High Temperature Resistant Tailor-Made Poly(meth)acrylates Bearing Adamantyl Group via Atom Transfer Radical Polymerization

This investigation reports preparation of tailor-made poly(meth)acrylates bearing adamantyl group using atom transfer radical homo and copolymerization via initiator as well as via monomer approach. The ATRP of methyl methacrylate was investigated using different initiators having adamantyl group (like AdMBr or AdBr) as well as conventional EBiB initiator and CuBr as catalyst in combination with PMDETA as ligand. It was observed that the incorporation of the bulky adamantyl group increased the rate of polymerization. The polymerization proceeded through first-order kinetics and molecular weights increased linearly with conversion, close to the targeted molecular weights. The living nature of the end-group was confirmed by MALDI-TOF-mass spectrometry and chain extension experiment. The homopolymerization of adamantyl methyl acrylate (AdMA) and its copolymerization with MA was successfully carried out using methylbromopropionate (MBrP) as initiator and CuBr/dNbpy as the catalyst. Interestingly, the resultant poly(meth)acrylates bearing the adamantyl group had excellent thermal stability and much better thermal stability than the similar polymers without adamantyl group as evidenced from thermogravimetry analysis (TGA) and isothermal TGA studies. Importantly, incorporation of adamantyl group adamantly increases rate of polymerization, thermal stability, and glass transition temperature of the polymers. All the polymers were characterized by NMR, MALDI-TOF-MS, DSC, and TGA analysis. (C) 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7101-7113, 2008