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Phenolic Resin Adhesives
Phenolic Resin Adhesives
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I. INTRODUCTION
Phenolic resins are the polycondensation products of the reaction of phenol with formal-
dehyde. Phenolic resins were the first true synthetic polymers to be developed commer-
cially. Notwithstanding this, even now their structure is far from completely clear, because
the polymers derived from the reaction of phenol with formaldehyde differ in one impor-
tant aspect from other polycondensation products. Polyfunctional phenols may react with
formaldehyde in both the ortho and para positions to the hydroxyl group. This means that
the condensation products exist as numerous positional isomerides for any chain length.
This makes the organic chemistry of the reaction particularly complex and tedious to
unravel. The result has been that although phenolic resins were developed commercially
as early as 1908, were the first completely synthetic resins ever to be developed, and have
vast and differentiated industrial uses today, and great strides have been made in both the
understanding of their structure and their technology and application, several aspects of
their chemistry are still only partially understood.
It may be argued with some justification that such a state of affairs is immaterial,
because satisfactory resins for many uses have been developed on purely empirical grounds
during the past 90 years. However, it cannot be denied that the gradual understanding of the
chemical structure and mechanism of reaction of these resins has helped considerably in
introducing commercial phenolic resins designed for certain applications and capable of
performances undreamed of in formulations developed earlier by the empirical rather than
the scientific approach. Knowledge of phenolic resin chemistry, structure, characteristic
reactions, and kinetic behavior remains an invaluable asset to the adhesive formulator in
designing resins with specific physical properties. The characteristic that renders these resins
invaluable as adhesives is their capability to deliver water, weather, and high-temperature
resistance to the cured glue line of the joint bonded with phenolic adhesives, at relatively
low cost.
II. CHEMISTRY
Phenols condense initially with formaldehyde in the presence of either acid or alkali to
form a methylolphenol or phenolic alcohol, and then dimethylolphenol. The initial attack
A. Acid Catalysis
Consideration must be given to the possibility of direct intervention by the catalyst in the
reaction. Hydrochloric acid is the most interesting case of an acid catalyst, as is ammonia
of an alkaline catalyst. When the PF reaction is catalyzed by hydrochloric acid, two
mechanisms may come into operation. Vorozhtov has proposed a reaction route that
passes through the formation of bischloromethyl ether (Cl–CH2–O–CH2–Cl) [4]. Ziegler
has suggested a route through the formation of a chloromethyl alcohol (Cl–CH2–OH) as
intermediate [5,6]. The second route appears to be the more probable. Both hypotheses
agree that chloromethylphenols are the principal intermediates. The chloromethylphenols
have been prepared and isolated by various means. They are highly reactive compounds
which, with phenols, form dihydroxydiphenylmethanes and complex methylene-linked
multiring polyphenols. Reaction is highly selective and takes place in the para position.
B. Alkaline Catalysis
Different mechanisms of alkaline catalysis have been suggested according to the alkali
used. When caustic soda is used as the catalyst, the type of mechanism which seems the
most likely is that which involves the formation of a chelate ring similar to that suggested
by Caesar and Sachanen [7]. The chelating mechanism was thought to initially cause the
formation of a sodium–formaldehyde complex or of a formaldehyde–sodium phenate
These intermediates contain nitrogen and have polybenzylamine chains. They react
further with more phenol causing splitting and elimination of the nitrogen as ammonia or
producing eventually nitrogen-free resins. However, as benzylamine bridges have been
shown to be much more temperature stable than previously thought, this requires a con-
siderable excess of phenol and a high temperature, or heating for a rather long time. With
phenol–hexamethylenetetramine resins of molar ratio 3:1, the nitrogen content of the resin
cannot be reduced to less than 7% when heated at 210 C. When the ratio is increased to
7:1, the nitrogen content on heating at 210 C can be reduced to less than 1%. Contrary to
what was widely believed it has been clearly demonstrated that in the preparation of PF
resins starting from hexamethylenetetramine the di- and trihydroxybenzylamine bridges
which are initially formed are very stable and are able to tolerate for a considerable length
of time a temperature as high as 100 C [13] yielding in certain aspects (only) resins of
upgraded characteristics. This behavior is closely tied to the reactions characteristic of
hexamethylenetetramine to form iminomethylene bases [14–16], which are discussed in the
melamine resins chapter in this volume (Chap. 32).
Ammonia-, ammine-, and amide-catalyzed phenolic resins are characterized by
greater insolubility in water than that of sodium hydroxide-catalyzed phenolic resins.
The more ammonia that is used, the higher the molecular weight and melting point that
are obtained without cross-linking. This is probably due to the inhibiting effect of the
nitrogen-carrying groups (i.e., –CH2–NH–CH3 or –CH2–NH2), which is caused by their
slow rate of subsequent condensation and loss of ammonia. Ammonia, amines, and
amides are sometimes used as accelerators during the curing of phenolic adhesives for
wood products.
The rate of metal exchange is solution [8,18] and the instability of the complex
formed determine the accelerating or inhibiting effect of the metal in the reaction of
phenol with formaldehyde. The more stable complex II is, the slower the reaction pro-
ceeds, to the formation of resin III. A completely stable complex II should stop the
reaction from proceeding to resin III. If complex II is not stable, the reaction will proceed
to form PF resins of type III. The rate of reaction is directly proportional to the instability
or the rate of metal exchange in solution of complex II. The acid catalysis due to the metal
ion differs only in degree from that of the hydrogen ion [19].
The effect of the metal is stronger than that of hydrogen ions, because of higher
charge and greater covalence, since its interaction with donor groups is often much greater
[19]. This allows phenolic resin adhesives to set in milder acid conditions. Most covalent
metals ions accelerate the PF reaction. The extent of acceleration depends on the type of
metal ion and the amount of it that is present. The capability of acceleration in order of
decreasing acceleration effectiveness has been reported to be [11] PbII, ZnII, CdII,
NiII > MnII, MgII, CuII, CoII, CoIII > MnIII, FeIII BeII, AlIII > CrIII, CoII. The most
important conclusion to be drawn is that the accelerating effect is indeed present in both
the manufacture of PF resin and its curing. Therefore, the fast rate of curing of high-ortho
phenolic resins can be ascribed only partially to the high proportion of para positions
available. The other reason for the fast rate of curing is that the metallic ion catalyst is still
present, and free to act, in the resin at the time of curing. In such a resin, a considerable
number of ortho positions (especially of methylol groups in ortho positions to the phenolic
hydroxyls) are still available for reaction and capable of complexing.
Figure 4 Cure retarding at high pH and ester acceleration effect of NaOH and KOH-catalysed PF
resins (ester ¼ propylene carbonate). Note curve 5, the effect of 4 months aging of the PF resin of
curve 1 on the extent and starting pH of the retardation effect. Compare the start of acceleration for
curves 4 and 6, showing the differences between propylene carbonate and triacetin esters, and
compare the starting point of acceleration at pH 5.5 and pH 7.1. The ‘‘bumps’’ on the curves at
pH 8–11 are caused by methylene ether formation, decomposition, and rearrangement [9].
of phenate ions, leading to a more complex variant of the Kolbe–Schmitt reaction. The
ester, or residue of its decomposition, attacks the negatively charged phenolic nuclei, and
its reaction is not limited to the ortho and para sites, transforming the phenolic nuclei in a
temporary condensation reagent of functionality higher than 3, leading to much earlier
gelling. Furthermore, temporary condensation occurs not only according to the PF
mechanism but also according to a second reaction superimposed on it [9,23] (Fig. 4).
Other explanations and mechanisms for this occurrence have also been advanced:
determination by TMA of the average number of freedom of polymer segments between
cross-linking nodes of PF resin hardened networks indicate that additive accelerated PF
It is the urea which contributes to the acceleration of resin cure by allowing the
following.
(i) The preparation of greater molecular mass linear oligomers needing fewer steps
to cure, hence curing faster. Copolymerization up to a certain level of urea
addition brings an easier and much faster reaction to the mainly linear higher
molecular weight oligomers; in a sense this is just a way to molecularly double
very quickly the molecular weight of a PF resin while still maintaining the
linearity of the higher molecular weight oligomers formed. The extent of copoly-
merization, however, needs to be limited and cannot be brought to an excess
otherwise the viscosity of the resin becomes unmanageable, although the pres-
ence of free urea is able to control this trend.
The PUF resins prepared are capable of further noticeable curing acceleration by
addition of ester accelerators, namely glycerol triacetate (triacetin), to reach gel times as
fast as those of catalyzed aminoplastic resins, but at wet strength values characteristic of
exterior PF resins [31,32]. Guanidine carbonate has also been shown to be an accelerator
of PF resins which, while yielding slightly slower gel times than triacetin when just added
to a PF resin glue-mix, is also capable of giving glue-mix pot-lives on the order of several
days, hence long enough to be premixed with the resin well before use [32]. Both triacetin
and guanidine carbonate used as simple glue-mix additives increase the ultimate strength
IV. APPLICATIONS
These are hardened by heating after the addition of small amounts of wax emulsion
and insecticide solution in the case of particleboard, and of vegetable or mineral fillers and
tackifiers in the case of plywood. Accelerators are sometimes added in both types of glue
mixes. The pH of these resins varies between 10 and 13.5 and is generally between 12
and 12.5.
In dealing with wood related factors that affect glue bonds, it is important to
remember that adhesion is at least 95% physicochemical in nature. The mechanical aspects
of bond formation (such as keying cured adhesive solid in the wood surface) contribute
negligibly to the bond strength or wood failure. The main chemical forces in thermosetting
resin adhesion are primary valence bonds, covalent bonds, and hydrogen bonds, plus
secondary forces such as van der Waals and London forces and any other types of
electrostatic, dipolar, and associative forces. It is therefore essential that the resin contains
a significant number of functional groups and that the wood surface presents a significant
Material Composition
5. Dry-Out Resistance
One of the more common difficulties in bonding pine veneers and chips is adhesive dry-
out. Dry-out is associated with the high liquid absorbancy of pine sapwood and it appears
especially during long assembly times. This problem can be overcome by using resins
modified through reaction with alkylated phenols, especially 3,4-xylenol [52]. Another
technique used to achieve similar results is the manipulation of synthesis procedures
used in preparing a standard PF resin [52]. The dry-out resistance imparted by alkylated
phenols is due to an initial semithermoplastic character in the resin. This is derived from
their monomer bifunctionality and the linear polymer that is consequently formed.
If a linear and essentially non-cross-linking prepolymer is prepared from phenol and
formaldehyde, it can be coreacted with a nonlinear and cross-linking prepolymer to form a
resin. The latter resin will have some initially semithermoplastic or dry flow character but
will be primarily thermosetting. The product is an alkaline novolak–resol copolymer.
(i) The formation of urethane bridges derived by the reaction of the isocyanate group
with the methylol group of the PF resin [33,56], which is perhaps one of the two dominant
reactions introducing better dissipation of energy at the interface and hence contributing
to strength improvement; (ii) the classical formation of methylene bridges in the PF resin
only [33,56,57]; (iii) the formation of polyurea networks due to the reaction of the poly-
meric polyisocyanate with the water carrier of the PF resin [33,56,57]; and (iv) the reaction
of the PF methylol group to form methylene bridges on the aromatic nuclei of polymeric
MDI [56].
Figure 7 Higher temperature zone detail of the TTT diagram of epoxy resin adhesives on non-
interacting glass fiber substrate.
E. Prediction of Properties
Only a small amount of work has been done up to now concerning the prediction of bond
strengths and other properties based on the results of the analysis of the PF resin.
Correlation equations evaluating the chemical structures in various PF resins with differ-
ent formaldehyde/phenol molar ratios and different types of preparation on the one hand
and the achievable internal bond as well as the subsequent formaldehyde emission on the
other hand have been developed [63]. These equations are valid only for well defined series
of resins. The basic aim of such equations is the prediction of the properties of the wood-
based panels on the basis of the composition and the properties of the resins used. For this
purpose various structural components of the liquid resin are determined by means of 13C
nuclear magnetic resonance (NMR) and their ratios related to board results, so to the
strength results of the hardened resin. Various papers in the chemical literature describe
examples of such correlations, in particular for UF, MF, MUF, and PF resins [63–67]. For
example, one type of equation correlating the dry internal bond (IB) strength (tensile
strength perpendicular to the plane of the panel) of a particleboard bonded with PF
adhesive resins is as follows [33,63]
where the IB strength is expressed in MPa; A is the sum of the peak areas of phenolic ortho
and para sites still free to react (110 to 122 ppm), B is the sum of the peak areas of phenolic
meta sites (125 to 137 ppm), C is the sum of the peak areas of phenolic ortho and para sites
already reacted (125 to 137 ppm), Mo is the sum of the peak areas of phenolic methylol
groups (59 to 66 ppm), and Me is the sum of the peak areas of methylene bridges con-
necting phenolic nuclei (30 to 45 ppm). The coefficients a, b, and c are characteristic of the
type of resin and depend on a variety of manufacturing parameters. Equation (1) is one of
the simpler equations of this type, the equations for UF resins in particular being in
general more complex. Similar equations correlating the level of crystallinity of hardened
aminoplastic resin, the IB strength of the board prepared with it, the level of cross-linking
of the resin and the formaldehyde emission of the panel and resin with the 13C NMR
spectrum of the liquid resin have also been presented [33, 64–67].
For certain boards, good correlation exists. However, it must be assumed that a
general correlation for various resins and various panels will not exist and that maybe
other correlation equations should be used. Nevertheless, these results are rather impor-
tant, because they show that at least for a special combination of resin type and board
type, correlation between analysis of the resin in its liquid state and the strength of the
same resin in hardened form exists, and that forecast of performance can be done based on
just the analysis of the liquid resin. Furthermore the various parameters corresponding to
chemical and physical groups in the liquid resin will also be the decisive parameters for
other resin combinations and manufacturing procedures, although the values of the coef-
ficients within the individual equations might differ. However, it also must be considered
that the range of molar ratio under investigation in the papers mentioned above is rather
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