Skip to main content
Journal of Wood Science

Official Journal of the Japan Wood Research Society

Download PDF
  • Original Article
  • Published:

Molecular complex of lignosulfonic acid/poly(vinyl pyridine) via ionic interaction: characterization of chemical composition and application to material surface modifications

Journal of Wood Science volume 54, pages 143–152 (2008)Cite this article

Abstract

Poly ion complexes of anionic lignosulfonic acid (LSA) with cationic poly(2-vinyl pyridine) or poly(4-vinyl pyridine) were prepared by mixing the polymer solutions in dimethyl sulfoxide or dilute hydrochloric acid. The complexes were formed as soon as the polymer solutions were mixed. Fourier transform infrared (FTIR) measurements for the complexes revealed the presence of strong ionic interactions between sulfonate anions of LSA and pyridinium cations of the vinyl pyridine (VPy) polymers. The strong interaction was supported by detection of a glass transition temperature (T g) much higher than pristine T g values of VPy polymers in differential scanning calorimetry. By using the ionic complexation, a coating of LSA onto VPy polymer films was undertaken to modify their original surface property. Formation of a thin complex film was confirmed by observation of absorption bands that are characteristic of the pyridinium cation in reflection FTIR spectra measurements, and by visualization of the attached LSA component in atomic force microscopy. This treatment resulted in the surface of the VPy polymer films becoming hydrophobic. An adhesion test was also conducted by pasting two veneered woods with the polymer complex, followed by shear-tearing them off. The adhesive strength of the complex was estimated to be 1.1 MPa.

References

  1. Ciemniecki SL, Glasser WG (1988) Multiphase materials with lignin: 2. Blends of hydroxypropyl lignin with poly(vinyl alcohol). Polymer 29:1030–1036

    Article  CAS  Google Scholar 

  2. Feldman D, Banu D, Lacasse M, Wang J, Luchian C (1995) Lignin and its polyblends. J Macromol Sci Pure Appl Chem A32:1613–1619

    Article  CAS  Google Scholar 

  3. Ghosh I, Jain RK, Glasser WG (2000) Blends of biodegradable thermoplastics with lignin esters. ACS Symp Ser 742:331–350

    Article  CAS  Google Scholar 

  4. Kadla JF, Kubo S, Venditti RA, Gilbert RD, Compere AL, Griffith W (2002) Lignin-based carbon fibers for composite fiber applications. Carbon 40:2913–2920

    Article  CAS  Google Scholar 

  5. Kadla JF, Kubo S, Venditti RA, Gilber RD (2002) Novel hollow core fibers prepared from lignin polypropylene blends. J Appl Polym Sci 85:1353–1355

    Article  CAS  Google Scholar 

  6. Kubo S, Kadla JF (2003) The formation of strong intermolecular interactions in immiscible blends of poly(vinyl alcohol) (PVA) and lignin. Biomacromolecules 4:561–567

    Article  CAS  PubMed  Google Scholar 

  7. Li Y, Mlynar J, Sarkanen S (1997) The first 85% kraft lignin-based thermoplastics. J Polym Sci Part B: Polym Phys 35:1899–1910

    Article  CAS  Google Scholar 

  8. Li Y, Sarkanen S (2002) Alkylated kraft lignin-based thermoplastic blends with aliphatic polyesters. Macromolecules 35:9707–9715

    Article  CAS  Google Scholar 

  9. Nishio Y (1994) Hyperfine composites of cellulose with synthetic polymers. In: Gilbert RD (ed) Cellulosic polymers, blends and composites. Carl Hanser, Munich, pp 95–113

    Google Scholar 

  10. Nishio Y (2006) Material functionalization of cellulose and related polysaccharides via diverse microcompositions. Adv Polym Sci 205:97–151

    Article  CAS  Google Scholar 

  11. Miyashita Y, Kimura N, Nishio Y, Suzuki H (1994) Transition behavior and phase structure of cellulose/poly(N-vinylpyrrolidone) composites prepared by a solution coagulation/bulk polymerization method. Koubunshi Ronbunshu 51:466–471

    Article  CAS  Google Scholar 

  12. Miyashita Y, Sato M, Kimura N, Nishio Y, Suzuki H (1996) An effect of deacetylation of chitin on the miscibility of chitin/ poly(vinyl alcohol) blends. Koubunshi Ronbunshu 53:149–154

    Article  CAS  Google Scholar 

  13. Miyashita Y, Yamada Y, Kimura NM, Suzuki H, Iwata M, Nishio Y (1997) Phase structure of chitin/poly(glycidylmethacrylate) composites synthesized by a solution coagulation/bulk polymerization method. Polymer 38:6181–6187

    Article  CAS  Google Scholar 

  14. Nishio Y, Matsuda K, Miyashita Y, Kimura N, Suzuki H (1997) Blends of poly(e-caprolactone) with cellulose alkyl esters: effect of the alkyl side-chain length and degree of substitution on miscibility. Cellulose 4:131–145

    Article  CAS  Google Scholar 

  15. Miyashita Y, Kimura N, Suzuki H, Nishio Y (1998) Cellulose/poly(acryloyl morpholine) composites: synthesis by solution coagulation/ bulk polymerization and analysis of phase structure. Cellulose 5:123–134

    Article  CAS  Google Scholar 

  16. Miyashita Y, Suzuki T, Nishio Y (2002) Miscibility of cellulose acetate with vinyl polymers. Cellulose 9:215–223

    Article  CAS  Google Scholar 

  17. Ohno T, Yoshizawa S, Miyashita Y, Nishio Y (2005) Interaction and scale of mixing in cellulose acetate/poly(N-vinyl pyrrolidone-co-vinyl acetate) blends. Cellulose 12:281–291

    Article  CAS  Google Scholar 

  18. de Meftahi MV, Frechet JMJ (1987) Study of the compatibility of blends of polymers and copolymers containing styrene, 4-hydroxystyrene and 4-vinylpyridine. Polymer 29:477–482

    Article  Google Scholar 

  19. Miyake M, Kakizawa Y (2002) Study on the interaction between polyelectrolytes and oppositely charged ionic surfactants. Solubilized state of the complexes in the postprecipitation region. Colloid Polym Sci 280:18–23

    Article  CAS  Google Scholar 

  20. Wang J, Cheung MK, Mi YL (2001) Miscibility in blends of poly(4-vinylpyridine)/poly(4-vinylphenol) as studied by 13C solid-state NMR. Polymer 42:3087–3093

    Article  CAS  Google Scholar 

  21. Masuda S, Minagawa K, Tsuda M, Tanaka M (2001) Spontaneous copolymerization of acrylic acid with 4-vinylpyridine and microscopic acid dissociation of the alternating copolymer. Eur Polym J 37:705–710

    Article  CAS  Google Scholar 

  22. Akiba I, Seki T, Akiyama S (2002) Complex formation and selective hydrogen bonding in poly(4-vinylphenol-co-methylmethacrylate)-poly(N-vinylpyrrolidone-co-vinyl acetate) systems. E-Polymers no. 008

  23. Tsai HA, Syu MJ (2005) Synthesis and characterization of creatinine imprinted poly(4-vinylpyridine-co-divinylbenzene) as a specific recognition receptor. Anal Chim Acta 539:107–116

    Article  CAS  Google Scholar 

  24. Kim KS, Vincent B (2005) pH and temperature-sensitive behaviors of poly(4-vinyl pyridine-co-N-isopropyl acrylamide) microgels. Polym J 37:565–570

    Article  CAS  Google Scholar 

  25. Masson JF, Manley RStJ (1991) Cellulose/poly(4-vinylpyridine) blends. Macromolecules 24:5914–5921

    Article  CAS  Google Scholar 

  26. Vanderhart D, Manley RStJ, Barnes J (1994) Proton spin diffusion studies of polymer blends having modest monomer size. 2. Blends of cellulose with either poly(acrylonitrile) or poly(4-vinylpyridine). Macromolecules 27:2826–2836

    Article  CAS  Google Scholar 

  27. Matsushita Y, Yasuda S (2005) Preparation and evaluation of lignosulfonates as a dispersant for gypsum paste from acid hydrolysis lignin. Bioresource Technol 96:465–470

    Article  CAS  Google Scholar 

  28. Matsushita Y, Sano H, Imai M, Imai T, Fukushima K (2007) Phenolization of hardwood sulfuric acid lignin and comparison of the behavior of the syringyl and guaiacyl units in lignin. J Wood Sci 53:67–70

    Article  CAS  Google Scholar 

  29. Lin SY, Dence CW (1992) Methods in lignin chemistry. Springer, Berlin Heidelberg New York

    Book  Google Scholar 

  30. Forss K, Collins JJ, Glasser WG, Gratzl JS, McCarthy JL (1972) Preparation, fraction, and preliminary characterization of gymnosperm lignin sulfonates from spent sulfite liquor and milled wood lignin. TAPPI 55:1329–1333

    CAS  Google Scholar 

  31. Shimatani K, Sano Y, Sasaya T (1994) Preparation of moderatetemperature setting adhesives from softwood kraft lignin. 2. Effect of some factors on strength properties and characteristics of ligninbased adhesives. Holzforschung 48:337–342

    Article  CAS  Google Scholar 

  32. Vazquez G, Antorrena G, Gonzalez J, Freire S (1997) FTIR, 1H and 13C NMR characterization of acetosolv-solubilized pine and eucalyptus lignins. Holzforschung 51:158–166

    Article  CAS  Google Scholar 

  33. Mathers AP, Pro MJ (1955) Spectrophotometric determination of methoxyl. Anal Chem 27:1662–1664

    Article  CAS  Google Scholar 

  34. Balogh DT, Curvelo AAS, De Groote RAMC (1992) Solvent effects on organosolv lignin from Pinus caribaea var. hondurensis. Holzforschung 46:343–348

    Article  CAS  Google Scholar 

  35. Kadla JF, Chang HM (2002) Reactions of lignin with cyanamide activated hydrogen peroxide. Holzforschung 56:76–84

    Article  CAS  Google Scholar 

  36. Sakurai K, Douglas EP, MacKnight WJ (1992) Spectroscopic study of an ionic blend made from the acid form of sulfonated polystyrene and poly[ethyl acrylate-co-(4-vinylpyridine)]. Macromolecules 25:4506–4510

    Article  CAS  Google Scholar 

  37. Chien WJ, Sauer JA, Hara M (2003) Synergistic enhancement in mechanical properties and microstructure of homoblends made of poly(styrene-co-styrenesulfonic acid) and poly(styrene-co-4-vinylpyridine). Polymer 44:7485–7493

    Article  Google Scholar 

  38. Chien WJ, Sauer JA, Hara M (2003) The effect of ionic cross-links on the deformation behavior of homoblends made of poly(styrene-co-styrenesulfonic acid) and poly(styrene-co-4-vinylpyridine). Polymer 44:7729–7738

    Article  Google Scholar 

  39. Ikkala O, Ruokolainen J, ten Brinke G, Torkkeli M, Serimaa R (1995) Mesomorphic state of poly(vinylpyridine)-dodecylbenzenesulfonic acid complexes in bulk and in xylene solution. Macromolecules 28:7088–7094

    Article  CAS  Google Scholar 

  40. Huglin MB, Webster L, Lobb ID (1996) Complex formation between poly(4-vinylpyridinium chloride) and poly[sodium(2-acrylamido-2-methyl propane sulfonate)] in dilute aqueous solution. Polymer 37:1211–1215

    Article  CAS  Google Scholar 

  41. Yoshida M (1997) Solution properties of polyvinylpyridine in acid — II. Solution properties of poly(4-vinylpyridine) in aqueous solution of hydrochloric acid. Eur Polym J 33:943–948

    Article  CAS  Google Scholar 

  42. Wang L, Pearce E, Kwei T (1991) Mesophase formation of hydroxypropyl cellulose as affected by miscibility with a flexible polymer. Polymer 32:249–259

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Division of Forest and Biomaterials Science, Graduate School of Agriculture, Kyoto University, Sakyo-ku, Kyoto, 606-8502, Japan

    Daisuke Hasegawa & Yoshiyuki Nishio

  2. Biomass Technology Research Center (BTRC), National Institute of Advanced Industrial Science and Technology (AIST), Hiroshima, 737-0197, Japan

    Yoshikuni Teramoto

Authors
  1. Daisuke Hasegawa
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Yoshikuni Teramoto
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Yoshiyuki Nishio
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Yoshiyuki Nishio.

Additional information

Part of this report was presented at the 55th (Kyoto, March 2005) and 56th (Akita, August 2006) Annual Meetings of the Japan Wood Research Society

Rights and permissions

Reprints and permissions

About this article

Cite this article

Hasegawa, D., Teramoto, Y. & Nishio, Y. Molecular complex of lignosulfonic acid/poly(vinyl pyridine) via ionic interaction: characterization of chemical composition and application to material surface modifications. J Wood Sci 54, 143–152 (2008). https://doi.org/10.1007/s10086-007-0922-8

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10086-007-0922-8

Key words