Poly(trialkylsilyl methacrylate)s: A family of hydrolysable polymers with tuneable erosion profiles

Polymers containing hydrolytically labile trialkylsilyl ester side groups were synthesised via a conventional and a controlled radical polymerization. The trialkylsilyl methacrylate monomer unit was chosen for its capacity to hydrolyse into basic, acid or sea water varying the hydrophilic character of the resulting polymer backbone with time. The hydrolysis or saponification reaction of the ester bond of the trialkylsilyl methacrylate was monitored through a ¹H NMR study showing the formation of siloxane side-products. Several copolymers and polymer blends were prepared as matrixes for controlled erodible systems. Their capacity to hydrolyse was demonstrated through SEM investigations with selective dissolution of free films containing hydrolysable copolymers and PMMA blends. Well-defined random and diblock copolymers with methyl methacrylate were investigated to show the effect of the microstructure on the erosion properties of the corresponding coatings. Poly(methyl methacrylate-b-tert-butyldimethylsilyl methacrylate) diblock copolymers synthesised through the RAFT process showed a better control of the erosion with a constant erosion rate over a long-time service in sea water at pH = 8.2. In addition, experiments showed that the erosion rate could be modulated by varying the molar proportion of hydrolysable side groups onto the copolymer backbone and the weight amount of copolymers mixed with PMMA in toluene solution.