Abstract
Highly crosslinked, cyclotriphosphazene-containing polymer nanotubes have been successfully synthesized by polycondensation between hexachlorocyclotriphosphazene and melamine with pyridine as solution and acid-acceptor. The obtained nanotubes with rough surface, closed at one end, of lengths in several micrometers range, outer diameter in the range of 50–250 nm, and two ends of inner diameters in the range of 50–100 and 100–200 nm, respectively have been investigated by SEM and TEM. The formation mechanism has been proposed and named as self-template directing approach. In order to verify this mechanism, the products at variable stages of polymerization were traced by SEM. In addition, the melamine played a crucial role during the polymerization, guiding the formation of nanotube’s structure. The nanotubes showed remarkable thermal performance with the initial decomposition temperature at 220 °C and the residual is more than 40 % at 800 °C. Also, the morphology of nanotubes has undergone a progress from monodispersed nanotubes, to aggregation state, and to sponge-like structure at 220, 350, and 800 °C, respectively.
Similar content being viewed by others
References
Okutan E, Çoşut B, Kayıran SB, Durmuş M, Kılıç A, Yeşilot S (2014) Synthesis of a dendrimeric phenoxy-substituted cyclotetraphosphazene and its non-covalent interactions with multiwalled carbon nanotubes. Polyhedron 67:344–350
Yuan WZ, Zhao H, Shen XY, Mahtab F, Lam JW, Sun JZ, Tang BZ (2009) Luminogenic polyacetylenes and conjugated polyelectrolytes: synthesis, hybridization with carbon nanotubes, aggregation-induced emission, superamplification in emission quenching by explosives, and fluorescent assay for protein quantitation. Macromolecules 42:9400–9411
Okutan E, Aydın GO, Hacıvelioğlu F, Beyaz SK, Yeşilot S, Kılıç A (2013) Preparation and properties of multi-walled carbon nanotube/poly (organophosphazene) composites. J Mater Sci 48:201–212. doi:10.1007/s10853-012-6729-z
Baldez EE, Robaina NF, Cassella RJ (2008) Employment of polyurethane foam for the adsorption of Methylene Blue in aqueous medium. J Hazard Mater 159:580–586
Ai LH, Jiang J, Zhang R (2010) Uniform polyaniline microspheres: a novel adsorbent for dye removal from aqueous solution. Synth Met 160:762–767
Gao X, Matsui H (2005) Peptide-based nanotubes and their applications in bionanotechnology. Adv Mater 17:2037–2050
Bong DT, Clark TD, Granja JR, Ghadiri MR (2001) Self-assembling organic nanotubes. Angew Chem Int Ed 40:988–1011
Abidian MR, Kim DH, Martin DC (2006) Conducting-polymer nanotubes for controlled drug release. Adv Mater 18:405–409
Coskun Y, Cirpan A, Toppare L (2007) Construction of electrochromic devices using thiophene based conducting polymers. J Mater Sci 42:368–372. doi:10.1007/s10853-006-1076-6
Sathy BN, Mony U, Menon D, Baskaran VK, Mikos AG, Nair S (2015) Bone tissue engineering with multilayered scaffolds—Part I: an approach for vascularizing engineered constructs in vivo. Tissue Eng Part A 21:2480–2494
Chen Z, Zhang J, Fu J, Wang M, Wang X, Han R, Xu Q (2014) Adsorption of methylene blue onto poly (cyclotriphosphazene-co-4, 4′-sulfonyldiphenol) nanotubes: Kinetics, isotherm and thermodynamics analysis. J Hazard Mater 273:263–271
Kameta N, Minamikawa H, Masuda M (2011) Supramolecular organic nanotubes: how to utilize the inner nanospace and the outer space. Soft Matter 7:4539–4561
Shimizu T, Masuda M, Minamikawa H (2005) Supramolecular nanotube architectures based on amphiphilic molecules. Chem Rev 105:1401–1444
Kang N, Park JH, Choi J, Jin J, Chun J, Jung IG, Jeong J, Park JG, Lee SM, Kim HJ, Son SU (2012) Nanoparticulate iron oxide tubes from microporous organic nanotubes as stable anode materials for lithium ion batteries. Angew Chem 124:6730–6734
Steinhart M (2008) Supramolecular organization of polymeric materials in nanoporous hard templates. Self-assembled nanomaterials II. Springer, Berlin, pp 123–187
Loscertales IG, Barrero A, Márquez M, Spretz R, Velarde-Ortiz R, Larsen G (2004) Electrically forced coaxial nanojets for one-step hollow nanofiber design. J Am Chem Soc 126:5376–5377
Allcock HR (2004) The crucial role of inorganic ring chemistry in the development of new polymers. Phosphorus Sulfur Silicon 179:661–671
Kajiwara M, Kimura T (1996) Oxygen gas permeability in water and mechanical properties of poly (n-butylamino)-(di-allylamino) phosphazene membranes cured with the irradiation. J Mater Sci 31:5457–5462. doi:10.1007/BF01159317
Xu J, He Z, Wu W, Ma H, Xie J, Qu H, Jiao Y (2013) Study of thermal properties of flame retardant epoxy resin treated with hexakis [p-(hydroxymethyl) phenoxy] cyclotriphosphazene. J Therm Anal Calorim 114:1341–1350
Nichol JL, Morozowich NL, Allcock HR (2013) Biodegradable alanine and phenylalanine alkyl ester polyphosphazenes as potential ligament and tendon tissue scaffolds. Polym Chem 4:600–606
Shim DH, Ko HJ, Volker G, Potter AA, Mutwiri G, Babiuk LA, Kweon MN (2010) Efficacy of poly [di (sodium carboxylatophenoxy) phosphazene](PCPP) as mucosal adjuvant to induce protective immunity against respiratory pathogens. Vaccine 28:2311–2317
Okutan E, Aydın GO, Hacıvelioğlu F, Kılıç A, Beyaz SK, Yeşilot S (2011) Synthesis and characterization of soluble multi-walled carbon nanotube/poly (organophosphazene) composites. Polymer 52:1241–1248
Okutan E, Çoşut B, Yeşilot S (2014) Synthesis and properties of fullerene (C60) substituted cyclophosphazene derivatives. Inorg Chem Commun 49:1–4
Fu J, Huang X, Zhu Y, Huang Y, Zhu L, Tang X (2008) Rapid fabrication and formation mechanism of cyclotriphosphazene-containing polymer nanofibers. Eur Polym J 44:3466–3472
Wei W, Huang X, Chen K, Tao Y, Tang X (2012) Fluorescent organic–inorganic hybrid polyphosphazene microspheres for the trace detection of nitroaromatic explosives. RSC Adv 2:3765–3771
Pan T, Huang X, Wei H, Wei W, Tang X (2012) Intrinsically fluorescent microspheres with superior thermal stability and broad ultraviolet-visible absorption based on hybrid polyphosphazene material. Macromol Chem Phys 213:1590–1595
Chen K, Wan C, Wei W, Huang X, Liu H (2015) Convenient one-pot approach for the preparation of novel atomically thin two-dimensional polymeric nanosheets, and its evolution in aqueous solution. Mater Lett 139:93–97
Chang F, Huang X, Wei H, Chen K, Shan C, Tang X (2014) Intrinsically fluorescent hollow spheres based on organic–inorganic hybrid polyphosphazene material: synthesis and application in drug release. Mater Lett 125:128–131
Wei W, Huang X, Zhao X, Zhang P, Tang X (2010) A rapid and efficient strategy for preparation of super-hydrophobic surface with cross-linked cyclotriphosphazene/6F-bisphenol A copolymer microspheres. Chem Commun 46:487–489
Zhu Y, Huang X, Fu J, Wang G, Tang X (2008) Morphology control between microspheres and nanofibers by solvent-induced approach based on crosslinked phosphazene-containing materials. Mater Sci Eng B 153:62–65
Wang Y, Shi L, Zhang W, Jiang Z, Mu J (2014) A comparative structure–property study of polyphosphazene micro-nano spheres. Polym Bull 71:275–285
Li Z, Wang G, Liang C, Zhang A (2015) Synthesis of cyclotriphosphazene-containing polymeric nanotubes and their use as metal-free photocatalysts for methylene blue degradation. Appl Surf Sci 347:541–547
Li G, Shrotriya V, Huang J, Yao Y, Moriarty T, Emery K, Yang Y (2005) High-efficiency solution processable polymer photovoltaic cells by self-organization of polymer blends. Nat Mater 4:864–868
Wu S (1982) Polymer interface and adhesion. M. Dekker, New York
Chen Z, Zhang J, Fu J, Wang M, Wang X, Han R, Xu Q (2014) Adsorption of methylene blue onto poly (cyclotriphosphazene-co-4, 4′-sulfonyldiphenol) nanotubes: kinetics, isotherm and thermodynamics analysis. J Hazard Mater 273:263–271
Guo L, Zhang L, Zhang J, Zhou J, He Q, Zeng S, Cui X, Shi J (2009) Hollow mesoporous carbon spheres—an excellent bilirubin adsorbent. Chem Commun 40:6071–6073
Zhu L, Xu Y, Yuan W, Xi J, Huang X, Tang X, Zheng S (2006) One-Pot Synthesis of Poly (cyclotriphosphazene-co-4, 4′-sulfonyldiphenol) Nanotubes via an In Situ Template Approach. Adv Mater 18:2997–3000
Fu J, Wang M, Zhang C, Xu Q, Huang X, Tang X (2012) Controlled fabrication of noble metal nanoparticles loaded on the surfaces of cyclotriphosphazene-containing polymer nanotubes. J Mater Sci 47:1985–1991. doi:10.1007/s10853-011-5994-6
Acknowledgements
The authors are grateful to the National Natural Science Funds of China for providing the financial support (Grant number 51373201).
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Li, Z., Wang, G., Ren, W. et al. Cyclotriphosphazene-containing polymeric nanotubes: synthesis, properties, and formation mechanism. J Mater Sci 51, 4096–4103 (2016). https://doi.org/10.1007/s10853-016-9731-z
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10853-016-9731-z