Schoonover Krista G, Hsieh Chia-Min, Sengoden Mani, Ahmed Naushad, Sivaperuman Kalairaj Manivannan, Ware Taylor H, Darensbourg Donald J, Pentzer Emily B, Wei Peiran
Department of Chemistry, Texas A&M University 3255 TAMU College Station TX 77843 USA
Department of Biomedical Engineering, Texas A&M University 3003 TAMU College Station TX 77843 USA.
Chem Sci. 2024 Aug 12;15(35):14228-40. doi: 10.1039/d4sc04593a.
CO-based aliphatic polycarbonates (aPCs), produced through the alternating copolymerization of epoxides with CO, present an appealing option for sustainable polymeric materials owing to their renewable feedstock and degradable characteristics. An ongoing challenge in working with aPCs is modifying their mechanical properties to meet specific demands. Herein, we report that monomer ratio and polymer architecture of aPCs impact not only printability by digital light processing (DLP) additive manufacturing, but also dictate the thermomechanical and degradation properties of the printed objects. We found that block copolymers exhibit tailorable thermomechanical properties ranging from soft elastomeric to strong and brittle as the proportion of hard blocks increases, whereas the homopolymer blend failed to print objects and statistical copolymers delaminated or overcured, displaying the weakest mechanical properties. In addition, the hydrolytic degradation of the prints was demonstrated under various conditions, revealing that BCP prints containing a higher proportion of hard blocks had slower degradation and that statistical copolymer prints degraded more slowly than their BCP counterparts. This study underscores that polymer composition and architecture both play key roles in resin printability and bulk properties, offering significant prospects for advancing sustainable materials in additive manufacturing through polymer design.
通过环氧化物与一氧化碳交替共聚制备的基于一氧化碳的脂肪族聚碳酸酯（aPCs），因其可再生原料和可降解特性，为可持续聚合物材料提供了一个有吸引力的选择。使用aPCs的一个持续挑战是调整其机械性能以满足特定需求。在此，我们报告aPCs的单体比例和聚合物结构不仅会影响数字光处理（DLP）增材制造的可打印性，还会决定打印物体的热机械性能和降解性能。我们发现，随着硬嵌段比例的增加，嵌段共聚物呈现出从软弹性体到坚硬脆性的可定制热机械性能，而均聚物共混物无法打印物体，统计共聚物会分层或过度固化，显示出最弱的机械性能。此外，在各种条件下展示了打印件的水解降解，结果表明含有较高比例硬嵌段的BCP打印件降解较慢，且统计共聚物打印件的降解速度比其BCP对应物更慢。这项研究强调，聚合物组成和结构在树脂可打印性和整体性能中都起着关键作用，为通过聚合物设计推动增材制造中的可持续材料发展提供了重要前景。
