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<p>The growing demand for environmentally responsible polymeric materials has accelerated the interest in renewable feedstocks as alternatives to petrochemical-based polymers. In this study, poly(ethyl oleate), a bio-based polymeric surfactant derived from palm oil, was synthesized via reversible addition–fragmentation chain transfer polymerization. Ethyl oleate monomer was prepared through esterification and subsequently polymerized using 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid as the chain transfer agent and azobisisobutyronitrile as the initiator. The effects of key RAFT polymerization parameters, including the monomer-to-CTA molar ratio ([M]/[CTA]), CTA-to-initiator molar ratio ([CTA]/[AIBN]), and reaction temperature, on the molecular weight (Mn) control, dispersity (Ð), and surfactant-related properties were systematically investigated. The resulting poly(ethyl oleate) exhibited number-average molecular weights (Mn) in the range of 1,473–1,896&#xa0;g·mol⁻1 and narrow dispersities (Ð = 1.11–1.22), confirming the effective control of the RAFT process. Structural characterization using FTIR, Raman spectroscopy, <sup>1</sup>H-NMR, and <sup>13</sup>C NMR verified the successful polymerization of ethyl oleate. Importantly, control over polymerization parameters translated into tunable interfacial performance, with hydrophilic–lipophilic balance (HLB) values ranging from 1.24 ± 0.065 to 8.37 ± 0.087, critical micelle concentrations (CMC) of 0.187 ± 0.002 to 0.382 ± 0.020 <InlineEquation ID="IEq1"> <EquationSource Format="TEX">\(mg.{mL}^{-1}\)</EquationSource> </InlineEquation>, and interfacial tension (IFT) values of 4.628 ± 0.179 to 10.744 ± 0.156 <InlineEquation ID="IEq2"> <EquationSource Format="TEX">\(mN.{m}^{-1}\)</EquationSource> </InlineEquation>. This study demonstrates, for the first time, that direct RAFT polymerization of ethyl oleate enables the synthesis of palm-oil-derived polymeric surfactants with controlled molecular characteristics and quantifiable interfacial properties. These findings highlight the potential of fatty acid ester monomers as sustainable building blocks for functional polymeric surfactants and contribute to the development of renewable polymers for environmentally relevant interfacial applications.</p> Graphical Abstract <p></p>

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Novel RAFT Polymerization of Ethyl Oleate Based on Palm Oil: Effect of Reaction Parameters and Characterization

  • 期刊论文

  • 发表日期：

    2026年6月18日

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  • Sri Budi Harmami,
  • Misri Gozan,
  • Yenny Meliana,
  • Dianursanti,
  • Anita Marlina,
  • Puji Wahyuningsih,
  • Ghislaine Mangoumou Ndonkeu,
  • Penjit Srinophakun

摘要

The growing demand for environmentally responsible polymeric materials has accelerated the interest in renewable feedstocks as alternatives to petrochemical-based polymers. In this study, poly(ethyl oleate), a bio-based polymeric surfactant derived from palm oil, was synthesized via reversible addition–fragmentation chain transfer polymerization. Ethyl oleate monomer was prepared through esterification and subsequently polymerized using 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid as the chain transfer agent and azobisisobutyronitrile as the initiator. The effects of key RAFT polymerization parameters, including the monomer-to-CTA molar ratio ([M]/[CTA]), CTA-to-initiator molar ratio ([CTA]/[AIBN]), and reaction temperature, on the molecular weight (Mn) control, dispersity (Ð), and surfactant-related properties were systematically investigated. The resulting poly(ethyl oleate) exhibited number-average molecular weights (Mn) in the range of 1,473–1,896 g·mol⁻1 and narrow dispersities (Ð = 1.11–1.22), confirming the effective control of the RAFT process. Structural characterization using FTIR, Raman spectroscopy, 1H-NMR, and 13C NMR verified the successful polymerization of ethyl oleate. Importantly, control over polymerization parameters translated into tunable interfacial performance, with hydrophilic–lipophilic balance (HLB) values ranging from 1.24 ± 0.065 to 8.37 ± 0.087, critical micelle concentrations (CMC) of 0.187 ± 0.002 to 0.382 ± 0.020 \(mg.{mL}^{-1}\) , and interfacial tension (IFT) values of 4.628 ± 0.179 to 10.744 ± 0.156 \(mN.{m}^{-1}\) . This study demonstrates, for the first time, that direct RAFT polymerization of ethyl oleate enables the synthesis of palm-oil-derived polymeric surfactants with controlled molecular characteristics and quantifiable interfacial properties. These findings highlight the potential of fatty acid ester monomers as sustainable building blocks for functional polymeric surfactants and contribute to the development of renewable polymers for environmentally relevant interfacial applications.

Graphical Abstract