Abstract
A general methodology for producing ca. 140-nm thermoplastic/thermoset, core-shell colloids that are used as an ink in roll-to-roll printing is demonstrated. The printed films are subsequently modified in-line through a dip-click approach using the copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC). The thermoplastic nature of the shell polymers in the particles allows the shell to delaminate when annealed above its glass transition temperature. This results in a printed film that is more robust and functional as it combines the durability of the thermoset core colloids and the flexibility of the thermoplastic shell polymers. The technique is demonstrated using core-shell particles with a crosslinked polystyrene core and co-/terpolymer shell that contains terminal alkynes for click functionalization. The core-shell particles were roll-to-roll printed and then annealed at 100 ∘C to yield coalesced films. The printed films were dipped in a solution containing an azide-modified fluorescein dye which resulted in the covalent attachment of the dye to the thin films via CuAAC. When the click reaction was allowed to proceed for 24 h, it was found that ca. 67% of the total functionalization occurred in the first hour. Due to the efficiency of this technique, the potential for large-scale production of printed films where an in-line chemical modification via CuAAC could be realized.
A general methodology for producing ca. 140 nm thermoplastic/thermoset, core-shell colloids that can be used as an ink in roll-to-roll printing is demonstrated. The printed films are subsequently modified inline through a dip-click approach using the copper(I)- catalyzed azide-alkyne cycloaddition (CuAAC). The thermoplastic nature of the shell polymers in the particles allows the shell to delaminate when annealed above its glass transition temperature. This results in a printed film that is more robust and functional as it combines the durability of a thermoset core colloid with the flexibility of an alkyne-functionalized thermoplastic shell.
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References
Sondergaard RR, Hosel M, Krebs FC (2013) Roll-to-roll fabrication of large area functional organic materials. J Polym Sci, Part B: Polym Phys 51(1):16–34
Baeg KJ, Caironi M, Noh YY (2013) Toward printed integrated circuits based on unipolar or ambipolar polymer semiconductors. Adv Mater 25(31):4210–4244
Choi HW, Zhou TL, Singh M, Jabbour GE (2015) Recent developments and directions in printed nanomaterials. Nanoscale 7(8):3338–3355
Erothu H, Kolomanska J, Johnston P, Schumann S, Deribew D, Toolan DTW, Gregori A, Dagron-Lartigau C, Portale G, Bras W, Arnold T, Distler A, Hiorns RC, Mokarian-Tabari P, Collins TW, Howse JR, Topham PD (2015) Synthesis, thermal processing, and thin film morphology of poly(3-hexylthiophene)-poly(styrenesulfonate) block copolymers. Macromolecules 48(7):2107–2117
Valimaki M, Apilo P, Po R, Jansson E, Bernardi A, Ylikunnari M, Vilkman M, Corso G, Puustinen J, Tuominen J, Hast J (2015) R2r-printed inverted opv modules—towards arbitrary patterned designs. Nanoscale 7(21):9570–80
Grau G, Kitsomboonloha R, Swisher SL, Kang HK, Subramanian V (2014) Printed transistors on paper: towards smart consumer product packaging. Adv Funct Mater 24(32):5067–5074
Larsen-Olsen TT, Andersen TR, Dam HF, Jorgensen M, Krebs FC (2015) Probing individual subcells of fully printed and coated polymer tandem solar cells using multichromatic opto-electronic characterization methods. Sol Energy Mater Sol Cells 137:154–163
Huebner CF, Tsyalkovsky V, Bandera Y, Burdette MK, Shetzline JA, Tonkin C, Creager SE, Foulger SH (2015) Nonvolatile optically-erased colloidal memristors. Nanoscale 7(4):1270–1279
Hernandez-Sosa G, Bornemann N, Ringle I, Agari M, Dorsam E, Mechau N, Lemmer U (2013) Rheological and drying considerations for uniformly gravure-printed layers: towards large-area flexible organic light-emitting diodes. Adv Funct Mater 23(25):3164–3171
Sandstrom A, Edman L (2015) Towards high-throughput coating and printing of light-emitting electrochemical cells: a review and cost analysis of current and future methods. Energ Technol 3(4):329–339
Khan S, Lorenzelli L, Dahiya RS (2015) Technologies for printing sensors and electronics over large flexible substrates: a review. IEEE Sensors J 15(6):3164–3185
Roeder RD, Rungta P, Tsyalkovskyy V, Bandera Y, Foulger SH (2012) Colloidal templating: seeded emulsion polymerization of a soluble shell with a controlled alkyne surface density. Soft Matter 8:5493–5500
Zhang Y, Foos R, Landfester K, Taden A (2014) Thermoset-thermoplastic hybrid nanoparticles and composite coatings. Polymer 55(10):2305–2315
Kolb HC, Finn MG, Sharpless KB (2001) Click chemistry: diverse chemical function from a few good reactions. Angew Chem Int Ed 40(11):2004
Hein JE, Fokin VV (2010) Copper-catalyzed azide–alkyne cycloaddition (cuaac) and beyond: new reactivity of copper (i) acetylides. Chem Soc Rev 39(4):1302–1315
Evanoff DD, Hayes SE, Ying Y, Shim GH, Lawrence JR, Carroll JB, Roeder RD, Houchins JM, Huebner CE, Foulger SH (2007) Functionalization of crystalline colloidal arrays through click chemistry. Adv Mater 19(21):3507
Haensch C, Hoeppener S, Schubert US (2008) Chemical surface reactions by click chemistry: coumarin dye modification of 11-bromoundecyltrichlorosilane monolayers. Nanotechnology 19:1–7
Santos CM, Kumar A, Kolar SS, Contreras-Caceres R, McDermott A, Cai C Z (2013) Immobilization of antimicrobial peptide ig-25 onto fluoropolymers via fluorous interactions and click chemistry. ACS Appl Mater Interfaces 5(24):12789– 12793
Ocepek M, Soucek MD, Berce P, Meng L (2015) Comparison of particle size techniques to investigate secondary nucleation in hema-rich latexes. Macromol Chem Phys 216(4):400–416
Smith WV, Ewart RH (1948) Kinetics of emulsion polymerization. J Chem Phys 16(6):592–599
Ugelstad J, El-Aasser MS, Vanderhoff JW (1973) Emulsion polymerization: initiation of polymerization in monomer droplets. J Polym Sci, Part C: Polym Lett 11(8):503–513
Ballard N, de la Cal JC, Asua JM (2015) The role of chain transfer agent in reducing branching content in radical polymerization of acrylates. Macromolecules 48(4):987–993
Bae S, Kim H, Lee Y, Xu X, Park J-S, Zheng Y, Balakrishnan J, Lei T, Kim HR, Song YI et al (2010) Roll-to-roll production of 30-inch graphene films for transparent electrodes. Nat Nanotechnol 5 (8):574
Krebs FC (2009) Polymer solar cell modules prepared using roll-to-roll methods: knife-over-edge coating, slot-die coating and screen printing. Sol Energy Mater Sol Cells 93(4): 465–475
Krebs FC, Fyenbo J, Jørgensen M (2010) Product integration of compact roll-to-roll processed polymer solar cell modules: methods and manufacture using flexographic printing, slot-die coating and rotary screen printing. J Mater Chem 20(41):8994–9001
Krebs FC, Gevorgyan SA, Alstrup J (2009) A roll-to-roll process to flexible polymer solar cells: model studies, manufacture and operational stability studies. J Mater Chem 19(30):5442–5451
Se HA, Guo LJ (2008) High-speed roll-to-roll nanoimprint lithography on flexible plastic substrates. Adv Mater 20(11):2044–2049
Acknowledgements
The authors thank Sheridan College for providing funding to complete this research.
Funding
The authors thank DARPA (Grant Number N66001-04-1-8933), the National Science Foundation (DMR-0236692 and DMR-1507266) and the Gregg-Graniteville Foundation for the financial support.
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Roeder, R.D., Huebner, C.F., Tonkin, C. et al. Click functionalization of thin films fabricated by roll-to-roll printing of thermoplastic/thermoset core-shell colloids. Colloid Polym Sci 296, 1679–1687 (2018). https://doi.org/10.1007/s00396-018-4382-z
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DOI: https://doi.org/10.1007/s00396-018-4382-z