Synthesis of highly reactive polyisobutylene with FeCl3/ether complexes in hexane; kinetic and mechanistic studies

Handle URI:
http://hdl.handle.net/10754/563932
Title:
Synthesis of highly reactive polyisobutylene with FeCl3/ether complexes in hexane; kinetic and mechanistic studies
Authors:
Kumar, Rajeev Ananda; De, Priyadarsi; Zheng, Bin; Huang, Kuo-Wei ( 0000-0003-1900-2658 ) ; Emert, Jack I.; Faust, Rudolf
Abstract:
The kinetics and mechanism of the polymerization of isobutylene catalyzed by FeCl3·ether complexes in hexane at 0°C were investigated. The polymerization rates increased in the diisopropyl ether< 2-chloroethyl ethyl ether < bis(2-chloroethyl) ether order, attributed to electronic effects. The polymerization rates increased with increasing initiator and catalyst concentrations. The first order plots, however, deviated from the linear suggesting that the cation concentration decreases with time. The previously proposed mechanism is inadequate to explain this finding. The decrease in the polymerization rate with time is explained by the low solubility of the H+ROR′FeCl4 - complexes that precipitate during polymerization. Based on mechanistic studies the revised mechanism now also includes the equilibrium H+ROR′FeCl4 - ⇋ HCl + FeCl3·ROR′.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division; Chemical Science Program; HCL
Publisher:
Royal Society of Chemistry (RSC)
Journal:
Polym. Chem.
Issue Date:
2015
DOI:
10.1039/c4py01039f
Type:
Article
ISSN:
17599954
Sponsors:
Financial support from Infineum USA is greatly acknowledged.
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.authorKumar, Rajeev Anandaen
dc.contributor.authorDe, Priyadarsien
dc.contributor.authorZheng, Binen
dc.contributor.authorHuang, Kuo-Weien
dc.contributor.authorEmert, Jack I.en
dc.contributor.authorFaust, Rudolfen
dc.date.accessioned2015-08-03T12:20:00Zen
dc.date.available2015-08-03T12:20:00Zen
dc.date.issued2015en
dc.identifier.issn17599954en
dc.identifier.doi10.1039/c4py01039fen
dc.identifier.urihttp://hdl.handle.net/10754/563932en
dc.description.abstractThe kinetics and mechanism of the polymerization of isobutylene catalyzed by FeCl3·ether complexes in hexane at 0°C were investigated. The polymerization rates increased in the diisopropyl ether< 2-chloroethyl ethyl ether < bis(2-chloroethyl) ether order, attributed to electronic effects. The polymerization rates increased with increasing initiator and catalyst concentrations. The first order plots, however, deviated from the linear suggesting that the cation concentration decreases with time. The previously proposed mechanism is inadequate to explain this finding. The decrease in the polymerization rate with time is explained by the low solubility of the H+ROR′FeCl4 - complexes that precipitate during polymerization. Based on mechanistic studies the revised mechanism now also includes the equilibrium H+ROR′FeCl4 - ⇋ HCl + FeCl3·ROR′.en
dc.description.sponsorshipFinancial support from Infineum USA is greatly acknowledged.en
dc.publisherRoyal Society of Chemistry (RSC)en
dc.titleSynthesis of highly reactive polyisobutylene with FeCl3/ether complexes in hexane; kinetic and mechanistic studiesen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentChemical Science Programen
dc.contributor.departmentHCLen
dc.identifier.journalPolym. Chem.en
dc.contributor.institutionPolymer Science Program, Department of Chemistry, University of Massachusetts Lowell, One University AvenueLowell, MA, United Statesen
dc.contributor.institutionPolymer Research Centre, Department of Chemical Sciences, Indian Institute of Science Education and Research KolkataMohanpur, Nadia, West Bengal, Indiaen
dc.contributor.institutionInfineum USA, 1900 E. Linden AvenueLinden, NJ, United Statesen
kaust.authorZheng, Binen
kaust.authorHuang, Kuo-Weien
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