Copolymerization of dodecyl‐4‐vinyl benzoate and dodecyl acrylate by conventional, atom transfer, and nitroxide‐mediated free‐radical polymerization

Abstract n‐Dodecyl acrylate (DA) and dodecyl‐4‐vinyl benzoate (DVB) were copolymerized by conventional free‐radical polymerization (CFRP); atom transfer radical polymerization (ATRP), and nitroxide‐mediated living free‐radical polymerization (NMLFRP) with benzoyl peroxide, 1‐phenyl ethyl chloride/cuprous chloride/2,2′‐bipyridine, and benzoyl peroxide/2,2,6,6‐tetramethylpiperidinyl‐1‐oxy initiator systems, respectively. In CFRP and NMLFRP, toluene and xylene were used as solvents, whereas ATRP was performed in bulk. Mayo–Lewis, Kelen–Tüdös, and Fineman–Ross methods were used for the determination of the monomer reactivity ratios (r1 and r2). They all gave nearly the same values of r1 and r2. The reactivity ratios of the two monomers in CFRP, ATRP, and NMLFRP were 0.17 ≤ r1 ≤ 0.4 (DA) and 1.0 ≤ r2 ≤ 1.24 (DVB). The side‐chain crystallinity of the copolymers decreased with an increasing DVB molar fraction.