Advances in Engineering Advances in Engineering features breaking research judged by Advances in Engineering advisory team to be of key importance in the Engineering field. Papers are selected from over 10,000 published each week from most peer reviewed journals.
Macromolecules, 2014, 47 (6), pp 1959–1965.
Rajeev Kumar †, Bin Zheng ‡, Kuo-Wei Huang ‡,Jack Emert §, Rudolf Faust *†
† Polymer Science Program, Department of Chemistry,University of Massachusetts Lowell, One University Avenue, Lowell, Massachusetts 01854, United States and
‡ KAUST Catalysis Center and Division of Physical Sciences and Engineering, King Abdullah University of Science and Technology, Thuwal 2355-6900, Saudi Arabia and
§Infineum USA, 1900 E. Linden Avenue, Linden, New Jersey 07036,United States.
Abstract
The 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 {Beta}-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.
Copyright © 2014 American Chemical Society.
