Synthesis of mono-, di- and trifunctional hydroxyl-terminated polyisobutylenes

  • Mikalai S. Bohdan Research Institute for Physical Chemical Problems, Belarusian State University, 14 Lieningradskaja Street, Minsk 220006, Belarus; Belarusian State University, 4 Niezaliezhnasci Avenue, Minsk 220030, Belarus
  • Dmitriy I. Shiman Research Institute for Physical Chemical Problems, Belarusian State University, 14 Lieningradskaja Street, Minsk 220006, Belarus
  • Ludmila V. Gaponik Research Institute for Physical Chemical Problems, Belarusian State University, 14 Lieningradskaja Street, Minsk 220006, Belarus
  • Sergei V. Kostjuk Research Institute for Physical Chemical Problems, Belarusian State University, 14 Lieningradskaja Street, Minsk 220006, Belarus; Belarusian State University, 4 Niezaliezhnasci Avenue, Minsk 220030, Belarus

Abstract

An effective method for the synthesis of polyisobutylene with terminal hydroxyl groups was developed. The method is based on the combination of controlled cationic polymerisation of isobutylene in the presence of FeCl3 ⋅ 1.4iPrOH as co-initiator and in situ alkylation of phenol by polyisobutylene catalysed by iron(III) and aluminium chlorides. To achieve high alkylation rate and functionalisation degree in the process of polyisobutylene modification the one should proceed at room temperature and the usage of excesses of phenol complexes with chosen Lewis acids. Mono-, di- and trifunctional hydroxyl-terminated polyisobutylenes were synthesised in a broad range of molecular weights (1000–10000 g/mol) with a low polydispersity (Mw /Mn = 1.2).

Author Biographies

Mikalai S. Bohdan, Research Institute for Physical Chemical Problems, Belarusian State University, 14 Lieningradskaja Street, Minsk 220006, Belarus; Belarusian State University, 4 Niezaliezhnasci Avenue, Minsk 220030, Belarus

junior researcher at the laboratory of catalysis of polymerisation processes, Research Institute for Physical Chemical Problems, Belarusian State University, and assistant at the department of macromolecular compounds, faculty of chemistry, Belarusian State University

Dmitriy I. Shiman, Research Institute for Physical Chemical Problems, Belarusian State University, 14 Lieningradskaja Street, Minsk 220006, Belarus

PhD (chemistry), docent; leading researcher at the laboratory of catalysis of polymerisation processes

 

Ludmila V. Gaponik, Research Institute for Physical Chemical Problems, Belarusian State University, 14 Lieningradskaja Street, Minsk 220006, Belarus

PhD (chemistry); senior researcher at the laboratory of catalysis of polymerisation processes

 

Sergei V. Kostjuk, Research Institute for Physical Chemical Problems, Belarusian State University, 14 Lieningradskaja Street, Minsk 220006, Belarus; Belarusian State University, 4 Niezaliezhnasci Avenue, Minsk 220030, Belarus

doctor of science (chemistry), full professor; chief researcher at the laboratory of catalysis of polymerisation processes, Research Institute for Physical Chemical Problems, Belarusian State University, and head of the department of macromolecular compounds, faculty of chemistry, Belarusian State University

 

References

  1. Brandrup J, Immergut EH, McDowell W, editors. Polymer handbook. 2nd edition. New York: John Wiley & Sons; 1975. [1408 p.].
  2. Le Floch P, Meixuanzi S, Tang J, Liu J, Suo Z. Stretchable seal. ACS Applied Materials and Interfaces. 2018;10(32):27333–27343. DOI: 10.1021/acsami.8b08910.
  3. Pinchuk L, Wilson GJ, Barry JJ, Schoephoerster RT, Parel J-M, Kennedy JP. Medical applications of poly(styrene-block-isobutylene-block-styrene) («SIBS»). Biomaterials. 2008;29(4):448–460. DOI: 10.1016/j.biomaterials.2007.09.041.
  4. Wang KS, Osborne JL, Hunt JA, Nelson MK, inventors; Alza Corporation, assignee. Polyisobutylene adhesives for transdermal devices. United States patent US 5508038. 1996 April 16.
  5. Zirbs R, Binder W, Gahleitner M, Machl D. «Grafting from»-living cationic polymerization of poly(isobutylene) from silicananoparticle surfaces. Macromolecular Symposia. 2007;254:93–96. DOI: 10.1002/masy.200750814.
  6. Puskas JE, Chen Y, Dahman Y, Padavan D. Polyisobutylene-based biomaterials. Journal of Polymer Science. Part A, Polymer Chemistry. 2004;42(13):3091–3109. DOI: 10.1002/pola.20114.
  7. Tripathy R, Ojha U, Faust R. Polyisobutylene modified bisphenol A diglycidyl ether based epoxy resins possessing improved mechanical properties. Macromolecules. 2011;44(17):6800–6809. DOI: 10.1021/ma201081y.
  8. 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 / i PrOH initiating system in nonpolar hydrocarbon media. Journal of Polymer Science. Part A, Polymer Chemistry. 2013;51(19):4200–4212. DOI: 10.1002/pola.26834.
  9. 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.
  10. 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(2):322–329. DOI: 10.1039/C4PY01039F.
  11. Yan P-F, Guo A-R, Liu Q, Wu Y-X. Living cationic polymerization of isobutylene coinitiated by FeCl3 in the presence of isopropanol. Journal of Polymer Science. Part A, Polymer Chemistry. 2012;50(16):3383–3392. DOI: 10.1002/pola.26126.
  12. Bohdan M, Shiman DI, Nikishau PA, Vasilenko IV, Kostjuk SV. Quasiliving carbocationic polymerization of isobutylene using FeCl3 as an efficient and water-tolerant Lewis acid: synthesis of well-defined telechelic polyisobutylenes. Polymer Chemistry. 2022;13(42):6010–6021. DOI: 10.1039/D2PY01106A.
  13. Szabό Á, Wacha A, Thomann R, Szarka G, Bόta A, Béla Iván. Synthesis of poly(methyl methacrylate)-poly(poly(ethylene glycol)methacrylate)-polyisobutylene ABCBA pentablock copolymers by combining quasiliving carbocationic and atom transfer radical polymerizations and characterization thereof. Journal of Macromolecular Science. Part A, Pure and Applied Chemistry. 2015;52(4):252–259. DOI: 10.1080/10601325.2015.1007268.
  14. Di Serio M, Garaffa R, Santacesaria E. Hydroformylation of polyisobutene. Journal of Molecular Catalysis. 1991;69(1):1–14. DOI: 10.1016/0304-5102(91)80099-O.
  15. Storey RF, Lee Y. Sulfonation of tert-alkyl chlorides: application to the tert-chloride-terminated polyisobutylene system. Journal of Polymer Science. Part A, Polymer Chemistry. 1991;29(3):317–325. DOI: 10.1002/pola.1991.080290304.
  16. 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.
  17. Boileau S, Mazeaud-Henri B, Blackborow R. Reaction of functionalised 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.
  18. Kulai I, Karpus A, Bergbreiter DE, Al-Hashimi M, Bazzi HS. Organocatalytic Michael addition as a method for polyisobutylene chain‐end functionalization. Macromolecular Rapid Communications. 2020;41(17):2000382. DOI: 10.1002/marc.202000382.
  19. Pásztói B, Trötschler TM, Szabó Á, Szarka G, Kerscher B, Mülhaupt R, et al. Synthesis of tosyl- and nosyl-ended polyisobutylenes with high extent of functionalities: the effect of reaction conditions. Polymers. 2020;12(11):2504. DOI: 10.3390/polym12112504.
  20. Samunual P, Bergbreiter DE. SN 2 reactions in hydrocarbon solvents using ammonium-terminated polyisobutylene oligomers as phase-solubilizing agents and catalysts. The Journal of Organic Chemistry. 2018;83(18):11101–11107. DOI: 10.1021/acs.joc.8b01718.
  21. Castano M, Alvarez A, Becker ML, Puskas JE. Synthesis of polyisobutylene-polycaprolactone block copolymers using enzyme catalysis. Express Polymer Letters. 2016;10(8):693–700. DOI: 10.3144/expresspolymlett.2016.62.
  22. Nikishau PA, Ksendzov EA, Shiman DI, Gaponik LV, Kostjuk SV. Synthesis of functionalized polyisobutylene and its block copolymers with D,L-lactide. Journal of the Belarusian State University. Chemistry. 2019;2:40 –50. Russian. DOI: 10.33581/2520-257X-2019-2-40-50.
  23. Toth K, Kekec NC, Nugay N, Kennedy JP. Polyisobutylene-based polyurethanes. VIII. Polyurethanes with —O—S—PIB— S—O—soft segments. Journal of Polymer Science. Part A, Polymer Chemistry. 2016;54(8):1119–1131. DOI: 10.1002/pola.27951.
  24. Prudnikau A, Shiman DI, Ksendzov E, Harwell J, Bolotina EA, Nikishau PA, et al. Design of cross-linked polyisobutylene matrix for efficient encapsulation of quantum dots. Nanoscale Advances. 2021;3(5):1443–1454. DOI: 10.1039/D0NA01012J.
  25. Morgan DL, Storey RF. End-quenching of quasi-living isobutylene polymerizations with alkoxybenzene compounds. Macromolecules. 2009;42(18):6844 –6847. DOI: 10.1021/ma901479n.
  26. 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.
  27. Lange A, Csihony S, Kleiner M, inventors; BASF SE, assignee. Process for preparing functionalized polyisobutenes and derivatives thereof. United States patent US 2015/0315309 A1. 2015 November 5.
  28. Gaffen JR, Bentley JN, Torre LC, Chu C, Baumgartner T, Caputo CB. A simple and effective method of determining Lewis acidity by using fluorescence. Chem. 2019;5(6):1567–1583. DOI: 10.1016/j.chempr.2019.03.022.
Published
2024-03-20
Keywords: cationic polymerisation, polyisobutylene, alkylation, phenol
Supporting Agencies The research was supported by the Ministry of Education of the Republic of Belarus (assignment 2.1.01.03 of the state programme of scientific research «Chemical processes, reagents and technologies, bioregulators and bioorgchemistry», state registration No. 20210512).
How to Cite
Bohdan, M. S., Shiman, D. I., Gaponik, L. V., & Kostjuk, S. V. (2024). Synthesis of mono-, di- and trifunctional hydroxyl-terminated polyisobutylenes. Journal of the Belarusian State University. Chemistry, 1, 51-62. Retrieved from https://journals.bsu.by/index.php/chemistry/article/view/6049
Issue
No 1 (2024): Journal of the Belarusian State University. Chemistry
Section
Original Articles

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