Polymer Bulletin

, Volume 69, Issue 2, pp 125–135 | Cite as

Synthesis and properties of poly(1,3-dialkoxybenzene)s from facile solvent-free grinding oxidative coupling polymerization

Original Paper


Soluble conjugated aromatic poly(1,3-dialkoxybenzene)s were obtained in high yield up to 80% in 30 min by grinding 1,3-dialkoxybenzene with anhydrous FeCl3 powder in a mortar at ambient and solvent-free condition. The polymers were characterized by FT-IR, 1H-NMR, 13C-NMR, and gel permeation chromatography. The structure of the aromatic rings linkage at meta-position was confirmed. Thermogravimetric analysis, UV–Vis, fluorescence spectroscopy, and four-probe a.c. technique were used to probe the thermal, optical, and electrical properties of the polymers. The polymers displayed high thermostability with the decomposition temperatures at about 382–388 °C. The optical energy gap (Eg) of the polymers was 4.23 eV and electrical conductivity at room temperature was 10−6 S cm−1. The fluorescence curve of the polymers displayed the maximum at 344 nm in CH2Cl2 solution. The morphology of the polymers was determined by X-ray diffraction and scanning electron microscope technique.


Poly(1,3-dialkoxybenzene)s Conjugated polymer Solvent-free grinding oxidative coupling polymerization 


  1. 1.
    Grimsdale AC, Müllen K (2006) Polyphenylene-type emissive materials: poly(para-phenylene)s, polyfluorenes, and ladder polymers. Adv Polym Sci 199:1–82CrossRefGoogle Scholar
  2. 2.
    Hong SY, Kim DY, Kim CY, Hoffmann R (2001) Origin of the broken conjugation in m-phenylene linked conjugated polymers. Macromolecules 34:6474–6481CrossRefGoogle Scholar
  3. 3.
    Simitzis J, Triantou D, Soulis S (2008) Synthesis and characterization of electrically conducting copolymers based on benzene and biphenyl. J Appl Polym Sci 110:356–367CrossRefGoogle Scholar
  4. 4.
    Goto H, Katagiri H, Furusho Y, Yashima E (2006) Oligoresorcinols fold into double helices in water. J Am Chem Soc 128:7176–7178CrossRefGoogle Scholar
  5. 5.
    Ben T, Furusho Y, Goto H, Miwac K, Yashima E (2009) Double helix formation of poly(m-phenylene)s bearing achiral oligo(ethylene oxide) pendants and transformation into an excess of one-handed single helix through cholate binding in water. Org Biomol Chem 7:2509–2512CrossRefGoogle Scholar
  6. 6.
    Yamamoto T, Hayashi Y, Yamamoto A (1978) Preparation of thermostable polyphenylene type polymers. Bull Chem Soc Jpn 51:2091–2097CrossRefGoogle Scholar
  7. 7.
    Fujioka Y (1984) Syntheses and physical properties of several polyphenylenes containing mixed linkages. Bull Chem Soc Jpn 57:3494–3506CrossRefGoogle Scholar
  8. 8.
    Xu MH, Lin ZM, Pu L (2001) Construction of an ortho-phenol polymer. Tetrahedron Lett 42:6235–6238CrossRefGoogle Scholar
  9. 9.
    Stanforth SP (1998) Catalytic cross-coupling reactions in biaryl synthesis. Tetrahedron 54:263–303CrossRefGoogle Scholar
  10. 10.
    Martínez Y, Hernãndez R, Kalaji M, Márquez J, Márquez OP (1998) Electrosynthesis and characterization of poly(1, 3-dimethoxybenzene). Synth Met 93:9–15CrossRefGoogle Scholar
  11. 11.
    Boden N, Bushby RJ, Lu Z, Headdock G (2000) Synthesis of dibromotetraalkoxybiphenyls using ferric chloride. Tetrahedron Lett 41:10117–10120CrossRefGoogle Scholar
  12. 12.
    Kovacic P, Kyriakis A (1963) Polymerization of benzene to p-polyphenyl by aluminum chloride-cupric chloride. J Am Chem Soc 85:454–458CrossRefGoogle Scholar
  13. 13.
    Bai WB, Zhan CM (2005) Regioregular poly(p-alkoxyphenylene)s prepared from facile solid-state oxidative coupling polymerization. Chem Lett 34:924–925CrossRefGoogle Scholar
  14. 14.
    Schlute AD, Wegner G (1993) Palladium and nickel catalyzed polycondensation—the key to structurally defined polyarylenes and other aromatic polymers. Acta Polym 44:59–69CrossRefGoogle Scholar
  15. 15.
    Mitsuru U, Tetsuya A, Hiroshi A (1992) Synthesis of poly(2,5-dialkoxyphenylene). Macromolecules 25:5125–5130CrossRefGoogle Scholar
  16. 16.
    Osaheni JA, Jenekhe SA, Perlstein J (1994) Photogeneration of charge carriers in bilayer assemblies of conjugated rigid-rod polymers. J Phys Chem 98:12727–12736CrossRefGoogle Scholar
  17. 17.
    Alexander RL (1956) The synthesis and infrared absorption spectra of some m-polyphenyls. J Org Chem 21:1464–1466CrossRefGoogle Scholar
  18. 18.
    Pang Y, Li J, Hu B, Karasz FE (1998) A processible poly(phenyleneethynylene) with strong photoluminescence: synthesis and characterization of poly[(m-phenyleneethynylene)-alt-(p-phenyleneethynylene)]. Macromolecules 31:6730–6732CrossRefGoogle Scholar
  19. 19.
    Bilici A, Kaya İ, Yıldırım M (2011) A comparative study of 9,9-bis(4-aminophenyl) fluorene polymers prepared by catalytic and non-catalytic oxidative polymerisation methods. Eur Polym J 47:1005–1017CrossRefGoogle Scholar
  20. 20.
    Li XG, Wang LX, Jin Y, Zhu ZL, Yang YL (2001) Preparation and identification of a soluble copolymer from pyrrole and o-toluidine. J Appl Polym Sci 82:510–518CrossRefGoogle Scholar

Copyright information

© Springer-Verlag 2011

Authors and Affiliations

  1. 1.College of Chemistry and Material ScienceFujian Normal UniversityFuzhouPeople’s Republic of China
  2. 2.Key Laboratory of Polymer MaterialsFuzhouPeople’s Republic of China

Personalised recommendations