View in EDS

A DFT-based mechanistic and catalyst design study on the copolymerization of ethylene with polar monomers catalyzed by [N, P]Ti complexes.

Saved in:
Bibliographic Details
Title: A DFT-based mechanistic and catalyst design study on the copolymerization of ethylene with polar monomers catalyzed by [N, P]Ti complexes.
Authors: Zhang, Jiaojiao1 (AUTHOR), Wu, Wenqi2 (AUTHOR), Cong, Wenwen1 (AUTHOR), Chen, Xia1 (AUTHOR), Sun, Qihang1 (AUTHOR), Cao, Jielun1 (AUTHOR), Li, Yi3 (AUTHOR) liyi@licp.cas.cn
Source: Journal of Polymer Research. May2026, Vol. 33 Issue 5, p1-13. 13p.
Subjects: Copolymerization, Titanium catalysts, Monomers, Density functional theory, Ligands (Chemistry), Fluorine, Polyolefins, Ethylene
Abstract: Density functional theory (DFT) calculations were employed to elucidate the mechanism of ethylene copolymerization with α-olefins (1-octene) and a polar monomer (9-decen-1-ol) catalyzed by titanium complexes bearing [N, P] ligands. The study systematically evaluates how fluorination versus methylation of the ligand framework influences the catalytic cycle through electronic and steric effects. Results demonstrate that electron-withdrawing fluorine substituents reduce insertion barriers for ethylene homopolymerization and improve incorporation kinetics for 1-octene. Most significantly, fluorination substantially elevates the energy barrier for β‑hydride elimination in systems containing 9‑decen‑1‑ol, thereby suppressing chain termination and facilitating the production of higher molecular weight polar-functionalized copolymers. Non‑covalent interaction analyses further reveal enhanced catalyst-monomer associations, correlating with higher activity. This work establishes a predictive DFT model that directly links ligand architecture to polymerization performance, offering a rational design strategy for next‑generation catalysts toward functionalized polyolefins. [ABSTRACT FROM AUTHOR]
Copyright of Journal of Polymer Research is the property of Springer Nature 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
FullText Text:
  Availability: 0
Header DbId: egs
DbLabel: Engineering Source
An: 194163063
AccessLevel: 6
PubType: Academic Journal
PubTypeId: academicJournal
PreciseRelevancyScore: 0
IllustrationInfo
Items – Name: Title
  Label: Title
  Group: Ti
  Data: A DFT-based mechanistic and catalyst design study on the copolymerization of ethylene with polar monomers catalyzed by [N, P]Ti complexes.
– Name: Author
  Label: Authors
  Group: Au
  Data: <searchLink fieldCode="AR" term="%22Zhang%2C+Jiaojiao%22">Zhang, Jiaojiao</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Wu%2C+Wenqi%22">Wu, Wenqi</searchLink><relatesTo>2</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Cong%2C+Wenwen%22">Cong, Wenwen</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Chen%2C+Xia%22">Chen, Xia</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Sun%2C+Qihang%22">Sun, Qihang</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Cao%2C+Jielun%22">Cao, Jielun</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Li%2C+Yi%22">Li, Yi</searchLink><relatesTo>3</relatesTo> (AUTHOR)<i> liyi@licp.cas.cn</i>
– Name: TitleSource
  Label: Source
  Group: Src
  Data: <searchLink fieldCode="JN" term="%22Journal+of+Polymer+Research%22">Journal of Polymer Research</searchLink>. May2026, Vol. 33 Issue 5, p1-13. 13p.
– Name: Subject
  Label: Subjects
  Group: Su
  Data: <searchLink fieldCode="DE" term="%22Copolymerization%22">Copolymerization</searchLink><br /><searchLink fieldCode="DE" term="%22Titanium+catalysts%22">Titanium catalysts</searchLink><br /><searchLink fieldCode="DE" term="%22Monomers%22">Monomers</searchLink><br /><searchLink fieldCode="DE" term="%22Density+functional+theory%22">Density functional theory</searchLink><br /><searchLink fieldCode="DE" term="%22Ligands+%28Chemistry%29%22">Ligands (Chemistry)</searchLink><br /><searchLink fieldCode="DE" term="%22Fluorine%22">Fluorine</searchLink><br /><searchLink fieldCode="DE" term="%22Polyolefins%22">Polyolefins</searchLink><br /><searchLink fieldCode="DE" term="%22Ethylene%22">Ethylene</searchLink>
– Name: Abstract
  Label: Abstract
  Group: Ab
  Data: Density functional theory (DFT) calculations were employed to elucidate the mechanism of ethylene copolymerization with α-olefins (1-octene) and a polar monomer (9-decen-1-ol) catalyzed by titanium complexes bearing [N, P] ligands. The study systematically evaluates how fluorination versus methylation of the ligand framework influences the catalytic cycle through electronic and steric effects. Results demonstrate that electron-withdrawing fluorine substituents reduce insertion barriers for ethylene homopolymerization and improve incorporation kinetics for 1-octene. Most significantly, fluorination substantially elevates the energy barrier for β‑hydride elimination in systems containing 9‑decen‑1‑ol, thereby suppressing chain termination and facilitating the production of higher molecular weight polar-functionalized copolymers. Non‑covalent interaction analyses further reveal enhanced catalyst-monomer associations, correlating with higher activity. This work establishes a predictive DFT model that directly links ligand architecture to polymerization performance, offering a rational design strategy for next‑generation catalysts toward functionalized polyolefins. [ABSTRACT FROM AUTHOR]
– Name: AbstractSuppliedCopyright
  Label:
  Group: Ab
  Data: <i>Copyright of Journal of Polymer Research is the property of Springer Nature 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.)
PLink https://search.ebscohost.com/login.aspx?direct=true&site=eds-live&db=egs&AN=194163063
RecordInfo BibRecord:
  BibEntity:
    Identifiers:
      – Type: doi
        Value: 10.1007/s10965-026-04901-x
    Languages:
      – Code: eng
        Text: English
    PhysicalDescription:
      Pagination:
        PageCount: 13
        StartPage: 1
    Subjects:
      – SubjectFull: Copolymerization
        Type: general
      – SubjectFull: Titanium catalysts
        Type: general
      – SubjectFull: Monomers
        Type: general
      – SubjectFull: Density functional theory
        Type: general
      – SubjectFull: Ligands (Chemistry)
        Type: general
      – SubjectFull: Fluorine
        Type: general
      – SubjectFull: Polyolefins
        Type: general
      – SubjectFull: Ethylene
        Type: general
    Titles:
      – TitleFull: A DFT-based mechanistic and catalyst design study on the copolymerization of ethylene with polar monomers catalyzed by [N, P]Ti complexes.
        Type: main
  BibRelationships:
    HasContributorRelationships:
      – PersonEntity:
          Name:
            NameFull: Zhang, Jiaojiao
      – PersonEntity:
          Name:
            NameFull: Wu, Wenqi
      – PersonEntity:
          Name:
            NameFull: Cong, Wenwen
      – PersonEntity:
          Name:
            NameFull: Chen, Xia
      – PersonEntity:
          Name:
            NameFull: Sun, Qihang
      – PersonEntity:
          Name:
            NameFull: Cao, Jielun
      – PersonEntity:
          Name:
            NameFull: Li, Yi
    IsPartOfRelationships:
      – BibEntity:
          Dates:
            – D: 01
              M: 05
              Text: May2026
              Type: published
              Y: 2026
          Identifiers:
            – Type: issn-print
              Value: 10229760
          Numbering:
            – Type: volume
              Value: 33
            – Type: issue
              Value: 5
          Titles:
            – TitleFull: Journal of Polymer Research
              Type: main
ResultId 1