c 2006 Wiley-VCH Verlag GmbH & Co.

KGaA, Weinheim
10.1002/14356007.a16 171.pub2
Melamine and Guanamines 1
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 G uthner, Degussa AG, Trostberg, Germany (Chap. 11)
Bernd Mertschenk, Degussa AG, Trostberg, Germany (Chap. 11)
1. Introduction . . . . . . . . . . . . . . . 1
2. Physical Properties . . . . . . . . . . . 2
3. Chemical Properties . . . . . . . . . . 2
3.1. Thermal Behavior . . . . . . . . . . . 2
3.2. Hydrolysis . . . . . . . . . . . . . . . . . 3
3.3. Salt Formation . . . . . . . . . . . . . . 3
3.4. Reaction with Aldehydes . . . . . . . 3
4. Production . . . . . . . . . . . . . . . . 4
4.1. Low-Pressure Processes . . . . . . . . 4
4.1.1. BASF Process . . . . . . . . . . . . . . . 5
4.1.2. Chemie Linz Process . . . . . . . . . . 5
4.1.3. Stamicarbon Process . . . . . . . . . . . 6
4.2. High-Pressure Processes . . . . . . . 7
4.2.1. Melamine Chemicals Process . . . . . 8
4.2.2. Montedison (Ausind) Process . . . . . 8
4.2.3. Nissan Process . . . . . . . . . . . . . . 9
5. Quality Specications . . . . . . . . . 10
6. Chemical Analysis . . . . . . . . . . . 10
7. Storage and Transportation . . . . . 10
8. Uses . . . . . . . . . . . . . . . . . . . . . 11
9. Economic Aspects . . . . . . . . . . . . 11
10. Toxicology . . . . . . . . . . . . . . . . . 11
11. Guanamines . . . . . . . . . . . . . . . 12
11.1. Production . . . . . . . . . . . . . . . . 13
11.2. Uses . . . . . . . . . . . . . . . . . . . . . 14
11.3. Toxicology . . . . . . . . . . . . . . . . . 15
12. References . . . . . . . . . . . . . . . . . 15
Melamines (2,4,6-triamino-1,3,5-triazines)
are produced fromurea. They are used in the fab-
rication of melamine formaldehyde resins for
laminating and adhesive applications. Melanine
is used as cross-linker in heat-cured and high-
solids paint systems.Guanamines (2,4-diami-
no-1,3,5-triazines) are produced from dicyan-
diamide and the corresponding nitrile by base-
catalyzed 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 functionali-
ties are present.
1. Introduction
Melamine was rst prepared and described
in 1834 by Liebig, who obtained it from fu-
sion of potassium thiocyanate with ammonium
chloride. In 1885, A. W. von Hoffmann pub-
lished its molecular structure. Melamine [108-
78-1] (2,4,6-triamino-1,3,5-triazine), C
3
N
6
H
6
,
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 form-
aldehyde resins.
Until about 1960, melamine was prepared
exclusively from dicyandiamide [461-58-5] (
Cyanamides, Chap. 3). This conversion was car-
2 Melamine and Guanamines
ried out in autoclaves at 10 MPa and 400

C in
the presence of ammonia, according to the equa-
tion
3 H
2
NC(NH) NHCN2 C
3
N
6
H
6
In the early 1940s, Mackay discovered that
melamine could also be synthesized from urea
[57-13-6] at 400

Cwith or without catalyst [6].
Today, melamine is producedindustriallyalmost
exclusively from urea. Most processes using di-
cyandiamide 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 350

C (subl.)
Density 1.573 g/cm
3
Dissociation constants
K
b1
(25

C) 1.110
9
K
b2
(25

C) 1.010
14
Heat of formation H
0
f
(25

C) 71.72 kJ/mol
Heat of combustion (25

C) 1967 kJ/mol
Heat of sublimation (25

C) 121 kJ/mol
Molar heat capacity (25

C) 155 J K
1
mol
1
Specic heat capacity c
p
,
J kg
1
K
1
at 273 353 K 1470
at 300 450 K 1630
at 300 550 K 1720
Entropy (25

C) 149 J K
1
mol
1
Entropy of formation S
0
f
(25

C) 835J K
1
mol
1
Free energy of formation
G
0
f
(25

C) 177 kJ/mol
Solubility (30

C), g/100 mL, in
Ethanol 0.06
Acetone 0.03
Dimethylformamide 0.01
Ethyl cellosolve 1.12
Water 0.5
The temperature dependence of the vapor
pressure (in 10
5
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 H
2
O) over the range 20 100

C coin-
cides closely with the relationship [10]:
log L = 5.101 1642/T
Reasonably reliable values can be obtained
by means of this equation down to 0

C.
Crystal Data. Melamine forms monoclinic
crystals, space group P2
1
/a with a = 1.0537, b
= 0.7477, c = 0.7275 nm, = 112

, and Z = 4
[11].
3. Chemical Properties
The chemical properties of melamine are sum-
marized 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 al-
kaline 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 NH
2
groups, which behave chemi-
cally as amido rather than amino functions.
3.1. Thermal Behavior
When melamine is heated above 300

C in the
absence of ammonia or at low ammonia par-
tial 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] (2,5,8-
triamino-1,3,4,6,7,9,9b-heptaazaphenalene):
Further heating to ca. 600

Cyields more am-
monia and melone [32518-77-7] [12]:
Melamine and Guanamines 3
Various sources disagree on hydrogen anal-
ysis 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-2-
yl)-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 be-
low 315

C, and it arises as a byproduct of
melamine synthesis.
The three deammoniation productsmelam,
melem and meloneare formed reversibly; ad-
dition of ammonia at high pressure and temper-
ature 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].
3.2. Hydrolysis
Melamine is hydrolyzed by mineral acid or inor-
ganic alkali. Hydrolysis proceeds stepwise, with
loss of one, two, or all three amino groups:
The product spectrum varies with tempera-
ture, 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 struc-
ture:
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
4 Melamine and Guanamines
Table 1. Industrially important melamine salts
Molecular formula Solubility (20

C), g per 100 g
H
2
O
M
r
mp,

C
C
3
N
6
H
6
H
3
PO
4
0.43 224.12 223
C
3
N
6
H
6
H
2
SO
4
0.19 350.33 380 *
C
3
N
6
H
6
HNO
3
0.68 189.14 298
*
C
3
N
6
H
6
C
17
H
35
COOH 0.17 410.42 154
C
3
N
6
H
6
HCOOH 1.56 172.16 250
(decomp.)
* Sublimes at 316

C.

Sublimes at 186

C.
important is the resinous material obtained from
the reaction of formaldehyde with melamine:
Me(NH
2
)
3
+6 CH
2
OMe[N(CH
2
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 ob-
served. The methylolmelamines are sparingly
soluble in most solvents and are very unsta-
ble due to further condensation or resinication,
e.g.,
MeNHCH
2
OH+H
2
NMe
MeNHCH
2
NHMe+H
2
O
2 MeNHCH
2
OH
MeNHCH
2
OCH
2
NHMe+H
2
O
Melamine formaldehyde condensation
products are characterized by good heat re-
sistance and superior water-resisting properties.
They are used, usually in combination with urea
formaldehyde resins, as glues in the wood-
working industry, as impregnating resins for
decorative laminates, and as a binder in mold-
ing materials containing a ller (e.g., cellulose
or sawdust). Methylolmelamines can be ether-
ied by heating with alcohol in the presence
of an acid catalyst. Industrially most important
are the products formed with methanol, n-bu-
tanol, 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. Production
Melamine can be synthesized from urea at 390
410

C:
6 H
2
NCONH
2
C
3
N
3
(NH
2
)
3
+6 NH
3
+3 CO
2
The overall reaction is endothermic, requir-
ing 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) pro-
cesses, and
2) catalytic, low-pressure processes (ca. 1 MPa).
Each type includes three stages:
synthesis
melamine recovery and purication
off-gas treatment
4.1. Low-Pressure Processes
Typical low-pressure processes utilize a u-
idized catalyst bed at pressures from atmo-
spheric to ca. 1 MPa and temperatures of 390
410

C. The uidizing gas is either pure am-
monia or the ammonia carbon dioxide mixture
formed during the course of the reaction. Cata-
lysts 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 reac-
tion gas (desublimation).
In the catalytic processes the rst reaction
step is decomposition of urea to isocyanic acid
Melamine and Guanamines 5
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 catalyti-
cally disproportionated into carbon dioxide and
cyanamide or carbodiimide, which then trimer-
izes 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 amme-
line, ammelide, and cyanuric acid. Ureidotri-
azine 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 deammo-
niation or hydrolysis occurs [20 29].
Worldwide, three low-pressure processes are
in commercial operation: the BASF process, the
Chemie Linz process, and the Stamicarbon pro-
cess.
4.1.1. BASF Process
The BASF process (see Fig. 1) is a one-
stage, low-pressure, catalytic vapor-phase pro-
cess. Molten urea is fed to the uidized catalytic
bed reactor (a) at 395 400

Cand atmospheric
pressure. Alumina is used as a catalyst, and u-
idization is accomplished with an NH
3
CO
2
mixture (the process off-gas).
The reactor temperature is held at ca. 395

C
by molten salt circulated through internal heat-
ing coils (b). The uidizing gas is also preheated
to 400

C. To secure an ammonia-rich atmo-
sphere 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 un-
reacted 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. Precipi-
tated melem, in the form of a ne powder, is re-
moved 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 countercur-
rently with recycled off-gas (140

C). The tem-
perature 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 with-
out 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 re-
cycled 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 decompositionof urea, the rst step
in melamine synthesis.
4.1.2. Chemie Linz Process
The Chemie Linz process (see Fig. 2) is a two-
stage process. In the rst step, molten urea is de-
composed 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 sup-
plied to the reactor by hot molten salt circulated
through internal heating coils. The gas stream
6 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) CO
2
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 fromthe quencher is fed to an ab-
sorber (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 ex-
ported. 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 cat-
alytic 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 sil-
ica alumina type, and melamine is recovered
from the reactor outlet gas by water quench and
recrystallization.
Melamine and Guanamines 7
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) Vacuumcrystallizer; 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 fedintothe lower part of the reac-
tor (b). The silica alumina catalyst is uidized
by preheated (150

C) ammonia, which enters
the reactor at two points: at the bottom of the re-
actor 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 recy-
cled mother liquor from the crystallization sec-
tion. The resulting melamine suspension is con-
centrated to ca. 35 wt %melamine in a hydrocy-
clone (h), after which it is fed to a desorption col-
umn (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 dis-
solves 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 u-
idizing 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 conden-
sate and uncondensed gas are then passed at 0.7
MPa to an absorption column (x). Liquid make-
up 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 dif-
fer 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 opera-
tion also lends itself to smaller reaction vessels,
but the highly corrosive nature of the systemdic-
8 Melamine and Guanamines
tates use of expensive, corrosion-resistant con-
struction materials such as titanium.
High-pressure reactions occur without cat-
alyst 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 conversiontomelamine. Suf-
cient residence time is providedinthe reactor to
ensure complete reaction, leading to melamine
with a purity > 94 %. Heat is supplied to the re-
actor 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 low-
pressure process.
4.2.1. Melamine Chemicals Process
Melamine Chemicals uses a continuous high-
pressure single-stage process that produces
melamine with a purity of ca. 96 99.5 %.
Molten urea is converted into melamine in a liq-
uid-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 pre-
heated by using it to scrub the reactor off-gas
stream. This scrubber performs various func-
tions, including (1) driving off any water that
may be present in the urea feed, (2) preheat-
ing 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

Cwith a heating-coil
system and pressurized to about 11 15 MPa.
Mixing is provided by heat convection and gen-
eration of gaseous reaction products.
Liquid melamine is separated from the off-
gas in a gas separator, the product being col-
lected at the bottom. The separator is held at
about the same temperature and pressure as the
reactor. The gaseous phase (ammonia and car-
bon 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 am-
monia to both cool and solidify melamine. This
is accomplished at a controlled temperature and
pressure to minimize formation of such impuri-
ties as melam and melem. Product is removed
from the pressurized cooling unit through a se-
ries of pressure-reducinghoppers. Dependingon
the required degree of purity, it may then be re-
crystallized [32].
The off-gas stream represents high-pres-
sure (> 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 systemcon-
sisting of concentric bayonet-type tubes.
Molten urea at 150

Cis fed to the reactor (a)
together with preheated ammonia. Average res-
idence time of the mixture in the reactor is about
20 min. As the reaction mixture leaves the reac-
tor, 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 car-
bon dioxide to precipitate melamine. The water-
saturated mixture of ammonia and carbon diox-
ide leaving the top of the quencher can be recy-
cled to a plant for urea or fertilizer production.
The aqueous melamine slurry remains in the
quencher at 160

Cfor 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 9
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 re-
moved. Off-gas from the stripper is dissolved in
water in an absorption column (d) and this solu-
tion is recycled to the quencher.
The ammonia- and carbon dioxide-free
melamine slurry leaving the bottom of the strip-
per is diluted with mother liquor to dissolve
melamine. Sodium hydroxide is also added, and
the solution is then claried with activated car-
bon (f). Melamine is crystallized from the clar-
ied solution in a crystallizer (g) operated adia-
batically under vacuum. Melamine crystals are
separated from the mother liquor in a rotary l-
ter (h), dried in a pneumatic conveyor dryer
(i), and stored.
4.2.3. Nissan Process
The Nissan melamine process (see Fig. 5) op-
erates at 10 MPa and 400

C. One characteris-
tic feature is urea washing of the reactor off-
gas. For this purpose, molten urea is also pres-
surized to 10 MPa and passed through a high-
pressure 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 by-
products 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
fromthe solution in an ammonia stripper (g) (op-
erated 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 crys-
tals are dried and crushed before storage.
Further treatment of the mother liquor starts
with an ammonia stripper (n), in which oxoami-
notriazines precipitate. The slurry from this am-
monia recovery tower is therefore alkalinized
before being fed to a third crystallizer (o) operat-
ing at reduced temperature and pressure. Addi-
tional melamine crystallizes here, and after sep-
aration from the liquid (p) it is returned to the
second crystallizer.
Lowering the pH of the mother liquor causes
oxoaminotriazines to precipitate; these are re-
moved 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) Steamdrum; e) Cushion vessel; f) Quencher; g) NH
3
-stripper; h) NH
3
-
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 ad-
ditional measurable criteria such as: content of
inorganic ash, moisture, and ammeline-related
compounds (alkali solubles); particle-size distri-
bution; 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 pro-
ducers.
6. Chemical Analysis
Melamine is difcult to characterize by tradi-
tional chemical methods. Purity specications
are usually based on differences obtained af-
ter subtracting determined impurity levels for
moisture, ash, and alkali solubles. Instrumental
analysis is possible using liquid chromatogra-
phy [33] and spectroscopic methods, although
melamine tends to formcomplexes with the pH-
control buffers used in liquid chromatography,
leading to variability in the UV absorption ob-
served at different pHs. Melamine can be precip-
itated for quantitative determination as the per-
chlorate 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 pow-
ders, it will pack and lump over extended storage
periods.
In the VDI guideline 2263 melamine is clas-
sied as having a burning index of 2, i.e., dur-
ing a re it ignites quickly but the ame is
rapidly extinguished. Flammability tests per-
formed in accordance with the EEC guideline
84/449 A 10 showed that a glowing platinum
wire (>1000

C) was not able to produce conti-
nous 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 Europe United States Japan
Laminates 47 35 6
Glue, adhesives 25 4 62
Molding compounds 9 9 16
Coatings 8 39 12
Paper, textiles 11 5 3
Other 8 1
Total 100 100 100
8. Uses
Most melamine is reacted with formaldehyde to
produce resins for laminating and adhesive ap-
plications [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 ma-
jor market for melamine.
Other uses include the preparation of
wet-strength resins for paper, water clarify-
ing resins, ion-exchange resins, plastic mold-
ing compounds, adhesives, re retardants in
polyurethane foams, and intumescent paints.
Important new applications are under develop-
ment in the eld of re retardants for polymeric
materials, especially polyurethane foams. Ap-
plications 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. Fromthe standpoint of acute
toxicity, melamine is not classied as a health
risk. The oral LD
50
for rats is > 5000 mg per
kilogramof bodyweight [35]. Melamine applied
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 BASF 42 000
Austria Chemie Linz 55 000
Netherlands DSM 90 000
Italy Ausind 28 000
France Norsolor 15 000
Western Europe 230 000
Poland Polimex Cekop 28 000
Rumania Romchim 12 000
Soviet Union Techmashimport 10 000
Eastern Europe 50 000
United States American Melamine
Ind.
50 000
Melamine Chem. 47 000
America 97 000
Japan Mitsubishi
Petrochemical
32 000
Mitsui Toatsu Chemical 38 000
Nissan Chemical 42 000
Korea Korea Fertilizer 16 000
Taiwan Taiwan Fertilizer 10 000
Saudi Arabia Safco 20 000
China Sichuan Chemical
Works
12 000
India Gujarat State Fertilizer 5 000
Middle and Far East 175 000
Total 552 000
Genetic Toxicity. Investigations into the po-
tential 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 conver-
sion) [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 melamine-
induced mutagenicity or damage to genetic ma-
terial 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 andCarcinogenicity. 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 kilogramof
body weight per day) over periods of 14 d, 90 d,
and 2 a. All studies led to changes in the kid-
ney (inammation, calcied concretions in the
proximal tubuli) and bladder (inammation, ul-
ceration, 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 toler-
ated 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 blad-
der stones are not expected to be carcinogenic.
Female rats in this study displayed neither blad-
der 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 treat-
ment (twice a week) with 10 nmol of a pro-
moter (12-O-tetradecanoylphorbol-13-acetate)
resulted in no increased incidence of tumor-
bearing animals.
Reproduction Toxicology. Astudy reported
by Thiersch on the reproduction toxicology
of melamine was published in 1957. Intraperi-
toneal 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 ma-
ternal 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 dis-
covery of other homologues. Weith recognized
in 1876 that this substance was in fact 2,4-di-
amino-6-methyl-1,3,5-triazine. The term gua-
namine has since been applied generally to
2,4-diamino-1,3,5-triazines substituted in the 6-
position 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], C
9
H
9
N
5
, M
r
187.20, and acetogua-
namine [542-02-9], C
4
H
7
N
5
, M
r
125.14 [49].
The physical properties of aceto-, benzo-, and
caprinoguanamine [5921-65-3], C
12
H
23
N
5
, M
r
237.35, are summarized in Table 4. Figure 6 il-
lustrates the most important reactions of aceto-
and 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
Acetoguanamine Benzoguanamine Caprinoguanamine
mp,

C 277 228 105 120
a
Solubility (at 20

C),
g/L, in
Water 11.2 0.3 insoluble
Acetone 1.04 18.0 25.2
Benzene 0.07 0.3 11.2
Dimethylformamide 0.88 120.0 67.0
a
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] in-
cluding 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, in-
volves the reactionof dicyandiamide (cyanogua-
nidine) with nitriles [60]:
14 Melamine and Guanamines
Use of dinitriles leads to bisguanamines. Re-
action 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 con-
centration of alkali. Aliphatic nitriles generally
react more slowly than aromatic nitriles. The re-
action 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 re-
action of acetoguanamine with formaldehyde.
Such resins display a high degree of water tol-
erance and can be cured thermally. The rate of
the condensation reaction is considerably less
dependent on pH than in the case of melamine.
Condensationmaybe carriedout inweaklybasic
or weakly acidic media. Compared to melamine
formaldehyde resins, the curing of acetogua-
namine resins occurs more slowly and at a more
acidic pH.
Acetoguanamine is normally used to mod-
ify 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 with-
out affecting surface hardness or thermal stabil-
ity [63]. Newer developments aim at reducing
the formaldehyde content of melamine ace-
toguanamine resins in order to avoid formalde-
hyde emissions after production [64]. Due to the
relativelyhighcost of acetoguanamine, mixtures
with other modifying agents, e.g., dicyandi-
amide have been applied, especially for short cy-
cle laminates on wood-based materials [65](see
also Wood). Partially alkoxylated acetogua-
namine formaldehyde resins have been pro-
posed for high-temperature bers with good
exibility [66]. Acetoguanamine cyanurate, ei-
ther 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 benzogua-
namine is in resins for industrial paints. Methy-
lolated benzoguanamine resins that have been
etheried with butanols are compatible with hy-
drocarbon solvents, oils, and various synthetic
resins (e.g., alkyd, polyester, epoxy [68] and
acrylic resins [69]). Uponcuring, these OHfunc-
tional resins react with the butoxymethyl groups
of the benzoguanamine resin to form new cross-
links, by splitting off butanol. In contrast to sim-
ilar melamine resins, benzoguanamine resins
give a lower cross-link density, and thus a higher
exibility and better surface quality. Typical ap-
plications are can coatings, coil coatings, and au-
tomotive basecoats. Benzoguanamine-carbox-
ylic acids have been proposed as cross-linkers
for water-borne coatings [70].
Due to its favorable physicochemical prop-
erties, tetra(methoxymethyl)benzoguanamine
[4588-69-6] has been proposed as a cross-linker
for powder coatings based on hydroxy poly-
esters [71, 72]. However, bubbles formed during
the elimination of methanol have limited its use
to date.
Fully condensed formaldehyde benzogua-
namine resins that mainly consist of methylene-
bridged 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 FR2-
type printed circuit boards [76]. In the same
way, it can be used as additive to urea form-
aldehyde foams [77] or bismaleimide copoly-
mer resins [78]. Both, acetoguanamine and ben-
zoguanamine 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 mi-
croelectronic encapsulation [79, 80]. By reac-
tionwith4,4-diaminodiphenyl ether, benzogua-
namine forms a bridged bisguanamine which
was proposed for resin applications [81].
Benzoguanamine can be used instead of di-
chlorophenyltriazine to produce Pigment Yel-
low 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 poly-
meric paraformaldehyde at low storage temper-
atures 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 ad-
ditive for melamine formaldehyde impregna-
tion 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 un-
saturated groups in the substituent R can
also be converted to polymers and copoly-
mers [86]. The compound CTU (bis-
3,9-cyanoethyl-2,4,8,10-tetraoxaspiro[5.5]-
undecan)-guanamine [22535-90-6] (formula
shown below) is employed (like benzogua-
namine) 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 ap-
plication in pharmacology as c-AMP specic
phosphodiesterase inhibitors [89], the most
prominent being Irsogladine maleate (2

,5

-Di-
chlorobenzoguanamine, [84504-69-8]).
11.3. Toxicology
The acute oral LD
50
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 LD
50
(rabbit) is > 2800 mg/kg [90]. All
three compounds are not irritating to skin and
eyes [91, 92]. Acetoguanamine and benzogua-
namine 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]. Benzogua-
namine was adoptedbythe Scientic Committee
on Food as a monomer for food contact mate-
rials in List 3 with a restriction of 5 mg/kg of
benzoguanamine in food [95]. The evaluation of
this substance under the OECD/HighProduction
Volume Programresulted in the conclusion, that
there is low priority for further work (no further
work recommended) [96].
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