Macromolecular Brushes Based on Poly(L-Lactide) and Poly(ε-Caprolactone) Single and Double Macromonomers via ROMP. Synthesis, Characterization and Thermal Properties

Single and double poly(L-lactide) (PLLA) and poly(ε-caprolactone) (PCL) macromonomers having a norbornenyl polymerizable group were prepared by conventional Ring Opening Polymerization (ROP). These macromonomers were further subjected to ring opening metathesis polymerization (ROMP) reactions in order to produce double polymer brushes consisting of PLLA or PCL side chains on a polynorbornene (PNBE) backbone. Statistical or block ring opening metathesis copolymerization of the PLLA and PCL macromonomers afforded the corresponding random and block double brushes. Sequential ROMP of the single PLLA, PCL and PLLA macromonomers resulted in the synthesis of the corresponding triblock copolymer brush. The molecular characteristics of the macromolecular brushes were obtained by (1)H-NMR spectroscopy and Size Exclusion Chromatography. The thermal properties of the samples were studied by thermogravimetric analysis, TGA, Differential Thermogravimetry, DTG and Differential Scanning Calorimetry, DSC.