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/2,2Ј-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-Tü dös, and Fineman-Ross methods were used for the determination of the monomer reactivity ratios (r 1 and r 2 ). They all gave nearly the same values of r 1 and r 2 . The reactivity ratios of the two monomers in CFRP, ATRP, and NMLFRP were 0.17 Յ r 1 Յ 0.4 (DA) and 1.0 Յ r 2 Յ 1.24 (DVB). The side-chain crystallinity of the copolymers decreased with an increasing DVB molar fraction.

Isobutylene‐rich macromonomers: Dynamics and yields of peroxide‐initiated crosslinking

“…Nonetheless, the results are somewhat surprising, given that propagation rate constants for acrylates at moderate temperatures are greater than those generally reported for styrenics and maleimides. The exceptional reactivity of IIR‐VBA may be due to an electron withdrawing effect of the para‐ester group, since the propagation rate constant for dodecyl‐4‐vinyl benzoate is known to exceed that of styrene …”

Atom transfer radical copolymerization of glycidyl methacrylate and methyl methacrylate

“…4). The conversion was kept within about 25 wt % because, at high conversions, the changes in the initial and final feed compositions were significant; this yielded a quite high error in monomer reactivity ratios, whereas at very low conversions, the composition may have been influenced by preferential initiation of one monomer by the initiating radical 28. According to the literature, it was expected that both methacrylate monomers should copolymerize with comparable reactivity, such as MMA and n ‐butyl methacrylate ( r 1 = 0.98, r 2 = 1.26),29 or a slightly higher reactivity of GMA, such as in the pair with allyl methacrylate ( r 1 = 1.22, r 2 = 0.82) 22.…”

Statistical copolymers of 2‐(trimethylsilyloxy)ethyl methacrylate and methyl methacrylate synthesized by ATRP

“…24,25 Nevertheless, some discrepancies may still occur and could be explained by different activation and/or deactivation rate constants for each two different propagating species. Also, different rates of homopropagation and cross-propagation play non-negligible part.…”