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Solvent-free lipase-catalyzed synthesis of linear and thermally stable polyesters obtained from diacids and diols
Brazilian Journal of Chemical Engineering ( IF 1.2 ) Pub Date : 2021-07-22 , DOI: 10.1007/s43153-021-00137-y
Ivone Sampaio Pereira Campisano 1 , Erika de Queiros Eugenio 1, 2 , Cláudia de Oliveira Veloso 1 , Marta Antunes Pereira Langone 1, 3 , Marcos Lopes Dias 4 , Aline Machado de Castro 5
Affiliation  

Aliphatic polyesters are widely used in biomedical and environmental areas, and their use has grown due to environmental issues. The use of lipases as catalysts for the synthesis of polyesters is an environmentally benign alternative. In this work, the effect of monomer chain length on polyester synthesis was studied with seven diacids and six diols in a bulk system using immobilized Candida antarctica lipase B (Novozym®435). Firstly, the reaction temperature and the thermal stability of Novozym®435 (N435) were evaluated. The half-life of the commercial lipase was 24.8 h at 90 °C, and N435 maintained a residual activity of 38% after 96 h of incubation. The biocatalyst played an essential role in the reactions using monomers with longer alkylene chain length diacids (azelaic and sebacic acids) and diols (1,4-butanediol, 1,6-hexanediol, and 1,8-octanediol), giving a higher reactivity than reactions of shorter chain-length diacids (oxalic, malonic, succinic, glutaric and adipic acids) and diols (ethylene glycol and 1,3-propanediol). Polycondensation reactions carried out with 2,3-butanediol did not present a significative molecular weight. Otherwise, the reaction performed with 1,6-hexanediol resulted in polyesters with weight-average molecular weights (Mw) of 18,346 g mol−1 and 27,121 g mol−1 by reacting with azelaic and sebacic acids, respectively, at 90 °C using 5 wt.% of N435. The thermal properties of polyazelates and polysebactes were analyzed by DSC and TGA, which showed that aliphatic polyesters are practically stable at up to 380 °C, indicating their high thermal stability.



中文翻译:

从二酸和二醇获得的线性和热稳定聚酯的无溶剂脂肪酶催化合成

脂肪族聚酯广泛用于生物医学和环境领域,由于环境问题,它们的使用量有所增长。使用脂肪酶作为合成聚酯的催化剂是一种环境友好的替代方法。在这项工作中,使用固定化的南极念珠菌脂肪酶 B (Novozym ® 435)在本体系统中使用七种二酸和六种二醇研究了单体链长对聚酯合成的影响。一、Novozym ®的反应温度和热稳定性435 (N435) 被评估。商品化脂肪酶在 90°C 下的半衰期为 24.8 小时,N435 在孵育 96 小时后仍保持 38% 的残留活性。生物催化剂在使用具有较长亚烷基链二酸(壬二酸和癸二酸)和二醇(1,4-丁二醇、1,6-己二醇和 1,8-辛二醇)的单体的反应中发挥了重要作用,具有更高的反应性短链二酸(草酸、丙二酸、琥珀酸、戊二酸和己二酸)和二醇(乙二醇和 1,3-丙二醇)的反应。用 2,3-丁二醇进行的缩聚反应没有显着的分子量。否则,与 1,6-己二醇进行的反应产生重均分子量 (M w ) 为 18,346 g mol -1的聚酯和 27,121 g mol -1通过分别与壬二酸和癸二酸在 90 °C 下使用 5 wt.% 的 N435 反应。通过 DSC 和 TGA 分析了聚壬二酸酯和聚癸二酸酯的热性能,结果表明脂肪族聚酯在高达 380°C 时实际上是稳定的,表明它们具有很高的热稳定性。

更新日期:2021-07-22
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