Arylsilane‐Bridged Dinuclear Half‐Titanocene Catalysts for High‐Temperature Ethylene Copolymerization: A Versatile Platform for Diverse Comonomers ^†

Comprehensive Summary

The copolymerization of ethylene with functionalized comonomers under industrially relevant high‐temperature conditions remains a great challenge in polyolefin catalysis. Herein, we report a series of arylsilane‐bridged dinuclear half‐titanocene catalysts designed to enhance thermal stability and comonomer incorporation capability. In ethylene/1‐octene copolymerization at 125 °C, the dinuclear catalysts exhibited high activities and achieved 1‐octene incorporations exceeding 20 mol%. By tuning reaction conditions, copolymers with molecular weights ranging from 33,000 to 191,000 and incorporations from 8.2 to 25.2 mol% were obtained, matching the metrics of commercial POE grades. More importantly, these catalysts demonstrated remarkable tolerance toward polar OH‐functionalized α‐olefins, with the dinuclear catalysts showing 2–4 fold higher activities than the mononuclear analogue. The catalysts also enabled efficient copolymerization of ethylene with a carbazole‐containing α‐olefin, achieving high activities (up to 2.11 × 10 ⁷ g·mol _Ti ^–1 ·h ^–1 ), high molecular weights (>580,000), and tunable carbazole incorporations (2.7–6.0 mol%). The carbazole‐functionalized polyethylenes exhibited unique fluorescence properties, tunable surface wettability, and significantly enhanced ductility. The dinuclear catalyst effect does not follow a universal rule, but is strongly correlated with the specific copolymerization reaction. This work demonstrates that dinuclear half‐titanocenes represent a versatile catalyst platform for high‐temperature synthesis of functional polyolefin materials with tailored properties.