FI catalysts: new olefin polymerization catalysts for the creation of value-added polymers.
FI catalysts: new olefin polymerization catalysts for the creation of value-added polymers.
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DOI：
10.1002/tcr.20010
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发表时间：
2004
期刊：
影响因子：
6.6
通讯作者：
M. Mitani;Junji Saito;S. Ishii;Y. Nakayama;H. Makio;Naoto Matsukawa;S. Matsui;Jun-ichi Mohri
中科院分区：
文献类型：
--
作者：
M. Mitani;Junji Saito;S. Ishii;Y. Nakayama;H. Makio;Naoto Matsukawa;S. Matsui;Jun-ichi Mohri
本文报道了苯氧基亚胺类烯烃聚合催化剂的发现和应用。配体导向的催化剂设计研究已经导致发现显着活性的乙烯聚合催化剂（FI催化剂），其基于与前过渡金属结合的电子柔性苯氧基亚胺螯合配体。在用合适的助催化剂活化后，FI催化剂可以表现出独特的聚合催化作用（例如，产物分子量的精确控制、高度等规和间规丙烯聚合、高级α-烯烃的区域无规聚合、乙烯和丙烯在高温下的高度受控活性聚合以及对聚合物形态的精确控制），从而为合成具有独特结构特征的增值聚合物提供了非凡的机会。通过使用FI催化剂可获得的许多聚合物以前无法通过其他聚合方法获得。例如，FI催化剂可以形成乙烯基封端的低分子量聚乙烯、超高分子量无定形乙烯-丙烯共聚物和无规立构聚丙烯、具有异常高的高峰熔融温度的高度全同立构和间同立构聚丙烯、明确限定和受控的多峰聚乙烯和高分子量区域无规聚（高级α-烯烃）。此外，与MgCl（2）基化合物组合的FI催化剂可以产生表现出期望的形态特征（例如，非常高堆积密度的聚乙烯和高度受控的颗粒尺寸的聚乙烯），这是用常规负载型催化剂难以获得的。此外，FI催化剂能够产生各种活性聚合基聚合物，包括末端官能化聚合物和乙烯、丙烯和高级α-烯烃的嵌段共聚物。此外，一些FI催化剂可以通过与适当的链转移剂组合来催化提供活性聚合基聚合物。因此，FI催化剂的发展使聚合催化和聚合物合成领域取得了一些关键性的进展。
This contribution reports the discovery and application of phenoxy-imine-based catalysts for olefin polymerization. Ligand-oriented catalyst design research has led to the discovery of remarkably active ethylene polymerization catalysts (FI Catalysts), which are based on electronically flexible phenoxy-imine chelate ligands combined with early transition metals. Upon activation with appropriate cocatalysts, FI Catalysts can exhibit unique polymerization catalysis (e.g., precise control of product molecular weights, highly isospecific and syndiospecific propylene polymerization, regio-irregular polymerization of higher alpha-olefins, highly controlled living polymerization of both ethylene and propylene at elevated temperatures, and precise control over polymer morphology) and thus provide extraordinary opportunities for the syntheses of value-added polymers with distinctive architectural characteristics. Many of the polymers that are available via the use of FI Catalysts were previously inaccessible through other means of polymerization. For example, FI Catalysts can form vinyl-terminated low molecular weight polyethylenes, ultra-high molecular weight amorphous ethylene-propylene copolymers and atactic polypropylenes, highly isotactic and syndiotactic polypropylenes with exceptionally high peak melting temperatures, well-defined and controlled multimodal polyethylenes, and high molecular weight regio-irregular poly(higher alpha-olefin)s. In addition, FI Catalysts combined with MgCl(2)-based compounds can produce polymers that exhibit desirable morphological features (e.g., very high bulk density polyethylenes and highly controlled particle-size polyethylenes) that are difficult to obtain with conventionally supported catalysts. In addition, FI Catalysts are capable of creating a large variety of living-polymerization-based polymers, including terminally functionalized polymers and block copolymers from ethylene, propylene, and higher alpha-olefins. Furthermore, some of the FI Catalysts can furnish living-polymerization-based polymers catalytically by combination with appropriate chain transfer agents. Therefore, the development of FI Catalysts has enabled some crucial advances in the fields of polymerization catalysis and polymer syntheses.