6

Melamine Resins

Melamine resins rely on 1,3,5-triazine-2,4,6-triamine and formaldehyde.

They are similar to urea formaldehyde polymers.

6.1 HISTORY

The industrial use of melamine resin started in the late 1930s when the
Swiss company CIBA began the industrial production of melamine from
dicyandiamide.1, 2 Earlier, the use of this resin was limited because of its
high price. Now melamine can be produced cheaper from urea, so the
economical situation is improved.

6.2 MONOMERS

6.2.1 Melamine
Melamine may be partially or totally replaced with other suitable amine-
containing compounds. Alternatives to melamine include urea, thiourea,
dicyandiamide, 2,5,8-triamino-1,3,4,6,7,9,9b-heptaazaphenalene (melem),
(N-4,6-diamino-1,3,5-triazin-2-yl)-1,3,5-triazine-2,4,6-triamine (melam),
melon, ammeline, ammelide, substituted melamines, and guanamines.3
The melamine homologues melam, melem, and melon have higher ther-
mal stability than pure melamine. These compounds are also used as flame
retardants.

299
300 Reactive Polymers Fundamentals and Applications

Substituted melamines include alkyl melamines and aryl melam-

ines. Representative examples of some alkyl-substituted melamines in-
clude methylmelamine, dimethylmelamine, trimethylmelamine, ethylme-
lamine, and 1-methyl-3-propyl-5-butylmelamine. Typical examples of an
aryl-substituted melamine are phenylmelamine or diphenylmelamine. Mel-
amine and related compounds are shown in Figure 6.1. Foams and fibers
exhibit increased elasticity, when some of the melamine is replaced by
a substituted melamine, e.g., N-mono-, N,N ′ -bis- and N,N ′ ,N ′′ -tris(5-hy-
droxy-3-oxapentyl)melamine.4 However, based on considerations of cost
and availability, standard melamine is generally preferred.

6.2.2 Other Modifiers

Suitable resin modifiers are ethylene diamine, melamine, ethylene ureas,
and primary, secondary, and tertiary amines. Dicyandiamide can be also
incorporated into the resin.
The concentrations of these modifiers in the reaction mixture may
vary typically from 0.05 to 5.00%. All these modifiers promote hydrolysis
resistance, polymer flexibility, and lower formaldehyde emissions.5

6.2.3 Synthesis
Similar to urea, melamine reacts with formaldehyde in weakly alkaline-
aqueous media to form methylol compounds. Melamine is hexafunctional,
so up to hexamethylol monomers can be formed. Hexamethylol melamine
is shown in Figure 6.2.
The further condensation proceeds under neutral and acidic condi-
tions, thereby forming methylene or dimethylene ether bonds. A pure mel-
amine resin gels within a few days at room temperature. Because of this
undesired property, melamine resins are blended with urea resins.

6.2.3.1 Etherified Resins

Etherified resins are prepared by the reaction of melamine with formalde-

hyde under the conditions of pH around 6 and reflux temperature in the
presence of a large amount of butanol. Xylene cycles out the water formed
by the condensation reaction by azeotropic distillation and accelerates the
etherification in this way.
 Melamine Resins 301

H
H 2N N NH2 H 2N N N N NH2

N N N N N N

NH2 NH2 NH2

Melamine Melam

NH2
NH2
N N
N N
N N N
N N N
H 2N N N NH
H 2N N N NH2
n
Melem Melon

H 2N N NH2
HH
N N H N H
N
C C
N N

H
Benzoguanamine Dicyandiamide

Figure 6.1: Melamine, Melam, Melem, Melon, Benzoguanamine, Dicyandiamide

302 Reactive Polymers Fundamentals and Applications

H 2N N NH2

N N + H 2C O

NH2

HOH2C CH2OH
N N N
CH2OH
HOH2C
N N

N
HOH2C CH2OH

Figure 6.2: Hexamethylol melamine from Melamine and Formaldehyde

6.2.4 Manufacture
Melamine is mixed with neutralized formaldehyde solution. The excess
of formaldehyde is about threefold. The mixture is heated to 75 to 85°C.
When the solution becomes cloudy, water is admixed. Then fillers can be
admixed for molding resins. The mixture is dried at 70 to 80°C. while the
condensation reaction still proceeds.
In the co-condensation of melamine and urea, due to the difference
in reactivity of melamine and urea, the condensation of melamine moiety
is quicker than the urea moiety.

6.3 PROPERTIES

Phenol/formaldehyde resins and melamine/formaldehyde resins are stan-

dard resins used for many products. The choice of resin depends on the
desired properties. Phenol/formaldehyde resins are strong and durable and
relatively inexpensive, but are generally colored resins. Melamine resins
are water clear but are more expensive. They are generally used for prod-
ucts where the color or pattern of the substrate is retained with a transparent
 Melamine Resins 303

melamine protective coating or binder.

The emission of formaldehyde in melamine/urea/formaldehyde re-
sins is decreased as the melamine content is increased.6 This is explained
due to the stronger bonding between triazine carbons of melamine than
those of urea carbons. Sulfonated melamine/formaldehyde resins exhibit
good solubility in water.7

6.4 APPLICATIONS AND USES

Melamine based resins are widely used as adhesives for wood, as resins for
decorative laminates, varnish, and moldings, and for improving the prop-
erties of paper and cellulosic textiles. In comparison to urea formaldehyde
resins, a melamine-based resin has higher resistance against heat and mois-
ture.
Etherified melamine resins are often used in combination with alkyd
resins for production of decorative laminates. Modification of textiles
by melamine is used to impart crease resistance and shrinkage. The wet
strength of paper is greatly improved by the use of melamine resins as
wet-end additives.
Acoustic ceiling tiles are backcoated with melamine resins in or-
der to make them more rigid and humidity-resistant when installed in sus-
pended ceilings. Melamine resins are also used for the preparation of deco-
rative or overlay paper laminates. This application is due to their excellent
color, hardness, and solvent, water, and chemical resistance, heat resis-
tance, and humidity resistance.
Molded articles, such as dinnerware, are prepared with a combinat-
ion of melamine/formaldehyde resins and urea/formaldehyde resins. The
resins are combined because the melamine/formaldehyde resin is too ex-
pensive by itself. The such articles made from these resins are generally
not very water-resistant or dimensionally stable.5

6.4.1 Wood Impregnation

Melamine/formaldehyde (MF) belongs to the hardest and stiffest isotropic
polymeric materials used for decorative laminates, molding compounds,
adhesives, coatings, and other products. Due the high hardness and stiff-
ness, and low flammability, MF resins can be used to improve the prop-
erties of solid wood. An MF resin can penetrate the amorphous region of
304 Reactive Polymers Fundamentals and Applications

wood. It has been established that significant portions of a suitable MF

resin penetrate the secondary cell wall layers and middle lamella of soft-
woods.8

6.5 SPECIAL FORMULATIONS

6.5.1 Resins with Increased Elasticity

In foams and fibers, with increased elasticity, the melamine is partly re-
placed by a hydroxy alkyl substituted melamine. To prepare these re-
sins, melamine and substituted melamine are polycondensed together with
formaldehyde. The feed may also contain small amounts of customary
additives, such as disulfite, formate, citrate, phosphate, polyphosphate, ur-
ea, dicyandiamide, or cyanamide.4 Moldings are produced by curing the
resins in a conventional manner by adding small amounts of acids, prefer-
ably formic acid. Foams can be produced by foaming an aqueous solu-
tion or dispersion containing the melamine/formaldehyde precondensate,
an emulsifier, a blowing agent and a curing agent.

6.5.2 Microspheres
Monodisperse melamine/formaldehyde microspheres have been prepared
via a dispersed polycondensation technique. The nucleation and growth
of the particles were achieved within short periods. A continuous coag-
ulation occurred even in the presence of surfactants.9 Microcapsules are
interesting because of the controlled-release properties of the respective
encapsulated substances. A fragrant oil could be microencapsulated by an
in-situ polymerization.10 The particle sizes ranged from 12 to 15 µ m. The
efficiency of encapsulation of the fragrant oil reached up to 67-81%.
Microcapsules were prepared in a capillary flow microreactor and
also in a batch experiment. The microcapsules obtained from the microre-
actor showed smaller particle diameters and a narrower particle size distri-
bution than those obtained in a batch experiment.11

REFERENCES
1. M. Higuchi. Melamine resins (overview). In J. C. Salamone, editor, The
Polymeric Materials Encyclopaedia: Synthesis, Properties and Applications,
pages 837–838. CRC Press, Boca Raton, FL, 1999.
 Melamine Resins 305

2. Gesellschaft für Chemische Industrie in Basel. Verfahren zur Herstellung

von 2.4.6-Triamino-1.3.5-triazin (Melamin). CH Patent 189 406, assigned to
Ciba AG, February 28 1937.
3. G. M. Crews, S. Ji, C. U. Pittman, Jr., and R. Ran. Ammeline-melamine-
formaldehyde resins (amfr) and method of preparation. US Patent 5 254 665,
assigned to Melamine Chemicals, Inc. (Donaldsonville, LA), October 19
1993.
4. J. Weiser, W. Reuther, G. Turznik, W. Fath, H. Berbner, and O. Graalmann.
Melamine resin moldings having increased elasticity. US Patent 5 162 487,
assigned to BASF Aktiengesellschaft (Ludwigshafen, DE), November 10
1992.
5. F. C. Dupre, M. E. Foucht, W. P. Freese, K. D. Gabrielson, B. D. Gapud,
W. H. Ingram, T. M. McVay, R. A. Rediger, K. A. Shoemake, K. K. Tutin,
and J. T. Wright. Cyclic urea-formaldehyde prepolymer for use in phenol-
formaldehyde and melamine-formaldehyde resin-based binders. US Patent
6 379 814, assigned to Georgia-Pacific Resins, Inc. (Atlanta, GA), April 30
2002.
6. S. Tohmura, A. Inoue, and S. H. Sahari. Influence of the melamine content
in melamine-urea-formaldehyde resins on formaldehyde emission and cured
resin structure. J. Wood Sci., 47(6):451–457, 2001.
7. L. H. Su, S. R. Qiao, J. Xiao, X. Tang, G. D. Zhao, and S. W. Fu. Synthesis
and properties of high-performance and good water-soluble melamine-form-
aldehyde resin. J. Appl. Polym. Sci., 81(13):3268–3271, September 2001.
8. W. Gindl, F. Zargar-Yaghubi, and R. Wimmer. Impregnation of softwood
cell walls with melamine-formaldehyde resin. Bioresour. Technol., 87(3):
325–330, May 2003.
9. I. W. Cheong, J. S. Shin, J. H. Kim, and S. J. Lee. Preparation of monodis-
perse melamine-formaldehyde microspheres via dispersed polycondensation.
Macromol. Res., 12(2):225–232, April 2004.
10. H. Y. Lee, S. J. Lee, I. W. Cheong, and J. H. Kim. Microencapsulation of
fragrant oil via in situ polymerization: effects of ph and melamine-formal-
dehyde molar ratio. J. Microencapsul., 19(5):559–569, September–October
2002.
11. T. Sawada, M. Korenori, K. Ito, Y. Kuwahara, H. Shosenji, Y. Taketomi,
and S. Park. Preparation of melamine resin micro/nanocapsules by using
a microreactor and telomeric surfactants. Macromol. Mater. Eng., 288(12):
920–924, December 2003.