In this work, an experiment was conducted to investigate the cationic polymerization of isobutylene (IB) with AlCl3 as the initiator; the experiment was carried out with C4 mixed gas as the raw material. The initial content of IB in the mixed C4 gas was 22% and the proportion of isobutylene in the mixed C4 was changed later by continuously adding pure IB. A suitable amount of the co-initiator toluene (C7H8) and a nucleophile such as diethyl ether (C4H10O) or ethyl acetate (C4H8O2) are suitably cited. We carried out experiments to investigate the effects of different initiator systems, different temperatures, different initiator additions, and other factors on polymerization products. The results show that we choose the initiation system: AlCl3 is 1% of the mass of isobutylene, and the two nucleophiles of diethyl ether and ethyl acetate account for 8% and 10% of the mass of AlCl3, respectively, at a reaction temperature of −30 °C, and the reaction time was controlled at 30 min. It is possible to obtain a relatively low molecular weight (Mn: 1000–4000) of a polyisobutylene product, a highly active polyisobutylene with a polydispersity coefficient (PDI) < 2.3 and an exo-olefin content of >70%. Through several experiments, we explored the impact of changing the experimental conditions on the polymerization products, and then provided a theoretical basis for the next industrial production.
This is a preview of subscription content, log in to check access.
Buy single article
Instant access to the full article PDF.
Price includes VAT for USA
Subscribe to journal
Immediate online access to all issues from 2019. Subscription will auto renew annually.
This is the net price. Taxes to be calculated in checkout.
Kostjuk SV, Yeong HY, Voit B (2013) Cationic polymerization of isobutylene at room temperature[J]. J Polym Sci A Polym Chem 51(3):471–486
Kumar R, Dimitrov P, Bartelson K-J et al (2012) Polymerization of isobutyleneby GaCl3 or FeCl3/ether complexes in nonpolar solvents[J]. Macromolecules 45(21):8598–8603
Faust R, Kennedy JP (1987) Living polymerization of isobutylene[M] advances in Polyolefins. Springer US
Kresge EN, Schatz R-H, Wang H-C (1985) Encyclopedia of polymer science and engineering. Wiley, New York, pp 423–450
Puskas I, Banas E-M, Nerheim A-G (2010) The nature of the double bond in low molecular weight polyisobutylenes and “polybutene” copolymers[J]. Journal of Polymer Science Polymer Symposia 56(1):191–202
Berrone P, Surroca J, Tribó JA. (1970) The present invention relates to new isobutene polymers and to a process for their manufacture[J]
Vasilenko IV, Shiman DI, Kostjuk SV (2012) Highly reactive polyisobutylenes via AlCl3OBu2-coinitiated cationic polymerization of isobutylene: effect of solvent polarity, temperature, and initiator[J]. J Polym Sci A Polym Chem 50(4):750–758
Vasilenko IV, Shiman DI, Kostjuk SV (2014) Alkylaluminum dichloride–ether complexes which are fully soluble in hydrocarbons as catalysts for the synthesis of exo-olefin terminated polyisobutylene at room temperature[J]. Polym Chem 5(12):3855
Vierle M, Zhang Y, Herdtweck E et al (2010) Highly reactive polyisobutenes prepared with manganese(II) complexes as initiators.[J]. Angew Chem 42(11):1307–1310
Radhakrishnan N, Hijazi AK, Komber H et al (2010) Synthesis of highly reactive polyisobutylenes using solvent-ligated manganese(II) complexes as catalysts[J]. Journal of Polymer Science Part A Polymer Chemistry 45(23):5636–5648
Zhang LB, Wu YX, Zhou P et al (2012) Synthesis of highly reactive polyisobutylene by selective polymerization with cresol/AlClinitiating system[J]. Polym Adv Technol 23(3):522–528
Shiman D I, Vasilenko I V, Kostjuk SV (2016). Cationic polymerization of isobutylene catalyzed by iBuAlCl2 in the presence of ethers: effect of catalyst pre-activation and mixture of two ethers[J]. Polymer, 2016:S0032386116305699
Kunal K, Paluch M, Roland CM et al (2008) Polyisobutylene: A most unusual polymer[J]. Journal of Polymer Science, Part B (Polymer Physics) 46(13):1390–1399
Puskas JE, Santos LD, Kaszas G (2006) Innovation in material science: The chameleon block copolymer[J]. Journal of Polymer Science, Part A (Polymer Chemistry) 44(21):6494–6497
Li Y, Wu Y, Xu X et al (2007) Electron-pair-donor reaction order in the cationic polymerization of isobutylene coinitiated by AlCl3[J]. Journal of Polymer Science Part A Polymer Chemistry 45(14):3053–3061
Puskas JE, Chen Y, Dahman Y et al (2004) Polyisobutylene-based biomaterials[J]. Journal of Polymer Science, Part A (Polymer Chemistry) 42(13):3091–3109
Byrikhin VS, Nesmelov AI, Murachev VB et al (1993) Cationic polymerization of hydrocarbon monomers under the action of acyl halide complexes with Lewis acids[J]. Russ Chem Bull 42(5):837–840
Kanazawa A, Kanaoka S, Aoshima S (2010) A stepping stone to stereospecific living cationic polymerization: cationic polymerization of vinyl ethers using iron(II) sulfate[J]. Journal of Polymer Science Part A Polymer Chemistry 48(16):3702–3708
Li BT, Wu YX, Cheng H et al (2012) Synthesis of linear isotactic-rich poly(p-methylstyrene) via cationic polymerization coinitiated with AlCl3[J]. Polymer:53(17)
Kumar R (2013) Cationic polymerization of isobutylene by FeCl3/ether complexes in hexanes: an investigation of the steric and electronic effects of ethers[J]. Polymer 54(18):4858–4863
Vierle M, Zhang Y, Santos AM et al (2005) Solventigated manganese(II) complexes for the Homopolymerization of isobutene and the copolymerization of isobutene and isoprene[J]. Chemistry 10(24):6323–6332
Karatasos K, Ryckaert J-P, Ricciardi R et al (2002) Methyl dynamics and β-relaxation in Polyisobutylene: comparison between experiment and molecular dynamics simulations[J]. Macromolecules 35(4):1451–1462
Grobelny Z, Golba S, Justyna J-S (2019) Characterization of new polyether-diols with different molar masses and modality prepared by ring opening polymerization of oxiranes initiated with anhydrous potassium hydroxide[J]. J Polym Res 26:274
Liu Q, Wu YX, Zhang Y et al (2010) A cost-effective process for highly reactive polyisobutylenes via cationic polymerization coinitiated by AlCl3[J]. Polymer 51(25):5960–5969
Li Y, Voon LT, Yeong HY, Hijazi AK, Radhakrishnan N, Köhler K, Voit B, Nuyken O, Kühn FE (2008) Solvent-ligated copper(II) complexes for the Homo polymerization of 2-Methylpropene[J]. Chemistry 14(26):7997–8003
Koo K, Marks TJ (1999) Silicon-modified Ziegler−Natta polymerization. Catalytic Approachesto Silyl-capped and Silyl-linked Polyolefins using “single-site”cationic Ziegler−Natta catalysts[J]. J Am Chem Soc 121(38):8791–8802
Ummadisetty S, Morgan DL, Stokes CD et al (2011) Synthesis exo-olefin terminated polyisobutylene by sulfide base quenching of living Polyisobutylene[J]. Macromolecules 44(20):7901–7910
Baojiao G, Dandan Z, Yanbin L (2018) Constituting a special redox surface-initiating system and realizing graft-polymerization of GMA on polysulfone microfiltration membrane[J]. J Polym Res 25(7):158
Morgan DL, Harrison JJ, Stokes CD et al (2011) Kinetics and mechanism of end-quenching of quasiliving polyisobutylene with sterically hindered bases[J]. Macromolecules 44(8):2438–2443
The authors acknowledge the Natural Science Foundation of Shandong Province, China (ZR2017QB006), and the Focus on research and development plan in Yantai city (2018XSCC038).
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
About this article
Cite this article
Deng, S., Tian, H., Sun, D. et al. Method for initiating cationic polymerization of isobutylene by AlCl3. J Polym Res 27, 55 (2020). https://doi.org/10.1007/s10965-020-2024-x
- Mixing C4 gas
- Nucleophilic reagent