Synthesis and Characterization of Poly(Ԑ-caprolactone-b-Styrene) Block Copolymer by Ring-Opening Polymerization and Reversible Addition-Fragmentation Chain Transfer Polymerization

The synthesis of the block copolymer was carried out using the RAFT polymerization technique and the ring-opening polymerization (ROP) technique using a novel two functional initiator (RAFT-ROP agent). For this purpose, RAFT-ROP agent was obtained using 5-bromo-2-hydroxybenzaldehyde and potassium salt of ethyl xanthogenate. RAFT-macro agent was synthesized by ROP of ɛ-caprolactone (CL) with RAFT-ROP agent. Then, poly(ɛ-caprolactone-b-styrene) block copolymer was synthesized using RAFT polymerization in the presence of RAFT-macro agent using styrene. The products were characterized using GPC, FT-IR and 1H-NMR analyses. Decomposition temperatures of the block copolymer were monitored by TGA method. Spectroscopic and thermal analyses revealed that the reactions were successfully carried out.

Anahtar Kelimeler:

Novel Two Functional Initiator, RAFT-Macro Agent, Block Copolymer, RAFT Polymerization, Ring-Opening Polymerization (ROP)

Synthesis and Characterization of Poly(Ԑ-caprolactone-b-Styrene) Block Copolymer by Ring-Opening Polymerization and Reversible Addition-Fragmentation Chain Transfer Polymerization

Keywords:

novel two functional initiator, RAFT-macro agent, block copolymer, RAFT Polymerization, Ring-Opening Polymerization (ROP),

PDF

___

Bağlan M, Yildiko, U, Cakmak, I, Tekeş, AT. (2018). Synthesis of PMMA-b-PEG-b-PMMA by controlled Polymerization Using Macro-RAFT Agents. Journal of the Institute of Science and Technology 8(3): 243-254.
Cai T, Li M, Neoh KG, Kang ET. 2012. Preparation of stimuli responsive polycaprolactone membranes of controllable porous morphology via combined atom transfer radical polymerization, ring-opening polymerization and thiol-yne click chemistry. Journal of Materials Chemistry 22(32): 16248-16258.
Chang X, Dong CM. 2013. Synthesis of hyperbranched polypeptide and PEO block copolymer by consecutive thiol-yne chemistry. Biomacromolecules 14(9): 3329-3337.
Chiefari J, Chong Y, Ercole F, Krstina J, Jeffery J, Le TP, Mayadunne RT, Meijs GF, Moad CL, Moad G. 1998. Living free-radical polymerization by reversible addition-fragmentation chain transfer: the RAFT process. Macromolecules 31(16): 5559-5562.
Cretu A, Gattin R, Brachais L, Barbier-Baudry D. 2004. Synthesis and degradation of poly(2-hydroxyethyl methacrylate)-graft-poly(ε-caprolactone) copolymers. Polymer Degradation and Stability 83(3): 399-404.
Çakmak İ, Öztürk, T, Yildiko, Ü, Yörük, A. (2017). Synthesis of poly[ε-caprolacton-b-epichlorohydryin-b-ε-caprolactone]-g-poly(styrene) Block-Graft Copolymers via Cationic Ring Opening and Atom Transfer Radical Polymerization Transformations. Journal of the Institute of Science and Technology 7(3): 161-169.
Göktaş M, Öztürk T, Atalar MN, Tekeş AT, Hazer B. 2014. One-step synthesis of triblock copolymers via simultaneous reversible-addition fragmentation chain transfer (RAFT) and ring-opening polymerization using a novel difunctional macro-RAFT agent based on polyethylene glycol. Journal of Macromolecular Science, Part A 51(11): 854-863.
Gross RA, Kumar A, Kalra B. 2001. Polymer synthesis by in vitro enzyme catalysis. Chemical Reviews 101(7): 2097-2124.
Kartal B, Yildiko, U, Ozturk, S, Ata, AC, Cakmak, I. (2014). Study of Solution Polymerization of Styrene in the Presence of Poly(ethylene glycol)-RAFT Agents Possessing Benzoyl Xanthate Derivatives. Journal of Macromolecular Science, Part A 51(12): 990-998.
Kobayashi S, Uyama H, Kimura S. 2001. Enzymatic Polymerization. Chemical Reviews 101(12): 3793-3818.
Matzner M, Noshay A, McGrath J. 1977. Effect of Hard Segment Chemical Structure on the Processibility of Organo‐Siloxane Block Copolymers. Transactions of the Society of Rheology 21(2): 273-290.
Nomura K, Abdellatif MM. 2010. Precise synthesis of polymers containing functional end groups by living ring-opening metathesis polymerization (ROMP): Efficient tools for synthesis of block/graft copolymers. Polymer 51(9): 1861-1881.
Noshay A, McGrath JE. 2013. Block Copolymers: Overview and Critical Survey, Elsevier.
Özturk, T, Yilmaz SS, Hazer B. 2008. Synthesis of a new macroperoxy initiator with methyl methacrylate and t-butyl peroxy ester by atom transfer radical polymerization and copolymerization with conventional vinyl monomers. Journal of Macromolecular Science, Part A 45(10): 811-820.
Öztürk, T, Atalar MN, Göktaş M, Hazer B. 2013. One-step synthesis of block-graft copolymers via simultaneous reversible-addition fragmentation chain transfer and ring-opening polymerization using a novel macroinitiator. Journal of Polymer Science Part A: Polymer Chemistry 51(12): 2651-2659.
Öztürk T, Göktaş M, Hazer B, 2010. One-step synthesis of triarm block copolymers via simultaneous reversible-addition fragmentation chain transfer and ring-opening polymerization. Journal of Applied Polymer Science 117(3): 1638-1645.
Öztürk T, Göktaş M, Savaş B, Işıklar M, Atalar MN, Hazer B. 2014. Synthesis and characterization of poly(vinyl chloride-graft-2-vinylpyridine) graft copolymers using a novel macroinitiator by reversible addition-fragmentation chain transfer polymerization. e-Polymers 14(1): 27-34.
Öztürk S, Çakmak, İ, Tekeş, AT, Yildiko, Ü. (2019). Synthesis and Characterization of Poly (lactic acid-b-ε-caprolactone) Block Copolymers. Journal of the Institute of Science and Technology 9(2): 1035-1045.
Patton DL, Mullings M, Fulghum T, Advincula RC. 2005. A facile synthesis route to thiol-functionalized α, ω-telechelic polymers via reversible addition fragmentation chain transfer polymerization. Macromolecules 38(20): 8597-8602.
Price C, Goodman I. 1982. Developments in Block Copolymers. Elsevier Applied Science, London.
Robin MP, Wilson P, Mabire AB, Kiviaho JK, Raymond JE, Haddleton DM, Reilly RKO. 2013. Conjugation-induced fluorescent labeling of proteins and polymers using dithiomaleimides. Journal of the American Chemical Society 135(8): 2875-2878.
Ruzette AV, Leibler L. 2005. Block Copolymers in Tomorrow's Plastics. Nature Materials 4(1): 19-31.
Schmidt BVKJ, Barner-Kowollik C. 2013. Polymer Chemistry: Macromolecules Made to Order. Nature Chemistry 5(12): 990-992.
Xie M, Dang J, Han H, Wang W, Liu J, He X, Zhang Y. 2008. Well-defined brush copolymers with high grafting density of amphiphilic side chains by combination of ROP, ROMP, and ATRP. Macromolecules 41(23): 9004-9010.
Yang G, Chai Y, Zhang P. 2011. Synthesis of PMMA-b-PS by RAFT Mini-emulsion Polymerization and their Self-Assembly. Journal of Polymer Materials 28(4): 517-523.