Mechanism of isotactic styrene polymerization with a C 6F 5-substituted bis(phenoxyimine) titanium system

Handle URI:
http://hdl.handle.net/10754/562411
Title:
Mechanism of isotactic styrene polymerization with a C 6F 5-substituted bis(phenoxyimine) titanium system
Authors:
Caporaso, Lucia; Loria, Marianna; Mazzeo, Mina; Michiue, Kenji; Nakano, Takashi; Fujita, Terunori; Cavallo, Luigi ( 0000-0002-1398-338X )
Abstract:
We report a combined, experimental and theoretical, study of styrene polymerization to clarify the regio- and stereocontrol mechanism operating with a C 6F 5-substituted bis(phenoxyimine) titanium dichloride complex. Styrene homopolymerization, styrene-propene and styrene-ethene-propene copolymerizations have been carried out to this aim. A combination of 13C NMR analysis of the chain-end groups and of the microstructure of the homopolymers and copolymers reveals that styrene polymerization is highly regioselective and occurs prevalently through 2,1-monomer insertion. DFT calculations evidenced that steric interaction between the growing chain and the monomer in the transition state insertion stage is at the origin of this selectivity. The formation of isotactic polystyrene with a chain-end like microstructure is rationalized on the base of a mechanism similar to that proposed for the syndiospecific propene polymerization catalyzed by bis(phenoxyimine) titanium dichloride complexes. Finally, a general stereocontrol mechanism operative in olefin polymerization with this class of complexes is proposed. © 2012 American Chemical Society.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division; Chemical Science Program
Publisher:
American Chemical Society (ACS)
Journal:
Macromolecules
Issue Date:
13-Nov-2012
DOI:
10.1021/ma301631b
Type:
Article
ISSN:
00249297
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorCaporaso, Luciaen
dc.contributor.authorLoria, Mariannaen
dc.contributor.authorMazzeo, Minaen
dc.contributor.authorMichiue, Kenjien
dc.contributor.authorNakano, Takashien
dc.contributor.authorFujita, Terunorien
dc.contributor.authorCavallo, Luigien
dc.date.accessioned2015-08-03T10:37:15Zen
dc.date.available2015-08-03T10:37:15Zen
dc.date.issued2012-11-13en
dc.identifier.issn00249297en
dc.identifier.doi10.1021/ma301631ben
dc.identifier.urihttp://hdl.handle.net/10754/562411en
dc.description.abstractWe report a combined, experimental and theoretical, study of styrene polymerization to clarify the regio- and stereocontrol mechanism operating with a C 6F 5-substituted bis(phenoxyimine) titanium dichloride complex. Styrene homopolymerization, styrene-propene and styrene-ethene-propene copolymerizations have been carried out to this aim. A combination of 13C NMR analysis of the chain-end groups and of the microstructure of the homopolymers and copolymers reveals that styrene polymerization is highly regioselective and occurs prevalently through 2,1-monomer insertion. DFT calculations evidenced that steric interaction between the growing chain and the monomer in the transition state insertion stage is at the origin of this selectivity. The formation of isotactic polystyrene with a chain-end like microstructure is rationalized on the base of a mechanism similar to that proposed for the syndiospecific propene polymerization catalyzed by bis(phenoxyimine) titanium dichloride complexes. Finally, a general stereocontrol mechanism operative in olefin polymerization with this class of complexes is proposed. © 2012 American Chemical Society.en
dc.publisherAmerican Chemical Society (ACS)en
dc.titleMechanism of isotactic styrene polymerization with a C 6F 5-substituted bis(phenoxyimine) titanium systemen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentChemical Science Programen
dc.identifier.journalMacromoleculesen
dc.contributor.institutionDepartment of Chemistry and Biology, University of Salerno, Via Ponte Don Melillo, 84084 Fisciano, Salerno, Italyen
dc.contributor.institutionCatalysis Science Laboratory, Research Center, Mitsui Chemicals, Inc., 580-32 Nagaura, Sodegaura-City Chiba 299-0265, Japanen
dc.contributor.institutionMaterial Science Laboratory, Research Center, Mitsui Chemicals, Inc., 580-32 Nagaura, Sodegaura-City Chiba 299-0265, Japanen
dc.contributor.institutionMitsui Chemicals Singapore RandD Center Pte. Ltd., Singapore Science Park II, 50 Science Park Road, #06-08 The Kendall, Singapore 117406, Singaporeen
kaust.authorCavallo, Luigien
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