transfer (RAFT) polymerization of TBDMSMA
Summary
Polymers containing hydrolysable bonds have been developed for many years in pharmaceutical, biomedical, and antifouling areas. Polymers containing trialkylsilyl esters as pendant groups have been developed as polymeric binders for self-polishing antifouling coatings [3,4] These silyl ester derivatives are readily subjected to alkaline hydrolysis in seawater yielding to a remaining acid-functional polymer, which becomes seawater-soluble and gradually swept from the surface of the coating. This chemically controlled erosion of the coating can be used in processes based on the leaching of active compounds such as biocides in antifouling paints. Polymeric resins bearing hydrolysable pendant groups have been prepared through chemical modification or polymerization methods [5]
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