Compared Reactivity of Allyl Ribosides in UV-Initiated Free Radical Copolymerization with Acceptor Monomers

Abstract

The free radical copolymerization of allyl ribosides with diethyl fumarate and 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 was conducted in solution as well as in liquid films of bulk reactants. Infrared spectroscopy was used to monitor the consumption of the allylic donor monomer and of the butenedicarboxylate acceptor monomers. The method allowed examining the influence of the nature of the monomer pair and of their relative concentration on the kinetic profiles. Comparison with reference vinyl ether monomers confirmed the expected lower reactivity of the blends containing allylic derivatives. SEC and NMR analysis supported the occurrence of degradative chain transfer during the reactions involving allylic monomers. However, allyl derivatives of glycerol as well as O-allyl ribosides were shown to undergo polymerization with high conversion of both monomers when blended in appropriate molar ratios.

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.…”

“…Bulk polymerization is more representative of the actual conditions in UV-curable compositions of technological interest. In both cases, copolymerizations were initiated by continuous photolysis of 2-hydroxy-2-methyl-1-phenylpropanone used as a Norrish type I PI present at low concentration in the bulk or diluted blend of monomers, under the conditions used in our previous studies [12]. For copolymerization in solution, DEF was mixed with donor monomers such as EVE or AEE in equimolar proportions with ethyl acetate (90 wt% monomers concentration).…”

“…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.…”

Syntheses of donor acceptor biobased photocurable water‐soluble resins based on poly‐l‐lysine

“…The donor/acceptor couple has been widely studied in polymerization under irradiation by J€ onsson and Clark 25 and recently, biosourced monomers from sugars have been studied according to the concept of donor/acceptor photopolymerization. 26 Nowadays, environmental legislation has become strict with coating industries and the curing of coatings using ultra-violet radiation has gained increasing interest due to their advantages such as solvent-free formulations, low energy consumption, cost efficiency, and high curing speed even at room temperature. 27,28 Peculiar techniques are emerging such as UV powder coating and UV waterborne coating.…”

“…Donor/acceptor functional groups are less reactive than acrylates but exhibit advantages like the ability to polymerize without the use of photoinitiators (PIs). The donor/acceptor couple has been widely studied in polymerization under irradiation by Jönsson and Clark and recently, biosourced monomers from sugars have been studied according to the concept of donor/acceptor photopolymerization …”