RAFT polymerization of fatty acid containing monomers: controlled synthesis of polymers from renewable resources

Abstract

The incorporation of bio-renewable resources such as fatty acids into the polymer chain allows tailoring the properties of products, for their widespread applications. A series of methacrylate monomers with sidechain fatty acids (FAMA) were synthesized by esterification of 2-hydroxyethyl methacrylate (HEMA) and fatty acids, such as caprylic, capric, lauric, mysritic, palmitic and stearic acid. Consequent polymerization of FAMAs via reversible addition-fragmentation chain transfer (RAFT) gave side-chain fatty acidcontaining well-defined polymers (PFAMA) with targeted molecular weights, narrow molecular weight distribution and precise chain-end functionality. The PFAMAs were subsequently used as macro-chain transfer agents (macro-CTA) for the polymerization of 2-(2-methoxyethoxy)ethyl methacrylate (MEO 2 MA) to obtain block copolymers. Homopolymers with fatty acid pendants display crystalline behaviour depending on the chain length of the fatty acids, evidenced by differential scanning calorimetry (DSC), polarized optical microscopy, small-angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS) techniques.

Synthesis of ethylene/vinyl ester copolymers with pendent linear branches via ring-opening metathesis polymerization of fatty acid-derived cyclooctenes

“…By comparing the T g values of unsaturated polymers to those of saturated polymers, the hydrogenation of polymers led to slightly higher T g values. However, because of the presence of longer linear alkyl side chains, the polymers with the branches of 12 or 16 carbon atoms started to crystallize with the lower T m values, which was in good agreement with other polymers bearing the saturated fatty acid‐derived side chains . As a result, the T m values at −30.6 and 10.6 °C were observed for the unsaturated polymers P3 and P4 , respectively.…”

“…As a result, the T m values at −30.6 and 10.6 °C were observed for the unsaturated polymers P3 and P4 , respectively. As the chain length of pendant linear branches increased, the crystallization of side chains might be enhanced, leading to the higher T m values and crystallinity of polymers . After the saturation of the backbone, the T m values for the saturated polymers HP3 and HP4 increased slightly, and there were two endothermic peaks observed for HP3 (–32.8 and −4.9 °C) and a shoulder peak alongside for HP4 .…”

“…Recently, the interest in synthesizing and utilizing biomass‐derived polymers is growing significantly, and fatty acid‐derived monomers have been broadly used in the synthesis of renewable materials using various polymerization methods . In this study, a series of 5‐substituted fatty acid‐derived cyclooctenes and their corresponding polymers via ROMP with Grubbs second‐generation catalyst ( G2 ) were synthesized.…”

Surface functionalized nano‐objects from oleic acid‐derived stabilizer via non‐polar RAFT dispersion polymerization

“…The 2,2′‐azobisisobutyronitrile (AIBN, 98%, Sigma) was recrystallized from methanol and BzMA (96%, Sigma) was passed through a basic alumina column to remove inhibitors/anti‐oxidants. 4‐Cyano‐4‐(dodecylsulfanylthiocarbonyl)sulfanylpentanoic acid (CDP) and oleic acid based methacrylate monomer 2‐(methacryloyloxy)ethyl oleate (MAEO) were synthesized as described elsewhere. The solvents such as hexanes (mixtures of isomers), n ‐heptane, methanol (MeOH), acetone, ethyl acetate, tetrahydrofuran (THF), dichloromethane (DCM), and so forth were purified by standard procedures.…”

Thermoplastic Elastomers from Vegetable Oils via Reversible Addition-Fragmentation Chain Transfer Polymerization

“…Maiti et al reported the incorporation of homopolymers with fatty acid pendants to block copolymers via Reversible Addition Fragmentation Chain Transfer polymerization (RAFT). These monomers displayed crystalline behavior dependent on the size of the fatty acids (25).…”