Effect of solvent polarity on the initiation and the propagation of ethylene polymerization with constrained geometry catalyst/MAO catalytic system

A density functional study with the conductor-like screening model

Sung Hoon Yang, June Huh, Won Ho Jo

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

The effect of solvent polarity on the initiation and propagation of ethylene polymerization with a constrained geometry catalyst (CGC) and MAO counterion was investigated by the density functional theory (DFT) with the conductor-like screening model (COSMO). Structures and energetics of reactant, π-complex, transition state, γ-agostic product, and β-agostic product during insertion of ethylene monomer into the catalytic active species of ionic pair or cationic catalyst are analyzed using the software DMol 3. A comparative analysis on the energetics of the ethylene insertion in the gas state and in solvents with different dielectric constants (∈) shows that the solvent polarity affects the energetics of monomer insertion very differently depending upon the model for active catalytic species and/or polymerization stage. This different behavior provides a very useful method for identifying the real active catalytic species in experiment. The two important features of molecular structure determining the dependency of enegetics on the solvent polarity are the degree of exposure of the Ti atom on the solvent medium and the degree of separation of ionic pair during monomer insertion.

Original languageEnglish
Pages (from-to)1402-1409
Number of pages8
JournalMacromolecules
Volume38
Issue number4
DOIs
Publication statusPublished - 2005 Feb 22
Externally publishedYes

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Monoamine Oxidase
Screening
Ethylene
Polymerization
Catalysts
Geometry
Monomers
Molecular structure
Density functional theory
Permittivity
Gases
ethylene
Atoms
Experiments

ASJC Scopus subject areas

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

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abstract = "The effect of solvent polarity on the initiation and propagation of ethylene polymerization with a constrained geometry catalyst (CGC) and MAO counterion was investigated by the density functional theory (DFT) with the conductor-like screening model (COSMO). Structures and energetics of reactant, π-complex, transition state, γ-agostic product, and β-agostic product during insertion of ethylene monomer into the catalytic active species of ionic pair or cationic catalyst are analyzed using the software DMol 3. A comparative analysis on the energetics of the ethylene insertion in the gas state and in solvents with different dielectric constants (∈) shows that the solvent polarity affects the energetics of monomer insertion very differently depending upon the model for active catalytic species and/or polymerization stage. This different behavior provides a very useful method for identifying the real active catalytic species in experiment. The two important features of molecular structure determining the dependency of enegetics on the solvent polarity are the degree of exposure of the Ti atom on the solvent medium and the degree of separation of ionic pair during monomer insertion.",
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T1 - Effect of solvent polarity on the initiation and the propagation of ethylene polymerization with constrained geometry catalyst/MAO catalytic system

T2 - A density functional study with the conductor-like screening model

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AU - Jo, Won Ho

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N2 - The effect of solvent polarity on the initiation and propagation of ethylene polymerization with a constrained geometry catalyst (CGC) and MAO counterion was investigated by the density functional theory (DFT) with the conductor-like screening model (COSMO). Structures and energetics of reactant, π-complex, transition state, γ-agostic product, and β-agostic product during insertion of ethylene monomer into the catalytic active species of ionic pair or cationic catalyst are analyzed using the software DMol 3. A comparative analysis on the energetics of the ethylene insertion in the gas state and in solvents with different dielectric constants (∈) shows that the solvent polarity affects the energetics of monomer insertion very differently depending upon the model for active catalytic species and/or polymerization stage. This different behavior provides a very useful method for identifying the real active catalytic species in experiment. The two important features of molecular structure determining the dependency of enegetics on the solvent polarity are the degree of exposure of the Ti atom on the solvent medium and the degree of separation of ionic pair during monomer insertion.

AB - The effect of solvent polarity on the initiation and propagation of ethylene polymerization with a constrained geometry catalyst (CGC) and MAO counterion was investigated by the density functional theory (DFT) with the conductor-like screening model (COSMO). Structures and energetics of reactant, π-complex, transition state, γ-agostic product, and β-agostic product during insertion of ethylene monomer into the catalytic active species of ionic pair or cationic catalyst are analyzed using the software DMol 3. A comparative analysis on the energetics of the ethylene insertion in the gas state and in solvents with different dielectric constants (∈) shows that the solvent polarity affects the energetics of monomer insertion very differently depending upon the model for active catalytic species and/or polymerization stage. This different behavior provides a very useful method for identifying the real active catalytic species in experiment. The two important features of molecular structure determining the dependency of enegetics on the solvent polarity are the degree of exposure of the Ti atom on the solvent medium and the degree of separation of ionic pair during monomer insertion.

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