Homogeneous and multiphase poly(methyl methacrylate) graft polymers via the macromonomer method

Anionic and group transfer polymerization processes were used to synthesize controlled molecular weight methacryloyloxy functionalized poly(dimethylsiloxane) and poly(methyl methacrylate) macromonomers having a narrow molecular weight distribution and high percent functionality. These macromonomers were anionically copolymerized with methyl methacrylate (MMA) to afford poly(methyl methacrylate)-graft-poly(methyl methacrylate) (PMMA-g-PMMA) and poly(methyl methacrylate)-graft-poly(dimethylsiloxane) (PMMA-g-PDMS) polymers having not only narrow molecular weight distribution graft parts but also backbone parts. The PMMA-g-PDMS system was fractionated using supercritical chlorodifluoromethane to determine its chemical composition distribution (CCD). The CCD for the PMMA-g-PDMS copolymerized in a living manner was substantially more narrow than the free radically copolymerized material. The PMMA-g-PMMA system was used to study the dilute solution properties of branched homopolymers. The appropriateness of the universal calibration gel permeation chromatography (GPC) method for branched systems exhibiting long chain branching was reaffirmed.