Amino Resins 1

Amino Resins
Hans Diem, BASF Aktiengesellschaft, Ludwigshafen/Rh., Federal Republic of Germany
Günther Matthias, BASF Aktiengesellschaft, Ludwigshafen/Rh., Federal Republic of Germany

1. Introduction . . . . . . . . . . . . . . . 1 7.1.1. Pure Urea – Formaldehyde Resins . . 13

2. Physical Properties . . . . . . . . . . . 2 7.1.2. Mixed Condensates . . . . . . . . . . . 14
3. Chemical Properties . . . . . . . . . . 2 7.1.3. Condensation of Urea with Other
4. Raw Materials . . . . . . . . . . . . . . 3 Aldehydes . . . . . . . . . . . . . . . . . 14
5. Production . . . . . . . . . . . . . . . . 5 7.1.4. Resins from Urea Derivatives . . . . . 14
5.1. Principle Aspects . . . . . . . . . . . . 5 7.1.5. Modified Urea Resins . . . . . . . . . . 15
5.1.1. Hydroxymethylation . . . . . . . . . . . 6 7.2. Melamine Resins . . . . . . . . . . . . 17
5.1.2. Condensation . . . . . . . . . . . . . . . 6 7.2.1. Unmodified Melamine Resins . . . . . 17
5.1.3. Principal Components of an Amino 7.2.2. Modified Melamine Resins . . . . . . . 17
Resin Solution . . . . . . . . . . . . . . . 7 7.3. Urethane Resins . . . . . . . . . . . . . 18
5.2. Production Processes . . . . . . . . . . 7 7.4. Cyanamide and Dicyanodiamide
5.2.1. Batchwise Production . . . . . . . . . . 7 Resins . . . . . . . . . . . . . . . . . . . . 18
5.2.2. Continuous Production . . . . . . . . . 10 7.5. Sulfonamide Resins . . . . . . . . . . . 18
5.2.3. Production of Special Products and 7.6. Aniline Resins . . . . . . . . . . . . . . 19
Foams . . . . . . . . . . . . . . . . . . . . 11 8. Analysis . . . . . . . . . . . . . . . . . . 19
6. Environmental Protection . . . . . . 12 9. Storage and Shipment . . . . . . . . . 20
7. Types of Resins 10. Uses . . . . . . . . . . . . . . . . . . . . . 21
and Their Properties . . . . . . . . . . 13 11. Economic Aspects . . . . . . . . . . . . 26
7.1. Urea Resins (UF Resins) . . . . . . . 13 12. References . . . . . . . . . . . . . . . . . 27

1. Introduction by A. Butlerov in 1859. However, the first in-

vestigations of urea – formaldehyde (UF) resins
Amino resins are condensates formed when car- were not carried out until about 1880. The first
bonyl compounds react with compounds con- reaction products were reported by B. Tollens
taining amino, imino, or amide groups, liber- (1884) and C. Goldschmidt (1887), and the ba-
ating water. Before they have hardened, these sic chemistry of the amino resins was established
products consist principally of oligomers, which about 1908 [14].
are also called prepolymers. F. Pollack and K. Ripper (1921) synthe-
A very large number of carbonyl- and sized a clear transparent material, which they
nitrogen-containing compounds yield conden- called “Pollopas.” This product never became
sates of relatively low molecular weight. The commercially important, but it did give rise to
type of interaction is determined by the a number of experiments. The first commer-
functional groups. Among such compounds, cial products, manufactured by E. C. Rossiter
formaldehyde, urea, and melamine have become of British Cyanides Co. in 1924 and 1925, led
the most important, especially because of their to molding materials still in use today.
relatively low prices. These products are ob- The melamine resins were introduced in Ger-
tained by large-scale production in modern in- many by Henkel in 1935 [15]. Their properties
dustrial plants. The amino resins offer technical are similar to those of the urea – formaldehyde
advantages in many applications. resins, but the resins are of higher quality. For ex-
ample, they are chemically stable after the resin
History. The history of amino resins began has hardened and become insoluble.
with the synthesis of the two main raw mate- An ever-increasing number of mixtures of
rials, urea and formaldehyde; the former was urea – formaldehyde and melamine – formalde-
prepared by F. Wöhler in 1824, and the latter hyde resins are produced for the most diverse

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a02 115
2 Amino Resins

uses. Lower costs and the better performance of the color of the additive to a greater or lesser
the products made from these mixtures account extent.
for their popularity.
Amino resins find their major use as ad-
hesives. They are used in the production of 3. Chemical Properties
plywood, waferboard, strandboard, and particle
board. Other types are employed for the produc- Even when they are prepared from only two
tion of laminated beams and parquet flooring, components, the amino resins are mixtures of
and for furniture assembly. Amino resins are also various substances. For example, in the case
used to strengthen paper, to produce molding of urea – formaldehyde resins the major compo-
compounds and the flexible backing of carpets, nents of the mixture are various hydroxymethyl
as leather auxiliaries and soil conditioners, and compounds and oligomers composed of differ-
for protective surface coatings. ent combinations of basic units and substituted
basic units. These oligomers are of different
sizes. As an approximation, the basic unit can
2. Physical Properties be described as methylene – urea (1), which can
carry various substituents at the nitrogen atoms:
Amino resins are available commercially as con-
centrated solutions or solids, e.g. powders. The
solutions generally contain water as a solvent,
but in the surface-coating resins the solvents are
alcohols. The solutions range from colorless and
clear to milky and cloudy and are tacky to the
touch. Their viscosities are substantially higher Hence, it is not possible to attribute specific
than that of water, from 20 to 70000 mPa · s – chemical properties to these substances, as in the
in general from 200 to 2000 mPa · s – measured case of a pure compound.
at 20 ◦ C. The amino resins can be odorless or, However, some chemical properties are com-
depending on the content of free formaldehyde, mon to all or most amino resins.
have a more or less sharp odor. The densities of The chemical properties given below are im-
the solutions at the commercially available con- portant with regard to processing the resins. The
centrations of 55 – 80 % solids are from 1.23 to equations given for urea – formaldehyde also ap-
1.31 g/cm3 . An important property of the resins ply in principle to other reactants employed for
is the amount of water that can be added with- these classes of products.
out precipitating solids. At relatively low tem- – Formaldehyde is slowly split off from hy-
peratures, i.e., below about 20 ◦ C, pronounced droxymethyl compounds and undergoes ad-
cloudiness and an unusually large increase in dition reactions with other amino groups in
viscosity are observed in many cases. accordance with the equilibrium equation
Some resin solutions exhibit the phenomenon [19], [20]:
of pseudoplasticity (thixotropy), which may or
may not be desirable. Thixotropy means that H2 N–CO–NH2 + CH2 O
H2 N–CO–NH–CH2 OH
the viscosity decreases as the shearing force in-
creases [16], [17]. – Hydroxymethyl compounds undergo slow
In powder form amino resins are white. In the condensation in the absence of heat or
spray-dried, commercially available form they react with urea to give methylene com-
have a particle size generally of 15 – 70 µm, but pounds, such as methylene – diurea or meth-
always < 200 µm. This particle size is a result ylene – oligourea:
of the spray-drying process [18]. The bulk den-
H2 N–CO–NH–CH2 OH + H2 N–CO–NH2 −→
sity of the commercially available products is
0.5 – 0.8 kg/L. The powder resins dissolve in wa- H2 N–CO–NH–CH2 –NH–CO–NH2 + H2 O
ter to give milky liquids. Flourlike additives can
2 H2 N–CO–NH–CH2 OH −→
be mixed with some resins, which then assume
H2 N–CO–NH–CH2 –NH–CO–NH2 + CH2 O + H2 O
 Amino Resins 3

These reactions are responsible for the grad- Only formaldehyde is important in industrial
ual increase in viscosity that amino resins production. Other aldehydes are employed, but
undergo during storage [21]. these play a very minor role.
– It is assumed that bis-methylene – urea ethers The most important amine-containing com-
(2) are formed [13, p. 324], [20], [22], but ponents are urea and melamine, but thiourea,
amino resin solutions contain only small guanidine, cyanamide, and dicyanodiamide, and
amounts of these ethers. Under certain pro- to a lesser extent acid amides, guanamines, and
duction conditions cyclic ethers, so-called aniline, are employed also. Further components
urones (3), also occur. include the derivatives of these compounds, e.g.,
substituted ureas.
Relevant information on raw materials used
to produce amino resins can be found in [1,
pp. 3 – 85].
Products that are added in relatively small
amounts to effect slight but often important
changes in the properties are called modifiers.
These include alcohols, amines, aminoalcohols,
– Amino resin solutions generally are rendered and a very large variety of other organic and in-
slightly alkaline, i.e., pH 8 – 9, in order to sta- organic substances [1, pp. 7 – 122].
bilize them, but the pH slowly decreases as Finally, it should also be mentioned that in-
formic acid is formed. ert inorganic salts sometimes are added during
the production or processing of glue resins [8,
These reactions, especially condensation p. 34], [24], [25].
with the formation of methylene bridges, are
accelerated by acid catalysts and elevated tem- Formaldehyde, CH2 O, M r 30.03, [50-00-0]
peratures. Hence, in processing amino resins, (production and properties → Formaldehyde).
acids or acid-forming substances are impor- In the production of amino resins, formalde-
tant as hardeners that accelerate the con- hyde is used either in the form of solid
densation. Alkali-catalyzed condensation [13, paraformaldehyde, in aqueous solution, or as a
pp. 331 – 332], [23] is of no practical impor- urea – formaldehyde precondensate containing
tance. from 4 to 5 mol of formaldehyde per mole of
The hydroxymethyl groups can be converted urea. Paraformaldehyde is a mixture of hydrated
with alcohols to the corresponding ethers. This polyoxymethylene molecules, with a degree of
reaction is utilized in surface-coating resins and polymerization of 6 – 100 units. The melting
to a lesser extent in glues for particle board and point ranges from 120 to 170 ◦ C, depending on
in textile and paper auxiliaries. the molecular mass.
The free formaldehyde, which is present in
concentrations of from 0.1 % to about 2 %, HO – [CH2 O]n – H n = 6 – 100
is of practical importance in many cases be-
cause it reacts with ammonium salts of acids to The most frequently used commercial form
give hexamethylenetetramine and the free acid, is a 30 – 55 % aqueous solution of formalde-
which acts as a hardener. hyde. These solutions are clear, caustic, and in-
Resin powders also condense over time to flammable, have a sharp odor, and are infinitely
give relatively high molecular mass products, miscible with water. Formaldehyde is present in
but in this case the reaction is slower by a factor aqueous solutions predominantly as the hydrate
of at least five. (HO–CH2 –OH), which is in equilibrium with its
oligomers:

n CH2 (OH)2
HO(CH2 O)n H + (n − 1) H2 O

4. Raw Materials
Depending on the method of production, the so-
The principal carbonyl component is formalde- lutions are contaminated with a few hundredths
hyde, but furfural and glyoxal are employed also. of a percent of formic acid and from 0.5 to 2 % of
4 Amino Resins

methanol. The content of formic acid and meth- the production method, the solutions contain
anol increases during storage, as a result of the 0.1 – 0.2 % acid constituents. The color number
Cannizzaro reaction: should have a maximum value of 15 (APHA).
Glyoxal is hydrated in the aqueous solution.
2 CH2 O + H2 O −→ HCOOH + CH3 OH
Urea [57-13-6], carbamide, diamide of car-
Moreover, on long-term storage at low tempera- bonic acid, H2 NCONH2 , M r 60.06 (→ Urea).
tures, paraformaldehyde separates as a hazy sus- Urea is available commercially as a white
pension or a precipitate. This process is retarded crystalline product or as prills. For amino resin
by the addition of stabilizers, e.g., up to 12 % of production, a technical-grade product is usually
methanol or triazine derivatives. adequate.
Depending on the concentration and It should be noted that fertilizer urea fre-
the methanol content, the flash point is quently is contaminated with ammonium salts,
about 60 – 85 ◦ C. The regulations governing and these may act as hardeners and cause the
flammable liquids do not apply to aqueous glue mixture to solidify even in the production
formaldehyde solutions. stage. Furthermore, the prilled urea can be mixed
Formaldehyde solutions can be stored and with sulfur or formaldehyde to keep it free flow-
transported in containers made of stainless ing. Sulfur-coated urea is not recommended for
steel, aluminum, polyester resin, or appropri- resin production. The formaldehyde forms insol-
ately lined iron. uble condensates on the surface of the prills, and
Finally, aqueous solutions of urea – form- these condensates can lead to a slight cloudiness
aldehyde precondensates also are employed. when the prills are dissolved.
Commercially available solutions contain from The dissolution of urea in water is an en-
70 to 80 % of the active ingredients, cal- dothermic process. The enthalpy of solution
culated as urea and formaldehyde. The mo- (∆H) is + 257.5 J/g, measured at 10 ◦ C in a 20-
lar ratio of formaldehyde to urea ranges from fold amount of water.
4 : 1 to 5 : 1, and the mass ratio is therefore In the production of amino resins, urea is
2 : 1 to 2.5 : 1. These solutions are substan- employed in solid form, in solution, or as a
tially more resistant to polymer precipitation urea – formaldehyde precondensate.
than are pure formaldehyde solutions. In the
urea – formaldehyde precondensates, the major
Thiourea [62-56-6], thiocarbamide,
part of the formaldehyde is present in the form
NH2 CSNH2 , M r 76.12 (→ Thiourea).
of urea – hydroxymethyl compounds, a smaller
Thiourea is a relatively expensive raw mate-
part as formaldehyde or its oligomers in the hy-
rial and is therefore not very important indus-
drated form, and a very small part as conden-
trially. Apart from its use in special products, it
sates. In this last case, the urea molecules are
serves only as a modifier, for example, in im-
linked mainly via methylene bridges.
pregnating resins. Thiourea improves the resin
Biologic Effect. The maximum allowable con-
properties, e.g., hardness, surface gloss, and wa-
centration (MAK value) recommended by the
ter resistance.
Senate Committee of the Deutsche Forschungs-
The melting point of thiourea is 180 ◦ C. Its
gemeinschaft (German Research Organization)
solubility in water is 9 % at 100 ◦ C, substantially
in the Federal Republic of Germany is 1 ppm.
lower than that of urea.
The corresponding values for the United States
of America (given by OSHA) and Japan are
Substituted Ureas. Cyclic ethylene ureas
3 ppm and 2 ppm, respectively. At present,
and propylene ureas (2-oxoimidazolidine and
regulations vary from country to country
2-oxohexahydropyrimidine) are employed for
(→ Formaldehyde, Chap. 10.).
the preparation of textile auxiliaries. Because of
their high price and their limited ability to form
Other Aldehydes. Other aldehydes play a
condensates, they are not used in large amounts
minor role. Glyoxal [107-22-2] is available com-
for any other purposes.
mercially in the form of 30 – 40 % aqueous so-
lutions. The purity is 97 – 99 %. Depending on
 Amino Resins 5

Melamine [108-78-1], 2,4,6-triamino- Further condensation leads to longer chains of

1,3,5-triazine, cyanurotriamide, M r 126.13 the basic unit
(→ Melamine and Guanamines). Melamine (4)
is a white powder that sublimes on heating.
The particle diameter depends on the produc-
tion process and varies from 5 to 300 µm. The Hydroxymethylation is carried out in a
rate of solubility in formaldehyde solutions de- slightly alkaline or slightly acidic medium,
pends on the particle size and is an important whereas the condensation requires a more
parameter given in the information leaflets of strongly acidic solution. The process for the pro-
melamine producers. The color number of a duction of the resin is continued until the re-
50 % melamine – formaldehyde solution may sulting product is an oligomeric mixture that is
not exceed 20 (APHA). This is important with still soluble or fusible. It is protected against fur-
respect to raw materials for surface coatings and ther condensation by rendering the medium al-
to impregnating resins. kaline. Condensation of the resin by means of
Melamine derivatives, e.g., benzoguanamine acid catalysis, i.e., cross-linking to give a sub-
(5), are employed as modifiers. stantially infusible product, is not carried out un-
til the resin is put to use. This process is called
curing. However, free hydroxymethyl groups are
present even in this state.
The monomolecular and hydroxymethyl
compounds with low degrees of polymerization
and up to six urea – formaldehyde units are virtu-
ally all known and can be prepared in pure form
Modifiers. A very large number of additives [1, p. 20]. Aqueous solutions of the oligomers
from all areas of organic and inorganic chem- with low degrees of polymerization do not have
istry have been used to modify amino resins; a sufficiently long shelf life. Only when the con-
most of these additives are no longer impor- centrations of hydroxymethyl and NH2 groups
tant [1, pp. 107 – 122]. Aliphatic alcohols, sug- are reduced by partial condensation or when the
ars, polysaccharides, and caprolactam are addi- products are present in solid form do they pos-
tives for special purposes and are still used today. sess an industrially useful shelf life, i.e., several
weeks or more.
Condensations carried out in an excess of an
5. Production alcohol, such as methanol or butanol, with the
addition of acid and removal of water as nec-
essary, produce curable etherified amino resins.
5.1. Principle Aspects These are soluble in nonaqueous solvents and
can be mixed with alkyd resins, epoxy resins,
Amino resin production consists of two
etc. They are used as starting materials in the
stages: hydroxymethylation and condensation.
production of surface coatings.
Depending on the reaction conditions, hy-
Resin glues based on urea, melamine, or both
droxymethylation is accompanied to a greater
have been subjected to partial etherification to
or lesser extent by condensation. The following
stabilize them against further condensation [26–
equations illustrate the process in a simple case,
28].
for example, for formaldehyde plus urea:
Preventing the resins from solidifying during
Hydroxymethylation:
the production process and selectively achieving
certain properties – such as long shelf life, low
NH2 CONH2 + 2 CH2 O
HOCH2 –NHCONH–CH2 OH
formaldehyde content, strength, and resistance
Condensation: to swelling of particle board after curing – are the
basic difficulties encountered. Frequently, novel
HOCH2 –NHCONH–CH2 OH + NH2 CONH2 −→ properties are required on short notice by the
HOCH2 –NHCONH–CH2 –NHCONH2 + H2 O market.
6 Amino Resins

5.1.1. Hydroxymethylation 5.1.2. Condensation

Hydroxymethylation can be carried out using The condensation is catalyzed by acids. Cataly-
either alkaline or acid catalysis, but the for- sis by strong alkalis has been described also, but
mer is faster. The reaction mechanisms in acidic the resulting amino resins are not important in-
and alkaline media differ. In acids, condensa- dustrially [23]. The condensation can take place
tion takes place at the same time. Hence, hy- by the following routes:
droxymethylation is carried out industrially in
an alkaline or slightly acidic solution.
In hydroxymethylation, a semiaminal bond is
formed:

This is cleaved readily, and hy-

droxymethylation reactions are reversible and Although the presence of methylene com-
establish an equilibrium [32]. Although mono-, pounds in amino resins can be established unam-
di-, and trihydroxymethylurea are formed and biguously by means of 13 C NMR, bis(ureameth-
isolated easily, tetrahydroxymethylurea is virtu- ylene) ethers can be detected only by an indirect
ally nonexistent in aqueous solution. The com- procedure [31]. Carbon-13 NMR spectroscopy
plete hydroxymethylation of all amino groups permits the elucidation of many of the structures
to form hexahydroxymethylmelamine can be but does not distinguish between the C atoms
carried out readily. The hydroxymethylation of shown in boldface in (6) and (7), although their
urea is slightly exothermic: third nearest neighbors are different.

H2 N-CO-NH2 + CH2 O
H2 N-CO-NH-CH2 OH

∆H = - 23 kJ/mol
This problem also occurs in the case of
The ∆H data given in the literature fluctuate melamine resins [33].
about this value by ± 5 kJ/mol. The enthalpy of The methylene bonds between two urea
hydroxymethylation of melamine, relative to the molecules are very stable and can be hydrolyzed
amount of formaldehyde, is − 15 kJ/mol [29], only by strong acids at elevated temperatures
[30]. (see Chap. 8). The condensation reaction is
Reaction rates have been measured fre- slightly exothermic; the enthalpy is − 28 kJ/mol
quently, but they are sensitive to many parame- [29]. The stability of the methylene-ether bond
ters [19], [29]. is between that of the hydroxymethyl bond and
Industrial processes produce variable mix- that of the methylene bond.
tures of oligomers with mixed repeat units, It is impossible to give a single reac-
so the overall reaction rate is also variable tion rate for the condensation process because
and cannot be defined. Moreover, the im- there are many different starting materials (hy-
portant resin properties have not been cor- droxymethyl compounds) and many end prod-
related with the individual reaction rates. In ucts (methylene compounds).
general, the hydroxymethylation rate increases The type of solvent also has an effect on the
with increased concentration, temperature, and condensation rate [34]. The dependence of the
pH. Substituents also have an effect; adjacent reactivity of hydroxymethyl compounds on the
electron-withdrawing groups reduce the reac- chemical composition of the amino compounds
tion rate, as do bulky substituents. can be interpreted on the basis of several quali-
tative rules [35].
 Amino Resins 7

5.1.3. Principal Components of an Amino number of parameters, the reaction must be con-
Resin Solution trolled carefully. Important reaction parameters
are:
It is possible to identify the most important struc-
1) purity or composition of the starting materi-
tural moieties of the oligomers in amino resin
als
solutions by means of 1 H and 13 C NMR spec-
2) molar ratio in each of the reaction stages
troscopy [22], [31], [36].
3) type and amount of modifier
4) reactant concentrations
5) the pH value at each stage of the reaction
6) temperature at each stage of the reaction
7) type and concentration of catalyst
8) amount of buffer salt
9) reaction time in each stage
The hydrates of the formaldehyde oligomers
HO(CH2 O)n H, where n is about 5, can be de- The large number of reaction parameters and
tected along with the following hydroxymethyl resultant adaptations of the process lead to a very
structures: extensive body of relevant literature, particularly
Ethers, such as hydroxymethyl methyl ether, patent literature. Only the important processes
also can be identified in the spectrum by distin- are described here, but a comprehensive review
guishing the C atoms of the parent alcohol. can be found in [1, pp. 101 – 105].
Finally, the structures (8) and (9) and ring
compounds, including cyclic ethers of the urone
type, also appear. 5.2.1. Batchwise Production

The batchwise procedure is the most widely used

method for the industrial production of amino
resins, but it has the disadvantage of a rela-
tively small production capacity. Nevertheless,
this process permits an extensive variety of prod-
In a typical particle board glue, the 13 C NMR ucts and frequent changes of product.
spectrum might show, for example, the follow- The reactions are carried out in stirred ket-
ing distribution of the carbon atoms of the orig- tles, in two or more stages, at 70 – 100 ◦ C. In
inal formaldehyde (mole fractions): the first stage, which is carried out in a slightly
acidic to alkaline solution, the principal reaction
formaldehyde 0.03 is hydroxymethylation. In subsequent stages, the
hydroxymethyl compounds 0.72 condensation is carried out, water is split off, and
methylene compounds 0.15 higher molecular weight products of increasing
cyclic compounds 0.10 viscosity are obtained. The duration of the con-
densation depends on the properties desired in
the product. In general, the products are concen-
trated to 60 – 70 % aqueous solutions by evapo-
5.2. Production Processes ration. The starting materials, urea or melamine,
are employed in powder form. Urea also can
Amino resins usually are prepared in 5 – 20 m3
be used in solution. Formaldehyde is employed
batches. However, continuous processes are em-
as a 37 – 55 % aqueous solution. In a few spe-
ployed also, particularly for the production of
cial cases, formaldehyde is used in the solid
resin glues. The patent literature describes pro-
form, paraformaldehyde. Finally, it is possible
cesses where a particular stage is operated con-
to employ urea – formaldehyde precondensates
tinuously while other stages are operated batch-
in concentrations of not more than 80 % by mass
wise.
of the active ingredients.
Because the reaction rate and the composi-
Figure 1 shows a diagram of a plant for the
tion of the end product are influenced by a large
batchwise production of aqueous solutions.
8 Amino Resins

Figure 1. Plant for the batchwise production of aqueous amino resin solutions
a) Stirred kettle; b) Raw material feed; c) Reflux condenser; d) Temporary container; e) Pump; f) Vaporizer; g) Container for
finished product; h) Condenser; i) Vacuum pump; k) Vessel for condensed vapors; l) Cooler

Aqueous Solutions. The reactor consists of into 158 parts of a 40 % formaldehyde solution
a kettle equipped with heating and cooling de- that has been rendered neutral. The mixture is
vices, a stirrer, inlets for feeding in the raw ma- kept at 80 ◦ C for 10 min, during which time hy-
terials and for measuring devices, a valve at the droxymethylation takes place. The pH is then
bottom for emptying the kettle, and a manhole brought to 4 – 5 by adding a 10 % formic acid
for cleaning. solution. The condensation causes the tempera-
The material used is mainly stainless steel, ture to rise to 97 – 100 ◦ C within a few minutes.
material No. St. 1.4541 or St. 1.4571. Internal This temperature is maintained for about 30 min
coils or external, welded-on, semicircular pipes or until a mixture of 1 part of reaction solution
provide for heating with steam or cooling with and 5 parts of water gives a white precipitate at
cold water. Stirring is carried out by means of a 15 ◦ C (sharp endpoint). The reaction mixture is
powerful unit consisting of disk or anchor stir- then brought to pH 7 with a 25 % sodium hydrox-
rers. Nozzles are welded on in order to meter in ide solution. This terminates the condensation.
the raw materials and to permit measurement of A further 16 parts (by mass) of urea are then
the temperature and pH. added, so that the molar ratio of formaldehyde
When the condensation is complete, the prod- to urea in the end product is 1.65. The resulting
uct is evaporated. This is carried out in the stirred solution has a solids content of 51 %. The resin
kettle, or more economically in a single- or mul- solution is evaporated under reduced pressure to
tistage tubular vaporizer, with the pressure re- the commercial concentration of 66 %.
duced to protect the resin. The quality of the This 66 % solution of amino resin forms
resin is then compared to its specifications and a milky solution and has a viscosity of
it is discharged into a storage container. about 500 mPa · s (at 20 ◦ C) and a density of
The product tanks and the pipelines can be 1.290 g/cm3 .
of aluminum or steel because the medium is A typical resin for the impregnation of paper
slightly alkaline. It is advantageous to provide webs used in producing decorative laminates can
lined iron tanks. be made as follows [12, p. 258]:
A typical, simple resin glue for particle board 126 parts (by mass) of melamine are intro-
production is made as follows [37], [38]: 60 duced into a stirred solution of 120 parts of a
parts (by mass) of solid urea are introduced 40 % formaldehyde solution and 70 parts of
 Amino Resins 9

Figure 2. Plant for the production of amino resin powders by spray drying [18, p. 501]
a) Starting material feed; b) Stirred kettle; c) Reflux condenser; d) Temporary container; e) Pump; f) Spray drier; g) Blower;
h) Air heater; i) Filter; j) Mixing bin; k) Vibrating sieve

water at room temperature. The reaction mix- a tower and in cyclone separators or filters. It
ture is brought to pH 9 by adding aqueous passes via a vibrating sieve into a mixing bin
sodium hydroxide solution and is then heated and then pours into sacks or drums.
very rapidly, i.e., in 20 – 30 min for an industrial-
scale mixture, to a temperature of 100 ◦ C. After Etherified Products Containing Solvent.
the melamine has dissolved, a process that takes Products of this type, which are used as starting
place exothermally, sodium hydroxide solution materials for making surface coatings, can be
is added continuously to keep the pH value of produced in a reactor like that described in the
the reaction mixture at 8.5 – 8.8 throughout the production of aqueous solutions of amino resins
condensation. Condensation is carried out, with (Fig. 3). The reactor must be equipped with a
gentle refluxing and stirring, until the reaction sufficiently large heat exchanger to vaporize the
mixture is compatible with water when mixed mixture of water and excess alcohol, e.g., bu-
in the ratio 1 : 1.5. This is the case when a sam- tanol. Downstream from the heat exchanger is
ple of the reaction mixture exhibits slight cloudi- a water separator. The separated aqueous phase
ness when water, at 1.5 times the amount of so- still contains from 1 to 2 % formaldehyde and
lution, is added at 20 ◦ C. The reaction solution 20 % alcohol and therefore must be worked up.
is then cooled rapidly and brought to pH 9.5 – 10 At the appropriate alcohol content, this solvent
at room temperature by the addition of sodium phase is recycled to the production process.
hydroxide solution. The resultant impregnating A butylated melamine – formaldehyde resin
resin solution has a solids content of about 55 % for surface coatings can be produced in the fol-
and is usually clear. lowing way [11, p. 69]:
60 parts (by mass) of melamine, 60 parts (by
Amino Resin Powders. In the production mass) of formaldehyde (calculated at 100 %)
of amino resin powders, an aqueous resin so- in the form of a 40 % aqueous solution, and
lution is first produced (Fig. 2) and then fed into 220 parts (by mass) of butanol are refluxed for
a spray drier, where it is atomized by a spray 30 min in a stirred kettle equipped for heating.
disk or nozzle. The resultant droplets are dried Distillation is then carried out until water no
in the stream of hot gas produced by heating air longer evaporates. Then a further 20 – 25 parts
indirectly in a heat exchanger or by mixing hot (by mass) of anhydrous butanol are distilled.
exhaust gas with air. The powder is collected in
10 Amino Resins

The mixture is cooled, the resin content is de- the differences include variations in the tem-
termined, and the concentration is then brought perature, pH, concentration, or modifiers. The
to 50 % with butanol. process and product flow otherwise remain un-
changed. In many cases the publications only de-
scribe laboratory- or pilot-scale plants that have
5.2.2. Continuous Production not been scaled up for industrial use. Of the con-
tinuous processes that have been described, only
The continuous industrial production of amino those with basic differences in type are discussed
resins was begun in order to meet rising demand. here.
The disadvantages of continuous production are
that the amount produced per unit time in a par- Aqueous Solutions. The apparatuses em-
ticular plant can vary only within relatively nar- ployed for the continuous production of aqueous
row limits because prolonged residence under amino resin solutions are tube reactors, stirred
otherwise constant conditions increases the pro- kettle cascades, or combinations of the two. The
portion of molecules with high degrees of con- danger of incrustation by highly condensed, in-
densation. Changing product is not simple ei- soluble products is greater in the continuous pro-
ther. If the plant is not cleaned out beforehand, cess than in the batch process. In the latter, the
a product having a composition between the old residues are dissolved by fresh resin solutions;
product and the new will be formed for a time. this is not the case in the continuous process be-
For this reason, the continuous production pro- cause very little backmixing occurs.
cess is employed where the variety of products A continuous two-reactor process was de-
is restricted to a relatively narrow range. On the scribed by the Girdler Corp., United States of
other hand, continuous procedures give a very America, in 1943 [39]. The reactants were mixed
uniform product quality. thoroughly in the first reactor and heated to about
150 ◦ C under pressure. In the second stage, the
solution under pressure was maintained at this
temperature and condensation was carried out.
The pressure of the reactor was then released,
with the result that volatile constituents, espe-
cially water, escaped from the resin and the so-
lution cooled.
According to a 1949 patent granted to Sher-
wood Paints, UK, the reaction is carried out in a
packed column [40] and water vapor is expelled
by means of a countercurrent gas stream.
A process of Allied Chemical Corp., United
States of America (1951), operates in a simi-
lar manner and employs a tubular coil as the
reactor [41]. The resin solution is subsequently
evaporated. Another process of Allied Chemi-
cal Corp. is carried out under pressure, using
injected steam (1952) [42].
According to an application by Spumalit-
Anstalt, Liechtenstein, the starting materials
Figure 3.Plant for the batchwise production of etherified are passed over a solid catalyst (polycar-
amino resins bamide resin) under a pressure of 400 kPa at
a) Raw material feed; b) Stirred kettle; c) Condenser; d) Vac-
uum pump; e) Separating vessel (water separator); f) Prod-
140 – 150 ◦ C to form the resin [43].
uct vessel; g) Pump A process of Rütgerswerke, Germany, from
1955 also uses a fixed-bed catalyst, an ion ex-
The patent literature describes a large number changer [44]. The resins obtained are used as
of continuous processes. They differ only in pro- starting materials for making molding com-
cess technology for the product flow. In general, pounds.
 Amino Resins 11

A Swedish application by Skanska Attifab- Konzentrat 244 fl. or 255 fl. (BASF), Formurea

riken AB from 1955 describes a process in which 80 (Montedison), and Saruform 80 (Chemische
starting materials are heated separately and then Werke Saar Lothringen).
sprayed into a chamber to undergo partial con- Stamicarbon [53] and American Cyanamid
densation [45]; the reaction is completed in an- [54] have described the continuous production
other chamber. The advantage claimed is that of concentrated, formaldehyde-rich melamine –
none of the final products participates in the ini- formaldehyde solutions. These too can be used
tial stages of the condensation. as starting materials for amino resins.
An application by Du Pont, United States
of America, in 1956, describes a con- Resins in Powdered Form. Resins in pow-
tinuous process for producing etherified dered form also can be produced by a continu-
formaldehyde – urea resins [46]. The stepwise ous procedure if the spray solutions, which in
reaction takes place in a cascade of two to four general are produced batchwise, are fed contin-
stirred kettles. The free alcohols (e.g., butanol, uously from a temporary container into a spray
isobutanol, and others) are distilled in the last tower [18].
stage, and some of them are recycled.
In a Meissner process from 1966, the hy-
droxymethylation stage is carried out continu- 5.2.3. Production of Special Products and
ously and the subsequent condensation stage is Foams
operated batchwise [47]. The continuously flow-
ing product stream from the first stage passes In addition to impregnating resins, special prod-
through a stirred kettle, which is one of a large ucts include foamed resins and resins for pa-
number of kettles, so that the product flow need per auxiliaries, label adhesives, concrete lique-
not be interrupted. fiers, leather auxiliaries, carpet coatings, micro-
Other continuous processes have been capsules, etc. Because of the relatively small in-
worked out by Rheinpreussen AG [48] and the dividual amounts and the large variety of prod-
St. Regis Paper Co. [49], but these processes ucts, these resins are produced virtually always
predominantly relate to phenoplasts. in batches. The principle of the production is the
A BASF process (1971) is shown diagram- same as that for the manufacture of resin glues.
matically in Figure 4 [50]. The reaction is car- The proprietary know-how relates to modifiers
ried out in a series of three or more stirred kettles. and small but important variations in the manner
At the beginning of the cascade predominantly in which the process is carried out.
hydroxymethylation takes place. Condensation The foamed resins (→ Foamed Plastics) are
occurs later in the cascade. The reaction is ter- an interesting type of amino resin. They are
minated in the last section by the addition of used to produce solid foams, which have a wide
sodium hydroxide solution. The resin solution variety of applications. The productions of the
passes into a temporary container and is sub- foamed resin solution and the end product, i.e.,
sequently evaporated under reduced pressure in the foam, are discussed together.
a single- or multi-stage vaporizer. The vapors, In 1927, E. C. Bayer discovered that porous,
containing about 2 % formaldehyde, are worked heat-insulating materials are obtained if a foam
up and the effluent is discharged for treatment. or a foam-forming substance is added to a glue
The end product is cooled and pumped into a solution and the mixture is foamed and allowed
tank. to harden. In 1933, a process for the production
Other cascade processes have been described of a foamed urea formaldehyde resin was devel-
in applications of SIR, Milano, Italy, (1972) [51] oped by I. G. Farbenindustrie. In this process, a
and Montedison (1980) [52]. foaming agent and air were used to produce a
Finally, mention should be made of the pro- primary foam that itself contained the acid, e.g.,
cess in which formaldehyde is absorbed directly phosphoric acid, for curing the amino resin. Cur-
in urea solutions to produce highly concentrated, ing begins after a few seconds and is complete
formaldehyde-rich solutions that are used as after 12 – 24 h at room temperature. After dry-
starting materials for glue resins. Examples of ing, the foamed urea formaldehyde resins have
conventional commercial products are Kaurit-
12 Amino Resins

Figure 4. Plant for the continuous production of aqueous amino resin solutions [50]
a) Starting material feeds; b) Stirred kettle; c) Reflux condenser; d) Flare; e) Temporary container; f) Pump; g) Vaporizer;
h) Product container; i) Cooler; k) Condenser; l) Vacuum pump; m) Container for condensed vapors

bulk densities of 5 – 70 kg/m3 . More than 60 % Regulations or recommendations concerning

of the foam is in the form of open cells. concentration of formaldehyde in rooms are:
Whereas UF foams previously could be
Denmark 0.15 mg/m3
prepared only in factories of fixed location,
Finland 0.15 mg/m3
W. Bauer in 1953 described a transportable ap-
Italy 0.12 mg/m3
paratus that permitted on-site production of the
Netherland 0.12 mg/m3
foam by means of compressed air [55]. A num-
Sweden 0.48 mg/m3
ber of other apparatuses subsequently were de-
Switzerland 0.24 mg/m3
veloped. The state of the art is reported in [56]
Germany 0.10 mg/m3
with respect to the design of foam-producing ap-
paratus and a novel high-performance apparatus
of this type is described. The development of Effluents [57]. The condensed vapors or ef-
foam-producing apparatuses led to much wider fluents from amino resin production may not
applications: soil conditioning in agriculture, be introduced into water without biologic treat-
heat insulation, sound insulation, filling of min- ment. It should be further ensured that these ef-
ing cavities, carrier material for cleaning fluids, fluents cannot penetrate into ground water.
and covering for landfills. Waste waters or partially hardened residues
inevitably result when machines and contain-
ers are cleaned. The amount of wash water or
solvent should be kept as small as possible. If
6. Environmental Protection the waste water contains predominantly urea or
All necessary measures possible, according to formaldehyde, it can be reused in the production
the state of the particular art, must be taken process. Otherwise, it is eliminated, for example,
during the production and processing of amino by incineration.
resins to avoid air and water pollution. Regula- The biologic treatment of industrial effluents
tions constantly become more stringent. from amino resin production is carried out pri-
 Amino Resins 13

marily because of the formaldehyde, which is process of condensation and the structural com-
toxic. The usual effluents contain formaldehyde position had long been impossible because of the
in concentrations that can be degraded readily by lack of suitable analytical methods. Industrial
bacteria, which are always present. In general, development took place largely on an empirical
a critical factor in the biologic treatment of any basis. However, using a combination of ana-
effluent is the concentration in which the various lytical methods, e.g., 1 H NMR spectroscopy,
13
toxic components are present. C NMR spectroscopy, C, H, N, O elemen-
tary analysis, determination of hydroxymethyl
Air. The treatment of waste gas by wash- groups, and determination of total formalde-
ing with water, catalytic combustion, or thermal hyde, it is possible in principle to determine the
combustion is used in industry. The waste gases structural units and their concentrations [22].
should be very concentrated to minimize treat- However, the relationship between the technical
ment costs. properties of the amino resins or the materials
produced from these resins and the distribution
Solid Wastes. Amino resins can be solidified of the structural units is still unclear in most
by hardening them with ammonium chloride or cases, so development is still largely empirical.
phosphoric acid, or they can be absorbed in saw-
dust or sand. In this form, they may be deposited
in a landfill in accordance with the relevant pro- 7.1.1. Pure Urea – Formaldehyde Resins
visos and legal requirements.
Important macroscopic parameters are the molar
ratio of formaldehyde to urea, the viscosity, and
the gelling time. Urea – formaldehyde conden-
7. Types of Resins and Their sates having a molar formaldehyde : urea ratio of
Properties 1 usually give insoluble polymethylene – ureas
that do not possess any adhesive properties. If,
In addition to the simple types of however, the molar ratio is reduced from a rel-
resin that are produced in the largest atively high value gradually or stepwise in the
amounts, i.e., the urea – formaldehyde and course of the reaction, the resultant resin pos-
melamine – formaldehyde resins, other types sesses adhesive properties. These properties im-
of resin with different properties have been prove as the molar ratio increases, but the un-
developed. These are modifications, i.e., ver- desirable release of formaldehyde increases si-
sions of a resin obtained by use of relatively multaneously.
small amounts of additive or by changing the The highly viscous resin solutions obtainable
aldehyde or amino component. However, even by prolonged industrial condensation of urea
where the composition is fixed the resin type can and formaldehyde are low molecular mass prod-
be varied by changing the reaction procedure. ucts. They contain about six to eight urea units,
This leads to different distributions of oligomers as can be determined by gel chromatographic
or to different substitutions of the repeat units. [21] and cryoscopic measurements and by end-
The distribution of hydroxymethyl groups is the group determinations. This also applies to the
determining feature. completely insoluble powdered or glassy con-
densates [58]. During storage, the concentra-
tion of methylene groups increases at the ex-
7.1. Urea Resins (UF Resins) pense of the hydroxymethyl groups. The vis-
cosity also increases, initially slowly and vir-
All the urea – formaldehyde condensates tually linearly, and then, after a critical time,
[9011-05-6] containing the repeat unit 1 (see rather steeply. Some or all of the hydroxymethyl
Chap. 3), from monomolecular product to high groups generally can be blocked by etherifica-
molecular weight ones, are useful substances. tion, and the shelf life of the amino resin is thus
In the past few years, a number of discoveries extended [27], [59], [60]. In principle the same
have been made concerning the composition of reactions take place when the resin is hardened
UF resins. Systematic investigations into the by the user, but they are substantially more rapid.
14 Amino Resins

However, a residual amount of hydroxymethyl 7.1.3. Condensation of Urea with Other

groups remains after hardening [21]. Because Aldehydes
they are susceptible to hydrolysis, even the cured
urea resins are more water sensitive than the Condensation of urea with isobutyraldehyde,
melamine or phenol resins. acetaldehyde, or crotonaldehyde is carried out
The gelling time [11, p. 174] or reactivity industrially to obtain sparingly soluble nitro-
of the resin is an important parameter for the gen fertilizers, i.e., controlled release fertilizers,
user. This time can be determined relatively pre- rather than resins [63], [64]. The condensation
cisely, and is the time in which the resin changes of urea or melamine with glyoxal gives prod-
from a fluid to a virtually immobile solid fol- ucts that can be employed as textile auxiliaries.
lowing the addition of a certain amount of hard- Products obtained by the subsequent condensa-
ener at a particular temperature. The reactivity tion of UF resins with glyoxal (e.g., DMDHEU
increases with increasing molar ratio, content [1854-26-8]) also are used for textile finishing
of hydroxymethyl groups, and content of free [65], [66].
formaldehyde.

7.1.4. Resins from Urea Derivatives

7.1.2. Mixed Condensates
Condensation with urea derivatives or substitu-
Industrial amino resins contain mixtures of var- tion products are well known, but these reactions
ious condensates and cocondensates. Amino are of industrial importance only for making tex-
resin solutions are always polymeric mixtures tile and paper auxiliaries. Reactions with alde-
having various degrees of condensation and dif- hydes can take place depending on the hydrogen
fering distributions of functional groups. Resin- atoms still present at the nitrogen, but the ability
forming monomers employed as textile auxil- to undergo condensation decreases sharply with
iaries constitute an exception, but these in them- the size and number of substituents.
selves are not resins. The term mixed conden- The reaction of a symmetrically disubstituted
sates is rather loosely applied to those resins urea derivative, e.g., N,N  -dimethylurea or dihy-
which are formed in the condensation of urea droxymethylurea dimethyl ether, with formalde-
and formaldehyde when the reaction is car- hyde in an acidic medium gives cyclic urea
ried out using substances that also form resins derivatives of the urone type [67, p. 9]:
with formaldehyde. These are, for example,
melamine, phenol, organic acid amides, sulfon-
amides, and carbamates. Therefore, in the pres-
ence of melamine or phenol, it is possible to
prepare urea resins with improved strength and
swelling properties for the manufacture of parti-
cle board, i.e., weather-resistant particle board. Dihydroxymethylurone dimethyl ether,
Modification with melamine gives resin glues bis(methoxymethyl)urone [7388-44-5] is used
that can be used to produce good-quality parti- industrially to provide cellulose fabrics with a
cle board even when the molar ratio of formalde- wrinkle-resistant finish. It has middling reactiv-
hyde to urea is low. ity and stability to hydrolysis [68, pp. 164 – 174].
Mixed resins with other resin formers, e.g., The urones do react with cellulose but form only
acrylic acid, acrylates [61], [62], acrylamide [1, minor amounts of self-cross-linked resins, such
pp. 109] and their derivatives, are also some- as the urea – formaldehyde compounds.
times advantageous. These are also mixtures of When S is substituted for O in urea, thiourea
polymers, of cocondensates, or of homologous is obtained. The latter undergoes all of the
polymers and cocondensates. principal condensation reactions of urea. In
a weakly alkaline medium, N-hydroxymethyl
compounds and S-hydroxymethyl compounds
are formed. The tautomeric structure NH2 –
C(SH) = NH may be assumed initially for the
 Amino Resins 15

latter. The thiourea – formaldehyde condensates resins have a longer shelf life [1, p. 115], [70],
are more water resistant than the corresponding [71]. In the starting materials for surface coat-
urea condensates. Some of the thiourea conden- ings, 20 – 100 % of the hydroxymethyl groups
sates are assumed to be cyclic compounds [69]. undergo etherification, depending on the type.
The amino resins etherified with butyl groups
are the most important for wood coatings, e.g.,
7.1.5. Modified Urea Resins parquet coating. Where complete etherification
takes place, the reaction is carried out using an
There is very extensive literature on the possible entraining agent – the alcohol itself, toluene, or
methods of modifying amino resins [1, pp. 95] xylene – and the water is distilled azeotropically.
and only the most important modifications are Ethers of one- to three-carbon alcohols
discussed here. with low molecular mass hydroxymethyl com-
pounds of urea, ethylene urea (imidazolidi-
Reactions with Alcohols. The hy- none [28906-87-8]), propylene urea (1,3-bis(hy-
droxymethyl groups can be etherified with alco- droxymethyl)tetrahydro-2-(1H)-pyrimidinone
hols in an acidic medium [13, pp. 334]. [65405-39-2]), and melamine have achieved
some importance in the field of textile auxil-
iaries [3, p. 168], [59], [68]. These compounds
are precondensates having relatively low molec-
ular masses, about 600.
The equilibrium constants for the etherifi- Urea resins etherified with butyl groups can
cation of monohydroxymethylurea and dihy- be employed as starting materials for mak-
droxymethylurea with methanol and ethanol ing surface coatings. However, when baked
have been measured [59]. The enthalpy of re- alone, they give brittle and water-sensitive films.
action, estimated from the temperature depen- Therefore they cannot be used alone as binders.
dence of the equilibrium constant, is ∆H = − 6 In combination with nitrocellulose, or with
to − 8 kJ/mol. The equilibrium constants (K) alkyd, epoxy, or acrylate resins, they give ex-
differ depending on the substitution: cellent baked finishes.

Reactions with Ammonia and Amines.

Amines are very reactive toward hydroxymethyl
compounds obtained from urea and formalde-
hyde. Ammonia reacts with the hydroxymethyl
group to form an amino or imino group, elimi-
nating water:
-NH-CH2 OH + NH3 −→ -NH-CH2 NH2 + H2 O

As the number of C atoms in the alco-

hol increases, the equilibrium is shifted and
the reaction rate reduced so that the etherifica-
tion becomes more difficult. The ethers of the
low-boiling alcohols can be transetherified with
higher boiling alcohols by heating the mixture
in weakly acidic solution and distilling the more
volatile alcohols [13, p. 336].
Frequently only some of the hydroxymethyl
groups of resin glues and impregnating resins
undergo etherification with monohydric or poly- The reaction of ammonia with formaldehyde
hydric alcohols of less than five carbon atoms. is exothermic (∆H = − 57 kJ/mol) [1, p. 49] and
As a result, some of the hydroxymethyl groups gives hexamethylenetetramine. This reaction
are protected against condensation, and the has been used industrially to trap formaldehyde
16 Amino Resins

from waste gases, for example, from particle This imparts an anionic character to the resins
board production [72–74]. The reaction of urea [3, p. 206]. The pH of the solution controls its
and aldehydes with primary amines gives cyclic sulfite content.
compounds (triazines) [75] of the type 10, where
R can be hydroxymethyl and its methyl and [SO3 H]−
[SO3 ]2− + H+
ethyl ethers.
To produce resins of this type, the reaction of,
e.g., urea and formaldehyde is begun in a neu-
tral or alkaline medium in order to achieve hy-
droxymethylation. When the desired degree of
conversion has been achieved, condensation is
carried out using sulfite or hydrogen sulfite in
a slightly acid solution [76]. However, the resin
Ammonia, primary or secondary amines, or can react with a hydrogen sulfite because many
polyamines containing two or more primary hydroxymethyl groups are still present. Water-
amino groups are used for the production of insoluble resins can even be rendered soluble
amino-modified resins [3, p. 206]. They are by posttreatment with a hydrogen sulfite. Al-
more stable to water than the unmodified resins though, like unmodified resins, the amino resins
produced by a similar procedure. produced using sulfites exhibit an increase in
As shown in the equation above, ammonia viscosity on aging, they remain water soluble
and amines can react with the hydroxymethyl because of their hydrophilic ionic groups.
groups in urea, in a weakly acidic or alka- The anionic resins are of particular industrial
line medium, to give N-aminomethyl groups. importance in the field of water-soluble or water-
In strongly acidic solution, these eliminate the dispersible adhesives. Other uses include textile
amine substituents to form condensates. This auxiliaries [77], paper auxiliaries [78], leather
condensation is similar to that starting with auxiliaries, and deodorants [79] for UF resins
hydroxymethyl groups. Even very highly con- [80].
densed urea resins are able to bind large amounts In addition to modification with sulfite, the
of ammonia and amines because a substantial relevant patents mention many other modifiers,
part of the formaldehyde is still present in the such as aldehydes and triazines. The affinity of
form of hydroxymethyl groups. This reaction is the anionic resins for cellulose (which carries a
utilized industrially, for example, to deodorize slight negative charge) is lower than that of the
resins or particle board [72]. cationic resins; therefore, the fibers must be post-
Condensation of the resin molecule with an treated with aluminum sulfate to fix the resins.
amine produces a resin that has a cationic charac- The modification of urea – formaldehyde
ter; this increases the resin’s affinity for cellulose resin glues with ligninsulfonic acid should be
fibers when it is used as an auxiliary for textiles mentioned also [81], [82]. The products are dark
or paper. These basic urea resins are therefore resin solutions that have been used from time to
mainly important because they improve the wet time in the woodworking industry. The mecha-
tensile strength of paper. nism involved in the incorporation of the nonuni-
form lignin is still unclear [1, p. 120]. Lignin
contains phenolic groups. Incorporation of the
Reaction with Sulfites. Just as formalde-
lignin components imparts relatively high water
hyde hydrate reacts with a sulfite, so the hy-
resistance, among other things. The lignins are
droxymethyl groups of the amino resins react
of different origins and compositions, so that the
with a hydrogen sulfite or a sulfite to give an
production process must be adapted empirically
aminomethanesulfonate [1, p. 120]:
to the different lignin varieties. This fact and the
dark coloration have prevented more extensive
R-NH-CH2 OH + [HSO3 ]−
use of lignin wastes from wood pulp production.
−→ [R-NH-CH2 SO3 ]− + H2 O
 Amino Resins 17

7.2. Melamine Resins because cross-linking otherwise competes with

etherification. The mono- to hexaalkyl ethers
7.2.1. Unmodified Melamine Resins of the C1 to C4 alcohols can be prepared read-
ily. Good conversions are obtained for higher
Melamine [9003-08-1], like urea, can react alcohols only by means of transetherification
with formaldehyde [9, p. 65]. The addition of [83].
formaldehyde at the amino group is carried out at Methyl ethers of melamine hydroxymethyl
pH 9 – 10 and takes place very rapidly. One mole compounds are readily soluble in water even
of melamine combines with 6 mol of formalde- at room temperature and crystallize readily [3,
hyde to form hexahydroxymethylmelamine. p. 361]. The aqueous solutions of the methyl
Melamine in itself is only slightly soluble even in ethers prepared from higher hydroxymethyl
hot water [9, p. 60]. However, it dissolves read- compounds, i.e., those with a higher molar ra-
ily in aqueous formaldehyde solutions, form- tio of hydroxymethyl groups, become cloudy on
ing hydroxymethylmelamines. A small part of heating and clarify again when cooled. Most
the melamine remains physically dissolved. of the methyl ethers are soluble not only in
When heated, hydroxymethylmelamines un- water but also in benzene and similar sol-
dergo cross-linking [9, pp. 66] and form resins vents. The products etherified with higher al-
that become more insoluble the longer they cohols, e.g., butanol or benzyl alcohol, are
are heated. Melamine condenses with formalde- water insoluble but are readily soluble in al-
hyde in acid solution to form hydroxymethyl cohols and some hydrocarbons. In addition
compounds. This is followed by a more rapid to monoalcohols, polyhydric alcohols, e.g.,
polycondensation, yielding cross-linked prod- ethylene glycol, glycerol, 3-hydroxymethyl-1,5-
ucts, than in the case of urea – formaldehyde [13, pentanediol, pentaerythritol, can be employed as
p. 359]. Melamine – formaldehyde resins can be etherification agents. This etherification must be
hardened thermally in the absence of a hardener carried out in neutral solution because the com-
or they can be hardened in the absence of heat, peting cross-linking reaction otherwise takes
using a very strongly acidic hardener. The hard- place more rapidly and forms insoluble prod-
ening processes, as in the case of the urea resins, ucts.
are not entirely clear. Crosslinking takes place Like the corresponding urea resins, the
principally via methylene bridges, but it also etherified melamine – formaldehyde resins used
has been suggested that methylene-ether bridges as starting materials for surface coatings are
play a role. The melamine formaldehyde con- condensates having low molecular masses,
densates possess good thermal stability, optical 600 – 1400 [84]. These are presumably triazine
properties, and water resistance [13, p. 350]. structures linked via methylene bridges and con-
tain from two to four melamine groups. The
ether groups are distributed randomly over the
7.2.2. Modified Melamine Resins triazine rings.

Reaction with Alcohols. Melamine hy- Reaction with Amines. Amines and
droxymethyl compounds can be etherified aminocarboxylic acids react readily
with alcohols in the same manner as hy- with the hydroxymethyl group of hy-
droxymethylurea compounds [13, p. 361]. droxymethylmelamines in the same way as with
The most important use of the products urea resins. Modification with amines or amino
is as surface-coating resins, but they also acids improves the hydrophilic character of
are used as textile auxiliaries and even as the melamine resins. Condensation with amino
melamine – urea – formaldehyde resins and im- acids gives alkali-soluble melamine resins that
pregnating resins. As in the case of the urea are used to produce impregnating or molding
resins, etherification is carried out at relatively materials [85]. Basic products, which form salts
high temperatures with acid catalysis. Where with acids, are obtained by modification with
etherification is carried out to a substantial de- aminoalcohols, e.g., aminoethanol [86], and are
gree, it is important to remove the water or used as textile auxiliaries. These products are
excess alcohol from the weakly acidic solution, not of major industrial importance.
18 Amino Resins

Reaction with Hydrogen Sulfite. Melamine resins have been described also. The reaction
resins, like urea resins, react with hydrogen sul- of cyanuric acid with polyhydric alcohols and
fites. Industrially, the cheapest product, i.e., formaldehyde gives resins that can be used as
sodium sulfite or sodium hydrogen sulfite, is paper and textile auxiliaries and as starting ma-
used, and the reaction is carried out in an acidic terials for surface coatings.
or basic medium. The products are readily water- In another procedure, urea is converted to the
soluble melamine resins that can be precip- appropriate carbamate by heating in the pres-
itated with acids. Hydrogen sulfite-modified ence of an alcohol and eliminating ammonia.
melamine – formaldehyde resins are used in- The subsequent reaction with formaldehyde and
dustrially as concrete liquefiers in the building cross-linking are carried out as described above
materials industry. In addition to sulfite, other [13, p. 374]. The resultant highly viscous solu-
modifiers described in the patent literature are tions can be used as label adhesives and for the
dithionite and formaldehyde sodium sulfoxylate adhesive bonding of cardboard boxes.
(NaHSO2 · CH2 O) [87], [88]. The properties of urethane resins vary de-
pending on the components and method of pro-
Other Modifiers. The modification of hy- duction. They range from oily to brittle de-
droxymethylmelamine resins with polyalcohols, pending on the degree of condensation. Lower
sugars, toluenesulfonamides, lactams, nitriles aliphatic and cycloaliphatic alcohols yield hard
[89–91], acrylates, and polyacrylonitrile [1, resins, whereas higher alcohols give waxlike
pp. 109], [92] is of great importance in the pro- resins.
duction of impregnating resins. Such modifica-
tions improve the large number of laminating
properties required and stabilize the resin solu- 7.4. Cyanamide and Dicyanodiamide
tion against clouding and excessively rapid in- Resins
crease in viscosity.
Mixed condensates and cocondensates of Cyanamide and dicyanodiamide react with
melamine with other compounds – e.g., phenol, formaldehyde both in acid and in alka-
urea, cyanamide, and dicyanodiamide – that re- line media [8, p. 199]. Cyanamide reacts
act with formaldehyde have also been described with an equimolar amount of formaldehyde
in a large number of publications. For example, at pH 6 – 7 to give a white precipitate,
phenol-modified melamine – urea – formalde- which loses water to form a crystalline com-
hyde resins are used as resin glues for weather- pound. In general, cyanamide and dicyanodi-
resistant particle board [93], [94]. These resins, amide are used as modifiers [1, pp. 118], [13,
too, can be modified in a large variety of ways. pp. 382]. Cyanamide – formaldehyde and di-
cyanodiamide – formaldehyde resins have been
used as mixed resins for starting materials in
7.3. Urethane Resins making molding compositions, as dyeing and
tanning auxiliaries, for textile finishing, and for
Condensation of a urethane (carbamate) of the preserving urea – formaldehyde foams.
formula H2 N–COOR with an aldehyde gives
a distinct compound or a resin, depending
on the production conditions [8, p. 220], [13, 7.5. Sulfonamide Resins
p. 371]. In an alkaline medium, carbamates react
with formaldehyde to give hydroxymethyl com- The most commonly used basic component for
pounds that split up into the starting materials at this type of resins is p-toluenesulfonamide:
higher temperatures. In an acidic medium, they
cross-link to form methylene bridges and pro-
duce resins that are used to manufacture mold-
ing materials. A patent has been applied for re-
garding the use of urethane resins derived from With formaldehyde, p-toluenesulfonamide
long-chain aliphatic alcohols as plasticizers [3, forms resins that are fusible but not curable,
p. 220]. Urethane – urea – formaldehyde mixed whereas disulfonamides or amides possessing
 Amino Resins 19

other groups capable of condensation give insol- Polymer chains are formed and water is elim-
uble products that are infusible [95]. The special inated in this process. In the presence of an
properties of p-toluenesulfonamide resins in- excess of formaldehyde, three-dimensional net-
clude compatibility with cellulose surface coat- works also form.
ings, pale natural color (in contrast to that of The amino groups have a directing function,
phenol resins), and low tendency to yellow. so tertiary aromatic amines also can form resins.
Only the p-toluenesulfonamide – formalde- Unlike the phenol resins, aniline resins do not
hyde condensates have become important in- harden further. The aniline resins are therefore
dustrially, and these only as cocondensates or thermoplasts in contrast to the resins discussed
modifiers. Only the combinations with urea – above, which are duroplasts. The aniline resins
melamine resins, phenol resins, and phthalate are not very important industrially. They have
resins are of importance [96]. They also are been used in small amounts in the production of
added to melamine – formaldehyde impregnat- molding materials [1, p. 120] and ion-exchange
ing resins as plasticizers in amounts of 3 – 8 % resins and, because of their high resistance to
[1, pp. 109]. tracking currents, they have been mixed with
epoxy resins and used for wire enamels and in-
sulating coatings [97].
7.6. Aniline Resins

Aniline resins include the condensates of 8. Analysis

formaldehyde with aromatic amines, such
as aniline [25214-70-4], toluidines, xylidines, Analysis, insofar as it is used for product control
naphthylamines, and phenylenediamines [13, during production, storage, and use, amounts to
pp. 192]. testing various types of resins for characteristic
In alkaline solution, the first stage, i.e., hy- parameters or selected specifications. Complete
droxymethylation, leads to a simple condensate: elucidation of the chemical structure, including
the sizes and amounts of the oligomers, would
entail an unacceptably great expense.
Characterization of the products usually
includes the following determinations [11,
pp. 171], [98–100]:
Condensation to give a cyclic product has
been reported also. density in g/cm3 (in the case of foams, in
kg/m3 )
solids content in % by mass
viscosity in mPa · s, usually at 20 ◦ C
free formaldehyde
total formaldehyde
free urea
The reaction with formaldehyde in an acid total urea
medium gives resins in which methylene groups melamine
link the aromatic rings directly, as in the case of methoxy content
the phenoplasts (→ Phenolic Resins). The para ash content (incombustible modifiers)
position is activated by salt formation at the The urea – formaldehyde or amino groups –
amino group, so formaldehyde can add at this formaldehyde molar ratio is calculated from the
position to form p-aminobenzyl alcohol. analytical data.
Further tests may be employed if special
properties are required of the resins. The de-
velopment of novel products and applications
increases the need for analytical effort.
Solids Content. The determination of the solids
content in resin solutions is a determination of
20 Amino Resins

the dry matter content. The value is useful only These substances are not determined during rou-
for comparison. It is determined by evaporating tine product control.
the volatile components at 100 – 130 ◦ C over a For research and development purposes, pa-
fixed period of time. This procedure removes not per chromatography, thin-layer chromatogra-
only the water present as a solvent and the free phy [106], column chromatography [107], gel
formaldehyde, but also the water and formalde- permeation chromatography, 13 C NMR spec-
hyde formed during the drying process in the troscopy [22], [31], [36], 15 N NMR spec-
condensation. Therefore the dry matter content troscopy [119], 1 H NMR spectroscopy (using
is by no means to be equated with the active in- dimethylsulfoxide as the solvent) [31], [108],
gredient content. More exact data are obtained and infrared spectroscopy are used.
by the determination of water by the Karl Fis-
cher method [101], by freeze drying, or, in or-
ganic solvents, by the Aufhauser method. In in- 9. Storage and Shipment
dustry, however, the water content is estimated
by the drying method detailed above because Aqueous or alcoholic solutions of amino resins
this method is simple and quick. are stored in steel tanks with or without inter-
Formaldehyde [102–104]. The free formalde- nal epoxide coatings, in stainless steel tanks,
hyde can be determined directly and the total or in containers made of fiberglass-reinforced
formaldehyde can be determined after the prod- polyester resin. Temperatures above 20 – 25 ◦ C
uct has been hydrolyzed completely. The hy- must be avoided because they bring on rapid
droxymethyl content can be determined by hy- condensation, which increases the viscosity and
drolysis under relatively mild conditions. The soon renders the resin unprocessible. Rotary
formaldehyde bonded in the form of methylene pumps or – in the case of highly viscous liquids –
groups is calculated by difference. positive-displacement pumps, e.g., gear pumps,
Urea. The total urea can be determined by hy- are employed.
drolysis and the Kjeldahl procedure. The free Powdered amino resins are packaged in air-
urea is degraded to ammonia by the enzyme ure- tight, plastic-lined paper sacks that are sealed
ase [105]. If no other form of nitrogen is present against moisture. Certain types of paper bags can
in the resin, the urea content can be calculated withstand tropical climates. Under high pres-
from the nitrogen content, which is determined sure, the materials may solidify. Spilled product
by combustion analysis. is taken to a waste dump.
Melamine in amino resins is determined by hy- Liquid resin loads of up to about 250 kg
drolysis of the product under mild conditions are dispatched in small polyethylene barrels,
followed by titration with perchloric acid. Resins whereas greater loads, up to about 1 t, are dis-
having a low degree of condensation can be patched in polyethylene containers encased in
titrated directly using a computerized automatic sheet metal. Larger amounts are transported in
apparatus. containers, railroad tank cars, tank trucks, or ma-
The molar ratio of urea to formaldehyde can rine tankers. Amino resins must be disposed of
be calculated from the total content of formalde- if they are damaged or become unstable during
hyde. This ratio provides information on the transport in tanks.
formaldehyde elimination to be expected. The relevant regulations governing the dis-
Methanol is generally present in the form posal of amino resins differ from country to
of methoxy groups bonded to hydroxymethyl country and even within some countries. A com-
groups via an ether bond; it is determined by mon feature of all the regulations, however, is
the Zeisel’s procedure. that the resin must be hardened by the addition
Other components are important, particularly of acid curing agents and must be delivered to
where the resins are used as paper or textile aux- a licensed landfill. Where leakage occurs during
iliaries or as starting materials for making sur- transport, it is advisable to absorb the resin solu-
face coatings. Some of these are maleic acid, gly- tion with any appropriate agent that is available
oxal, phenol, and amines and sulfites. The meth- (e.g., sand or sawdust) and then to deliver the
ods of determination are discussed in textbooks resulting material for incineration. In the Fed-
on analysis or, for example, in specific articles. eral Republic of Germany, amino resins are not
 Amino Resins 21

included among substances regarded as endan- melamine resins can be cured at 120 ◦ C. Com-
gering water. pared to the melamine or phenol resin glues, the
particle board made from urea resin glue has
lower water resistance and is not resistant to boil-
10. Uses ing. If these properties are required, melamine
resin glues or mixed condensates of formalde-
The properties of amino resins have been hyde, urea, melamine, and/or phenol are em-
adapted by industry to a very large number of ployed.
applications. New uses are being developed con- In addition to water resistance, the tendency
stantly and any list is bound to be incomplete. to release formaldehyde is very important. If a
Uses include the following: adhesives; im- low level of formaldehyde release is desired, the
pregnating resins; molding materials; starting formaldehyde content of the resin glue must be
materials for making surface coatings; auxil- correspondingly low. In some countries the glue
iaries for paper, textiles, leather, and flotation; must receive the approval of the authorities.
strengtheners for building materials; concrete Over the past few years, MDF (medium-
liquefiers; binders for glass fibers and foundry density fiberboard) resins have become increas-
sand casting; fire lighters; emery papers; flame ingly important. The MDF resins are pure or
retardant coatings; flameproofed combustible melamine-modified urea – formaldehyde resins
items; foamed resins for many purposes; grind- that have a low viscosity, about 200 mPa · s.
ing wheels; ion-exchange resins; sewage floccu- Other modifiers may be used also. Medium-
lants; and microcapsule production. density fiberboard is used in the production of
The largest amount of amino resins is con- furniture with structured surfaces [1, pp. 179],
sumed by the woodworking industry. These [109, pp. 266 – 275].
resins, along with the phenol resins, have largely From an economic point of view, the urea
replaced the natural glues based on proteins resins are the most important amino resin glues
(glutin, casein, soybean, and blood albumin because they are inexpensive and possess tech-
glues). Impregnating resins are used as resin nical properties adequate for most purposes.
glues in the particle board, plywood, and fur- The main use is in the production of wood
niture industries. Impregnating resins also are particle board. These resins also play an im-
used to impregnate papers for decorative lami- portant role as glues for plywood and block-
nates and for coating wood particle board. board and for furniture construction. The gluing
of load-bearing wood components and shutter
Resin Glues for the Woodworking Indus- panels and the production of shaped articles are
try. The amino resins used as glues in the wood- further examples of the large variety of uses of
working industry are available commercially amino resin wood glues.
predominantly in the form of 55 – 70 % aqueous
solutions or as solids, for example, powders. The Impregnating Resins. Urea – formaldehyde
powder resins entail lower transport costs but are or melamine – formaldehyde impregnating
more expensive because of the costs involved in resins are used to treat papers for decorative pur-
drying them and must be dissolved by the user. poses. The resins themselves are brittle products
Whereas the powder resins have shelf lives of 1 and it may be necessary to modify them with
year or longer if stored correctly, the liquid prod- a plasticizer. Because of their good properties,
ucts, depending on the type, have shelf lives of i.e., hardness, abrasion resistance, scratch re-
only 2 – 6 months. During this period the viscos- sistance, and stability to light, the amino resins
ity remains within limits that permit the resin are particularly suitable for this purpose. The
to be pumped with a conventional pump. The impregnated papers are used either to produce
amino resins are more or less stable intermedi- decorative laminates or for coating wood parti-
ates; condensation is completed by the addition cle board. Papers impregnated with melamine
of a curing agent and/or by heat treatment. A resin are more heat stable than those impreg-
curing agent, e.g., ammonium chloride, is virtu- nated with urea resin [110].
ally always required for the urea resins, whereas The paper webs impregnated with the amino
resin are dried in a furnace at 70 – 200 ◦ C and
22 Amino Resins

are stored under air-conditioning until they are most important are papers that impart a decora-
used. tive pattern to the board which itself consists of
Table 1. Trade names of amino resins used as resin glues and im-
several layers of phenol resin-impregnated kraft
pregnating resins paper.
Supplier Urea Melamine
Ground films and decorative films are like-
resins resins wise amino resin-impregnated papers and are
used in the same way as wood veneers in the
Nobel Hoechst Chim. Nobelamine Nobelamine
France furniture industry. These films generally are pro-
Société Chimique des Pressamine Pressamine duced from urea resins and to a certain extent
Charbonnages S.A.
CdF-Chimie also from melamine – urea resin mixtures.
France
BP Chemicals Cellobond –
UK
Molding Materials. Molding materials con-
Montedison Xylocolla – sist of a filler, e.g., cellulose or sawdust, and a
Italy binder, which can be a urea resin or a melamine
Società Italiana Resine Sirit –
SIR resin. The molding materials obtained from
Italy melamine resins are superior to those obtained
Aika Aika-Uri –
Japan
from urea resins because of their better harden-
Dainippon Ink Plyamine – ing properties, higher mechanical strength, and
Japan greater resistance to tracking currents and mois-
Mitsui Toatsu Chemical Uramin –
Japan ture [3, pp. 68 – 100].
Nippon Carbide – Nika Resin The molding materials are employed for ob-
Japan
Nippon Chemical – Suntop
jects in daily use; e.g., white electrical plugs,
Japan switches, covers, telephone accessories, and but-
Nippon Kasei Suiso-Bond – tons are made from urea resin. Melamine resin
Japan
Shooei Chemical S-Resin – is used for camping, hospital, and canteen table-
Japan ware, and for junction boxes and insulating com
Sumitomo Bakelite Igeta –
Japan
ponents. Mixed resins that combine some of the
Dyno Industrier Dynomin Dynomin properties of the individual resins are also used.
Norway The most important trade names of amino
Ciba-Geigy Aerolite Melolam
Switzerland resins used as resin glues and impregnating
Amer. Cyanamid UFR Cymel resins are given in Table 1.
USA Urac Melurac
Borden Cascomite –
USA Raw Materials for Surface Coatings. Pure
Monsanto – Scripset
USA – Resimene
amino resins are not very useful as surface
Reichhold Floramine Diaron coatings. The majority of the commercially
USA available amino resins used as starting mate-
Rohm and Haas Uformite Uformite
USA rials for surface coatings are etherified with
BASF Kaurit Kauramin butanol or isobutanol and dissolved therein [3,
FRG
Cassella (Hoechst) – Madurit
pp. 124 – 148]. Special brands are also modified
FRG with methanol, ethanol, or propanols.
CSL, Chemische Werke SAR – Because the surface coatings obtained using
Saar Lothringen
FRG amino resins are too brittle, these resins cannot
Henkel – Pressal be used alone as binders. However, they are very
FRG
Resart – Resart
useful in combination with other binders. Urea
FRG resins and melamine resins are the most impor-
Südwestchemie Supraplast Supraplast tant cross-linking components for alkyd resins.
FRG
Physically drying finishes are obtained by
adding amino resins to nitrocellulose finishes.
The addition of these resins improves the hard-
Various types of amino resin-impregnated pa- ness, body, and stability to light. The principal
pers are required for decorative laminates. The field of use is in furniture finishing.
 Amino Resins 23
Table 2. Trade names of amino resins used as surface coating resins Acid-curable finishes are obtained by adding
Supplier Urea Melamine alkyd resins or saturated polyester resins. These
resins resins finishes can be hardened by adding an acid, e.g.,
Vianova Viamin Viamin
hydrochloric acid, p-toluenesulfonic acid, or a
Austria phosphoric acid derivative, at an elevated tem-
UCB – Synkamine perature. The resulting coatings are very hard
Belgium
Syntova Syntamine Syntamine and resistant to scratches, solvents, and the ef-
France fects of light [3, p. 130]. Urea resins are more
British Industrial Plastics – Beetle important than melamine resins, particularly in
(BIP Chemicals)
UK furniture finishing and parquet sealing.
British Resin Prod. Epok Epok Coatings that can be cross-linked by heat
UK
British Paints – Syntex treatment alone are obtained by combining
UK amino resins with alkyd resins, saturated
ICI Paralac –
UK
polyester resins, heat-curable acrylate resins, or
Resia – Resmelin epoxy resins. Because of their good mechani-
Italy cal properties, their gloss, and their resistance,
Società Italiana Resine Siramin Siramin
SIR these baked finishes are extremely important in
Italy industrial metal finishing, for example, for auto-
Hitachi Kasei Melan Melan
Japan
mobile bodywork, household appliances, metal
Mitsui Toatsu Uvan Uvan furniture, and containers [111, p. 177].
Chemical Because they are etherified and essentially
Japan
Sanwa Chemical – Nikalac free of water, the amino resins used in the
Japan surface-coating industry have shelf lives of from
Sumitomo Chemical Sumimal Sumimal
Japan
6 months to several years at room temperature.
Scado-Archer-Daniels Scadonur Scadomex They are dispatched in plain or galvanized sheet
Netherlands metal containers. Only stainless steel or alu-
Synres Nederland Synresin Synresin
Netherlands minum tanks are used for transport by tanker
Synthese Setamine Setamine trucks and railroad tank cars.
Netherlands
Dyno Industrier Dynomin U Dynomin M
The most important trade names of urea and
Norway melamine resins used as starting materials for
Perstorp Peramin – surface coatings are summarized in Table 2.
Norway
Svenska Olieslageri Soamin Soamin
Sweden Paper Auxiliaries. In the paper industry,
Ciba-Geigy Cibamin H Cibamin M amino resins are used to increase the dry tensile
Switzerland
Plüss Staufer – Plusamid strength and especially the wet tensile strength
Switzerland of the product [3, pp. 205 – 209], [112], [113].
Allied Chemicals Plaskon Plaskon
USA
In contrast to the procedure followed in the tex-
Amer. Cyanamid – Plaskon tile industry (see Textile Auxiliaries below), the
USA resin components are added to the paper stock
Monsanto – Resimene
USA before condensation. They are adsorbed onto the
Reichhold Plyamin Super fiber and then undergo condensation in an acid
USA Beckamine
Rohm and Haas Uformite Uformite
medium. The maximum strength of the paper
USA is reached only after a maturing period of 2 – 4
Texaco – Pantoxyl weeks. Based on the fiber, 1 – 5 wt% of resin
USA
BASF Plastopal Luwipal is sufficient to achieve good wet strength. The
FRG amino resins also are used for the surface finish-
Hendricks & Sommer Heso-amin Heso-amin
FRG
ing of papers. They impart water resistance to
Hoechst – Maprenal starch-containing paper-coating compositions.
FRG The urea resins, which constitute the most
Jäger Jägamin Jägamin
FRG important group, are generally hydroxymethyl
Stickstoffwerk Piesteritz Piadurol Meladurol compounds that have been modified by the ad-
FRG
dition of amines to give them a cationic character
24 Amino Resins

or by the addition of sulfites to provide an an- nantly monomeric, and therefore should not be
ionic character. After modification, these com- regarded as resins. They contain only unavoid-
pounds are subjected to a condensation reaction able, small, random amounts of higher conden-
in an acid medium. The resultant ionic resins are sates. The molecules react with the primary hy-
water soluble. The ionic character also enables droxyl groups of the cellulose on contact with the
them to be adsorbed onto anionic paper pulp, cellulose fibers. The relatively weak hydrogen
but anionic resins must be used with aluminum bridges of the cellulose molecules are thereby
sulfate [112, p. 43]. supplemented by additional, stronger covalent
Melamine resins also are important to the wet bonds. Self-condensation takes place on the sur-
strength of paper. In the absence of other modi- face of synthetic fibers, which do not react with
fiers, they react with acids to form strongly acid the “amino resin” monomers. This type of aux-
cationic colloids that are stabilized by an elec- iliary is discussed here, as are others that stiffen
tric charge and consist of partially condensed hy- the finish of synthetic fabrics.
droxymethyl melamines. Melamine resins mod- The pure urea – formaldehyde adducts,
ified with aminocaproic acid are also suitable mono- and dihydroxymethylurea, are water sol-
substitutes, either alone or in combination with uble and crystallize readily. In crystalline form,
other polymers, for some or all of the colophony they possess the largest share of the market for
soaps used in the internal sizing of paper [112, easy-care and wrinkle-resistant finishes for cel-
p. 42]. lulose textiles and mixtures of cellulose fibers
A further field of use is the production of with synthetics and wool. The pastes also consist
moisture-resistant starch pastes for the adhesive principally of these basic substances, but some
bonding of corrugated board [114]. of them are etherified with lower alcohols and
Trade names for aminoplasts used as paper exhibit a minor amount of condensation. They
auxiliaries are summarized in Table 3. are therefore used to provide wrinkle-resistant
and wash-and-wear finishes as well as stiff-
Table 3. Amino resins used as paper auxiliaries ened finishes on synthetic fabrics. The fabrics
treated in this manner possess improved wash
Supplier Resin
resistance. Hydroxymethyl compounds of urea
Rousselot Resin that exhibit a high degree of condensation and
France possess a high concentration of ether groups
British Industrial Plastics Beetle Resin
(BIP Chemicals) are used to produce highly elastic stiffening
UK effects and good wash resistance in cellulose
Mitsui Toatsu Chemical Uramin
Japan
fabrics. Because of the relatively low concen-
Sumitomo Chemical Sumires Resin tration of “amino resin” monomers (about 1 mol
Japan of resin per kg of cellulose), cross-linking be-
AKZO Etadurin
Netherlands tween the cellulose groups is strongly favored
Chemanord Casco-Resin over self-cross-linking. A disadvantage of this
Norway
Amer. Cyanamid Parez class of products is the relatively low stability
USA Paramel Regular of the acid treatment liquors in the bath, where
Resin condensation can take place easily between the
Hercules Powder Kymene
USA hydroxymethylurea molecules.
Monsanto Scriptite An important group is constituted by hy-
USA Resloom
Rohm and Haas Uformite droxymethyl compounds of cyclic urea deriva-
USA tives; examples are dihydroxymethylethylene
BASF Urecoll urea (11), dihydroxymethylpropylene urea (12),
FRG
Hoechst Madurit and dihydroxymethylurone (13).
FRG Acyclic compounds, such as various alkyl
carbamates, are also typical finishing agents. In
contrast to the pure urea – formaldehyde com-
Textile Auxiliaries. The textile auxiliaries pounds, these exhibit little tendency to form self-
based on derivatives of urea, melamine, and cross-linked resins and react predominantly with
formaldehyde [3, pp. 166 – 181] are predomi-
 Amino Resins 25

ferred for embossed finishes (Everglaze) where

the fabric can be damaged mechanically.
The most important trade names of the tex-
tile auxiliaries based on amino resins are sum-
marized in Table 4.

Table 5. Trade names of amino resins used as leather auxiliaries

Supplier Resin

cellulose to cross-link the fibers. The other ad- Hodgson Neosyn

vantages, over and above the mechanical prop- UK
BASF Relugan
erties, are resistance to chlorinated water, light- FRG
fastness, and shade constancy. These are closely Bayer Retingan
FRG
related to the chemical structure and the resis- Henkel Drasil
tance of the C–N and N–O bonds to hydrolysis. FRG
Chemtan Chemtan
USA

Table 4. Amino resins used as textile auxiliaries

Supplier Resin
Leather Auxiliaries. Resin retannage of
PCUK Diamonine chrome-tanned leather is carried out using
France
Dai Nippon Ink and Chemicals Beckamin hydroxymethyl compounds of urea, thiourea,
Japan melamine, dicyanodiamide, and ethers of these
Mitsui Toatsu Chemical Uramin [3, p. 211], [80]. Aqueous solutions of the resins
Japan
Sumitomo Chemical Sumitex Resin should penetrate the hide before condensation
Japan begins. The acid condensation catalyst (pH
Sandoz Finish
Switzerland 3.9 – 4.5) should not reduce the period of ac-
Monsanto Resloom tivity of the tanning liquor or damage the hide.
USA
Sun Chemical Permafresh
As in the case of the paper auxiliaries, the resins
USA are rendered cationic using amines or anionic by
BASF Fixapret means of a bisulfite. The anionic resins based on
FRG Kaurit
Ciba-Geigy/Pfersee Knittex melamine or dicyanodiamide make leather very
FRG Lyofix strong and supple and leave the color unchanged.
Henkel Stabitex
FRG
The hydroxymethyl groups react with the active
Hoechst Arkofix groups of the collagen fiber, which has a high
FRG content of glycine, proline, and oxyproline.
Hoechst Cassurit
FRG The trade names of a few leather auxiliaries
Thor-Chemie Quecodur are given in Table 5.
FRG

Other Uses of Amino Resins. The number

of possible uses is increasing constantly. The
Hydroxymethyl melamine derivatives and
uses listed at the beginning of this section are
their ethers are of some importance for provid-
summarized with the appropriate references in
ing high-grade finishes, i.e., embossed finishes,
Table 6.
Schreiner finishes, chintz finishes, and plisse fin-
The importance of many uses, e.g., flame-
ishes, but they have largely been replaced by
proofing agents, has declined greatly. Some ap-
the reactant types. The finishes obtained using
plications, e.g., casting resins, have proved un-
hydroxymethylmelamines are more wash resis-
satisfactory in practice, whereas others are only
tant than those made with hydroxymethylureas.
at the development stage and their industrial suit-
Hydroxymethylmelamine compounds are pre-
ability cannot yet be assessed.
26 Amino Resins
Table 6. Uses for amino resins

Application Resin and use References

Binders for glass fiber webs Reinforcing glass fibers in webs by means of urea resins [9, pp. 201, 214]

Foams Soil conditioning, covering landfills, heat insulation, lining [115], [1, pp. 196], [3,
tunnels in mines (→ Foamed Plastics) p. 161]

Foundry sand binders Binders for sand-casting in the foundry industry; casting molds [3, pp. 122]
and cores; modification with furfuryl alcohol

Concrete liquefiers and auxiliaries Sulfite-modified melamine resins [87], [88]

for building materials

Flame-proofing agents Flame-proofing wood by means of amino resins containing [1, p. 206], [3, p. 215]
phosphorus, boron, bromine, etc.

Ion-exchange resins Melamine-formaldehyde condensates modified with amines [3, p. 225]

Used for recovering silver from photographic effluents

Coatings for abrasive papers Urea – formaldehyde – furfuryl alcohol condensates for [3, p. 226]
imparting water-resistance

Wood preservatives Melamine – formaldehyde condensates impart good aging [3, p. 227]
resistance; no shrinkage; no seasoning cracks

Microcapsules Urea – formaldehyde resins [1, p. 289], [116]

Firelighters Emulsion of urea – formaldehyde resin with a liquid fuel and [117]
hardeners is processed to give small moldings. Lighting
oil-fired furnaces, charcoal grills, etc.

Sewage flocculants Urea – formaldehyde resins cause flocculation [118]

Table 7. Production of amino resins in the OECD countries

11. Economic Aspects
Year Production (106 tons)

1969 1.95
Amino resins have become increasingly im-
1970 2.03 portant since World War II. The OECD statis-
1971 2.20 tics “The chemical industry” and the production
1972 2.55
1973 3.13 statistics of the Federal Statistics Office of the
1974 2.79 Federal Republic of Germany refer the produc-
1975 2.47
1976 2.79
tion for the OECD countries shown in Table 7.
1977 2.94 The figures for Europe, USA and Japan are
1978 3.09 given in Table 8.
1979 3.33
1980 3.14 The production of particle board, which con-
1981 3.01 sumes the largest amount of amino resins in the
1982 2.69 Federal Republic of Germany, reached a high
1983 2.66
level by the late 1970s but diminished thereafter.
Comments: The figures for 1974 to 1976 and for 1979 exclude
Portugal. The figures include the phenol resins produced in the
Federal Republic of Germany. However, this qualification does
not greatly change the above figures for world production of
amino resins.

Table 8. Production of amino resins for Europe, USA and Japan

Production in 103 tons

1978 1979 1980 1981 1982 1983

Europe 1790 1890 1810 1690 1560 1420

USA 600 711 604 610 524 613
Japan 706 734 716 629 606 632
 Amino Resins 27

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 Amino Resins 29

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