Advertisement

Polymer Bulletin

, Volume 76, Issue 1, pp 139–152 | Cite as

Styrene-co-divinylbenzene/silica hybrid supports for immobilization transitional metals and their application in catalysis

  • A. PopaEmail author
  • G. Ilia
  • S. Iliescu
  • N. Plesu
  • R. Ene
  • V. ParvulescuEmail author
Original Paper
  • 38 Downloads

Abstract

The functionalization of S–1% DVB copolymer was carried out with aminophosphonate groups, and then the samples were covered with silica to obtain hybrid materials. The obtained hybrid materials were used as supports for impregnation of transition metal ions [Cu(II) and Mn(II)], and they were subsequently used as catalysts in oxidation reactions. The supports and catalysts were characterized by FTIR and UV–Vis spectroscopy, thermal analysis, SEM, and TEM electron microscopy. The results of FTIR spectroscopy indicated the formation of a hybrid of silica and an aminophosphonate polymer by the sol–gel route. The UV–Vis spectra showed a strong interaction of Cu(II) and a weak interaction of Mn(II) with aminophosphonate groups of the supports. The catalytic tests confirm different interactions between the metal cations and obtained supports. The formation of the immobilized Cu(II) complexes shows the possibility of using these materials selectively in oxidation of various organic compounds (anisole, cyclohexene, toluene, styrene, phenol). The purpose of this article is to develop some new poly(aminophosphonates)/silica hybrid materials immobilized with transition metal such as Cu(II) and Mn(II) ions for future use in the oxidation process.

Keywords

Polymeric hybrid materials Aminophosphonate groups Cu(II) immobilized complexes Mn(II) supported catalysts Oxidation reactions 

References

  1. 1.
    Tong X, Xu J, Miao H, Yang G, Ma H, Zhang Q (2007) Highly efficient and metal-free oxidation of olefins by molecular oxygen under mild conditions. Tetrahedron 63:7634–7639.  https://doi.org/10.1016/j.tet.2007.05.038 CrossRefGoogle Scholar
  2. 2.
    Salavati-Niasari M, Hassani-Kabutarkhani M, Davar F (2006) Alumina-supported Mn(II), Co(II), Ni(II) and Cu(II) N,N-bis(salicylidene)-2,2-dimethylpropane-1,3-diamine complexes: synthesis, characterization and catalytic oxidation of cyclohexene with tert-butylhydroperoxide and hydrogen peroxide. Catal Commun 7:955–962.  https://doi.org/10.1016/j.catcom.2006.04.005 CrossRefGoogle Scholar
  3. 3.
    Gupta KC, Sutar AK (2009) Polymer-supported Schiff base complexes in oxidation reactions. Coord Chem Rev 253:1926–1946.  https://doi.org/10.1016/j.ccr.2009.03.019 CrossRefGoogle Scholar
  4. 4.
    Sherrington DC (2000) Polymer-supported metal complex alkene epoxidation catalysts. Catal Today 57:87–104.  https://doi.org/10.1016/S0920-5861(99)00311-9 CrossRefGoogle Scholar
  5. 5.
    Jia A, Lou L, Zhang C, Zhang Y, Liu S (2009) Selective oxidation of benzyl alcohol to benzaldehyde with hydrogen peroxide over alkali-treated ZSM-5 zeolite catalysts. J Mol Catal A Chem 306:123–129.  https://doi.org/10.1016/j.molcata.2009.02.035 CrossRefGoogle Scholar
  6. 6.
    Asaftei IV, Sandu IG, Birsa LM, Manea LR, Earar K (2015) Conversion of industrial feedstock mainly with butanes and butenes over B-HZSM-5 and Zn-HZSM-5 modified catalysts. Rev Chim (Bucharest) 66(3):336–341Google Scholar
  7. 7.
    Silva AR, Freitas MMA, Freire C, deCastro B, Figueiredo JL (2002) Heterogenization of a functionalized copper(II) Schiff base complex by direct immobilization onto an oxidized activated carbon. Langmuir 18:8017–8024.  https://doi.org/10.1021/la025833c CrossRefGoogle Scholar
  8. 8.
    Mureseanu M, Parvulescu V, Ene R, Cioatera AN, Pasatoiu TD, Andruh M (2009) Cu(II) complexes imobilized on functionalized mesoporous silica as catalysts for biomimetic oxidations. J Mater Sci 44:6795–6804.  https://doi.org/10.1007/s10853-009-3682-6 CrossRefGoogle Scholar
  9. 9.
    Murphy FE, Schmid L, Buergi T, Maciejewski M, Baiker A, Guenther D, Schneider M (2001) Nondestructive sol–gel immobilization of metal(salen) catalysts in silica aerogels and xerogels. Chem Mater 13:1296–1304.  https://doi.org/10.1021/cm001187w CrossRefGoogle Scholar
  10. 10.
    Khare S, Chokhare R (2012) Oxidation of cyclohexene catalyzed by Cu(Salen) intercalated-zirconium phosphate using dry tert-butylhydroperoxide. J Mol Catal A Chem 353–354:138–147.  https://doi.org/10.1016/j.molcata.2011.11.017 CrossRefGoogle Scholar
  11. 11.
    Ahmadjo S, Damavandi S, Zohuri GH, Farhadipour A, Samadieh N, Etemadinia Z (2017) Synthesis and application of fluorinated α-diimine nickel catalyst for ethylene polymerization: deactivation mechanism. Polym Bull 74:3819–3832.  https://doi.org/10.1007/s00289-017-1924-3 CrossRefGoogle Scholar
  12. 12.
    Chr Turmanova Sevdalina, Dimitrov Ivaylo V, Ivanova Emilya D, Vassilev Krassimir G (2015) Complexes of hybrid copolymers with heavy metals: preparation, properties and application as catalysts for oxidation. Polym Bull 72(6):1301–1317.  https://doi.org/10.1007/s00289-015-1338-z CrossRefGoogle Scholar
  13. 13.
    Islama SM, Sanghamitra Mukherjee PM, Roy AS, Bhaumik A (2011) A reusable polymer anchored copper(II) complex catalyst for the efficient oxidation of olefins and aromatic alcohol. Polym Adv Technol 22:933–941.  https://doi.org/10.1002/pat.1598 CrossRefGoogle Scholar
  14. 14.
    Chang Y, Zha F, Su B, Wang Y (2006) Oxidation of styrene with molecular oxygen catalyzed by polymer-supported O-aminobenzoic acid salicylaldehyde Schiff-base copper(II) complex. J Macromol Sci Pure Appl Chem 43:923–931.  https://doi.org/10.1080/10601320600653772 CrossRefGoogle Scholar
  15. 15.
    Gupta KC, Sutar AK (2008) Catalytic activities of polymer-supported metal complexes in oxidation of phenol and epoxidation of cyclohexene. Polym Adv Technol 19:186–200.  https://doi.org/10.1002/pat.994 CrossRefGoogle Scholar
  16. 16.
    Gupta KC, Sutar AK (2007) Polymer supported Schiff base complexes of iron(III), cobalt(II) and nickel(II) ions and their catalytic activity in oxidation of phenol and cyclohexene. J Macromol Sci Pure Appl Chem 44:1171–1185.  https://doi.org/10.1080/10601320701561106 CrossRefGoogle Scholar
  17. 17.
    Chang Y, Chen H, Lv Y, Zha F, Liu H (2011) Oxidation of cyclohexene with oxygen catalyzed by supported dinuclear Schiff-base complex. J Macromol Sci Pure Appl Chem 48:441–446.  https://doi.org/10.1080/10601325.2011.573324 CrossRefGoogle Scholar
  18. 18.
    Islam SM, Roy AS, Mondal P, Salam N (2012) Efficient allylic oxidation of olefins catalyzed by polymer supported metal Schiff base complexes with peroxides. J Inorg Organomet Polym 22:717–730.  https://doi.org/10.1007/s10904-012-9666-z CrossRefGoogle Scholar
  19. 19.
    Jia T, N-n Zheng, W-q Cai, Zhang J, Ying L, Huang F, Cao Y (2017) Microwave-assisted one-pot three-component polymerization of alkynes, aldehydes and amines toward amino-functionalized optoelectronic polymers. Chin J Polym Sci 35(2):269–281.  https://doi.org/10.1007/s10118-017-1890-0 CrossRefGoogle Scholar
  20. 20.
    Parvulescu V, Niculescu V, Ene R, Popa A, Mureseanu M, Ene CD, Andruh M (2013) Supported monocationic copper(II) complexes obtained by coordination with dialkylphosphonate groups on styrene–divinylbenzene copolymer as catalysts for oxidation of organic compounds. J Mol Catal A Chem 366:275–281.  https://doi.org/10.1016/j.molcata.2012.10.005 CrossRefGoogle Scholar
  21. 21.
    Davidescu C-M, Ardelean R, Popa A, Ilia G, Iliescu S, Negrea A, Motoc M (2014) Removal of phenolic compounds from aqueous solutions using poly(styrene-co-divinylbenzene) functionalized with aminophosphonic acid. Rev Chim (Bucharest) 65(4):444–446Google Scholar
  22. 22.
    Popa A, Ene R, Visinescu D, Dragan ES, Ilia G, Iliescu S, Parvulescu V (2015) Transitional metals immobilized by coordination on aminophosphonate functionalized copolymers and their catalytic properties. J Mol Catal A Chem 408:262–270.  https://doi.org/10.1016/j.molcata.2015.07.035 CrossRefGoogle Scholar
  23. 23.
    Popa A, Parvulescu V, Iliescu S, Plesu N, Ilia G, Macarie L, Pascariu A (2008) Synthesis and characterisations of aminophosphonate styrene–divinylbenzene–silica hybrid materials. Plast Rubber Compos 37(5/6):193–197.  https://doi.org/10.1179/174328908X309295 CrossRefGoogle Scholar
  24. 24.
    Popa A, Ilia G, Iliescu S, Davidescu CM, Pascariu A, Bora A (2003) The arbuzov reaction used in the synthesis of phosphonates-based resins. Rev Chim (Bucuresti) 54:834–836Google Scholar
  25. 25.
    Popa A, Parvulescu V, Ene R, Ilia G, Iliescu S (2010) Phosphonate/Phosphonic acid grafted on St-DVB polymer/SiO2 hybrid. Optoelectron Adv Mat 4(8):1203–1207Google Scholar
  26. 26.
    Ogoshi T, Chujo Y (2005) Organic–inorganic polymer hybrids prepared by the sol–gel method. Compos Interfaces 11(8–9):539–566.  https://doi.org/10.1163/1568554053148735 CrossRefGoogle Scholar
  27. 27.
    Popa A, Parvulescu V, Tablet C, Ilia G, Iliescu S, Pascariu A (2008) Heterogeneous catalysts obtained by incorporation of polymer-supported phosphonates into silica used in oxidation reactions. Polym Bull 60:149–158.  https://doi.org/10.1007/s00289-007-0844-z CrossRefGoogle Scholar
  28. 28.
    Popa A, Ilia G, Davidescu CM, Iliescu S, Plesu N, Pascariu A, Zhang Z (2006) Wittig–Horner reactions on styrene–divinylbenzene supports with benzaldehyde side-groups. Polym Bull 57:189–197.  https://doi.org/10.1007/s00289-006-0553-z CrossRefGoogle Scholar
  29. 29.
    Gumienna-Kontecka E, Gałęzzowska Drązg J, Latajka R, Kafarski P, Kozłowski H (2004) Coordination abilities of substituted β-aminophosphonates towards Cu2+ and Zn2+ ions. Inorg Chim Acta 357:1632–1636.  https://doi.org/10.1016/j.ica.2003.11.033 CrossRefGoogle Scholar
  30. 30.
    Kiss T, Jezowska-Bojczuk M, Kozlowski H, Kafarski P, Antczak K (1991) Complexes of aminophosphonates. Part 7. Copper(II) complexes of some aliphatic, alicyclic and aromatic aminophosphonous and aminophosphinic acids. J Chem Soc Dalton Trans 9:2275–2279.  https://doi.org/10.1039/DT9910002275 CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Institute of Chemistry Timisoara of Romanian AcademyRomanian AcademyTimisoaraRomania
  2. 2.Institute of Physical ChemistryRomanian AcademyBucharestRomania

Personalised recommendations