Cationic Polymerization of Isobutylene and C4 Mixed Feed Using Complexes of Lewis Acids with Ethers: A Comparative Study
- Corresponding author: Sergei V. Kostjuk, kostjuks@bsu.by;kostjuks@rambler.ru
Citation:
Dmitriy I. Shiman, Ivan A. Berezianko, Irina V. Vasilenko, Sergei V. Kostjuk. Cationic Polymerization of Isobutylene and C4 Mixed Feed Using Complexes of Lewis Acids with Ethers: A Comparative Study[J]. Chinese Journal of Polymer Science,
;2019, 37(9): 891-897.
doi:
10.1007/s10118-019-2290-4
Mach, H.; Rath, P. Highly reactive polyisobutene as a component of a new generation of lubricant and fuel additives. Lubr. Sci. 1999, 11-2, 175–185.
Kostjuk, S. V.; Yeong, H. Y.; Voit, B. Cationic polymerization of isobutylene at room temperature. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 471–486.
doi: 10.1002/pola.26423
Kostjuk, S. V. Recent progress in the Lewis acids co-initiated cationic polymerization of isobutylene and 1,3-dienes. RSC Adv. 2015, 5, 13125–13144.
doi: 10.1039/C4RA15313H
Li, Y.; Cokoja, M.; Kühn, F. E. Inorganic/organometallic catalysts and initiators involving weakly coordinating anions for isobutene polymerization. Coord. Chem. Rev. 2011, 255, 1541–1557.
doi: 10.1016/j.ccr.2010.12.007
Ummadisetty, S.; Storey, R. F. Quantitative synthesis of exo-olefin-terminated polyisobutylene: ether quenching and evaluation of various quenching methods. Macromolecules 2013, 46, 2049–2059.
doi: 10.1021/ma4000286
Lichtenthaler, M. R.; Higelin, A.; Kraft, A.; Hughes, S.; Steffani, A.; Plattner, D. A.; Slattery, J. M.; Krossing, I. Univalent gallium salts of weakly coordinating anions: Effective initiators/catalysts for the synthesis of highly reactive polyisobutylene. Organometallics 2013, 32, 6725–6735.
doi: 10.1021/om4005516
Guerrero, A.; Kulbaba, K.; Bochmann, M. " Highly reactive” poly(isobutene)s via room temperature polymerization with a new zinc-based initiator system. Macromolecules 2007, 40, 4124–4126.
doi: 10.1021/ma070430a
Burrington, J. D.; Johnson, J. R.; Pudelski, J. K. Cationic polymerization using heteropolyacid salt catalysts. Topics in Catal. 2003, 23, 175–181.
doi: 10.1023/A:1024892925055
Vasilenko, I. V.; Frolov, A. N.; Kostjuk, S. V. Cationic polymerization of isobutylene using AlCl3OBu2 as a co-initiator: Synthesis of highly reactive polyisobutylene. Macromolecules 2010, 43, 5503–5507.
doi: 10.1021/ma1009275
Liu, Q.; Wu, Y. X.; 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, 5960–5969.
doi: 10.1016/j.polymer.2010.10.012
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, 1866–1875.
doi: 10.1021/ma1027017
Guo, A. R.; Yang, X. J.; Yan, P. F.; Wu, Y. H. Synthesis of highly reactive polyisobutylenes with exo-olefin terminals via controlled cationic polymerization with H2O/FeCl3/iPrOH initiating system in nonpolar hydrocarbon media. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4200–4212.
doi: 10.1002/pola.26834
Kumar, R.; Dimitrov, P.; Bartelson, K. J.; Emert, J.; Faust, R. Polymerization of isobutylene by GaCl3 or FeCl3/ether complexes in nonpolar solvents. Macromolecules 2012, 45, 8598–8603.
doi: 10.1021/ma3017585
Bartelson, K. J.; 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, 4858–4863.
doi: 10.1016/j.polymer.2013.07.024
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. Polym. Chem. 2015, 6, 322–329.
doi: 10.1039/C4PY01039F
Yang, X. J.; Guo, A. R.; Xu, H. C.; Wu, Y. H. Direct synthesis of highly reactive polyisobutylenes via cationic polymerization of isobutylene co-initiated with TiCl4 in nonpolar hydrocarbon media. J. Appl. Polym. Sci. 2015, 132, 42232-42244.
Li, X.; Wu, Y.; Zhang, J.; Li, X.; Zhang, M.; Yang, D.; Wang, H.; Shang, Y.; Guo, W.; Yan, P. Syntesis of highly reacive polyisobutylene via cationic polymerization in ionic liquids: characteristisc and mechanism. Polym. Chem. 2019, 10, 201-208.
doi: 10.1039/C8PY01141A
Faust, R.; Dimitrov, P.; Kumar, R.; Emert, J.; Hua, J., 2013, U.S. Pat., 20130158217A1.
Vasilenko, I. V.; Shiman, D. I.; Kostjuk, S. V. Highly reactive polyisobutylenes via AlCl3OBu2-coinitiated cationic polymerization of isobutylene: effect of solvent polarity, temperature, and initiator. J. Polym. Sci., Part A: Polym. Chem. 2012, 50, 750–758.
doi: 10.1002/pola.25830
Kostjuk, S. V.; Vasilenko, I. V.; Shiman, D. I.; Frolov, A. N.; Gaponik, L. V. Highly reactive polyisobutylenes via cationic polymerization of isobutylene by AlCl3/ether complexes in non-polar media: scope and limitations. Macromol. Symp. 2015, 349, 94–103.
doi: 10.1002/masy.v349.1
Shiman, D. I.; Vasilenko, I. V.; Kostjuk, S. V. 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, 2235–2242.
doi: 10.1016/j.polymer.2013.02.039
Kumar, R.; Zheng, B.; Huang, K.-W.; Emeret, J.; Faust, R. Synthesis of highly reactive polyisobutylene catalyzed by EtAlCl2/bis(2-chloroethyl) ether soluble complex in hexanes. Macromolecules 2014, 47, 1959–1965.
doi: 10.1021/ma500042f
Banerjee, S.; Emert, J.; Wright, P.; Skourlis, T.; Severt, R.; Faust, R. Polymerization of isobutylene catalyzed by EtAlCl2/bis(2-chloroethyl) ether complex in steel vessels. Polym. Chem. 2015, 6, 4902–4910.
doi: 10.1039/C5PY00624D
S Banerjee, S.; Jha, B. N.; De, P.; Emert, J.; Faust, R. Kinetic and mechanistic studies of the polymerization of isobutylene catalyzed by EtAlCl2/bis(2-chloroethyl) ether complex in hexanes. Macromolecules 2015, 48, 5474–5480.
doi: 10.1021/acs.macromol.5b01441
Rajasekhar, T.; Emert, J.; Faust, R. Synthesis of highly reactive polyisobutylene by catalytic chain transfer in hexanes at elevated temperatures: determination of the kinetic parameters Polym. Chem. 2017, 8, 2852–2859.
Rajasekhar, T.; Haldar, U.; Emert, J.; Dimitrov, P.; Severt, R.; Faust R. Catalytic chain transfer polymerization of isobutylene: the role of nucleophilic impurities. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 3697–3704.
doi: 10.1002/pola.v55.22
Rajasekhar, T.; Emert, J.; Wolf, L. M.; Faust, R. Controlled catalytic chain transfer polymerization of isobutylene in the presence of tert-butanol as exo-enhancer. Macromolecules 2018, 51, 3041–3049.
doi: 10.1021/acs.macromol.8b00327
Vasilenko, I. V.; Shiman, D. I.; Kostjuk, S. V. Alkylaluminum dichloride-ether complexes which are fully soluble in hydrocarbons as catalysts for the synthesis of exo-olefin terminated polyisobutylene at room temperature. Polym. Chem. 2014, 5, 3855–3866.
doi: 10.1039/C4PY00069B
Shiman, D. I.; Vasilenko, I. V.; Kostjuk, S. V. Cationic polymerization of isobutylene by complexes of alkylaluminum dichlorides with diisopropyl ether: an activating effect of water. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 2386–2393.
doi: 10.1002/pola.v52.16
Vasilenko, I. V.; Nikishev, P. A.; Shiman, D. I.; Kostjuk, S. V. Cationic polymerization of isobutylene in toluene: toward well-defined exo-olefin terminated medium molecular weight polyisobutylenes under mild conditions. Polym. Chem. 2017, 8, 1417–1425.
doi: 10.1039/C6PY02131J
Shiman, D. I.; Vasilenko, I. V.; Kostjuk, S. V. Cationic polymerization of isobutylene catalyzed by iBuAlCl2 in the presence of ethers: effect of catalyst pre-activation and mixture of two ethers. Polymer 2016, 99, 633–641.
doi: 10.1016/j.polymer.2016.07.014
Zhu, S.; Lu, Y.; Faust, R. Micromixing enhanced synthesis of HRPIBs catalyzed by EADC/(bis(2-chloroethyl)ether complex. RSC Adv. 2017, 7, 27629–27636.
doi: 10.1039/C7RA05246D
Vasilenko, I. V.; Berezianko, I. A.; Shiman, D. I.; Kostjuk, S. V. New catalyst for the synthesis of highly reactive polyisobutylene: chloroaluminate imidazole-based ionic liquid in the presence of diisopropyl ether. Polym. Chem. 2016, 7, 5615–5619.
doi: 10.1039/C6PY01325B
Berezianko, I. A.; Vasilenko, I. V.; Kostjuk, S. V. Acidic imidazole-based ionic liquids in the presence of diisopropyl ether as catalysts for the synthesis of highly reactive polyisobutylene: effect of ionic liquid nature, catalyst aging, and sonication. Polymer 2018, 145, 382–390.
doi: 10.1016/j.polymer.2018.04.059
Zhang, L. B.; Wu, Y. X.; Zhou, P.; Xu, R. W. Synthesis of highly reactive polyisobutylene by selective polymerization with o-cresol/AlCl3 initiating system. Polym. Adv. Technol. 2012, 23, 522–528.
doi: 10.1002/pat.v23.3
Zhang, L. B.; Wu, Y. X.; Zhou, P.; Wu, G. Y.; Yang, W. T.; Yu, D. S. Synthesis of highly reactive polyisobutylenes with BF3·cyclohexanol initiating system. Chinese J. Polym. Sci. 2011, 29, 360–367.
doi: 10.1007/s10118-011-1042-x
Rajasekhar, T.; Haldar, U.; De, P.; Emert, J.; Faust, R. Cationic copolymerization and multicomponent polymerization of isobutylene with C4 olefins. Macromolecules. 2017, 50, 8325–8333.
doi: 10.1021/acs.macromol.7b01941
De, P.; Faust, R. Relative reactivity of C4 olefins toward the polyisobutylene cation. Macromolecules 2006, 39, 6861–6870.
doi: 10.1021/ma0611725
Hailong He , Wenbing Wang , Wenmin Pang , Chen Zou , Dan Peng . Double stimulus-responsive palladium catalysts for ethylene polymerization and copolymerization. Chinese Chemical Letters, 2024, 35(7): 109534-. doi: 10.1016/j.cclet.2024.109534
Jinjie Lu , Qikai Liu , Yuting Zhang , Yi Zhou , Yanbo Zhou . Antibacterial performance of cationic quaternary phosphonium-modified chitosan polymer in water. Chinese Chemical Letters, 2024, 35(9): 109406-. doi: 10.1016/j.cclet.2023.109406
Rongjian Chen , Jiahui Liu , Caixia Lin , Yuanming Li , Yanhou Geng , Yaofeng Yuan . Synthesis and properties of tetraphenylethene cationic cyclophanes based on o-carborane skeleton. Chinese Chemical Letters, 2024, 35(12): 110074-. doi: 10.1016/j.cclet.2024.110074
Zhengzhong Zhu , Shaojun Hu , Zhi Liu , Lipeng Zhou , Chongbin Tian , Qingfu Sun . A cationic radical lanthanide organic tetrahedron with remarkable coordination enhanced radical stability. Chinese Chemical Letters, 2025, 36(2): 109641-. doi: 10.1016/j.cclet.2024.109641
Chong Liu , Ling Li , Jiahui Gao , Yanwei Li , Nazhen Zhang , Jing Zang , Cong Liu , Zhaopei Guo , Yanhui Li , Huayu Tian . The study of antibacterial activity of cationic poly(β-amino ester) regulating by amphiphilic balance. Chinese Chemical Letters, 2025, 36(2): 110118-. doi: 10.1016/j.cclet.2024.110118
Bing Niu , Honggao Huang , Liwei Luo , Li Zhang , Jianbo Tan . Coating colloidal particles with a well-defined polymer layer by surface-initiated photoinduced polymerization-induced self-assembly and the subsequent seeded polymerization. Chinese Chemical Letters, 2025, 36(2): 110431-. doi: 10.1016/j.cclet.2024.110431
Juan CHEN , Guoyu YANG . A porous-layered aluminoborate built by mixed oxoboron clusters and AlO4 tetrahedra. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 193-200. doi: 10.11862/CJIC.20240341
Haoran Shi , Jiaxin Wang , Yuqin Zhu , Hongyang Li , Guodong Ju , Lanlan Zhang , Chao Wang . Highly selective α-C(sp3)-H arylation of alkenyl amides via nickel chain-walking catalysis. Chinese Chemical Letters, 2024, 35(7): 109333-. doi: 10.1016/j.cclet.2023.109333
Xu Zhang , Jiang Li , Kai-Zhou Lu , Ya-Nan Yang , Jian-Shuang Jiang , Xiang Yuan , Zi-Ming Feng , Fei Ye , Pei-Cheng Zhang . Neosophoflavonoids A–C, A class of highly oxidized hybrid flavonoids from Sophora flavescens with antidiabetic effects. Chinese Chemical Letters, 2024, 35(10): 109456-. doi: 10.1016/j.cclet.2023.109456
Xue Zhao , Mengshan Chen , Dan Wang , Haoran Zhang , Guangzhi Hu , Yingtang Zhou . Ultrafine nano-copper derived from dopamine polymerization & synchronous adsorption achieve electrochemical purification of nitrate to ammonia in complex water environments. Chinese Chemical Letters, 2024, 35(8): 109327-. doi: 10.1016/j.cclet.2023.109327
Jian Song , Shenghui Wang , Qiuge Liu , Xiao Wang , Shuo Yuan , Hongmin Liu , Saiyang Zhang . N-Benzyl arylamide derivatives as novel and potent tubulin polymerization inhibitors against gastric cancers: Design, structure–activity relationships and biological evaluations. Chinese Chemical Letters, 2025, 36(2): 109678-. doi: 10.1016/j.cclet.2024.109678
Yingying Yan , Wanhe Jia , Rui Cai , Chun Liu . An AIPE-active fluorinated cationic Pt(Ⅱ) complex for efficient detection of picric acid in aqueous media. Chinese Chemical Letters, 2024, 35(5): 108819-. doi: 10.1016/j.cclet.2023.108819
Na Wang , Wang Luo , Huaiyi Shen , Huakai Li , Zejiang Xu , Zhiyuan Yue , Chao Shi , Hengyun Ye , Leping Miao . Crystal engineering regulation achieving inverse temperature symmetry breaking ferroelasticity in a cationic displacement type hybrid perovskite system. Chinese Chemical Letters, 2024, 35(5): 108696-. doi: 10.1016/j.cclet.2023.108696
Ziqin Li , Kai Hao , Longwei Xiang , Huayu Tian . Cationic covalent organic framework nanocarriers integrating both efficient gene silencing and real-time gene detection. Chinese Chemical Letters, 2025, 36(4): 109943-. doi: 10.1016/j.cclet.2024.109943
Zhongyu Wang , Lijun Wang , Huaixin Zhao . DNA-based nanosystems to generate reactive oxygen species for nanomedicine. Chinese Chemical Letters, 2024, 35(11): 109637-. doi: 10.1016/j.cclet.2024.109637
Xianchen Hu , Junli Yang , Fang Gao , Zhiyong Zhao , Simin Liu . Highly selective [4+4] cross-photodimerization of (4a-azonia)anthracenes driven by confinement of D-A hetero-guest pair in cucurbit[10]uril host. Chinese Chemical Letters, 2025, 36(3): 109967-. doi: 10.1016/j.cclet.2024.109967
Luyu Zhang , Zirong Dong , Shuai Yu , Guangyue Li , Weiwen Kong , Wenjuan Liu , Haisheng He , Yi Lu , Wei Wu , Jianping Qi . Ionic liquid-based in situ dynamically self-assembled cationic lipid nanocomplexes (CLNs) for enhanced intranasal siRNA delivery. Chinese Chemical Letters, 2024, 35(7): 109101-. doi: 10.1016/j.cclet.2023.109101
Zhenyu Hu , Zhenchun Yang , Shiqi Zeng , Kun Wang , Lina Li , Chun Hu , Yubao Zhao . Cationic surface polarization centers on ionic carbon nitride for efficient solar-driven H2O2 production and pollutant abatement. Chinese Chemical Letters, 2024, 35(10): 109526-. doi: 10.1016/j.cclet.2024.109526
Fei Yin , Erli Yang , Xue Ge , Qian Sun , Fan Mo , Guoqiu Wu , Yanfei Shen . Coupling WO3−x dots-encapsulated metal-organic frameworks and template-free branched polymerization for dual signal-amplified electrochemiluminescence biosensing. Chinese Chemical Letters, 2024, 35(4): 108753-. doi: 10.1016/j.cclet.2023.108753
Dan Ouyang , Huan Huang , Yanting He , Jiajing Chen , Jiali Lin , Zhuling Chen , Zongwei Cai , Zian Lin . Utilization of hydralazine as a reactive matrix for enhanced detection and on-MALDI-target derivatization of saccharides. Chinese Chemical Letters, 2024, 35(5): 108885-. doi: 10.1016/j.cclet.2023.108885