Direct grafting poly(methyl methacrylate) from TiO₂ nanoparticles via Cu²⁺‐amine redox‐initiated radical polymerization: An advantage of monocenter initiation

Abstract

Cu2+ can oxidize amines to generate radicals to initiate radical polymerization of electron‐deficient monomers under mild conditions. Here, CuSO4‐catalyzed redox‐initiated radical polymerizations of methyl methacrylate from amino‐functionalized TiO2 nanoparticles (TiO2‐NH2 nanoparticles) was performed to prepare TiO2 nanoparticles grafted with poly(methyl methacrylate) (TiO2‐g‐PMMA hybrid nanoparticles) in dimethylsulfoxide or N,N‐dimethylformamide at 90°C. Infrared spectroscopy, thermogravimetric analysis, and X‐ray photoelectron spectroscopy confirmed the presence of the grafted PMMA and the grafting yield was about 50 wt%. Microscopy and particle‐size analysis indicated that TiO2‐g‐PMMA nanoparticles had a good affinity to organic media. Because only aminyl radical (NH•) on TiO2 nanoparticles formed in Cu2+‐amine redox‐initiation step, there was no free PMMA chains formed during polymerization. Thus, our protocol provides a facile strategy to prepare inorganic/organic hybrid nanoparticles via one‐pot Cu2+‐amine redox‐initiated free radical polymerization. POLYM. ENG. SCI., 55:735–744, 2015. © 2014 Society of Plastics Engineers

Ultra-High Molecular Weight Alpha-Amino Poly(Methyl Methacrylate) with HighTgthrough Emulsion Polymerization by Using Transition Metal Cation-Tertiary Amine Pairs as a Mono-Centered Initiator

“…Typical transition metal cations such as Cu 2+ and Fe 3+ can be used as oxidants to form redox initiation pairs with tertiary amines, which generate C alpha radicals only, and give rise to the reduced intermediate, Cu + and Fe 2+ , which can be easily oxidized back by aerobic dioxygen (O 2 ). Therefore, such redox initiation not only ensures a homogeneous alpha functionality of final polymer, but also minimizes the dosage of oxidizing agents (Scheme ). Very recently, we reported the Cu II –tertiary amine redox‐initiated conventional or controlled radical polymerization of methyl methacrylate (MMA) in dimethylsulfoxide (DMSO) .…”

UV‐laser marking of a TiO2‐containing ABS material

“…b and c) in an effort to understand how laser irradiation influences the Ti composition. In the original unmarked ABS samples, peaks for Ti 2p 3/2 and Ti 2p 1/2 were detected at 458.9 and 464.4 eV, respectively, and these correspond to titanium dioxide . In marked samples, other peaks for Ti were observed in addition to those mentioned above at 454.5 eV for 2p 3/2 and 460.4 eV for 2p 1/2 and these correspond to a reduced state of titanium (see Fig.…”

One pot synthesis of free standing highly conductive polymer nanocomposite films: Towards rapid BTX vapor sensor

“…The main challenge in fabrication PMMA/NGPs lies in the establishment of uniform dispersion of NGPs in PMMA matrix because NGP has inherent inert nature which have strong tendency to aggregate and can easily agglomerate due to Van der Waals interaction . So far, various methods have been developed to support dispersion of filler within the polymer matrix such as solution blending, grafting, melt mixing etc .…”