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Synthesis of hybrid crosslinked polyphosphazenes and investigation of their properties

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Abstract

Novel organic/inorganic hybrid polyphosphazenes were prepared by free radical UV copolymerization of linear polyphosphazenes and vinyl monomers. In this work, linear polyphosphazenes grafted by allyl amino and n-butylamino groups have been synthesized via nucleophilic substitution reaction at an anhydrous and anaerobic atmosphere. By regulating the molar ratio of allyl amino and n-butylamino groups, five different linear polyphosphazenes were prepared. The hybrid polyphosphazenes have been crosslinked using the linear polyphosphazenes and vinyl monomers including styrene, methyl methacrylate, and lauryl methacrylate as intermediates via free radical UV copolymerization. By changing the quantity of vinyl monomers participating in the crosslinking reaction, series of hybrid polyphosphazene membranes were obtained. The linear polyphosphazenes have been characterized by Nuclear magnetic resonance, Fourier transform infrared (FTIR), Thermogravimetric analysis (TGA), Differential scanning calorimeter, Dynamic mechanical analyzer and Drop Shape Analysis (DSA). The hybrid polyphosphazenes have also been studied via FTIR, TGA and DSA. The test results proved that the linear polymers were successfully synthesized. Moreover, the water contact angles showed that the hybrid crosslinked polyphosphazenes had a better hydrophobicity and thermal stability than the linear polyphosphazenes and the hydrophobicity of hybrid membranes have a regular changing tendency with the quantities of UV-monomers and ratio of allylamino. The initial decomposition temperatures of the hybrid polymers also had a regular change due to the difference and quantities of vinyl monomers.

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References

  1. Allcock HR, Maher AE, Ambler CM (2003) Side group exchange in poly(organophosphazenes) with fluoroalkoxy substituents. Macromolecules 36:5566–5572

    Article  CAS  Google Scholar 

  2. Allcock HR (2003) Chemistry and applications of polyphosphazenes, vol 1. Wiley, Hoboken

    Google Scholar 

  3. Weikel AL, Krogman NR, Nguyen NQ, Nair LS, Laurencin CT, Allcock HR (2009) Polyphosphazenes that contain dipeptide side groups: synthesis, characterization, and sensitivity to hydrolysis. Macromolecules 42:636–639

    Article  CAS  Google Scholar 

  4. Morozowich NL, Weikel AL, Nichol JL, Chen C, Nair LS, Laurencin CT, Allcock HR (2011) Polyphosphazenes containing vitamin substituents: synthesis, characterization, and hydrolytic sensitivity. Macromolecules 44:1355–1364

    Article  CAS  Google Scholar 

  5. Chen C, Liu X, Tian ZC, Allcock HR (1994) Trichloroethoxy-substituted polyphosphazenes: synthesis, characterization, and properties. Macromolecules 45:9085–9091

    Article  Google Scholar 

  6. Allcock HR, Smith DE, Kim YB (1994) Poly(organophosphazenes) containing allyl side groups: crosslinking and modification by hydrosilylation. Macromolecules 27:5206–5215

    Article  CAS  Google Scholar 

  7. Minto F, Gleria M, Bertani R, Noto VD, Vidali M (1998) Photochemical behavior of poly(organophosphazenes). 15. Light-induced cross-linking of [(4-benzoylphenoxy) x (methoxyethoxyethoxy)2− x ] phosphazene copolymers. J Inorg Organom Polym 8:67–68

    Article  CAS  Google Scholar 

  8. Deng M, Nair LS, Nukavarapu SP, Jiang T, Kanner WA, Li XD, Kumbar SG, Weikel AL, Krogman NR, Allcock HR, Laurencin CT (2010) Dipeptide-based polyphosphazene and polyester blends for bone tissue engineering. Biomaterials 31:4898–4908

    Article  CAS  Google Scholar 

  9. Barrett EW, Phelps MVB, Silva RJ, Gaumond RP, Allcock HR (2005) Patterning poly(organophosphazenes) for selective cell adhesion applications. Biomacromolecules 6:1689–1697

    Article  CAS  Google Scholar 

  10. Krogman NR, Weikel AL, Kristhart KA, Nukavarapu SP, Deng M, Nair LS, Laurencin CT, Allcock HR (2009) The influence of side group modification in polyphosphazenes on hydrolysis and cell adhesion of blends with PLGA. Biomaterials 30:3035–3041

    Article  CAS  Google Scholar 

  11. Taylor TJ, Soto AP, Huynh K, Lough AJ, Swain AC, Norman NC, Russell CA, Manners I (2010) Synthesis of poly(alkyl/arylphosphazenes) via the ambient temperature phosphite-mediated chain-growth polycondensation of (N-silyl)bromophosphoranimines. Macromolecules 43:7446–7452

    Article  CAS  Google Scholar 

  12. Chen-Yang YW, Hwang JJ, Huang AY (2000) Polyphosphazene electrolytes. 2. Synthesis and properties of new polymer electrolytes based on poly((amino)[(2-methoxyethoxy)ethoxy])phosphazenes. Macromolecules 33:1237–1244

    Article  CAS  Google Scholar 

  13. Gleria M, Minto F, Po R, Cardi N, Fiocca L, Spera S (1998) Thermally induced grafting reactions of maleates containing oxazoline groups onto aryloxy–substituted poly(organophosphazenes). Macromol Chem Phys 199:2477–2487

    Article  CAS  Google Scholar 

  14. Allcock HR, Dembek AA, Kim C (1991) Second-order nonlinear optical poly(organophosphazenes): synthesis and nonlinear optical characterization. Macromolecules 24:1000–1010

    Article  CAS  Google Scholar 

  15. Allcock HR, Kugel RL (1965) Synthesis of high polymeric alkoxy- and aryloxyphosphonitriles. J Am Chem Soc 87:4216–4217

    Article  CAS  Google Scholar 

  16. Allcock HR, Kugel RL (1966) Phosphonitrilic compounds. VII. High molecular weight poly(diaminophosphazenes). Inorg Chem 5:1716–1718

    Article  CAS  Google Scholar 

  17. Allcock HR, Kugel RL, Valan KJ (1966) Phosphonitrilic compounds. VI. High molecular weight poly(alkoxy- and aryloxyphosphazenes). Inorg Chem 5:1709–1715

    Article  CAS  Google Scholar 

  18. Cheng XJ, Peng C, Zhang DH, Liu SZ, Zhang AQ, Huang H, Lian JS (2013) A facile method for the preparation of thermally remendable cross-linked polyphosphazenes. J Polym Sci Part A: Polym Chem 51:1205–1214

    Article  CAS  Google Scholar 

  19. Huang X, Huang XJ, Yu AG, Wang C, Dai ZW, Xu ZK (2011) “Click Chemistry” as a facile approach to the synthesis of polyphosphazene glycopolymers. Macromol Chem Phys 212:272–277

    Article  CAS  Google Scholar 

  20. Lee SB, Song S (2005) Hydrolysis-improved thermosensitive polyorganophosphazenes with α-amino-ω-methoxy-poly(ethylene glycol) and amino acid esters as side groups. Polym Int 54:1225–1232

    Article  CAS  Google Scholar 

  21. Jaglowskit AJ, Singler RE, Atkins EDT (1995) Liquid crystalline behavior of poly[((6-(4-phenylphenoxy)hexyl)oxy)(trifluoroethoxy)phosphazene]. Macromolecules 28:1668–1672

    Article  Google Scholar 

  22. Allcock HR, Kim C (1991) Photochromic polyphosphazenes with spiropyran units. Macromolecules 24:2846–2851

    Article  CAS  Google Scholar 

  23. Zheng L, Lu HQ, Fan HS, Zhang XD (2013) Reinforcement and chemical cross-linking in collagen-based scaffolds in cartilage tissue engineering: a comparative study. Iran Polym J 22:833–842

    Article  CAS  Google Scholar 

  24. Allcock HR, Austin PE, Neenan TX (1982) Phosphazene high polymers with bioactive substituent groups: prospective anesthetic aminophosphazenes. Macromolecules 15:689–693

    Article  CAS  Google Scholar 

  25. Huang XB, Yin L, Tang XZ (2008) Synthesis and characterization of a new organic-inorganic hybrid polyphosphazene polymer. Sci China Ser B-Chem 51:46–50

    Article  CAS  Google Scholar 

  26. Allcock HR, Cameron CG (1994) Synthesis and characterization of photo-cross-linkable small-molecule and high-polymeric phosphazenes bearing cinnamate groups. Macromolecules 27:3125–3130

    Article  CAS  Google Scholar 

  27. Huang YW, Pan Y, Fu JW, Huang XB, Tang XZ (2009) Study of crosslinking of polyphosphazene with allyl pendant groups initiated by benzoyl peroxide. J Appl Polym Sci 113:2353–2360

    Article  CAS  Google Scholar 

  28. Lee SC, Chang JY (2009) Preparation of molecularly imprinted polymers using photo-cross-linkable polyphosphazene and selective rebinding of amino acids. Macromol Res 17:522–527

    Article  CAS  Google Scholar 

  29. Allcock HR, Steely LB, Singh A (2006) Hydrophobic and superhydrophobic surfaces from polyphosphazenes. Polym Int 55:621–625

    Article  CAS  Google Scholar 

  30. Chaudhuri S, Chakraborty R, Bhattacharya P (2013) Optimization of biodegradation of natural fiber (Chorchoruscapsularis): HDPE composite using response surface methodology. Iran Polym J 22:865–875

    Article  CAS  Google Scholar 

  31. Yan ZL, Liu WQ, Gao N, Sun Y, Chen HS (2012) Surface properties of the epoxy resin modified by a novel functional fluorinated oligomer. Iran Polym J 21:721–730

    Article  CAS  Google Scholar 

  32. Doi M (1997) Introduction to polymer physics [M]. Clarendon Press, Oxford, Eng

    Google Scholar 

Download references

Acknowledgments

The authors would like to thank the financial support of NSFC (41240026) and Scientific Research Foundation for the Returned Overseas Chinese Scholars, State Education Ministry.

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Authors and Affiliations

  1. School of Chemistry and Materials Science, South-Central University for Nationalities, Wuhan, 430074, People’s Republic of China

    Lei Hu, Aiqing Zhang, Yun Yu, Zhi Zheng, Shixing Du & Xinjian Cheng

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  1. Lei Hu
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  2. Aiqing Zhang
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  3. Yun Yu
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  4. Zhi Zheng
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  5. Shixing Du
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  6. Xinjian Cheng
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Correspondence to Xinjian Cheng.

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Hu, L., Zhang, A., Yu, Y. et al. Synthesis of hybrid crosslinked polyphosphazenes and investigation of their properties. Iran Polym J 23, 689–698 (2014). https://doi.org/10.1007/s13726-014-0263-6

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  • DOI: https://doi.org/10.1007/s13726-014-0263-6

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