{"title":"聚(丙烯-co-降冰片烯)具有高摩尔质量,降冰片烯含量和性质可调,在氯乙酰胺修饰的半二茂钛催化剂上产率高","authors":"Simona Losio, Laura Boggioni, Adriano Vignali, Fabio Bertini, Akito Nishiyama, Kotohiro Nomura, Incoronata Tritto","doi":"10.1039/d5py00549c","DOIUrl":null,"url":null,"abstract":"The ketimide-modified half-titanocene catalysts, Cp’TiCl<small><sub>2</sub></small>(N=C<em>t</em>Bu<small><sub>2</sub></small> [Cp’ = C<small><sub>5</sub></small>H<small><sub>5</sub></small>(<strong>1</strong>), C<small><sub>5</sub></small>Me<small><sub>5</sub></small> (<strong>2</strong>), Me<small><sub>3</sub></small>SiC<small><sub>5</sub></small>H<small><sub>4</sub></small> (<strong>3</strong>)], afforded high molecular weight copolymers of propene (P) and norbornene (N) with efficient N incorporation in the presence of MAO. The poly(P-<em>co</em>-N)s obtained were studied in detail by determining microstructure and comonomer contents by <small><sup>13</sup></small>C-NMR spectra, molar masses, thermal and mechanical properties. The ketimide Cp’TiCl<small><sub>2</sub></small>(N=CtBu<small><sub>2</sub></small>) catalysts <strong>1</strong> and <strong>3</strong> exhibited higher catalytic activities and yielded the copolymers with higher N contents and molar mass than the ketimide-modified Cp*TiCl<small><sub>2</sub></small>(N=CtBu<small><sub>2</sub></small>) (<strong>2</strong>); the resultant copolymer by catalyst <strong>1</strong> contained 61.7 mol % of N and <em>M</em><small><sub>w</sub></small> equal to 657 kg mol<small><sup>-1</sup></small> possessing uniform composition. The copolymers show very different tensile behaviours passing from ductile and tough materials to stiff and fragile ones as N content increases.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"96 1","pages":""},"PeriodicalIF":4.1000,"publicationDate":"2025-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Poly(propene-co-norbornene)s with high molar masses, tunable norbornene contents and properties, in high yield by ketimide-modified half-titanocene catalysts\",\"authors\":\"Simona Losio, Laura Boggioni, Adriano Vignali, Fabio Bertini, Akito Nishiyama, Kotohiro Nomura, Incoronata Tritto\",\"doi\":\"10.1039/d5py00549c\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"The ketimide-modified half-titanocene catalysts, Cp’TiCl<small><sub>2</sub></small>(N=C<em>t</em>Bu<small><sub>2</sub></small> [Cp’ = C<small><sub>5</sub></small>H<small><sub>5</sub></small>(<strong>1</strong>), C<small><sub>5</sub></small>Me<small><sub>5</sub></small> (<strong>2</strong>), Me<small><sub>3</sub></small>SiC<small><sub>5</sub></small>H<small><sub>4</sub></small> (<strong>3</strong>)], afforded high molecular weight copolymers of propene (P) and norbornene (N) with efficient N incorporation in the presence of MAO. The poly(P-<em>co</em>-N)s obtained were studied in detail by determining microstructure and comonomer contents by <small><sup>13</sup></small>C-NMR spectra, molar masses, thermal and mechanical properties. The ketimide Cp’TiCl<small><sub>2</sub></small>(N=CtBu<small><sub>2</sub></small>) catalysts <strong>1</strong> and <strong>3</strong> exhibited higher catalytic activities and yielded the copolymers with higher N contents and molar mass than the ketimide-modified Cp*TiCl<small><sub>2</sub></small>(N=CtBu<small><sub>2</sub></small>) (<strong>2</strong>); the resultant copolymer by catalyst <strong>1</strong> contained 61.7 mol % of N and <em>M</em><small><sub>w</sub></small> equal to 657 kg mol<small><sup>-1</sup></small> possessing uniform composition. The copolymers show very different tensile behaviours passing from ductile and tough materials to stiff and fragile ones as N content increases.\",\"PeriodicalId\":100,\"journal\":{\"name\":\"Polymer Chemistry\",\"volume\":\"96 1\",\"pages\":\"\"},\"PeriodicalIF\":4.1000,\"publicationDate\":\"2025-07-15\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Polymer Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1039/d5py00549c\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"POLYMER SCIENCE\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Polymer Chemistry","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d5py00549c","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
Poly(propene-co-norbornene)s with high molar masses, tunable norbornene contents and properties, in high yield by ketimide-modified half-titanocene catalysts
The ketimide-modified half-titanocene catalysts, Cp’TiCl2(N=CtBu2 [Cp’ = C5H5(1), C5Me5 (2), Me3SiC5H4 (3)], afforded high molecular weight copolymers of propene (P) and norbornene (N) with efficient N incorporation in the presence of MAO. The poly(P-co-N)s obtained were studied in detail by determining microstructure and comonomer contents by 13C-NMR spectra, molar masses, thermal and mechanical properties. The ketimide Cp’TiCl2(N=CtBu2) catalysts 1 and 3 exhibited higher catalytic activities and yielded the copolymers with higher N contents and molar mass than the ketimide-modified Cp*TiCl2(N=CtBu2) (2); the resultant copolymer by catalyst 1 contained 61.7 mol % of N and Mw equal to 657 kg mol-1 possessing uniform composition. The copolymers show very different tensile behaviours passing from ductile and tough materials to stiff and fragile ones as N content increases.
期刊介绍:
Polymer Chemistry welcomes submissions in all areas of polymer science that have a strong focus on macromolecular chemistry. Manuscripts may cover a broad range of fields, yet no direct application focus is required.