A complete kinetic study of a versatile functional monomer: acetoacetoxyethyl methacrylate (AAEMA)

Abstract

The current study reports the complete kinetic analysis of acetoacetoxyethyl methacrylate (AAEMA). The temperature dependent propagation rate coefficient, k_p, was accessed by pulsed laser polymerization-size exclusion chromatography (PLP-SEC), affording the following Arrhenius parameters: A = 2.13 × 10⁶ L mol⁻¹ s⁻¹ and E_a = 19.69 kJ mol⁻¹. For the SEC-analysis, the Mark–Houwink–Kuhn–Sakurada (MHKS) parameters of the corresponding polymer were determined (K = 0.0250 mL g⁻¹; α = 0.547) via multiple detection SEC. Furthermore, reactivity ratios for the copolymerization with methyl methacrylate (MMA) at 75 °C in ethyl 3-ethoxypropionate (EEP) were obtained by the Meyer–Lowry method (r_MMA = 0.89; r_AAEMA = 0.98), supported by a detailed kinetic simulation using the PREDICI simulation package. In addition, copolymerization was carried out at ambient temperature with a bicomponent dibenzoyl peroxide (BPO)/dihydroxyethyl-p-toluidine (DHEPT) initiator system, demonstrating a strong increase of the rate of copolymerization with increasing AAEMA content (i.e. 40% decrease of the gel time by adding 10 mol% of AAEMA).