Complexes of aluminum, iron(III), and gallium(III) chlorides with ethers in synthesis of highly reactive polyisobutylene
Abstract
In this review, the latest achievements in the field of cationic polymerization of isobutylene catalyzed by the complexes of conventional Lewis acids with ethers are presented. The experimental and computational data on the influence of steric structure and basicity of ether used for the preparation of the Lewis acid-ether complex on the catalyst activity and regioselectivity of β-H abstraction are discussed here. Complexes of metal halides with linear (Bu2O) and moderately branched (iPr2O) ethers of moderate basicity (pKa from –4.3 to –5.4) displayed the highest activity and regioselectivity in the cationic polymerization of isobutylene affording highly reactive polyisobutylene (HR PIB) – the key intermediate in the preparation of motor oil and fuel additives. The review is also focusing on the adaptation of the developed catalytic system to the industry, which consists in using non-polar hydrocarbon solvents, high temperatures and monomer concentrations.
References
- Ivan B, Kennedy JP, Chang VSC. New telechelic polymers and sequential copolymers by polyfunctional initiator – transfer agents (inifers). VII. Synthesis and characterization of α,ω-di(hydroxy)polyisobutylene. Journal of Polymer Science: Polymer Chemistry Edition. 1980;18(11):3177–3191. DOI: 10.1002/pol.1980.170181104.
- Keki S, Deák G, Mayer‐Posner FJ, Zsuga M. MALDI-TOF MS characterization of dihydroxy telechelic polyisobutylene. Macromolecular Rapid Communications. 2000;21(11):770–774. DOI: 10.1002/1521-3927(20000701)21:11<770::AID-MARC770>3.0.CO;2-W.
- Ummadisetty S, Kennedy JP. Quantitative synthesis of novel polyisobutylenes fitted with terminal primary -Br, -OH, -NH2, and methacrylate termini. Journal of Polymer Science. Part A: Polymer Chemistry. 2008;46:4236–4242. DOI: 10.1002/pola.22716.
- Magenau AJD, Chan JW, Hoyle ChE, Storey RF. Facile polyisobutylene functionalization via thiol-ene click chemistry. Polymer Chemistry. 2010;1:831–833. DOI: 10.1039/C0PY00094A.
- Gorski U, Maenz K, Stadermann D. Functionalized polyisobutylenes by SH-en addition. Die Angewandte Makromolekulare Chemie. 1997;253(1):51–64. DOI: 10.1002/apmc.1997.052530104.
- Boileau S, Mazeaud-Henri B, Blackborow R. Reaction of functionalized thiols with oligoisobutenes via free-radical addition. Some new routes to thermoplastic crosslinkable polymers. European Polymer Journal. 2003;39(7):1395–1404. DOI: 10.1016/S0014-3057(02)00388-9.
- Nemes S, Peng KL, Wilczek L, Kennedy JP. Oxyethylation and carbonation of telechelic polyisobutylene anions. Polymer Bulletin. 1990;24:187–194. DOI: 10.1007/BF00297316.
- Castano M, Becker ML, Puskas JE. New method for the synthesis of fully aliphatic telechelic α,ω-dihydroxy-polyisobutylene. Polymer Chemistry. 2014;5:5436–5442. DOI: 10.1039/C4PY00569D.
- Lubnin AV, Kennedy JP, Goodall BL. Synthesis and characterization of aldehyde-capped polyisobutylenes. Polymer Bulletin. 1993;30:19–24. DOI: 10.1007/BF00296229.
- Nagy M, Kéki S, Orosz L, Deák G, Herczegh P, Lévai A, et al. Novel and simple synthesis of carboxyl-terminated polyisobutylene. Macromolecules. 2005;38(10):4043–4046. DOI: 10.1021/ma050075t.
- Kemp LK, Donnalley AD, Storey RF. Synthesis and characterization of carboxylic acid-terminated polyisobutylenes. Journal of Polymer Science. Part A: Polymer Chemistry. 2008;46(10):3229–3240. DOI: 10.1002/pola.22662.
- Kwon Y, Faust R, Chen CX, Thomas EL. Synthesis and characterization of poly(isobutylene-b-pivalolactone) diblock and poly(pivalolactone-b-isobutylene-b-pivalolactone) triblock copolymers. Macromolecules. 2002;35(9):3348–3357. DOI: 10.1021/ma011739b.
- Wollyung KM, Wesdemiotis C, Nagy A, Kennedy JP. Synthesis and mass spectrometry characterization of centrally and terminally amine-functionalized polyisobutylenes. Journal of Polymer Science. Part A: Polymer Chemistry. 2005;43:946–958. DOI: 10.1002/pola.20566.
- Zhang C-L, Wu Y-X, Xu X, Li Y, Feng L, Wu G-Y. Synthesis of polyisobutylene with arylamino terminal group by combination of cationic polymerization with alkylation. Journal of Polymer Science. Part A: Polymer Chemistry. 2008;46(3):936–946. DOI: 10.1002/pola.22437.
- Zhang C-L, Wu Y-X, Meng X-Y, Huang Q, Wu G-Y, Xu R-W. Synthesis of polyisobutylene with sec-arylamino terminal group by combination of cationic polymerization with alkylation. Chinese Journal of Polymer Science. 2009;27:551–559.
- Chang VSC, Kennedy JP. New telechelic polymers and sequential copolymers by polyfunctional initiator-transfer agents (inifers). Polymer Bulletin. 1981;5(7):379–384. DOI: 10.1007/BF00282687.
- Kennedy JP, Hiza M. New telechelic polymers and sequential copolymers by polyfunctional initiator-transfer agents (inifers). XXX. Synthesis and quantitative terminal functionalization of α,ω-diarylpolyisobutylenes. Journal of Polymer Science: Polymer Chemistry Edition. 1983;21(12):3573–3590. DOI: 10.1002/pol.1983.170211218.
- Bergbreiter DE, Hobbs C, Tian J, Koizumi H, Su H-L, Hongfa C. Synthesis of aryl-substituted polyisobutylenes as precursors for ligands for greener, phase-selectively soluble catalysts. Pure and Applied Chemistry. 2009;81(11):1981–1990. DOI: 10.1351/PACCON-08-10-09.
- Kennedy JP, Chang VSC, Francik WP. New telechelic polymers and sequential copolymers by polyfunctional initiator-transfer agents (inifers). XVIII. Epoxy and aldehyde telechelic polyisobutylenes. Journal of Polymer Science: Polymer Chemistry Edition. 1982;20:2809–2817. DOI: 10.1002/pol.1982.170201007.
- Sen MY, Puskas JE, Ummadisetty S, Kennedy JP. Green polymer chemistry. II. Enzymatic synthesis of methacrylate-terminated polyisobutylenes. Macromolecular Rapid Communications. 2008;29(19):1598–1602. DOI: 10.1002/marc.200800359.
- Bergbreiter DE, Priyadarshani N. Synthesis of terminally functionalized polyisobutylene derivatives using diazonium salts. Journal of Polymer Science. Part A: Polymer Chemistry. 2011;49(8):1772–1783. DOI: 10.1002/pola.24601.
- Bergbreiter DE, Sung SD, Li J, Ortiz D, Hamilton PN. Designing polymers for biphasic liquid/liquid separations after homogeneous reactions. Organic Process Research and Development. 2004;8(3):461–468. DOI: 10.1021/op034183w.
- Li J, Sung SD, Tian J, Bergbreiter DE. Polyisobutylene supports-a non-polar hydrocarbon analog of PEG supports. Tetrahedron. 2005;61(51):12081–12092. DOI: 10.1016/j.tet.2005.07.119.
- Priyadarshani N, Benzine CW, Cassidy B, Suriboot J, Liu P, Sue H-J, et al. Polyolefin soluble polyisobutylene oligomer-bound metallophthalocyanine and azo dye additives. Journal of Polymer Science. Part A: Polymer Chemistry. 2014;52(4):545–551. DOI: 10.1002/pola.27031.
- Gunther W, Maenz K, Stadermann D. Structural investigations on low-molecular-weight polyisobutenes. Die Angewandte Makromolekulare Chemie. 1996;234(1):71–90. DOI: 10.1002/apmc.1996.052340108.
- Argo C, Gillam SM, Orsini F. Identification of olefin end groups in commercial polybutene oligomers. Polymer Bulletin. 2000;44:71–78. DOI: 10.1007/s002890050575.
- Puskas I, Meyerson S. Anomalous carbon numbers in cationic oligomers of propylene and butylenes. The Journal of Organic Chemistry. 1984;49(2):258–262. DOI: 10.1021/jo00176a009.
- Harrison JJ, Young DC, Mayne CL. 2D-INADEQUATE structural assignment of polybutene oligomers. The Journal of Organic Chemistry. 1997;62(3):693–699. DOI: 10.1021/jo961851l.
- Harrison JJ, Mijares CM, Cheng MT, Hudson J. Negative ion electrospray ionization mass spectrum of polyisobutenylsuccinic anhydride: implications for isobutylene polymerization mechanism. Macromolecules. 2002;35(7):2494–2500. DOI: 10.1021/ma011799h.
- Dimitrov P, Emert J, Hua J, Keki S, Faust R. Mechanism of isomerization in the cationic polymerization of isobutylene. Macromolecules. 2011;44(7):1831–1840. DOI: 10.1021/ma102645w.
- Mach H, Rath P. Highly reactive polyisobutylene as a component of a new generation of lubricant and fuel additives. Lubrication Science. 1999;11(2):175–185. DOI: 10.1002/ls.3010110205.
- Balzano F, Pucci A, Rausa R, Uccello‐Barretta G. Alder-ene addition of maleic anhydride to polyisobutene: nuclear magnetic resonance evidence for an unconventional mechanism. Polymer International. 2012;61(8):1256–1262. DOI: 10.1002/pi.4228.
- Kostjuk SV. Recent progress in the Lewis acid co-initiated cationic polymerization of isobutylene and 1,3-dienes. RSC Advances. 2015;5(17):13125–13144. DOI: 10.1039/C4RA15313H.
- Rach SF, Kuhn FE. On the way to improve the environmental benignity of chemical processes: novel catalysts for a polymerization process. Sustainability. 2009;1(1):35–42. DOI: 10.3390/su1010035.
- Boerzel P, Bronstert K, Hovemann F, inventors; BASF SE, assignee. Polyisobutenes. United States patent 4,152,499A. 1979 May 1. English.
- Rath P, Hoffmann F, Reuter P, Mach H, inventors; BASF SE, assignee. Preparation of polyisobutene. United States patent 5,191,044. 1993 March 2. English.
- Rath HP, inventors; BASF SE, assignee. Preparation of highly reactive polyisobutenes. United States patent 5,286,823. 1994 February 15. English.
- Rath HP, Kanne U, van Deyck F, inventors; BASF SE, assignee. Method for producing low-molecular, highly reactive polyisobutylene. United States patent 6,407,186B1. 2002 June 18. English.
- Kostjuk SV, Yeong HY, Voit B. Cationic polymerization of isobutylene at room temperature. Journal of Polymer Science. Part A: Polymer Chemistry. 2013;51(3):471–486. DOI: 10.1002/pola.26423.
- Hijazi AK, Yeong HY, Zhang Y, Herdtweck E, Nuyken O, Kühn FE. Isobutene polymerization using [CuII(NCMe)6]2+ with non-coordinating anions as catalysts. Macromolecular Rapid Communications. 2007;28(5):670–675. DOI: 10.1002/marc.200600139.
- Li Y, Voon LT, Yeong HY, Hijazi AK, Radhakrishnan N, Köhler K, et al. Solvent-ligated copper(II) complexes for the homopolymerization of 2-methylpropene. Chemistry a European Journal. 2008;14(26):7997–8003. DOI: 10.1002/chem.200701928.
- Hijazi AK, Radhakrishnan N, Jain KR, Herdtweck E, Nuyken O, Walter H-M, et al. Molybdenium(III) compounds as catalysts for 2-methylpropene polymerization. Angewandte Chemie. International Edition. 2007;46(38):7290–7292. DOI: 10.1002/anie.200700748.
- Diebl B, Li Y, Cokoja M, Kühn FE, Radhakrishnan N, Zschoche S, et al. Synthesis and application of molybdenium(III) complexes bearing weakly coordinating anions as catalysts of isobutylene polymerization. Journal of Polymer Science. Part A: Polymer Chemistry. 2010;48(17):3775–3786. DOI: 10.1002/pola.24162.
- Vasilenko IV, Frolov AN, Kostjuk SV. Cationic polymerization of isobutylene using AlCl3OBu2 as a co-initiator: synthesis of highly reactive polyisobutylene. Macromolecules. 2010;43(13):5503–5507. DOI: 10.1021/ma1009275.
- Kostjuk SV, Dubovik AYu, Vasilenko IV, Frolov AN, Kaputsky FN. Kinetic and mechanistic study of the quasiliving cationic polymerization of styrene in the 2-phenyl-2-propanol/AlCl3 · OBu2 initiating system. European Polymer Journal. 2007;43(3):968–979. DOI: 10.1016/j.eurpolymj.2006.12.011.
- Liu Q, Wu Y-H, Zhang Y, Yan P-F, Xu R-W. A cost-effective process for highly reactive polyisobutylenes via cationic polymerization coinitiated by AlCl3. Polymer. 2010;51(25):5960–5969. DOI: 10.1016/j.polymer.2010.10.012.
- Dimitrov P, Emert J, Faust R. Polymerization of isobutylene by AlCl3/ether complexes in nonpolar solvent. Macromolecules. 2012;45(8):3318–3325. DOI: 10.1021/ma3003856.
- Kanazawa A, Kanaoka S, Aoshima S. Major progress in catalysts for living cationic polymerization of isobutyl vinyl ether: effectiveness of a variety of conventional halides. Macromolecules. 2009;42(12):3965–3972. DOI: 10.1021/ma900116s.
- Shiman DI, Vasilenko IV, Kostjuk SV. Cationic polymerization of isobutylene by AlCl3/ether complexes in non-polar solvents: effect of ether structure on the selectivity of β-H elimination. Polymer. 2013;54(9):2235–2242. DOI: 10.1016/j.polymer.2013.02.039.
- Liu Q, Wu Y, Yan P, Zhang Y, Xu R. Polyisobutylene with high exo-olefin content via β-H elimination in the cationic polymerization of isobutylene with H2O/FeCl3/dialkyl ether initiating system. Macromolecules. 2011;44(7):1866–1875. DOI: 10.1021/ma1027017.
- Zhang LB, Wu YX, Zhou P, Xu RW. Synthesis of highly reactive polyisobutylene by selective polymerization with o-cresol/AlCl3 initiating system. Polymers for Advanced Technologies. 2012;23(3):522–528. DOI: 10.1002/pat.1908.
- Bartelson KJ, De P, Kumar R, Emert J, Faust R. Cationic polymerization of isobutylene by FeCl3/ether complexes in hexanes: an investigation of the steric and electronic effects of ethers. Polymer. 2013;54(18):4858–4863. DOI: 10.1016/j.polymer.2013.07.024.
- Miller DB. Reactions of alkylaluminum compounds with cyclic ethers. Journal of Organometallic Chemistry. 1968;14(2):253–259. DOI: 10.1016/S0022-328X(00)87664-0.
- Vasilenko IV, Nikishev PA, Shiman DI, Kostjuk SV. Cationic polymerization of isobutylene in toluene: toward well-defined exo-olefin terminated medium molecular weight polyisobutylenes under mild conditions. Polymer Chemistry. 2017;8:1417–1425. DOI: 10.1039/C6PY02131J.
- Vasilenko IV, Shiman DI, Kostjuk SV. Highly reactive polyisobutylenes via AlCl3OBu2-coinitiated cationic polymerization of isobutylene: effect of solvent polarity, temperature, and initiator. Journal of Polymer Science. Part A: Polymer Chemistry. 2012;50(4):750–758. DOI: 10.1002/pola.25830.
- Kostjuk SV, Vasilenko IV, Shiman DI, Frolov AN, Gaponik LV. Highly reactive polyisobutylenes via cationic polymerization of isobutylene by AlCl3/ether complexes in non-polar media: scope and limitations. Macromolecular Symposia. 2015;349:94–103. DOI: 10.1002/masy.201400016.
- Ramchandani RK, Wakharkar RD, Sudalai A. AlCl3-catalyzed regiospecific alkylation of aromatics with chlorobenzotrifluorides: a high yield preparation of 1,1-dichlorodiphenylmethanes. Tetrahedron Letters. 1996;37(23):4063–4064. DOI: 10.1016/0040-4039(96)00733-2.
- Guo A-R, Yang X-J, Yan P-F, Wu Y-X. Synthesis of highly reactive polyisobutylenes with exo-olefin terminals via controlled cationic polymerization with H2O/FeCl3/ iPrOH initiating system in nonpolar hydrocarbon media. Journal of Polymer Science. Part A: Polymer Chemistry. 2013;51(19):4200–4212. DOI: doi.org/10.1002/pola.26834.
- Kumar R, Dimitrov P, Bartelson KJ, Emert J, Faust R. Polymerization of isobutylene by GaCl3 or FeCl3/ether complexes in nonpolar solvents. Macromolecules. 2012;45(21):8598–8603. DOI: 10.1021/ma3017585.
- Kumar R, De P, Zheng B, Huang K-W, Emert J, Faust R. Synthesis of highly reactive polyisobutylene with FeCl3/ether complexes in hexane; kinetic and mechanistic studies. Polymer Chemistry. 2015;6:322–329. DOI: 10.1039/C4PY01039F.
- Kumar R, Emert J, Faust R. The polymerization of isobutylene catalyzed by FeCl3·i-Pr2O complex prepared in non-halogenated solvents. Polymer Bulletin. 2015;72(1):49–60. DOI: 10.1007/s00289-014-1258-3.
- Yang X-J, Guo A-R, Xu H-C, Wu Y-X. Direct synthesis of highly reactive polyisobutylenes via cationic polymerization of isobutylene co-initiated with TiCl4 in nonpolar hydrocarbon media. Journal of Applied Polymer Science. 2015;132(29):42232. DOI: 10.1002/app.42232.
Copyright (c) 2020 Journal of the Belarusian State University. Chemistry
This work is licensed under a Creative Commons Attribution-NonCommercial 4.0 International License.
The authors who are published in this journal agree to the following:
- The authors retain copyright on the work and provide the journal with the right of first publication of the work on condition of license Creative Commons Attribution-NonCommercial. 4.0 International (CC BY-NC 4.0).
- The authors retain the right to enter into certain contractual agreements relating to the non-exclusive distribution of the published version of the work (e.g. post it on the institutional repository, publication in the book), with the reference to its original publication in this journal.
- The authors have the right to post their work on the Internet (e.g. on the institutional store or personal website) prior to and during the review process, conducted by the journal, as this may lead to a productive discussion and a large number of references to this work. (See The Effect of Open Access.)