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dc.contributor.authorKumar, Rajeev Ananda
dc.contributor.authorZheng, Bin
dc.contributor.authorHuang, Kuo-Wei
dc.contributor.authorEmert, Jack I.
dc.contributor.authorFaust, Rudolf
dc.date.accessioned2015-08-03T11:51:56Z
dc.date.available2015-08-03T11:51:56Z
dc.date.issued2014-03-10
dc.identifier.citationKumar, R., Zheng, B., Huang, K.-W., Emert, J., & Faust, R. (2014). Synthesis of Highly Reactive Polyisobutylene Catalyzed by EtAlCl2/Bis(2-chloroethyl) Ether Soluble Complex in Hexanes. Macromolecules, 47(6), 1959–1965. doi:10.1021/ma500042f
dc.identifier.issn00249297
dc.identifier.doi10.1021/ma500042f
dc.identifier.urihttp://hdl.handle.net/10754/563455
dc.description.abstractThe polymerization of isobutylene (IB) to yield highly reactive polyisobutylene (HR PIB) with high exo-olefin content using GaCl3 or FeCl3·diisopropyl ether complexes has been previously reported.1 In an effort to further improve polymerization rates and exo-olefin content, we have studied ethylaluminum dichloride (EADC) complexes with diisopropyl ether, 2-chloroethyl ethyl ether (CEEE), and bis(2-chloroethyl) ether (CEE) as catalysts in conjunction with tert-butyl chloride as initiator in hexanes at different temperatures. All three complexes were readily soluble in hexanes. Polymerization, however, was only observed with CEE. At 0 °C polymerization was complete in 5 min at [t-BuCl] = [EADC·CEE] = 10 mM and resulted in PIB with ∼70% exo-olefin content. Studies on complexation using ATR FTIR and 1H NMR spectroscopy revealed that at 1:1 stoichiometry a small amount of EADC remains uncomplexed. By employing an excess of CEE, exo-olefin contents increased up to 90%, while polymerization rates decreased only slightly. With decreasing temperature, polymerization rates decreased while molecular weights as well as exo-olefin contents increased, suggesting that isomerization has a higher activation energy than β-proton abstraction. Density functional theory (DFT) studies on the Lewis acid·ether binding energies indicated a trend consistent with the polymerization results. The polymerization mechanism proposed previously for Lewis acid·ether complexes1 adequately explains all the findings. © 2014 American Chemical Society.
dc.description.sponsorshipFinancial support from Infineum USA is greatly appreciated.
dc.publisherAmerican Chemical Society (ACS)
dc.titleSynthesis of highly reactive polyisobutylene catalyzed by EtAlCl 2/Bis(2-chloroethyl) ether soluble complex in hexanes
dc.typeArticle
dc.contributor.departmentChemical Science Program
dc.contributor.departmentHomogeneous Catalysis Laboratory (HCL)
dc.contributor.departmentKAUST Catalysis Center (KCC)
dc.contributor.departmentPhysical Science and Engineering (PSE) Division
dc.identifier.journalMacromolecules
dc.contributor.institutionPolymer Science Program, Department of Chemistry, University of Massachusetts Lowell, One University Avenue, Lowell, MA 01854, United States
dc.contributor.institutionInfineum USA, 1900 E. Linden Avenue, Linden, NJ 07036, United States
kaust.personZheng, Bin
kaust.personHuang, Kuo-Wei
dc.date.published-online2014-03-10
dc.date.published-print2014-03-25


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