4. Chemical Reactions in EPI Adhesives
The reactivity of different isocyanates varies widely, and the most reactive NCO
groups can react with almost any compound that contains an active hydrogen [1,
2, 16]. The reactivity of the nucleophilic groups also varies; primary amines are
more reactive towards NCO than primary alcohols, followed by water, secondary
and tertiary alcohols, other urethanes, carboxylic acids, and carboxylic acid amides
in that order [16]. The isocyanate will, of course, react with the water present in the
EPI formulation to form amines followed by further reactions producing urea and
biuret. The mechanism of this reaction is shown in Fig. 5. As can be seen from the
reaction mechanism CO2 is a byproduct of this reactionTheisocyanate will also react with hydroxyl groups in the EPI adhesive as shown
in Fig. 6. The reaction between isocyanate and hydroxyl gives urethane linkage.
The main source of hydroxyl groups in the adhesive is usually the PVA, but
hydroxyl and other functional groups such as carboxyl groups and amines on the
emulsion polymer chain can also react with the isocyanate, provided that they are
physically available. In addition, the hydroxyl groups in the wood may take part in
the reaction with isocyanate to some degree [1, 2, 12]. Most of the reactions taking
place in the EPI adhesive mixture are irreversible.
The reaction mechanism of isocyanate in EPI glue mixes has been studied by
Raman spectroscopy. This showed that the reaction with water to give urea was
the most dominant reaction [17]. However, biuret and urethane were formed in
higher amounts than expected. The reaction rate over time was investigated by FTIR
analysis and during the first 12 h of reaction large amounts of urea and biuret
were formed. In this step there was still sufficient water in the system to enable the
NCO to react with water instead of with hydroxyl. After 12 h the glueline was solid
and the samples had constant weight. Monitoring of the reaction showed that the
extent of reaction between isocyanate and hydroxyl groups to form urethane groups
increased as seen by a gradual reduction of the amount of NCO groups.
Due to the large number of competing reactions between components of widely
different concentrations, it is difficult to predict to what extent the different reactions
occur in an EPI adhesive mixture. Due to the large amount of water in the adhesive
mix, it is clear, however, that there is extensive reaction between the isocyanate and
water.
5. Gluing Process and Glueline Properties of EPI Adhesives
Since the EPI adhesives are emulsion based but cross-linked with isocyanate, they
share characteristics with both thermosetting and thermoplastic adhesives. The ad-hesives are multi-phase systems comprising emulsion particles, polymer solution,
cross-linker droplets and filler particles. Just as for other emulsion adhesives, the
coalescence of the emulsion particles [18, 19] and the distribution of these in the
glue film is important for the bond quality. The cross-linking in the adhesive film is
also of great importance for the bond quality as well as for the moisture resistance
and heat resistance of the adhesive.
During gluing with an EPI adhesive a number of potential reactions and
processes can occur simultaneously. These are:
•Water transport away from the glueline;
•Coalescence of the emulsion particles to form a glue film;
•Reaction of –NCO groups with water;
•Reaction of –NCO groups with other –NCO groups;
•Reaction of –NCO groups with –OH groups present in PVA or with other
hydroxyl-functional groups in the water phase;
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•Reaction of the –NCO groups with functional groups available in/on the emulsion
polymer;
•Reaction of –NCO groups with hydroxyl groups on the wood cell walls.
These processes/reactions occur in parallel to each other and at different rates.
The rate and extent of each of these depend on the composition of the EPI adhesive
and the actual gluing conditions (temperature, gluespread, wood moisture
content (MC), etc.). Hence, it is virtually impossible to accurately describe what is
occurring at any given time during the gluing process. An attempt to discuss the
individual processes and what may affect them will, however, be made
The initial film formation to obtain a glue film may take from minutes up to one
hour, depending on factors such as temperature, emulsion type(s), solids content,
gluespread, wood species and wood moisture content. The coalescence of the emulsion
particles may, however, continue for days after the gluing is performed [16].
Although the film formation process is relatively fast even at room temperature,
higher temperature will increase the water transport away from the glueline and result
in faster film formation. The effect of the increasing temperature is, however,
small in this physical process compared to the effect the increased temperature has
on the reactivity and chemical processes of thermosetting adhesives. How fast the
initial strength of the glueline builds up depends, to a large extent, on the time taken
for removal of water from the glueline and how quickly the coalescence process
proceeds [2, 6].
The chemical cross-linking reactions between the isocyanate and the adhesive
components occur before, during and after the film formation process and may continue
for days after the gluing has been performed [16]. The choice of type(s) andamount of PVA polymer is important for the isocyanate cross-linking reactions occurring
in the water phase. If the EPI is not formulated correctly with respect to this,
the cross-link density will suffer, resulting in inferior moisture resistance. Reaction
with hydroxyl functional groups in or on the emulsion polymer is also possible,
provided that the functional groups are physically and sterically available for reaction.
Even reaction between the isocyanate and the hydroxyl groups in the wood
substrate has been reported [1, 2, 12] although recent research indicates that this is
still open for debate [20, 21]. The contents of water and hydroxyl groups are very
high in EPI adhesive gluelines, hence the probability of reaction between isocyanate
and hydroxyl groups in the wood is most likely very low. The adhesion between the
glue and the wood will, however, be improved by ionic interactions and mechanical
and chemical bonds, e.g., hydrogen bonds [4, 6].
The glueline will have very good mechanical properties if the coalescence of the
emulsion particles is optimal. However, if the isocyanate reaction proceeds too far
before the glue film is formed, i.e., the glue mix is too old before it is used (cf.
‘pot-life’ Section 6.1), adequate coalescence will not be possible and the glueline
will have a more rubbery consistency [2]. Hence, a good balance between these
processes is essential.
By cross-linking with isocyanate [3] the glueline properties change from those
of a typical thermoplastic to those similar to thermosetting adhesives. The EPI
adhesives are unique in that the emulsion-based component can be formulated to
have low glass transition temperature (Tg) and minimum film forming temperature
(MFFT) to facilitate formation of a good glue film at room temperature. The final
glueline will still have low creep, high heat and moisture resistance, and high Tg
due to the isocyanate cross-linking reactions. Unfortunately, there is little information
available on how the Tgof the different emulsions influences the Tgof the final
glueline [2]. Qiaoet al. describe the variation in Tgfor EPI adhesives based on