4 Aminos

A. Pizzi and C.C. Ibeh

LERMAB, University of Lorraine, Epinal, France and King Abdulaziz University, Jeddah, Saudi Arabia

O U T L I N E

Introduction 75 General Principles of Manufacture and

Application 80
Raw Materials 76
Applications of Amino Resins 88
Chemistry of UF Resins: Urea
Formaldehyde
Condensation 76 References 91
Chemistry of MF Resins:
Melamine
Formaldehyde Condensation 78

Introduction Work with urea and urea
formaldehyde resins

may have begun as early as the 1880s in France
The two most popular and viable amino resins are and Germany by Einhorn, Holzer, and Goldschmidt
urea
formaldehyde and melamine
formaldehyde et al. H. John and F. Pollack introduced them com-
resins. Urea
formaldehyde (UF) resins are the most mercially into the U.S. in 1928 [3
7].
important and most used class of amino resin adhe- Melamine
formaldehyde (MF) and melami-
sives. Amino resins are polymeric condensation pro- ne
urea
formaldehyde (MUF) resins are among
ducts of the reaction of aldehydes with compounds the most used adhesives for exterior and semi-
carrying aminic or amidic groups. Formaldehyde is exterior wood panels and for the preparation and
by far the primary aldehyde used. The advantage of bonding of both low- and high-pressure paper lami-
UF adhesives are their (1) initial water solubility nates and overlays. Their much higher resistance to
(this renders them eminently suitable for bulk, and water attack is their main distinguishing character-
relatively inexpensive, production), (2) hardness, (3) istic from urea
formaldehyde (UF) resins. MF
nonflammability, (4) good thermal properties, (5) adhesives are expensive. For this reason, MUF
absence of color in cured polymers, and (6) easy resins that have been cheapened by addition of a
adaptability to a variety of curing conditions [1,2]. greater or lesser amount of urea are also often used.
Thermosetting amino resins produced from urea Notwithstanding their widespread use and econom-
are built up by condensation polymerization. Urea is ical importance, the literature on melamine resins
reacted with formaldehyde, which results in the forma- is only a small fraction of that dedicated to
tion of addition products such as methylol compounds. urea
formaldehyde resins. Often MFs and MUFs
Further reaction and the concurrent elimination of are described in the literature as a subset of UF
water leads to the formation of low-molecular-weight amino resins. This is not really the case, as they
condensates that are still soluble. Higher-molecular- have peculiar characteristics and properties all of
weight products, which are insoluble and infusible, are their own which in certain respects are very differ-
obtained by further condensing the low-molecular- ent from those of UF adhesives.
weight condensates. The greatest disadvantage of the MF resins are used as adhesives for exterior and
amino resins is their bond deterioration caused by semi-exterior-grade plywood and particleboard. In
water and moisture. This is due to the hydrolysis of this application their handling is very similar to that
their aminomethylenic bond. Therefore, pure UF of urea
formaldehyde resins for the same use, with
adhesives are used only for interior applications. the added advantage of their excellent water and

Handbook of Thermoset Plastics. DOI: http://dx.doi.org/10.1016/B978-1-4557-3107-7.00004-X

© 2014 Elsevier Inc. All rights reserved. 75
76 HANDBOOK OF THERMOSET PLASTICS

weather resistance. Melamine
formaldehyde resins 2NH3+ CO2 150-200°C NH22COHN2+ H2O

are also used for the impregnation of paper sheets
in the production of self-adhesive overlays for the
surface of wood-based panel products and of self-
1400-1500 psi
adhesive laminates. In this application the impreg-
nation substrate, a cellulose paper, is thoroughly Ammonia + carbon dioxide Urea + Water
impregnated by immersing it in the resin solution,
Scheme 4.1
squeezing it between rollers, and drying without
curing it to proper flow by passing it through an
air-draft tunnel oven at 70 to 120°C at 6 10 m/s.
The dry MF impregnated sheets can then be bonded Melamine (C3N3(NH2)3) and formaldehyde are the
by one of two main processes: raw materials for melamine
formaldehyde resins.
For furan resins, the raw materials are furfural and
1. The sheets of MF-impregnated paper, consist- its derivatives, and phenol.
ing of one surface layer, or a few surface
layers, are bonded together and with a sub-
strate of paper sheets impregnated with phe- Urea
nolic resins to form laminates of variable Urea, a white crystalline solid, is a diamide of
thickness. In the impregnated papers is the carbonic acid. Wohler’s work in 1824 in urea syn-
dry but still active MF resin, which functions thesis marks a cornerstone in the connection
as the adhesive of the MF-impregnated sheet between the chemistry of living and inanimate
to both MF-impregnated sheets and at the matter. Wohler’s process for synthesizing urea
interface between MF-impregnated and PF- involved the molecular rearrangement of ammo-
impregnated layers. These laminates are high- nium cyanate.
pressure laminates. Urea is synthesized from the high-pressure reaction
2. The MF in an impregnated paper sheet is not between carbon dioxide and ammonia (Scheme 4.1).
completely cured but still has a certain
amount of residual activity and is applied
directly in a hot press, in a single sheet, and
Melamine
on a wood-based panel to which it bonds by Melamine is the triamide of cyanuric acid
completing the MF adhesive curing process. (2,4,6-triamino-l,3,5-triazine) from the Ciba-Geigy
process patented in 1936; calcium cyanamide is
The melamine
formaldehyde resins were converted to cyanamide, and the cyanamide is
brought into the market in 1935. In addition to their reacted with ammonia under pressure to yield mel-
light-coloredness, they exhibit enhanced water and amine [7].
heat resistance. These resins have completely
replaced thiourea-formaldehyde resins, which were
also produced in the 1930s. American Cyanamid
Chemistry of UF Resins:
Company is the major producer of melamine-
formaldehyde resins having begun the first com- Urea
Formaldehyde
mercial manufacture in the U.S. in 1939. Other Condensation
companies producing these resins are Fiberite
Corp., Ciba-Geigy Corp., and Allied Corp. The reaction between urea and formaldehyde is
complex. The combination of these two chemical
compounds results in both linear and branched
polymers, as well as tridimensional networks, in
Raw Materials the cured resin. This is due to a functionality of 4
in urea, which is because of the presence of four
Urea (NH2CONH2) and formaldehyde (CH2O) replaceable hydrogen atoms. In reality, urea is
are the raw materials of urea
formaldehyde resins. only tri-functional, as tetramethylol urea has never
4: AMINOS 77

been isolated, except in the formation of substi- methylolureas, are low-molecular-weight methylene
tuted urons [2]. There is a fuctionality of 2 in ureas [8]:
formaldehyde. The most important factors deter-
mining the properties of the reaction products are H2 NCONHðCH2 NHCON14Þn H
the following: (1) the relative molar proportion of
urea and formaldehyde, (2) the reaction tempera- These contain methylol end groups in some
ture, and (3) the various pH values at which con- cases, through which it is possible to continue the
densation takes place. These factors influence the reaction to harden the resin. The methylolureas
rate of increase of the molecular weight of the formed copolymerize by acid catalysis and produce
resin. Therefore the characteristics of the reaction polymers and then highly branched and cured net-
products differ considerably when lower and high- works (Scheme 4.3).
er condensation stages are compared, especially The kinetics of the formation and condensation
solubility, viscosity, water retention, and the rate of mono- and dimethylolureas and of simple
of curing of the adhesive. These all depend to a urea
formaldehyde condensation products has
large extent on molecular weights. been studied extensively. The formation of mono-
The reaction between urea and formaldehyde is methylolurea in weak acid or alkaline aqueous
divided into two stages. The first stage is the alka- solutions is characterized by an initial fast phase
line condensation to form mono-, di-, and tri- followed by a slow bimolecular reaction [9,10].
methylolureas (tetramethylolurea has never been The first reaction is reversible and is an equilib-
isolated). The second stage is the acid condensa- rium that proceeds to product due to the uptake of
tion of the methylolureas, first to soluble, and then the products; the methylolureas are by the second
to insoluble cross-linked resins. On the alkaline reaction. The rate of reaction varies according to
side, the reaction of urea and formaldehyde at the pH with a minimum rate of reaction in the pH
room temperature leads to the formation of methy- range of 5 to 8 for a urea
formaldehyde molar
lolureas. When condensed, they form methyle- ratio of 1:1, and a pH of 6.5 for a 1:2 molar ratio
ne
ether links between the urea molecules. The [11]. The 1:2 urea
formaldehyde reaction has
alkaline products from urea and formaldehyde, and been proved to be three times slower than the 1:1
from mono- and dimethylolureas, are as shown in molar ratio reaction [12].
Scheme 4.2. The rapid initial addition reaction of urea and
The reaction also produces cyclic derivatives: formaldehyde is followed by a slower condensation,
uron, monomethyloluron, and dimethyloluron. which results in the formation of polymers [12]. The
On the acid side, the products precipitated from rate of condensation of urea, with monomethylolurea
aqueous solutions of urea and formaldehyde, or from to form methylene-bisurea (or UF “dimmers”), is

CH2OH
HOCH2 NHCONH
CH2OH CH2OH
NH2CONH2 + HCHO NH2CONH + + HOCH2 NHCON
CH2OH
CH2OH
NH2CON
CH2OH
Monomethylol urea Dimethylol ureas Trimethylol urea

Scheme 4.2

n HOCH2 NHCONH HOCH2 NHCONH CH2 NHCONH H CROSS-LINKED RESIN

n-1

Scheme 4.3
78 HANDBOOK OF THERMOSET PLASTICS

also pH-dependent. It decreases exponentially from amido
methylene link and its lability in weak acid
a pH of 2 to 3 to neutral. No condensation occurs at moisture. It explains the slow release of formalde-
alkaline pH values. hyde over a long time in particleboard and other
The initial addition of formaldehyde to urea is wood products manufactured with UF resins.
reversible and is subject to general acid and base
catalysis. Different energies of activation are
reported for the forward methylolation and back-
ward demethylolation reaction. The forward bimo- Chemistry of MF Resins:
lecular reaction is reported to have an activation Melamine
Formaldehyde
energy of 13 kcal/mol when the reverse unimolecu- Condensation
lar reaction has an activation energy of 19 kcal/mol
[10]. Other sources report values of 17.5 and The condensation reaction of melamine with
17.1 kcal/mol for the same reactions, respectively formaldehyde (Scheme 4.4) is similar to but differ-
[13]. If one considers that the reaction of mono- ent from the reaction of formaldehyde with urea.
methylation of urea at pH 7 is of the order of As for urea, formaldehyde first attacks the amino
1 3 10-4 l/(mol s) for each site and in the order of groups of melamine, forming methylol compounds.
3 3 1024 l/(mol s) at rather alkaline pH it is possi- However, formaldehyde addition to melamine
ble to deduce what occurs at alkaline pH when urea occurs more easily and completely than does addi-
reacts with formaldehyde to form methylolated tion to urea. The amino group in melamine accepts
ureas. The inverse reaction of decomposition of the easily up to two molecules of formaldehyde. Thus
methylolurea will limit, however, the proportion of complete methylolation of melamine is possible,
methylolated urea prepared, the reaction running to which is not the case with urea. Up to six mole-
completion only as methylolated ureas react to cules of formaldehyde are attached to a molecule of
form dimers and higher oligomers when the pH is melamine. The methylolation step leads to a series
lowered in the condensation phase. If the condensa- of methylol compounds with two to six methylol
tion phase is not affected, a calculation of the groups. Because melamine is less soluble than urea
degree of advancement of the reaction of methylo- in water, the hydrophilic stage proceeds more rap-
lation of urea yields a degree of advancement idly in MF resins formation. Therefore, hydropho-
where p 5 0.60; hence, at equilibrium under the bic intermediates of the MF condensation appear
conditions used, 60% of the urea is present as early in the reaction. Another important difference
methylolureas. This compares well with a degree of is that MF condensation to give resins, and their
conversion of 65% at the equilibrium of the more curing, can occur not only under acid conditions,
reactive melamine extrapolated by reported kinetic but also under neutral or even slightly alkaline con-
values [9] to the same conditions used herewith. ditions. The mechanism of the further reaction of
The advancement of the reaction may eventually methylol melamines to form hydrophobic inter-
proceed to even higher degrees of conversion, even mediates is the same as for UF resins, with splitting
in an alkaline environment, only as a consequence off of water and formaldehyde. Methylene and
of the subsequent formation of methylene ether- ether bridges are formed and the molecular size of
linked oligomers. the resin increases rapidly. These intermediate con-
The rates of introduction into the urea molecule densation products constitute the bulk of the com-
of one, two, and three methylol groups have been mercial MF resins. The final curing process
estimated to have the ratio 9:3:1, respectively. The transforms the intermediates to the desired MF
formation of N,N’-dimethylolurea from mono- insoluble and infusible resins through the reaction
methylolurea is three times that of monomethylo- of amino and methylol groups which are still avail-
lurea from urea. able for reaction.
Methylene-bisurea and higher oligomers undergo A simplified schematic formula of cured MF
further condensation with formaldehyde [14] and resins has been given by Koehler [16] and Frey
monomethylolurea [15], behaving like urea. The [17]. They emphasize the presence of many ether
capability of methylene-bisurea to hydrolyze to bridges besides unreacted methylol groups and
urea and methylolurea in weak acidic solutions methylene bridges. This is because in curing MF
(pH 3 to 5) indicates the reversibility of the resins at temperatures up to 100°C, no substantial
4: AMINOS 79

H2N N NH2
C C
N N
C
NH2

melamine

NH2 NH2 NHCH2OH

C C C
N N N N N N
+ HCHO + etc.
C C C C C C
H2N N NH2 H2N N NHCH2OH H2N N NHCH2OH

NHCH2OH NHCH2OH
C C
N N N N
C C C C
H2N N NHCH2OCH2HN N NH2

NHCH2OH NHCH2OH NHCH2OH NHCH2OH

C C C C
N N N N N N N N
+
C C C C C C C C
H2N N NHCH2OH H2N N NHCH2OH H2N N NHCH2HN N NHCH2OH

NHCH2OH NHCH2OH
C C
N N N N
C C C C
H2N N NHCH2N N NH2
CH2OH

Scheme 4.4

amounts of formaldehyde are liberated. Only small subsequent MF resin production, due to their acidic
quantities are liberated during curing up to 150°C. nature. If present, both must be removed from
However, UF resins curing under the same condi- crude melamine by an alkali wash and/or crystalli-
tions liberate a great deal of formaldehyde. zation of the crude melamine.
At the condensation stage attention must be paid
to the formation of hydrolysis products of the mela-
mine before preparation starts. The hydrolysis pro- Mixed Melamine Resins
ducts of melamine are obtained when the amino With regard to melamine
urea
formaldehyde,
groups of melamine are gradually replaced by copolymers can be prepared which are generally used
hydroxyl groups. Complete hydrolysis produces to cheapen the cost of MF resins, but which also show
cyanuric acid. some worsening of properties. Copolymerization was
Ammeline and ammelide can be regarded as par- proven by means of model compounds and polycon-
tial amides of cyanuric acid. They are acid and densates [18]. MUF resins obtained by copolymeriza-
have no use in resin production. They are very tion during the resin preparation stage are superior in
undesirable by-products of the manufacture of mel- performance to MUF resins prepared by mixing
amine because of their catalytic effect in the preformed UF and MF resins, especially because
80 HANDBOOK OF THERMOSET PLASTICS

processing of such mixtures is quite difficult P

[19]. The relative mass proportions of melamine U U M U M U U M U M
to urea used in these MUF resins is generally in U M U M P P
the melamine:urea range 50:50 to 30:70 [20]. U U U U M U P U U
Melamine
phenol
formaldehyde resins, which M P M U
in some respects show better properties than P
P pendant without
those of their corresponding MF and PF resins, contribution to the P included in the network
have also been prepared [21
23]. Analysis of the network
molecular structure of those resins in both their + P unreacted
uncured and cured states appeared to show that
Scheme 4.5
no co-condensates of phenol and melamine form
and that two separate resins coexist. This is due
to the difference in reactivity of the phenolic and (MUF) network without contributing at all to its
melamine methylol groups as a function of pH. performance (Scheme 4.5) [27,28].
Also, in their cured state, an interpenetrating net- Also defined is the best reaction order necessary
work of the separate PF and MF resins (as a poly- to obtain PMUF resins in which phenol provides a
mer blend) is formed, not a copolymer of the two positive contribution to the performance of the
[24
26]. Today MUF resins are produced in hardened network [28]. PMUF resins are still used,
greater quantity than MF resins in the field of adhe- and some good resins of this type are indeed used,
sives due to the relatively high cost of melamine. in the unrealistic expectation that they outperform
Their formulation has progressed to such a level equivalent MUF resins; it has been shown clearly
that often no difference in performance exists that they perform best as a MUF adhesive present-
between a good MUF resin and a pure melamine ing the same number of moles of melamine for the
MF resin. MF resins are still more extensively used total moles of phenol plus melamine of the PMUF
at this stage in the paper impregnation/laminates itself. The idea that the addition of small percen-
fields, although both MUF copolymers as well as tages of phenol to a MUF resin yields resins of bet-
separate, double application of UF (paper core) and ter exterior durability is then an incorrect myth
MF (paper surfaces) resins are making considerable perpetuated in the wood panels industry. Newer
inroads in this area. MUF resins instead totally formulations of MUF resins always outperform the
dominate the wood adhesives field today. Paper corresponding PMUF. PMUFs are not bad resins,
laminates and wood adhesives are the two main they are simply resins in which one of the materials
application areas of these resins. (phenol) is often wasted for no purpose.
A type of resin also used today is the so-called
PMUF (or MUPF, depending on the author) adhe-
sives. These are fundamentally MUF resins in
which a minor proportion of phenol (between 3% General Principles of Manufacture
and 10%, P:M:U by weight of 10:30:60, for exam- and Application
ple) has been hopefully coreacted to further
upgrade weather resistance of the bonded joint. It is very important in the commercial production
Unfortunately the alleged superior performance of of urea
formaldehyde (UF) resins to be able to
such resins is often only wishful thinking as the control the size of the molecules by the condensa-
phenol has frequently not been properly reacted tion reaction since their properties change continu-
with the other materials, and consequently the ously as they grow larger. The most perceptible
PMUF resin will have worse performance than a change is the increase in viscosity. Low-viscosity
comparable top of the line MUF resin. This was syrups are formed first. These change into high-
confirmed by the demonstration that it depends viscosity syrups, which are clear to turbid.
exclusively on the resin manufacturing parameters, Molecular weight may vary from a few hundred to a
and materials reaction order used, whether the phe- few thousand, with a wide range of molecular size.
nol coreacts or not with many PMUF adhesives. These molecules are built up by water splitting off
This shows that often the phenol remains as a use- at random between reactive groups of neighboring
less pendant group in the hardened aminoplastic molecules, thereby increasing their size. Once their
4: AMINOS 81

solubility, viscosity, pH, concentration, and so on Control of the average molecular size of the fin-
have been determined, they constitute the resins ished resin is essential for correct flow in plywood
available commercially. The most important factors and particleboard applications while in the hot press
influencing the final properties of aminoplastic prior to curing. Too low a level of condensation (i.e.
resins in industrial manufacture are the purity of the low-molecular-weight resins) may give too much
reagents, the molar proportions of the materials flow; the resin “runs away” from the wood or sinks
used, the preparation process used, and the pH vari- into it rapidly under pressure, leaving “starved” glue
ation and control. lines. This can be corrected by lowering the pH by
The most common method of preparation for adding an acid or acid-producing substance, usually
commercial UF resin adhesives is the addition of a a curing agent, hardening catalyst, or simply, hard-
second amount of urea during the preparation reac- ener. If a resin of too high a condensation stage (i.e.
tion. This consists of reacting urea and formalde- high-molecular-weight resins) is on hand, its flow
hyde in more than equivalent proportions. under normal pressure and temperature may be too
Generally, an initial urea/formaldehyde molar ratio low to produce good results. This can usually be cor-
of 1:2.0 to 2.2 is used. Methylolation can in this rected by adding flow agents to it, provided that at
case be carried out in a much shorter time by using least some flow is left in the resin. It is generally an
temperatures of up to 90
95°C. The mixture is advantage to produce resins with ample flow in the
then maintained under reflux. When the exotherm factory. Their storage life is longer and finishing can
subsides (usually after 10 to 30 min), the methylol be done at any time, at short notice, to specification,
compounds have formed and the reaction is com- particularly by adjusting the flow and speed of cure.
pleted under reflux by adding a trace of an acid to Resins that have lost part of their flow during man-
decrease the pH to the UF polymer-building stage ufacture or storage must be corrected by the addition
(pH 5.0 to 5.3). As soon as the right viscosity is of a flow agent. The simplest means is often the addi-
reached, the pH is increased to stop polymer build- tion of water sprayed on the compound and mixed in
ing, and the resin solution is cooled to about 25 to well. If a resin is still capable of flowing, this proce-
30°C. More urea (called second urea) is added to dure produces a resin with properties that are still
consume the excess of formaldehyde until the acceptable. In cases where moisture content control is
molar ratio of urea to formaldehyde is in the range critical, it may be necessary to allow a little more
1:1.1 to 1:1.7. After this addition of urea, the resin time for “heating” to let the added moisture escape.
is left to react at 25 to 30°C for as long as 24 h. However, if the flow is very low, and large quantities
The excess water is eliminated by vacuum distilla- of water must be used to bring the flow back to nor-
tion until a resin solids concentration of 64 to 65% mal, this method is not recommended. The large
is reached, and the pH is adjusted to achieve amount of water would cause longer “breathing”
suitable shelf life or storage life. times to be necessary due to excessive volatile com-
The final addition of urea can be done in one oper- ponents; excessive shrinkage may take place, causing
ation or the urea may be added at suitable intervals in excessive stress on the glue lines. It must be kept in
smaller lots. Second or further ureas can be added at mind that excessive water addition causes UF resin
a temperature slightly higher than ambient, or can be precipitation. The best way to correct flow in these
added at higher temperatures of 60 to 90°C according cases is to mix the resin with large amounts of an
to the type of final resin wanted [29
32]. Increasing equal resin of the same quality that has a higher flow.
second or further urea additions tends to improve Any proportion may be used to bring the flow back to
bond quality, especially at low formaldehyde/urea normal. If increased flow is desired, 0.5 to 2.0% of
molar ratios [29
32]. Higher-molar-ratio resins tend spray-dried UF or MF resin can also be added to
to exhibit an overall better initial bond quality [14], function as a flow agent. Methylol compounds, such
but present an exponentially increased formaldehyde as dimethylol urea, also increase flow, but they
emission problem [16], most often disqualifying them increase the water released during reaction more than
from many, or most, modern uses. Some UF resins do spray-dried resins. Lubricating agents such as cal-
used for joinery are also produced without a final, or cium stearate are also able to give a fair degree of
second, urea addition. The pH used during the con- flow increase.
densation reaction (not the methylolation) is generally Many substances have been suggested as curing
in the range 4.8 to 5.3. agents. These include the following acid products:
82 HANDBOOK OF THERMOSET PLASTICS

Figure 4.1 Light-colored amino resin-based coasters compared to dark-colored phenolic resin-based coasters.

(1) boric acid, (2) phosphoric acid, (3) acid sulfates, 4 NH4Cl + 6 HCHO → 4 HCl + (CH2)8N4 + 6 H20
(4) hydrochlorides, (5) ammonium salts of phospho-
Hexamethylene
ric or polyphosphoric acid, (6) sodium or barium
tetramine
ethyl sulfate, (7) acid salts of hexamethylenetetra-
mine, (8) phthalic anhydride, (9) phthalic acid, (10) Scheme 4.6
acid resins such as poly(basic acid)
poly(hydric
alcohol), (11) oxalic acid or its ammonium salts,
and many others. However, the most widely used
curing agents in the wood products industry are still Often, particularly in cold-setting UF resins for
ammonium chloride or ammonium sulfate. Their joinery, hardeners consisting of mixtures of a salt
effect can be altered by retarding the resin reaction. such as ammonium chloride or ammonium sulfate
This is done by the simultaneous addition of small with an acid such as phosphoric acid, citric acid, or
amounts of ammonia solution (which is eliminated others are used to regulate pot life and rate of cur-
during hot curing) to lengthen the pot life of the ing. Both pot life and rate of curing of the resin can
glue mix. Latent catalysts that produce acid only on then be regulated by (1) varying the concentration
heating may also be used, such as dimethyloxalate of the hardener in the resin, (2) by changing the rel-
and other easily hydrolizable esters, or halogenated ative proportions of acid and salt, and (3) by chang-
substances such as 0.1 to 0.2% bromohydrocin- ing the type of acid and/or salt composing the
namic acid and others. hardener. Acting on these three principles, setting
The driving force in the use of these salts as times of between a few minutes and several hours
hardeners is their capacity to release acid, which can easily be obtained.
decreases the pH of the resin and thereby acceler-
ates curing. The speed of the reaction between the
ammonium salt and formaldehyde (or ammonia and Adhesive and Bonding Resins
formaldehyde when this is present) also determines, Urea
formaldehyde and melamine
formaldehyde
together with the amount of heat supplied, the rate resins, usually in the liquid or spray-dried forms,
of acid release and therefore the rate of curing are used as adhesives (see Figures 4.1 and 4.2).
(Scheme 4.6). Though the melamine
formaldehyde resins are more
Ammonium chloride is a better hardener than water- and heat-resistant and give more durable adhe-
hydrochloric acid, as the latter produces weaker sives and bonding resins than the urea
formaldehyde
joints. resins, their higher costs limit their use.
4: AMINOS 83

The processing or pressing conditions for amino

resins are typically 70°C and 200 psi (cold pressing)
for up to 24 hours. Melamine
formaldehyde resins
can be cured or pressed without a catalyst but only
at a higher processing temperature (hot pressing).
Amino resin adhesives are typically applied in
the bonding of wood. The bonding strength of ami-
nos is most effective with heat and pressure for
wood particles of the 40 to 80 mesh range. Hot
pressing causes the amino resins to seep through the
pores of the wood core and polymerize (cross-link)
inside the wood. This cross-linking binds the wood
together, resulting in a structure that is stronger and
more moisture-resistant than the original wood.
Some amino resin-based adhesives are made from
blends of urea and melamine resins. The American
Cyanamid Company’s McClure resin is a co-spray
dried melamine
urea
formaldehyde adhesive in a
free-flowing powdered form designed for exterior
waterproofing applications.

Coating Resins
Amino resins serve as cross-linking agents for
hydroxyl, carboxyl, and amide functional polymers
Figure 4.2 Fabricated items made from such as acrylics, polyesters, epoxies, and alkyds.
particleboard. Particleboard has superior structural Liquid amino coating resins are produced by react-
strength and is less expensive than medium-density ing the initial methylolated species, dimethylol
fiberboard. (Courtesy of Weyerhaeuser.) urea, and hexamethylol-melamine, with either
n-butanol or methanol. This step results in an
amino resin that is more soluble in, and compatible
with, the coating resins. The increased compatibil-
Their durability and water-resistant characteris- ity enhances the ether exchange reaction between
tics promote the use of melamine
formaldehyde the amino resins and the reactive sites of the coat-
resins in outdoor and marine applications. The ing polymers to produce coating films with a very
light-colored amino resins are attractive for deco- high degree of cross-linking.
rative plywood veneers without encountering the Urea
formaldehyde coating resins cure more
associated problem of discoloration caused by rapidly but have lower moisture resistance than
resin bleed-through. Typically, the adhesive and melamine
formaldehyde coating resins. In general,
bonding resins have urea:formaldehyde ratios of melamine-based coating resins have better overall
1:1.5 to 2.0 and a melamine:formaldehyde ratio of performance, but, again, their higher costs limit
1:3.0. The reactions are carried out at a pH of 7.5 their use. It is common to use a combination of
to 8.0 and at reflux for up to 8 hours until 50 to urea/melamine-based resins to achieve the right
60% solid composition is attained. The pH is low- balance of properties, costs, and performance.
ered as viscosity is increased; the reaction is then Beetle, Cymel, and Melmac are trade names of
stopped and the resin is stabilized using caustic American Cyanamid Company’s liquid coating
soda by raising the pH to 8.0. The typical formula- resins [33].
tion of adhesive resins is about 15% resin; wood The Beetle grades are butylated and iso-butylated
flour, pecan, and walnut shells are the common fil- urea
formaldehyde resins with low-temperature cure
lers. Acid catalysts are favored in adhesive and characteristics, very good substrate/intercoat adhe-
bonding amino resins. siveness, and low cost. These urea
formaldehyde
84 HANDBOOK OF THERMOSET PLASTICS

coating resins are compatible with hydroxyl-bearing dispersions containing 0.5 to 1.0 percent alcohol as
polymers such as amine-catalyzed epoxy resins, oil- a surfactant. The alcohol surfactant reduces the sur-
alkyd resins, epoxy-ester resins, cellulosics, and con- face tension of the resin solution and increases fiber
version varnishes. wettability. Typical colloid composition is of the
The Cymel grades are either methylated or melamine resin
acid
water ratio of 1:1:6.5 by
butylated melamine-form-aldehyde resins with weight.
UV-resistance, chemical resistance, exterior dura- Saturation of the fiber material with the resin
bility, fast-cure characteristics, and very good typically involves the free-turning
roll-pulling of
adhesiveness. These melamine-form-aldehyde fiber material through a resin solution bath. The
coating resins exhibit compatibility for a wide resin-saturated web is then drawn to the dryer. The
range of resin types with thio, hydroxyl, carboxyl, resin concentration, pulling speed, and residence
and amide functional groups such as alkyd and time of the fiber in the bath influence the rate of
polyester resins, epoxy resins, acrylics, vinyl poly- impregnation. The dryer and drying process are an
mers, and cellulosics. Compatible cellulosics integral part of the laminating process. The drying
include ethyl cellulose, hydroxyethyl cellulose, process helps to evaporate the resin solvent and
nitrocellulose, and carboxylated cellulose deriva- enhance the degree of resin polymerization.
tives. They are also good wetting and dispersing
agents for carbon black and organic pigments.
Some Cymel resins require the presence of strong Amino Molding Resins
acid catalysts for effectiveness and a high degree Granule and powder forms of urea
formaldehyde
of cross-linking. p-Toluene sulfonic acid is the and melamine
formaldehyde resins are used in
most popular catalyst used with Cymel resins. The molding resins (Table 4.1). Their characteristic clar-
other catalysts are dodecylbenzene sulfonic acid, ity promotes their use in a variety of colored pro-
oxalic acid, maleic acid, hexamic acid, and metal ducts. Amino-molding compounds are commonly
salts. Metal salts like magnesium bromide formulated with fillers for strength and dimensional
(MgBr2), aluminum nitrate (A1(NO3)3), and zinc stability. Chemically purified alpha cellulose fibers
nitrate (Zn(NO3)2) are used to achieve hardness are the most popular fillers for amino molding
and solvent resistance, but they cause discolor- resins. The other fillers are talc, mica, glass fibers,
ation and low gloss. chopped cotton flock, and wood flour.
Common mole ratios of urea or melamine to
formaldehyde in amino resins are 2:3 and 3:4. The
resinification process is carried beyond the point of
Laminating Resins water solubility, and then the resin-filler mixture is
Amino laminating resins are predominantly heated at controlled humidity conditions. The resin-
melamine
formaldehyde resins based. Typically, to-filler ratio, filler type, catalyst type, and degree
1 mole of melamine reacts with 2 moles of form- of polymerization are varied to achieve different
aldehyde at a pH of 8 to 10 to achieve a 50 to molding properties.
65% solids resin. Catalysts and plasticizers are Compression transfer methods for processing
usually added to enhance cure and flexibility. and injection (screw and cold manifold) molding
Melamine
formaldehyde laminating resins have are the major amino-molding resins. Molding tem-
characteristic hardness, clarity, stain resistance, peratures are 260
340°F for urea
formaldehyde
and UV-resistance. Spray drying is sometimes resins and 260
360°F for melamine
formaldehyde
used to achieve long shelf life. resins. Compression molding pressures of 2000 to
The methylolated melamine
formaldehyde resins 8000 psi are common for amino resins. Processing
form stable cationic colloids in the presence of such is enhanced by the presence of an acid catalyst
acids as carboxylics. The colloidal melamine resins such as phthalic anhydride and an inhibitor such as
impregnate and form strong ionic bonds with cellu- hexamethylenetetramine (“HEXA”). Small amounts
lose fibers (paper) in water dispersions [5] with a of the inhibitor help to stabilize the molding resin
consequent increase in wet tensile strength. The during storage and prior to molding, and to control
degree of impregnation is enhanced by using water the cure rate during molding.
Table 4.1 Properties of Amino (Urea, Melamine) Molding Compounds

Urea Melamine Formaldehyde

ASTM Alpha
Test Cellulose- Glass Fiber-
Materials Properties Method Filled Cellulose-Filled Reinforced
Processing 1. Melting temperature, °C. Thermoset Thermoset Thermoset
Tm
(crystalline)
Tg
(amorphous)
2. Processing temperature range, °F. C: 275
350 C: 280
370 C:280
350
(C 5 compression; T 5 transfer. I - I: 290
320 I: 200
340
injection; E 5 extrusion)
T: 270
300 T: 300
3
3. Molding pressure range, 10 p.s.i. 2
20 8
20 2
8
4. Compression ratio 2 2
3.0 2.1
3.1 5
10
5. Mold (linear) shrinkage, in./in. D955 0.006
0.014 0.005
0.015 0.001
0.006
Mechanical 6. Tensile strength at break, p.s.i. D638 5500
13.000 5000
13.000 5000
10,500
7. Elongation at break, % D638 ,1 0.6
1 0.6
8. Tensile yield strength, p.s i. D638
9. Compressive strength (rupture or yield), D695 25,000
45.000 33,000
45,000 20,000
35,000
p.s.i.
10. Flexural strength (rupture or yield), p.s i D790 10,000
18,000 9000
16,000 14,000
23,000
3
11. Tensile modulus, 10 p.s.i. 0638 1000
1500 1100
1400 1600
2400
3
12. Compressive modulus, 10 p.s.i. D695
13. Flexural modulus, 73° F. D790 1300
1600 1100
103 p.s.i. 200° F D790
250° F D790
300° F D790

14. Izod impact, ft. lb./in of (notch in thick D256A 0 25
0.40 0 2
0.4 0 6
18
specimen)
15. Hardness Rockwell 0785 M110
120 M115
125 M115
Shore/ 02240/
Barcol D2583
(Continued )
Table 4.1 (Continued)

Urea Melamine Formaldehyde

ASTM Alpha
Test Cellulose- Glass Fiber-
Materials Properties Method Filled Cellulose-Filled Reinforced
Thermal 16. Coefficient of linear thermal expansion. 0696 22
36 40
45 15
28
1026 in. /in./°C.
17. Deflection 264 p s i D648 260
290 350
390 375
400
temperature under 66 p s i D648
flexural load. °F.
18. Thermal conductivity. 10
4 cal-cm/sec C 177 7
10 6.5
10 10
11.5
-cm2.°C.
Physical 19. Specific gravity D792 1.47
1.52 1.47
1.52 1 5.20
20. Water absorption 24 hr. D570 0.4 0.8 0 1
08 009.1
( -in. thick Saturation D570
specimen). %
21. Dielectric strength ( in thick D149 300
400 270
400 130
370
specimen), short time. v /ml 175
215 100 °
C
Melamine Phenolic
ASTM Test Wood Flour and Cellulose-
Materials Properties Method Filled
Processing 1. Melting temperature. °C Thermosat
Tm
(crystalline)
Tg
(amorphous)
2. Processing temperature range, °F. (C 5 compression; C: 300
350
T 5 transfer; I 5 injection; E 5 extrusion) 1: 350
400
3
3. Molding pressure range, 10 p.s.i. 5
20
4. Compression ratio 2.1
4.4
5. Mold (linear) shrinkage, in./in. D955 0.009
0.010
Mechanical 6. Tensile Strength at break, p.s.i. D638 6000
8000
 Melamine Phenolic
ASTM Test Wood Flour and Cellulose-
Materials Properties Method Filled
7. Elongation at break, % D638 0.4
0.8
8. Tensile yield strength, p.s i. 0638
9. Compressive strength (rupture or yield), p.s.i. D695 26.000
30.000
10. Flexural strength (rupture or yield), p.s.i D790
3
11. Tensile modulus. 10 p.s.i. D638 800
1700
3
12. Compressive modulus. 10 p.s.i. D695
3
13. Flexural modulus. 10 p.s.i. 73°F.
200° F. D790 1000
1200
250° F D790
300° F. D790
D790
14. Izod impact, ft.-ID./in. of notch (Vi-in. thick specimen) D256A 0.2
0.4
15. Hardness Rockwell
Shore/Barcol D785 E95
100
02240/D2583
5
Thermal 16. Coef of linear thermal expansion, 10 in./in./°C. D696 10
40
17. Deflection temperature under (lexural 264 p.s.i. D648 285
310
load, °F. 66 p s i. 0648
-4 2
18. Thermal conductivity, 10 cal.-cm/sec.-cm. -°C. C177 4
7
Physical 19. Specific gravily D792 1.5
1.7
20. Water absorption (% in. thick specimen), 24 hr. D570 0.3
0.65
% Saturation D570

21. Dielectric strength ( -in. thick specimen), short time. v./ D149 220
325
mil
Reprinted by permission of Modem Plastics Encyclopedia, McGraw-Hill, Inc.
88 HANDBOOK OF THERMOSET PLASTICS

Applications of Amino Resins protective coating resins such as acrylics, alkyds,

epoxies, and polyesters. Butanolated amino resins
[3,4,7,33
35]
dominate the coating market, but methylolated
Adhesive and Bonding melamine
formaldehyde resins are preferred for
moisture-resistant, chemical-resistant, high-solids,
Amino resins totaling 1.44 billion pounds were outdoor coating systems in automotive topcoats,
consumed in 1993 through adhesive and bonding beverage cans, appliances, metal decorating, and
applications (Table 4.2), mainly fibrous and granu- prefabricated metals. Urea
formaldehyde resin-
lated wood products (composite wood materials based coatings are typically used for the indoor
other than plywood). The major amino resins used coating of metals and wood. Urea
formaldehyde
to bond wood products are urea
formaldehyde resins are also used, for instance, in carborundum-
resin, melamine
formaldehyde resin, and melamine
based abrasive, and fiber glass insulation coatings.
urea copolymer resins. Floor finishes based on urea-form
aldehyde/epoxy
Composite wood materials or composition copolymers are also common.
boards, such as fiberboard, particleboard, wafer-
board, and oriented strand board (OSB), account
for more than 70% of the amino resins adhesive Textile Treatment and Coating
and bonding market. Other uses include boat hulls, Wool, cotton, and other cellulosic textiles resist
flush doors, furniture, bag seam pastes, glass and creasing by being impregnated with, typically, low-
mineral fiber mats, foundry sand cores (lost cores molecular-weight, highly methylolated resins (espe-
and molds), coated abrasive paper (emery), ortho- cially dimethylolated resins). About a 10 to 15%
pedic casts and bandages, urea
formaldehyde resin solid solution, with aluminum acetate or for-
foams, and general assembly bonding. mic acid added, is used to impregnate alkaline fab-
Medium density fiberboard (MDF) and particle- ric. The impregnated fabric is squeezed and pressed
board are the largest application areas for the adhe- to twice its dry weight, and then dried and cured at
sive and bonding market. Particleboard is wood- about 140
160°C for 2 minutes. Textile treatment
based, whereas fiberboard is paper-based, but both and coating enhance strength, minimize shrinkage,
find major use in interior applications, mainly due to and impart chlorine resistance, abrasion and wear
the low moisture resistance of urea
formaldehyde resistance, mildew proofing, and wash and wear
resin. Outdoor application types are generally based (permanent press) characteristics.
on melamine-type amino resins.
The waferboard and OSB markets are dominated
by phenolic resin-type adhesives, designed mainly Paper Treatment and Coating
for exterior (outdoor) and structural applications. Enhancing strength is the major reason for
Polymer concrete typically has a composition of impregnating paper with resin. Sulfate pulp paper,
about 10% resin and 90% aggregate. The aggregate Kraft paper, and unbleached sulfite cellulose paper
is made up of 50% pea gravel, 35% fine sand, and are impregnated with amino resins typically at a pH
15% fly ash. Due to its chemical resistance, it is of about 4 to 5. Urea
formaldehyde is the most
mainly used for manholes, road repairs, seamless commonly used amino resin, but melamine-based
flooring, and corrosion-resistant bricks. resins are used more for unbleached sulfite cellu-
lose paper. Resin-impregnated Kraft paper is used
Coatings for making bags, printing paper, and towel paper.
Amino resin coatings have three principal appli- Other paper products include shrinkage-free sheets
cations: protective coatings, paper treatment, and from urea
formaldehyde-impregnated cellulose
textile treatment (Table 4.3). The protective coating pulp and water-proof corrugated cardboard.
applications predominate, with about 47 million
pounds of amino resins used in 1993.
Laminating
Protective Coatings Plywood, which by definition of being a
Alkylated (butanolated and methylolated) amino sandwich-type construction, is a laminate but is
resins are used mainly as cross-linking agents for never categorized as such, commands more usage
4: AMINOS 89

Table 4.2 Trends in Amino (Urea and Melamine-Based) Resin Consumptions

Year (kTons/yr) [36] (kTons/yr) [37]

1989 2655
1999 3484 7975 (7105 UF 1 870 MF)
2004 4215 Approx. 9700 (estimated)

2010 approximate estimate of amino resins yearly consumption is in excess of 11 million tons/year.

Table 4.3 Trends in Amino (Urea-Formaldehyde and Melamine-Formaldehyde) Coating Resins Consumption
(106 lb/yr) [5,11]

Amino Coating Resins

Year Protective Paper Treatment Textile Treatment
1983 35 33 31
1984 84 98 23
1985 90 98 18
1986 103 100 21
1987 111 87 24
1988 111 58 25
1989 100 52 27
1990 104 57 34
1991 92 55 24
1992 138 50 19
1993 147

of amino resins than all other laminates combined. and electrical switch gears. Other laminate applica-
These are mainly urea
formaldehyde-based resins, tions include light reflectors and diffusers, refriger-
and are typically used for interior applications. ator breaker strips, and name plates.
Phenolic resin-based plywood is used instead for
exterior applications, hence its domination of the
plywood market. Molding
Melamine resins, which dominate the amino Approximately 40 thousand tons of amino mold-
resin laminate market, are used more for decorative ing compounds were used in 1993. About 73%
than for electrical and industrial purposes. Amino were urea-type resins (Tables 4.4 and 4.5), due
resin laminates are paper, cloth, veneers (wood), mainly to the higher costs of melamine resins (in
and glass (cloth and mat) based, sandwich-type spite of their better properties). The major areas of
constructions with high percentages of amino amino molding resins application are electrical, clo-
resins. Stacks of heat-cured sheets are pressed sures, housewares, buttons, and sanitaryware.
together to produce laminates having the desired Alpha cellulose-filled melamine molding resins
characteristics. Decorative laminates are used are used to make housewares such as dinnerware
mainly for furniture construction, kitchen counter (dishes, cups), ash trays, utensil handles, knobs,
tops, cabinets, and vertical wall surfaces. Industrial appliance components, control buttons, and sani-
laminates are used for printed circuit boards, elec- taryware such as toilet seats and bowls and shaver
trical panels, welding torch electrode insulators, housings.
90 HANDBOOK OF THERMOSET PLASTICS

Table 4.4 Trends in Urea-Formaldehyde Molding Resins Consumption (106 lb/yr) [5,11]

Urea-Formaldehyde Molding Resins

Year Electrical Closures Other Total
1983 14 5 1 20
1984 40 9 2 51
1985 35 8 2 45
1986 33 7 2 42
1987 35 8 3 46
1988 30 7 3 40
1989 49.3 3.3 1.6 54.2
1990 50.7 3.8 0.8 55.3
1991 49.6 3.4 0.8 53.8
1992 52 3.4 1.2 56.6
1993 54 3 1.5 58.5

Table 4.5 Trends in Melamine Molding Resins Consumption (106 lb/yr) [5,11]

Year Houseware Buttons Sanitary ware Other Total

1983 11 1 1 1 14
1984 18 2 2 2 24
1985 15.0 2 2 2 21
1986 15.0 2 2 2 21
1987 15 2 2 3 22
1988 14 1.5 1.5 3 20
1989 16 2.0 2 3 23
1990 19.7 2.4 2 0.5 24.7
1991 18.7 1.4 1.5 0.4 21.3
1992 19 1.9 1.5 0.4 22.1
1993 20

Alpha cellulose-filled urea molding resins are Miscellaneous

used to make electrical wiring devices, such as
circuit breakers, receptacles, electric blanket con- Filled urea resins, which can develop a dielectric
trol housings, toothpaste tube housing, and knob strength of up to 1500 V/mm and electrical resis-
handles. tances of up to 1013 ohm/cm, are used for electrical
Wood flour-filled melamine molding resins insulation.
are used for industrial electrical parts and mili- Urea formaldehyde foam is used as artificial soil
tary specifications. Glass- and mineral-filled to grow plants and grass (plastoponics 1/m intro-
melamine resins are also used for military duced by Baumann in 1967) [38]. Urea foam is
specifications. also used in road construction projects to protect
4: AMINOS 91

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way abutments. Kolloid Z. 103: 138 (1943).
Modified urea resins are being used in glass mat [17] Frey R. Helv Chim Acta 1935;18:491.
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shingles have higher resistance than tarpaper shin- Chem 1988;156:1 135: 193 (1985).
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forms are used for concrete pouring such as shutter Holzverwertung 1994;46(3):51.
boards. Melamine resin-impregnated slag cotton is [21] Bachmann A, Bertz T. Aminoplaste, VEB Verlag
used in acoustic tiles for sound and fire-proofing. fur Grundstoffindustrie, Leipzig 1967:81.
[22] Knop A, Scheib W. Chemistry and Application
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