cis-Selective Acyclic Diene Metathesis Polymerization of α,ω-Dienes.
cis-Selective Acyclic Diene Metathesis Polymerization of α,ω-Dienes.
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α,β-二烯的顺式选择性无环二烯复分解聚合。
DOI：
10.1021/jacs.3c03978
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发表时间：
2023
影响因子：
15
通讯作者：
Michaudel,Quentin
中科院分区：
文献类型：
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作者：
Kempel,SamuelJ;Hsu,Ting-Wei;Nicholson,JakeL;Michaudel,Quentin
聚合物中重复烯烃的顺式/反式立体化学为调节这些软材料的热性能和机械性能提供了强有力的手段，但精确地规定该参数的合成方法仍然很少。本文报道了具有高官能团耐受性的易得α，ω-二烯单体的酸选择性无环二烯复分解（ADMET）聚合。一种高立体选择性的环化钌催化剂的鉴定允许合成一系列顺式含量高达99%的聚合物。利用该平台研究了对称几何形状对聚烯烃热性能和机械性能的影响，包括通过用d，l-丙交酯延伸富含酸的遥爪聚辛烯合成的阿坝三嵌段共聚物。这些结果表明，顺式选择性ADMET提供了一个有效的策略，以调整各种聚合物的性能。
Thecis/transstereochemistry 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 acis-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 withciscontents up to 99%. This platform was leveraged to study the impact of thecisgeometry on the thermal and mechanical properties of polyalkenamers, including an ABA triblock copolymer synthesized via extension of acis-rich telechelic polyoctenamer withd,l-lactide. These results suggest thatcis-selective ADMET affords an efficient strategy to tune the properties of a variety of polymers.