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Acid-Induced Room Temperature RAFT Polymerization: Synthesis and Mechanistic Insights

  • Joke Vandenbergh
    Joke Vandenbergh
    Polymer Reaction Design Group, Institute for Materials Research (IMO), Hasselt University, Campus Diepenbeek, Building D, B-3590 Diepenbeek, Belgium
  • Bertrand Schweitzer-Chaput
    Bertrand Schweitzer-Chaput
    Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, Germany
  • Martin Klussmann*
    Martin Klussmann
    Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, Germany
    *(M.K.) Telephone +49 (0)208 306 2453. Fax: +49 (0)208 306 2980. E-mail: [email protected]
  • , and 
  • Tanja Junkers*
    Tanja Junkers
    Polymer Reaction Design Group, Institute for Materials Research (IMO), Hasselt University, Campus Diepenbeek, Building D, B-3590 Diepenbeek, Belgium
    IMEC Division IMOMEC, Wetenschapspark 1, B-3590 Diepenbeek, Belgium
    *(T.J.) Telephone + 32 (0)11 26 83 18. Fax: + 32 (0)11 26 83 01. E-mail: [email protected]
Cite this: Macromolecules 2016, 49, 11, 4124–4135
Publication Date (Web):May 20, 2016
https://doi.org/10.1021/acs.macromol.6b00192
Copyright © 2016 American Chemical Society

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    Abstract

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    An acid-induced cyclohexanone/tert-butylhydroperoxide initiation system for ambient temperature reversible addition–fragmentation transfer (RAFT) polymerization of vinyl monomers is presented. The reaction system is optimized for the synthesis of poly(n-butyl acrylate) of various chain length. The polymerization shows typical living characteristics and polymers with dispersities close to 1.1 are obtained. Analysis of the polymer end groups by means of soft ionization mass spectrometry reveals the typical distribution of polymer containing both R and Z RAFT end groups and a minor distribution of a RAFT polymer carrying a cyclohexanone end group in α position. This observation demonstrates that the polymerization is initiated solely by ketone radicals despite a relatively complex initiation mechanism that involves several intermediates. The room temperature-derived homopolymers are successfully chain extended with tert-butyl acrylate resulting in well-defined block copolymer structures. To demonstrate the versatility of the approach, the room temperature RAFT polymerization is also applied to synthesize styrene and N-isopropylacrylamide, yielding best results for polystyrene. Finally, also a bisperoxide structure is tested as an alternative for the ketone/peroxide mixture. Polymerization proceeds substantially faster in this case and successful controlled polymerization to full conversion is achieved even at 0 °C. In general the proposed room temperature RAFT technique is very easy to carry out, in principle easily up scalable, metal free and shows high potential toward the synthesis of well-defined temperature sensitive materials.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.macromol.6b00192.

    • ESI–MS spectra of PnBuA obtained from room temperature CH/TBHP RAFT polymerization using 0.2 equiv of acid, molar mass distributions and kinetic plots of PnBuA using a monomer:RAFT-agent ratio of 400:1, the molar mass distribution of PnBuA obtained from BTBPC (1 equiv) free radical polymerization using 0.05 equiv of acid for 24 h at 0 °C, and the molar mass distribution of PnBuA obtained from ambient (air, room temperature) CH/TBHP (5/1 equiv) or BTBPC (1 equiv) RAFT polymerization using 0.05 equiv of acid for 24 h, structures of speicies identifued, and table of masses for products (PDF)

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    This article is cited by 20 publications.

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    3. Thomas G. McKenzie Amin Reyhani Mitchell D. Nothling Greg G. Qiao . Hydroxyl Radical Activated RAFT Polymerization. 2018, 307-321. https://doi.org/10.1021/bk-2018-1284.ch014
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    9. Semiha Duygu Sütekin, Olgun Güven. Preparation of poly( tert ‐butyl acrylate)‐poly(acrylic acid) amphiphilic copolymers via radiation‐induced reversible addition–fragmentation chain transfer mediated polymerization of tert ‐butyl acrylate. Polymer International 2020, 69 (8) , 693-701. https://doi.org/10.1002/pi.6004
    10. Renee L. Timmins, Olivia R. Wilson, Andrew J. D. Magenau. Arm‐first star‐polymer synthesis in one‐pot via alkylborane‐initiated RAFT. Journal of Polymer Science 2020, 58 (10) , 1463-1471. https://doi.org/10.1002/pol.20200089
    11. Amin Reyhani, Thomas G. McKenzie, Qiang Fu, Greg G. Qiao. Fenton‐Chemistry‐Mediated Radical Polymerization. Macromolecular Rapid Communications 2019, 40 (18) https://doi.org/10.1002/marc.201900220
    12. Jinsheng Zhou, Lin Ye, Yanming Lin, Ling Wang, Li Zhou, Huiyuan Hu, Qilong Zhang, Hui Yang, Zhongkuan Luo. Surface modification PVA hydrogel with zwitterionic via PET‐RAFT to improve the antifouling property. Journal of Applied Polymer Science 2019, 136 (24) https://doi.org/10.1002/app.47653
    13. Baki Hazer, Hülya Arslan, Yetkin Senemoğlu, Şadi Şen. Synthesis of block/graft copolymers based on vinyl benzyl chloride via reversible addition fragmentation chain transfer (RAFT) polymerization using the carboxylic acid functionalized Trithiocarbonate. Journal of Polymer Research 2019, 26 (5) https://doi.org/10.1007/s10965-019-1763-z
    14. Anna Székely, Martin Klussmann. Molecular Radical Chain Initiators for Ambient‐ to Low‐Temperature Applications. Chemistry – An Asian Journal 2019, 14 (1) , 105-115. https://doi.org/10.1002/asia.201801636
    15. Amin Reyhani, Thomas G. McKenzie, Qiang Fu, Greg G. Qiao. Redox-Initiated Reversible Addition–Fragmentation Chain Transfer (RAFT) Polymerization. Australian Journal of Chemistry 2019, 72 (7) , 479. https://doi.org/10.1071/CH19109
    16. Adem Kocyigit, Mete Bakir, Osman S. Cifci, Brian Enders, Iwona Jasiuk, Munir H. Nayfeh. Imparting optical functionality to aromatic thermosetting copolyester by luminescent silicon nanoparticles cross-linked via in situ thermal polymerization reaction. European Polymer Journal 2018, 103 , 351-361. https://doi.org/10.1016/j.eurpolymj.2018.04.024
    17. Martin Klussmann. Alkenyl and Aryl Peroxides. Chemistry – A European Journal 2018, 24 (18) , 4480-4496. https://doi.org/10.1002/chem.201703775
    18. Xiangyu Tian, Junjie Ding, Bin Zhang, Feng Qiu, Xiaodong Zhuang, Yu Chen. Recent Advances in RAFT Polymerization: Novel Initiation Mechanisms and Optoelectronic Applications. Polymers 2018, 10 (3) , 318. https://doi.org/10.3390/polym10030318
    19. Jonathan Yeow, Robert Chapman, Adam J. Gormley, Cyrille Boyer. Up in the air: oxygen tolerance in controlled/living radical polymerisation. Chemical Society Reviews 2018, 47 (12) , 4357-4387. https://doi.org/10.1039/C7CS00587C
    20. Jonathan Yeow, Cyrille Boyer. Photoinitiated Polymerization-Induced Self-Assembly (Photo-PISA): New Insights and Opportunities. Advanced Science 2017, 4 (7) , 1700137. https://doi.org/10.1002/advs.201700137

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