Synthesis and radical polymerization of ethyl α‐acetoacetoxymethylacrylate

Abstract

AbstractEthyl α‐acetoacetoxymethylacrylate (1) was prepared by reaction of diketene and ethyl α‐hydroxymethylacrylate which was obtained from the reaction of triethyl phosphonoacetate and an aqueous solution of formaldehyde. 1 contains 27% of the enol tautomer. The polymerization of 1 in benzene initiated with dimethyl 2,2′‐azoisobutyrate (2) was investigated kinetically. The overall activation energy of polymerization was determined to be 84,8 kJ/mol. The polymerization rate (Rp) at 50°C is expressed by Rp = k[2]0,5 [1]1,1. From an electron spin resonance study, the polymerization system was revealed to involve persistent propagating poly(1) radicals. The rate constants of propagation and termination were estimated to be kp = 300 and kt = 1,0 · 106 1 · mol− · s− at 60°C, respectively, using the polymer radical concentration and assuming stationary state conditions. Copolymerization of 1 (M1) and styrene (M2) was examined at 50°C, and the following copolymerization parameters were obtained; r1 = 0,28, r2 = 0,22, Q1 = 1,2, and e1 = +0,87.