Biomedical Engineering, Russ College of Engineering, Ohio University, Athens, Ohio 45701, United States.
Molecular and Chemical Biology, Ohio University, Athens, Ohio 45701, United States.
Biomacromolecules. 2022 Jun 13;23(6):2342-2352. doi: 10.1021/acs.biomac.2c00085. Epub 2022 May 24.
Green manufacturing and reducing our cultural dependency on petrochemicals have been topics of growing interest in the past decade, particularly for three-dimensional (3D) printable photopolymers where often toxic solvents and reagents have been required. Here, a simple solvent-free, free-radical polymerization is utilized to homo- and copolymerize limonene and β-myrcene monomers to produce oligomeric photopolymers ( < 11 kDa) displaying Newtonian, low viscosities (∼10 Pa × s) suitable for thiol-ene photo-cross-linking, yielding photoset materials in a digital light processing (DLP)-type 3D printer. The resulting photosets display tunable thermomechanical properties (poly(limonene) displays elastic moduli exceeding 1 GPa) compared with previous works focusing on monomeric terpenes as well as four-dimensional (4D) shape memory behavior. The utility of such photopolymers for biomedical applications is briefly considered on the premise of the hydrophilic nature (measured by contact angle) as well as their cytocompatibility upon seeding films with macrophages. These terpene-derived, green 4D photopolymers are shown to have promising physical behaviors suitable for an array of manufacturing and 3D printing applications.
在过去十年中，绿色制造和减少对石化产品的文化依赖一直是人们越来越感兴趣的话题，特别是对于需要使用有毒溶剂和试剂的 3D 可打印光聚合物而言。在这里，利用无溶剂自由基聚合将柠檬烯和β-蒎烯单体均聚和共聚，生成低粘度（<11 kDa）的低聚物光聚合物（<11 kDa），呈牛顿流体，粘度约为 10 Pa × s，适用于硫醇-烯光交联，在数字光处理（DLP）型 3D 打印机中生成光聚合材料。与以前专注于单体萜烯以及四维（4D）形状记忆行为的工作相比，所得光聚合材料显示出可调节的热机械性能（聚（柠檬烯）的弹性模量超过 1 GPa）。在亲水性质（通过接触角测量）以及在巨噬细胞接种薄膜后细胞相容性的前提下，简要考虑了此类光聚合物在生物医学应用中的用途。这些源自萜烯的绿色 4D 光聚合物具有适合各种制造和 3D 打印应用的有前途的物理性能。
