New Developments and Application in Chemical Reaction

Engineering

A. Optimum Formulation for MUF Resin

The MUF resin formulation is built up from combination of certain amount of formalin, melamine
and urea (in initial and post refluxing stages) and also sorbitol. Variation on the formulation gives
different resin properties. The optimum resin properties give the optimum MUF resin formulation.
From the properties analysis data, the optimum formulation is determined by using Mixture
Experimental Design D-optimal criterion. The selective criteria for optimum resin properties
should have good viscosity, maximum solubility in water, minimum curing period at room
temperature and maximum storage life. The optimum resin properties is obtained from the MUF
resin with formulation consisting of 59% formalin, 30% of melamine, 4% of urea added initially,
6% of urea added after post-refluxing and 1% of sorbitol. This resin has 96cp viscosity, lower
curing period and long storage life period.

Adhesives for wood composites

A.1 Urea formaldehyde

Urea formaldehyde resin was developed in the 1930s (Dinwoodie, 1979) and is widely used in the
composites industry. Ninety percent of the world’s particleboard is produced using UF resin
(Dinwoodie, 1979). The advantages of UF resins were listed by Pizzi (1994) as follows:

1. The hardness of the resin.

2. The low flammability of the resin.
3. The good thermal properties of the resin.
4. The absence of colour in the cured polymer.
5. The adaptability of the resin to a variety of curing conditions.
The initial water solubility renders UF resins suitable for bulk and inexpensive production.
However, UF resin has disadvantages, the major problem being that UF resin is subject to
hydrolytic degradation when in the presence of moisture and/or acids. This degradation is mainly
due to the hydrolysis of the amino plastic and the methylene bridges.

A.1.1 The manufacture of urea formaldehyde resin

The manufacture of UF resin is complex. Urea is manufactured from carbon dioxide and ammonia
at a temperature of 135–200 °C and at a pressure of 70–230 atmospheres. Formaldehyde is
manufactured by the oxidation of methanol which can be produced from the reaction of carbon
dioxide with hydrogen or can be derived from petroleum.

The combination of the urea and the formaldehyde gives both branched and linear polymers as
well as the three-dimensional matrix that can be found in the cured resin. These different structures
are due to the functionality of the urea and the formaldehyde. Urea has a functionality of four (due
to the presence of four replaceable hydrogen atoms) and formaldehyde has a functionality of two
(Figure 3.1).

Figure 3.1. Urea and formaldehyde.

The most important factors affecting the properties of the reaction products are:

● The relative molarities or the reactants.

● The reaction temperature.
● The pH at which the condensation reaction takes place.

These factors influence the rate of increase of the molecular weight of the resin (Pizzi and Mittel,
1994), therefore the reaction products vary widely with the changes in reaction criteria. Solubility,
viscosity, water retention and final rate of cure all vary with molecular weight.
The reaction of urea and formaldehyde is divided into two stages. The first stage is alkaline
condensation to form mono-, di- and trimethylolureas (Figure 3.2).

Figure 3.2. Alkaline condensation of urea and formaldehyde.

The reaction also produces cyclic derivatives such as uron, monomethyloluron and
dimethyloluron. The second stage is an acid condensation of the methylolureas to form firstly
soluble and then insoluble cross-linked resins.

When acid condensation takes place, the products that precipitate from an aqueous solution of urea
and formaldehyde, or from methylolureas, are low molecular weight methyleneureas (Figure 3.3).
Figure 3.3. Low molecular weight methyeneurea.

These contain methylol end groups in some cases, through which it is possible to continue the
hardening process. The monomethylolureas copolymerise by acid catalysis and produce polymers
and then highly branched and cured networks (Figure 3.4).

Figure 3.4. Copolymerisation of monomethylolureas.

The kinetics of the formation of mono and dimethylolureas and of the simple condensation
products have been studied extensively. The formation of the monomethylolurea molecules in a
weak acid or alkaline solutions is characterised by an initial fast phase followed by a slow
bimolecular reaction. The rate of reaction varies with the pH of the system. A minimum rate of
reaction is achieved with a pH of 5–8 for a urea/formaldehyde ratio of 1:1 and a pH value of ± 6.5
for a 1:2 molar ratio (Figure 3.5).
Figure 3.5. Influence of pH on the addition and condensation reactions of urea and formaldehyde
(Pizzi and Mittel, 1994).

The rate of formation of the methylenebisurea molecules by the condensation of urea with
monomethyleneurea is also pH dependent. The rate of reaction decreases exponentially from a pH
of 2–3 to a neutral pH. The reaction does not take place in alkaline conditions.

The initial addition of formaldehyde to urea is reversible. The rates of introduction of the one, two
and three methylol groups have been estimated to be 9:3:1, respectively. The formation of N,N′-
dimethylolurea to monomethylolurea is three times that of monomethylolurea to urea.

The methylenebisurea and higher oligomers undergo further condensation with formaldehyde and
monomethylurea, which behaves like urea (Pizzi and Mittel, 1994). The capacity of
methylenebisurea to hydrolyse to urea and methylolurea in weak acid solutions (pH 3–5) indicates
the reversibility of the aminomethylene link and its proneness to chemical change in weak acid
moisture.

A.1.2 Commercial production of urea formaldehyde resins

In the commercial production of UF resin the most important property that has to be controlled is
the size of the molecules. As the size of the molecules increases, the properties of the resin change,
the most perceptible being the increase in viscosity (Pizzi and Mittel, 1994). The increase in
molecular weight is due to water molecules splitting off the resin molecules at random thus
presenting reactive groups for further condensation. However, the condensation reaction is not
favoured in aqueous conditions. Once the viscosity has been established and the pH, concentration
and solubility have been determined the resin can be used.

The most common method of preparation for commercial UF resin is the addition of a second
amount of urea during the reaction. The ratio of urea to formaldehyde is between 1:2 and 1:2.2 and
therefore methylolation can take place at in a short amount of time at temperatures between 90 and
95 °C, with a mixture being maintained under reflux. The formation of the resin is completed after
the exotherm has subsided. Acid is then added to decrease the pH to allow the polymer building
stage to begin (usually with a pH of 5.0–5.3). As soon as the correct viscosity, is reached the pH
is increased to stop the polymers increasing in size. The second urea is added to mop up any free
formaldehyde until a ratio of 1:1.1 to 1:1.7 has been established. The resin is then left to react for
another 24 h at a temperature of 25–30 °C after which the resin solids content is adjusted
appropriately and the pH is altered to give maximum shelf life.

A.1.3 The Curing mechanism of urea formaldehyde

Although the curing of urea formaldehyde can take place at room temperature using the addition
of an acid catalyst (such as citric or formic acid) to drive the reaction, the manufacture of panel
products is generally driven by speed or production and therefore the reactions take place in the
presence of heat. During the hot curing of UF resin two condensation reactions take place and a
ridged three-dimensional structure is created. The first condensation reaction occurs between
adjacent polymers with the adjacent nitrogen within the amide group (originating on the
formaldehyde molecule) forming methylene bridges. The second condensation reaction is between
the methylol groups, and these form an ether bridge. As the UF resin cures, it first increases in
viscosity and gels until finally complete cross linking has taken place.
SURFACES, CHEMISTRY & APPLICATIONS
B. UF-resins
Urea-formaldehyde resins are based on the manifold reactions of urea and formaldehyde. Using
different conditions of reaction and preparation a more or less innumerable variety of condensed
structures is possible. UF-resins are thermosetting resins and consist of a mix of linear or branched
oligomers and polymers, always containing some amount of monomers. Unreacted urea is often
welcome to achieve special effects, e.g. a better storage stability. Free formaldehyde, however, can
have an ambivalent role. On the one hand it is necessary to induce the hardening reaction, while
on the other hand it causes a certain amount of formaldehyde emission during the press cycle. At
times, even in the hardened state some residual formaldehyde leads to some displeasing subsequent
emission from the finished boards. This fact has changed significantly UF-resin composition and
preparation during the last 20 years. The problem of the subsequent formaldehyde emission can
be attested to have now been solved for at least the last 10 years. This is especially true in parts of
Europe, where the most stringent formaldehyde emission regulations are in place.

After hardening, UF-resins consist of insoluble, more or less three-dimensional networks and
cannot be melted or thermoformed again. At their application stage, UF-resins are still soluble or
dispersed in water or are spray dried powders, which in most cases are redissolved and redispersed
in water for application.

Despite the fact that the two main components of UF-resins are urea and formaldehyde, a broad
variety of possible reactions and structures in the resins can be obtained. At the molecular level,
the basic characteristics of UF-resins can be explained as follows: (1) high reactivity; (2) water
solubility and dispersibility, which renders the resins ideal for use in the woodworking industry;
and (3) the reversibility of the aminomethylene link, which also explains the low resistance of the
UF-resins against the influence of water and moisture, especially at higher temperatures. This is
also one of the reasons for the subsequent formaldehyde emission.

The reaction of urea and formaldehyde to form UF-resins is basically a two-step process, usually
an alkaline methylolation followed by an acidic condensation.
The methylolation step, which usually is performed at high formaldehyde (F) to urea (U) molar
ratio (F/U = 1.8 to 2.5), consists of the addition of up to three (four in theory) molecules of the
bifunctional formaldehyde to one molecule of urea to give the so-called methylolureas. The types
of methylolureas formed and their relative proportions depend on the molar ratio, F/U. Each
methylolation step has its own rate constant ki, with different values for the forward and the
backward reaction. The formation of these methylols mostly depends on the molar ratio, F/U, and
tends with higher molar ratios to the formation of higher methylolated species.

The UF-resin itself is formed in the acid condensation step, where the same high molar ratio as in
the alkaline methylolation step is used (F/U = 1.8 to 2.5): the methylolureas, urea and the residual
free formaldehyde react to form linear and partly branched molecules with medium and even
higher molar masses, forming polydispersed UF-resins composed of oligomers and polymers of
different molar masses. Molar ratios lower than approx. 1.7-1.8 during this acid condensation step
might cause resin precipitation.

The low molar ratio of the final UF-resin is adjusted by the addition of the so-called second urea,
which might also be added in several steps. Particular care and know-how are needed during this
acid condensation step in order to produce resins of good performance, especially at the very low
molar ratios usually in use today in the production of particleboard and MDF. This last reaction
step generally also includes the vacuum distillation of the resin solution to the usual 63–66% solid
content syrup in which form the resin is delivered. The distillation is performed in the
manufacturing reactor itself or in a thin layer evaporator. Industrial preparation procedures are
usually proprietary and are described in the literature in only a few cases.

The type of bridges between the urea molecules in the resin depends on the conditions used.
Methylene ether bridges (-CH2-O-CH2-) as well as the more stable methylene bridges (-CH2-) are
both formed in different relative proportions according to the conditions used. Methylene ether
bridges rearrange with temperature-induced relative ease to methylene bridges with emission of
one molecule of formaldehyde. One ether bridge needs two formaldehyde molecules to form it
and, additionally, it is not as stable as a methylene bridge. It is highly recommended to avoid and
minimize, when possible, the proportion of such ether groups in UF-resins.
In the literature, various other types of resin preparation procedures are described, e.g. yielding
uron structures or triazinone rings in the resins. The last ones are formed by the reaction of urea
and an excess of formaldehyde under basic conditions in the presence of ammonia or an amine,
respectively. These resins are used to enhance the wet strength of paper.

In the UF-resin itself, different chemical species are present:

• Free formaldehyde, which is in steady state equilibrium with the remaining methylol groups and
the post-added urea
• Monomeric methylols, which have been formed mainly by the reaction of the post-added urea
with the high content of free formaldehyde at the still high molar ratio of the acid condensation
step
• Oligomeric methylols, which have not reacted further in the acid condensation reaction or which
have been formed by the above-mentioned post-added urea reaction
• Molecules with higher molar masses, which are resin molecules in the closer sense of the word.

The condensation reaction and the increase of the molar mass can also be monitored by GPC. With
longer duration of the acid condensation step, oligomers of higher molar masses are progressively
formed.

Forced by the necessity to limit the subsequent formaldehyde emission, the UF-resin molar ratio,
F/U, has been progressively decreased to very low values. The main differences between UF-resins
with high and with low content of formaldehyde, are: (1) the reactivity of the resin due to the
different content of free formaldehyde, and (2) the degree of crosslinking in the cured network.

For example, a UF-resin for particleboard at the end of the 1970s would have had a F/U molar
ratio of approx. 1.6-1.8. To day a UF-resin for the same application has a molar ratio of between
1.02 and 1.08, but the requirements for the boards, as given in the quality standards, are still the
same. The degree of crosslinking of the cured resins as well as the reactivity of the hardening
reaction depends on the availability of free formaldehyde in the system.

However, it has to be considered that it is neither the content of free formaldehyde itself nor the
molar ratio which eventually should be taken as the decisive and the only criterion for the
classification of a resin concerning the subsequent formaldehyde emission from the finished board.
In reality, the composition of the glue mix as well as the various process parameters during the
board production also determine both performance and formaldehyde emission. Depending on the
type of board and the manufacturing process, it is sometimes recommended to use a UF-resin with
a low molar ratio F/U (e.g. F/U = 1.03), hence low content of free formaldehyde, while sometimes
the use of a resin with a higher molar ratio (e.g. F/U = 1.10) and the addition of a formaldehyde
catcher/depressant will give better results. Which of these two, or other possible approaches, is the
better one in practice can only be decided in each case by trial and error.

The higher the F/U molar ratio, the higher is the content of free formaldehyde in the resin.
Assuming stable conditions in the resins, that means that post-added urea has had enough time to
react with the resin, and the content of free formaldehyde is very similar even for different cooking
procedures. In a coarse scale, the content of free formaldehyde in a straight UF-resin is approx.
0.1% at F/U = 1.1 and 1 % at F/U = 1.8. It also decreases with time due to ageing reactions and to
the free formaldehyde reacting further.

Table 4 summarizes the various influences of the molar ratio on various properties of wood-based
panels. Table 5 summarizes the molar ratios F/U and F/(NH2)2, respectively, of pure and melamine-
fortified UF-resins currently in use in the wood-based panels industry

Table 4. Influences of the molar ratio on various properties of UF-bonded wood panels

Decreasing the molar ratio leads to:

a decrease of the formaldehyde emission during the production of the wood based panels
the subsequent formaldehyde emission
the mechanical properties
the degree of hardening
an increase of the thickness swelling and water absorption
the susceptibility to hydrolysis
Table 5. Molar ratios F/U and F/(NH2)2, respectively, of pure and melamine-fortified UF-resins
currently in use in the wood-based panels industry

Classical plywood UF-resin, also cold setting; use is only possible with special
1.55 to
hardeners and additives, e.g. melamine containing glue mixes for an enhanced water
1.85
resistance.
UF-plywood resin; use for interior boards without special requirements concerning
1.30 to
water resistance; in order to produce panels with low subsequent formaldehyde
1.60
emission, the addition of formaldehyde catchers is necessary.
1.20 to Plywood or furniture resin with low content of formaldehyde; also without addition of
1.30 catchers, products with low subsequent formaldehyde emission can be produced.
El-particleboard and El-MDF-resins; especially in the MDF-production further
1.00 to
addition of catchers is necessary. In case of modification or fortification with
1.10
melamine.
Below Special glue resins for boards with a very low formaldehyde emission; in most cases
1.00 modified or fortified with melamine.

Aminoplastics
C. Other Applications
Modification of urea–formaldehyde resins with other reagents gives rise to a number of useful
materials. For example, co-condensation of urea–formaldehyde and a monohydric alcohol in the
presence of small quantities of an acidic catalyst will involve simultaneous etherification and
resinification. n-Propanol, n-butanol and isobutanol are commonly used for this purpose. As an
example n-butanol will react with the methylol urea as shown in Figure 24.4.

Figure 24.4. Reaction between n-butanol and methylol urea

By varying reaction conditions and reactant proportions differing products may be obtained. Many
of the alkoxy groups are retained during cure and the resins have a degree of thermoplasticity.
Soluble in organic solvents and used in conjunction with plasticising alkyd resins, these materials
form useful stoving lacquers. Air-drying lacquers, suitable as wood finishes, may be obtained by
addition of acid hardeners.

Whereas the butylated resins have enhanced solubility in organic solvents, enhanced solubility in
water (which is rather limited in resins of high molecular weight) is required for some purposes
and this may be achieved in a number of ways. For example, in acid condensation of urea and
formaldehyde in the presence of sodium bisulphite the following reaction takes place:

Ionisation occurs in aqueous solution to give a resin of negative charge, as in, for example, a
number of ‘anionic resins’:

Modification of urea resins with certain organic bases, e.g. triethylenetetramine, will give resins
with basic groups which form ionisable salts in the presence of acids:

These resins are referred to as ‘cationic resins’. Paper with improved wet strength may be obtained
by adding an ionic resin at the beater stage of a paper-making operation. For the best results a high
molecular weight resin is required.

Urea resins find extensive use in textile finishing. For example, cellulose fabrics may be padded
into aqueous solutions of hydroxymethyl ureas or their methyl ethers. Excess material is removed
and the resins are hardened in situ, using metal salt catalysts, by passing the fabric through ovens
at 130–160°C. Although there is negligible difference in the appearance of the fabric, a
considerable measure of crease resistance is acquired. Such resin treatment does, however, lead to
two immediate problems. Firstly the cellulose fabric has lower tear and tensile strengths. This
problem is partially overcome by mercerisation (steeping in sodium hydroxide solution) before
resin treatment. The second problem occurs where the fabric is subjected to repeated bleaching
action since the resin reacts with hypochlorite bleach to give chloramines, which break down on
ironing, forming hydrochloric acid, which tenderises the fabric. This problem has been
progressively reduced in recent years by the use of cyclic urea derivatives which do not form
chloramines.

Step Polymerization
D. History
According to Meyer1 the history of urea–formaldehyde (UF) resins can be divided into five
different periods:

(i) Synthesis of the raw materials urea and formaldehyde. This period started with the
synthesis of urea by Wöhler in 1824. Formaldehyde was first recognized by Butlerov
in 1859 when attempting to synthesize methanediol.
(ii) Investigations of the resinous products resulting from the reaction of urea with
formaldehyde. The first attempt to investigate the structure of the products of the urea–
formaldehyde reaction was made by Tollens in 1884.2 In the following years a large
number of authors worked on the structure of these resins.
(iii) Commercialization of the UF-resins. This period started with Goldschmidt’s patent in
18973 to use UF-resins as a disinfectant. In the following decades, more and more
applications were described in the literature.4–11 After about 1930 it is very difficult to
comprehensively cover all the literature about the applications of UF-resins, which
indicates the great importance of these materials.
(iv) Adjustment of the UF-resins. In the fourth period the properties of the UF-resins were
improved (1930–1975), but a lot of applications were also lost in favour of
thermoplastic materials.
(v) Adaptation of the UF-condensates to modern applications. About 10 years ago
condensation products from urea and formaldehyde again became important, due to
their good properties and reasonable prices.
The history of melamine–formaldehyde (MF) resins began with the discovery of melamine in 1834
by Liebig. The industrial production of melamine started in 1935;12, 13 in the same year the
production of MF-resins began.12 MF-resins are superior to UF-resins in heat- and water-resistance.

During the practical development of UF- and MF-resins, many investigations were done with
respect to resin structure and reaction mechanisms. On the following pages the results of these
investigations will be discussed.

Wood: Adhesives
E. Amino–Formaldehyde Resin Adhesives
E.1 Urea–formaldehyde resin adhesives

Well over 106 t of UF resin are produced annually. More than 70% of this resin is used by the
forest products industry (White, 1995). The UF resin is used by the forest products industry in the
production of particleboard (61%), medium-density fiberboard (27%), and hardwood plywood
(5%), and it is used as a laminating adhesive (7%) for bonding furniture overlays to panels and for
interior flush doors, for example. The UF resins are prime examples of the class of adhesives
referred to as amino resins (Pizzi, 1983, 1994; Pizzi and Mittal, 1994) and comprise about 80% of
the amino resins produced worldwide (Williams, 1991). MF resins constitute the remainder of this
class of resins, except for minor amounts of resins produced from other aldehydes or amino
compounds (especially aniline), or both. The major use of UF resins by the forest products industry
is due to a number of advantages, including low cost, ease of use under a wide variety of curing
conditions, low cure temperatures, water solubility, resistance to microorganisms, hardness,
excellent thermal properties, and lack of color of the cured resin.

The major disadvantages associated with UF adhesives compared with PF or isocyanate adhesives
is the lack of resistance to moist conditions, especially in combination with heat. These conditions
lead to a reversal of the bond-forming reactions and the release of formaldehyde. For this reason,
UF resins are usually limited to the manufacture of products for interior use only. However, even
when used for interior purposes, the slow release of formaldehyde is a major concern that has come
under close scrutiny by regulatory agencies in the USA and other countries (Meyer et al., 1986).
Industry has taken great strides since the 1980s to greatly reduce the amount of formaldehyde
being released.

The synthesis of UF resin takes place in two stages. In the first stage, urea is hydroxymethylated
by the addition of formaldehyde to the amino groups (Figure 3). This reaction is in reality a series
of reactions that leads to the formation of mono-, di-, and tri-hydroxymethylureas.
Tetrahydroxymethylurea is apparently not produced, at least in any detectable quantity. The
addition of formaldehyde to urea takes place across the entire pH range but is faster under acidic
and basic conditions than under neutral conditions. The second stage of UF resin synthesis consists
of the condensation of the hydroxymethylureas to low molecular weight polymers. The rate at
which these condensation reactions occur is very dependent on the pH and, for all practical
purposes, occurs only at acidic pH.

Figure 3. Addition of formaldehyde to urea to form mono-, di-, and tri-hydroxymethylureas.

The increase in the molecular weight of the UF resin under acidic conditions is thought to be a
combination of reactions leading to the formation of:

(i) methylene bridges between amido nitrogens by reaction of hydroxymethyl and amino
groups on reacting molecules (Figure 4(a));
(ii) methylene ether linkages by the reaction of two hydroxymethyl groups (Figure 4(b));
 (iii) methylene linkages from methylene ether linkages by the splitting out of formaldehyde
(Figure 4(c)); and
(iv) methylene linkages by the reaction of hydroxymethyl groups splitting out water and
formaldehyde (Figure 4(d)).

Figure 4. Condensation reactions of hydroxymethylureas.

The difference between the pH profiles of the two stages of UF resin synthesis is used as an
advantage in the production of UF adhesive resins. In general, the commercial production of UF
adhesive resins is carried out in two major steps. The first step consists of the formation of the
hydroxymethylureas at a pH of about 8–9. This step is carried out under basic conditions to allow
the hyroxymethylation reactions to proceed in the absence of reactions involving the condensation
of the hydroxymethylureas. In the second step, the reaction mixture is made acidic (about pH 5)
and the condensation reactions are carried out until a desired viscosity is reached. Then the reaction
mixture is cooled and neutralized. Water is removed by vacuum distillation to give a resin with a
desired solids content (typically 60–65%). Urea is often added in two, or sometimes more, steps.
The initial addition of urea is made during the hydroxymethylation step, in which the
formaldehyde-to-urea (F/U) ratio is typically large (about 1.6–2). Usually the second addition of
urea is made during the condensation step. The second and any subsequent additions of urea lower
the final F/U ratio to the desired level for the final resin.

These procedures for the synthesis of UF adhesive resin offer a wide range of conditions that make
possible the synthesis of resins with important properties such as tack, gel time, and spreadability
of the uncured resin. Formaldehyde emissions and the durability of the cured resin can be
controlled and specifically tailored for the final end use of the resin. An acid-cure catalyst is usually
added to the UF resin before its use as an adhesive. Ammonium chloride and ammonium sulfate
are the most widely used catalysts for resins used by the forest products industry. A variety of
other acids can be used as a catalyst including formic acid, boric acid, phosphoric acid, oxalic acid,
and the acid salts of HMTA.

Resin cure is conducted at a temperature of about 120 °C and a pH<5. The reactions that occur
during the final cure of the resin are thought to be similar to those that occur during the acid
condensation of the hydroxymethylureas. The traditional viewpoint is that these reactions lead to
the formation of a cross-linked polymeric network for the cured resin. However, there is evidence
that a colloidal phase also occurs during resin cure (Stuligross and Koutsky, 1985). This evidence
illustrates the lack of a full understanding of the physical and chemical processes leading to the
cure of UF resin systems and the need for continued research. The reactions that occur during UF
resin synthesis and cure are apparently reversible. In the forward direction, water is eliminated;
therefore, the reverse reaction can be viewed as hydrolysis, which leads to the release of
formaldehyde. Because most, if not all, of these reactions are catalyzed by acid, the use of an acid
catalyst to hasten bond cure unfortunately also increases the rate of hydrolysis and formaldehyde
liberation.

The reduction in formaldehyde emissions from products bonded with UF adhesive resins has been
achieved by employing one or more of several technological methods. In general, these methods
include:

(i) changing the formulation of the UF adhesive resin (e.g., lowering the F/U ratio);
(ii) adding formaldehyde-scavenging materials directly to the UF resin;
(iii) separately adding formaldehyde-scavenging materials to the wood furnish;
 (iv) treating panels after manufacture either with a formaldehyde scavenger or by applying
coatings or laminates; and
(v) changing to an entirely different adhesive system.

The most widely used approach for reducing formaldehyde emission from bonded products has
been decreasing the F/U ratio of the UF adhesive resin. Ratios of about 1.6 that were common in
the 1970s and 1980s have now been reduced to values as low as 1.0 and in some cases even lower.
Unfortunately, lowering the F/U ratio produces resins with less tolerance for processing variations.
These modifications that lower formaldehyde emissions have allowed UF resins to maintain their
prominent position as a versatile adhesive system for bonding wood products.

E.2 Melamine–urea–formaldehyde and melamine–formaldehyde adhesive resins

MUF and MF resins are more resistant to moist environments than are UF resins. However,
melamine is much more expensive than urea. The MF and MUF resins are used for scarf jointing
of plywood and end jointing of structural lumber that can be used in protected exterior exposure.
In addition, these resins are used for bonding low- and high-pressure laminates and overlays. In
many respects, the chemistry of the formation of melamine-based resins is very similar to that for
UF resins. However, the addition of formaldehyde to the amino groups of melamine is faster and
more complete than is the addition of formaldehyde to urea. Thus, complete hydroxymethylation
of melamine occurs (Pizzi, 1983), which as mentioned above, is not the case with urea. Another
important difference is that the condensation reactions of the hydroxymethylated melamines occur
not only under acid conditions but under neutral and slightly alkaline conditions as well (Pizzi,
1994; Pizzi and Mittal, 1994). In addition, products bonded with MF resins seem to be less
susceptible to the release of formaldehyde than are products bonded with UF resin.
Quantitative High-Resolution Online NMR Spectroscopy in
Pharmaceutical Reaction and Process Monitoring

F. Hydroxymethylation of urea

The conversion of formaldehyde and urea to urea–formaldehyde resins is an important process in

the wood industry. These resins are the most important binding agents for the production of fiber
boards and are produced on a very large scale. Numerous attempts have been made on qualitative
and quantitative characterization of this system during the past 80 years. For process design the
kinetic parameters of the chemical reactions occurring during the two-stage production process
have been of chief interest. In recent years, the reduction of formaldehyde emissions from cured
resins in the final wood product has been in focus, as formaldehyde emissions received more
attention as a thread to public health.

The production process consists of two steps, as shown in Figure 7. In the first step, urea reacts
with an aqueous solution of formaldehyde under slightly basic conditions to form several different
hydroxymethylated ureas. The degree of substitution depends on the ratio of formaldehyde to urea
as well as on other reaction conditions. During the second step, these hydroxymethylated ureas
condense under slightly acidic conditions to form methylene and ether bridges between the urea
molecules. Long polymer chains and even cross-links can be formed this way. The degree of
polymerization is usually being controlled by viscosity measurements.
Figure 7. Simplified reaction network of the reaction of urea with formaldehyde.
Hydroxymethylation during the first step, condensation during second step, and the last step
including cross-linking occurs after application to the wood fiber.

The reaction network is very complex, as urea theoretically may react with up to four molecules
of formaldehyde. Because of this high number of possible combinations many different
intermediates can be formed. Higher intermediates can also be formed through different pathways.
All reactions are equilibra, which makes isolation and characterization impossible for all but the
most simple intermediates. Attempts have been made in the past to synthesize many of these
intermediates.29 Later kinetic studies have been done by titration30 of excessive formaldehyde and
formaldehyde liberating compounds. Unfortunately, these were not able to distinguish between
different intermediates, so these studies gave only overall kinetics. Recent works mainly focus on
the analysis of cured resins by IR31 and NMR spectroscopy in solid form and in solution32–34 as well
as on chromatographic35,36 and rheological investigations.37
To analyze in detail the kinetics of a reaction system with such a complex and permanently
changing composition, it is essential to monitor formation and decomposition of as many single
components as possible. Time-consuming sample preparation is not an option here, because any
changes to the sample will inevitably lead to a change in composition due to the ongoing relatively
fast equilibrium reactions. Online NMR spectroscopy is very well suited for analysis of this
system. The sample transfer is quick and the largest part of the reaction mixture is permanently
accessible for manipulations. For this reaction system, it is very important to keep the pH constant,
which would be impossible if the analysis was carried out in a standard NMR tube. Figure 8 shows
the reaction progress of the hydroxymethylation of urea at a formaldehyde–urea ratio of 2:1 and a
reaction temperature of 343 K. The conversion of urea and formation of hydroxymethylated
products can be followed quantitatively and with appropriate data workup and modeling the kinetic
parameters can be derived.

Figure 8. Observation of the reaction of urea with formaldehyde over a course of 2 h at a

temperature of 343 K and pH 8.5. The molar ratio of formaldehyde to urea was 2:1. Consumption
of urea (•) and formation of two different hydroxymethyl ureas (⋆,◊) can be distinguished clearly
making use of the amide protons. Protons of methylene groups cannot be used for quantification
because of overlap with formaldehyde signals.
Aldehyde Polymers

G. Urea–Formaldehyde Resins

Instead, the adhesive market is of great importance for UF resins, with particular importance in
the production of the particle board, plywood, and in the furniture industry. To prepare a suitable
resin, formalin is first neutralized. The mixture is boiled under reflux, typically for about 15 min,
to give dimethylol urea and other low molar mass products. The resins is then acidified to pH 4,
with formic acid, and reacted for a further 5–20 min. The resulting resin is then stabilized by
neutralizing to a pH 7.5, to give a water-soluble resin with about 50% solids content, normally
reduced to a 70% solids by vacuum distillation. The resulting product is QC tested for viscosity,
solids content, pH value (must be between 7.3 and 7.5), and its reactivity with a standard hardener.
Resins are commonly available with urea to formaldehyde molar ratios ranging from 1:1.05 to
1:2.2. Higher formaldehyde ratios give greater clarity, the best water resistance, marginally
superior mechanical properties, longer shelf-life (up to two years), and greatest reactivity. The
degree of condensation is quite important to achieve only limited absorbance into wood (for
adhesive keying) and good thin film coverage as a continuous layer of adhesive over a substrate's
surface (i.e., to maximize other forms of adhesive bonding). Rye or wood flour applied to the wood
substrate reduces the extent of resin penetration, improves adhesive spreading properties, and
limits the amount of adhesive applied.

The resins are hardened by acidic conditions. Ammonium chloride or phosphoric acid, an acid
donor, is employed. This reacts with formaldehyde to give hydrochloric acid. Hexamine is also
formed during this reaction:

4NH4Cl + 6CH2O → N4(CH2)6 + 6H2O + 4HCl

About 1.5 parts ammonium chloride per 100 parts of the resin solution are generally used, the
hardener being added as an aqueous solution.

At one time, UF was used extensively in the manufacture of plywood, but today it is less important.
For this purpose, a resin (typically urea-formaldehyde molar ratio of 1:1.8) -hardener mixture is
coated onto a wood veneer. This is plied together with other treated veneers and pressed at
95–110 °C under pressure at 1.4–5.5 MPa. UF-bonded plywood is suitable for indoor application,
but is generally unsuitable for external use. So-called marine plywoods are more suitable for
exterior use, where PF, resorcinol–formaldehyde, or melamine-modified resins are employed.

UF resins continue to be used in large quantities in general wood assembly work in the furniture
industry. In most cases, a resin-hardener mixture is applied to the surfaces to be joined and then
clamped under pressure while hardening occurs. It is also possible to coat the resin onto one surface
and the hardener onto the other surface, allowing them to come into contact in situ and thus
avoiding the short pot-life of the mixture. Gap-filling resins may be produced by incorporating
plasticizers (e.g., furfuryl alcohol), and fillers to reduce shrinkage, cracking, and crazing.

One of the largest applications of UF resins nowadays is in the manufacture of chipboard. Wood
chips are mixed with about 10% of resin-hardener solution and the mixture is pressed in a multi-
daylight press for about 8 min at 150 °C. Resins with low free formaldehyde content are used to
minimize odor, both during processing and from the finished product in service. A rather high urea
to formaldehyde ratio subjected to only a low degree of condensation is necessary in order to
achieve a low, free formaldehyde content.

Wood chipboard is free from grain and is thus essentially anisotropic, with mechanical properties
being approximately the same as the average of the properties of the original wood measured along
and across the grain. The water resistance of chipboard is poor but, being isotropic, it does not
warp as long as it is able to swell freely in all directions.
Wood: Adhesives
H. Melamine–urea–formaldehyde and melamine–formaldehyde adhesive
resins
MUF and MF resins are more resistant to moist environments than are UF resins. However,
melamine is much more expensive than urea. The MF and MUF resins are used for scarf jointing
of plywood and end jointing of structural lumber that can be used in protected exterior exposure.
In addition, these resins are used for bonding low- and high-pressure laminates and overlays. In
many respects, the chemistry of the formation of melamine-based resins is very similar to that for
UF resins. However, the addition of formaldehyde to the amino groups of melamine is faster and
more complete than is the addition of formaldehyde to urea. Thus, complete hydroxymethylation
of melamine occurs (Pizzi 1983), which as mentioned above, is not the case with urea. Another
important difference is that the condensation reactions of the hydroxymethylated melamines occur
not only under acid conditions but under neutral and slightly alkaline conditions as well (Pizzi
1994, Pizzi and Mittal 1994). In addition, products bonded with MF resins seem to be less
susceptible to the release of formaldehyde than are products bonded with UF resin.
Solid State NMR of Polymers
I. Urea-formaldehyde resins
Currently, one of the most important commercially available materials today are the urea-
formaldehyde (U-F) resins. Their applications include coatings, adhesives, castings, moulding
compounds and textiles. Maciel et al. have produced a series of extensive papers in this area
concentrating on both 13C and 15N CP/MAS [13–16].

A systematic 13C CP/MAS study was undertaken of a large array of different U-F resins synthesised
under a wide range of conditions including pH, concentration, and U:F ratio [13]. Catalyzed by
both acid and base a great variety of reactions can occur leading to a large and complex range of
moieties depending upon the synthetic conditions. At high pH the principal linkages present are
methylol urea (65, 72 ppm) and dimethylene ether (69, 70 ppm), also present under the basic
conditions is a small amount of methylene methyl ethers (55 ppm). Under acidic conditions other
reactions predominate. In addition to the formation of linear methylene linkages (47, 54, 60 ppm)
resins contained a substantial amount of crosslinking methylene linkages (69, 76 ppm) which
increase as the F:U ratio increases. At very high F:U ratios methylene dimethylene ethers, methylol
and hemi-formals occurred (69-72 ppm). Also present in large quantities were disubstituted urons
(75, 79 ppm) which increased as pH increased.

In an attempt to formulate alternative [14] resins N,N′-dimethylolurea or paraformaldehyde was

used as a different source of formaldehyde to crosslink the urea molecules. The resins produced
by these methods generally exhibited similarities to those previous synthesised using
formaldehyde [13]. Small differences between the resins produced by the different synthetic route
appeared to be due principally to the problems of solubility of the N,N′-dimethylolurea or
paraformaldehyde.

A large volume rotor MAS system was used to examine the natural abundance 15N present in urea-
formaldehyde resins [15]. Increasing the amount of material which is examined has enabled the
investigation of the isotopically low 15N present (0.37%) in the resins without having to resort to
synthesising 15N enriched materials. There are four possible interaction sites between urea and
formaldehyde (Fig. 15.2.11).
Fig. 15.2.11. Structural units present in UF resins.

For resins synthesised under acidic conditions tertiary amides initially seen by 13C CP/MAS were
confirmed by 15N CP/MAS. Under neutral or basic conditions the main constituents of the resin
are N,N′-dimethylolurea (102 ppm), monomethylolurea (102 and 78 ppm) and dimethylene ether
linkages (90 ppm). Using dipolar dephasing and cross-polarisation times it was possible to
distinguish primary, secondary and tertiary substituted nitrogens. These results confirmed the
existence of many moieties postulated by 13C CP/MAS.

The widespread application of U-F resins has meant understanding the mechanism of the
degradation process is important if an improvement in resin stability is to be obtained [16].
Therefore the way in which U-F resins change when they undergo hydrolysis was examined. The
resins have been described previously [13]. There are a number of possible mechanisms which
involved the hydrolysis of the moieties in the U-F resins. A typical degraded resin is shown in Fig.
15.2.12.

Fig. 15.2.12. (a) 50.3 MHz 13C CP/MAS NMR spectrum of a UF resin sample prepared from
formalin (F) and urea (U) with an equivalent F/U/water ratio of 2.00/1.00/1.07 at pH 3 and (b) its
solid residue after hydrolytic treatment at pH 4 and 86°C for 20 h. Spinning side bands are marked
with asterisks.

It was demonstrated that resins prepared with an equivalent molar ratio of F:U gave the highest
stability towards hydrolytic treatment. Resins which contained higher F:U ratio (2.0:1.0) contained
a wide range of moieties which were more readily susceptible to hydrolysis, the products formed
include dimethylene ether linkages, poly(oxymethylene glycols) and methylols attached to tertiary
amine groups. These moieties are the sources of formaldehyde when the resin degrades. Resins of
different composition showed similar degradation patterns.