Synthesis of thermo- and photoresponsive polysilsesquioxane containing tetraethylene glycol chains and an azobenzene group

Alimada, Bagus; Yamamoto, Shin-ichi; Moriya, Osamu

doi:10.1038/pj.2013.92

Note
Published: 25 December 2013

Polymer Synthesis and Reactions

Synthesis of thermo- and photoresponsive polysilsesquioxane containing tetraethylene glycol chains and an azobenzene group

Bagus Alimada¹,
Shin-ichi Yamamoto¹ &
Osamu Moriya¹

Polymer Journal volume 46, pages 243–249 (2014)Cite this article

1106 Accesses
7 Citations
Metrics details

Subjects

Polymer synthesis

Polysilsesquioxane (PSQ) is known as a new member of the silicone family, which has a main chain that usually consists of T-type siloxane units.^{1, 2, 3} Various PSQs have been functionalized to be useful hybrid materials by modification of their organic substituents.^{4, 5, 6, 7} Because of the introduced organic group based on the inorganic polysiloxane backbone, the modified PSQ is expected to exhibit properties such as durability for heat and weatherability based on the inorganic polysiloxane backbone. Recently, the reversible thermoresponsive phase separation of synthetic polymers in aqueous solutions have attracted much attention.^{8, 9, 10} PSQs with the thermoresponsive property are expected to be practical hybrids, because such functionalized PSQs seem applicable to absorbents, biosensors, microencapsulation materials, drug delivery reagents and adhesives. Because of the interests in these expanded usages, we have continuously investigated the thermoresponsive PSQs by introducing polymeric and low-molecular-weight organic substituents.

Our studies have showed that the simple oxyethylene substituents with hydrophobic alkyl groups, such as methyl and ethyl groups, are effective in providing the thermoresponsive property to PSQs.^{11, 12, 13} Furthermore, in the previous works, the presence of polymeric ethylene glycols is reported to enable sensitive phase separation, easy tuning of the lower critical solution temperature (LCST) and multifunctionalization.^{14, 15} In addition, the polymeric oxyethylene structure possesses advantages, such as biocompatibility, amphiphilicity and high flexibility.^{16, 17, 18, 19, 20, 21, 22, 23} Therefore, the oxyethylene structures have been introduced into various polymers to lead to the stimuli-responsive properties in an aqueous solution.^{24, 25, 26} These studies suggest that the combination of the polysiloxane backbone with ethylene glycol chains provides a new multistimuli-responsive hybrid material that can be employed in various situations with environmental compatibility. This promising finding has led us to investigate the new thermoresponsive PSQs that contain the ethylene glycol chains.

References

Baney, R. H. & Cao, X. In Silicon-Containing PolymersJohns R. G., Ando W., Chojnowski J. Eds. (Kluwer, Dordrecht, 2000).
Google Scholar
Brown, J. F. Jr, Vogt, L. H. Jr, Katchman, A., Eustance, J. W., Kaiser, K. M. & Krantz, K. W. Double chain polymers of phenylsilsesquioxane. J. Am. Chem. Soc. 82, 6194–6195 (1960).
Article CAS Google Scholar
Roy, D. A. & Shea, K. J. Bridged polysilsesquioxanes. highly porous hybrid organic-inorganic materials. Chem. Rev. 95, 1431–1442 (1995).
Article Google Scholar
Kondo, T., Yoshi, K., Horie, K. & Itoh, M. Photoprove study of siloxane polymers. 3. Local free volume of polymethylsilsesquioxane proved by photoisomerization of azobenzene. Macromolecules 33, 3650–3658 (2000).
Article CAS Google Scholar
Gunji, T., Iizuka, Y., Arimitsu, K. & Abe, Y. Preparation and properties of alkoxy(methyl)silsesquioxanes as coating agents. J. Polym. Sci. A Polym. Chem. 42, 3676–3684 (2004).
Article CAS Google Scholar
Chauhan, B. P. S. & Latif, U. Inorganic/ organic hybrid nanoreactors based on cyclic and cubic siloxane scaffolds. Macromolecules 38, 6231–6235 (2005).
Article CAS Google Scholar
Chang, C.-L. & Ma, C.-C. M. Synthesis, characterization, and properties of novel ladderlike phosphorus-containing polysilsesquioxanes. J. Polym. Sci. Polym. Chem. 41, 1371–1379 (2003).
Article Google Scholar
Heskins, M. & Guillet, J. E. Solution properties of poly(N-isopropylacrylamide). J. Macromol. Sci. Chem. 2, 1441–1455 (1968).
Article CAS Google Scholar
Chen, G. H. & Hoffman, A. S. Graft copolymers that exhibit temperature induced phase transitions over a wide range of pH. Nature 373, 49–52 (1995).
Article CAS Google Scholar
Meyer, S. & Richtering, W. Influence of polymerization conditions on the structure of temperature-sensitive poly(N-isopropylacrylamide) microgels. Macromolecules 38, 1517–1519 (2005).
Article CAS Google Scholar
Matsuoka, T., Yamamoto, S. & Moriya, O. A new amphiphilic and thermoresponsive polysilsesquioxane having alkoxyethylamide group. Chem. Lett. 37, 772–773 (2008).
Article CAS Google Scholar
Matsuoka, T., Yamamoto, S., Moriya, O., Kashio, M. & Sugizaki, T. Synthesis of thermoresponsive polysilsesquioxane with methoxyethylamide group and crown ether. Polym. J. 42, 313–318 (2010).
Article CAS Google Scholar
Minami, F., Yamamoto, S., Miyasaka, Y. & Moriya, O. Synthesis of thermo- and pH-responsive polysilsesquioxane with carboxylic acid group. Polymer 52, 4744–4752 (2011).
Article CAS Google Scholar
Aoshima, S. & Sugihara, S. Syntheses of stimuli-responsive block copolymers of vinyl ethers with side oxyethylene groups by living cationic polymerization and their thermosensitive physical gelation. J. Polym. Sci. A Polym. Chem. 38, 3962–3965 (2000).
Article CAS Google Scholar
Sugihara, S., Kanaoka, S. & Aoshima, S. Double thermosensitive diblock copolymers of vinyl ethers with pendant oxyethylene groups: Unique physical gelation. Macromolecules 38, 1919–1927 (2005).
Article CAS Google Scholar
Lin, H.-H. & Cheng, Y.-L. In-Situ thermoreversible gelation of block and star copolymers of poly(ethylene glycol) and poly(N-isopropylacrylamide) of varying architectures. Macromolecules 34, 3710–3715 (2001).
Article CAS Google Scholar
Han, S., Hagiwara, M. & Ishizone, T. Synthesis of thermally sensitive water-soluble polymethacrylate by living anionic polymerization of oligo(ethylene glycol) methyl ether methacrylates. Maclomolecules 36, 8312–8319 (2003).
Article CAS Google Scholar
Gil, E. S. & Hudson, S. M. Stimuli-responsive polymers abd their bioconjugates. Prog. Polym. Sci. 29, 1173–1222 (2004).
Article CAS Google Scholar
Hua, F., Jiang, X. & Zhao, B. Temperature-induced self-association of doubly thermosensitive Diblock copolymers with pendant metoxytris(oxyethylene) groups in dilute aqueous solutions. Macromolecules 39, 3476–3479 (2006).
Article CAS Google Scholar
Yamamoto, S., Pietrasik, J. & Matyjaszewski, K. ATRP synthesis of thermally responsive molecular brushes from oligo(ethylene oxide) methacrylates. Macromolecules 40, 9348–9353 (2007).
Article CAS Google Scholar
Thommas, J. D., Fussell, G., Sarkar, S., Lowman, A. M. & Marcolongo, M. Synthesis and recovery characteristics of branched and grafted PNIPAAm-PEG hydrogels for the development of an injectable load-bearing nucleus pulposus replacement. Acta Biomater. 6, 1319–1328 (2010).
Article Google Scholar
Nagasaki, Y. Construction of a densely poly(ethylene glycol)-chain-tethered surface and its performance. Polym. J. 43, 949–958 (2011).
Article CAS Google Scholar
Weber, C., Hoogenboom, R. & Schubert, U. S. Temperature responsive bio-compatible polymers based on poly(ethylene oxide) and poly(2-oxazoline)s. Prog. Polym. Sci. 37, 686–714 (2012).
Article CAS Google Scholar
Zeng, Y. & Pitt, W. G. Poly(ethylene oxide)-b-poly(N-isopropylacrylamide) nanoparticles with crosslinked cores as drug carriers. J. Biomater. Sci. Polym. Ed. 16, 371–380 (2005).
Article CAS Google Scholar
Garćia-Garćia, J. M., Liras, M., Quijada-Garrido, I., Gallardo, A. & París, R. Swelling control in thermo-responsive hydrogels based on 2-(2-methoxyethoxy)ethyl methacrylate by crosslinking and copolymerization with N-isopropylacrylamide. Polym. J. 43, 887–892 (2011).
Article Google Scholar
Lutz, J.-F. & Hoth, A. Preparation of ideal PEG anlogues with a tunable thermosensitivity by controlled radical copolymerization of 2-(2-methoxyethoxy)ethyl methacrylate and oligo(ethylene glycol) mathacrylate. Macromolecules 39, 893–896 (2006).
Article CAS Google Scholar
Fissi, A. & Pierori, O. Photoresponsive polypeptides. Photomodulation of the macromolecular structure in azo-modified poly(L-glutamic acid). Macromolecules 22, 1115–1120 (1989).
Article CAS Google Scholar
Beattie, M. S., Jackson, C. & Jaycox, G. D. Azobenzene modified poly(aryl ether ketone amide)s. 2. Photo- and thermo-responsive behavior in dilute solution. Polymer 39, 2597–2605 (1998).
Article CAS Google Scholar
Yoshida, T., Kanaoka, S. & Aoshima, S. Photo-responsive copolymers with azobenzene side groups synthesized by living cationic polymerization: efficient amplification of photosensitivity in aqueous photo-switching system. J. Polym. Sci. A Polym. Chem. 43, 5337–5342 (2006).
Article Google Scholar
Akiyama, H. & Tamaoki, N. Synthesis and photoinduced phase transitions of poly(N-isoproplacrylamide) derivative functionalized with terminal azobenzene units. Macromolecules 40, 5129–5132 (2007).
Article CAS Google Scholar
Ishii, N., Mamiya, J., Ikeda, T. & Winnik, F. M. Solvent induced amplification of the photoresponsive properties of a,w-di[4-cyanophenyl-4′-(6-hexyloxy)-azobenzene]-poly(N-isopropylacrylamide) in aqueous media. Chem. Commun. 47, 1267–1269 (2011).
CAS Google Scholar
Tang, X., Liang, X., Gao, L., Fan, X. & Zhou, Q. Water-soluble triply-responsive homopolymers of N,N-dimethylaminoethyl methacrylate with a terminal azobenzene moiety. J. Polym. Sci. A Polym. Chem. 48, 2564–2570 (2010).
Article CAS Google Scholar
Jochum, F. D., Boorg, L. Z., Roth, P. J. & Theato, P. Thermo- and light-responsive polymers containing photoswitcable azobenzene end group. Macromolecules 42, 7854–7862 (2010).
Article Google Scholar
Liu, J., Chen, G., Guo, M. & Jiang, M. Dual stimuli-responsive supramolecular hydrogel based on hybrid inclusion complex (HIC). Macromolecules 43, 8086–8093 (2010).
Article CAS Google Scholar
Hu, J. & Liu, S. Responsive polymers for detection and sensing applications: current status and future development. Macromolecules 43, 8315–8330 (2010).
Article CAS Google Scholar
Dirani, A., laloyaux, X., Fernandes, A. E., Mathy, B., Schicke, O., Riant, O., Nysten, B. & Jonas, A. M. Reversible photomodulation of the swelling of poly(oligo(ethylene glycol) methacrylate) thermoresponsive polymer brushes. Macromolecules 45, 9400–9408 (2012).
Article CAS Google Scholar
Matsubara, Y., Konishi, W., Sugizaki, T. & Moriya, O. Synthesis of poly(phenylsilsesquioxane) having organostannyl groups. J. Polym. Sci. A Polym. Chem. 39, 2125–2133 (2001).
Article CAS Google Scholar
Uchida, E. & Kawatsuki, N. Influence of wavelength of light on photochemical orientation of azobenzene–containing polymethacrylate film. Polym. J. 38, 724–731 (2006).
Article CAS Google Scholar
Ravi, P., Sin, S. L., Gan, L. H., Gan, Y. Y., Tam, K. C., Xia, X. L. & Hu, X. New water soluble azobenzene-containing diblock copolymers: synthesis and aggregation behavior. Polymer 46, 137–146 (2003).
Article Google Scholar
Marie, E. & Tribet, C. Reverse variation of cloud points of light-responsive assemblies of azobenzene-modified amphiphilic polymers. Chem. Lett. 41, 1093–1095 (2012).
CAS Google Scholar

Download references

Author information

Authors and Affiliations

Department of Applied Chemistry, National Defense Academy, Yokosuka, Japan
Bagus Alimada, Shin-ichi Yamamoto & Osamu Moriya

Authors

Bagus Alimada
View author publications
Search author on:PubMed Google Scholar
Shin-ichi Yamamoto
View author publications
Search author on:PubMed Google Scholar
Osamu Moriya
View author publications
Search author on:PubMed Google Scholar

Corresponding author

Correspondence to Osamu Moriya.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Alimada, B., Yamamoto, Si. & Moriya, O. Synthesis of thermo- and photoresponsive polysilsesquioxane containing tetraethylene glycol chains and an azobenzene group. Polym J 46, 243–249 (2014). https://doi.org/10.1038/pj.2013.92

Download citation

Received: 17 September 2013
Revised: 30 October 2013
Accepted: 30 October 2013
Published: 25 December 2013
Issue date: April 2014
DOI: https://doi.org/10.1038/pj.2013.92

Keywords

This article is cited by

Competition between the micellization and the liquid–liquid phase separation in amphiphilic block copolymer solutions
- Takahiro Sato
- Rintaro Takahashi
Polymer Journal (2017)
Small-angle X-ray scattering from the concentrated bulk phase separated from an amphiphilic block-copolymer solution
- Masaaki Kondo
- Rintaro Takahashi
- Takahiro Sato
Polymer Journal (2017)
Organic/inorganic fusion materials: cyclodextrin-based polymer/CaCO3 hybrids incorporating dye molecules through host–guest interactions
- Fangjie Zhu
- Tatsuya Nishimura
- Takashi Kato
Polymer Journal (2015)

Synthesis of thermo- and photoresponsive polysilsesquioxane containing tetraethylene glycol chains and an azobenzene group

Subjects

Log in or create a free account to read this content

References

Author information

Authors and Affiliations

Corresponding author

Rights and permissions

About this article

Cite this article

Keywords

This article is cited by

Competition between the micellization and the liquid–liquid phase separation in amphiphilic block copolymer solutions

Small-angle X-ray scattering from the concentrated bulk phase separated from an amphiphilic block-copolymer solution

Organic/inorganic fusion materials: cyclodextrin-based polymer/CaCO3 hybrids incorporating dye molecules through host–guest interactions

Search

Quick links

Subjects

Log in or create a free account to read this content

References

Author information

Authors and Affiliations

Corresponding author

Rights and permissions

About this article

Cite this article

Share this article

Keywords

This article is cited by

Competition between the micellization and the liquid–liquid phase separation in amphiphilic block copolymer solutions

Small-angle X-ray scattering from the concentrated bulk phase separated from an amphiphilic block-copolymer solution

Organic/inorganic fusion materials: cyclodextrin-based polymer/CaCO3 hybrids incorporating dye molecules through host–guest interactions

Search

Quick links