Phenoxide-Modified Half-Titanocenes Supported on Star-Shaped ROMP Polymers as Catalyst Precursors for Ethylene Copolymerization
Phenoxide-Modified Half-Titanocenes Supported on Star-Shaped ROMP Polymers as Catalyst Precursors for Ethylene Copolymerization
复制标题
星形 ROMP 聚合物负载酚盐改性半二茂钛作为乙烯共聚催化剂前体
DOI：
10.1021/acs.organomet.0c00365
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发表时间：
2020
期刊：
影响因子：
2.8
通讯作者：
Nomura Kotohiro
中科院分区：
文献类型：
--
作者：
Sun Zelin;Unruean Palawat;Aoki Hirotaka;Kitiyanan Boonyarach;Nomura Kotohiro
采用降冰片烯（NBE）连续一锅活性开环易位聚合（ROMP）和亚烷基钼催化剂交联剂，探索了可溶性星形聚合物链端（表面）负载芳氧基配体的半茂钛的合成和鉴定。 Ti K 边 XANES 光谱（在 25 °C 的甲苯中）表明，原始配合物 Cp*TiMe2(O-iPr2C6H3) (1) 的基本几何形状和电子性质保留在星形 ROMP 聚合物上的负载催化剂中。负载型催化剂对乙烯聚合表现出较高的催化活性，其催化活性低于线性ROMP聚合物链端负载型催化剂的1，但高于线性ROMP聚合物链端的负载型催化剂；这种星形负载型催化剂也证明了乙烯/1-己烯共聚中 1-己烯的有效结合。
The synthesis and identification of half-titanocenes containing an aryloxide ligand supported at the chain end (surface) of soluble star-shaped polymers, by adopting sequential one-pot living ring-opening metathesis polymerizations (ROMP) of norbornene (NBE) and a cross-linking reagent using a molybdenum alkylidene catalyst, have been explored. The Ti K-edge XANES spectra (in toluene at 25 °C) indicate that the basic geometry and electronic nature of the original complex, Cp*TiMe2(O-iPr2C6H3) (1), were preserved in the supported catalyst on the star-shaped ROMP polymers. The supported catalyst showed high catalytic activities for ethylene polymerization, which are lower than that by1but higher than that by the supported catalyst at the linear ROMP polymer chain end; efficient 1-hexene incorporation in the ethylene/1-hexene copolymerization has also been demonstrated in this star-shaped supported catalyst.