Synthesis of cyclohexanone formaldehyde resin-methylmethacrylate block-graft copolymers via ATRP

Well defined block-graft copolymers of cyclohexanone-formaldehyde resin (CFR) and methylmethacrylate (MMA) were prepared via atom transfer radical polymerization (ATRP). In the first step, cyclohexanone formaldehyde resin (CFR) containing hydroxyl groups were modified with 2-bromopropionyl bromide. Resulting multifunctional macroinitiator was used in the ATRP of MMA using copper bromide (CuBr) and N,N,N',N'',N''-pentamethyl-diethylenetriamine (PMDETA) as catalyst system at 90°C. The chemical composition and structure of the copolymers were characterized by nuclear magnetic resonance (¹H-NMR) spectroscopy, Fourier transform infrared (FTIR) spectroscopy, and molecular weight measurement. Molecular weight distributions of the CFR graft copolymers were measured by gel permeation chromatography (GPC). M_n values up to 19,000 associated with narrow molecular weight distributions (polydispersity index (PDI) < 1.6) were obtained with conversions up to 49%. Coating properties of synthesized graft copolymers such as adhesion and gloss values were measured. They exhibited good adhesion properties on Plexiglas substrate. The thermal behaviors of all polymers were conducted using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA).