Maastricht University-Aachen Maastricht Institute for Biobased Materials (AMIBM), Urmonderbaan 22, Geleen 6167 RD, The Netherlands.
Department of Polymers and Advanced Materials: Physics, Chemistry and Technology, Faculty of Chemistry, University of the Basque Country UPV/EHU and POLYMAT, Paseo Manuel de Lardizabal, 3, Donostia-San Sebastián 20018, Spain.
Biomacromolecules. 2024 Nov 11;25(11):7392-7409. doi: 10.1021/acs.biomac.4c01073. Epub 2024 Oct 21.
We synthesize four series of novel biodegradable poly(alkylene succinate--caprolactone) random copolyesters using a two-step ring-opening/transesterification and polycondensation process with ε-caprolactone (PCL) as a common comonomer. The second comonomers are succinic acid derivatives, with variations in the number of methylene groups () in the glycol segment, = 2, 4, 8, and 12. The obtained copolyesters were poly(ethylene succinate--PCL) (ESCL), poly(butylene succinate--PCL) (BSCL), poly(octamethylene succinate--PCL) (OSCL), and poly(dodecylene succinate--PCL) (DSCL). We discovered a new mixed isodimorphic/comonomer exclusion crystallization in ESCL copolymers. The BSCL, OSCL, and DSCL copolymers display isodimorphic behavior. Our findings revealed a significant variation in the pseudoeutectic point position, from mixed isodimorphism/comonomer exclusion crystallization to isodimorphism with pseudoeutectic point variation from 54% to up to 90%. Moreover, we established a link between the melting temperature depression slope variation and the comonomer inclusion/exclusion balance, providing valuable insights into the complex topic of isodimorphic random copolymers.
我们使用两步开环/酯交换和缩聚工艺，以 ε-己内酯（PCL）为常见共聚单体，合成了四组新型可生物降解聚（烷撑琥珀酸酯-己内酯）无规共聚酯。第二个共聚单体是琥珀酸衍生物，二醇部分的亚甲基数（）有变化，=2、4、8 和 12。得到的共聚酯为聚（乙撑琥珀酸酯-PCL）（ESCL）、聚（丁撑琥珀酸酯-PCL）（BSCL）、聚（辛撑琥珀酸酯-PCL）（OSCL）和聚（十二撑琥珀酸酯-PCL）（DSCL）。我们在 ESCL 共聚物中发现了一种新的混合等规晶型/共聚单体排除结晶。BSCL、OSCL 和 DSCL 共聚物呈现等规晶型行为。我们的发现表明，假等比点位置发生了显著变化，从混合等规晶型/共聚单体排除结晶到等规晶型，假等比点变化从 54%到 90%。此外，我们还建立了熔融温度下降斜率变化与共聚单体包容/排除平衡之间的联系，为等规随机共聚酯这一复杂课题提供了有价值的见解。
