Evaluation of 3-Allyl-5-vinylveratrole in Latex Copolymerization with an Acrylic Monomer from High Oleic Soybean Oil

Abstract

Renewable 3-allyl-5-vinylveratrole (AVV) has been evaluated and classified as a biobased cross-linkable vinyl monomer in free-radical chain polymerization. AVV can be readily synthesized in four steps from vanillin, a compound available from lignin. Retained during macromolecular backbone formation, allylic unsaturation can be utilized in post-polymerization crosslinking and contribute to polymer network formation. The glasstransition temperature of the homopolymer from AVV (T g = 77 °C) indicates that incorporating its fragments into copolymers might considerably change the intermolecular interactions and physicochemical properties of the resulting materials. Reactivity ratios (r 1 , r 2 ) obtained in AVV copolymerization with styrene and calculated Q − e parameters of AVV confirm that this monomer copolymerization is described with the classical Mayo−Lewis equation. In this work, latexes from AVV and a renewable acrylic monomer from high oleic soybean oil were synthesized using the miniemulsion process. When the resulting biobased latex films are oxidatively cured, thermomechanical properties of the latex network are determined by the cross-link density, controlled by the ratio of "rigid" and "soft" fragments of AVV and the high oleic soybean oil-based monomer, respectively. Depending on the monomer ratio in the feed, polymeric materials with essentially different viscoelastic behaviors were obtained. Being a structural analogue to styrene, 3-allyl-5-vinylveratrole may function as its renewable replacement in free-radical polymerization, particularly in sustainable latexes. Assuming a variety of plant/vegetable oil-based acrylic monomers available, combining such monomers with AVV can become a promising platform for controlling properties of biobased latex polymer networks and their performance.

Recent advances in radical polymerization of bio-based monomers in aqueous dispersed media

“…In a similar way, Voronov and coworkers conceived a promising platform based on 3-allyl-5-vinylveratrole (AVV), a monomer derived from vanillin. 97 First, they performed AVV homopolymerization in toluene solution and conrmed by 1 H NMR spectroscopy that the allylic unsaturation was retained during homopolymerization and could thus be utilized postpolymerization to form a cross-linked network. Then, they copolymerized AVV and a vegetable-oil-based acrylic monomer (HOSBM) using a batch miniemulsion polymerization process (solids content about 30%) to prepare fully bio-based latexes (84-86% monomer conversion).…”

Efficient Miniemulsion Polymerization of Plant Oil-Based Acrylate Monomer toward Waterborne Epoxy Resins

“…Polymers can be obtained by washing away the unpolymerized plant oil-acrylic (or acrylamide) monomer in an organic solvent, a step that would cause more volatile organic compound contamination. 39 In our previous work, 40 we have demonstrated that the plant oil-acrylate monomer can be converted to an epoxy monomer by using 3-chloroperoxybenzoic acid. The double bond of fatty acid chains can be converted to epoxy groups, while the acrylate double bonds were not affected.…”

“…Moreover, when using plant oil with a higher degree of unsaturation as a raw material, the monomer conversion rate and the molecular weight of the obtained polymer are significantly reduced in miniemulsion polymerization. ,, These latexes cannot be used directly without purification due to the existence of the remaining monomers. Polymers can be obtained by washing away the unpolymerized plant oil-acrylic (or acrylamide) monomer in an organic solvent, a step that would cause more volatile organic compound contamination . In our previous work, we have demonstrated that the plant oil-acrylate monomer can be converted to an epoxy monomer by using 3-chloroperoxybenzoic acid.…”

Biobased Composites from Eugenol- and Coumarin-Derived Methacrylic Latex and Hemp Nanocellulose: Cross-Linking via [2 + 2] Photocycloaddition and Barrier Properties

“…Synthesis of latexes from renewable resources has already been reported in the literature but mainly from vegetable oils, sugars, or terpenes . Although there have been some recent works on cardanol, vanillin, ferulic acid, or eugenol derivatives, − including those of our team, − the emulsion polymerization of biobased aromatic monomers remains underdeveloped, in particular the synthesis of aromatic copolymers.…”