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<p>Development of the novel cyclic tin(IV) macroinitiators (DTMCL) based on <i>ε</i>-caprolactone (<i>ε</i>-CL) and dibutyltin(IV) maleate (DBTML) were successfully conducted via the facile synthesis method and characterized by various techniques. The prepared DTMCL macroinitiators contained the reactive Sn–O bond which could further initiate the polymerization of <i>ε</i>-CL. The performance of DTMCL macroinitiators in controlled ring-opening polymerization (ROP) of <i>ε</i>-CL was potentially investigated by the non-isothermal differential scanning calorimetry (DSC) at the heating rates of 5, 10, 15, and 20&#xa0;°C&#xa0;min<sup>−1</sup>. From the DSC study, the ROP of <i>ε</i>-CL could be occurred and completed by the DTMCL12 macroinitiator under non-isothermal conditions. DTMCL2, DTMCL4, and DTMCL8 could not promote and drive the ROP of <i>ε</i>-CL to occur and complete under non-isothermal conditions. The polymerization exotherms of <i>ε</i>-CL occurred at lower temperatures when the concentration of DTMCL12 increased. The kinetic parameters such as activation energy (<i>E</i><sub>a</sub>) and pre-exponential factor (<i>A</i>) were completely determined from the isoconversional method and model fitting. The activation parameters such as activation enthalpy (Δ<i>H</i><sup>≠</sup>) and activation entropy (Δ<i>S</i><sup>≠</sup>) of transition state formulation for the ROP of <i>ε</i>-CL with DTMCL12 macroinitiator were also determined by the DSC technique. From kinetic and thermodynamic analyses, the polymerization rate of <i>ε</i>-CL increased with increasing DTMCL12 concentration. Effectiveness of all DTMCLs in the synthesis of poly(<i>ε</i>-caprolactone) (PCL) via solvent-free polymerization was studied at a temperature of 150&#xa0;°C, DTMCL12 also acted as the most effective macroinitiator that produced PCL with the number average molecular mass (<i>M</i><sub>n</sub>) and %yield of 1.10 × 10<sup>4</sup>–3.96 × 10<sup>4</sup>&#xa0;g&#xa0;mol<sup>−1</sup>, and 91–95%. From the study of the polymerization mechanism, PCL was synthesized via the insertion of <i>ε</i>-CL into the molecule of the DTMCL macroinitiator, and the PCL chain growth occurred by the ring-expansion process.</p> Graphical abstract <p></p>

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The novel cyclic tin(IV) macroinitiators for utilizing in the solvent-free ring-opening polymerization of ε-caprolactone: non-isothermal kinetics, thermodynamics, and polymer synthesis

  • 期刊论文

  • 发表日期：

    2025年5月28日

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  • Wanich Limwanich,
  • Puttinan Meepowpan,
  • Manita Dumklang,
  • Samuch Taweekasemsombut,
  • Winita Punyodom

摘要

Development of the novel cyclic tin(IV) macroinitiators (DTMCL) based on ε-caprolactone (ε-CL) and dibutyltin(IV) maleate (DBTML) were successfully conducted via the facile synthesis method and characterized by various techniques. The prepared DTMCL macroinitiators contained the reactive Sn–O bond which could further initiate the polymerization of ε-CL. The performance of DTMCL macroinitiators in controlled ring-opening polymerization (ROP) of ε-CL was potentially investigated by the non-isothermal differential scanning calorimetry (DSC) at the heating rates of 5, 10, 15, and 20 °C min−1. From the DSC study, the ROP of ε-CL could be occurred and completed by the DTMCL12 macroinitiator under non-isothermal conditions. DTMCL2, DTMCL4, and DTMCL8 could not promote and drive the ROP of ε-CL to occur and complete under non-isothermal conditions. The polymerization exotherms of ε-CL occurred at lower temperatures when the concentration of DTMCL12 increased. The kinetic parameters such as activation energy (Ea) and pre-exponential factor (A) were completely determined from the isoconversional method and model fitting. The activation parameters such as activation enthalpy (ΔH≠) and activation entropy (ΔS≠) of transition state formulation for the ROP of ε-CL with DTMCL12 macroinitiator were also determined by the DSC technique. From kinetic and thermodynamic analyses, the polymerization rate of ε-CL increased with increasing DTMCL12 concentration. Effectiveness of all DTMCLs in the synthesis of poly(ε-caprolactone) (PCL) via solvent-free polymerization was studied at a temperature of 150 °C, DTMCL12 also acted as the most effective macroinitiator that produced PCL with the number average molecular mass (Mn) and %yield of 1.10 × 104–3.96 × 104 g mol−1, and 91–95%. From the study of the polymerization mechanism, PCL was synthesized via the insertion of ε-CL into the molecule of the DTMCL macroinitiator, and the PCL chain growth occurred by the ring-expansion process.

Graphical abstract