5 Urea/Formaldehyde Resins
Urea/formaldehyde glue resins are the most important
type of urea/formaldehyde resins. Monographs on the
chemistry of urea/formaldehyde resins include those
by Dunky, Meyer, Pizzi, and van Dijk [1–4].
The industrial production of urea/formaldehyde
glue resins for the woodworking industry started in
1931. Environmental concerns demanded a change
of the formulation of urea/formaldehyde resins to
decrease the molar ratio of formaldehyde to urea to
avoid formaldehyde emissions.
5.1 History
The reaction of urea with formaldehyde was first noted
in 1884, with commercial interest in the polymers
commencing in about 1918 with a patent issued to
John (1891–1942) [5–7]. However, in 1896 Gold-
schmidt described precipitates formed when aque-
ous solutions of urea and formaldehyde were reacted
under acidic conditions [8]. It is believed that the
primary precipitate formed by Goldschmidt and
empirically identified as C5 H10 O3 N4 was, in fact, a
cyclically structured condensation product [9].
5.2 Synthesis of Resin
5.2.1 Formaldehyde
Formaldehyde is available in many forms. Paraform
(solid, polymerized formaldehyde) and formalin solu-
tions (aqueous solutions of formaldehyde, sometimes
with methanol, in 37%, 44%, or 50% formaldehyde
concentrations) are commonly used forms. Formalde-
hyde is also available as a gas. Typically, formalin
solutions are the preferred source of formaldehyde.
5.2.2 Urea
Solid urea, such as prill, and urea solutions, typically
aqueous solutions, are commonly available. Further,
urea may be combined with another moiety, typically
formaldehyde, often in an aqueous solution.
Fink: Reactive Polymers Fundamentals and Applications. http://dx.doi.org/10.1016/B978-1-4557-3149-7.00005-X
© 2013 Elsevier Inc. All rights reserved.
5.2.3 Ammonia
Ammonia is used to reduce the free formaldehyde
content. Ammonia is available in various gaseous and
liquid forms, particularly including aqueous solutions
at various concentrations. Any of the commercially
available aqueous ammonia-containing solutions is
the preferred form.
Such solutions typically contain between 10% and
35% ammonia. A solution having 35% ammonia can
be used, provided stability and control problems can
be overcome. An aqueous solution containing about
28% ammonia is particularly preferred.
Ammonia or late additions of urea are com-
monly used to reduce free formaldehyde levels
in urea/formaldehyde polymer systems. Ammonia
reduces the cured polymers’ resistance to hydrolysis.
The addition of urea tends to produce a polymer that
releases smoke during the cure cycle [10].
5.2.4 Diketones
Small additions of acetyl acetone and ammonia to
urea/formaldehyde resin can bind the free formalde-
hyde [11]. The addition causes the formation of
2,6-dimethyl-3,5-diacetyl-1,4-dihydropyridine (3,5-
diacetyl-1,4-dihydrolutidine) by a Hantz reaction, as
shown in Figure 5.1.
5.2.5 Dimethoxy Ethanal
The acetal of glyoxal with methanol is dimethoxy
ethanal. A process for the continuous preparation of
dimethoxy ethanal has been described [12]. An aque-
ous solution of glyoxal is continuously reacted with
methanol in the presence of a cation exchange resin.
The reaction is shown in Figure 5.2.
CH3
CH3 H 3C C
C O O
CH2O, NH4OH
CH2 H N
C O O
H 3C C
CH3
CH3
Figure 5.1 Binding of formaldehyde by acetyl
acetone.
179
180 REACTIVE POLYMERS FUNDAMENTALS
O O O O CH3
H3C OH
H O CH3
H H
Figure 5.2 Synthesis of dimethoxy ethanal.
This aldehyde is water clear, nontoxic, and non-
volatile. Thus the properties seem to be ideal for its
replacement with formaldehyde. However, its reac-
tivity is considerably lower in comparison to that of
formaldehyde [13]. Alterative formulations have been
developed with enhanced crosslinking activity of this
monomer. To achieve this, isocyanates are added to
the formulations.
5.2.6 Specialities
5.2.6.1 Cationic Urea/Formaldehyde
Resins
A water-soluble cationic resin is prepared by initially
reacting urea and formaldehyde at a formaldehyde to
urea mole ratio of 2–3 together with triethanolamine in
a urea to triethanolamine mole ratio of 2–3. The resin
formed is made cationic by acidifying it to a pH of 1.5,
with a strong inorganic acid such as hydrochloric, sul-
furic, or nitric acid, followed by prompt neutralization
to a pH of 6–7. A pH above 7 is discouraged as this
retards the cure of the resin.
Cationic urea/formaldehyde resins with polymers
containing vinylamine units improve the proper-
ties of paper with respect to dry strength and wet
strength [14].
Suitable polymers containing polymerized vinyl-
amine units can be prepared by hydrolysis of
homopolymers and copolymers containing polymer-
ized N-vinylamide units.
Examples of such polymers are a homopolymer of
N-vinylformamide and a copolymer of methacrylic
acid and N-vinylformamide. The amide group is often
only partly hydrolyzed, say to an extent of 25%.
The cationic urea/formaldehyde resins are infinitely
dilutable with water.
Aqueous solutions of cationic urea/formaldehyde
resins typically have a solid content between 25% and
45%. The aqueous resin solutions or the solid products
obtained therefrom are used as additives for increasing
the dry and wet strength of paper in papermaking. The
resins, in the form of aqueous solutions, are added to
the paper stock prior to sheet formation.
AND APPLICATIONS
Water-soluble Resins. Water-soluble cationic
urea/formaldehyde resins are obtained by condensing
urea and formaldehyde in the presence of polyamines.
The reactants are first precondensed in alkaline pH
range, then condensed in the acidic pH range until
gel formation begins. They are subjected to post-
condensation, for example with formaldehyde, and
are subsequently neutralized [14].
5.2.6.2 Melamine-modified Resins
Urea is the standard nitrogen-containing component
in urea/formaldehyde resins. Resins with improved
properties can be obtained by substitution of the urea
with melamine. Sulfitation of the methylol groups can
improve the resin properties. Still another approach is
the co-condensation with amines and the introduc-
tion of urea-terminated amines. Melamine improves
the resistance against attack by humidity and water,
especially at elevated temperatures. Melamine con-
tents up to 25% are used. 1,1,2,2-Tetramethoxyethane
is a high boiling point diacetal (165 ◦ C). It can be syn-
thesized from glyoxal. Such acetals improve the per-
formance of melamine/urea/formaldehyde resins. The
acetal as cosolvent increases the solubility of both the
unreacted melamine and the oligomers in water. Thus
a more effective reaction can be achieved [16]. The
improvement of mechanical properties by the addition
of acetals such as methylal and ethylal occurs because
of the increased effectiveness and participation of the
melamine in the crosslinking reactions [17].
Iminoamino methylene base intermediates are
obtained by the decomposition of hexamethylene-
tetramine in the presence of strong anions such
as SO2− 4 and HSO− 4 . These compounds improve
the weathering resistance of hardened melamine/
urea/formaldehyde resins [18].
Urea/formaldehyde (UF) resins modified with
melamine were synthesized using four different cata-
lysts. The catalysts and the properties of the products
are shown in Table 5.1.
With H2 SO4 , HCl, and H3 PO4 as catalysts, the
resins were prepared by a two-stage pH adjustment.
In the first stage, the pH was adjusted to 1.25 and in
the second stage the pH was set at 5.0. In the case
of the NaOH/NH4 OH catalyst, the pH was adjusted
to pH 5.0 from the start. Of the four catalysts, the
HCl catalyzed resins, with the highest free urea and
lowest free formaldehyde, yield the lowest formalde-
hyde emission. The NaOH/NH4 OH catalyst resulted
5: UREA/FORMALDEHYDE RESINS 181

Table 5.1 Properties of Modified Resins [15]

Catalyst Viscosity (cP) Solids (%) Free CHO (%) Gel Time (min) pH
H2 SO4 73 46.55 0.40 62.89 6.28
HCl 57 46.43 0.34 64.66 6.29
H3 PO4 27 46.83 0.39 21.92 5.93
NaOH/NH4 OH 47 47.93 0.35 64.15 6.17

in the best bond strength at dry conditions and after O O

C + H2 C O C
24 h cold-water soaking [15].
H2N NH 2 H2N N H CH 2 OH

5.2.7 Polymerization O
The synthesis of a UF resin proceeds via the methyl- C
olation of urea and condensation of the methylol H 2N N H CH2 OH
groups. The reaction can be conducted in an aqueous
medium because of the good solubility of both urea
and formaldehyde. The basic reactions are shown in
Figure 5.3. The methylolation of urea is done in alka-
line or slightly acidic solution in a twofold excess
O O
of formaldehyde. Following methylolation, further
C C
condensation into methylene urea oligomers occurs, H2N N H CH 2 O CH2 N NH 2
with a degree of oligomerization of 4–8. Because of
the functionality of the nitrogen, branched products
can be formed. Ether bridges also may be formed.
These ether bridges can be rearranged into methylene
bridges, expelling formaldehyde. Dimethylol urea is
O O
not a stable compound. In the presence of another
formaldehyde reactive compound, dimethylol urea C C
H2 N N H CH2 N NH2
will donate its two formaldehyde groups to the more
stable phenol, ammonia, melamine, etc. This leaves Figure 5.3 Basic reactions of urea and formal-
raw urea in the resin, which reduces the durability dehyde.
significantly [10].

5.2.7.1 UF Three-step Preparation 3. If the resin is not used immediately, a third neu-
tralization step should be employed, preferably
The resin is prepared by reacting urea and formalde- with sodium hydroxide.
hyde in a three-step process.

Use of ammonia or late additions of urea are com-

1. Urea and formaldehyde are reacted in the pres-
ence of ammonia, at an excess formaldehyde
of 1.2–1.8. A cyclic triazone/triazine polymer is
formed at 85–95 ◦ C within 2 h.
2. A thermosetting polymer is formed from the
cyclic polymer. To the reaction mixture contain-
ing triazole/triazine polymer, an additional por-
tion of formaldehyde is added, preferably with
additional urea, to yield a higher cumulative F/U
mole ratio of 2 to 2.7. The pH is adjusted from
6.0 to 6.4.
mon techniques for reducing free formaldehyde con-
tent of urea/formaldehyde polymer systems.
5.2.7.2 Synthesis Procedure
An example of a synthesis procedure is given
here. The reactants that are used to prepare a
urea/formaldehyde resin are listed in Table 5.2. The
resin is prepared by charging the 50% formalin, ethy-
lene diamine, and urea into a reactor and heating the
mixture to 45 ◦ C to dissolve the urea. Then NH4 OH
182 REACTIVE POLYMERS FUNDAMENTALS
Table 5.2 Feed for a Urea/formaldehyde Resin [19]
Reactant (mol)
Formalin solution, 50% CH2 O 14.5
Ethylene diamine 0.3
Urea (first charge) 12.1
NH4 OH, 28% 6.1
UFC 85: watera 14.4
CH2 O 34.5
Urea 7.2
Urea (second charge) 3.5
Alum (KAlSO4 · 12H2 O) 50% 0.2
NaOH 25% 0.02
Latent catalyst 0.02
Water 1.6
a 25% urea, 60% formaldehyde, and 15% water
is added, which causes the mixture to undergo an
exothermic reaction reaching a temperature of 83 ◦ C.
The reaction mixture is heated further to 95 ◦ C and
maintained at that temperature for 90 min. A cyclic
polymer is formed in this initial phase of the chemical
reaction. The triazone concentration can be over 50%
of the total polymer mix at this stage of the synthesis,
depending on the molar ratios of the ingredients. The
pH of the mixture is maintained between 8.7 and 9.3
by adding 25% NaOH as needed (a total of 0.4 mol).
The reaction mixture is then cooled to 85 ◦ C. UFC 85
(25% urea, 60% formaldehyde, and 15% water) and a
second charge of urea are added to the reaction mix-
ture. The temperature is thereafter maintained at 85 ◦ C
for 10 min. The pH is adjusted from about 6.2 to 6.4 by
adding a total of 0.2 mol of alum (KAlSO4 · 12H2 O)
in increments over a course of 25 min. The reaction
mixture is cooled to 80 ◦ C, and after 15 min further
cooled to 75 ◦ C. After 7 min, the reaction mixture is
cooled to 55 ◦ C, 26.9 g 25% NaOH is added, and then
the mixture is further cooled to 35◦ C. A latent cata-
lyst was added and the reaction mixture is cooled to
25 ◦ C. The pH is finally adjusted to 7.6–8.2 with 25%
NaOH. The free formaldehyde content of the resin
is 0.59%. After 24 h the free formaldehyde content
drops to 0.15%. The viscosity of the resin is 573 cP.
5.2.7.3 Cyclic Melamine/Urea/
Formaldehyde Prepolymer
Cyclic urea prepolymers may be used as mod-
ifiers of thermosetting phenol/formaldehyde and
melamine/formaldehyde-based resins for a variety of
end uses. These prepolymers are urea/formaldehyde
AND APPLICATIONS
polymers containing at least 20% triazone and sub-
stituted triazone compounds. The use of cyclic urea
prepolymer in such resin binders provides proper-
ties superior to those obtained from using the resin
alone in many applications. The resins are modified
with the cyclic urea prepolymer, either by reacting
into the base resin system, blending with the com-
pleted base resin system, or blending into a binder
preparation. Suitable primary amines can be used in
the formulation, such as methylamine, ethylamine,
and propylamine, ethanolamine, cyclopentylamine,
ethylene diamine, hexamethylene diamine, and linear
polyamines.
A methylolated cyclic urea prepolymer is typically
prepared by reacting urea, ammonia, and formalde-
hyde and then reacting with 2 mol of formaldehyde to
produce a methylolated cyclic urea prepolymer hav-
ing 50% solids. 13 C NMR indicates that 42.1% of the
urea is contained in the triazone ring structure, 28.5%
of the urea is di/tri-substituted, 24.5% of the urea is
mono-substituted, and 4.9% of the urea is free. This
cyclic urea prepolymer is then reacted into a standard
phenol/formaldehyde resin during the cook cycle of
the phenol/formaldehyde resin. In many systems, a
cyclic prepolymer is either cooked into the resin or
added to a resin [10].
5.2.8 Manufacture
The production of UF resins is usually achieved in
three stages [3]:
1. Methylolation: Urea reacts with aqueous
formaldehyde under alkaline conditions at
temperatures up to 100 ◦ C.
2. Condensation: The condensation of methylols
in slightly acidic medium yields oligomers with
different molar mass and various functionalities.
The condensation is then stopped by adding alka-
line substances.
3. Post-treatment: Evaporation of excess water and
formaldehyde, or addition of secondary urea to
decrease the ratio of formaldehyde to urea.
The multistage process is useful to fulfill the
requirements of retaining the reactivity and the
strength of the cured resin under the condition of min-
imal emission of formaldehyde during service.
5: UREA/FORMALDEHYDE RESINS
5.3 Special Additives
5.3.1 Modifiers
One requirement is that the additives do not increase
the viscosity of the suspension significantly, but
improve the toughness and the moisture resistance
of UF resin. Thermoplastic acrylic copolymers with
different degrees of hydrophilicity were added to a
UF resin. The copolymers consist of two or three
monomers selected from methyl methacrylate, acryl-
amide, acrylic acid, 1-vinyl-2-pyrrolidinone, ethyl
acrylate, and vinyl acetate. The SEM micrographs
of cured thermoplastic-modified UF showed a phase
separated thermoplastic structure in a continuous UF
phase when UF was modified with a self-dispersed
and surfactant-stabilized polymer type. However,
when the UF was modified with a water-soluble poly-
mer, a single phase was detected [20,21].
A water-soluble, styrene maleic anhydride copoly-
mer can be used as a modifier for binder resins. Glass
fiber mats made with the modified binder composi-
tion exhibit an enhanced wet tensile strength, wet-
mat strength, tear strength, and dry tensile strength.
Because of this strength improvement, the mat pro-
cessing speeds through the cure oven can be sig-
nificantly increased without risking breakage of the
continuous mat [22].
Biopolymers with amide groups such as
acrylamide-modified maize starch have advan-
tages with respect to environmental aspects, in
particular the free formaldehyde content. Also,
products with satisfactory mechanical properties can
be fabricated [23].
5.3.2 Fillers
Natural products and otherwise waste products that
can be used with UF resins as fillers are summarized
in Table 5.3.
Table 5.3 Natural Products as Fillers
Product References
Bagasse [24]
Sanding dusts [25]
Tomato stalk [26]
Oil palm trunks [27]
Paper mill sludge [28,29]
Kenaf [30]
Starch derivatives [31]
Defatted soy flour [32]
183
5.3.2.1 Bagasse
Bagasse is a waste product from sugarcane process-
ing. In Brazilia large amounts of such waste residues
are produced. It exhibits a low density, which allows
compression to higher density during pressing. The
influence of bagasse particles in the surface layer on
the bending strength of three-layer particleboard pan-
els has been investigated.
A series of compositions with different curing tem-
peratures and surface layers was performed. Three
levels of urea/formaldehyde resin were selected for
the surface layers. The shelling ratio is the relation of
bagasse and wood particles in the surface and middle
layers. The results of these experiments are shown in
Table 5.4. The results show that bagasse increases the
bending strength of the boards [24].
Chipboard panels made with sugarcane bagasse
with UF and MF resins were compared. The panels
were obtained from sugarcane bagasse and pine or
eucalyptus wood particles. Also, in some experiments
paraffin was added to the formulation. The formula-
tions were tested for water absorption and swelling
characteristics. Bagasses with pine particles absorb
more water than the panels made with eucalyptus par-
ticles [33].
The use of melamine formaldehyde results in a bet-
ter abrasion resistance than using urea/formaldehyde
or melamine urea/formaldehyde resins [38].
5.3.2.2 Waste Sanding Dusts
For particleboards waste sanding dusts were used as
additives for UF resin adhesives. The addition of 10%
and 15% waste sanding dusts improves the physi-
cal and mechanical properties. However, more than
this amount has a negative influence on the perfor-
mance. Also, the ratio of formaldehyde to urea has
an influence on the properties. An increasing ratio of
formaldehyde to urea significantly improves the prop-
erties of the particleboards [25].
5.3.2.3 Montmorillonite
The overall performance of UF resin has been
improved by the addition of montmorillonite. A vac-
uum pressure/vacuum impregnation method was used
for the modification. Best results were obtained with
14% sodium montmorillonite and 20% UF resin
[39]. The bending resistance, compressive resistance,
and elastic modulus increased by 19.37%, 30.24%,
and 50.06%, respectively. Elevated levels of sodium
184 REACTIVE POLYMERS FUNDAMENTALS AND APPLICATIONS

Table 5.4 Bending Strength of Samples [24]

Shelling Ratio Press Temperature (◦ C) Resin Content (%) Bending Strength (MPa)
3:7 165 8 8.2
3:7 165 10 9.8
3:7 165 12 11.7
3:7 180 8 8.8
3:7 180 10 11.56
3:7 180 12 12.91
4:6 165 8 11.2
4:6 165 10 13.1
4:6 165 12 14.8
4:6 180 8 11.8
4:6 180 10 15.14
4:6 180 12 17.41

montmorillonite cause a decrease of the impact tough- Table 5.5 Global Production/Consumption Data of
ness and the wear rate. Important Monomers and Polymers [34]
In another study it was stated that the addition Monomer Mill. Metric Tons Year Reference
of small amounts of sodium montmorillonite nan- Urea 110 2002 [35]
oclay does not much improve the performance of Formaldehyde 24 2003 [36]
phenol/formaldehyde and phenol urea/formaldehyde Amino resins 8.4 2002 [37]
resins for use as adhesives for plywood and for wood
particleboard [40]. DSC measurements indicated that
sodium montmorillonite has no accelerating effect on N
the curing process. However, the authors add that this
H2C O
is contrary to ordinary UF resins. N N
+
N
(NH 4)2 SO4
+
5.3.3 Flame Retardants H 2 SO4
As flame retardants, ammonium hydrogen phosphate Figure 5.4 Reaction of ammonium sulfate with form-
((NH4 )2 HPO4 ) and sodium tetraborate (Na2 B4 O7 ) aldehyde.
were tested together with mineral fillers such as vermi-
culite, phlogopite, clay, etc. The increased flame resis-
tance results from the evolution of noncombustible 5.4 Curing
gases [41]. During curing, an insoluble, infusible, three-
dimensional network is constructed. Curing is ini-
5.3.4 Production Data of Important tiated by lowering the pH. This is achieved by the
addition of acids, such as phosphoric acid or maleic
Monomers acid. Acidic salts, e.g., aluminum sulfate or urea
Production data of important raw materials are shown phosphate, can be added. Further anhydrides, such
in Table 5.5. Urea is mostly used as a fertilizer. as maleic anhydride, decompose in aqueous medium
Only a small fraction is used for urea/formaldehyde into acids. Ammonium sulfate reacts with formalde-
resins. Formaldehyde is not used exclusively for urea/ hyde to form hexamethylenetetramine and sulfuric
formaldehyde resins. Other major uses are phenol/ acid, as shown in Figure 5.4.
formaldehyde resins, polyacetal resins, pentaeryth- Ammonium chloride is now avoided for acidifica-
ritol 1,4-butanediol, and hexamethylenetetramine. tion in favor of ammonium sulfate. Residual ammo-
Amino resins include melamine/formaldehyde resins nium chloride forms hydrochloric acid during the
and melamine/urea/formaldehyde resins, besides combustion of wood-based panels. It is suspected that
urea/formaldehyde resins. the chlorine promotes the formation of chlorodioxins.
5: UREA/FORMALDEHYDE RESINS
Usually 2–3% of ammonium salt based on the solid
content of resin are sufficient as catalyst. Excess
catalyst causes over-curing. Brittle resins are then
formed, with less water resistance. Formaldehyde is
the primary reactive component in urea/formaldehyde
resins.
A higher reactivity and a higher crosslinking den-
sity of the final network formation can be achieved
by a higher formaldehyde-to-urea ratio. On the other
hand, free formaldehyde is undesirable for toxicolog-
ical reasons. Resins with very low formaldehyde con-
tent exhibit several drawbacks of the final product.
These can be minimized, however, by a special con-
densation process, the use of special accelerators, and
by the modification of the formulation with melamine.
A possible catalytic effect of cold water extracts of
different wood species on the hardening characteristic
has been investigated. The curing behavior indicated
that cold water wood extracts have little or no effect
on the curing progress of the resins [42].
The mechanism of the polycondensation was stud-
ied by 13 C NMR spectroscopy. Trishydroxymethyl
urea was identified by curing in alkaline conditions.
On the other hand, methylene groups linked to sec-
ondary or tertiary amino groups are found only under
acidic curing conditions. Bishydroxymethyl groups
are not active under acid curing. Oligomers with
methylenes adjacent to secondary amino groups and
singly bonded urea are characteristic when heat treat-
ment has been carried out [43].
For a certain UF molding composition it has been
suspected that an over-curing occurs during a ther-
mal curing. This effect has been investigated. Sam-
ples with different degrees of curing were formed by
ultrasonic curing. The experiments revealed that the
curing time has a significant influence on the glass
transition temperatures of the compositions. Further,
longer curing times result in an improved impact
toughness rather than in a brittleness as one would
expect. Actually, no over-curing was observed for cur-
ing for typical and reasonable times that are common
in industrial processing [44].
A latent catalyst such as ammonium sulfate cre-
ates hexamine as a by-product in the course of cur-
ing. This hexamine, when undergoing hydrolysis, may
contribute to a release of formaldehyde during the ser-
vice time. This is not desired in the case of wood-based
panels.
For this reason, alternative catalysts for curing have
been studied [45]. For example, orthophosphoric acid
185
catalyzes the curing procedure without the formation
of by-products.
Both catalysts, i.e., orthophosphoric acid and
ammonium sulfate, have been compared and their per-
formance and properties were evaluated: formalde-
hyde content, internal bond, moisture content, and
swelling.
Particleboards cured by means of orthophosphoric
acid exhibited similar properties, but a lower
formaldehyde content than those produced with
ammonium sulfate as curing agent [45].
5.5 Measurement of Curing
Curing can be monitored by thermal methods, as well
as utilizing spectroscopic methods. The curing reac-
tion in an ammonium chloride catalyzed system starts
at around 100 ◦ C, whereas in an uncatalyzed system
the curing reaction starts between 120 and 180 ◦ C
[46]. In comparison to PF resins, the activation energy
of curing of UF resins is generally higher. Neverthe-
less, the curing rates of UF resins are faster [47]. The
pH values in UF formulations have a significant influ-
ence on the rate constants, but they affect the activation
energy of curing marginally.
The curing reaction in the presence of wood has
been measured using 15 N distortionless enhance-
ment by polarization transfer (DEPT) nuclear mag-
netic resonance spectroscopy [48]. A DEPT pulse
sequence was employed to follow the curing of
urea/formaldehyde resin.
5.6 Properties
5.6.1 Formaldehyde Release
Typically, when urea/formaldehyde resins are cured,
they release formaldehyde into the environment.
Formaldehyde can also be released from the cured
resin, particularly when the cured resin is exposed
to acidic environments. Such formaldehyde release
is undesirable, particularly in enclosed environments.
Formaldehyde is malodorous and is considered haz-
ardous to human and animal health. Various tech-
niques have been used to reduce formaldehyde
emission from urea/formaldehyde resins.
Use of formaldehyde scavengers and methods for
resin formulation, including addition of urea as a
reactant late in the resin formation reaction, are
techniques used to reduce formaldehyde emission.
186
However, the use of formaldehyde scavengers often
is undesirable, not only because of the additional
cost, but also because it affects the properties of the
resin. For example, using ammonia as a formalde-
hyde scavenger reduces the resistance of the cured
resin to hydrolysis. Later addition of urea to reduce
free formaldehyde concentration in the resin generally
yields a resin that must be cured at a relatively low rate
to avoid smoking. The stability of the resin can also
be adversely affected by such treatments [19]. Instead
of urea, triethanolamine can be added to a mixture of
urea and formaldehyde.
Sludge from pulp and paper mills has natural adhe-
sive properties. The primary sludge contains fibers
and the secondary sludge contains proteins. The latter
can be of interest as an additive for UF resins. Pro-
teins in the secondary sludge can react readily with
formaldehyde. Measurements of the gel time showed
a high reactivity to the UF resins. Further, the sec-
ondary sludge reduced the formaldehyde emissions
by some 68% and the internal bond strength was
maintained. In addition, the sludge reduces the perfor-
mance of bending and its dimensional stability [29].
Particleboards with newly formulated UF and
melamine urea/formaldehyde resins were fabricated.
The formaldehyde emission and strength properties of
these fabricated particleboards were investigated [49].
The surface-to-core ratio used in a three-layered
particleboard for both resin formulations influences
considerably the strength properties and the formalde-
hyde emission. Melamine urea/formaldehyde resin-
based particleboards with 40% surface and 60% core
showed the lowest formaldehyde emissions and the
highest strengths. Thus melamine urea/formaldehyde
resins are superior to pure UF resins [49].
A method for the preparation of a UF composi-
tion with low formaldehyde emission has been pre-
sented. The prepolymer can impregnate wood along
the trachea from the ends using an impregnation
method under pressure. Eventually, by heating and
pressing the prepolymer is polymerized into its final
state [50].
As the main adhesive types in wood-based panel
industry, urea/formaldehyde has such shortcomings
as high levels of free formaldehyde content and
formaldehyde emission of its bonding product. In this
experiment, we attempt to modify urea/formaldehyde.
A UF resin composition has been optimized to have
low toxicity with keratin. The addition of keratin also
reduces the costs of the compositions [51].
REACTIVE POLYMERS FUNDAMENTALS AND APPLICATIONS
5.6.2 Storage
During storage, urea/formaldehyde resins undergo
reactions that result in structural changes. Methy-
lene groups adjacent to secondary amino groups are
formed by the main reaction. This reaction proceeds
between the free terminal hydroxymethyl and amino
groups [52].
5.6.3 Hydrolytic Stability
The relationship between the hydrolytic stability and
the morphological structure was investigated. With
decreasing amounts of formaldehyde, the hydrolytic
stability of the resins is improved. However, the
hydrolytic stability decreases when the particle size
of the resin is reduced. The crystalline regions of
the cured resins were quantified by X-ray analy-
sis. The results revealed that UF resins with higher
formaldehyde content have an amorphous struc-
ture that becomes partially crystalline with molar
formaldehyde to urea ratios of less than 1.2. This phe-
nomenon may explain to some extent the improved
hydrolytic stability of such resins [53].
5.7 Applications and Uses
5.7.1 Glue Resins
The main application of urea/formaldehyde resins is
in the adhesive industry. Urea/formaldehyde glues are
used in pressed wood products such as particleboard,
and plywood as laminating resins. Because of the
potential for formaldehyde release, UF resins have
been modified for indoor applications. Formaldehyde
is a potent primary irritant.
A low mole ratio of formaldehyde to urea makes
plywood more environmentally friendly with respect
to formaldehyde emissions. An optimized formula-
tion has been developed that uses a mole ratio of
formaldehyde to urea of 0.99:1 and melamine is added
in amounts of 3–4% [54].
Agricultural wastes, such as oil palm trunk veneer
and oil palm empty fruit bunch mat, were used for the
fabrication of hybridized plywood. As gluing agent
a UF resin was used. It was demonstrated that the
hybrid biocomposite improves some properties of ply-
wood, such as flexural strength, screw withdrawal, and
shear strength. In addition, the hybrid composition has
better physical properties such as thickness swelling
and water absorption in comparison to oil palm
5: UREA/FORMALDEHYDE RESINS
trunk plywood. The panels exhibit good thermal resis-
tance and good adhesion [55].
5.7.2 Binders
Typical binders used to bind glass fiber mats include
urea/formaldehyde resins, phenolic resins, melamine
resins, bone glue, poly(vinyl alcohol)s, and latices.
These binder materials are impregnated directly into
the fibrous mat and set or cured by heating to obtain
the desired integrity in glass fibers. The most widely
used glass mat binder is urea/formaldehyde, because
it is relatively inexpensive [19].
5.7.3 Emulsion Paints
Copolymers from urea/formaldehyde and urea/acet-
aldehyde were successfully synthesized [56]. The
monomers are shown in Figure 5.5.
The copolymer resins have better optical proper-
ties, flexibility, and softness. In addition, formalde-
hyde emission is superior to conventional UF resins.
In Figure 5.6, the formaldehyde emission versus the
content of urea/acetaldehyde is shown.
In summary, the properties of these copolymers
closely resemble those of formulations that are used
in paints. Therefore, the copolymer resins have been
suggested as a potential binder for emulsion paint for-
mulations [56].
A series of other copolymer composites was
prepared and tested for applications as emulsion-
based paint binders based on methylol urea and tri-
ethanolamine as well as methylol urea and soybean
oil [57–59].
5.7.4 Foundry Sands
In the manufacture of low nitrogen-containing
foundry sands, the hexamine crosslinker is replaced
partly with another crosslinking agent that does not
contain nitrogen. Nitrogen, when present in coated
foundry sand, can give rise to nitrogen defects dur-
ing steel casting. It is preferable to have as low
a nitrogen content as possible. Usually this other
H O H O
HO CH2 N C N CH2 OH N C N CH2 CH2 OH
H H
CH2
HO
Figure 5.5 Monomers for urea/formaldehyde and
urea/acetaldehyde resins [56].
187
0.12
Formaldehyde emission/[ppm]
0.1
0.08
0.06
0.04
0.02
0
0 10 20 30 40 50 60 70 80 90
Concentration of urea/acetaldehyde[%]
Figure 5.6 Formaldehyde emission [56].
crosslinking agent is a thermosetting resol phe-
nol/formaldehyde resin. During the manufacture of
low nitrogen-containing sands, a novolak resin is
added, followed by the resol resin and then the hex-
amine [10].
5.7.5 Electrical Applications
A composition derived from thiourea and urea was
checked for its use as an electrochemical capacitor
[60]. The polymer from urea and thiourea was used
as the starting material for a heat treatment at 700–
900 ◦ C to get an activated carbon material. The capac-
itance value of an activated carbon from thiourea
obtained by a heat treatment at 800 ◦ C is 138.8 F g−1
at a current density of 50 mA g−1 , whereas a com-
mercial activated carbon under the same conditions
reaches 107.1 F g−1 .
X-ray photoelectron spectroscopy measurements
suggest that nitrogen in the materials is present as in
pyridine at the edge part of the graphitic structure and
like a quaternary nitrogen in the graphite layers [60].
5.7.6 Formation of Nanopowders
Small-sized alumina powders have been prepared in
the course of the formation of a UF resin with sub-
sequent pyrolysis. Aluminum acetate and inorganic
salts, i.e., aluminum sulfate and aluminum phos-
phate hydrate, were added during the formation of
the resin [61].
After polymerization, powders were obtained after
burning out the organic material. It was shown that the
results are dependent on the nature of the aluminum
precursors.
188 REACTIVE POLYMERS FUNDAMENTALS
Aluminum acetate does not participate in crosslink-
ing during curing. Thus this type of alumina powder
is the result of the combustion of the ester. In contrast,
the aluminum from the other two precursors partici-
pates in the structure of the resin. The sulfate precursor
results in an alumina powder with a crystallite size of
some 30 nm. However, the aluminum from aluminum
phosphate hydrate participates in the structure of the
resin, but during heating obviously some agglomera-
tions occurs.
5.7.7 Waste Water Cleaning
A polystyrene sulfonamide urea resin with a total
nitrogen content of 3.5 mmol g−1 can selectively
absorb mercury from aqueous solutions [62]. The
capacity of the resin is around 1.60 mmol g−1 under
non-buffered conditions. The absorbed mercury can
be eluted by repeated treatment with hot acetic acid
without hydrolysis of the amide groups. Other metal
ions can be also absorbed by such a resin.
5.8 Special Formulations
5.8.1 Ready-use Powders
For small-scale applications, e.g., as adhesive, ready-
use powders of urea/formaldehyde resins are dis-
solved in water. The formulation contains fillers,
extenders, hardeners, scavengers, and other additives
which have to be mixed with water only.
5.8.2 Cyclic Urea Prepolymer in PF
Laminating Resins
Phenol/formaldehyde resins used to manufacture
high-pressure laminates are typically produced by
reacting phenol and formaldehyde by means of an
alkaline catalyst such as sodium hydroxide [10].
Typical mole ratios of formaldehyde to phenol
range from 1.2 to 1.9 mol of formaldehyde per mol
of phenol. Catalyst levels range from 0.5% to 3%.
The materials are reacted to a suitable endpoint,
cooled under vacuum, and usually distilled to remove
the water present from the formaldehyde solution as
well as the water of condensation from the polymer-
ization reaction. They may be used in this state or
an organic solvent such as methanol can be added to
reduce the solids concentration and viscosity of the
mixture.
AND APPLICATIONS
A cyclic urea prepolymer in phenol/formaldehyde
resins acts as a plasticizer for the resin. This makes
the laminate more post-formable and tougher. Prod-
ucts produced with such resins resist chipping and
breakage during machining steps. Diluting the phe-
nol/formaldehyde resin with cyclic urea prepolymer
reduces the free phenol and other volatile pheno-
lic moiety levels of the phenol/formaldehyde resin
which reduces air pollution. Because of the plasticiz-
ing effect achieved with the cyclic urea prepolymer,
higher F/P mole ratio PF resins (traditionally more
brittle) can be used, which further reduces the free
phenol and volatile phenolic moiety levels.
5.8.3 Liquid Fertilizer
Urea/formaldehyde-based liquid fertilizers can
provide nitrogen to the soil. In addition to nitrogen,
phosphorus and potassium are considered major
nutrients essential for plant growth. Long-term
stability of high nitrogen liquid urea/formaldehyde
fertilizers can be achieved by forming either a high
percentage (more than 30%) of cyclic triazone struc-
tures or by condensing the urea/formaldehyde resin
into small urea/formaldehyde polymer chains [63].
5.8.4 Soil Amendment
Urea/formaldehyde resin foams are used as a soil
amendment for agricultural applications. The amend-
ment by UF foams does not influence the pH and
causes insignificant alterations to the physical prop-
erties of the soil by slightly increasing total porosity,
water availability, and the porosity, and by reducing
the bulk density [64].
5.8.5 Microencapsulation
Microcapsules are used in various applications, such
as pharmaceuticals, dyes, coatings, food additives,
catalysts, or energy storage [65].
Microcapsules based on UF materials can be pre-
pared by [65]:
1. the preparation of a precondensate and
2. encapsulation.
The precondensate is synthesized from a mixture of
urea and formaldehyde at a pH of 8–9 in the presence
of triethanolamine or NaOH. For the encapsulation the
5: UREA/FORMALDEHYDE RESINS
precondensate is dissolved in water and a hydrophobic
material is emulsified therein. By the addition of acid,
the pH is reduced and the crosslinking reaction starts.
Finally a three-dimensional structure that is not sol-
uble in water is formed which precipitates and thus
catches the oil drops [65]. Alternatively, microcap-
sules can be prepared in a single-step procedure [66].
The role of the emulsifier on the formation of
the microcapsules has been investigated in detail.
Three emulsifiers, sodium dodecylbenzene sulfonate,
poly(ethylene-alt-maleic anhydride), and gum arabic,
were used to improve the dispersion of the oil phase
in the water phase [65].
When no surfactant is used, the microcapsules
exhibit irregular shapes. Gum arabic can effectively
slow down the deposition rate of the resin onto the
oil-water interface. This may result in a more smooth
and compact surface of the microcapsules [65].
Self-healing polymers and composites with
microencapsulated healing agents offer a possi-
bility for long-lived polymeric materials. Heal-
ing agents have been microencapsulated using
urea/formaldehyde resins. The microcapsules must
have sufficient strength to remain intact during
polymer processing. However, the microcapsules
should break when the polymer is damaged [67].
Shell microcapsules filled with linseed oil have
been prepared by in situ polymerization. Their effec-
tiveness for healing cracks in paints and coatings and
the properties of the regions after self-healing were
studied. The linseed oil-healed area showed good anti-
corrosive properties [68].
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