Abstract
Porous films are attractive materials used in numerous fields, such as catalysis, templating, and separation. In previous examples of porous films prepared from block polymers, the pore size was usually determined by various factors, including mutual interaction between polymer chains, and was hard to precisely manipulate by modification of the block polymers. Herein, we report a novel method of preparing porous films from cyclic block copolymers with the pore size determined by the size of individual components. The incompatibility of the dangling polystyrene arms and cyclic polysiloxane backbones drove the assembly, which then led to the vertical alignment of the cyclic polysiloxane backbone to form porous films. Coarse-grained molecular dynamics simulations were also implemented to gain insight into the assembly process and the film microstructure at the molecular scale.
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References
Bernards DA, Desai TA. Nanoscale porosity in polymer films: fabrication and therapeutic applications. Soft Matter. 2010;6:1621–31.
Hillmyer MA. Nanoporous materials from block copolymer precursors, In: Abetz V, editor. Block Copolymers II. 2005. p. 137–81 (Springer: Berlin, Heidelberg).
Amsden JJ, Domachuk P, Gopinath A, White RD, Negro LD, Kaplan DL, Omenetto FG. Rapid nanoimprinting of silk fibroin films for biophotonic applications. Adv Mater. 2010;22:1746–9.
Li HW, Huck WTS. Ordered block-copolymer assembly using nanoimprint lithography. Nano Lett. 2004;4:1633–6.
Ryu JH, Park S, Kim B, Klaikherd A, Russell TP, Thayumanavan S. Highly ordered gold nanotubes using thiols at a cleavable block copolymer interface. J Am Chem Soc. 2009;131:9870–1.
Zalusky AS, Olayo-Valles R, Wolf JH, Hillmyer MA. Ordered nanoporous polymers from polystyrene-polylactide block copolymers. J Am Chem Soc. 2002;124:12761–73.
Kang M, Moon B. Synthesis of photocleavable poly(styrene-block-ethylene oxide) and its self-assembly into nanoporous thin films. Macromolecules. 2009;42:455–8.
Park C, La Y, An TH, Jeong HY, Kang S, Joo SH, Ahn H, Shin TJ, Kim KT. Mesoporous monoliths of inverse bicontinuous cubic phases of block copolymer bilayers. Nat Commun. 2015;6:6392.
Jenekhe SA, Chen XL. Self-assembly of ordered microporous materials from rod-coil block copolymers. Science. 1999;283:372–5.
Zhang A, Bai H, Li L. Breath figure: a nature-inspired preparation method for ordered porous films. Chem Rev. 2015;115:9801–68.
Widawski G, Rawiso M, François B. Self-organized honeycomb morphology of star-polymer polystyrene films. Nature. 1994;369:387–9.
Josse T, De Winter J, Gerbaux P, Coulembier O. Cyclic polymers by ring-closure strategies. Angew Chem Int Ed Engl. 2016;55:13944–58.
Jia Z, Monteiro MJ. Cyclic polymers: methods and strategies. J Polym Sci Part A. 2012;50:2085–97.
Yamamoto T, Tezuka Y. Topological polymer chemistry: a cyclic approach toward novel polymer properties and functions. Polym Chem. 2011;2:1930–41.
Schappacher M, Deffieux A. Synthesis of macrocyclic copolymer brushes and their self-assembly into supramolecular tubes. Science. 2008;319:1512–5.
Yu J, Liu Y. Cyclic polysiloxanes with linked cyclotetrasiloxane subunits. Angew Chem Int Ed Engl. 2017;56:8706–10.
Wu CY, Yu JY, Li QS, Liu YZ. High molecular weight cyclic polysiloxanes from organocatalytic zwitterionic polymerization of constrained spirocyclosiloxanes. Polym Chem. 2017;8:7301–6.
Luo YD, Montarnal D, Kirn S, Shi WC, Barteau KP, Pester CW, Hustad PD, Christianson MD, Fredrickson GH, Kramer EJ, Hawker CJ. Poly(dimethylsiloxane-b-methyl methacrylate): a promising candidate for sub-10 nm patterning. Macromolecules. 2015;48:3422–30.
Rubinsztajn S, Cella JA. A new polycondensation process for the preparation of polysiloxane copolymers. Macromolecules. 2005;38:1061–3.
Ribelli TG, Fantin M, Daran JC, Augustine KF, Poli R, Matyjaszewski K. Synthesis and characterization of the most active copper ATRP catalyst based on tris[(4-dimethylaminopyridyl)methyl]amine. J Am Chem Soc. 2018;140:1525–34.
Wang WP, Fei M, Jie XX, Wang P, Cao HM, Yu JA. Synthesis and characterization of star-shaped block copolymers with polyhedral oligomeric silsesquioxane (POSS)core via ATRP. Polym Bull. 2010;65:863–72.
Huang HY, Hu ZJ, Chen YZ, Zhang FJ, Gong YM, He TB, Wu C. Effects of casting solvents on the formation of inverted phase inblock copolymer thin films. Macromolecules. 2004;37:6523–30.
Sabzi F, Boushehri A. Sorption phenomena of organic solvents in polymers: Part II. Eur Polym J. 2005;41:2067–87.
Plimpton S. Fast parallel algorithms for short-range molecular dynamics. J Comput Phys. 1995;117:1–19.
Cusola O, Kivisto S, Vierros S, Batys P, Ago M, Tardy BL, Greca LG, Roncero MB, Sammalkorpi M, Rojas OJ. Particulate coatings via evaporation-induced self-assembly of polydisperse colloidal lignin on solid interfaces. Langmuir. 2018;34:5759–71.
Acknowledgements
YZL is grateful for financial support from Youth 1000 Talent Fund KZ37029501, and the 111 Project (B14009). YJ is grateful for financial support from the National Natural Science Foundation of China (21622401, 21574006). HPL is grateful for funding support from the China Postdoctoral Science Foundation (2018M641141).
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Liu, H., Li, H., Yu, J. et al. Porous films from cyclic block copolymers. Polym J 52, 449–455 (2020). https://doi.org/10.1038/s41428-019-0291-3
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DOI: https://doi.org/10.1038/s41428-019-0291-3