The innovation of Ziegler-Natta (Z-N) catalysts opened a novel aspect of chemistry in terms of polyolefin formation. Significant progress of more than fifty years in catalytic olefin polymerization simplified polyolefin production by optimizing the reaction conditions and internal donors. In this review, we particularly emphasized on recent development on different internal donor based Z-N catalyst systems, the role of external electron donors and co-catalyst chemistry. Furthermore, the Ziegler-Natta catalyst system, polymerization reaction, and polymer process technologies gradually upgrading to produce different polyolefin products. In particular, polyolefin fibers, composites, foam, blends and polyolefin-based 3D-printing products targeted in this review for substantial benefits of both society and highly diversified industries.

齐格勒-纳塔（ZN）催化剂的创新为聚烯烃的形成打开了化学领域的新篇章。通过优化反应条件和内部给体，催化烯烃聚合五十多年来的重大进展简化了聚烯烃的生产。在这篇综述中，我们特别强调了基于不同内部供体的ZN催化剂体系，外部电子给体的作用和助催化剂化学的最新进展。此外，Ziegler-Natta催化剂体系，聚合反应和聚合物加工技术逐渐升级以生产不同的聚烯烃产品。尤其是，本综述针对的是聚烯烃纤维，复合材料，泡沫，混合物和基于聚烯烃的3D打印产品，目的是为社会和高度多元化的行业带来巨大利益。