LIVING FUNCTIONALIZATION OF POLYMETHACRYLATES BY GROUP-TRANSFER POLYMERIZATION (GTP) USING LOW CEILING TEMPERATURE MONOMERS

A living functionalization method for group transfer polymerization (GTP) has been developed for poly(alkyl methacrylates) using the sterically hindered monomer, methyl-2-phenylpropenoate (MPHA). The end-capping reactions of MPHA with living trimethylsilyl ketene acetal-ended poly(methyl methacrylate) (PMMA) chain ends have been systematically studied and characterized by size exclusion chromatography, vapor pressure osmometry, ultraviolet-visible, H-1 and C-13 nuclear magnetic resonance spectroscopy. Although oligomerization of MPHA is observed at -78-degrees-C, this is reversible and only monoaddition is observed at room temperature. In principle, various functional groups can be introduced into poly(alkyl methacrylates) via substituents on the aromatic ring of MPHA and related monomers. Amino-functionalized PMMA was prepared by end-capping reactions of living trimethylsilyl ketene acetal-ended PMMA with methyl E-3-(2-dimethylaminophenyl)-2-phenylacrylate.