Synthesis and Characterization of Poly (2-hydroxyethyl methacrylate) Homopolymer at Room Temperature via Reversible Addition–Fragmentation Chain Transfer (RAFT) Polymerization Technique

Abstract

Synthesis and characterization of Poly (2-hydroxyethyl methacrylate) (PHEMA) by RAFT technique at room temperature was first reported in this study. In this context, molecular weight, monomer conversion and semi-logarithmic kinetic curves of the RAFT polymerization, which is one of the controlled-living polymerization techniques, were determined by ATR-FTIR and NMR at certain time intervals. Linear change of molecular weight and monomer conversion with time, semi-logarithmic kinetic curve to the first degree kinetics of the synthesized PHEMA shows that the growth of polymer chains in a controlled manner. PHEMA polymers synthesized by RAFT technique at room temperature without the use of catalyst and metal types have the potential to be easily used in bio applications. It is also important for peptide and protein adsorption that this polymer has functional properties due to the carboxylic acid at the end of the RAFT agent.

Keywords

• RAFT,PHEMA,NMR,ATR-FTIR

References

1. 1. Georges M K, Veregin R P N, Kazmaier P M, Georges H. Narrow molecular weight resins by a free-radical polymerization process. Macromolecules 26 (11) (1993) 2987-2988.
2. 2. Hawker C J, Bosman A W, Harth E. New Polymer Synthesis by Nitroxide Mediated Living Radical Polymerizations. Chem. Rev. 101 (12) (2001) 3661-3688.
3. 3. Kato M, Kamigaito M, Sawamoto M, Higashimura T. Polymerization of Methyl Methacrylate with the Carbon Tetrachloride/Dichlorotris(triphenylphosphine)ruthenium(II)/Methylaluminum Bis(2,6-di-tert-butylphenoxide) Initiating System: Possibility of Living Radical Polymerization. Macromolecules 28 (5) (1995) 1721-1723.
4. 4. Wang J S, Matyjaszewski K. Controlled/"living" radical polymerization. atom transfer radical polymerization in the presence of transition-metal complexes. J. Am. Chem. Soc. 117 (20) (1995) 5614-5615.
5. 5. Chiefari J, Chong Y K, Ercole F, Krstina J, Jeffery J, Le T P T, Mayadunne R T A, Meijs F G, Moad C L, Moad G, ERizzardo E, Thang H S. Living Free-Radical Polymerization by Reversible Addition−Fragmentation Chain Transfer:  The RAFT Process. Macromolecules 31 (16) (1998) 5559-5562.
6. 6. Bütün V, Bennett C E, Vamvakaki M, Lowe A B, Billingham N C, Armes S P. Selective betainisation of tertiary amine methacrylate block copolymers. Journal of Materials Chemistry 7(9) (1997) 1693-1965.
7. 7. Boyer C, Bulmus V, Davis TP, Ladmiral V, Liu J, Perrier S. Bioapplications of RAFT Polymerization. Chem. Rev., 2009, 109 (11), pp 5402–5436.
8. 8. Jennings J, He G, Howdle S M, Zetterlund P. B. Block copolymer synthesis by controlled/living radical polymerisation in heterogeneous systems. Chem. Soc. Rev. 45 (2016) 5055-5084.

9. 9. Hill M G, Carmean R N, Sumerlin B S. Expanding the Scope of RAFT Polymerization: Recent Advances and New Horizons. Macromolecules 48 (16) (2015) 5459–5469.
10. 10. Moad G. RAFT polymerization to form stimuli-responsive polymers. Polym. Chem. 8 (2017) 177-219.
11. 11. Cobo I, Li M, Sumerlin B S, Perrier S, Smart hybrid materials by conjugation of responsive polymers to biomacromolecules. Nat. Mater., 14 (2015) 143–159.
12. 12. Yildirim E, Turan E, Caykara T. Construction of myoglobin imprinted polymer films by grafting from silicon surface. J. Mater. Chem. 22 (2012) 636-642.
13. 13. Cimen D., Caykara T. Biofunctional oligoN-isopropylacrylamide brushes on silicon wafer surface. J. Mater. Chem. 22 (2012) 13231-13238.
14. 14. Flynn L, Dalton P D, Shoichet M S. Fiber templating of poly(2-hydroxyethyl methacrylate) for neural tissue engineering. Biomaterials. 24(23) (2003) 4265-72.
15. 15. Xinming L, Yingde C, Lloyd A W, Mikhalovsky S V, Sandeman S R, Howel C A, Liewen L. Polymeric hydrogels for novel contact lens-based ophthalmic drug delivery systems: A review. Cont. Lens Anterior Eye. 31(2) (2008) 57-64.
16. 16. Das D, Pal S. Dextrin/poly (HEMA): pH responsive porous hydrogel for controlled release of ciprofloxacin. Int J Biol Macromol. 72 (2015) 171-178.
17. 17. Gómez M L, Gallastegui A, Spesia M B, Montejano A H, Williams R J, Previtali C M. Synthesis of poly (HEMA‐co‐AAm) hydrogels by visible‐light photopolymerization of aqueous solutions containing aspirin or ibuprofen: analysis of the initiation mechanism and the drug release. Polym. Adv. Technol. 28 (4) (2017) 435-442.
18. 18. Cadotte A J, DeMarse T B.Poly-HEMA as a drug delivery device for in vitro neural networks on micro-electrode arrays. J Neural Eng. 2 (4) (2005) 114-122.
19. 19. Shanmugam X S, Duonga H T,Boyer C. Organo-photocatalysts for photoinduced electron transfer-reversible addition–fragmentation chain transfer (PET-RAFT) polymerization. Polym. Chem. 6 (2015) 5615-5624.