O. Steinhof et al.
NMR spectroscopy. The results were confirmed by 2D NMR spec-
troscopy and by direct synthesis. The change in 15N chemical
shift of the nitrogen centers of urea upon addition of formalde-
hyde was determined. The existence of hemiformals of methy-
lol ureas was confirmed, and their chemical shifts were deter-
mined. No uron-type structures were identified under the studied
conditions, but these structures were prepared otherwise and
characterized. It was shown that reaction mixtures as they are
commonly used in the industrial production of UF resins can be
quantitatively analyzed by a combination of 15N and 13C NMR
spectroscopy, resulting in a detailed description of the mixtures’
composition at different feed ratios and pH values. The varia-
tion in pH value leads to a slight change in mixture composition
due to the acid-catalyzed condensation reactions but did not
measurably affect hydroxymethylation and formation of hemifor-
mals. The results open a new route for characterizing the studied
complex mixtures and ultimately for optimizing the UF resin pro-
duction based on the knowledge of the true composition of the
reacting mixtures.
[39] B. Tomita, S. Hatono, J. Polym. Sci., Part A: Polym. Chem. 1978, 16,
2509–2525.
[40] R. Rammon, W. E. Johns, J. Magnuson, K. Dunker, J. Adhesion 1986,
19, 115–135.
[41] M. G. Kim, L. W. Amos, Chem. Ber. 1990, 29, 208–212.
[42] P. Christjanson, T. Pehk, K. Siimer, J. Appl. Polym. Sci. 2006, 100,
1673–1680.
[43] K. Siimer, P. Christjanson, T. Kaljuvee, T. Pehk, I. Lasn, I. Saks, J. Therm.
Anal. Calorim. 2008, 92, 19–27.
[44] A. Despres, A. Pizzi, H. Pasch, A. Kandelbauer, J. Appl. Polym. Sci. 2007,
106, 1106–1128.
[45] J. Ebdon, P. E. Heaton, T. N. Huckerby, W. T. S. O’Rourke, J. Parkin,
Polymer 1984, 25, 821.
[46] J. Ebdon, B. J. Hunt, W. T. S. O’Rourke, J. Parkin, Brit. Polym. J. 1988, 20,
327–334.
[47] R. A. Thomson, M. Manley-Harris, B. D. Gill, Magn. Reson. Chem. 2003,
41, 622–625.
[48] A. S. Angelatos, M. I. Burgar, N. Dunlop, F. Separovic, J. Appl. Polym.
Sci. 2004, 91, 3504–3512.
[49] A. Philbrook, C. J. Blake, N. Dunlop, C. J. Easton, M. A. Keniry, J. S.
Simpson, Polymer 2005, 46, 2153–2156.
[50] O. Steinhof, NMR-spektroskopische Aufklärung des bei der Umsetzung
von Harnstoff mit Formaldehyd auftretenden Reaktionsnetzwerks. PhD
Thesis, Cuvillier Verlag Göttingen, Universität Stuttgart, 2010.
[51] E. J. Kibrik, O. Steinhof, G. Scherr, W. R. Thiel, H. Hasse, Ind. Eng. Chem.
Res. (submitted 2014).
References
[52] H. G. Schecker, W. Jost, Ber. Bunsen-Ges. Phys. Chem. 1969, 73,
521–526.
[53] H. G. Schecker, G. Schulz, Z. Phys. Chem. (Frankfurt, Ger.) 1969,
65, 221–224.
[54] I. Hahnenstein, H. Hasse, C. G. Kreiter, G. Maurer, Ind. Eng. Chem. Res.
1994, 33, 1022–1029.
[1] W. Keim, Kunststoffe, Wiley-VCH Verlag, Weinheim, Germany, 2006.
[2] X. Tanga, Y. Bai, A. Duong, M. T. Smith, L. Li, L. Zhang, Environ. Int.
2009, 35, 1210–1224.
[3] M. Dunky, P. Niemz, Holzwerkstoffe und Leime, Springer-Verlag, Berlin
Heidelberg, 2002.
[4] H Kadowaki, Bull. Chem. Soc. Jpn. 1936, 11, 248–261.
[5] L. E. Smythe, J. of Phys. and Colloid Chem. 1947, 51, 369–378.
[6] L. E. Smythe, J. Am. Chem. Soc. 1951, 73, 2735–2738.
[7] L. E. Smythe, J. Am. Chem. Soc. 1953, 75, 1508–1510.
[8] G. A. Crowe, C. C. Lynch, J. Am. Chem. Soc. 1948, 70, 3795–3797.
[9] G. A. Crowe, C. C. Lynch, J. Am. Chem. Soc. 1949, 71, 3731–3733.
[10] J. de Jong, Recl. Trav. Chim. Pay. B. 1950, 69, 1566.
[11] J. de Jong, J. de Jonge, Recl. Trav. Chim. Pay. B. 1952, 71, 890–898.
[12] J de Jong, J de Jonge, Recl. Trav. Chim. Pay. B. 1952, 71, 643–660.
[13] J. de Jong, J. de Jonge, Recl. Trav. Chim. Pay. B. 1953, 72, 139–156.
[14] J. de Jong, J. de Jonge, Recl. Trav. Chim. Pay. B. 1953, 72, 169–172.
[15] J. de Jong, J. de Jonge, Recl. Trav. Chim. Pay. B. 1953, 72, 1027–1036.
[16] J. de Jong, J. de Jonge, Recl. Trav. Chim. Pay. B. 1953, 72, 213–217.
[17] J. de Jong, J. de Jonge, H. A. K. Eden, Recl. Trav. Chim. Pay. B. 1952, 71,
661–667.
[55] I. Hahnenstein, H. Hasse, Y.-Q. Liu, G. Maurer, AIChE Symp. Ser. 1994,
90, 141–157.
[56] H. Dahn, P. Pechy, Magn. Reson. Chem. 1996, 34, 723–724.
[57] M. Maiwald, H. H. Fischer, Y. K. Kim, H. Hasse, Anal. Bioanal. Chem.
2003, 375, 1111–1115.
[58] M. Maiwald, H. H. Fischer, M. Ott, R. Peschla, C. Kuhnert, C. G. Kreiter,
G. Maurer, H. Hasse, Ind. Eng. Chem. Res. 2003, 42, 259–266.
[59] C. Kuhnert, M. Albert, S. Breyer, I. Hahnenstein, H. Hasse, G. Maurer,
Ind. Eng. Chem. Res. 2006, 45, 5155–5164.
[60] S. Cannizzaro, Liebigs Ann. Chem. 1853, 88, 129–130.
[61] D. Luther, H. Koch, Chem. Ber. 1966, 99, 2227–2236.
[62] M. Ott, H. H. Fischer, M. Maiwald, K. Albert, H. Hasse, Chem. Eng.
Process. 2005, 44, 653–660.
[63] B. R. Glutz, H. Zollinger, Helv. Chim. Acta 1969, 52, 1976–1984.
[64] E. J. Kibrik, O. Steinhof, G. Scherr, W. R. Thiel, H. Hasse, J. Appl. Polym.
Sci. 2012, 128, 3957–3963.
[65] E. J. Kibrik, O. Steinhof, G. Scherr, W. R. Thiel, H. Hasse, J. Polym. Res.
2013, 20, 1–10.
[66] P. Christjanson, I. Lasn, K. Siimer, T. Pehk, Holz als Roh- und Werkstoff
2002, 60, 379–384.
[67] P. Christjanson, T. Pehk, K. Siimer, Proc. EstonianAcad. Sci. Chem. 2006,
55, 212–225.
[68] I. S. Chuang, G. E. Maciel, Macromolecules 1992, 25, 3204–3226.
[69] C. Goldschmidt, J. Prakt. Chem. 1897, 46, 460.
[70] K. Siimer, T. Pehk, P. Christjanson, Macromol. Symp. 1999, 148,
149–156.
[71] G. Zigeuner, H. Fitz, Monatsh. Chem. 1959, 90, 211–221.
[72] V. Horn, G. Benndorf, K. P. Rädler, Plaste Kautsch 1978, 25, 570–575.
[73] R. Kveton, Collect. Czech. Chem. Commun. 1959, 24, 2068–2071.
[74] T. Mejdell, H. K. Schjønsby, Macromol. Symp. 2004, 206, 241–254.
[75] C. Soulard, C. Kamoun, A. Pizzi, J. Appl. Polym. Sci. 1999, 72, 277–289.
[76] G. Zigeuner, W. Knierzinger, K. Voglar, E. Wiesenberger, M. Sobotka,
Monatsh. Chem. 1951, 82, 847–855.
[77] M. T. Beachem, P. D. Schickedanz, J. C. Oppelt, D. V. Maier, F. M. Cowen,
J. Org. Chem. 1963, 28, 1876.
[78] W. Gao, J. Li, Maderas. Ciencia y Tecnologia 2012, 14, 3–12.
[79] J. H. Meessen, Ullmann’s Encyc. of Indust. Chem. 2010, 37, 657–693.
DOI: 10.1002/14356007.a27_333.pub2
[18] J. de Jong, J. de Jonge, H. A. K. Eden, Recl. Trav. Chim. Pay. B. 1953, 72,
88–90.
[19] N. Landqvist, Acta Chem. Scand. 1955, 9, 1127–1142.
[20] N. Landqvist, Acta Chem. Scand. 1955, 9, 1459–1465.
[21] N. Landqvist, Acta Chem. Scand. 1955, 9, 1466–1470.
[22] N. Landqvist, Acta Chem. Scand. 1955, 9, 1471–1476.
[23] N. Landqvist, Acta Chem. Scand. 1955, 9, 1477–1483.
[24] N. Landqvist, Acta Chem. Scand. 1956, 10, 244–248.
[25] N. Landqvist, Acta Chem. Scand. 1957, 11, 776–779.
[26] N. Landqvist, Acta Chem. Scand. 1957, 11, 792–803.
[27] N. Landqvist, Acta Chem. Scand. 1957, 11, 780–785.
[28] N. Landqvist, Acta Chem. Scand. 1957, 11, 786–791.
[29] R. Kveton, Collect. Czech. Chem. Commun. 1956, 21, 593–606.
[30] BFA, Formaldehyd – Gefährlicher als bisher angenommen? Stellung-
nahme vom 29. November 2004, 2004.
[31] I. Hahnenstein, M. Albert, H. Hasse, C. G. Kreiter, G. Maurer, Ind. Eng.
Chem. Res. 1995, 34, 440–450.
[32] H. Hasse, G. Maurer, Ind. Eng. Chem. Res. 1991, 30, 2195–2200.
[33] J. F. Walker, Formaldehyde (3ed.), ACS Monograph Series, Reinhold
Publishing Corporation, New York City, 1964.
[34] M. Chiavarini, N. Delfanti, R. Bigatto, Angew. Makromol. Chem. 1975,
46, 151–162.
[35] S. M. Kambanis, R. C. Vasishth, J. Appl. Polym. Sci. 1971, 15, 1911–1919.
[36] W. Dankelman, J. M. H. Daemen, A. J. J. de Breet, J. L. Mulder, W. G. B.
Huysmans, J. de Wit, Angew. Makromol. Chem. 1976, 54, 187–201.
[37] A. J. J. de Breet, W. Dankelman, W. G. B. Huysmans, J. de Wit, Angew.
Makromol. Chem. 1977, 62, 7–31.
[80] R. K. Harris, E. D. Becker, S. M. C. D. Menezes, R. Goodfellow, P. Granger,
Pure Appl. Chem. 2001, 73, 1795–1818.
[81] T. D. Claridge, High-resolution NMR Techniques in Organic Chemistry
(1st edn), Elsevier Ltd., Oxford, 1999.
[38] J. R. Ebdon, P. E. Heaton, Polymer 1977, 18, 971–974.
wileyonlinelibrary.com/journal/mrc
Copyright © 2014 John Wiley & Sons, Ltd.
Magn. Reson. Chem. 2014, 52, 138–162