Synthesis of Poly(methyl methacrylate)- b -poly( N -isopropylacrylamide) Block Copolymer by Redox Polymerization and Atom Transfer Radical Polymerization

Melahat Göktaş; Guodong Deng

doi:10.22146/ijc.28645

Synthesis of Poly(methyl methacrylate)-b-poly(N-isopropylacrylamide) Block Copolymer by Redox Polymerization and Atom Transfer Radical Polymerization

https://doi.org/10.22146/ijc.28645

Melahat Göktaş^(1*), Guodong Deng⁽²⁾

(1) Yüzüncü Yıl University, Department of Science Education, Van, 65100, Turkey
(2) University of Akron, Department of Polymer Engineering, 250 S Forge St, Akron, OH 44325 USA
(*) Corresponding Author

Abstract

Poly(methyl methacrylate)-b-poly(N-isopropylacrylamide) [PMMA-b-PNIPAM] block copolymers were obtained by a combination of redox polymerization and atom transfer radical polymerization (ATRP) methods in two steps. For this purpose, PMMA macroinitator (ATRP-macroinitiator) was synthesized by redox polymerization of methyl methacrylate and 3-bromo-1-propanol using Ce(NH₄)₂(NO₃)₆as a catalyst. The synthesis of PMMA-b-PNIPAM block copolymers was carried out by means of ATRP of ATRP-macroinitiator and NIPAM at 60 °C. The block copolymers were obtained in high yield and high molecular weight. The characterization of products was accomplished by using multi instruments and methods such as nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, gel permeation chromatography, and thermogravimetric analysis.

Keywords

atom transfer radical polymerization; redox polymerization; macroinitiator; block copolymer; methyl methacrylate

Full Text:

Full Text PDF

References

[1] Zaremski, M., Eremeev, I., Garina, E., Borisova, O., and Korolev, B., 2017, Controlled synthesis of random, block-random and gradient styrene, methyl methacrylate and acrylonitrile Terpolymers via nitroxide-mediated free radical polymerization, J. Polym. Res., 24 (9), 151.

[2] Okada, S., and 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.

[3] Han, D.H., and Pan, C.Y., 2007, Preparation and characterization of heteroarm H-shaped terpolymers by combination of reversible addition-fragmentation transfer polymerization and ring-opening polymerization, J. Polym. Sci., Part A: Polym. Chem., 45 (5), 789–799.

[4] Shipp, D.A., Wang, J., and Matyjaszewski, K., 1998, Synthesis of acrylate and methacrylate block copolymers using atom transfer radical polymerization, Macromolecules, 31 (23), 8005–8008.

[5] Wi, Y., Lee, K., Hyung, B., and Choe, S., 2008, Soap-free emulsion polymerization of styrene using poly(methacrylic acid) macro-RAFT agent, Polymer, 49 (26), 5626–5635.

[6] Göktaş, M., Öztürk, T., Atalar, M.N., Tekeş, A.T., and 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 Pure Appl. Chem., 51 (11), 854–863.

[7] Hong, J., Wang, Q., and Fan, Z., 2006, Synthesis of multiblock polymer containing narrow polydispersity blocks, Macromol. Rapid. Commun., 27, 57–62.

[8] Rwei, S.P., Chuang, Y.Y., and Way, T.F., 2015, Preparation of thermo-responsive star copolymers via ATRP and its use in drug release application, Colloid Polym. Sci., 293 (2), 493–503.

[9] Öztürk, T., Göktaş, M., and Hazer, B., 2010, One-step synthesis of triarm block copolymers via simultaneous reversible-addition fragmentation chain transfer and ring-opening polymerization, J. Appl. Polym. Sci., 117 (3), 1638–1645.

[10] Wang, J.S., and Matyjaszewski, K., 1995, Controlled/"Living" radical polymerization. Halogen atom transfer radical polymerization promoted by a Cu(I)/Cu(II) redox process, Macromolecules, 28 (23), 7901–7910.

[11] Öztürk, T., Yavuz, M., Göktaş, M., and Hazer, B., 2016, One-step synthesis of triarm block copolymers by simultaneous atom transfer radical and ring-opening polymerization, Polym. Bull., 73 (6), 1497–1513.

[12] Ozturk, T., Yilmaz, S.S., and 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, J. Macromol. Sci. Part A Pure Appl. Chem., 45 (10), 811–820.

[13] Yu, W.N., Liu, S.X., Wang, H.M., and Tian, R., 2012, Synthesis an micellization of P(NIPAM-co-HMAM)-b-P(NIPAM-co-HMAM) triblock copolymers, J. Polym. Res., 19 (11), 9989.

[14] Öztürk, T., Kayğın, O., Göktaş, M., and Hazer, B., 2016, Synthesis and characterization of graft copolymers based on polyepichlorohydrin via reversible addition-fragmentation chain transfer polymerization, J. Macromol. Sci. Part A Pure Appl. Chem., 53 (6), 362–367.

[15] Hazer, B., Çakmak, İ., Denizligil, S., and Yağcı, Y., 1992, Preparation of multiphase block copolymers by redox polymerization, Angew. Makromol. Chem., 195 (1), 121–127.

[16] Erciyes, A.T., Erim, M., Hazer, B., and Yağcı, Y., 1992, Synthesis of polyacrylamide flocculants with PEG segments by redox polymerization, Angew. Makromol. Chem., 200, 163–171.

[17] Arslan, H., Eroglu, M.S., and Hazer, B., 2001, Ceric ion initiation of methyl methacrylate from poly(glycidyl azide)-diol, Eur. Polym. J., 37 (3), 581–585.

[18] Stoeckel, N., Wieland, P.C., and Nuyken, O., 2002, New synthesis of graft copolymers using the DPE-technique: ATRP graft copolymerization, Polym. Bull., 49 (4), 243–250.

[19] Öztürk, T., Atalar., M.N., Göktaş, M., and 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.

[20] Öztürk, T., and 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 Appl. Chem., 47 (3), 265–272.

[21] Öztürk, T., Göktaş, M., Savaş, B., Işıklar, M., Atalar, M.N., and 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.

[22] Hazer, B., 1991, Synthesis of styrene-tetrahydrofuran branched block copolymers, Eur. Polym. J., 27 (9), 975–978.

[23] Öztürk, T., Göktaş, M., and 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 Pure Appl. Chem., 48 (1), 65–72.

[24] Bosman, A.W., Vestberg, R., Heumann, A., Frechet, J.M.J., and Hawker, C.J.J., 2003, A modular approach toward functionalized three-dimensional macromolecules: From synthetic concepts to practical applications, J. Am. Chem. Soc., 125 (3), 715–728.

[25] Haraguchi, N., and Hirao, A., 2003, Synthesis of well-deﬁned star-linear block polystyrenes by coupling reaction of chain-functionalized polystyrenes with a deﬁnite number of benzyl bromide moieties with polystyryllithiums, Macromolecules, 36 (25), 9364–9372.

[26] Li, Z., Hillmyer, M.A., and Lodge, T.P., 2004, Synthesis and characterization of triptych μ-ABC star triblock copolymers, Macromolecules, 37 (24), 8933–8940.

[27] Shinoda, H., and Matyjaszewski, K., 2001, Improving the structural control of graft copolymers. Copolymerization of poly (dimethyl siloxane) macromonomer with methyl methacrylate using RAFT polymerization, Macromol. Rapid Commun., 22 (14), 1176–1181.

[28] Chen, M., Ghiggino, K.P., Launikonis, A., Mau, AWH., Rizzardo, E., Sasse, WHF., Thang, SH., and Wilson, G.J., 2003, RAFT synthesis of linear and star-shaped light harvesting polymers using di- and hexafunctional ruthenium polypyridine reagents, J. Mater. Chem., 13 (11) 2696–2700.

[29] Roy, D., Guthrie, J.T., and Perrier, S., 2005, Graft polymerization: grafting poly(styrene) from cellulose via reversible addition-fragmentation chain transfer (RAFT) polymerization, Macromolecules, 38 (25), 10363–13372.

[30] Fragouli, P.G., Iatrou, H., Hadjichristidis, N., Sakurai, T., and Hirao, A., 2006, Synthesis and characterization of model 3-miktoarm star copolymers of poly(dimethylsiloxane) and poly(2-vinylpyridine), J. Polym. Sci., Part A: Polym. Chem., 44 (1), 614–619.

DOI: https://doi.org/10.22146/ijc.28645