Living 3,4-Isoselective (Co)polymerization of Biobased β-Farnesene Catalyzed by Phosphine-Functionalized Fluorenyl Rare-Earth Metal Catalysts,Macromolecules

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Living 3,4-Isoselective (Co)polymerization of Biobased β-Farnesene Catalyzed by Phosphine-Functionalized Fluorenyl Rare-Earth Metal Catalysts
Macromolecules ( IF 5.1 ) Pub Date : 2022-06-09 , DOI: 10.1021/acs.macromol.2c00887
Fen You ₁ , Xiaohui Kang ₂ , Masayoshi Nishiura ₃ , Jingjing Zhai ₁ , Suting Xu ₁ , Jixing Wang ₁ , Xiaochao Shi ₁ , Zhaomin Hou _{3,

4}

Affiliation

With an objective to reduce petrochemical dependency, synthesis of biobased polymers from renewable feedstocks has been widely investigated. In this study, we report that living and highly 3,4-isoselective polymerization of the biobased monomer β-farnesene (100% 3,4-, >99% mmmm) can be realized at room temperature using a phosphine-functionalized fluorenyl-ligated yttrium catalytic system with ultrahigh activity. Detailed investigations suggested that the coordinated phosphine group plays a pivotal role in the high regio- and stereoselectivity of 1-Y-catalyzed β-farnesene polymerization, and the density functional density (DFT) calculation offered important insights into the 3,4-isoselectivity. Additionally, block copolymers featuring rigid 3,4-isospecific polyisoprene blocks and amorphous 3,4-isospecific polyfarnesene blocks were successfully prepared. The morphology and mechanical properties of these elastomeric copolymers were studied by using atomic force microscopy and stress–strain experiments, respectively.

中文翻译：

膦官能化芴基稀土金属催化剂催化生物基 β-法尼烯的活性 3,4-异构（共）聚合

为了减少对石化的依赖，已广泛研究了从可再生原料合成生物基聚合物。在这项研究中，我们报道了生物基单体 β-法呢烯（100% 3,4-，>99% mmmm）的活性和高度 3,4-异构聚合可以在室温下使用膦官能化芴基配体实现。具有超高活性的钇催化体系。详细研究表明，配位膦基团在1-Y的高区域和立体选择性中起关键作用催化的 β-法呢烯聚合和密度泛函密度 (DFT) 计算提供了对 3,4-异构选择性的重要见解。此外，还成功制备了具有刚性 3,4-异规聚异戊二烯嵌段和无定形 3,4-异规聚法呢烯嵌段的嵌段共聚物。分别使用原子力显微镜和应力-应变实验研究了这些弹性共聚物的形态和机械性能。

更新日期：2022-06-09

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