Emulsion Copolymerization of Vegetable Oil Macromonomers Possessing both Acrylic and Allylic Functionalities

Abstract

Summary: A soybean oil-based vegetable oil macromonomer (VOMM) was incorporated as a comonomer into an all-acrylic copolymer via semi-continuous emulsion polymerization. Structurally, VOMMs are comprised of long hydrocarbon fatty acid moieties with allylic double bonds which enable auto-oxidative crosslinking at ambient temperature. VOMMs facilitate low temperature film formation and the fatty acid chains tethered to the polymer backbone auto-oxidize upon film formation to yield crosslinked films. Latexes with varying VOMM levels were synthesized to elucidate the effect of VOMMs on the pre-cure and post-cure glass transition temperature (T g ) and minimum film formation temperature (MFT). Thermoplastic control latexes (without VOMM) were also synthesized via copolymerization of butyl acrylate and methyl methacrylate. This paper details the characterization performed to validate and quantify the VOMM allylic unsaturation retention before, during, and after polymerization, and to quantify and confirm the increase in T g resulting from auto-oxidative crosslinking via solid state 13 C nuclear magnetic resonance spectroscopy and differential scanning calorimetry.

Synergistic Effects of Cardanol- and High Oleic Soybean Oil Vinyl Monomers in Miniemulsion Polymers

“…The incorporation of plant oil-based monomers in copolymerization with conventional petroleum-based counterparts provides several benefits to the final copolymers such as plasticizing properties, the elimination of coalescence aids in latex applications, reducing minimum film formation temperature and film-forming properties. The ability of fatty acid fragments to undergo autoxidation (due to presence of allylic double bonds in resulting macromolecules) after latex application and yield the crosslinked polymer networks can balance the mechanical properties of final latex products, which can be beneficial as well 13,17,20 .…”

“…The ability of fatty acid fragments to undergo autoxidation (due to presence of allylic double bonds in resulting macromolecules) after latex application and yield the cross-linked polymer networks can balance the mechanical properties of final latex products, which can be beneficial as well. 13,17,20 Another interesting plant-based renewable resource which has attracted a lot of attention in the past few years is cardanol. This is a byproduct from the cashew nut industry and refers to an aromatic class of organic compounds.…”

“…In recent years, the incorporation of acrylate groups and OH-groups into plant oil molecular structures and the epoxidizing of plant oil fatty acid double bonds have been successfully demonstrated. , Furthermore, various newly synthesized plant oil-based monomers have been investigated in the formation of polymer latex materials through emulsion and miniemulsion processes. ,, The incorporation of plant oil-based monomers in copolymerization with conventional petroleum-based counterparts provides several benefits to the final copolymers such as plasticizing properties, the elimination of coalescence aids in latex applications, the reduction of minimum film formation temperature, and film-forming properties. The ability of fatty acid fragments to undergo autoxidation (due to presence of allylic double bonds in resulting macromolecules) after latex application and yield the cross-linked polymer networks can balance the mechanical properties of final latex products, which can be beneficial as well. ,, …”

Biobased latexes from natural oil derivatives

“…[11][12][13][14] In this regard, Kaya et al reported synthesis of latexes with varying amounts of soybean oilbased macromonomers in copolymerization with methyl methacrylate. 15 Moreno et al used miniemulsion polymerization to polymerize monomer synthesized by incorporation of methacrylic functionality into linoleic acid. 16 Fully renewable polymer latexes based on naturally occurring α-methylene-γ-butyrolactone were synthesized in miniemulsion in.…”

Synthesis and characterization of a soybean oil‐based macromonomer

“…Vegetable oil macromonomers (VOMMs) have distinct characteristics that are advantageous in the synthesis of environmentally responsible emulsions: (1) by virtue of its molecular length and large monomer size, the monomers are typically excellent plasticizers and readily facilitate coalescence without the necessity for solvent‐based coalescing agents, (2) the monomers readily copolymerize in emulsion polymerization with a variety of vinyl monomers through the acrylate functionality and reduce minimum filming temperature (MFT) during film formation while preserving the allylic functional group (at the polymerization stage), and (3) the allylic functionalities within the fatty acid residue, i.e., monomer tail, react auto‐oxidatively after application and slowly during coalescence at ambient temperature, resulting in crosslinked film networks that improve mechanical strength through upward shifted resulting T g s. The synergistic combination of allylic vegetable oil fatty acids and an acrylic backbone provides mechanically stable, self‐crosslinking emulsions with unique structure and design capabilities for utilization in reduced or zero VOC emission coatings …”