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Metallocene‐catalyzed long‐chain branched POE: Kinetic mechanism and structure–property relationships.

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Title: Metallocene‐catalyzed long‐chain branched POE: Kinetic mechanism and structure–property relationships.
Authors: Li, Feng1 (AUTHOR), Liu, Weifeng1 (AUTHOR) weifengliu@scut.edu.cn, Zhu, Shiping2 (AUTHOR), Zhou, Yin‐Ning3 (AUTHOR), Qiu, Xueqing4 (AUTHOR)
Source: AIChE Journal. Apr2026, Vol. 72 Issue 4, p1-20. 20p.
Subjects: Metallocene catalysts, Polymerization kinetics, Materials science, Molecular weights, Polymers, Chain-propagating reactions, Copolymerization, Rheology
Abstract: Polyolefin elastomer (POE) is widely used in photovoltaic encapsulation films but suffers from low melt strength, high extrusion energy consumption, and slow cross‐linking during melt processing. Incorporating long chain branches (LCBs) offers a promising solution for these issues. In this study, a trace amount of 1,9‐decadiene was incorporated into the ethylene/1‐octene copolymerization system catalyzed by a metallocene zirconium catalyst, significantly increasing the weight‐average molecular (Mw) from 28.5 to 105.8 kDa. Rheological analyses confirmed enhanced zero‐shear viscosity and a pronounced decrease in viscosity with increasing frequency, indicating successful LCB formation. The long‐chain branch frequency reached 0.0667/1000C, as determined by triple‐detection gel permeation chromatography. A kinetic model was established, proposing that the insertion of 1,9‐decadiene generated macromonomers with pendant double bonds, which reinserted into ethylene‐terminated active sites and continued propagating to form LCBs. The strong consistency agreement between the experimental data and model predictions validated this mechanism. [ABSTRACT FROM AUTHOR]
Copyright of AIChE Journal is the property of Wiley-Blackwell 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.)
Database: Engineering Source
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DbLabel: Engineering Source
An: 192223918
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PubTypeId: academicJournal
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  Data: Metallocene‐catalyzed long‐chain branched POE: Kinetic mechanism and structure–property relationships.
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  Data: <searchLink fieldCode="AR" term="%22Li%2C+Feng%22">Li, Feng</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Liu%2C+Weifeng%22">Liu, Weifeng</searchLink><relatesTo>1</relatesTo> (AUTHOR)<i> weifengliu@scut.edu.cn</i><br /><searchLink fieldCode="AR" term="%22Zhu%2C+Shiping%22">Zhu, Shiping</searchLink><relatesTo>2</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Zhou%2C+Yin‐Ning%22">Zhou, Yin‐Ning</searchLink><relatesTo>3</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Qiu%2C+Xueqing%22">Qiu, Xueqing</searchLink><relatesTo>4</relatesTo> (AUTHOR)
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  Data: <searchLink fieldCode="JN" term="%22AIChE+Journal%22">AIChE Journal</searchLink>. Apr2026, Vol. 72 Issue 4, p1-20. 20p.
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  Data: <searchLink fieldCode="DE" term="%22Metallocene+catalysts%22">Metallocene catalysts</searchLink><br /><searchLink fieldCode="DE" term="%22Polymerization+kinetics%22">Polymerization kinetics</searchLink><br /><searchLink fieldCode="DE" term="%22Materials+science%22">Materials science</searchLink><br /><searchLink fieldCode="DE" term="%22Molecular+weights%22">Molecular weights</searchLink><br /><searchLink fieldCode="DE" term="%22Polymers%22">Polymers</searchLink><br /><searchLink fieldCode="DE" term="%22Chain-propagating+reactions%22">Chain-propagating reactions</searchLink><br /><searchLink fieldCode="DE" term="%22Copolymerization%22">Copolymerization</searchLink><br /><searchLink fieldCode="DE" term="%22Rheology%22">Rheology</searchLink>
– Name: Abstract
  Label: Abstract
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  Data: Polyolefin elastomer (POE) is widely used in photovoltaic encapsulation films but suffers from low melt strength, high extrusion energy consumption, and slow cross‐linking during melt processing. Incorporating long chain branches (LCBs) offers a promising solution for these issues. In this study, a trace amount of 1,9‐decadiene was incorporated into the ethylene/1‐octene copolymerization system catalyzed by a metallocene zirconium catalyst, significantly increasing the weight‐average molecular (Mw) from 28.5 to 105.8 kDa. Rheological analyses confirmed enhanced zero‐shear viscosity and a pronounced decrease in viscosity with increasing frequency, indicating successful LCB formation. The long‐chain branch frequency reached 0.0667/1000C, as determined by triple‐detection gel permeation chromatography. A kinetic model was established, proposing that the insertion of 1,9‐decadiene generated macromonomers with pendant double bonds, which reinserted into ethylene‐terminated active sites and continued propagating to form LCBs. The strong consistency agreement between the experimental data and model predictions validated this mechanism. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of AIChE Journal is the property of Wiley-Blackwell 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:
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        Value: 10.1002/aic.70214
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        Text: English
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        PageCount: 20
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      – SubjectFull: Metallocene catalysts
        Type: general
      – SubjectFull: Polymerization kinetics
        Type: general
      – SubjectFull: Materials science
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      – SubjectFull: Molecular weights
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      – SubjectFull: Polymers
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      – SubjectFull: Chain-propagating reactions
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      – SubjectFull: Copolymerization
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      – SubjectFull: Rheology
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      – TitleFull: Metallocene‐catalyzed long‐chain branched POE: Kinetic mechanism and structure–property relationships.
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            NameFull: Li, Feng
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            NameFull: Liu, Weifeng
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            NameFull: Zhu, Shiping
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            NameFull: Zhou, Yin‐Ning
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              M: 04
              Text: Apr2026
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              Y: 2026
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