Copolymerization of methyl acrylate and vinyl acetate catalyzed by ethylaluminium chlorides

Abstract

The copolymerization of vinyl acetate with methyl acrylate in the presence of Et2AlCl, Et1.5AlCl1.5, and Et2AlCl‐benzoyl peroxide systems has been investigated. The influence of monomer ratios and organoaluminium compound concentration on the copolymer yield and composition have been determined and discussed. The monomer sequences distribution has been studied by means of 13C‐NMR. It was found that organoaluminium compounds in the studied systems catalyze not only the alternating copolymerization, but also the homopropagation of both monomers. An alternating copolymer was obtained in reactions carried out at −78°C, when a large excess of vinyl acetate was used in the monomer feed.

Mn2(CO)10‐induced controlled/living radical copolymerization of vinyl acetate and methyl acrylate: Spontaneous formation of block copolymers consisting of gradient and homopolymer segments

“…The copolymerization of MA and VAc was then carried out with Mn 2 (CO) 10 in conjunction with ethyl 2‐iodoisobutyrate (EMA‐I) as the initiator in the fluoroalcohols ( 1 and 2 ) or in bulk at 40 °C under visible light irradiation ([MA] 0 /[VAc] 0 = 1/1). As shown in Figure 2, the copolymerization of MA and VAc smoothly proceeded both in bulk and in the fluoroalcohols, where MA was much faster consumed than VAc due to the lower copolymerizability of VAc ( r VAc < 0.05, r MA > 5) 49, 50. This indicates the formation of copolymers with high MA contents in the early stages of the polymerization and increasing VAc contents as the reaction proceeds.…”

Sequence determination of vinyl acetate–methyl acrylate copolymers by NMR spectroscopy

“…The methine carbon of the M-monomeric unit and the methylene carbons of the V-as well as the M-monomeric units appear in the region 6 34.0-41. 3 ppm as a multiplet and are configurational as well as compositional-sensitive. This region can provide information about M-centered compositional triad sequences.…”