Spontaneous synthesis of a homogeneous thermoresponsive polymer network composed of polymers with a narrow molecular weight distribution
Source abstract
Abstract
We have developed a method to obtain a polymer gel consisting of a relatively homogeneous network structure composed of polymers with a narrow molecular weight simply by mixing the necessary compounds. In this method, a radical chain polymerization reaction with a fast reaction rate is combined with a radical addition cross-linking reaction that has a sufficiently slow reaction rate compared with the polymerization reaction. For the polymerization reaction, a multifunctional initiator with a strictly controlled number of polymerization initiation sites was used to prepare a star polymer with a chain number and length determined by living radical polymerization. In the cross-linking reaction, a multifunctional terminating agent was used to prepare a star polymer from a polymer with a narrow molecular weight via living radical polymerization followed by coupling with multiple polymer chains using a termination reaction. As a result, two kinds of reactions with greatly different kinetics occurred sequentially only when all of the compounds were mixed and allowed to stand at a constant temperature, and a relatively homogeneous network structure comprising cross-linked polymers with a low molecular weight distribution was inherently constructed. Japanese researchers have developed an easy method for synthesizing networks of more uniformly sized polymer molecules which produce soft materials with a greater range of functionality. Polymer gels are made of three-dimensional chains of connected polymer molecules within a swollen solvent. These soft materials have potential applications in drug delivery, as shape memory materials and in soft robotics. Many polymer gels, however, are made up of chains of polymers with different molecular weights. These inhomogeneous networks may not have the all the functionality of a uniform polymer. Kotaro Satoh and Yukikazu Takeoka from Nagoya University and colleagues have now developed a method for synthesizing a network structure composed of polymers of similar size. The polymer gel can be created by simply mixing the necessary compounds together. We have developed a method to obtain a polymer gel consisting of a relatively homogeneous network structure composed of polymers of narrow molecular weight simply by mixing the necessary compounds. In this method, two kinds of reactions with greatly different kinetics occurred sequentially only when all the compounds were mixed and allowed to stand at a constant temperature, and a relatively homogeneous network structure comprising cross linked polymers of low-molecular-weight distribution was spontaneously constructed.
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Research context
OpenAlex topics: Advanced Polymer Synthesis and Characterization · Hydrogels: synthesis, properties, applications · Innovative Microfluidic and Catalytic Techniques Innovation
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (32)
Show source-provided references
1. Osada, Y. & Gong, J. P. Soft and wet materials: polymer gels. Adv. Mater. 10, 827 (1998).10.1002/(SICI)1521-4095(199808)10:11<827::AID-ADMA827>3.0.CO;2-L ↗
2. Tanaka, T. Gels. Sci. Am. 244, 124 (1981).10.1038/scientificamerican0181-124 ↗
3. Imran, A. B. et al. Extremely stretchable thermosensitive hydrogels prepared by introducing polyrotaxane-based slide-ring cross-linkers and ionic groups into the polymer network. Nat. Commun. 5, 5124 (2014).
4. Alvarez-Lorenzo, T. et al. Polymer gels that memorize elements of molecular conformation. Macromolecules 33, 8693 (2000).10.1021/ma000603v ↗
5. Takeoka, Y. et al. First order phase transition and evidence for frustrations in polyampholytic gels. Phys. Rev. Lett. 82, 4863 (1999).10.1103/PhysRevLett.82.4863 ↗
6. Takeoka, Y. & Seki, T. Visualizing conformations of subchains by creating optical wavelength-sized periodically ordered structure in hydrogel. Langmuir 22, 10223 (2006).10.1021/la061945i ↗
7. Nakayama, D., Takeoka, Y., Watanabe, M. & Kataoka, K. Simple and precise preparation of a porous gel for a colorimetric glucose sensor by a templating technique. Angew. Chem. Int. Ed. 42, 4197 (2003).10.1002/anie.200351746 ↗
8. Matsubara, K., Watanabe, M. & Takeoka, Y. A thermally adjustable multicolor photochromic hydrogel. Angew. Chem. Int. Ed. 46, 1688 (2007).10.1002/anie.200603554 ↗
9. Shibayama, M. Small-angle neutron scattering on polymer gels: phase behavior, inhomogeneities and deformation mechanisms. Polym. J. 43, 18 (2011).10.1038/pj.2010.110 ↗
10. Bromberg, L., Grosberg, A. Y., Matsuo, E. S., Suzuki, Y. & Tanaka, T. Dependency of swelling on the length of subchain in poly(N,N-dimethylacrylamide)-based gels. J. Chem. Phys. 106, 2906 (1997).10.1063/1.474084 ↗
11. Bastide, J., Leibler, L. & Prost, J. Scattering by deformed swollen gels - butterfly isointensity patterns. Macromolecules 23, 1821 (1990).10.1021/ma00208a044 ↗
12. Urayama, K. & Kohjiya, S. Crossover of the concentration dependence of swelling and elastic properties for polysiloxane networks crosslinked in solution. J. Chem. Phys. 104, 3352 (1996).10.1063/1.471018 ↗
13. Urayama, K., Kawamura, T. & Kohjiya, S. Elastic modulus and equilibrium swelling of networks crosslinked by end-linking oligodimethylsiloxane at solution state. J. Chem. Phys. 105, 4833 (1996).10.1063/1.472320 ↗
14. Ida, S., Kimura, R., Tanimoto, S. & Hirokawa, Y. End-crosslinking of controlled telechelic poly (N-isopropylacrylamide) toward a homogeneous gel network with photo-induced self-healing. Polym. J. 49, 237 (2017).10.1038/pj.2016.112 ↗
15. Sakai, T. et al. Design and fabrication of a high-strength hydrogel with ideally homogeneous network structure from tetrahedron-like macromonomers. Macromolecules 41, 5379 (2008).10.1021/ma800476x ↗
16. Matsumoto, A. et al. Demonstration of thermo-sensitive tetra-gel with implication for facile and versatile platform for a new class of smart gels. J. Biomater. Sci. Polym. Ed. 28, 1000 (2017).10.1080/09205063.2017.1316536 ↗
17. Wang, J. et al. Preparation of well-defined propargyl-terminated tetra-arm poly(N-isopropylacrylamide)s and their click hydrogels crosslinked with _-cyclodextrin. Polymers 8, 93 (2016).10.3390/polym8040093 ↗
18. 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 28, 1721 (1995).10.1021/ma00109a056 ↗
19. Rizzardo, E. et al. RAFT polymerization: adding to the picture. Macromol. Symp. 248, 104 (2007).10.1002/masy.200750211 ↗
20. Hawker, C. J. Molecular-weight control by a living free-radical polymerization process. J. Am. Chem. Soc. 116, 11185 (1994).10.1021/ja00103a055 ↗
21. Nguyen, N. H., Rosen, B. M. & Percec, V. SET-LRP of N,N-dimethylacrylamide and of N-isopropylacrylamide at 25 degrees C in protic and in dipolar aprotic solvents. J. Polym. Sci. Pol. Chem. 48, 1752 (2010).10.1002/pola.23940 ↗
22. Masci, G., Giacomelli, L. & Crescenzi, V. Atom transfer radical polymerization of N-isopropylacrylamide. Macromol. Rapid Commun. 25, 559 (2004).10.1002/marc.200300140 ↗
23. Millard, P. E., Mougin, N. C., Boker, A. & Muller, A. H. E. Controlling the fast ATRP of N-isopropylacrylamide in water. ACS Sym Ser. 1023, 127 (2009).10.1021/bk-2009-1023.ch009 ↗
24. Mizutani, M., Satoh, K. & Kamigaito, M. Metal-catalyzed simultaneous chain- and step-growth radical polymerization: marriage of vinyl polymers and polyesters. J. Am. Chem. Soc. 132, 7498 (2010).10.1021/ja1023892 ↗
25. Mizuntani, M., Satoh, K. & Kamigaito, M. Degradable Poly(N-isopropylacrylamide) with tunable thermosensitivity by simultaneous chain- and step-growth radical polymerization. Macromolecules 44, 2382 (2011).10.1021/ma2000465 ↗
26. Rosen, B. M. & Percec, V. Single-electron transfer and single-electron transfer degenerative chain transfer living radical polymerization. Chem. Rev. 109, 5069 (2009).10.1021/cr900024j ↗
27. Amiya, T., Hirokawa, Y., Hirose, Y., Li, Y. & Tanaka, T. Reentrant phase-transition of N-isopropylacrylamide gels in mixed-solvents. J. Chem. Phys. 86, 2375 (1987).10.1063/1.452740 ↗
28. Jung, S. C., Oh, S. Y. & Bae, Y. C. Reentrant swelling behavior of thermosensitive N-isopropylacrylamide nano-sized gel particles. Polymer 50, 3370 (2009).10.1016/j.polymer.2009.05.011 ↗
29. Kojima, H. & Tanaka, F. Reentrant volume phase transition of cross-linked poly(N-isopropylacrylamide) gels in mixed solvents of water/methanol. Soft Matter 8, 3010 (2012).10.1039/c2sm06883d ↗
30. Costa, R. O. R. & Freitas, R. F. S. Phase behavior of poly(N-isopropylacrylamide) in binary aqueous solutions. Polymer 43, 5879 (2002).10.1016/S0032-3861(02)00507-4 ↗
31. Hirokawa, Y. et al. Sponge-like heterogeneous gels: hierarchical structures in Poly(N-isopropylacrylamide) chemical gels as observed by combined scattering and confocal microscopy method. Macromolecules 41, 8210 (2008).10.1021/ma800518t ↗
32. Halperin, A., Kroger, M. & Winnik, F. M. Poly(N-isopropylacrylamide) phase diagrams: fifty years of research. Angew. Chem. Int. Ed. 54, 15342 (2015).10.1002/anie.201506663 ↗