Reactivity of Vinyl Ethers and Vinyl Ribosides in UV-Initiated Free Radical Copolymerization with Acceptor Monomers

Abstract

The reactivity of various vinyl ethers and vinyloxy derivatives of ribose in the presence of diethyl fumarate or diethyl maleate was investigated for evaluating the potential of donor-acceptor-type copolymerization applied to unsaturated monomers derived from renewable feedstock. The photochemically induced polymerization of model monomer blends in the bulk state was monitored by infrared spectroscopy. The method allowed us to examine the influence of monomer pair structure on the kinetic profiles. The simultaneous consumption of both monomers was observed, supporting an alternating copolymerization mechanism. A lower reactivity of the blends containing maleates compared with fumarates was confirmed. The obtained kinetic data revealed a general correlation between the initial polymerization rate and the Hansen parameter δ(H) associated with the H-bonding aptitude of the donor monomer.

Organizations join forces to confront global cancer crisis

“…This last study even compared the transetherification with the Williamson reaction. More recently, Pichavant74 reported the synthesis of a vinyl ether by transetherification catalyzed by a palladium (II) complex in the presence of ethyl vinyl ether in dichloromethane.…”

Photo-initiated copolymerization of allyl and vinyl ethers with dialkyl fumarates: A mechanistic investigation by ESI mass spectrometry

“…Other monomers, Allyl hexyl ether (AHE) and allyl isopropylidene glycerol or 4-(allyloxymethyl)-2,2-dimethyl-1,3-dioxolane (AIG), Vinyl hexyl ether (VHE) and racemic vinyl isopropylidene glycerol or 2,2-dimethyl-4-(vinyloxymethyl)-1,3-dioxolane (VIG) were prepared and purified as previously reported [12,13]. The photoinitiator (PI) for free-radical copolymerization, 2-hydroxy-2-methyl-1-phenylpropanone (Additol HDMAP) was obtained from Allnex.…”

“…In the frame of our current research on pentose-based unsaturated monomers, we have examined the reactivity of two series of allyl and vinyl ethers in photo-initiated free radical copolymerization with diethyl fumarate (DEF) and diethyl maleate (DEM) [12,13]. The comparison between the two series of monomers which cover a broad range of chemical structures, confirmed the lower reactivity of allyl ethers with respect to their vinyl analogs, but still the allyl esters were shown to significantly insert into the copolymer.…”

Synthesis and characterization of novel functional vinyl ethers that bear various groups

“…To the best of our knowledge, only two other examples of catalyzed transfer vinylation were reported in the literature: vinylation of steroids [22] and synthesis of glycidol vinyl ether [26]. In 2010, Pichavant et al described the synthesis of a VE by transetherification catalyzed by a palladium (II) complex in the presence of ethyl vinyl ether (EVE) in dichloromethane [27]. The iridium-catalyzed reaction of vinyl acetate with alcohols later appeared as a complementary method to palladium-catalyzed transetherification [16,17].…”