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Polymerization of Bio‐Derived Conjugated Dienes with Rare‐Earth‐Metal Complexes

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Chemistry - An Asian Journal
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Fen You
Fen You
Fen You
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Wenyu Shi
Wenyu Shi
Wenyu Shi
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Xuyang Yan
Xuyang Yan
Xuyang Yan
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Xiaoyu Wang
Xiaoyu Wang
Xiaoyu Wang
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The reliance of both our life and industry on fossil resource and the alarming accumulation of polymeric materials in the environment have presented huge challenges to sustainable society. Nowadays, utilization of renewable monomers as building blocks for polymeric materials has emerged as a hot topic and increasingly gained attention from chemists. As a class of biomass with abundance and low cost, terpenes are typical hydrocarbon‐rich natural compounds, and some of them, such as myrcene and farnesene, are inherently suitable for coordination polymerization. In this review, we focus on the rare‐earth metal catalyzed highly regio‐ and stereoselective polymerization of bio‐based conjugated dienes, especially the ones from terpene‐derived compounds with or without modifications. This review also discusses the future direction on the modification of these bio‐based conjugated dienes.
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Polymerization of Bio-Derived Conjugated Dienes with
Rare-Earth-Metal Complexes
Fen You, Wenyu Shi, Xuyang Yan, Xiaoyu Wang, and Xiaochao Shi*[a]
Review
doi.org/10.1002/asia.202200892
www.chemasianj.org
Chem Asian J. 2022,17, e202200892 (1 of 11) © 2022 Wiley-VCH GmbH
Wiley VCH Donnerstag, 24.11.2022
2223 / 270425 [S. 24/34] 1
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The growing environmental pollution and the expected depleting of fossil resources have sparked interest in recent years for polymers obtained from monomers originating from renewable sources. Furthermore, nature can provide a variety of building blocks with special structural features (e. g. side groups or stereo‐elements) that cannot be obtained so easily via fossil‐based pathways. In this context, terpenes are widespread natural compounds coming from non‐food crops, present in a large variety of structures, and ready to use as monomers with or without further modifications. The present review aims to provide an overview of how chemists can stereospecifically polymerize terpenes, particularly the acyclic ones like myrcene, ocimene, and farnesene, using different metal catalyst systems in coordination‐insertion polymerization. Attention is also paid to their copolymers, which have recently been disclosed, and to the possible applications of these bio‐based materials in various industrial sectors such as in the field of elastomers. © 2021 The Authors. ChemPlusChem published by Wiley‐VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution Non‐Commercial License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes.
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Article
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  • POLYM TEST
A range of confined iminopyridine iron complexes with skeleton of 8-(arylimino)-5,6,7-trihydroquinolyl have been prepared and well characterized by HRMS spectroscopy, FT-IR spectroscopy as well as elemental analysis. These iron complexes (Fe1–Fe5) serve as highly efficient pre-catalysts for conjugated dienes polymerization. By adjusting substituents of ligand framework, the stereoselectivity about 1,4-cis/trans could be switched from <1/99 to 96/4. An outstanding polymerization activity up to 10⁸ g mol⁻¹ h⁻¹ was achieved with high molecular weight by employing Fe1 as pre-catalyst under optimum experimental conditions. What's more, the Fe1/MAO catalytic system showed excellent thermostability, which could lead to full conversion even at 100 °C within 10 min. Surprisingly, the polymerization activities of bio-based monomer β-farnesene and β-myrcene were able to reach 10⁶ g mol⁻¹ h⁻¹ by Fe-1/MAO catalytic system, which was the highest activity of iron complex family to deliver the “green rubbers” with high molecular weights.
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