Ionizing Radiation-Induced Copolymerization of 2-Ethylhexyl Acrylate and Acrylic Acid and Ionomer Formation
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The ionizing radiation-induced polymerization of acrylate esters is a technique employed for the curing of such materials for a variety of adhesive, coating, ink, and lithographic applications. The work presented in this dissertation involves the synthesis of a copolymer composed of 2-ethylhexyl acrylate (2-EHA) and acrylic acid (AA) using pulsed electron beam and gamma irradiation. The structure and synthesis kinetics of this copolymer were investigated by 1H nuclear magnetic resonance (NMR), electron pulse radiolysis with kinetic spectroscopic detection (PR-KSD), and Fourier transform infrared spectroscopy (FTIR). The effects of total dose, dose rate, and acrylic acid content on the polymerization reaction were studied. The conversion of 2-EHA monomer into polymer at a given total dose was found to be enhanced at lower dose rates and higher concentrations of acrylic acid. The pulse radiolysis investigation of the polymerization of 2-EHA and AA was performed through studies of four different types of systems: (i) neat 2-EHA, (ii) 2-EHA/methanol (MeOH) solutions, (iii) mixtures of 2-EHA and AA, and (iv) 2-EHA/AA/MeOH solutions. The build-up of carbon-centered neutral 2-EHA free radicals in neat 2-EHA was found to obey a second order rate law with a rate coefficient of ((7 ± 3) ´ 108)eEHA, whereas in 2-EHA/AA mixtures it was found to obey a pseudo-first order rate law with a rate coefficient of (1.5 ± 0.3) ´ 1010 mol-1 dm3 s-1. This phenomenon is suggested to originate in the increased H+ ion concentration in the presence of acrylic acid, which leads to a faster neutralization step of 2-EHA radical anions as they are transformed into neutral free radicals during the initiation step of the reaction. An investigation of the formation of ion-containing copolymers (known as ionomers) was performed using the radiation-synthesized poly(2-EHA-co-AA) and iron cations. Verification of successful incorporation of iron into the copolymer was identified by an asymmetric carboxylate stretch at 1600 cm-1 of the FTIR spectrum. TEM analysis of poly(2-EHA-co-AA)/Fe2+ ionomers formed from formulated compositions involving a 2:1 mole ratio of ferrous acetate to acrylic acid exhibited ionic clusters of approximately 100 nm in diameter, which may include up to 350 ferrous cations.