Combination of olefin insertion polymerization and olefin metathesis to extend the topology and composition of polyolefins
Combination of olefin insertion polymerization and olefin metathesis to extend the topology and composition of polyolefins
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DOI：
10.1007/s11426-020-9724-9
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发表时间：
2020-04
期刊：
影响因子：
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通讯作者：
Tianwei Yan;Damien Guironnet
中科院分区：
文献类型：
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作者：
Tianwei Yan;Damien Guironnet
自从Ziegler，Hogan和Banks对烯烃催化聚合的开创性发现以来，已经报道了许多代催化剂[1-5]。包括从原始的多相催化剂(Ziegler和Phillips)向均相催化剂的过渡，这些催化剂包括茂金属催化剂、后茂金属催化剂和后过渡金属催化剂。新型催化剂的开发使人们能够更好地控制聚烯烃的结构和组成。尽管在过去的几十年里取得了巨大的成就，但催化烯烃聚合提供的化学可调性仍然有限。因此，人们开发了替代策略，以进一步扩展现有方法所实现的化学和拓扑控制，并最终提高聚合物的材料性能。一种将插入聚合和烯烃歧化相结合的策略已经成为一种将化学官能化引入聚烯烃的替代方法。这两个反应在同一底物(烯烃)上的正交反应性为扩大聚烯烃的拓扑结构和组成提供了一条独特的途径(图1)。根据烯烃插入聚合和烯烃歧化的执行顺序，已开发出三种方法。第一种方法包括首先进行插入聚合以产生聚烯烃，然后进行烯烃歧化后聚合功能化以引入官能团
Since Ziegler, Hogan and Banks’ seminal discoveries for the catalytic polymerization of olefins, many generations of catalysts have been reported [1–5]. These include the transition from the original heterogeneous catalysts (Ziegler and Phillips) to homogeneous catalysts combining metallocene, post-metallocene and late transition metal-based catalysts. The development of new catalysts has enabled a higher control over polyolefin architecture and composition. Despite the tremendous achievements made in the last few decades, the chemical tunability offered by catalytic olefin polymerization remains limited. Therefore, alternative strategies have been developed to further expand the chemical and topological control achieved by current methods and ultimately to advance the material properties of the polymers. A strategy combining insertion polymerization and olefin metathesis has emerged as an alternative way to introduce chemical functionalities to polyolefins. The orthogonal reactivity of these two reactions while sharing the same substrate (olefin) provides a unique avenue to expanding the topology and composition of polyolefins (Figure 1).Three approaches, distinguished by the order at which the olefin insertion polymerization and olefin metathesis are performed, have been developed. The first approach consists of performing the insertion polymerization first to yield a polyolefin, followed by an olefin metathesis post-polymerization functionalization to introduce functional groups