Synthesis of zirconocene complexes and their use in slurry-phase polymerisation of ethylene
A new family of zirconocene complexes of the type (3-RInd#)2ZrX2 (where Ind# = C6Me5H and R = Me, Et and Ph) have been synthesised and fully characterised. Six new crystal structures have been reported (meso-(3-EtInd#)2ZrBr2, rac-(3-EtInd#)2ZrCl2, rac-(3-EtInd#)2Zr(CH2Ph)2, meso-(3-EtInd#)2Zr(CH2Ph)...
| Príomhchruthaitheoirí: | , , , , |
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| Formáid: | Journal article |
| Teanga: | English |
| Foilsithe / Cruthaithe: |
Royal Society of Chemistry
2021
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| _version_ | 1826288652502695936 |
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| author | Angpanitcharoen, P Lamb, JV Buffet, J-C Turner, ZR O'Hare, D |
| author_facet | Angpanitcharoen, P Lamb, JV Buffet, J-C Turner, ZR O'Hare, D |
| author_sort | Angpanitcharoen, P |
| collection | OXFORD |
| description | A new family of zirconocene complexes of the type (3-RInd#)2ZrX2 (where Ind# = C6Me5H and R = Me, Et and Ph) have been synthesised and fully characterised. Six new crystal structures have been reported (meso-(3-EtInd#)2ZrBr2, rac-(3-EtInd#)2ZrCl2, rac-(3-EtInd#)2Zr(CH2Ph)2, meso-(3-EtInd#)2Zr(CH2Ph)2, meso-(3-MeInd#)2ZrBr2 and meso-(3-MeInd#)2Zr(CH2Ph)2). The complexes were studied for slurry-phase ethylene polymerisation when immobilised on solid polymethylaluminoxane (sMAO). Variation in the initiation group was found to have greater influence over polymerisation activity for meso-catalysts than rac-catalysts, with meso-alkyl catalysts showing higher polymerisation activities than meso-halide. Below 70 °C, polymerisation activity follows the order sMAO-meso-(3-EtInd#)2Zr(CH2Ph)2, sMAO-meso-(3-EtInd#)2ZrCl2 and sMAO-meso-(3-EtInd#)2ZrBr2 (activities of 657, 561, and 452 kgPE molM−1 h−1 bar−1, respectively). sMAO-meso-(3-EtInd#)2ZrBr2 produces HDPE with the highest molecular weight, followed by sMAO-meso-(3-EtInd#)2ZrCl2 and sMAO-meso-(3-EtInd#)2Zr(CH2Ph)2 (Mw of 503, 406, and 345 kg mol−1, respectively, at 50 °C). sMAO-meso-(3-MeInd#)2ZrBr2 produced HDPE with almost identical molecular weights to sMAO-meso-(3-EtInd#)2ZrCl2 (395 kg mol−1 at 50 °C). |
| first_indexed | 2024-03-07T02:16:57Z |
| format | Journal article |
| id | oxford-uuid:a2957f71-b15e-4510-967a-d2553e3477c5 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T02:16:57Z |
| publishDate | 2021 |
| publisher | Royal Society of Chemistry |
| record_format | dspace |
| spelling | oxford-uuid:a2957f71-b15e-4510-967a-d2553e3477c52022-03-27T02:21:05ZSynthesis of zirconocene complexes and their use in slurry-phase polymerisation of ethyleneJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:a2957f71-b15e-4510-967a-d2553e3477c5EnglishSymplectic ElementsRoyal Society of Chemistry2021Angpanitcharoen, PLamb, JVBuffet, J-CTurner, ZRO'Hare, DA new family of zirconocene complexes of the type (3-RInd#)2ZrX2 (where Ind# = C6Me5H and R = Me, Et and Ph) have been synthesised and fully characterised. Six new crystal structures have been reported (meso-(3-EtInd#)2ZrBr2, rac-(3-EtInd#)2ZrCl2, rac-(3-EtInd#)2Zr(CH2Ph)2, meso-(3-EtInd#)2Zr(CH2Ph)2, meso-(3-MeInd#)2ZrBr2 and meso-(3-MeInd#)2Zr(CH2Ph)2). The complexes were studied for slurry-phase ethylene polymerisation when immobilised on solid polymethylaluminoxane (sMAO). Variation in the initiation group was found to have greater influence over polymerisation activity for meso-catalysts than rac-catalysts, with meso-alkyl catalysts showing higher polymerisation activities than meso-halide. Below 70 °C, polymerisation activity follows the order sMAO-meso-(3-EtInd#)2Zr(CH2Ph)2, sMAO-meso-(3-EtInd#)2ZrCl2 and sMAO-meso-(3-EtInd#)2ZrBr2 (activities of 657, 561, and 452 kgPE molM−1 h−1 bar−1, respectively). sMAO-meso-(3-EtInd#)2ZrBr2 produces HDPE with the highest molecular weight, followed by sMAO-meso-(3-EtInd#)2ZrCl2 and sMAO-meso-(3-EtInd#)2Zr(CH2Ph)2 (Mw of 503, 406, and 345 kg mol−1, respectively, at 50 °C). sMAO-meso-(3-MeInd#)2ZrBr2 produced HDPE with almost identical molecular weights to sMAO-meso-(3-EtInd#)2ZrCl2 (395 kg mol−1 at 50 °C). |
| spellingShingle | Angpanitcharoen, P Lamb, JV Buffet, J-C Turner, ZR O'Hare, D Synthesis of zirconocene complexes and their use in slurry-phase polymerisation of ethylene |
| title | Synthesis of zirconocene complexes and their use in slurry-phase polymerisation of ethylene |
| title_full | Synthesis of zirconocene complexes and their use in slurry-phase polymerisation of ethylene |
| title_fullStr | Synthesis of zirconocene complexes and their use in slurry-phase polymerisation of ethylene |
| title_full_unstemmed | Synthesis of zirconocene complexes and their use in slurry-phase polymerisation of ethylene |
| title_short | Synthesis of zirconocene complexes and their use in slurry-phase polymerisation of ethylene |
| title_sort | synthesis of zirconocene complexes and their use in slurry phase polymerisation of ethylene |
| work_keys_str_mv | AT angpanitcharoenp synthesisofzirconocenecomplexesandtheiruseinslurryphasepolymerisationofethylene AT lambjv synthesisofzirconocenecomplexesandtheiruseinslurryphasepolymerisationofethylene AT buffetjc synthesisofzirconocenecomplexesandtheiruseinslurryphasepolymerisationofethylene AT turnerzr synthesisofzirconocenecomplexesandtheiruseinslurryphasepolymerisationofethylene AT ohared synthesisofzirconocenecomplexesandtheiruseinslurryphasepolymerisationofethylene |