(Trialkylsilyl-cyclopentadienyl)titanium(iv) dichloride complexes containing ketimide ligands, Cp′TiCl2(NCtBu2) (Cp′ = Me3SiC5H4, Et3SiC5H4), as efficient catalysts for ethylene copolymerisation with norbornene and tetracyclododecene†

IF 4.4 3区化学 Q2 CHEMISTRY, PHYSICAL

Catalysis Science & Technology Pub Date : 2025-03-17 DOI:10.1039/d5cy00160a

Minaho Kawatsu , Taiga Fujioka , Simona Losio , Incoronata Tritto , Kotohiro Nomura

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Abstract

Trialkylsilyl-substituted half sandwich titanium complexes containing ketimide ligands, (RC₅H₄)TiCl₂(NC^tBu₂) (R = SiMe₃, SiEt₃), especially the SiEt₃ analogue, exhibited superior catalytic activities with efficient norbornene (NBE) incorporation (25 700–91 400 kg polymer per mol Ti h⁻¹; NBE 36.2–72.7 mol%) in the ethylene/NBE copolymerisation at 50 °C to afford high molecular weight copolymers with high NBE contents (NBE > 60 mol%). These complexes also displayed superior capability for efficient synthesis of ethylene copolymers with tetracyclododecene (TCD) at 50 °C, and synthesis of high molar mass copolymers with high glass transition temperatures (T_g = 255 °C, TCD 52.3 mol%) has been achieved. Efficient synthesis of high molar mass cyclic olefin copolymers (COCs) possessing high T_g values has been demonstrated by using these catalysts.

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（三烷基硅-环戊二烯基）二氯钛配合物含氯胺配体Cp ' ticcl2 (NCtBu2) （Cp ' = Me3SiC5H4, Et3SiC5H4）作为降冰片烯和四环十二烯†共聚乙烯的有效催化剂

含酮胺配体（RC5H4）TiCl2(NCtBu2) （R = SiMe3, SiEt3）的三烷基硅基取代半夹心钛配合物，特别是SiEt3类似物，在降冰片烯（NBE）的有效掺入下（25 700-91 400 kg聚合物/ mol Ti h−1）表现出优异的催化活性；NBE 36.2-72.7 mol%)在乙烯/NBE中在50℃下共聚得到高分子量、高NBE含量的共聚物(NBE >；60摩尔%)。这些配合物在50℃下还能高效合成四环十二烯（TCD）乙烯共聚物，并能合成高玻璃化转变温度（Tg = 255℃，TCD为52.3 mol%）的高摩尔质量共聚物。使用这些催化剂可有效合成高Tg值的高摩尔质量环烯烃共聚物（COCs）。

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来源期刊

Catalysis Science & Technology CHEMISTRY, PHYSICAL-

CiteScore

8.70

自引率

6.00%

发文量

587

审稿时长

1.5 months

期刊介绍： A multidisciplinary journal focusing on cutting edge research across all fundamental science and technological aspects of catalysis. Editor-in-chief: Bert Weckhuysen Impact factor: 5.0 Time to first decision (peer reviewed only): 31 days