Influence of Type and Content of Various Comonomers on Long-Chain Branching of Ethene/α-Olefin Copolymers
One polyethylene and nine ethene/α-olefin copolymers differing in amount (0.4−2.9 mol %) and molar mass of the comonomer were characterized by NMR, SEC-MALLS, and rheology. Samples were polymerized using a [Ph2C(2,7-di-t-BuFlu)(Cp)]ZrCl2/MAO catalyst, with octene, octadecene, and hexacosene as comon...
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| Veröffentlicht in: | Macromolecules 2006-02, Vol.39 (4), p.1474-1482 |
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| creator | Stadler, Florian J Piel, Christian Klimke, Katja Kaschta, Joachim Parkinson, Matthew Wilhelm, Manfred Kaminsky, Walter Münstedt, Helmut |
| description | One polyethylene and nine ethene/α-olefin copolymers differing in amount (0.4−2.9 mol %) and molar mass of the comonomer were characterized by NMR, SEC-MALLS, and rheology. Samples were polymerized using a [Ph2C(2,7-di-t-BuFlu)(Cp)]ZrCl2/MAO catalyst, with octene, octadecene, and hexacosene as comonomers, resulting in polymers of M w ≈ 190 kg/mol. The comonomer content was determined by melt-state NMR. For the homopolymer 0.37 and 0.30 LCB/molecule were found by NMR and SEC-MALLS, respectively. Rheological quantities, such as the zero shear rate viscosity (η0), increased with LCB as compared to linear samples of the same M w. The shape of the viscosity function and the linear steady-state elastic compliance ( ) showed a dependence on comonomer content and length. These findings are used to elucidate the various long-chain branching architectures. The highest comonomer content samples behaved like typical linear polymers in rheological experiments, while those with less comonomer contents were found to be long-chain branched. Besides the comonomer content, the type of comonomer has an influence on the branching structure. |
| doi_str_mv | 10.1021/ma0514018 |
| format | Article |
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Samples were polymerized using a [Ph2C(2,7-di-t-BuFlu)(Cp)]ZrCl2/MAO catalyst, with octene, octadecene, and hexacosene as comonomers, resulting in polymers of M w ≈ 190 kg/mol. The comonomer content was determined by melt-state NMR. For the homopolymer 0.37 and 0.30 LCB/molecule were found by NMR and SEC-MALLS, respectively. Rheological quantities, such as the zero shear rate viscosity (η0), increased with LCB as compared to linear samples of the same M w. The shape of the viscosity function and the linear steady-state elastic compliance ( ) showed a dependence on comonomer content and length. These findings are used to elucidate the various long-chain branching architectures. The highest comonomer content samples behaved like typical linear polymers in rheological experiments, while those with less comonomer contents were found to be long-chain branched. Besides the comonomer content, the type of comonomer has an influence on the branching structure.</description><identifier>ISSN: 0024-9297</identifier><identifier>EISSN: 1520-5835</identifier><identifier>DOI: 10.1021/ma0514018</identifier><identifier>CODEN: MAMOBX</identifier><language>eng</language><publisher>Washington, DC: American Chemical Society</publisher><subject>Applied sciences ; Copolymerization ; Exact sciences and technology ; Organic polymers ; Physicochemistry of polymers ; Preparation, kinetics, thermodynamics, mechanism and catalysts</subject><ispartof>Macromolecules, 2006-02, Vol.39 (4), p.1474-1482</ispartof><rights>Copyright © 2006 American Chemical Society</rights><rights>2006 INIST-CNRS</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a289t-d58cc2ddf4d65bf883ec4e9032a8ecd50e4c06b3b0a6464c55644dd94ced4c253</citedby><cites>FETCH-LOGICAL-a289t-d58cc2ddf4d65bf883ec4e9032a8ecd50e4c06b3b0a6464c55644dd94ced4c253</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/ma0514018$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/ma0514018$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,780,784,2765,27076,27924,27925,56738,56788</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=17727633$$DView record in Pascal Francis$$Hfree_for_read</backlink></links><search><creatorcontrib>Stadler, Florian J</creatorcontrib><creatorcontrib>Piel, Christian</creatorcontrib><creatorcontrib>Klimke, Katja</creatorcontrib><creatorcontrib>Kaschta, Joachim</creatorcontrib><creatorcontrib>Parkinson, Matthew</creatorcontrib><creatorcontrib>Wilhelm, Manfred</creatorcontrib><creatorcontrib>Kaminsky, Walter</creatorcontrib><creatorcontrib>Münstedt, Helmut</creatorcontrib><title>Influence of Type and Content of Various Comonomers on Long-Chain Branching of Ethene/α-Olefin Copolymers</title><title>Macromolecules</title><addtitle>Macromolecules</addtitle><description>One polyethylene and nine ethene/α-olefin copolymers differing in amount (0.4−2.9 mol %) and molar mass of the comonomer were characterized by NMR, SEC-MALLS, and rheology. Samples were polymerized using a [Ph2C(2,7-di-t-BuFlu)(Cp)]ZrCl2/MAO catalyst, with octene, octadecene, and hexacosene as comonomers, resulting in polymers of M w ≈ 190 kg/mol. The comonomer content was determined by melt-state NMR. For the homopolymer 0.37 and 0.30 LCB/molecule were found by NMR and SEC-MALLS, respectively. Rheological quantities, such as the zero shear rate viscosity (η0), increased with LCB as compared to linear samples of the same M w. The shape of the viscosity function and the linear steady-state elastic compliance ( ) showed a dependence on comonomer content and length. These findings are used to elucidate the various long-chain branching architectures. The highest comonomer content samples behaved like typical linear polymers in rheological experiments, while those with less comonomer contents were found to be long-chain branched. 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Samples were polymerized using a [Ph2C(2,7-di-t-BuFlu)(Cp)]ZrCl2/MAO catalyst, with octene, octadecene, and hexacosene as comonomers, resulting in polymers of M w ≈ 190 kg/mol. The comonomer content was determined by melt-state NMR. For the homopolymer 0.37 and 0.30 LCB/molecule were found by NMR and SEC-MALLS, respectively. Rheological quantities, such as the zero shear rate viscosity (η0), increased with LCB as compared to linear samples of the same M w. The shape of the viscosity function and the linear steady-state elastic compliance ( ) showed a dependence on comonomer content and length. These findings are used to elucidate the various long-chain branching architectures. The highest comonomer content samples behaved like typical linear polymers in rheological experiments, while those with less comonomer contents were found to be long-chain branched. 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| subjects | Applied sciences Copolymerization Exact sciences and technology Organic polymers Physicochemistry of polymers Preparation, kinetics, thermodynamics, mechanism and catalysts |
| title | Influence of Type and Content of Various Comonomers on Long-Chain Branching of Ethene/α-Olefin Copolymers |
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