Urea-Formaldehyde Resin
Submitted by: L. Boldizar1
Checked by: H. Roth 2
1. Procedure
Low methanol-37% formalin (2840 g, 35 mol, Note 1), 2 g of 80% triethanolamine, and urea
(1133 g, 18.9 mol) are charged with agitation into a 5 L, three-necked flask equipped with stirrer,
reflux condenser, and thermometer. The urea is dissolved while the temperature of the solution
is maintained between 20o and 25oC (Note 2). When the urea is in solution, the pH is adjusted to
7.2-7.4 with triethanolamine or 5 N formic acid (Note 3). The reaction mixture is heated to reflux
in 30-40 min, maintaining a uniform temperature rise, using a heating mantle attached to a 1KVA
variable transformer at 110 volts. The batch is refluxed 1-2 h between 98o and 102oC with vigorous
agitation until the reaction is complete.
After 5 min of reflux, a sample is obtained and cooled to 25 oC for Ph and viscosity tests (Note
4). The Ph should be 6.4-6.8. The viscosity is checked every 10 min and the readings plotted
against time until a value of 17-19 cp is anticipated by extrapolation. When this viscosity is
reached, heat is removed, the batch cooled with a cold water or ice bath, and about 2 g of
triethanolamine is added to raise the Ph to 7.5-7.7. The resin is concentrated under vacuum (Note
5) until a viscosity of 150-250 cp (Note 6) is reached; the pH should be 7.8-8.0 (Note 7).
2. Characterization
The resin-solids content of the syrup obtained by the described procedure is about 60% (Note
8), and the free formaldehyde in the syrup is between 2% and 4% (Note 9). The composition of
the resin is UF1.7. This means that, because of the equilibrium between the combined and
unreacted formaldehyde, about 2.5 mol of the 35 mol of CH2O charged is not reacted and is lost
during concentration. Less than 50% of the combined formaldehyde is converted into methylene
bridges during resinification. It can be assumed that the resin is a blend of mono- and dimethylol
ureas, partially crosslinked, forming linear or branched units, or both. These units are probably
dimers and trimers; however, no molecular weight data are available.
3. Notes
1. The formalin should contain less than 2% methanol. If methanol-stabilized formalin (6-7%
methanol) is used, the resinification is carried out at a somewhat lower pH level.
202
Urea Resin 203
2. The urea is added slowly to maintain the desired temperature. The checker found that, if
the total urea charge is added at one time, the temperature drops to 5-10oC because of the
negative heat of solution, necessitating rapid external heating back to 20-25oC. The
resultant syrup is slightly opaque and, although it has the required pH and solids content, the
viscosity is higher than desired.
3. If the temperature is allowed to rise above 25oC, a rapid reaction starts with constantly
changing pH. The pH is measured on a 25-50 g sample with a glass electrode at 25 oC.
4. A Brookfield LVF viscometer with No. 1 spindle is used at 60 rpm.
5. The temperature of the syrup should not exceed 50oC. About 910 g of condensate should
be collected.
6. A Brookfield LVF viscometer with No. 2 spindle is used at 60 rpm.
7. The equipment is cleaned with hot water immediately.
8. A 5 g sample, weighed in a 3 in diameter aluminum dish, is dried in an oven at 115oC for 5
h to determine solids content.
9. The free formaldehyde is determined by the sodium sulfite method. A 5.0 g sample of the
resin is weighed into a 250 ml beaker and dissolved in 100 ml of distilled water.
Thymolphthalein solution (10-15 drops) is added and the solution is neutralized with 0.5 N
NaOH. Exactly 5.0 ml of 0.5 N HCl is added from a buret with stirring. A saturated sodium
sulfite solution (25 ml) is added, the mixture is stirred for a few seconds and titrated with 0.5
N NaOH to the endpoint. A blank is run by diluting 25 ml of saturated sodium sulfite solution
with 100 ml of distilled water. Thymolphthalein indicator (10 drops) is added and the solution
is titrated to the endpoint with 0.5 N HCl. The % free formaldehyde is calculated as:
4. Method of Preparation
The condensation of urea and formaldehyde has been widely investigated, and numerous
review articles have been published.3,4,5,6,7,8,9 The resin syrup as described above has a shelf life
of at least 6 months. When properly catalyzed with acids or acid salts, it can be used in many
binder applications, especially as wood adhesives.
5. References
1. Plastics and Resins Division, American Cyanamid Co., Wallingford, CT 06492; current
address - Plastics Department, American Cyanamid Co., Stamford, CT 06904.
2. Central Research Laboratories, Inmont Corp., Clifton, NJ 07015.
3. Einhorn, A. Ann. Chem., 1905, 343, 307.
4. Einhorn, A.; Hamburger, A. Ber. Deut. Chem. Ges., 1908, 41, 24.
5. Ellis, C. The Chemistry of Synthetic Resins; Reinhold Publishing Corp.: New York,
1935; p 613.
6. Kadowaki, H. Bull. Chem. Soc. Japan, 1936, 11, 248.
7. deJong, J. I.; deJonge, J. Rec. trav. chim., 1953, 72, 139, 1027.
8. Wohnsiedler, H. P. In Amino Resins and Plastics; Encyclopedia of Chemical
Technology, Vol. 2, 2nd Ed.; Interscience Publishers: New York, 1963, pp 225-258.
9. Sorenson, W. R.; Campbell, T. W. Preparative Methods of Polymer Chemistry;
Interscience Publishers: New York, 1961; p 300.
