Abstract
Poly(azomethine)s are generally thermally and environmentally stable polymers that are formed under moderate polymerization conditions and require no additional reagents, so they are high-purity polymeric materials. Hybrid polymers incorporating high concentrations of double-decker-shaped phenyl-substituted silsesquioxane (DDSQ) in the main chains lead to beads-on-string-shaped architectures, exhibiting excellent molding processabilities, optical transparencies, and good heat resistance. In this study, bis(3-aminopropyl)-DDSQ (2) was used in polymerizations with various aromatic dialdehydes to obtain poly(azomethine)s with high DDSQ contents. The polymerization behavior of 2 was also compared with that of 3,13-bisanilinyl-DDSQ (1) to determine whether the structures of the diamine monomers affect their polymerization reactions. Introducing the flexible propylene linkers into the DDSQ unit provided flexible and optically transparent free-standing films, while polymerization of 1 provided fragile films and no free-standing films were obtained. We found that their mechanical properties were highly dependent on the structures of the dianhydride comonomers. The storage modulus (E’) of poly(azomethine) (5c) made from biphenyldialdehyde with 2 was significantly lower than those of the others. Introducing the flexible chains in poly(azomethine) (5e), which was made from 1,8-bis(4-formylphenoxy)octane with 2 increased the E’ value. The lower E’ of 5c was due to inhibited entanglement of the interpolymer chains, while the longer flexible linker chains in 5e provided more packing structures.
This is a preview of subscription content, access via your institution
Access options
Subscribe to this journal
Receive 12 print issues and online access
$259.00 per year
only $21.58 per issue
Rent or buy this article
Prices vary by article type
from$1.95
to$39.95
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
References
Laine RM. Nanobuilding blocks base on the [OSiO1.5]x (x = 6, 8, 10) octasilsesquioxanews. J Mater Chem. 2005;15:3725–44.
Chujo Y, Tanaka K. New polymeric materials based on element-blocks. Bull Chem Soc Jpn. 2015;88:633–43.
Li G, Wang L, Ni H, Pittman CU Jr. Polyhedral oligomeric silsesquioxane (POSS) polymers and copolymers. J Inorg Org Polym. 2001;11:123–54.
Yoshimatsu M, Komori K, Ohnagamitsu Y, Sueyoshi N, Kawashima N, Chinen S, et al. Necklace-shaped dimethylsiloxane polymers bearing a polyhedral oligomeric silsesquioxane cage prepared by polycondensation and ring-opening polymerization. Chem Lett. 2012;41:622–4.
Maegawa T, Irie Y, Fueno H, Tanaka K, Naka K. Synthesis and polymerization of a para-disubstituted T8-caged hexaisobutyl-POSS monomer. Chem Lett. 2014;43:1532–4.
Maegawa T, Irie Y, Imoto H, Fueno H, Tanaka K, Naka K. para-Bisvinylhexaisobutyl-substituted T8 caged monomer: Synthesis and hydrosilylation polymerization. Polym Chem. 2015;6:7500–4.
Maegawa T, Miyashita O, Irie Y, Imoto H, Naka K. Synthesis and properties of polyimides containing hexaisobutyl-substituted T8 cages in their main chains. RSC Adv. 2016;6:31751–7.
Feher FJ, Newman DA, Walzer JF. Silsesquioxanes as models for silica surfaces. J Am Chem Soc. 1989;111:1741–8.
Lichtenhan JD, Vu NQ, Carter JA, Gilman JW, Feher FJ. Silsesquioxane-siloxane copolymers from polyhedral silsesquioxanes. Macromolecules. 1993;26:2141–2.
Wright ME, Schorzman DA, Feher FJ, Jin R-Z. Synthesis and thermal curing of aryl-ethynyl-terminated coPOSS imide oligomers: New inorganic/organic hybrid resins. Chem Mater. 2003;15:264–8.
Feher FJ, Terroba R, Ziller JW. A new route to incompletely-condensed silsesquioxanes: base-mediated cleavage of polyhedral oligosilsesquioxanes. Chem Commun. 1999;35:2309–10.
Raftopoulos KN, Jancia M, Aravopoulou D, Hebda E, Pielichowski K, Pissis P. POSS along the hard segments of polyurethane. Phase separation and molecular dynamics. Macromolecules. 2013;46:7378–86.
Asuncion MZ, Laine RM. Fluoride rearrangement reactions of polyphenyl- and polyvinylsilsesquioxanes as a facile route to mixed functional phenyl, vinyl T10 and T12 silsesquioxanes. J Am Chem Soc. 2010;132:3723–36.
Jung JH, Laine RM. Beads on a chain (BOC) polymers formed from the reaction of [NH2PhSiO1.5]x[PhSiO1.5]10–x and [NH2PhSiO1.5]x[PhSiO1.5]12–x mixtures (x = 2–4) with the diglycidyl ether of bisphenol A. Macromolecules. 2011;44:7263–72.
Jung JH, Furgal JC, Clark S, Schwartz M, Chou K, Laine RM. Beads on a chain (BoC) polymers with model dendronized beads. Copolymerization of [(4-NH2C6H4SiO1.5)6(IPhSiO1.5)2] and [(4-CH3OC6H4SiO1.5)6(IPhSiO1.5)2] with 1,4-diethynylbenzene (DEB) gives through-chain, extended 3-D conjugation in the excited state that is an average of the corresponding homopolymers. Macromolecules. 2013;46:7580–90.
Tokunaga T, Koga S, Mizumo T, Ohshita J, Kaneko Y. Facile preparation of a soluble polymer containing polyhedral oligomeric silsesquioxane units in its main chain. Polym Chem. 2015;6:3039–45.
Hoque MA, Kakihana Y, Shinke S, Kawakami Y. Polysiloxanes with periodically distributed isomeric double-decker silsesquioxane in the main chain. Macromolecules. 2009;42:3309–15.
Wu S, Hayakawa T, Kikuchi R, Grunzinger SJ, Kakimoto M, Oikawa H. Synthesis and characterization of semiaromatic polyimides containing POSS in main chain derived from double-decker-shaped silsesquioxane. Macromolecules. 2007;40:5698–705.
Wei K, Wang L, Zheng S. Organic–inorganic polyurethanes with 3, 13-dihydroxypropyloctaphenyl double-decker silsesquioxane chain extender. Polym Chem. 2013;4:1491–501.
Wu S, Hayakawa T, Kakimoto M, Oikawa H. Synthesis and characterization of organosoluble aromatic polyimides containing POSS in main chain derived from double-decker-shaped silsesquioxane. Macromolecules. 2008;41:3481–7.
Liu N, Wei K, Wang L, Zheng S. Organic–inorganic polyimides with double decker silsesquioxane in the main chains. Polym Chem. 2016;7:1158–67.
Ishida A, Fujii S, Sumida A, Kamitani T, Minami S, Urayama K, et al. Supramolecular organogel formation behaviors of beads-on-string shaped poly(azomethine)s dependent on POSS structures in the main chains. Polym Chem. 2021;12:3169–76.
Kamitani T, Imoto H, Naka K. Soluble and processable thermoplastic hybrid polyimides containing POSS in main chains. Polym Chem. 2022;13:5145–51.
Wojtkowaki PW. Aromatic-aliphatic azomethine ether polymers and fibers. Macromolecules. 1987;20:740–8.
Morgan PW, Kwolek SL, Pletcher TC. Aromatic azomethine polymers and fibers. Macromolecules. 1987;20:729–39.
Natansohn A, Yang H, Clark C. Polyimines from terephthalaldehyde and aliphatic diamines. Macromolecules. 1991;24:5489–96.
Thomas O, Inganäs O, Andersson MR. Synthesis and properties of a soluble conjugated poly(azomethine) with high molecular weight. Macromolecules. 1998;31:2676–8.
Zhao D, Moore JS. Folding-Driven Reversible Polymerization of oligo(m-phenylene ethynylene) imines: Solvent and starter sequence studies. Macromolecules. 2003;36:2712–20.
Lei ZQ, Xie P, Rong MZ, Zhang MQ. Catalyst-free dynamic exchange of aromatic schiff base bonds and its application to self-healing and remolding of crosslinked polymers. J Mater Chem A. 2015;3:19662–8.
Chow C-F, Fujii S, Lehn J-M. Crystallization-driven constitutional changes of dynamic polymers in response to neat/solution conditions. Chem Commun. 2007;43:4363–5.
Janeliunas D, van Rijn P, Boekhoven J, Minkenberg CB, van Esch JH, Eelkema R. Aggregation-driven reversible formation of conjugated polymers in water. Angew Chem Int Ed. 2013;52:1998–2001.
Tsai FC, Chang CC, Liu CL, Chen WC, Jenekhe SA. New thiophene-linked conjugated poly(azomethine)s:Theoretical electronic structure, synthesis, and properties. Macromolecules. 2005;38:1958–66.
Sek D, Iwan A, Jarzabek B, Kaczmarczyk B, Kasperczyk J, Mazurak Z, et al. Hole transport triphenylamine−azomethine conjugated system: Synthesis and optical, photoluminescence, and electrochemical properties. Macromolecules. 2008;41:6653–63.
Niu H, Kang H, Cai J, Wang C, Bai X, Wang W. Novel soluble polyazomethines with pendant carbazole and triphenylamine derivatives: preparation, characterization, and optical, electrochemical and electrochromic properties. Polym Chem. 2011;2:2804–17.
Bolduc A, Barik S, Lenze MR, Meerholz K, Skene WG. Polythiophenozaomethines – alternate photoactive materials for organic photovoltaics. J Mater Chem A. 2014;2:15620–6.
Park SB, Kim H, Zin WC, Jung JC. Synthesis and properties of polyazomethines having flexible (n-alkyloxy)methyl side chains. Macromolecules. 1993;26:1627–32.
Fujii S, Minami S, Urayama K, Suenaga Y, Naito H, Miyashita O, et al. Beads-on-string-shaped poly(azomethine) applicable for solution processing of bilayer devices using a same solvent. ACS Macro Lett. 2018;7:641–5.
Ishii J, Kosugi M, Hasegawa M. Ultra-low modulus polyazomethines and enhanced adhesion strength with copper foils. Polym Adv Technol. 2016;27:477–85.
Geng H, Wang Y, Yu Q, Gu S, Zhou Y, Xu W, et al. Vanillin-based polyschiff vitrimers: Reprocessability and chemical recyclability. ACS Sustainable Chem Eng. 2018;6:15463–70.
Zhao D, Moor JS. Folding-driven reversible polymerization of oligo(m-phenylene ethylene) imines: Solvent and starter sequence studies. Macromolecules. 2003;36:2712–20.
Menard KP. Dynamic Mechanical Analysis: A Practical Introduction. 1st ed. Boca Raton: CRC Press; 1999.
Acknowledgements
This work was supported by Grant-in-Aid for Scientific Research (No. 19H02764 and 21K19003) from the Ministry of Education, Culture, Sports, Science, and Technology, Government of Japan. We thank Dr Tsuneaki Sakurai of Kyoto Institute of Technology for XRD analysis.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declare no competing interests.
Additional information
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary information
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
Hirosawa, Y., Kamitani, T., Imoto, H. et al. Thermal and mechanical behaviors of beads-on-string-shaped poly(azomethine)s based on their linker structures. Polym J 55, 849–858 (2023). https://doi.org/10.1038/s41428-023-00778-5
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/s41428-023-00778-5