Department of Chemistry, Texas A&M University, College Station, Texas 77843, United States.
Department of Materials Science & Engineering, Texas A&M University, College Station, Texas 77843, United States.
J Am Chem Soc. 2023 Jun 14;145(23):12459-12464. doi: 10.1021/jacs.3c03978. Epub 2023 May 31.
The / stereochemistry of repeating alkenes in polymers provides a powerful handle to modulate the thermal and mechanical properties of these soft materials, but synthetic methods to precisely dictate this parameter remain scarce. We report herein a -selective acyclic diene metathesis (ADMET) polymerization of readily available α,ω-diene monomers with high functional group tolerance. Identification of a highly stereoselective cyclometalated Ru catalyst allowed the synthesis of a broad array of polymers with contents up to 99%. This platform was leveraged to study the impact of the geometry on the thermal and mechanical properties of polyalkenamers, including an ABA triblock copolymer synthesized via extension of a -rich telechelic polyoctenamer with d,l-lactide. These results suggest that -selective ADMET affords an efficient strategy to tune the properties of a variety of polymers.
聚合物中重复烯烃的立体化学为调节这些软材料的热学和力学性能提供了有力的手段，但精确控制这一参数的合成方法仍然很少。我们在此报告了一种具有高官能团容忍度的易得的 α,ω-二烯单体的 -选择性非环二烯复分解（ADMET）聚合。对高立体选择性的环金属化 Ru 催化剂的鉴定使得能够合成具有高达 99%内容的广泛的聚合物。该平台被用于研究 几何形状对聚烯丙基的热学和力学性能的影响，包括通过扩展富含 -的遥爪聚辛烯与 d,l-丙交酯合成的 ABA 三嵌段共聚物。这些结果表明， -选择性 ADMET 提供了一种有效的策略来调节各种聚合物的性能。
