This work investigates the enzymatic ring-opening polymerization of poly(ω-pentadecalactone-co-globalide) using supercritical carbon dioxide as a solvent. Copolymerizations were carried out in a high-pressure variable-volume view cell to evaluate the influence of CO2:monomers mass ratios and the use of chloroform as a cosolvent. Also, Novozym® 435 and Lipura® Flex were compared as catalysts. The highest molar mass obtained with the use of a cosolvent (Mn = 24,380 g mol−1) was achieved in the 1:2:1 (CO2:monomers:chloroform) condition, reflecting the combined effect of the cosolvent and a higher concentration of the monomers, while reactions without it showed better results for molar mass (Mn up to 27,902 g mol−1). Dispersity was higher when a cosolvent was used (Dispersity up to 7.51) than reactions with supercritical carbon dioxide only (Dispersity up to 5.36). Monomer conversions above 97 % and reaction yields from 55.77 wt% up to 79.61 wt% were achieved for copolymerizations with and without a cosolvent, using Novozym® 435 as catalyst. Lipura® Flex produced copolymers with high molar mass (Mn up to 21,605 g mol−1), reaction yields up to 73 wt%, and monomer conversions from 82 % to 96 %.

中文翻译：

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脂肪酶催化在超临界二氧化碳中合成聚（ω-十五内酯-co-globalide）


本工作研究了以超临界二氧化碳为溶剂的聚（ω-十五内酯-co-globalide）的酶促开环聚合。在高压可变体积视图池中进行共聚，以评估 CO2：单体质量比和使用氯仿作为助溶剂的影响。此外，将 Novozym® 435 和 Lipura® Flex 作为催化剂进行了比较。使用助溶剂 （Mn = 24,380 g mol-1） 获得的最高摩尔质量是在 1：2：1 （CO2：单体：氯仿） 条件下获得的，这反映了助溶剂和较高浓度单体的联合作用，而没有助溶剂的反应显示出更好的摩尔质量结果（Mn 高达 27,902 g mol-1）。使用助溶剂时的分散度（分散度高达 7.51）高于仅使用超临界二氧化碳的反应（分散度高达 5.36）。使用 Novozym® 435 作为催化剂，在有和没有助溶剂的情况下，共聚实现了超过 97% 的单体转化率和 55.77 wt% 到 79.61 wt% 的反应产率。Lipura® Flex 生产的高摩尔质量（Mn 高达 21,605 g mol-1）的共聚物，反应产率高达 73 wt%，单体转化率从 82 % 到 96%。