Synthesis of multiarm star block copolymer based on host-guest inclusion complexation

Year 2022, Volume: 2 Issue: 1, 1 - 15, 31.01.2022

Neşe Çakır Yiğit Gürkan Hızal Ümit Tunca

https://doi.org/10.29228/JIENS.54191

Abstract

Supramolecular multiarm star block copolymer ((CD-PEG)p-(Ada-PS)n-polyDVB) was prepared by host-guest interaction of -cyclodextrin ( -CD) end functionalized polyethylene glycol (-CD-PEG) and adamantane peripherally functionalized multiarm star polymer ((Ada-PS)n-polyDVB). The -CD-PEG was synthesized by copper-catalyzed azide/alkyne cycloaddition reaction (CuAAC) of alkyne functional PEG with mono azide functional β-CD (β-CD-N3). Adamantane functional polystyrene (Ada-PS) was prepared by atom transfer radical polymerization (ATRP) of styrene (St) and was allowed to react with divinyl benzene (DVB) as a linking agent giving (Ada-PS)n-polyDVB multiarm star polymer. The structures of -CD-PEG and (Ada-PS)n-polyDVB multiarm star formation were determined by 1H NMR and GPC. 2D ROESY NMR and DLS analysis of (CD-PEG)p-(Ada-PS)n-polyDVB were carried out to validate the formation of the inclusion complex. The evidence of increased molecular weights and size distributions supported the supramolecular multiarm star block copolymer formation.

Keywords

Star Polymer, ATRP, CuAAC click, Host-guest interaction

References

• Gao H, Matyjaszewski K (2007) Low-polydispersity star polymers with core functionality by crosslinking macromonomers using functional ATRP initiators. Macromolecules 40(3):399–401. https://doi.org/10.1021/ma062640d
• Gao H, Matyjaszewski K (2008) Synthesis of star polymers by a new, ‘‘Core-First’’ method: sequential polymerization of cross-linker and monomer. Macromolecules 41(4):1118–1125. https://doi.org/10.1021/ma702560f
• Hadjichristidis N (1999) Synthesis of miktoarm star (-star) polymers. J Polym Sci, Part A: Polym Chem 37(7):857–871. https://doi.org/10.1002/(SICI)1099-0518(19990401)37:7<857::AID-POLA1>3.0.CO;2-P
• Hadjichristidis N, Pitsikalis M, Pispas S, Iatrou H (2001) Polymers with complex architecture by living anionic polymerization. Chem Rev 101(12):3747–3792. https://doi.org/10.1021/cr9901337
• Blencowe A, Tan JF, Goh TK, Qiao GG (2009) Core cross-linked star polymers via controlled radical polymerisation. Polymer 50(1):5–32. https://doi.org/10.1016/j.polymer.2008.09.049
• Ren JM, McKenzie TG, Fu Q, Wong EHH, Xu J, An Z, Shanmugam S, Davis TP, Boyer C, Qiao GG (2016) Star polymers. Chem Rev 116(12):6743–6836. https://doi.org/10.1021/acs.chemrev.6b00008
• Kuckling D, Wycisk A (2013) Stimuli-responsive star polymers. J Polym Sci, Part A: Polym Chem 51(14):2980–2994. https://doi.org/10.1002/pola.26696
• Altintas O, Vogt AP, Barner-Kowollik C, Tunca U (2012) Constructing star polymers via modular ligation strategies. Polym Chem UK 3(1):34. https://doi.org/10.1039/c1py00249j
• Altintas, O, Schulze-Suenninghausen, D, Luy, B, Barner-Kowollik, C (2013). Facile Preparation of Supramolecular H-Shaped (Ter)polymers via Multiple Hydrogen Bonding. Acs Macro Lett 2(3):211-216. https://doi.org/10.1021/mz400066r
• Fustin, C. A, Guillet, P, Schubert, U. S, Gohy, J. F (2007). Metallo-Supramolecular Block Copolymers. Advanced Materials 19(13):1665-1673. https://doi.org/10.1002/adma.200602170
• Chen, G, Jiang, M (2011). Cyclodextrin-based inclusion complexation bridging supramolecular chemistry and macromolecular self-assembly. Chemical Society reviews 40(5):2254-2266. https://doi.org/10.1039/C0CS00153H
• Zou, C, Zhao, P, Ge, J, Lei, Y, Luo, P (2012). -Cyclodextrin modified anionic and cationic acrylamide polymers for enhancing oil recovery. Carbohydr. Polym 87(1):607–613. https://doi.org/10.1016/j.carbpol.2011.08.031
• Xiao, H, Cezar, N (2005). Cationic-modified cyclodextrin nanosphere/anionic polymer as flocculation/sorption systems. Colloid Interface Sci 283(2):406–413. https://doi.org/10.1016/j.jcis.2004.09.008
• Stadermann, J, Komber, H, Erber, M, Däbritz, F, Ritter, H, Voit, B (2011). Diblock Copolymer Formation via Self-Assembly of Cyclodextrin and Adamantyl End-Functionalized Polymers. Macromolecules 44(9):3250-3259. https://doi.org/10.1021/ma200048a
• Zeng, J, Shi, K, Zhang, Y, Sun, X, Zhang, B (2008). Construction and micellization of a noncovalent double hydrophilic block copolymer. Chem Commun 32:3753-3755. https://doi.org/10.1039/B806858E
• Liu, H, Zhang, Y, Hu, J, Li, C, Liu, S (2009). Multi-Responsive Supramolecular Double Hydrophilic Diblock Copolymer Driven by Host-Guest Inclusion Complexation between β-Cyclodextrin and Adamantyl Moieties. Macromol Chem Phys 210: 2125-2137. https://doi.org/10.1002/macp.200900279
• Bertrand, A, Stenzel, M, Fleury, E, Bernard, J (2012). Host–guest driven supramolecular assembly of reversible comb-shaped polymers in aqueous solution. Polym Chem 3(2):377-383. https://doi.org/10.1039/C1PY00478F
• Zhang, Z.-X, Liu, X, Xu, F. J, Loh, X. J, Kang, E.-T, Neoh, K.-G, Li, J (2008). Pseudo-Block Copolymer Based on Star-Shaped Poly(N-isopropylacrylamide) with a β-Cyclodextrin Core and Guest-Bearing PEG: Controlling Thermoresponsivity through Supramolecular Self-Assembly. Macromolecules 41(16):5967-5970. https://doi.org/10.1021/ma8009646
• Setijadi, E, Tao, L, Liu, J, Jia, Z, Boyer, C, Davis, T. P (2009). Biodegradable star polymers functionalized with beta-cyclodextrin inclusion complexes. Biomacromolecules 10(9):2699-2707. https://doi.org/10.1021/bm900646g
• Schmidt, B. V. K. J, Hetzer, M, Ritter, H, Barner-Kowollik, C (2013). UV Light and Temperature Responsive Supramolecular ABA Triblock Copolymers via Reversible Cyclodextrin Complexation. Macromolecules 46(3):1054-1065. https://doi.org/10.1021/ma302386w
• Schmidt, B. V. K. J, Hetzer, M, Ritter, H, Barner-Kowollik, C (2012). Miktoarm star polymers via cyclodextrin-driven supramolecular self-assembly. Polym Chem-Uk 3(11):3064-3067. https://doi.org/10.1039/C2PY20214J
• Schmidt, B. V. K. J, Rudolph, T, Hetzer, M, Ritter, H, Schacher, F. H, Barner-Kowollik, C (2012). Supramolecular three-armed star polymers via cyclodextrin host–guest self-assembly. Polym Chem-Uk 3(11):3139-3145. https://doi.org/10.1039/C2PY20293J
• Schmidt, B. V. K. J, Barner-Kowollik, C (2014). Supramolecular X- and H-shaped star block copolymers via cyclodextrin-driven supramolecular self-assembly. Polym Chem-Uk 5(7):2461-2472. https://doi.org/10.1039/C3PY01580G
• Huan, X, Wang, D, Dong, R, Tu, C, Zhu, B, Yan, D, Zhu, X (2012). Supramolecular ABC Miktoarm Star Terpolymer Based on Host–Guest Inclusion Complexation. Macromolecules 45(15):5941-5947. https://doi.org/10.1021/ma300693h
• Cakir, N, Hizal, G, Becer C. R (2015). Supramolecular glycopolymers with thermo-responsive self-assembly and lectin binding. Polym Chem-Uk 6 (37):6623-6631. https://doi.org/10.1039/C5PY00939A
• Durmaz, H, Dag, A, Altintas, O, Erdogan, T, Hizal, G, Tunca, U (2007). One-Pot Synthesis of ABC Type Triblock Copolymers via in situ Click [3 + 2] and Diels−Alder [4 + 2] Reactions. Macromolecules 40 (2): 191-198. https://doi.org/10.1021/ma061819l
• Cakir, N, Tunca, U, Hizal, G, Durmaz, H (2016). Heterofunctionalized multiarm star polymers via sequential thiol-para-fluoro and thiol-ene double “click” reactions. Macromol Chem Phys 217: 636-645. https://doi.org/10.1002/macp.201500300
• Cakir Yigit, N, Hizal, G, Tunca, U (2018). A powerful tool for preparing peripherally post-functionalized multiarm star block copolymer. Polym Bull 75:3523–3538. https://doi.org/10.1007/s00289-017-2218-5