Bulk ring-opening polymerization of l-lactide with an effective liquid tin(II) n-butoxide initiator for biomedical applications: a comparative kinetics study

IF 3.6 4区化学 Q2 POLYMER SCIENCE

Polymer International Pub Date : 2025-07-15 DOI:10.1002/pi.70003

Montira Sriyai, Tawan Chaiwon, Robert Molloy, Patnarin Worajittiphon, Puttinan Meepowpan, Winita Punyodom

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Abstract

In this study, liquid tin(II) n-butoxide (Sn(OnBu)₂) is employed as an initiator in the bulk ring-opening polymerization of l-lactide. Its effectiveness is compared with the conventional tin(II) octoate/n-butanol (Sn(Oct)₂/n-BuOH) initiating system by analyzing kinetics parameters derived from monomer conversion data obtained through gravimetry, ¹H NMR spectroscopy and Fourier transform infrared (FTIR) spectroscopy. Gravimetry kinetics studies of l-lactide ring-opening polymerization in bulk at 120 °C for 24 h reveal that both Sn(OnBu)₂ and Sn(Oct)₂/n-BuOH achieve high conversions (>90%), with first-order rate constants of 0.0432 and 0.0157 min⁻¹, respectively. These results indicate that the highly soluble liquid Sn(OnBu)₂ leads to a faster polymerization rate and higher molecular weight (M_n = 1.45 × 10⁴ g mol⁻¹) than Sn(Oct)₂/n-BuOH (M_n = 6.03 × 10³ g mol⁻¹). However, kinetics studies using ¹H NMR and FTIR suggest that liquid Sn(OnBu)₂ and Sn(Oct)₂/n-BuOH exhibit similar effectiveness in terms of monomer conversion. Finally, the high efficiency of liquid Sn(OnBu)₂ is demonstrated in the first-time synthesis of medical-grade poly(l-lactide) at a large scale (500 g). This advancement paves the way for biomedical applications, such as absorbable surgical sutures, demonstrating performance comparable to commercial medical-grade poly(l-lactide) products. © 2025 Society of Chemical Industry.

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l-丙交酯与有效液态锡（II）正丁醇引发剂的体积开环聚合：生物医学应用的比较动力学研究

本研究以液态锡（II） n-丁醇（Sn(OnBu)2）为引发剂，进行了l-丙交酯的本体开环聚合。通过对单体转化数据的动力学参数进行分析，通过重量法、1H NMR光谱和傅里叶变换红外（FTIR）光谱分析，比较了其与传统的锡（II）八酸盐/正丁醇（Sn(Oct)2/正丁醇）引发体系的有效性。l-丙交酯在120°C下开环聚合24 h的失重动力学研究表明，Sn(OnBu)2和Sn(Oct)2/n-BuOH均获得了较高的转化率（>90%），一级速率常数分别为0.0432和0.0157 min−1。结果表明，高可溶性的Sn(OnBu)2溶液比Sn(Oct)2/n-BuOH溶液（Mn = 6.03 × 103 g mol−1）聚合速度更快，分子量更高（Mn = 1.45 × 104 g mol−1）。然而，利用1H NMR和FTIR进行的动力学研究表明，液态Sn(OnBu)2和Sn(Oct)2/n-BuOH在单体转化方面表现出相似的效果。最后，在首次大规模（500 g）合成医用级聚（l-丙交酯）中，证明了液体Sn(OnBu)2的高效率。这一进步为生物医学应用铺平了道路，例如可吸收的外科缝合线，展示了与商业医疗级聚（l-丙交酯）产品相当的性能。©2025化学工业协会。

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来源期刊

Polymer International 化学-高分子科学

CiteScore

7.10

自引率

3.10%

发文量

135

审稿时长

4.3 months

期刊介绍： Polymer International (PI) publishes the most significant advances in macromolecular science and technology. PI especially welcomes research papers that address applications that fall within the broad headings Energy and Electronics, Biomedical Studies, and Water, Environment and Sustainability. The Journal’s editors have identified these as the major challenges facing polymer scientists worldwide. The Journal also publishes invited Review, Mini-review and Perspective papers that address these challenges and others that may be of growing or future relevance to polymer scientists and engineers.