We succeeded in developing a novel class of acrylic acid (AA)-based superabsorbent polymers (SAPs) with remarkably improved absorption performance by applying iodine transfer polymerization (ITP). A specific organoiodine chain transfer agent was newly developed and found to provide moderate to good control over the polymerization of AA in aqueous solution. Dynamic light scattering (DLS) measurements revealed that the polymer network prepared using our ITP technology is relatively homogeneous. Our new SAP exhibits a good balance between absorption capacity and gel strength, and it enables a quick response to diversified customer needs in the diaper industry. To the best of our knowledge, this work is the first case in which reversible-deactivation radical polymerization (RDRP) has been practically applied to commodity polymer products. This review focuses on how we connected the old but highly practical ITP and SAP production.
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Buchholzs, FL, Graham, AT, editors Modern superabsorbent polymer technology. New York: Wiley-VCH; 1998.
Tatemoto M, Suzuki T, Tomoda M, Furukawa Y, Ueta Y. Fluorine-containing polymer easily curable and its curable composition. JP S53-125491A. Japan: Daikin Kogyo Co., Ltd; 1978.
Oka M, Tatemoto M. Vinylidene fluoride-hexafluoropropylene copolymer having terminal iodines. Contemp Top Polym Sci. 1984;4:763–77.
Tatemoto M. Development of “iodine transfer polymerization” and its applications to telechelically reactive polymers. Kobunshi Ronbunshu. 1992;49:765–83.
David G, Boyer C, Tonnar J, Ameduri B, Lacroix-Desmazes P, Boutevin P. Use of iodocompounds in radical polymerization. Chem Rev. 2006;106:3936–62.
Ni Y, Zhang L, Cheng Z, Zhu X. Iodine-mediated reversible-deactivation radical polymerization: a powerful strategy for polymer synthesis. Polym Chem. 2009;10:2504–15.
Flory, PJ. Principles of polymer chemistry. Ithaca: Cornell University Press; 1953. p.589.
Shibayama M. Spatial inhomogeneity and dynamic fluctuations of polymer gels. Macromol Chem Phys. 1998;199:1–30.
Lorenzo FD, Seiffert S. Nanostructural heterogeneity in polymer networks and gels. Polym Chem. 2015;6:5515–28.
Seiffert S. Origin of nanostructural inhomogeneity in polymer-network gels. Polym Chem. 2017;8:4472–87.
Matyjaszewski K, Müller AHE, editors Controlled and living polymerizations. Wiley-VCH Verlag GmbH & Co. KGaA; 2010.
Jenkins AD, Jones RG, Moad G. Terminology for reversible deactivation radical polymerization previously called “controlled” radical or “living” radical polymerization. Pure Appl Chem. 2009;82:483–91.
Norisuye T, Morinaga T, Tran-Cong-Miyata Q, Goto A, Fukuda T, Shibayama M. Comparison of the gelation dynamics for polystyrenes prepared by conventional and living radical polymerization: a time-resolved dynamic light scattering study. Polymer. 2005;46:1982–94.
Gao H, Matyjaszewski K. Synthesis of functional polymers with controlled architecture by CRP of monomers in the presence of cross-linkers: from stars to gels. Prog Polym Sci. 2009;34:317–50.
Voit B. New polymers: Beautiful structures, but how can we bring them to the market? Angew Chem Int Ed. 2017;56:2810–1.
Georges MK, Veregin RPN, Kazmaier PM, Hamer GK. Narrow molecular weight resins by a free-radical polymerization process. Macromolecules. 1993;26:2987–8.
Wang J-S, Matyjaszewski K. Controlled/“living” radical polymerization. Atom transfer radical polymerization in the presence of transition-metal complexes. J Am Chem Soc. 1995;117:5614–5.
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. 1995;28:1721–3.
Chiefari J, Chong YK, Ercole F, Krstina J, Jeffery J, Le TPT, Mayadunne RTA, Meijs GF, Moad CL, Moad G, Rizzardo E, Thang SH. Living free-radical polymerization by reversible addition-fragmentation chain transfer: the RAFT process. Macromolecules. 1998;31:5559–62.
Yamago S, Iida K, Yoshida J. Organotellurium compounds as novel initiators for controlled/living radical polymerizations. Synthesis of functionalized polystyrenes and end-group modifications. J Am Chem Soc. 2002;124:2874–5.
Lei L, Tanishima M, Goto A, Kaji H, Yamaguchi Y, Komatsu H, Jitsukawa T, Miyamoto M. Systematic study on alkyl iodide initiators in living radical polymerization with organic catalysts. Macromolecules. 2014;47:6610–8.
Matsubara Y, Miyajima T. Water-absorbent resin particles and method for producing same. WO2017-57706A1, Japan: SDP Global Co., Ltd; 2017.
Shibayama M, Norisuye T, Nomura S. Cross-link density dependence of spatial inhomogeneities and dynamic fluctuations of poly(N-isopropylacrylamide) gels. Macromolecules. 1996;29:8746–50.
Tanishima M, Goto A, Lei L, Ohtsuki A, Kaji H, Nomura A, Tsujii Y, Yamaguchi Y, Komatsu H, Miyamoto M. Macromolecular architectures designed by living radical polymerization with organic catalysts. Polymers. 2014;6:311–26.
Destarac M. Industrial development of reversible-deactivation radical polymerization: is induction period over? Polym Chem. 2018;9:4947–67.
Destarac M. Controlled radical polymerization: Industrial stakes, obstacles and achievements. Macromol React Eng. 2010;4:165–79.
The authors would like to thank Prof. A. Goto from Nanyang Technological University for helpful discussions and insightful suggestions.
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Miyajima, T., Matsubara, Y., Komatsu, H. et al. Development of a superabsorbent polymer using iodine transfer polymerization. Polym J 52, 365–373 (2020). https://doi.org/10.1038/s41428-019-0292-2
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