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Title: | Alcohol-based PISA in batch and flow: exploring the role of photoinitiators | Authors: | ZAQUEN, Neomy Azizi, Wan A. A. W. Yeow, Jonathan Kuchel, Rhiannon P. JUNKERS, Tanja Zetterlund, Per B. Boyer, Cyrille |
Issue Date: | 2019 | Publisher: | ROYAL SOC CHEMISTRY | Source: | POLYMER CHEMISTRY, 10(19), p. 2406-2414 | Abstract: | Polymerization-induced self-assembly (PISA) via PhotoRAFT (photoinduced reversible addition-fragmentation chain transfer) in less polar solvents via continuous flow reactors was investigated. At first, a batch protocol was designed for the activation of the trithiocarbonate-derived poly(oligo ethylene glycol methacrylate) (POEGMA) macroRAFT under blue light in the presence of benzyl methacrylate (BzMA). A variety of solvents, photoinitiators as well as light intensities were tested, leading to improved reaction conditions in batch. With the optimized batch protocol, POEGMA-b-PBzMA particle synthesis was adapted for flow processing, demonstrating the potential of continuous tubular reactors for the synthesis of nanoparticles with different morphologies via alcoholic RAFT dispersion PISA. As the addition of various photoinitiators did not lead to the anticipated increase in polymerization rate, we further investigated the initiation mechanism using (meth) acrylates. POEGMA as well as the acrylate-based analogue (POEGA) were chain extended using different acrylates/methacrylates under photoiniferter and photoinitiation conditions. Due to the weaker C-S bond of the methacrylate-based macroRAFT, the additional generation of radicals from the photoinitiator TPO had less significant impact on the polymerization rate than for the acrylate-based macroRAFT, which underwent much slower photoiniferter activation. Methacrylate-based macroRAFT was converted into an acrylate-based macroRAFT when extended with acrylate monomer, thus explaining why this particular case does lead to a rate increase in addition of TPO, unlike for the extension with a methacrylate. | Notes: | [Zaquen, Neomy; Azizi, Wan A. A. W.; Yeow, Jonathan; Zetterlund, Per B.; Boyer, Cyrille] Univ New South Wales, Sch Chem Engn, CAMD, Sydney, NSW 2052, Australia. [Zaquen, Neomy; Yeow, Jonathan; Boyer, Cyrille] Univ New South Wales, Australian Ctr Nanomed, Sydney, NSW 2052, Australia. [Zaquen, Neomy; Junkers, Tanja] Univ Hasselt, Organ & Biopolymer Chem OBPC, Agoralaan Bldg D, B-3590 Diepenbeek, Belgium. [Kuchel, Rhiannon P.] Monash Univ, Sch Chem, Polymer React Design Grp, Melbourne, Vic 3800, Australia. | Keywords: | Polymer Science | Document URI: | http://hdl.handle.net/1942/29037 | ISSN: | 1759-9954 | e-ISSN: | 1759-9962 | DOI: | 10.1039/c9py00166b | ISI #: | 000467972800003 | Rights: | The Royal Society of Chemistry 2019 | Category: | A1 | Type: | Journal Contribution | Validations: | ecoom 2020 |
Appears in Collections: | Research publications |
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