Photo Nitroxide-Mediated Living Radical Polymerization of Hindered Amine-Supported Methacrylate
DOI:
https://doi.org/10.6000/1929-5995.2018.07.02.1Keywords:
2, 6, 6-Tetramethyl-4-piperidyl methacrylate (TPMA), Hindered amine, Photo nitroxide-mediated living radical polymerization (photo NMP), Photo NMP-induced self-assembly, Giant vesicles, Single bilayer structure.Abstract
With the aim of obtaining giant polymer vesicles supporting a hindered amine that is converted into a redox catalyst on the vesicle shells, the living nature of the photo nitroxide-mediated living radical polymerization (photo NMP) of a monomer containing a hindered amine and the formation of the vesicles consisting of an amphiphilic diblock copolymer by the polymerization-induced self-assembly were investigated. The photo NMP of 2,2,6,6-tetramethyl-4-piperidyl methacrylate (TPMA) was performed in methanol using 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl (MTEMPO) as the mediator, 2,2’-azobis[2-(2-imidazolin-2-yl)propane] (V-61) as the initiator, and (4-tert-butylphenyl)diphenylsulfonium triflate as the accelerator by UV irradiation at room temperature. The first-order time-conversion plots had an induction period in which the MTEMPO molecules were captured by the initiator radicals and the monomer radicals generated by the initiation. It was confirmed that the polymerization proceeded by a living mechanism based on linear correlations of the molecular weight of the poly(TPMA) (PTPMA) versus the monomer conversion and the reciprocal of the initial concentration of V-61. Based on the livingness of the polymerization, the photo NMP-induced self-assembly for the block copolymerization of methyl methacrylate (MMA) using the PTPMA end-capped with MTEMPO was carried out in methanol to produce microsized giant spherical vesicles consisting of the amphiphilic PTPMA-block-poly(MMA) diblock copolymer. A differential scanning calorimetry study demonstrated that the vesicles had a single bilayer structure.
References
Minagawa M. New developments in polymer stabilization. Polym Degrad Stab 1989; 25: 121-41. https://doi.org/10.1016/S0141-3910(89)81004-3 DOI: https://doi.org/10.1016/S0141-3910(89)81004-3
Padron AJC. Performance and mechanisms of hindered amine light stabilizers in polymer photostabilization. J Macromol Sci Rev Macromol Chem 1990; C30: 107-54. https://doi.org/10.1080/07366579008050906 DOI: https://doi.org/10.1080/07366579008050906
Lee CS, Lau WWY, Lee SY, Goh SH. Polymerization behavior of 2,2,6,6-tetramethylpiperindinyl methacrylate: A monomer carrying a hindered amine group. J Polym Sci, Part A, Polym Chem 1992; 30: 983-8. https://doi.org/10.1002/pola.1992.080300604 DOI: https://doi.org/10.1002/pola.1992.080300604
Jiangqing P, Cheng W, Song Y, Hu X. Preparation and characterization of new copolymers containing hindered amine. Polym Degrad Stab 1993; 39: 85-91. https://doi.org/10.1016/0141-3910(93)90128-6 DOI: https://doi.org/10.1016/0141-3910(93)90128-6
Kurosaki T, Lee KW, Okawara M. Polymers having stable radicals. I. Synthesis of nitroxyl polymers from 4-methacryloyl derivatives of 2,2,6,6-tetramethylpiperidine. J Polym Sci, Polym Chem Ed 1972; 10: 3295-310. https://doi.org/10.1002/pol.1972.170101116 DOI: https://doi.org/10.1002/pol.1972.170101116
Yoshida E, Takata T, Endo T. Efficient and selective oxidation of a polymeric terminal diol with Cu(II) mediated by nitroxyl radical. J Polym Sci, Part A Polym Chem Ed 1992; 30: 1193-7. https://doi.org/10.1002/pola.1992.080300627 DOI: https://doi.org/10.1002/pola.1992.080300627
Yoshida E, Takata T, Endo T. Oxidation of polymeric terminal diols with iron(III) or copper(II) salts mediated by the nitroxyl radical. Macromolecules 1992; 25: 7282-5. https://doi.org/10.1021/ma00052a032 DOI: https://doi.org/10.1021/ma00052a032
Yoshida E. Giant vesicles prepared by nitroxide-mediated photo-controlled/living radical polymerization-induced self-assembly. Colloid Polym Sci 2013; 291: 2733-9. https://doi.org/10.1007/s00396-013-3056-0 DOI: https://doi.org/10.1007/s00396-013-3056-0
Yoshida E. Morphology control of giant vesicles by manipulating hydrophobic-hydrophilic balance of amphiphilic random block copolymers through polymerization-induced self-assembly. Colloid Polym Sci 2014; 292: 763-9. https://doi.org/10.1007/s00396-013-3154-z DOI: https://doi.org/10.1007/s00396-013-3154-z
Yoshida E. Preparation of giant vesicles containing quaternary ammonium salt of 2-(dimethylamino)ethyl methacrylate through photo nitroxide-mediated controlled/living radical polymerization-induced self-assembly. J. Polym Res 2018; 25: 109 (1-12). https://doi.org/10.1007/s10965-018-1509-3 DOI: https://doi.org/10.1007/s10965-018-1509-3
Yoshida E. PH response behavior of giant vesicles comprised of amphiphilic poly(methacrylic acid)-block-poly(methyl methacrylate-random-mathacrylic acid). Colloid Polym Sci 2015; 293: 649-53. https://doi.org/10.1007/s00396-014-3482-7 DOI: https://doi.org/10.1007/s00396-014-3482-7
Yoshida E. Fabrication of anastomosed tubular networks developed out of fenestrated sheets through thermo responsiveness of polymer giant vesicles. ChemXpress 2017; 10(1): 118 (1-11).
Yoshida E. Fission of giant vesicles accompanied by hydrophobic chain growth through polymerization-induced self-assembly. Colloid Polym Sci 2014; 292: 1463-8. https://doi.org/10.1007/s00396-014-3216-x DOI: https://doi.org/10.1007/s00396-014-3216-x
Yoshida E. Morphology transformation of micrometer-sized giant vesicles based on physical conditions for photopolymerization-induced self-assembly. Supramol Chem 2015; 27: 274-80. https://doi.org/10.1080/10610278.2014.959014 DOI: https://doi.org/10.1080/10610278.2014.959014
Yoshida E. Morphology control of giant vesicles by com-position of mixed amphiphilic random block copolymers of poly(methacrylic acid)-block-poly(methyl methacrylate-random-methacrylic acid. Colloid Polym Sci 2015; 293: 249-56. https://doi.org/10.1007/s00396-014-3403-9 DOI: https://doi.org/10.1007/s00396-014-3403-9
Yoshida E. Giant vesicles comprised of mixed amphiphilic poly(methacrylic acid)-block-poly(methyl methacrylate-random-methacrylic acid) diblock copolymers. Colloid Polym Sci 2016; 293: 3641-8. https://doi.org/10.1007/s00396-015-3763-9 DOI: https://doi.org/10.1007/s00396-015-3763-9
Yoshida E. Worm-like vesicle formation by photo-controlled/living radical polymerization-induced self-assembly of amphiphilic poly(methacrylic acid)-block-poly(methyl methacrylate-random-methacrylic acid). Colloid Polym Sci 2016; 294: 1857-63. https://doi.org/10.1007/s00396-016-3935-2 DOI: https://doi.org/10.1007/s00396-016-3935-2
Yoshida E. Fabrication of microvillus-like structure by photopolymerization-induced self-assembly of an amphiphilic random block copolymer. Colloid Polym Sci 2015; 293: 1841-5. https://doi.org/10.1007/s00396-015-3600-1 DOI: https://doi.org/10.1007/s00396-015-3600-1
Yoshida E. Morphological changes in polymer giant vesicles by intercalation of a segment copolymer as a sterol model in plasma membrane. Colloid Polym Sci 2015; 293: 1835-40. https://doi.org/10.1007/s00396-015-3577-9 DOI: https://doi.org/10.1007/s00396-015-3577-9
Yoshida E. Morphology transformation of giant vesicles by a polyelectrolyte for an artificial model of a membrane protein for endocytosis. Colloid Surf Sci 2018; 3: 6-11. https://doi.org/10.11648/j.css.20180301.12 DOI: https://doi.org/10.11648/j.css.20180301.12
Venditti P, Stefano LD, Meo SD. Mitochondrial metabolism of reactive oxygen species. Mitochondrion 2013; 13: 71-82. https://doi.org/10.1016/j.mito.2013.01.008 DOI: https://doi.org/10.1016/j.mito.2013.01.008
Bleier L, Dröse S. Superoxide generation by complex III: From mechanistic rationales to functional consequences. Biochim Biophys Acta 2013; 1827: 1320-31. https://doi.org/10.1016/j.bbabio.2012.12.002 DOI: https://doi.org/10.1016/j.bbabio.2012.12.002
Rochaix J. Reprint of: Regulation of photosynthetic electron transport. Biochim Biophys Acta 2011; 1807: 878-86. https://doi.org/10.1016/j.bbabio.2011.05.009 DOI: https://doi.org/10.1016/j.bbabio.2011.05.009
Miyazawa T, Endo T, Shiihashi S, Ogawara M. Selective oxidation of alcohols by oxoaminium salts (R2N:O+ X-). J Org Chem 1985; 50: 1332-4. https://doi.org/10.1021/jo00208a047 DOI: https://doi.org/10.1021/jo00208a047
Kita Y, Gotanda K, Murata K et al. Practical radical additions under mild conditions using 2,2’-azobis(2,4-dimethyl-4-methoxyvaleronitrile) [V-70] as an initiator. Org Process Res Dev 1998; 2: 250-4. https://doi.org/10.1021/op970059z DOI: https://doi.org/10.1021/op970059z
Yoshida E. Effects of illuminance and heat rays on photo-controlled/living radical polymerization mediated by 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl. ISRN Polym Sci 2012; 102186: 1-6. https://doi.org/10.5402/2012/102186 DOI: https://doi.org/10.5402/2012/102186
Kobayashi S, Uyama H, Yamamoto I, Matsumoto Y. Error! Hyperlink reference not valid. Polym J 1990; 22: 759-61. https://doi.org/10.1295/polymj.22.759 DOI: https://doi.org/10.1295/polymj.22.759
Israelachvili, JN. Intermolecular and Surface Forces. 3rd ed, Waltham: Academic Press 2011. DOI: https://doi.org/10.1016/B978-0-12-391927-4.10001-5
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