SYNTHESIS AND CHARACTERIZATION OF NOVEL INORGANIC AND ORGANIC HYBRID POLY[CYCLOTRIPHOSPHAZENE-co-(4,4'-DIAMINODIPHENYLMETHANE)] MICROSPHERES via ONE-POT SELF-ASSEMBLY POLYCONDENSATION APPROACH

Abstract

Abstract: Cross-linked cyclomatrix polyphosphazene microspheres have been successfully synthesized via self-assembly polycondensation reaction between hexachlorocyclotriphosphazene (HCCP) and 4,4¢-diaminodiphenylmethane (DADPM) in acetonitrile. The absence of any stabilizing agent or surfactant and usage of only an ultrasonic bath have been the advantages for this reaction. HCCP and DADPM ratios have been attempted to obtain the best morphology by SEM-EDX. The size of microspheres were ranging from 4.46 to 4.74 μm. The inorganic-organic hybrid microspheres were characterized by FTIR, TGA, UV, Fluorescence and XRD.

References

1. Pan T, Huang X, Wei H, Tang X. Controlled Fabrication of Uniform Hollow Bowl-Shaped Microspheres Based on Polyphosphazene Material. Macromolecular Chemistry and Physics. 2012 Dec 21;213(24):2606–10. DOI: 10.1002/macp.201200441.
2. Zhu Y, Huang X, Fu J, Wang G, Tang X. Morphology control between microspheres and nanofibers by solvent-induced approach based on crosslinked phosphazene-containing materials. Materials Science and Engineering: B. 2008 Sep;153(1-3):62–5. DOI: 10.1016/j.mseb.2008.10.027.
3. Mathew D, Nair CR, Ninan K. Phosphazene-triazine cyclomatrix network polymers: some aspects of synthesis, thermal- and flame-retardant characteristics. Polymer International. 2000 Jan;49(1):48–56. DOI: 10.1002/(SICI)1097-0126(200001)49:1<48::AID-PI309>3.0.CO;2-M.
4. Zhang T, Cai Q, Wu D-Z, Jin R-G. Phosphazene cyclomatrix network polymers: Some aspects of the synthesis, characterization, and flame-retardant mechanisms of polymer. Journal of Applied Polymer Science. 2005 Feb 15;95(4):880–9. DOI: 10.1002/app.21295.
5. Gleria M, De Jaeger R. Polyphosphazenes: A Review. In: New Aspects in Phosphorus Chemistry V [Internet]. Springer; p. 165–251. (Topics in Current Chemistry; vol. 250). ISBN: 978-3-540-22498-3.
6. Stone DA, Allcock HR. A New Polymeric Intermediate for the Synthesis of Hybrid Inorganic−Organic Polymers. Macromolecules. 2006 Jul;39(15):4935–7. DOI: 10.1021/ma061079g.
7. Zhou Y, Huang X, Kang X, Fu J, Zhu Y, Tang X. Synthesis and Characterization of Novel Polyurethane Composites Based on Hybrid Inorganic/Organic Phosphazene-Containing Microspheres. Macromolecular Materials and Engineering. 2009 Sep 14;294(9):605–10. DOI: 10.1002/mame.200900161.
8. Shim D-H, Ko H-J, Volker G, Potter AA, Mutwiri G, Babiuk LA, et al. Efficacy of poly[di(sodium carboxylatophenoxy)phosphazene] (PCPP) as mucosal adjuvant to induce protective immunity against respiratory pathogens. Vaccine. 2010 Mar;28(11):2311–7. DOI: 10.1016/j.vaccine.2009.12.069.

9. Nichol JL, Morozowich NL, Allcock HR. Biodegradable alanine and phenylalanine alkyl ester polyphosphazenes as potential ligament and tendon tissue scaffolds. Polym Chem. 2013;4(3):600–6. DOI: 10.1039/C2PY20631E.
10. Allcock HR. THE CRUCIAL ROLE OF INORGANIC RING CHEMISTRY IN THE DEVELOPMENT OF NEW POLYMERS. Phosphorus, Sulfur, and Silicon and the Related Elements. 2004 Apr;179(4-5):661–71. DOI: 10.1080/10426500490426386.
11. Zhu Y, Fu J, Zhu L, Tang X, Huang X. Preparation of novel hybrid inorganic-organic hollow microspheres via a self-template approach. Polymer International. 2008 Mar;57(3):449–53. DOI: 10.1002/pi.2366.
12. Singh A, Krogman NR, Sethuraman S, Nair LS, Sturgeon JL, Brown PW, et al. Effect of Side Group Chemistry on the Properties of Biodegradable L -Alanine Cosubstituted Polyphosphazenes. Biomacromolecules. 2006 Mar;7(3):914–8. DOI: 10.1021/bm050752r.
13. Zhu L, Zhu Y, Pan Y, Huang Y, Huang X, Tang X. Fully Crosslinked Poly[cyclotriphosphazene-co-(4,4′-sulfonyldiphenol)] Microspheres via Precipitation Polymerization and Their Superior Thermal Properties. Macromolecular Reaction Engineering. 2007 Jan 9;1(1):45–52. DOI: 10.1002/mren.200600005.
14. Fu J, Huang Y, Pan Y, Zhu Y, Huang X, Tang X. An attempt to prepare carbon nanotubes by carbonizing polyphosphazene nanotubes with high carbon content. Materials Letters. 2008 Sep;62(25):4130–3.
15. Zhang P, Huang X, Fu J, Huang Y, Tang X. Fabrication of Amino-Terminated Multiwalled Carbon Nanotubes via Layer-by-Layer Self-Assembly Approach. Macromolecular Materials and Engineering. 2010 Mar 2;4130 – 4133. DOI: 10.1016/j.matlet.2008.06.020. DOI: 10.1002/mame.200900306.
16. Zhang P, Huang X, Fu J, Huang Y, Zhu Y, Tang X. A One-Pot Approach to Novel Cross-Linked Polyphosphazene Microspheres with Active Amino Groups. Macromolecular Chemistry and Physics. 2009 May 6;210(9):792–8. DOI: 10.1002/macp.200800597.
17. Wang Y, Mu J, Li L, Shi L, Zhang W, Jiang Z. Preparation and properties of novel fluorinated cross-linked polyphosphazene micro-nano spheres. High Performance Polymers. 2012 May 1;24(3):229–36. DOI: 10.1177/0954008311436221.
18. Pan T, Huang X, Wei H, Wei W, Tang X. Intrinsically Fluorescent Microspheres with Superior Thermal Stability and Broad Ultraviolet-Visible Absorption Based on Hybrid Polyphosphazene Material. Macromolecular Chemistry and Physics. 2012 Aug 14;213(15):1590–5. DOI: 10.1002/macp.201200099.
19. Wei W, Huang X, Chen K, Tao Y, Tang X. Fluorescent organic–inorganic hybrid polyphosphazene microspheres for the trace detection of nitroaromatic explosives. RSC Advances. 2012;2(9):3765. DOI: 10.1039/c2ra20263h.
20. Köhler J, Kühl S, Keul H, Möller M, Pich A. Synthesis and characterization of polyamine-based cyclophosphazene hybrid microspheres. Journal of Polymer Science Part A: Polymer Chemistry. 2014 Feb 15;52(4):527–36. DOI: 10.1002/pola.27028.
21. Wang M, Fu J, Chen Z, Wang X, Xu Q. In situ growth of gold nanoparticles onto polyphosphazene microspheres with amino-groups for alcohol oxidation in aqueous solutions. Materials Letters. 2015 Mar;143:201–4. DOI: 10.1016/j.matlet.2014.12.114.
22. Zhao Z, Ji J. Synthesis and Tribological Behaviors of Epoxy/Phosphazene-Microspheres Coatings under Dry Sliding Condition: Synthesis and Behaviors of Epoxy/Phosphazene-Microspheres Coatings. Advanced Engineering Materials. 2014 Aug;16(8):988–95. DOI: 10.1002/adem.201300491.
23. Mohanty P, Landskron K. Simple systematic synthesis of size-tunable covalent organophosphonitridic framework nano- and microspheres. New Journal of Chemistry. 2010;34(2):215. DOI: 10.1039/b9nj00446g.
24. Xu R, Pang W, Huo Q, editors. Modern inorganic synthetic chemistry. Amsterdam: Elsevier; 2011. 590 p. ISBN: 9780444535993.
25. Hu Y, Meng L, Niu L, Lu Q. Highly Cross-Linked and Biocompatible Polyphosphazene-Coated Superparamagnetic Fe 3 O 4 Nanoparticles for Magnetic Resonance Imaging. Langmuir. 2013 Jul 23;29(29):9156–63. DOI: 10.1021/la402119s.
26. Tarassoli A, Sedaghat T, Ansari-Asl Z. Surface functionalization of phosphazenenanosphere derivatives by Schiff-base-assisted metal complexes through a Si-spacer. Journal of Industrial and Engineering Chemistry. 2014 Jul;20(4):2287–91. DOI: 10.1016/j.jiec.2013.10.003.
27. Wang X, Fu J, Chen Z, Li Q, Wu X, Xu Q. Hollow polyphosphazene microspheres with cross-linked chemical structure: synthesis, formation mechanism and applications. RSC Adv. 2015;5(43):33720–8. DOI: 10.1039/C5RA00560D.