Abstract
In this study, novel zwitterionic diblock copolymers, namely poly(2-(N-morpholino)ethyl methacrylate))-block-poly(2-(methacryloyloxy)ethyl phosphate) (PMEMA-b-PMOEP) and poly(2-(N-morpholino)ethyl methacrylate))-block-poly ((methacryloyloxy)methyl phosphonic acid) (PMEMA-b-PMOMP), were synthesized via reversible addition-fragmentation chain transfer controlled radical polymerization. Solution properties of these phosphorus-based diblock copolymers were investigated using dynamic light scattering, transmission electron microscopy and proton nuclear magnetic resonance spectroscopy. Since the PMEMA block has both salt- and thermo-responsive properties, PMEMA-b-PMOEP and PMEMA-b-PMOMP diblock copolymers formed core-shell micelles in basic aqueous media as the PMEMA block formed insoluble micelle core with the addition of Na2SO4 or an increase in temperature in basic solution. Additionally, PMEMA-b-PMOMP diblock copolymers interacted strongly with calcium cations and yielded reverse micellar structures via complexation of phosphate with metal cation in aqueous media.
Similar content being viewed by others
References
Y. L. Gefter, in Organophosphorus Monomers and Polymers, Pergamon Press, 1962, pp 265–288.
E. D. Weil, in Encyclopedia of Polymer Science and Technology, 3, 447 (2001).
E. D. Weil, in Encyclopedia of Polymer Science and Engineering, 11, 96 (1988).
J. Kaiser, B. Schied, N. Trautmann, and W. Vogt, Makromol. Chem. Macromol. Chem. Phys., 193, 799 (1992).
K. Kaluzynski, J. Pretula, G. Lapienis, M. Basko, Z. Bartczak, A. Dworak, and S. Penczek, J. Polym. Sci. Part A: Polym. Chem., 39, 955 (2001).
S. Monge, B. Canniccioni, A. Graillot, and J. J. Robin, Biomacromolecules, 12, 1973 (2011).
Y. Iwasaki, C. Nakagawa, M. Ohtomi, K. Ishihara, and K. Akiyoshi, Biomacromolecules, 5, 1110 (2004).
J. Wang, H. Q. Mao, and K. W. Leong, J. Am. Chem. Soc., 123, 9480 (2001).
Y. D. Lei, T. X. Wang, J. W. Mitchell, L. Zaidel, J. H. Qiu, and L. Kilpatrick-Liverman, RSC Adv., 4, 49053 (2014).
Y. Kim, D. Priddy, and H. J. Harwood, Polymer, 44, 4165 (2003).
J. R. Ebdon, D. Price, B. J. Hunt, P. Joseph, F. G. Gao, G. J. Milnes, and L. K. Cunliffe, Polym. Degrad. Stab., 69, 267 (2000).
E. Bayer, P.-A. Grathwohl, and K. Geckeler, Angew. Makromol. Chem., 113, 141 (1983).
P.-L. Kuo, J.-S. Wang, P.-C. Chen, and L.-W. Chen, Macromol. Chem. Phys., 202, 2175 (2001).
D. Derouet, F. Morvan, and J.-C. Brosse, Eur. Polym. J., 37, 1297 (2001).
G.-N. Wang, P. S. Lau, Y. Li, and X.-S. Ye, Tetrahedron, 68, 9405 (2012).
J. Wen and R. X. Zhuo, Macromol. Rapid Commun., 19, 641 (1998).
S. Penczek, J. Polym. Sci. Part C: Polym. Symp., 149 (1980).
G. David, Z. El Asri, S. Rich, P. Castignolles, Y. Guillaneuf, P. Lacroix-Desmazes, and B. Boutevin, Macromol. Chem. Phys., 210, 631 (2009).
B. Canniccioni, S. Monge, G. David, and J. J. Robin, Polym. Chem., 4, 3676 (2013).
G. Moad, E. Rizzardo, and S. H. Thang, Polymer, 49, 1079 (2008).
S. Suzuki, M. R Whittaker, L. Grondahl, M. J. Monteiro, and E. Wentrup-Byrne, Biomacromolecules, 7, 3178 (2006).
R. Menard, C. Negrell-Guirao, L. Ferry, R. Sonnier, and G. David, Eur. Polym. J., 57, 109 (2014).
Y. Iwasaki, A. Matsumoto, and S.-I. Yusa, ACS Appl. Mater. Interfaces, 4, 3254 (2012).
A. Hanisch, P. Yang, A. N. Kulak, L. A. Fielding, F. C. Meldrum, and S. P. Armes, Macromolecules, 49, 192 (2016).
B. Canniccioni, S. Monge, G. David, and J.-J. Robin, Polym. Chem., 4, 3676 (2013).
G. David, C. Negrell, A. Manseri, and B. Boutevin, J. App. Polym. Sci., 114, 2213 (2009).
J. Y. Huang and K. Matyjaszewski, Macromolecules, 38, 3577 (2005).
J. C. Tom, R. Brilmayer, J. Schmidt, and A. Andrieu-Brunsen, Polymers (Basel, Switz.), 9, 539/1 (2017).
H. T. T. Duong, Y. H. Chen, S. A. Tawfik, S. H. Wen, M. Parviz, O. Shimoni, and D. Y. Jin, RSC Adv., 8, 4842 (2018).
T. Huang, H. Liu, P. Liu, P. Liu, L. Li, and J. Shen, J. Mater. Chem. B, 5, 5380 (2017).
B. Canniccioni, S. Monge, G. David, and J.-J. Robin, Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.), 52, 645 (2011).
D. B. Hua, J. Tang, J. L. Jiang, and X. L. Zhu, Polymer, 50, 5701 (2009).
D. Hua, J. Tang, J. Jiang, X. Zhu, and R. Bai, Macromolecules, 42, 8697 (2009).
P. G. Falireas, C. Negrell, and G. David, Polymers-Basel, 10 (2018).
M. Jasieniak, S. Suzuki, M. Monteiro, E. Wentrup-Byrne, H. J. Griesser, and L. Grondahl, Langmuir, 25, 1011 (2009).
F. Azemar, D. Gomes-Rodrigues, J. J. Robin, and S. Monge, Dalton T, 45, 1881 (2016).
M. Douverne, Y. Ning, A. Tatani, F. C. Meldrum, and S. P. Armes, Angew. Chem. Int. Ed., 58, 8692 (2019).
C. Tian, T. C. Xu, L. F. Zhang, Z. P. Cheng, and X. L. Zhu, RSC Adv., 6, 34659 (2016).
B. Rixens, R. Severac, B. Boutevin, P. Lacroix-Desmazes, and Y. Hervaud, Macromol. Chem. Phys., 206, 1389 (2005).
C. Bouilhac, C. Travelet, A. Graillot, S. Monge, R. Borsali, and J. J. Robin, Polym. Chem., 5, 2756 (2014).
K. H. Markiewicz, L. Seiler, I. Misztalewska, K. Winkler, S. Harrisson, A. Z. Wilczewska, M. Destarac, and J. D. Marty, Polym. Chem., 7, 6391 (2016).
X. H. Liu, X. Tan, R. Rao, Y. Y. Ren, Y. H. Li, X. L. Yang, and W. Liu, ACS Appl. Mater. Interfaces, 8, 23450 (2016).
Y. Iwasaki, A. Matsumoto, and S. Yusa, ACS Appl. Mater. Interfaces, 4, 3254 (2012).
A. Graillot, S. Monge, C. Faur, D. Bouyer, and J. J. Robin, Polym. Chem., 4, 795 (2013).
C. Dolan, B. Naysmith, S. F. R. Hinkley, I. M. Sims, M. A. Brimble, D. E. Williams, and J. Y. Jin, Aust. J. Chem., 68, 680 (2015).
I. Blidi, O. Coutelier, and M. Destarac, J. Polym. Sci. Pol. Chem., 52, 2616 (2014).
Y. Y. Mai and A. Eisenberg, Chem. Soc. Rev., 41, 5969 (2012).
S. B. Darling, Prog. Polym. Sci., 32, 1152 (2007).
G. Kocak C. Tuncer, and V. Bütün, Polym. Chem., 8, 144 (2017).
C. Giacomelli, V. Schmidt, K. Aissou, and R. Borsali, Langmuir, 26, 15734 (2010).
H. C. Kim, S. M. Park, and W. D. Hinsberg, Chem. Rev., 110, 146 (2010).
X. B. Xiong, A. Falamarzian, S. M. Garg, and A. Lavasanifar, J. Control. Release, 155, 248 (2011).
V. Butun, S. P. Armes, and N. C. Billingham, Polymer, 42, 5993 (2001).
V. Butun, F. F. Taktak, and C. Tuncer, Macromol. Chem. Phys., 212, 1115 (2011).
V. Butun, A. B. Lowe, N. C. Billingham, and S. P. Armes, J. Am. Chem. Soc., 121, 4288 (1999).
V. Butun, X. S. Wang, M. V. D. Banez, K. L. Robinson, N. C. Billingham, S. P. Armes, and Z. Tuzar, Macromolecules, 33, 1 (2000).
T. Wang, Y. Lei, J. W. Mitchell, L. Zaidel, J. Qiu, and M. Hassan, US Patent, US 2015/0283061 A1 (2015).
D. J. Phillips, M. Wilde, F. Greco, and M. I. Gibson, Biomacromolecules, 16, 3256 (2015).
C. Chang, H. Wei, J. Feng, Z. C. Wang, X. J. Wu, D. Q. Wu, S. X. Cheng, X. Z. Zhang, and R. X. Zhuo, Macromolecules, 42, 4838 (2009).
G. Kocak and V. Butun, Colloid. Polym. Sci., 293, 3563 (2015).
Author information
Authors and Affiliations
Corresponding author
Additional information
Supporting information
Information is available regarding the experimental procedure for the synthesis of monomers and diblock copolymers and their characterizations. The materials are available via the Internet at http://www.springer.com/13233.
Publisher’s Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Footnote: The image from this article is used as the cover image of the Volume 28, Issue 12.
Acknowledgments: Y. Samav thanks The Scientific and Technological Research Council of Turkey for the financial support given under its BIDEB 2211-A Domestic Graduate Scholarship Program.
Supporting information
Rights and permissions
About this article
Cite this article
Samav, Y., Akpinar, B., Kocak, G. et al. Preparation of Responsive Zwitterionic Diblock Copolymers Containing Phosphate and Phosphonate Groups. Macromol. Res. 28, 1134–1141 (2020). https://doi.org/10.1007/s13233-020-8148-3
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s13233-020-8148-3