Synthesis of PMMA-b-PEG-b- PMMA by controlled Polymerization Using Macro-RAFT Agents

Abstract

In this work controlled radical polymerization (CRP) of methyl methacrylate was carried out in the

presence of the Poly(ethylene glycol)(PEG) xanthate reversible addition fragmentation (RAFT) chain transfer

agent designated as (CTA1) and (CTA2). Firstly, PEGs having different molecular weights (400 and 600 g/mol)

were reacted KOH and CS2 and the terminated 4-chloro benzoyl chloride to obtain PEG-xathates. RAFT agent

possessing PEG chain was used in the RAFT polymerization of MMA to yield PMMA-b-PEG-b-PMMA tri-block

copolymers which can be used in various potential applications. With the gravimetric follow of the reaction, the

control mechanism works well and the molecular weight has grown linearly. The structures of the synthesized

macro RAFT agents and polymers were characterized by 1H-NMR, 13C-NMR and FT-IR spectroscopic methods.

Keywords

• Block Copolymer,Controlled Radical Polymerization,Polyethylene Glycol,RAFT

References

1. Ballard, N., M. Aguirre, A. Simula, J. R. Leiza, S. van Es and J. M. Asua (2017). "Nitroxide mediated suspension polymerization of methacrylic monomers." Chemical Engineering Journal 316: 655-662.
2. Barsbay, M. and O. Güven (2018). "Nanostructuring of polymers by controlling of ionizing radiation-induced free radical polymerization, copolymerization, grafting and crosslinking by RAFT mechanism." Radiation Physics and Chemistry.
3. Beija, M., J.-D. Marty and M. Destarac (2011). "RAFT/MADIX polymers for the preparation of polymer/inorganic nanohybrids." Progress in Polymer Science 36(7): 845-886.
4. Chmielarz, P. (2016). "Synthesis of α-d-glucose-based star polymers through simplified electrochemically mediated ATRP." Polymer 102: 192-198.
5. Foster, J. C., S. C. Radzinski, S. E. Lewis, M. B. Slutzker and J. B. Matson (2015). "Norbornene-containing dithiocarbamates for use in reversible addition–fragmentation chain transfer (RAFT) polymerization and ring-opening metathesis polymerization (ROMP)." Polymer 79: 205-211.
6. Fu, X., Y. Lei, B. Wu, X. Chen, J. Wang, C. Zhou and J. Lei (2017). "Molecular design and synthesis of acrylic resin film-forming materials with wide applicable temperature range via RAFT emulsion polymerization." Progress in Organic Coatings 104: 263-270.
7. Gu, R., W. Z. Xu and P. A. Charpentier (2014). "Synthesis of graphene-polystyrene nanocomposites via RAFT polymerization." Polymer 55(21): 5322-5331.
8. Hemp, S. T., A. E. Smith, W. C. Bunyard, M. H. Rubinstein and T. E. Long (2014). "RAFT polymerization of temperature- and salt-responsive block copolymers as reversible hydrogels." Polymer 55(10): 2325-2331.

9. Kermagoret, A. and D. Gigmes (2016). "Combined nitroxide mediated radical polymerization techniques for block copolymer synthesis." Tetrahedron 72(48): 7672-7685.
10. Li, J., C. Ding, Z. Zhang, J. Zhu and X. Zhu (2017). "Photo-induced reversible addition-fragmentation chain transfer (RAFT) polymerization of acrylonitrile at ambient temperature: A simple system to obtain high-molecular-weight polyacrylonitrile." Reactive and Functional Polymers 113: 1-5.
11. Liu, Y. and C. E. Hobbs (2018). "Phase-selectively soluble, polymer-supported salen catalyst prepared using atom transfer radical polymerization (ATRP)." Polymer 135: 25-29.
12. Ma'Radzi, A. H., S. Sugihara, S. Miura, N. Konegawa and Y. Maeda (2014). "Synthesis of thermoresponsive block and graft copolymers via the combination of living cationic polymerization and RAFT polymerization using a vinyl ether-type RAFT agent." Polymer 55(8): 1920-1930.
13. Neugebauer, D. (2015). "Two decades of molecular brushes by ATRP." Polymer 72: 413-421.
14. Nicolas, J., Y. Guillaneuf, C. Lefay, D. Bertin, D. Gigmes and B. Charleux (2013). "Nitroxide-mediated polymerization." Progress in Polymer Science 38(1): 63-235.Sütekin, S. D. and O. Güven (2018). "Radiation-induced controlled polymerization of acrylic acid by RAFT and RAFT-MADIX methods in protic solvents." Radiation Physics and Chemistry 142: 82-87.
15. West, A. G., C. Barner-Kowollik and S. Perrier (2010). "Poly(ethylene glycol) as a ‘green solvent’ for the RAFT polymerization of methyl methacrylate." Polymer 51(17): 3836-3842.
16. Yan, M., F.-Y. Lin and E. W. Cochran (2017). "Dynamics of hyperbranched polymers derived from acrylated epoxidized soybean oil." Polymer 125: 117-125.
17. Yang, L., Y. Luo, X. Liu and B. Li (2009). "RAFT miniemulsion polymerization of methyl methacrylate." Polymer 50(18): 4334-4342.
18. Yeole, N. and D. Hundiwale (2011). "Effect of hydrophilic macro-RAFT agent in surfactant-free emulsion polymerization." Colloids and Surfaces A: Physicochemical and Engineering Aspects 392(1): 329-334.