{"title":"(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","authors":"Minaho Kawatsu , Taiga Fujioka , Simona Losio , Incoronata Tritto , Kotohiro Nomura","doi":"10.1039/d5cy00160a","DOIUrl":null,"url":null,"abstract":"<div><div>Trialkylsilyl-substituted half sandwich titanium complexes containing ketimide ligands, (RC<sub>5</sub>H<sub>4</sub>)TiCl<sub>2</sub>(NC<sup><em>t</em></sup>Bu<sub>2</sub>) (R = SiMe<sub>3</sub>, SiEt<sub>3</sub>), especially the SiEt<sub>3</sub> analogue, exhibited superior catalytic activities with efficient norbornene (NBE) incorporation (25 700–91 400 kg polymer per mol Ti h<sup>−1</sup>; 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 (<em>T</em><sub>g</sub> = 255 °C, TCD 52.3 mol%) has been achieved. Efficient synthesis of high molar mass cyclic olefin copolymers (COCs) possessing high <em>T</em><sub>g</sub> values has been demonstrated by using these catalysts.</div></div>","PeriodicalId":66,"journal":{"name":"Catalysis Science & Technology","volume":"15 9","pages":"Pages 2757-2765"},"PeriodicalIF":4.4000,"publicationDate":"2025-03-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"(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†\",\"authors\":\"Minaho Kawatsu , Taiga Fujioka , Simona Losio , Incoronata Tritto , Kotohiro Nomura\",\"doi\":\"10.1039/d5cy00160a\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Trialkylsilyl-substituted half sandwich titanium complexes containing ketimide ligands, (RC<sub>5</sub>H<sub>4</sub>)TiCl<sub>2</sub>(NC<sup><em>t</em></sup>Bu<sub>2</sub>) (R = SiMe<sub>3</sub>, SiEt<sub>3</sub>), especially the SiEt<sub>3</sub> analogue, exhibited superior catalytic activities with efficient norbornene (NBE) incorporation (25 700–91 400 kg polymer per mol Ti h<sup>−1</sup>; 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 (<em>T</em><sub>g</sub> = 255 °C, TCD 52.3 mol%) has been achieved. Efficient synthesis of high molar mass cyclic olefin copolymers (COCs) possessing high <em>T</em><sub>g</sub> values has been demonstrated by using these catalysts.</div></div>\",\"PeriodicalId\":66,\"journal\":{\"name\":\"Catalysis Science & Technology\",\"volume\":\"15 9\",\"pages\":\"Pages 2757-2765\"},\"PeriodicalIF\":4.4000,\"publicationDate\":\"2025-03-17\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Catalysis Science & Technology\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/org/science/article/pii/S2044475325001364\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Catalysis Science & Technology","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/org/science/article/pii/S2044475325001364","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
(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†
Trialkylsilyl-substituted half sandwich titanium complexes containing ketimide ligands, (RC5H4)TiCl2(NCtBu2) (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 (Tg = 255 °C, TCD 52.3 mol%) has been achieved. Efficient synthesis of high molar mass cyclic olefin copolymers (COCs) possessing high Tg values has been demonstrated by using these catalysts.
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