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

Rajeev Ananda Kumar; Priyadarsi De; Bin Zheng; Kuo-Wei Huang; Jack I. Emert; Rudolf Faust

doi:10.1039/c4py01039f

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

Rajeev Ananda Kumar, Priyadarsi De, Bin Zheng, Kuo-Wei Huang, Jack I. Emert, Rudolf Faust

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30 Scopus citations

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′.

Original language	English (US)
Pages (from-to)	322-329
Number of pages	8
Journal	Polym. Chem.
Volume	6
Issue number	2
DOIs	https://doi.org/10.1039/c4py01039f
State	Published - 2015

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: Financial support from Infineum USA is greatly acknowledged.

ASJC Scopus subject areas

Biochemistry
Organic Chemistry
Biomedical Engineering
Bioengineering
Polymers and Plastics

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

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′.",

author = "Kumar, {Rajeev Ananda} and Priyadarsi De and Bin Zheng and Kuo-Wei Huang and Emert, {Jack I.} and Rudolf Faust",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: Financial support from Infineum USA is greatly acknowledged.",

year = "2015",

doi = "10.1039/c4py01039f",

language = "English (US)",

volume = "6",

pages = "322--329",

journal = "Polym. Chem.",

issn = "1759-9954",

publisher = "Royal Society of Chemistry",

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TY - JOUR

T1 - Synthesis of highly reactive polyisobutylene with FeCl3/ether complexes in hexane; kinetic and mechanistic studies

AU - Kumar, Rajeev Ananda

AU - De, Priyadarsi

AU - Zheng, Bin

AU - Huang, Kuo-Wei

AU - Emert, Jack I.

AU - Faust, Rudolf

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: Financial support from Infineum USA is greatly acknowledged.

PY - 2015

Y1 - 2015

N2 - 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′.

AB - 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′.

UR - http://hdl.handle.net/10754/563932

UR - http://xlink.rsc.org/?DOI=C4PY01039F

UR - http://www.scopus.com/inward/record.url?scp=84916596940&partnerID=8YFLogxK

U2 - 10.1039/c4py01039f

DO - 10.1039/c4py01039f

M3 - Article

SN - 1759-9954

VL - 6

SP - 322

EP - 329

JO - Polym. Chem.

JF - Polym. Chem.

IS - 2

ER -

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

Abstract

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