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<p>A novel class of 3-methylphenol alkoxy aluminum complexes was developed for the ring-opening polymerization (ROP) of ε-caprolactone (ε-CL) under mild conditions (60&#xa0;°C, 30&#xa0;min). Through systematic optimization of Al/CL molar ratios (5:1000 ~ 4:1000), monomer concentrations (1&#xa0;mol/L), and reaction parameters, high polymer yield (99.9% ± 0.1%) was achieved, yielding polycaprolactone (PCL) with tunable molecular weights (M<sub>n</sub> up to 34&#xa0;kg/mol) and narrow dispersity (PDI = 1.38). Structural characterization via <sup>1</sup>H NMR and FTIR confirmed successful PCL formation. GPC analysis validated controlled chain growth and uniformity (PDI &lt; 1.5), while thermal properties were assessed via DSC and TGA, showing semicrystalline behavior and high thermal stability. Kinetic studies showed linear molecular weight progression with polymer yield, while sequential monomer feeding experiments confirmed living polymerization characteristics, with M<sub>n</sub> increasing proportionally and maintaining low PDI. Compared to conventional metal-based systems, this catalytic platform operates at lower temperatures with reduced toxicity risks, enabling energy-efficient synthesis of biodegradable polyester for biomedical and packaging applications.</p>

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3-methylphenol alkoxy aluminum complexes for ring-opening polymerization of ε-caprolactone under mild conditions

  • 期刊论文

  • 发表日期：

    2025年9月21日

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  • Xuan Zhao,
  • Liu Yang,
  • Xinyu Sun,
  • Kun Zhou,
  • Shuai Yuan

摘要

A novel class of 3-methylphenol alkoxy aluminum complexes was developed for the ring-opening polymerization (ROP) of ε-caprolactone (ε-CL) under mild conditions (60 °C, 30 min). Through systematic optimization of Al/CL molar ratios (5:1000 ~ 4:1000), monomer concentrations (1 mol/L), and reaction parameters, high polymer yield (99.9% ± 0.1%) was achieved, yielding polycaprolactone (PCL) with tunable molecular weights (Mn up to 34 kg/mol) and narrow dispersity (PDI = 1.38). Structural characterization via 1H NMR and FTIR confirmed successful PCL formation. GPC analysis validated controlled chain growth and uniformity (PDI < 1.5), while thermal properties were assessed via DSC and TGA, showing semicrystalline behavior and high thermal stability. Kinetic studies showed linear molecular weight progression with polymer yield, while sequential monomer feeding experiments confirmed living polymerization characteristics, with Mn increasing proportionally and maintaining low PDI. Compared to conventional metal-based systems, this catalytic platform operates at lower temperatures with reduced toxicity risks, enabling energy-efficient synthesis of biodegradable polyester for biomedical and packaging applications.