Synthesis and characterization of poly(styrene-b-methyl methacrylate) block copolymers via ATRP and RAFT

Year 2019, Volume: 9 Issue: 1, 139 - 149, 01.03.2019

Melahat Göktaş

https://doi.org/10.21597/jist.435934

Cited By: 9

Abstract

Well-defined block copolymers of styrene (S) and methyl methacrylate (MMA) poly(Styrene-b-methyl methacrylate) [poly(S-b-MMA)] with narrow molecular weight distribution were synthesized via atom transfer radical polymerization (ATRP) and recycle additive fragmentation chain transfer (RAFT) polymerization methods using macro RAFT macroinitiator in two step. Poly-S based RAFT macroinitiator was reported from the reaction of potassium salt of ethyl xanthegonate and homo Poly-S which is synthesized by atom transfer radical polymerization of styrene using 3-chloro-1-propanol initiator. Subsequently, the synthesis of poly(S-b-MMA) block copolymers were acquired via RAFT of poly-S based RAFT macroinitiator and MMA at 90 0C. Poly(S-b-MMA) block copolymers were comparatively acquired in high yield and high molecular weight. The characterization of homo poly-S, RAFT macroinitiator, and poly(S-b-MMA) block copolymers were carried out by nuclear magnetic resonance spectroscopy, fourier transform infrared spectroscopy, gel permeation chromatography, thermogravimetric analysis and elemental analysis.

Keywords

ATRP , RAFT macroinitiator , block copolymer , methyl methacrylate , styrene

References

• Chiefari J, Chong YK, Ercole F, Krstina J, Jeffery J, Le TPT, Mayadunne RTA, Meijs GF, Moad CL, Moad E, Rizzardo E, Thang SH. 1998. “Living Free-Radical Polymerization by Reversible Addition-Fragmentation Chain Transfer: The RAFT Process” Macromolecules, 31(16): 5559-5562.
• Conzatti G, Cavalie S, Combes C, Torrisani J, Carrere N, Tourrette A, 2017. “PNIPAM grafted surfaces through ATRP and RAFT polymerization: Chemistry and bioadhesion.” Colloids and Surfaces B: Biointerfaces, 151: 143-155.
• Çakmak İ, Öztürk T, Yıldıko 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”, Iğdır Univ. J. Inst. Sci. & Tech. 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.” J Macromol Sci Part A, 51(11):854-863.
• Hazer B, 1991. “Synthesis of styrene-tetrahydrofuran branched block copolymers.” Eur Polym J, 27(9):975–978.
• Heidenreich AJ, Puskas JE, 2008. “Synthesis of Arborescent (Dendritic) Polystyrenes via Controlled Inimer-Type Reversible Addition-Fragmentation Chain Transfer Polymerization.” J Polym Sci Part A Polym Chem, 46(23):7621-7627.
• 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: 990-98.
• Liu H, Tang D, Tang R, Zhao Y, 2015. “Synthesis of multifunctional ABC stars with a reduction-labile arm by consecutive ROP RAFT and ATRP processes.” Science China Chemistry, 58(11):1724-1733.
• Luan B, Zhang BQ, Pan CY, 2006. “Synthesis and characterizations of well-defined branched polymers with AB(2) branches by combination of RAFT polymerization and ROP as well as ATRP.” J Polym Sci Part A Polym Chem, 44(1):549-560.
• Maitrayee Saikia, Somip Borphukan, Urmilla Baruah, Arvind Gautam, Prakash J. Saikia, Shashi D. Baruah, 2018. “Poly(ethylene-co-BMA) via dual concurrent ATRP–RAFT and its thermokinetic study.” J Therm Anal Calorim, 131(2):1517–1526.
• Mishra AK, Choi C, Maiti S, Seo Y, Lee KS, Kim E, Kim JK, 2018. “Sequential synthesis of well-defined poly(vinyl acetate) blockpolystyreneand poly(vinyl alcohol)-block-polystyrene copolymers using difunctional chloroamide-xanthate iniferter” Polymer, 139: 68-75.
• Mugang P, Decheng W, Junlian H, 2010. “Preparation of a Novel Coplymer of Hyperbranched poly-glyserol with Multi-arms of poly(N-isopropylacrylamide).” Chin J Chem, 28(4):499-503.
• Okada S, Matyjaszewski K (2015) “Synthesis of Bio-Based poly(N-phenylitaconimide) by Atom Transfer Radical polymerization.” J Polym Sci Part A Polym Chem, 53(6):822–827.
• 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.” J Polym Sci Part A Polym Chem, 51(12):2651–2659.
• Öztürk T, Hazer B, 2010. “Synthesis and characterization of a Novel Macromonomer Initiator for Reversible Addition Fragmentation Chain Transfer (RAFT). Evaluation of the polymerization Kinetics and Gelation Behaviors. J Macromol Sci Part A Pure and Appl Chem, 47(3):265-272.
• Öztürk T, Göktaş M, Hazer B, 2011. “Synthesis and Characterization of Poly(methyl methacrylate-block-ethylene glycol-block-methyl methacrylate) Block Copolymers by Reversible Addition-Fragmentation Chain Transfer Polymerization.” J Macromol Sci Part A, 48(1):65-72.
• Öztürk T, Kayğın O, Göktaş M, Hazer B, 2016. “Synthesis and Characterization of Graft Copolymers Based on Polyepichlorohydrin via Reversible Addition-Fragmentation Chain Transfer Polymerization.” Journal of Macromolecular Science, 53(6):362–367.
• Öztürk T, Meyvacı E, 2017. “Synthesis and Characterization Poly(Ɛ-Caprolactone-b- Ethylene Glycol-b-Ɛ-Caprolactone) Block Copolymers via "Click" Chemistry and Ring Opening Polymerization.” J Macromol Sci Part A, 54(9):575–581.
• Öztürk T, Göktaş M, Savaş B, Işıklar M, Atalar MN, Hazer B, 2014. “Synthesis and characterization of poly(vinylchloride-graft-2-vinylpyridine) graft copolymersusing a novel macroinitiator by reversible addition-fragmentation chain transfer polymerization.” e-Polymers, 14(1):27–34.
• Öztürk T, Yavuz M, Göktaş M, Hazer B, 2016. “One-step synthesis of triarm block copolymers by simultaneous atom transfer radical and ring-opening polymerization.” Polymer Bulletin, 73(6):1497–1513.
• 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.
• Syang-Peng R, Chuang YY, Way TF, 2015. “Preparation of thermo-responsive star copolymers via ATRP and its use in drug release application.” Colloid and Polymer Science, 293(2):493-503.
• Spiridon MC, Aissou K, Mumtaz M, Brochon C, Cloutet E, Fleury G, Hadziioannou G, 2018. “Surface relief gratings formed by microphase-separated disperse red 1 acrylate-containing diblock copolymers.” Polymer, 137: 378-384.
• Wang Z, Wang Z, Pan X, Fu L, Lathwal S, Olszewski M, Yan J, Enciso AE, Wang Z, Xia H, Matyjaszewski K, 2018. “Ultrasonication-Induced Aqueous Atom Transfer Radical Polymerization” ACS Macro Letters, 7(3):275−280.
• Wang JS, Matyjaszewski K, 1995. “Controlled/"Living" Radical Polymerization. Halogen Atom Transfer Radical Polymerization Promoted by a Cu(I)/Cu( 11) Redox Process.” Macromolecules, 28(23):7901-7910.
• Wilson OR, Magenau AJD, 2018. “Oxygen Tolerant and Room Temperature RAFT through Alkylborane Initiation” ACS Macro Letters, 7(3): 370−375.
• Wi Y, Lee K, Hyung B, Choe, S, 2008. “Soap-free emulsion polymerization of styrene using poly (methacrylic acid) macro-RAFT agent.” Polymer, 49(26):5626–5635.
• Zaremski M, Eremeev I, Garina E, Borisova O, Korolev B, 2017. “Controlled synthesis of random, block-random and gradient styrene methyl methacrylate and acrylonitrile Terpolymers via Nitroxide-mediated free radical polymerization.” Journal of polymer research, 24(9): 151.
• Zhang WA, Wang SH, Li XH, Yuan JY, Wang SL, 2012. “Organic/inorganic hybrid star-shaped block copolymers of poly(L- lactide) and poly(N-isopropylacrylamide) with a polyhedral oligomeric silsesquioxane core: Synthesis and self-assembly.” European polymer Journal, 48(4):720-729.