Skip to main content
Journal of Wood Science

Official Journal of the Japan Wood Research Society

Download PDF
  • Original Articles
  • Published:

Formaldehyde emission and high-temperature stability of cured urea-formaldehyde resins

Journal of Wood Science volume 46, pages 303–309 (2000)Cite this article

Abstract

A test method for measuring formaldehyde from urea-formaldehyde (UF) resins at high temperature was developed and used to assess the influence of the reaction pH on the formaldehyde emission and heat stability of the cured resins. Additionally, solid-state13C CP/MAS nuclear magnetic resonance (NMR) techniques were used to investigate the structure of cured UF resins before and after high temperature heating. Formaldehyde emissions during the cure were related to the UF resins' methylol group content. The heat stability of cured UF resins synthesized under strongly acidic conditions was much higher than that of the other resins, which were prepared in weakly acidic and alkaline media. Solid-state13C CP/MAS NMR spectra showed that formaldehyde emission from cured UF resins after heating is mainly ascribable to decreased methylol groups and dimethylene ether linkages. Significantly, it was revealed that uron structures characteristically found in the cured UF resin synthesized under strongly acidic medium indicated high heat stability.

References

  1. Ko K (1976) How to control pollution of formaldehyde for formaldehyde series thermosetting resin adhesives (in Japanese). Settyaku Kyokaishi 12:160–166

    CAS  Google Scholar 

  2. Tomita B (1980) How chemical structure of UF resin affects formaldehyde emission (in Japanese). Mokuzai Kogyo 35:193–199

    CAS  Google Scholar 

  3. McVey D (1982) Great strides forward-formaldehyde emission from the production standpoint. In:16th International particleboard symposium, Washington State University, Pullman, WA, pp 21–34

    Google Scholar 

  4. Sundin B (1982) Present status of formaldehyde problems and regulations. In:16th International particleboard symposium, Washington State University, Pullman, WA, pp 3–20

    Google Scholar 

  5. Myers GE (1984) How mole ratio of UF resin affects formaldehyde emission and other properties: a literature critique. For Prod J 34(5):35–41

    CAS  Google Scholar 

  6. Hse C-Y, Xia Z-Y, Tomita B (1994) Effects of reaction pH on properties and performance of urea-formaldehyde resins. Holzforschung 48:527–532

    Article  CAS  Google Scholar 

  7. Myers GE (1985) Effect of separate additions to furnish or veneer on formaldehyde emission and other properties: a literature review (1960–1984). For Prod J 35(6):57–62

    CAS  Google Scholar 

  8. Myers GE (1986) Effects of post-manufacture board treatments on formaldehyde emission: a literature review (1960–1984). For Prod J 36(6):41–51

    CAS  Google Scholar 

  9. DeJong JI, deJonge J (1952) The reaction of urea with formaldehyde. Rec Trav Chim 71:643–660

    Article  CAS  Google Scholar 

  10. DeJong JI, deJonge J (1952) The formation and decomposition of dimethylolurea. J Rec Trav Chim 71:661–667

    Article  CAS  Google Scholar 

  11. DeJong JI, deJonge J (1953) The hydrolysis of methylenediurea. Rec Trav Chim 72:202–205

    Article  CAS  Google Scholar 

  12. Landqvist N (1955) On the reaction between urea and formaldehyde in neutral and alkaline solutions. Acta Chem Scand 9:1471–1476

    Article  CAS  Google Scholar 

  13. Landqvist N (1955) On the reaction between urea and formaldehyde in neutral and alkaline solutions. Acta Chem Scand 9:1466–1470

    Article  CAS  Google Scholar 

  14. Crowe GA, Lynch CC (1949) Polarographic urea-formaldehyde kinetic studies. J Am Chem Soc 71:3731–3733

    Article  CAS  Google Scholar 

  15. Dunn AS (1957) The urea-formaldehyde polycondensatioa. I. Kinetics of the hydrolysis of methoxymethylurea. J Chem Soc 75:1508–1510

    Google Scholar 

  16. Smythe LE (1953) Urea-formaldehyde kinetics studies. IV. Reactions of methylenebisureas. J Am Chem Soc 75:1508–1510

    Article  CAS  Google Scholar 

  17. Dunky M, Lederer K (1982) Studies of molecular weight distributions of urea-formaldehyde resinous glues. Angew Makrowmol Chem 102:199–213

    Article  CAS  Google Scholar 

  18. Kundin K, Simonson R (1978) Urea-formaldehyde resins. 1. Separation of low molecular weight components in urea-formaldehyde resins by means of liquid chromatography. Angew Makrowmol Chem 68:175–184

    Article  Google Scholar 

  19. Ludlam RR, King JG (1984) Size exclusion chromatography of urea formaldehyde resins in dimethylformamide containing lithium chloride. J Appl Polym Sci 29:3863–3872

    Article  CAS  Google Scholar 

  20. Ebdon JR, Heaton PE, Hucherby TN, O'Rourke WTS (1984) Characterization of urea-formaldehyde and melamineformaldehyde adducts and resins by 15N NMR spectroscopy. Polymer 25:821–825

    Article  CAS  Google Scholar 

  21. Kopf PW, Wagner ER (1973) Formation and cure of novolacs: NMR study of transient molecules. J Polym Sci Polym Chem Ed 11:939–960

    Article  CAS  Google Scholar 

  22. Nair BR, Francis DJ (1983) Kinetics and mechanism of ureaformaldehyde reaction. Polymer 24:626–630

    Article  CAS  Google Scholar 

  23. Slonim IY, Alekseeva SG, Urman YG, Arshava BM, Akselrod BY (1978) Study of equilibriums in the urea-formaldehyde system by carbon-13NMR. Vysokomol Soed 20:1477–1485

    CAS  Google Scholar 

  24. Tomita B, Hirose Y (1976) Urea-formaldehyde resins: NMR study on base-catalyzed reaction of formaldehyde with urea in deuterium oxide. J Polym Sci Polym Chem Ed 14:387–401

    Article  CAS  Google Scholar 

  25. Myers GE (1985) Resin hydrolysis and mechanisms of formaldehyde release from bonded wood products. In:Wood adhesives in 1985. FPRS, Madison, WI, pp 119–156

    Google Scholar 

  26. Troughton GE (1969) Effect of degree of cure on the acidhydrolysis rates of formaldehyde glue-wood samples. J Inst Wood Sci 4(5):51–56

    Google Scholar 

  27. Gu J, Higuchi M, Morita M, Hse C (1995) Synthetic conditions and chemical structures of urea-formaldehyde resins. I. Properties of the resins synthesized by three different procedures. Mokuzai Gakkaishi 41:1115–1121

    CAS  Google Scholar 

  28. Tomita B, Hatono Y (1978) Urea-rormaldehyde resins. III. Constitutional characterization by13C Fourier transform NMR spectroscopy. J Polym Sci 16:2509–2525

    CAS  Google Scholar 

  29. Maciel GE, Szeverinyi NM, Early TA, Myers GE (1983)13CNMR studies of solid urea-formaldehyde resins using cross polarization and magic-angle spinning. Macromolecules 16:598–604

    Article  CAS  Google Scholar 

  30. Chuang I-S, Maciel GE (1992)13C CP/MAS NMR study of the structural dependence of urea-formaldehyde resins on formaldehyde-to-urea molar ratios at different urea concentrations and pH values. Macromolecules 25:3204–3226

    Article  CAS  Google Scholar 

  31. Chuang I-S, Maciel GE (1994) NMR study of the stabilities of urea-formaldehyde resin components toward hydrolytic treatments. J Appl Polym Sci 52:1637–1651

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Forestry and Forest Products Research Institute, Tsukuba Norin Kenkyu Danchi, PO Box 16, 305-8687, Ibaraki, Japan

    Shin -ichiro Tohmura

  2. Southern Research Station, USDA, Forest Service, 71360, Pineville, Louisiana, USA

    Chung -Yun Hse

  3. Faculty of Agriculture, Kyushu University, 812-8581, Fukuoka, Japan

    Mitsuo Higuchi

Authors
  1. Shin -ichiro Tohmura
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Chung -Yun Hse
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Mitsuo Higuchi
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Shin -ichiro Tohmura.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Tohmura, S.i., Hse, C.Y. & Higuchi, M. Formaldehyde emission and high-temperature stability of cured urea-formaldehyde resins. J Wood Sci 46, 303–309 (2000). https://doi.org/10.1007/BF00766221

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF00766221

Keywords