Comonomer Reactivity Trends in Catalytic Ethene/1-Alkene Copolymerizations to Linear Low-Density Polyethylene.
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| Title: | Comonomer Reactivity Trends in Catalytic Ethene/1-Alkene Copolymerizations to Linear Low-Density Polyethylene. |
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| Authors: | Galasso, Gianluigi1 (AUTHOR), Cipullo, Roberta1 (AUTHOR), Busico, Vincenzo1 (AUTHOR) busico@unina.it, Vittoria, Antonio1 (AUTHOR) antonio.vittoria@unina.it |
| Source: | Polymers (20734360). Sep2025, Vol. 17 Issue 17, p2290. 15p. |
| Subjects: | Copolymerization, Catalysts, Alkenes, Metallocenes, Heterogeneous catalysts, Catalytic activity, Low density polyethylene, Vinyl polymers |
| Abstract: | Linear Low-Density Polyethylene (LLDPE) is a versatile polyolefin made by copolymerizing ethene with minor amounts of a 1-alkene. The short side chain branches in the comonomer units partly hinder the ability of the polyethylene main chain to crystallize, thus providing a way to fine-tune material properties between the extremes of a thermoplastic and a moderate elastomer. In this function, higher 1-alkenes such as 1-hexene or 1-octene are more effective than shorter homologs like propene or 1-butene, because their alkyl substituents are fully incompatible with the polyethylene lattice. On the other hand, the former comonomers are also more expensive and, above all, poorly reactive with heterogeneous Ziegler–Natta (ZN) catalysts, the workhorses of the polyolefin industry; as a matter of fact, they can only be used with technologically more demanding molecular catalysts. The molecular kinetic factors governing this important and complicated catalytic reactivity are still poorly understood, and perusal of the literature led us to conclude that data reliability is often questionable due to experimental limitations in reaction equipment and protocols, particularly in academic laboratories. In this study, we made use of a state-of-the-art High-Throughput Experimentation workflow to measure the reactivity ratios with ethene of two representative higher 1-alkenes, namely 1-hexene and 1-decene, in the presence of a variety of well-defined molecular catalysts of metallocene and post-metallocene nature comparatively with a typical MgCl2/TiCl4 ZN catalyst for polyethylene application. We found that the two comonomers react almost identically with molecular catalysts, whereas a major decrease in reactivity for 1-decene compared with 1-hexene was observed idiosyncratically for the ZN catalyst. In our opinion, the overall results suggest that in the latter case, surface effects can be dominant over direct comonomer interactions with the coordination sphere of the active metal in dictating the observed molecular kinetic behavior. [ABSTRACT FROM AUTHOR] |
| Copyright of Polymers (20734360) is the property of MDPI and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.) | |
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| Header | DbId: egs DbLabel: Engineering Source An: 187979784 AccessLevel: 6 PubType: Academic Journal PubTypeId: academicJournal PreciseRelevancyScore: 0 |
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| Items | – Name: Title Label: Title Group: Ti Data: Comonomer Reactivity Trends in Catalytic Ethene/1-Alkene Copolymerizations to Linear Low-Density Polyethylene. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Galasso%2C+Gianluigi%22">Galasso, Gianluigi</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Cipullo%2C+Roberta%22">Cipullo, Roberta</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Busico%2C+Vincenzo%22">Busico, Vincenzo</searchLink><relatesTo>1</relatesTo> (AUTHOR)<i> busico@unina.it</i><br /><searchLink fieldCode="AR" term="%22Vittoria%2C+Antonio%22">Vittoria, Antonio</searchLink><relatesTo>1</relatesTo> (AUTHOR)<i> antonio.vittoria@unina.it</i> – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22Polymers+%2820734360%29%22">Polymers (20734360)</searchLink>. Sep2025, Vol. 17 Issue 17, p2290. 15p. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Copolymerization%22">Copolymerization</searchLink><br /><searchLink fieldCode="DE" term="%22Catalysts%22">Catalysts</searchLink><br /><searchLink fieldCode="DE" term="%22Alkenes%22">Alkenes</searchLink><br /><searchLink fieldCode="DE" term="%22Metallocenes%22">Metallocenes</searchLink><br /><searchLink fieldCode="DE" term="%22Heterogeneous+catalysts%22">Heterogeneous catalysts</searchLink><br /><searchLink fieldCode="DE" term="%22Catalytic+activity%22">Catalytic activity</searchLink><br /><searchLink fieldCode="DE" term="%22Low+density+polyethylene%22">Low density polyethylene</searchLink><br /><searchLink fieldCode="DE" term="%22Vinyl+polymers%22">Vinyl polymers</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: Linear Low-Density Polyethylene (LLDPE) is a versatile polyolefin made by copolymerizing ethene with minor amounts of a 1-alkene. The short side chain branches in the comonomer units partly hinder the ability of the polyethylene main chain to crystallize, thus providing a way to fine-tune material properties between the extremes of a thermoplastic and a moderate elastomer. In this function, higher 1-alkenes such as 1-hexene or 1-octene are more effective than shorter homologs like propene or 1-butene, because their alkyl substituents are fully incompatible with the polyethylene lattice. On the other hand, the former comonomers are also more expensive and, above all, poorly reactive with heterogeneous Ziegler–Natta (ZN) catalysts, the workhorses of the polyolefin industry; as a matter of fact, they can only be used with technologically more demanding molecular catalysts. The molecular kinetic factors governing this important and complicated catalytic reactivity are still poorly understood, and perusal of the literature led us to conclude that data reliability is often questionable due to experimental limitations in reaction equipment and protocols, particularly in academic laboratories. In this study, we made use of a state-of-the-art High-Throughput Experimentation workflow to measure the reactivity ratios with ethene of two representative higher 1-alkenes, namely 1-hexene and 1-decene, in the presence of a variety of well-defined molecular catalysts of metallocene and post-metallocene nature comparatively with a typical MgCl2/TiCl4 ZN catalyst for polyethylene application. We found that the two comonomers react almost identically with molecular catalysts, whereas a major decrease in reactivity for 1-decene compared with 1-hexene was observed idiosyncratically for the ZN catalyst. In our opinion, the overall results suggest that in the latter case, surface effects can be dominant over direct comonomer interactions with the coordination sphere of the active metal in dictating the observed molecular kinetic behavior. [ABSTRACT FROM AUTHOR] – Name: AbstractSuppliedCopyright Label: Group: Ab Data: <i>Copyright of Polymers (20734360) is the property of MDPI and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.) |
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| RecordInfo | BibRecord: BibEntity: Identifiers: – Type: doi Value: 10.3390/polym17172290 Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 15 StartPage: 2290 Subjects: – SubjectFull: Copolymerization Type: general – SubjectFull: Catalysts Type: general – SubjectFull: Alkenes Type: general – SubjectFull: Metallocenes Type: general – SubjectFull: Heterogeneous catalysts Type: general – SubjectFull: Catalytic activity Type: general – SubjectFull: Low density polyethylene Type: general – SubjectFull: Vinyl polymers Type: general Titles: – TitleFull: Comonomer Reactivity Trends in Catalytic Ethene/1-Alkene Copolymerizations to Linear Low-Density Polyethylene. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Galasso, Gianluigi – PersonEntity: Name: NameFull: Cipullo, Roberta – PersonEntity: Name: NameFull: Busico, Vincenzo – PersonEntity: Name: NameFull: Vittoria, Antonio IsPartOfRelationships: – BibEntity: Dates: – D: 01 M: 09 Text: Sep2025 Type: published Y: 2025 Identifiers: – Type: issn-print Value: 20734360 Numbering: – Type: volume Value: 17 – Type: issue Value: 17 Titles: – TitleFull: Polymers (20734360) Type: main |
| ResultId | 1 |
