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Enzymatic ring-opening polymerization (ROP) of lactides and lactone in ionic liquids and organic solvents: digging the controlling factors

机译:丙酸酯和离子液体和有机溶剂中的酶开环聚合(ROP)和内酯:挖掘控制因子

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摘要

Polylactides (PLAs) and polylactones are sustainable and biodegradable polymers with important applications in packaging, horticultural materials, and biomedical fields. The enzymatic ring-opening polymerization (ROP) method represents a 'green' approach to the synthesis of these polyesters. However, there are lots of discrepancies in the literature on the lipase specificity towards a particular monomer (such as L-lactide), and many disagreements on the molecular weights produced by similar methods. To provide a better understanding of the key factors regulating the ROP reaction, we carried out a systematic investigation of the polymerization process under different temperatures catalyzed by different types and batches of lipases with various water contents, in different solvents including ionic liquids with known water contents, and by using different initiators. Our data clearly indicate that the key reaction parameters include the types of lipases and solvents, the amount of solvents, water contents in both enzymes and solvents, and the reaction temperature. N, N-Dimethylacetamide (DMA) and 1-butyl3- methylimidazolium hexafluorophosphate ([BMIM][PF6]) at low concentrations were found suitable for the ROPs of lactides and 3-caprolactone leading to Mw of about 20 000 (polydispersity indexes mostly below 1.8) and moderately high yields (up to 60%). Our study suggests that all of these reaction parameters need to be fully controlled during the enzymatic ROP reaction although some earlier studies often neglected some conditions (such as the exact water content in enzymes and solvents).
机译:聚丙乙酯(PLAS)和聚萘酮是可持续的和可生物降解的聚合物,具有包装,园艺材料和生物医学领域的重要应用。酶开环聚合(ROP)方法代表了对这些聚酯的合成的“绿色”方法。然而,文献中的脂肪酶特异性对特定单体(例如L-丙交酯)的特异性存在大量差异,以及许多关于通过类似方法产生的分子量的分歧。为了更好地理解调节ROP反应的关键因素,我们在不同类型和批量脂肪酶催化的不同温度下进行了对聚合过程的系统研究,其具有各种水含量,包括具有已知水含量的离子液体的不同溶剂,并使用不同的发起者。我们的数据清楚地表明关键反应参数包括脂肪酶和溶剂类型,溶剂量,酶和溶剂中的水含量以及反应温度。在低浓度下,发现N,N-二甲基乙酰胺(DMA)和1-丁基3-甲基咪唑鎓六氟磷酸锂([Bmim] [PF6]),适用于丙酸酯和3-己内酯的多孔,导致MW为约20 000(主要是下方的多分散指标1.8)和中度高收益率(高达60%)。我们的研究表明,所有这些反应参数都需要在酶ROP反应过程中完全控制,尽管一些早期的研究经常被忽略一些条件(例如酶和溶剂的确切水含量)。

著录项

  • 来源
    《RSC Advances》 |2017年第77期|共10页
  • 作者单位

    Univ Northern Colorado Dept Chem &

    Biochem Greeley CO 80639 USA;

    Savannah State Univ Dept Chem &

    Forens Sci Savannah GA 31404 USA;

    Savannah State Univ Dept Chem &

    Forens Sci Savannah GA 31404 USA;

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  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 化学;
  • 关键词

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