Melamine and Guanamines

Melamine and Guanamines

George M. Crews, Melamine Chemicals, Inc., Donaldsonville, Louisiana, United States (Chap. 1, 2, 3, 4, 5,
6, 7, 8 and 9)
Willi Ripperger, BASF Aktiengesellschaft, Ludwigshafen, Germany (Chap. 1, 2, 3, 4, 5, 6, 7, 8 and 9)
Dietrich Burkhard Kersebohm, BASF Aktiengesellschaft, Ludwigshafen, Germany (Chap. 10)

Thomas Guthner,
Degussa AG, Trostberg, Germany (Chap. 11)
Bernd Mertschenk, Degussa AG, Trostberg, Germany (Chap. 11)

1.
2.
3.
3.1.
3.2.
3.3.
3.4.
4.
4.1.
4.1.1.
4.1.2.
4.1.3.
4.2.
4.2.1.

Introduction . . . . . . . . . .
Physical Properties . . . . . .
Chemical Properties . . . . .
Thermal Behavior . . . . . .
Hydrolysis . . . . . . . . . . . .
Salt Formation . . . . . . . . .
Reaction with Aldehydes . .
Production . . . . . . . . . . .
Low-Pressure Processes . . .
BASF Process . . . . . . . . . .
Chemie Linz Process . . . . .
Stamicarbon Process . . . . . .
High-Pressure Processes . .
Melamine Chemicals Process

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1
2
2
2
3
3
3
4
4
5
5
6
7
8

Melamines (2,4,6-triamino-1,3,5-triazines)
are produced from urea. They are used in the fabrication of melamine formaldehyde resins for
laminating and adhesive applications. Melanine
is used as cross-linker in heat-cured and highsolids paint systems.Guanamines (2,4-diamino-1,3,5-triazines) are produced from dicyandiamide and the corresponding nitrile by basecatalyzed cyclocondensation. They are used in
similar polymer applications as for melamine.
They give a lower cross-link density and higher
exibility because only two amino functionalities are present.

1. Introduction
Melamine was rst prepared and described
in 1834 by Liebig, who obtained it from fusion of potassium thiocyanate with ammonium
chloride. In 1885, A. W. von Hoffmann published its molecular structure. Melamine [108c 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim


10.1002/14356007.a16 171.pub2

4.2.2.
4.2.3.
5.
6.
7.
8.
9.
10.
11.
11.1.
11.2.
11.3.
12.

Montedison (Ausind) Process

Nissan Process . . . . . . . . .
Quality Specications . . . .
Chemical Analysis . . . . . .
Storage and Transportation
Uses . . . . . . . . . . . . . . . .
Economic Aspects . . . . . . .
Toxicology . . . . . . . . . . . .
Guanamines . . . . . . . . . .
Production . . . . . . . . . . .
Uses . . . . . . . . . . . . . . . .
Toxicology . . . . . . . . . . . .
References . . . . . . . . . . . .

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8
9
10
10
10
11
11
11
12
13
14
15
15

78-1] (2,4,6-triamino-1,3,5-triazine), C3 N6 H6 ,
M r 126.13, exists mainly in the amino form:

Not until 100 years later did melamine

nd industrial application in the production
of melamine formaldehyde resins ( Amino
Resins). The rst commercial plants came on
stream in the late 1930s. Since that time
melamine has become an increasingly important
chemical commodity. In 1970, world capacity
was estimated at 200 000 t. Production in 1994
is 610 000 t/a. Most of the melamine produced is
still used in the fabrication of melamine formaldehyde resins.
Until about 1960, melamine was prepared
exclusively from dicyandiamide [461-58-5] (
Cyanamides, Chap. 3). This conversion was car-

Melamine and Guanamines

ried out in autoclaves at 10 MPa and 400 C in

the presence of ammonia, according to the equation

log L = 5.101 1642/T

3 H2 NC (NH) NHCN2 C3 N6 H6

Crystal Data. Melamine forms monoclinic

crystals, space group P 21 /a with a = 1.0537, b
= 0.7477, c = 0.7275 nm, = 112 9 , and Z = 4
[11].

In the early 1940s, Mackay discovered that

melamine could also be synthesized from urea
[57-13-6] at 400 C with or without catalyst [6].
Today, melamine is produced industrially almost
exclusively from urea. Most processes using dicyandiamide as raw material were discontinued
or replaced at the end of the 1960s.

2. Physical Properties
Melamine is manufactured and sold as ne,
white, powdered crystals. The most important
physical data for melamine are summarized in
the following list [7, 8]:
mp
Density

Dissociation constants
Kb1 (25 C)
Kb2 (25 C)
Heat of formation H 0f (25 C)
Heat of combustion (25 C)
Heat of sublimation (25 C)
Molar heat capacity (25 C)
Specic heat capacity cp ,
J kg1 K1
at 273 353 K
at 300 450 K
at 300 550 K
Entropy (25 C)
Entropy of formation S 0f (25 C)
Free energy of formation
G0f (25 C)
Solubility (30 C), g/100 mL, in
Ethanol
Acetone
Dimethylformamide
Ethyl cellosolve
Water

350 C (subl.)
1.573 g/cm3
1.1109
1.01014
71.72 kJ/mol
1967 kJ/mol
121 kJ/mol
155 J K1 mol1

Reasonably reliable values can be obtained

by means of this equation down to 0 C.

3. Chemical Properties
The chemical properties of melamine are summarized in detail in [1] and [2]. The s-triazine
ring is very stable and cleaves only under drastic
conditions (e.g., heating above 600 C or fusion
with alkali compounds).
By X-ray diffraction studies, crystalline
melamine has been shown to exist only in the
symmetrical triamino structure; the same is true
for the vapor phase and for both neutral and alkaline solutions. Although reactions are in some
cases observed at the ring nitrogen atoms (the
products being substituted isomelamines), the
most important commercial reactions involve
only the NH2 groups, which behave chemically as amido rather than amino functions.

3.1. Thermal Behavior

1470
1630
1720
149 J K1 mol1
835 J K1 mol1
177 kJ/mol
0.06
0.03
0.01
1.12
0.5

When melamine is heated above 300 C in the

absence of ammonia or at low ammonia partial pressure, deammoniation and condensation
lead to compounds with higher molecular mass.
Degradation starts with the release of ammonia
and the formation of melem [1502-47-2] (2,5,8triamino-1,3,4,6,7,9,9b-heptaazaphenalene):

The temperature dependence of the vapor

pressure (in 105 Pa) in the range 417 615 K
is described by the following equation [9]:
log p = 9.7334 6484.9/T
Melamine solubility in water (in grams per
100 g of H2 O) over the range 20 100 C coincides closely with the relationship [10]:

Further heating to ca. 600 C yields more ammonia and melone [32518-77-7] [12]:

Melamine and Guanamines

3.2. Hydrolysis
Melamine is hydrolyzed by mineral acid or inorganic alkali. Hydrolysis proceeds stepwise, with
loss of one, two, or all three amino groups:

Various sources disagree on hydrogen analysis and other analytical data for melone. The
material may represent a mixture of substances
such as 1 and 2.
Melam
[(N-4,6-diamino-1,3,5-triazin-2yl)-1,3,5-triazine-2,4,6-triamine], [3576-88-3]
seems not to be an intermediate in the thermal
degradation of melamine although the evidence
is not entirely clear [12 14]. This substance
can be prepared by heating melamine salts below 315 C, and it arises as a byproduct of
melamine synthesis.

The product spectrum varies with temperature, pH, and concentration; the end product is
cyanuric acid [108-80-5]. Even small amounts
of the oxotriazines (especially cyanuric acid and
ammelide) markedly effect the condensation of
melamine with formaldehyde by increasing the
rate of condensation [16].

3.3. Salt Formation

Melamine is a weak base, forming well-dened
salts with both organic and inorganic acids. The
melamine ion is assigned the following structure:

The three deammoniation productsmelam,

melem and meloneare formed reversibly; addition of ammonia at high pressure and temperature regenerates melamine. Indeed, processes
for melamine production invariably rely upon
excess ammonia to suppress formation of these
byproducts. If melamine is heated to 600 C
or higher it is partially cracked, leading to
cyanamide along with other products. Hydrogen
cyanide may also appear in the crack products,
especially in the absence of oxygen [15].

The water solubility of organic and inorganic

salts of melamine is no higher than that of free
melamine (see Table 1). Melamine cyanurate,
melamine picrate, and melamine perchlorate are
very insoluble in water, and are useful in the
quantitative determination of melamine.

3.4. Reaction with Aldehydes

Melamine reacts with aliphatic and aromatic
aldehydes to give a variety of products. Most

Melamine and Guanamines

Table 1. Industrially important melamine salts

Molecular formula

Solubility (20 C), g per 100 g M r

H2 O

mp, C

C3 N6 H6 H3 PO4
C3 N6 H6 H2 SO4
C3 N6 H6 HNO3
C3 N6 H6 C17 H35 COOH
C3 N6 H6 HCOOH

0.43
0.19
0.68
0.17
1.56

223
380 *
298 *
154
250
(decomp.)

224.12
350.33
189.14
410.42
172.16

* Sublimes at 316 C.

Sublimes at 186 C.

important is the resinous material obtained from

the reaction of formaldehyde with melamine:
Me(NH2 )3 +6 CH2 OMe[N(CH2 OH)2 ]3
where Me represents that part of the melamine
molecule that is not involved in the reaction.
All hydrogen atoms on the melamine
molecule can be replaced by methylol groups,
and products ranging from the monomethylol
to the hexamethylol derivatives have been observed. The methylolmelamines are sparingly
soluble in most solvents and are very unstable due to further condensation or resinication,
e.g.,
MeNHCH2 OH+H2 NMe
MeNHCH2 NHMe+H2 O
2 MeNHCH2 OH

4. Production
Melamine can be synthesized from urea at 390
410 C:
6 H2 N CO NH2
C3 N3 (NH2 )3 +6 NH3 +3 CO2
The overall reaction is endothermic, requiring 649 kJ per mole of melamine starting with
molten urea at 135 C.
The processes themselves may be subdivided
into two categories:
1) noncatalytic, high-pressure ( 8 MPa) processes, and
2) catalytic, low-pressure processes (ca. 1 MPa).
Each type includes three stages:
synthesis
melamine recovery and purication
off-gas treatment

MeNHCH2 OCH2 NHMe+H2 O

Melamine formaldehyde
condensation
products are characterized by good heat resistance and superior water-resisting properties.
They are used, usually in combination with urea
formaldehyde resins, as glues in the woodworking industry, as impregnating resins for
decorative laminates, and as a binder in molding materials containing a ller (e.g., cellulose
or sawdust). Methylolmelamines can be etheried by heating with alcohol in the presence
of an acid catalyst. Industrially most important
are the products formed with methanol, n-butanol, and isobutanol. They are used as curing
agents for surface coatings and as auxiliaries in
the paper and textile industries. For additional
information see Amino Resins [17].

4.1. Low-Pressure Processes

Typical low-pressure processes utilize a uidized catalyst bed at pressures from atmospheric to ca. 1 MPa and temperatures of 390
410 C. The uidizing gas is either pure ammonia or the ammonia carbon dioxide mixture
formed during the course of the reaction. Catalysts include alumina and materials of the silica
alumina type. Melamine leaves the reactor in
gaseous form together with the uidizing gas; it
is separated from ammonia and carbon dioxide
by quenching the gas stream either with water
(followed by crystallization) or with cold reaction gas (desublimation).
In the catalytic processes the rst reaction
step is decomposition of urea to isocyanic acid

Melamine and Guanamines

and ammonia, after which the isocyanic acid is
transformed into melamine:

The overall reaction mechanism is not yet

fully understood, but isocyanic acid from the
decomposition of urea is believed to be catalytically disproportionated into carbon dioxide and
cyanamide or carbodiimide, which then trimerizes to melamine [18 20]:

The melamine yield is ca. 90 95 % based

on urea. Byproducts include melam, melem, and
melone, as well as oxotriazines such as ammeline, ammelide, and cyanuric acid. Ureidotriazine is also observed as a product of reaction
between melamine and isocyanic acid.
Some byproducts are formed in the reactor
during synthesis; others are not generated until
the melamine recovery section, where deammoniation or hydrolysis occurs [20 29].
Worldwide, three low-pressure processes are
in commercial operation: the BASF process, the
Chemie Linz process, and the Stamicarbon process.
4.1.1. BASF Process
The BASF process (see Fig. 1) is a onestage, low-pressure, catalytic vapor-phase process. Molten urea is fed to the uidized catalytic
bed reactor (a) at 395 400 C and atmospheric
pressure. Alumina is used as a catalyst, and uidization is accomplished with an NH3 CO2
mixture (the process off-gas).
The reactor temperature is held at ca. 395 C
by molten salt circulated through internal heating coils (b). The uidizing gas is also preheated
to 400 C. To secure an ammonia-rich atmosphere in the reaction zone, make-up ammonia
is added to both the uidizing gas and the urea
nozzles.

Gas leaving the reactor is a mixture of

gaseous melamine, traces of melem, and unreacted urea (in the form of its decomposition
products isocyanic acid and ammonia), as well
as ammonia and carbon dioxide (part newly
formed, part uidizing gas). In addition, the
gas mixture contains entrained catalyst nes;
coarser catalyst particles are retained by cyclone
separators inside the reactor.
The gas mixture leaving the reactor is cooled
in the gas cooler (d) to a temperature at which
only the byproduct melem crystallizes. Precipitated melem, in the form of a ne powder, is removed together with the entrained catalyst nes
in adjacent gas lters (e).
The ltered gas mixture enters the top of the
crystallizer (f ) where it is blended countercurrently with recycled off-gas (140 C). The temperature in the crystallizer is thereby reduced
to 190 200 C, and more than 98 % of the
melamine crystallizes as ne crystals. Melamine
is recovered from the gas in a cyclone (g), after
which it is cooled and stored. It can be used without further treatment and has a minimum purity
of 99.9 %.
The nearly melamine-free gas stream from
the cyclone is fed to the urea washing tower (i)
where it is scrubbed with molten urea (135 C),
which provides both cooling and washing. Clean
gas leaving the urea scrubber (after passing
through droplet separators) is partially recycled
to the reactor as uidizing gas and partially recycled to the crystallizer as quenching gas. The
surplus is fed to an off-gas treatment unit.
A single-stage reactor has the advantage of
converting the corrosive intermediate isocyanic
acid immediately to melamine; also, the heat of
this exothermic reaction is used directly for the
endothermic decomposition of urea, the rst step
in melamine synthesis.
4.1.2. Chemie Linz Process
The Chemie Linz process (see Fig. 2) is a twostage process. In the rst step, molten urea is decomposed in a uidized sand-bed reactor (b) to
ammonia and isocyanic acid at ca. 350 C and
0.35 MPa. Ammonia is used as the uidizing
gas. Heat required for the decomposition is supplied to the reactor by hot molten salt circulated
through internal heating coils. The gas stream

Melamine and Guanamines

Figure 1. BASF process

a) Reactor; b) Heating coils; c) Fluidizing gas preheater; d) Gas cooler; e) Gas lter; f) Crystallizer; g) Cyclone; h) Blower;
i) Urea washing tower; j) Heat exchanger; k) Urea tank; l) Pump; m) Droplet separator; n) Compressor

Figure 2. Chemie Linz process

a) Heat exchanger; b) Urea decomposer; c) Converter; d) Quencher; e) Heat exchanger; f) Suspension tank; g) Heat exchanger;
h) Centrifuge; i) Mother-liquor vessel; j) Disk dryer; k) Elevator; l) Delumper; m) CO2 absorption column; n) Compressor;
o) Heat exchanger

is then fed to the xed-bed catalytic reactor (c)

where isocyanic acid is converted to melamine
at ca. 450 C and near-atmospheric pressure.
Melamine is recovered from the reaction gas
by quenching with water and mother liquor from
the centrifuges (h). The quencher (d) is specially
designed to work quickly, thereby preventing
signicant hydrolysis of melamine to ammelide
and ammeline. The melamine suspension from
the quencher is cooled further to complete the
melamine crystallization process. After being
centrifuged, the crystals are dried, milled, and
stored. A separate recrystallization step is not
required.
Exhaust gas from the quencher is fed to an absorber (m) where carbon dioxide is removed as
ammonium carbamate by washing with a lean
carbamate solution from the off-gas treatment

section. The wet ammonia gas is dried with

make-up ammonia. Part of it is compressed and
recycled to the urea decomposer, and part is exported. Remaining ammonia and carbon dioxide
in the liquid efuent are then recovered in the
off-gas treatment section.
4.1.3. Stamicarbon Process
Like the BASF process, the DSM Stamicarbon
process (see Fig. 3) involves only a single catalytic stage. However, it differs from the former
in that it is operated at 0.7 MPa, the uidizing
gas is pure ammonia, the catalyst is of the silica alumina type, and melamine is recovered
from the reactor outlet gas by water quench and
recrystallization.

Melamine and Guanamines

Figure 3. Stamicarbon process

a) Urea tank; b) Reactor; c) Preheater; d) Heating coils; e) Internal cyclone; f) Quench cooler; g) Scrubber; h) Hydrocyclone;
i) Desorption column; j) Heat exchanger; k) Heat exchanger; l) Mixing vessel; m) Heat exchanger; n) Dissolving vessel;
o) Precoat lter; p) Vacuum crystallizer; q) Pump; r) Heat exchanger; s) Mother-liquor vessel; t) Hydrocyclone; u) Centrifuge;
v) Pneumatic dryer; w) Hydrocyclone; x) Absorption column; y) Compressor

Urea melt is fed into the lower part of the reactor (b). The silica alumina catalyst is uidized
by preheated (150 C) ammonia, which enters
the reactor at two points: at the bottom of the reactor to uidize the catalyst bed, and at the urea
nozzles to atomize the urea feed. The reaction is
maintained at 400 C by circulating molten salt
through heating coils within the catalyst bed.
The melamine-containing reaction mixture
from the reactor is quenched rst in a quench
cooler (f ) and then in a scrubber (g) with recycled mother liquor from the crystallization section. The resulting melamine suspension is concentrated to ca. 35 wt % melamine in a hydrocyclone (h), after which it is fed to a desorption column (i) where part of the ammonia and carbon
dioxide dissolved in the suspension is stripped
off and returned to the scrubber. The preceding
steps are all carried out at reaction pressure; for
the following stages, the pressure is reduced.
The suspension leaving the bottom of the
desorber is diluted with recycled and preheated
mother liquor and water. Activated carbon and
lter aids may also be added. The melamine dissolves completely, although separate dissolving
vessels (n) are necessary to allow sufcient time
for dissolution. The resulting solution is ltered
using precoat-type lters (o). Crystallization of
melamine is carried out in a vacuum crystallizer

(p ), and crystals are separated from the mother

liquor by hydrocyclone (t) and centrifuge (u).
The crystals are dried in a pneumatic dryer and
then conveyed to product bins.
Surplus ammonia must be recovered as uidizing gas from the wet ammonia carbon
dioxide mixture leaving the desorption column
and the scrubber. The hot gas mixture is partly
condensed by heat-exchange (k) with the mother
liquor from melamine dissolution. The condensate and uncondensed gas are then passed at 0.7
MPa to an absorption column (x). Liquid makeup ammonia is fed to the top of this column to
condense any carbon dioxide remaining in the
ammonia gas. The ammonia is then compressed
and recycled as uidizing and urea-atomization
gas for the reactor.

4.2. High-Pressure Processes

High-pressure melamine synthesis systems differ from low-pressure processes by producing
melamine in the liquid instead of the vapor
phase. They have the advantage of providing
high-pressure off-gas more suitable for use in
the urea synthesis facility. Liquid phase operation also lends itself to smaller reaction vessels,
but the highly corrosive nature of the system dic-

Melamine and Guanamines

tates use of expensive, corrosion-resistant construction materials such as titanium.

High-pressure reactions occur without catalyst at > 7 MPa and > 370 C. In general,
molten urea is injected at high pressure into a
molten melamine urea mixture in the reactor,
where it undergoes conversion to melamine. Sufcient residence time is provided in the reactor to
ensure complete reaction, leading to melamine
with a purity > 94 %. Heat is supplied to the reactor either by electric heater elements or by a
molten salt heat-transfer system. Various types
of off-gas separation and melamine purication
follow.
High-pressure synthesis of melamine from
urea proceeds via the intermediate cyanuric acid,
which is subsequently converted to melamine
under high pressure in an ammonia environment
[30, 31]:

The net reaction is the same as in the lowpressure process.

4.2.1. Melamine Chemicals Process
Melamine Chemicals uses a continuous highpressure single-stage process that produces
melamine with a purity of ca. 96 99.5 %.
Molten urea is converted into melamine in a liquid-phase reactor. The off-gases (ammonia and
carbon dioxide) are separated in a gas-separating
vessel. Liquid melamine is then quenched in a
cooling unit, where liquid ammonia is used to
solidify the crystals.
Process Description. Incoming urea is preheated by using it to scrub the reactor off-gas
stream. This scrubber performs various functions, including (1) driving off any water that
may be present in the urea feed, (2) preheating the molten urea, (3) removing melamine
from the off-gases, and (4) recovering excess
heat energy for subsequent use.
The reactor
is heated to ca. 370 425 C with a heating-coil

system and pressurized to about 11 15 MPa.

Mixing is provided by heat convection and generation of gaseous reaction products.
Liquid melamine is separated from the offgas in a gas separator, the product being collected at the bottom. The separator is held at
about the same temperature and pressure as the
reactor. The gaseous phase (ammonia and carbon dioxide, saturated with melamine vapor)
is removed overhead to a urea scrubber. The
melamine stream leaving this separator is then
injected into the product cooling unit.
The product cooling unit employs liquid ammonia to both cool and solidify melamine. This
is accomplished at a controlled temperature and
pressure to minimize formation of such impurities as melam and melem. Product is removed
from the pressurized cooling unit through a series of pressure-reducing hoppers. Depending on
the required degree of purity, it may then be recrystallized [32].
The off-gas stream represents high-pressure (> 10 MPa) ammonia and carbon dioxide,
which can be used directly as feed to the urea
facility. Alternatively, this gas stream can be
treated in a monoethanolamine (MEA) scrubber
to recover ammonia and remove carbon dioxide.
4.2.2. Montedison (Ausind) Process
The Montedison process (see Fig. 4) operates at
370 C and 7 MPa. The required temperature is
maintained by a molten-salt heating system consisting of concentric bayonet-type tubes.
Molten urea at 150 C is fed to the reactor (a)
together with preheated ammonia. Average residence time of the mixture in the reactor is about
20 min. As the reaction mixture leaves the reactor, the pressure is lowered to 2.5 MPa, and the
mixture is treated at 160 C in a quencher (b)
with an aqueous solution of ammonia and carbon dioxide to precipitate melamine. The watersaturated mixture of ammonia and carbon dioxide leaving the top of the quencher can be recycled to a plant for urea or fertilizer production.
The aqueous melamine slurry remains in the
quencher at 160 C for some time to decompose
unconverted urea and such byproducts as biuret
and triuret to ammonia and carbon dioxide. It
is then fed to a steam stripper (c), where any

Melamine and Guanamines

Figure 4. Montedison process

a) Reactor; b) Quencher; c) Stripper; d) Absorption column; e) Heat exchanger; f) Filter; g) Vacuum crystallizer; h) Filter;
i) Pneumatic dryer; j) Heat exchanger; k) Cyclone; l) Blower

remaining ammonia and carbon dioxide are removed. Off-gas from the stripper is dissolved in
water in an absorption column (d) and this solution is recycled to the quencher.
The ammonia- and carbon dioxide-free
melamine slurry leaving the bottom of the stripper is diluted with mother liquor to dissolve
melamine. Sodium hydroxide is also added, and
the solution is then claried with activated carbon (f). Melamine is crystallized from the claried solution in a crystallizer (g) operated adiabatically under vacuum. Melamine crystals are
separated from the mother liquor in a rotary lter (h), dried in a pneumatic conveyor dryer
(i), and stored.
4.2.3. Nissan Process
The Nissan melamine process (see Fig. 5) operates at 10 MPa and 400 C. One characteristic feature is urea washing of the reactor offgas. For this purpose, molten urea is also pressurized to 10 MPa and passed through a highpressure washing tower (c) where it absorbs any
melamine and unreacted urea present in off-gas
leaving the reactor. The urea then ows into the
reactor (a) by gravity. Ammonia is also fed to
the reactor.
In a so-called level tank (b), efuent from
the reactor is separated into gaseous and liquid
phases. The gaseous phase passes through the
previously described urea washing tower to an
off-gas treatment facility. The liquid phase con-

sists mainly of molten melamine. This melt is

mixed with hot gaseous ammonia and fed to a
cushion vessel (e) for aging (i.e., to allow byproducts to be reconverted to melamine).
After aging, the melamine melt is quenched
(f) under pressure with aqueous ammonia, in
which it dissolves. The resulting 20 30 wt %
melamine solution is retained in the quencher
at 180 C until any remaining impurities have
decomposed.
Most of the added ammonia is next removed
from the solution in an ammonia stripper (g) (operated at 1.5 MPa) and the solution is ltered.
Recovered ammonia is recycled. Crystallization
takes places in two crystallizers (k) operated in
series. Mother liquor and melamine crystals are
separated in centrifuges (l), after which the crystals are dried and crushed before storage.
Further treatment of the mother liquor starts
with an ammonia stripper (n), in which oxoaminotriazines precipitate. The slurry from this ammonia recovery tower is therefore alkalinized
before being fed to a third crystallizer (o) operating at reduced temperature and pressure. Additional melamine crystallizes here, and after separation from the liquid (p) it is returned to the
second crystallizer.
Lowering the pH of the mother liquor causes
oxoaminotriazines to precipitate; these are removed by decantation (q). The clear mother
liquor is used to absorb ammonia leaving the
crystallizers and is subsequently recycled to the

10

Melamine and Guanamines

Figure 5. Nissan process

a) Reactor; b) Level tank; c) Off-gas washing tower; d) Steam drum; e) Cushion vessel; f) Quencher; g) NH3 -stripper; h) NH3 distillation column; i) Absorber; j) Filter; k) Crystallizers; l) Centrifuge; m) Pneumatic dryer; n) Ammonia recovery tower;
o) Crystallizer; p) Separator; q) Decanter

quencher together with ammonia released in the

ammonia recovery tower.

5. Quality Specications
Many consumers of melamine are satised with
a purity of 99.9 %. Some, however, specify additional measurable criteria such as: content of
inorganic ash, moisture, and ammeline-related
compounds (alkali solubles); particle-size distribution; pH; resin reaction time; and resin color.
Average particle sizes ranging from 15 to 100
m are available for various applications. The
rate of dissolution of melamine in formaldehyde
solutions depends on particle size, an important
parameter that is generally also reported by producers.

6. Chemical Analysis
Melamine is difcult to characterize by traditional chemical methods. Purity specications
are usually based on differences obtained after subtracting determined impurity levels for
moisture, ash, and alkali solubles. Instrumental
analysis is possible using liquid chromatography [33] and spectroscopic methods, although

melamine tends to form complexes with the pHcontrol buffers used in liquid chromatography,
leading to variability in the UV absorption observed at different pHs. Melamine can be precipitated for quantitative determination as the perchlorate or picrate salt (see Section 3.3).

7. Storage and Transportation

Melamine is stable when stored under normal
warehouse conditions. Although not particularly
hygroscopic, powdered melamine must still be
protected from wetting because, like most powders, it will pack and lump over extended storage
periods.
In the VDI guideline 2263 melamine is classied as having a burning index of 2, i.e., during a re it ignites quickly but the ame is
rapidly extinguished. Flammability tests performed in accordance with the EEC guideline
84/449 A 10 showed that a glowing platinum
wire (>1000 C) was not able to produce continous burning of melamine.
Shipping considerations are typical of those
for other nonhazardous powders. Melamine is
available in standard-weight paper bags and
semibulk bags. Bulk shipment is by truck and
railroad car.

Melamine and Guanamines

11

Table 2. Melamine applications, in percent, by region

Application
Laminates
Glue, adhesives
Molding compounds
Coatings
Paper, textiles
Other
Total

8. Uses
Most melamine is reacted with formaldehyde to
produce resins for laminating and adhesive applications [16, 17, 34]. One of the major uses
of melamine is in the upper sheet of laminated
counter- and tabletops.
Another important use of melamine is as the
amino cross-linker in heat-cured paint systems.
In this case the methylated methylolmelamine
is used, with varying molar ratios of melamine,
formaldehyde, and alcohol for different paint
system applications. High-solids paint systems
for automotive applications also constitute a major market for melamine.
Other uses include the preparation of
wet-strength resins for paper, water clarifying resins, ion-exchange resins, plastic molding compounds, adhesives, re retardants in
polyurethane foams, and intumescent paints.
Important new applications are under development in the eld of re retardants for polymeric
materials, especially polyurethane foams. Applications and uses of melamine differ widely
among the main consumer countries or regions.
Estimates are provided in Table 2.

9. Economic Aspects
About 18 melamine producers exist worldwide.
Rated annual production capacity is ca. 550
000 t (data for 1990/1991; see Table 3). In the
last decade the average annual growth rate for
melamine consumption was ca. 2 %.

10. Toxicology
Acute Toxicity. From the standpoint of acute
toxicity, melamine is not classied as a health
risk. The oral LD50 for rats is > 5000 mg per
kilogram of body weight [35]. Melamine applied

Europe
47
25
9
8
11
100

United States

Japan

35
4
9
39
5
8
100

6
62
16
12
3
1
100

to the skin and eyes of rabbits is a non-irritant

[35]. Skin sensitization could not be provoked
by patch tests on humans [36] or guinea pigs
[37].
Table 3. Melamine production capacity worldwide
Country

Company

Capacity, t/a

Fed. Rep. Germany

Austria
Netherlands
Italy
France
Western Europe

BASF
Chemie Linz
DSM
Ausind
Norsolor

42 000
55 000
90 000
28 000
15 000
230 000

Poland
Rumania
Soviet Union
Eastern Europe

Polimex Cekop
Romchim
Techmashimport

28 000
12 000
10 000
50 000

United States

American Melamine
Ind.
Melamine Chem.

50 000

America
Japan

Korea
Taiwan
Saudi Arabia
China
India
Middle and Far East
Total

Mitsubishi
Petrochemical
Mitsui Toatsu Chemical
Nissan Chemical
Korea Fertilizer
Taiwan Fertilizer
Safco
Sichuan Chemical
Works
Gujarat State Fertilizer

47 000
97 000
32 000
38 000
42 000
16 000
10 000
20 000
12 000
5 000
175 000
552 000

Genetic Toxicity. Investigations into the potential genetic effects of melamine have included
the following tests:
In vitro methods
1) Bacterial tests
2) Ames Test [38]
Escherichia coli plate test [39]
3) Test with eukaryotes
4) Test with eukaryotes

12

Melamine and Guanamines

Saccharomyces cerevisiae (gene conversion) [39]

Rat hepatocytes (DNA repair) [40]
Mouse lymphoma test (point mutation) [41]
CHO cells (chromosomal aberrations) [42]
In vivo methods
Drosophila melanogaster (sex-related lethal
test) [43]
Mouse micronucleus test (oral administration
of 1000 mg per kilogram of body weight)
[44]
In none of these studies could melamineinduced mutagenicity or damage to genetic material be demonstrated.
Metabolism. Investigations
into
the
metabolism and toxicokinetics of melamine
showed that a single oral dose of 0.38 mg of
14
C-labeled melamine administered to a rat was
eliminated unchanged in the urine to the extent
of 90 % [45]. The plasma half-life was found
to be 2.7 h, with highest concentrations in the
bladder and kidneys.
Chronic Toxicity and Carcinogenicity. The
target organ system for melamine toxicity after
prolonged administration to mice and rats is the
urinary tract. Both species were administered, in
some cases extremely high doses in the diet (750
30 000 ppm; ca. 62 2490 mg per kilogram of
body weight per day) over periods of 14 d, 90 d,
and 2 a. All studies led to changes in the kidney (inammation, calcied concretions in the
proximal tubuli) and bladder (inammation, ulceration, epithelial hyperplasia, bladder stones).
Daily dosages up to 15 000 ppm for mice and
5000 ppm for rats administered in the diet over
14 d produced no changes. Female rats tolerated doses of 9000 ppm/d for 13 weeks without
symptoms. The incidence of bladder carcinoma
increased only for male rats receiving melamine
in the diet over a two-year period (dosage: 4500
ppm). Of eight rats displaying tumors, seven
also had bladder stones, suggesting that chronic
mechanical irritation of the mucous membranes
of the bladder may have been responsible for
the tumors. Dosages that do not result in bladder stones are not expected to be carcinogenic.
Female rats in this study displayed neither bladder stones nor carcinoma [39, 46].

An initiation-promotion study on female

mouse skin failed to reveal any tumor-inducing
effect [47]. A single dermal application of 1
mol of melamine followed by a 31-week treatment (twice a week) with 10 nmol of a promoter (12-O-tetradecanoylphorbol-13-acetate)
resulted in no increased incidence of tumorbearing animals.
Reproduction Toxicology. A study reported
by Thiersch on the reproduction toxicology
of melamine was published in 1957. Intraperitoneal administration of a dose of 70 mg/kg to
pregnant rats on days 4 and 5, 7 and 8, or 11 and
12 of pregnancy had no inuence on the maternal or fetal development, nor was there any
teratogenic effect [48].

11. Guanamines
In the course of heating guanidine acetate,
Nencki (1874) obtained a new compound to
which he assigned the name guanamine; later
he changed it to acetoguanamine after the discovery of other homologues. Weith recognized
in 1876 that this substance was in fact 2,4-diamino-6-methyl-1,3,5-triazine. The term guanamine has since been applied generally to
2,4-diamino-1,3,5-triazines substituted in the 6position with alkyl, aryl, or alkaryl residues.
Such substances are named on the basis of the
carboxylic acid that contains one more carbon
atom than is present in the substituent on the
triazine ring:

Compounds of this type that have major

commercial signicance are benzoguanamine
[91-76-9], C9 H9 N5 , M r 187.20, and acetoguanamine [542-02-9], C4 H7 N5 , M r 125.14 [49].
The physical properties of aceto-, benzo-, and
caprinoguanamine [5921-65-3], C12 H23 N5 , M r
237.35, are summarized in Table 4. Figure 6 illustrates the most important reactions of acetoand benzoguanamine [50 53]. For information
regarding other guanamines and their reactions,
see [54 56].

Melamine and Guanamines

13

Table 4. Physical properties of the most important guanamines

mp, C
Solubility (at 20 C),
g/L, in
Water
Acetone
Benzene
Dimethylformamide
a

Acetoguanamine

Benzoguanamine

Caprinoguanamine

277

228

105 120a

0.3
18.0
0.3
120.0

insoluble
25.2
11.2
67.0

11.2
1.04
0.07
0.88

Liquid crystalline intermediate phase

Figure 6. Reactions of guanamines

11.1. Production
2,4-Diamino-1,3,5-triazines can be prepared
from several aliphatic C-N-compounds [5] including the historic synthesis from biguanides
with esters [57, 58]. Aromatic guanamines can

be obtained by Pd-catalyzed Suzuki coupling

from 1,3,5-triazine precursors [59]. The only
method of industrial relevance, however, involves the reaction of dicyandiamide (cyanoguanidine) with nitriles [60]:

14

Melamine and Guanamines

Use of dinitriles leads to bisguanamines. Reaction occurs at 105 120 C in the presence of
alkaline catalysts (e.g., KOH) in polar solvents,
usually alcohols, and high yields are obtained.
The rate of reaction depends on the structure of
the nitrile, the nature of the solvent, and the concentration of alkali. Aliphatic nitriles generally
react more slowly than aromatic nitriles. The reaction can also be performed under microwave
irradiation [61] or in ionic liquids [62].

11.2. Uses
Acetoguanamine is used as a condensation
component in amino resins. Occasional use is
made of the pure resins that result from reaction of acetoguanamine with formaldehyde.
Such resins display a high degree of water tolerance and can be cured thermally. The rate of
the condensation reaction is considerably less
dependent on pH than in the case of melamine.
Condensation may be carried out in weakly basic
or weakly acidic media. Compared to melamine
formaldehyde resins, the curing of acetoguanamine resins occurs more slowly and at a more
acidic pH.
Acetoguanamine is normally used to modify melamine formaldehyde resins, conferring
improved elasticity, higher gloss, and reduced
resin shrinkage. Main application is in the
decorative layer of high-pressure laminates
(HPL) used for ooring and, e.g., kitchen
plates. Acetoguanamine-modied melamine
resins provide high gloss, low stain receptivity,
and postforming properties. Even low amounts
of acetoguanamine (5-10% based on melamine)
are sufcient to allow small bending radii without affecting surface hardness or thermal stability [63]. Newer developments aim at reducing
the formaldehyde content of melamine acetoguanamine resins in order to avoid formaldehyde emissions after production [64]. Due to the
relatively high cost of acetoguanamine, mixtures
with other modifying agents, e.g., dicyandiamide have been applied, especially for short cycle laminates on wood-based materials [65](see
also Wood). Partially alkoxylated acetogua-

namine formaldehyde resins have been proposed for high-temperature bers with good
exibility [66]. Acetoguanamine cyanurate, either alone or with melamine cyanurate, serves as
an effective ame retardant in polyamides [67,
97].
Benzoguanamine is also used primarily in
amino resins. Compared to acetoguanamine,
benzoguanamine produces signicantly more
hydrophobic resins that have lower lightfastness
due to the aromatic ring.
The most important application of benzoguanamine is in resins for industrial paints. Methylolated benzoguanamine resins that have been
etheried with butanols are compatible with hydrocarbon solvents, oils, and various synthetic
resins (e.g., alkyd, polyester, epoxy [68] and
acrylic resins [69]). Upon curing, these OH functional resins react with the butoxymethyl groups
of the benzoguanamine resin to form new crosslinks, by splitting off butanol. In contrast to similar melamine resins, benzoguanamine resins
give a lower cross-link density, and thus a higher
exibility and better surface quality. Typical applications are can coatings, coil coatings, and automotive basecoats. Benzoguanamine-carboxylic acids have been proposed as cross-linkers
for water-borne coatings [70].
Due to its favorable physicochemical properties, tetra(methoxymethyl)benzoguanamine
[4588-69-6] has been proposed as a cross-linker
for powder coatings based on hydroxy polyesters [71, 72]. However, bubbles formed during
the elimination of methanol have limited its use
to date.
Fully condensed formaldehyde benzoguanamine resins that mainly consist of methylenebridged structures are amorphous, insoluble
solids with high thermal stability. Due to their
high refractive index, these resins are used as
white pigments or colorants in plastics [73] or, in
conjunction with uorescent dyes, as pigments
for daylight uorescent inks and paints [74, 75].
Benzoguanamine is used as a exibilizing agent
in phenolic resins to improve the punchability,
water resistance, and ame-retardance of FR2type printed circuit boards [76]. In the same
way, it can be used as additive to urea formaldehyde foams [77] or bismaleimide copolymer resins [78]. Both, acetoguanamine and benzoguanamine have been proposed as epoxy cur-

Melamine and Guanamines

15

Table 5. Typical storage lifetime of formaldehyde solutions stabilized with guanamines

Formaldehyde concentration

Guanamine added

Storage temperature

Storage lifetime

40 %

0.1 % benzoguanamine

10 C

2 weeks

40 %

0.05 % caprinoguanamine

10 C

4 weeks

50 %

0.05 % caprinoguanamine

40 C

4 weeks

ing agents with improved properties for microelectronic encapsulation [79, 80]. By reaction with 4,4-diaminodiphenyl ether, benzoguanamine forms a bridged bisguanamine which
was proposed for resin applications [81].
Benzoguanamine can be used instead of dichlorophenyltriazine to produce Pigment Yellow 184, an anthraquinone dye with a triazine
subunit [82].
Caprinoguanamine is one of the best known
stabilizers for aqueous formaldehyde solutions.
It prevents or retards the precipitation of polymeric paraformaldehyde at low storage temperatures and/or high formaldehyde concentrations
[83]. Though less effective, benzoguanamine is
sometimes used for the same purpose. Typical
stability data of aqueous formaldehyde solutions
is given in Table 5.
Caprinoguanamine has been applied as additive for melamine formaldehyde impregnation resins with improved wetting characteristics
[84]. It is also used in styrenic foams to improve
the foam structure and provide ame retardancy
[85] (see Flame Retardants).
Other Guanamines. Guanamines with unsaturated groups in the substituent R can
also be converted to polymers and copolymers [86]. The compound CTU (bis3,9-cyanoethyl-2,4,8,10-tetraoxaspiro[5.5]undecan)-guanamine [22535-90-6] (formula
shown below) is employed (like benzoguanamine) primarily in paints [87].

Guanamines with imidazole side chains,

e.g., 2,4-diamino-6-(2 -methylimidazol-1 -yl)ethyl-1,3,5-triazine are used as epoxy curing
agents and accelerators as such or in form of
adducts with, e.g., cyanuric acid [88].
Guanamine structures have also found application in pharmacology as c-AMP specic

phosphodiesterase inhibitors [89], the most

prominent being Irsogladine maleate (2 ,5 -Dichlorobenzoguanamine, [84504-69-8]).

11.3. Toxicology
The acute oral LD50 for acetoguanamine
in rats is 2740 mg/kg; for benzoguanamine,
1470 mg/kg. The corresponding value for
caprinoguanamine is > 10 000 mg/kg, and its
dermal LD50 (rabbit) is > 2800 mg/kg [90]. All
three compounds are not irritating to skin and
eyes [91, 92]. Acetoguanamine and benzoguanamine did not reveal mutagenic activity in the
Ames test [93]. Long term feeding studies with
benzoguanamine in male rats and mice failed
to reveal carcinogenic potential [94]. Benzoguanamine was adopted by the Scientic Committee
on Food as a monomer for food contact materials in List 3 with a restriction of 5 mg/kg of
benzoguanamine in food [95]. The evaluation of
this substance under the OECD/High Production
Volume Program resulted in the conclusion, that
there is low priority for further work (no further
work recommended) [96].

12. References
General References
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3. SRI International: Melamine, Report No 122,
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4. The Manufacture of Non-Fertilizer Nitrogen
Products, Nitrogen 139 (1982) 32 39.
5. Houben-Weyl, Science of Synthesis, vol. 17
(2004), 449 ff.

16

Melamine and Guanamines

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17

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18

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