Holz als Roh- und Werkstoff 54 (1996) 85-88 ~ Springer-Verlag 1996
Influence of PMUF resins preparation method on their molecular
structure and performance as adhesives for plywood
C. Cremonini, A. Pizzi, P. Tekely
The preparation method of a PMUF resin manufactured in
a single synthesis procedure has been shown to have
fundamental importance both at the molecular level and for
the resin application performance. ~3CNMR spectra of PMUF
resins present excellent correspondence with applied tensile
strength results of plywood prepared with the same resins.
PMUF resins prepared by initial reaction of phenol with
formaldehyde followed by standard MUF preparation
procedures present better results than resins prepared with the
phenol either added during the preparation or added at the end
of the MUF resin preparation. The reason for this is the reaction
procedure itself which ensures that the phenol is copolymerized
with the main MUF chain to form a block copolymer and
that both PF and MUF resin blocks still present consistent
amounts of reactive methylol groups. Progressive deviation
from these molecular level requirements during the course of
PMUFs preparation also ensures a progressive deviation from
their optimal performance, even leading to PMUF resins of
worse performance than their corresponding MUF resin to
which phenol has not been added.
EinfluB der Pra'parationsmethode yon PMUF-Harzenauf
Molekularstruktur und Klebereigenschaftenim Hinblick
auf die 5perrholzherstellung
Die Pr~parationsmethode eines PMUF-Harzes hats eine
grundlegende Bedeutung sowohl fiir die Molekfilstruktur als
auch das Klebeverhalten. ~3CNMR Spektren der Harze stehen
in ansgezeichneter Obereinstimmung mit der Festigkeit der
damit hergestellten Sperrh61zer. Wenn vor der Standard-
priiparation des PMUF-Harzes zuniichst eine Phenol/
Formaldehyd-Kondensation gestartet wird, erhiilt man bessere
Ergebenisse als bei sp~iterer Zugabe des Phenols. Auf diese
Weise wird eine Kopolimerisation der MUF-Ketteu mit Phenol
schergestellt. In diesem Block-Kopolymer weisen beide
Harzkomponenten noch gen~gend reaktive Methylol-
gruppen auf. Abweichungen yon dieser Pr~parationsmethode
fthhren zu entsprechenden Verschlechterungen der
Klebereigenschaften, bis dahin, dab sogar minderwertigere
PMUF-Harze entstehen k6nnen als ensprechende MUF-Harze
ohne Phenolzusatz.
C. Cremonini
Compensati Toro S.p.A., Azeglio, Italy
A. Pizzi1
ENSTIB,University of Nancy 1, Epinal, France
P. Tekely
NMR MethodologyLaboratory, University of Nancy 1, Nancy, France
To whom correspondence should be addressed
85
1
Introduction
Phenol-melamine-urea-formaldehyde (PMUF) resins have
acquired in the last few years a certain popularity and diffusion
as wood panel adhesives (Cremonini et al. 1996; van Niekerk,
Pizzi 1994). These resins were born from the need to firstly
prepare melamine-urea-formaldehyde (MUF) resins of
improved exterior durability and water- and weather-resistance,
and secondly to prepare resins of even lower melamine content,
hence of even lower cost which still present a light-coloured
glue-line. The proportions of phenol added are low, generally
5% to 10% of total resin solids. The concept behind a PMUF
resin is that copolymerisation of phenol within the main chain
of the liquid MUF resin and its inclusion in the cross-linked,
hardened network of the adhesive, would allow a better weather-
and water resistance of the bonded joint. This concept is correct,
but it relies on the copolymerisation of the phenol with the MUF
resin really occurring. However, many modern PMUF resins,
for reasons of ease of manufacture, rely on the addition of
a small addition of phenol at the end of the MUF resin
preparation period, thus under conditions which, at least in
theory, should not be conducive to copolymerisation of the
phenol in the resin network (Pizzi 1994). Under the final,
alkaline conditions at pH 9.5-10.0 of a MUF resin preparation,
the reactivity of melamine with formaldehyde and methylol
groups is quite low, but still greater than that of phenol, the
reactivity of which would only start to slowly dominate the
system at pH I1 to 12 (Pizzi 1994). Even lengthening of the
reaction time would not help much. Furthermore, hardening
of the resin, as for all mainly aminoplastic resins, occurs in
mildly acid conditions, at pH 3.5 to 4, hence at the pH of
minimum reactivity of phenol (Pizzi 1983). The reactivity of
both urea and melamine at these pHs is very much greater than
that of phenol. The real danger exists then that phenol is neither,
or very little, linked to the liquid MUF resin skeleton nor to its
hardened, tridimensional network. It will remain at best as
a useless pendant side group not able to fulfill the function for
which it has been added (Higuchi et al. 1994), or even worse
will mainly remain as free phenol, or free monomeric methylol
phenols, which are liable to leach with ease from the hardened
glue-line (Toro 1995). In both cases no contribution to weather
resistance of the hardened adhesive will occur, and often
the resin will rather behave as a poorer MUF due to the
melamine having been lowered (Cremonini et al. 1996). In the
second case, considerable leaching of phenol and low molecular
weight phenolic compounds wiU occur, putting a considerable
strain on the user factory to fulfill government regulations
on waste water free phenol content (Toro 1995).
A few resin producers have clearly identified the problem
and have solved it well by adding to the MUF resin, even at
reaction end, a low condensation phenol-formaldehyde resin
(PF) (Dunky 1995), which ensures reaction of the melamine
groups with the methylol groups carried by the phenolic resin.
This however, is not a universally adopted solution because it
 entails the preparation of two separate resins, the MUF and the
PF, followed by their coreaction. Ease of industrial preparation
is thus worse. A majority of the smaller adhesives manu-
facturers, often unaware of the problems outlined above and
of their likely cause at molecular level, still add phenol at
reaction end or other unsuitable periods during the resin
preparation. As a consequence, many of the users of this type
of PMUF resin have very often experienced, and are continuing
to experience considerable problems in their application.
This paper is aimed at investigating the effect of adding
phenol at different stages in the preparation of a PMUF resin
and to ascertain both at the applied and at the molecular levels
86
what are the consequences, the results and the performance
obtainable.
2 above.
Experimental
2.1
Preparation of basic MUF resin
To 113 parts by weight of Formurea (a formaldehyde
concentrate stabilized by urea, of mass content of 57%
formaldehyde and 23% urea) are added 13 parts urea and 30
parts water. The pH is set at 10-10.5 and the temperature
brought to 92-93 C under mechanical stirring. The pH is then
lowered to 7.8-8.0 by addition of formic or acetic acid, and the
reaction continued at the same temperature, allowing the pH
to fall by itself over a period of 1 hour to I hour 30 minutes
to a value of 5.2 (if the pH falls under 5, it is adjusted with NaOH
30% solution to maintain it between 5.0 and 5.3). The pH is then
brought to 9.5 or higher by addition of 30% NaOH, then 41 parts
of melamine premixed with 19 parts of water are added to
the reaction mixture. The water tolerance of the reaction
mixture is checked every 10 minutes while the pH is allowed
to fall by itself. When the water tolerance reached is of
200% -220% and the pH is of 7.7-8, 6.5 parts of second urea
is added and the pH again brought to 9.5. The reaction is con-
tinued for I0-15 minutes but never to a water tolerance point
lower than 150% and possibly of 170%-180%. The pH is
then readjusted to 9.5 and the resin cooled and stored.
2.2 dimensions were prepared from beech veneers (Fagus sylvatica)
Preparation of PMUF resin with phenol addition at reaction end by using the following glue mix in parts by weight:
The preparation procedure used is identical to the previous one,
but the second urea addition is eliminated and in its place 10.2
parts of phenol are added. The pH is adjusted to 10-10.5 and
the reaction is continued for 15-30 minutes until the water
tolerance point is of approximately 200%. At the end of this
phase the pH will be of approximately 7.5-8.0. After this only the
6.5 parts of second urea is then added and the reaction
continued for approximately 10 minutes. The pH is then
corrected to 10-10.5 and the reaction mix cooled and stored.
2.3
Preparation of PMUF resin with phenol added during
the reaction
To 72 parts Formurea are added 22.5 parts urea and the pH is
adjusted with 33% NaOH to 9.5-10. The temperature is
increased to 90-93 C and after 10 minutes the pH is lowered
by addition of formic acid or acetic acid to 7.8-8.0 and the
mixture is made to react for 10 minutes. The pH is again
increased to 10 and 30.6 parts of phenol are added. After
15 minutes reaction, 267 parts of Formurea and 16.5 parts of
urea are added, the pH is lowered and the reaction continued
exactly in the same manner as for the basic MUF formulation
described above.
2.4
Preparation of PMUF resin with phenol added at
the beginning of reaction
To 10.2 parts by mass of phenol are added 0.8 parts methanol,
6 parts fine paraformaldehyde powder 96% grade, 3.4 parts
water. Under stirring the temperature is maintained at 40 C and
during a period of 30 minutes three lots of 0.17 parts of 33%
NaOH are added. The temperature is then increased to 90 C
during a period of 30 minutes, at the midpoint of which another
lot of 0.17 parts 33% NaOH are added. After maintaining the
temperature at 90 C for 5 minutes 19 parts of urea are added.
After further reaction at 90-93 C for another 15 minutes
(the pH at this stage of the reaction was of 9.5), 113 parts by mass
of Formurea were added. The pH is adjusted to 7.8-8.0 and the
reaction is continued exactly as for the basic MUF resin outlined
2.5
13CNMR of PMUF resins
Liquid resins ~3CNMR spectra were obtained on a Bruker MSL
300 FT-NMR spectrometer. Chemical shifts were calculated
relative to (CH3)~Si(CH2)3SO~ Na dissolved in D20 for NMR
control. About 1.0 mi of liquid resin was placed in an NMR tube
and diluted with 0.4 ml deuterium oxide added directly to the
sample. The spectra were done at 75.47 MHz. Acquisition
time was of 1.08 seconds and number of transients were of
approximately 1000. The solid state CP-MAS ~3CNMR spectrum
of the resin gelled with 2% ammonium chloride was also
obtained with a MSL 300 FT-NMR at a frequency of 75.47 MHz
with the sample spin at 4.0 kHz. Chemical shifts were calculated
relative to TMS for NMR control. Acquisition time was of 0.026
seconds with number of transients of about 5000. All spectra
were run with relaxation delay of 5 seconds and were accurate
to I ppm. The spectra were run without suppression of spinning
side bands and spectral width of 20 000. Typical spin lattice
relaxation times for the types of compounds analyzed were
taken from the literature (Breitmaier, Voelter 1987).
2.6
Preparation and testing of plywood panels
Five plys triplicate plywood panels of 400 x 400 x 12.6 mm
PMUF liquid resin 100 parts by weight
coconut shell flour, 200 mesh 8 parts by weight
wheat flour 2 parts by weight
water 6 parts by weight
NH4C140% solution 2.5 parts by weight
glue spread used was of 380 g/m 2 double glue line, press
temperature was 120 C, pressure was of 18 kg/cm2, and pressing
time was of 7 minutes ( = 1 min/mm till the furthest glue-line
+ 2 minutes). The panels were then cut and tested according
to European Norm UNI EN314 (1993) for exterior plywood,
which entails tensile testing after a 4 hours boiling water step
followed by a 16 hours oven drying step again followed by
another 4 hours boiling water step. The results obtained are
shown in Table 1.
3
Discussion
The results of plywood panels prepared with the three types of
PMUF resins, namely with phenol added at the end, during and
at the beginning of the reaction, clearly indicate that there are
considerable differences in performance of the PMUF resin
according to the method of preparation used (Table 1). Thus
Table 1. Tensile test results of plywood panels bonded with
PMUF resins prepared according to different procedures Resin type Tensile strength (kN) (EN314)
Standard deviation in parenthesis
PMUF, phenol at end 1.21 (0.16)
PMUF, phenol in react, middle 1.58 (0.28)
PMUF, phenol at the beginning 1.96 (0.30)
MUF, control 1.39 (0.19)

the PMUF resin with phenol added at reaction end performs

worse, and with phenol added during the reaction performs
better (these two cases being the most commonly used 87
manufacturing techniques), while the PMUF resin in which
phenol is used to start the reaction performs best (Table 1).
What are the reasons at molecular level for such
discrepancies of behaviour? The ~3CNMR spectra of the three
resins prepared give an indication of what occurs (Figs. 1, 2 and
3). In Fig 1 the ~C NMR spectrum of the liquid PMUF resin
prepared with phenol at reaction end indicates clearly that the
phenol contained in the resin is practically all free phenol. This
is shown by the marked intensity of the bands at 116, 119 and

180 160 140 120 100 80 60 40 20 0

ppm

Fig. 3. ~C NMR spectrum of liquid PMUF adhesive resin prepared by

addition of 10% phenol at the beginning of the main MUF preparation
procedure
Bild 3. ~C NMR Spektrum eines fliissigen PMUF-Harzes, dem zu
Beginn der Priiparation 10% Phenol zugesetzt wurde

129 ppm, which represent respectively free ortho sites, free para
sites and meta sites on the phenolic aromatic ring. The relative
proportions of the areas of these three bands are of approx-
imately 2:1:2, hence in approximately the proportions in
'"1 ......... I ......... i ......... I .........
phenol itself, indicating that the bulk of the 10% phenol added
I ......... i " " ' , , , ' 1 ......... i ......... I ......... I ......

180 160 140 120 100 80 60 40 20 0

ppm
Fig. 1. ~3CNMR spectrum of liquid PMUF adhesive resin prepared by phenol has reacted with formaldehyde to form some
addition of 10% phenol at the end of the main MUF preparation
procedure
Bild 1. ~3CNMR Spektrum eines flfissigen PMUF-Harzes mit Zusatz
yon 10% Phenol am Ende der MUF-Pr~iparation
has not reacted with formaldehyde. The very small band at
127 ppm only indicates that a very small proportion of the
methylolated phenols (also free). Phenolic methylene bridges
signals, at 36.5 and 31 ppm, are totally absent from this spectrum
indicating that the very small proportion of phenol which has
been able to react with formaldehyde is still in free monomeric
form, and thus also leachable. Free formaldehyde (the small
peak at 82.14 ppm) is present only in traces. The overall
impression of the resin which emerges when phenol is added

y last is then of a PMUF resin in which the phenol is just present

as free phenol ( > 95%) and free monomeric methylol phenols
( < 5%) and thus neither linked nor copolymerised with the
MUF resin skeleton. On acid hardening by addition of NH4CI
the free phenol will remain free, and so are likely to do most of
the methylol phenols, both constituting a leaching hazard of
phenolic species from the hardened adhesive network. Such free
phenols will also detract from the water resistance of the MUF
resin. Thus, in Table I the strength results of the PMUF resin
with end phenol addition are lower than the results of a
200 150 100 50 0 pure MUF prepared without phenol and according to the same
ppm formulation.
The ~C NMR spectrum presented in a previous article
Fig. 2, Solid State CP MASZ3CNMR spectrum of PMUF adhesive resign (Cremonini et al. 1996, Fig. 4), of the PMUF resin in which the
prepared by addition of 10% phenol during the main MUF preparation
procedure, after hardening phenol was added well after the initial urea and just before
Bild 2. FestkiSrper ~3CNMR Spektrum (CP-MAS)eines PMUF-Harzen melamine addition, thus in the middle of the reaction, still
mit Zusatz yon 10% Phenol w~ihrend des Herstellungsprozesses nach presents a considerable number of phenolic ortho and para free
dem Aush/irten sites (116, 119 ppm), but the number of free sites at which -CH2-
 and -CH2OH groups are now attached is considerably higher
(bands at 126 ppm). Very few methylene bridges connecting two
phenolic rings are present (see very small, broad bonds at 39
and 34 ppm) indicating that little condensation of phenolic
ring to phenolic ring has occurred. A small number of methylene
(-CH2-) bridges connecting melamine to phenol are also
present (small band at 54.5 ppm) indicating that a small amount
of phenol was capable of linking to the MUF resin skeleton and
is present on this as a pendant side group, of mostly single
phenols. From the above this resin not only contains free
formaldehyde (82 ppm band), but also a noticeable amount of
free phenol or free monomeric phenolic species: at least a certain
88
amount of phenol has started to link onto the main skeleton
of the MUF resin.
A solid state ~3CNMR CP-MAS spectrum of the hardened
resin confirms the above (Fig. 2). Thus, the relative area
proportions of the 130, 120 and 116 ppm (superimp. to 558)
peaks indicate that meta sites + reacted ortho/para phenolic
sites predominate, and free ortho and para sites remain in the
same relative proportion. More interesting is that as regards
methylene bridges, those between melamine and melamine/urea
clearly predominate (46-48 ppm band), but phenolic to
melamine methylene bridges are also clearly visible as
a shoulder at 55 ppm even in the hardened state of the resin
(Fig. 3). It is interesting to also note that a huge amount of
aminomethylol groups are still unreacted (band at 67 ppm), but
also that a considerable increase in relative proportion of
-N(-CH2-)-CH2OH potential branching groups (the shoulder
at 70-72 ppm), thus of methylols already linked to a long chain,
has occurred in the hardened resin in relation to what observed
in the liquid resin (Fig. 4 in Cremonini et aL 1996). A new
peak at 106 ppm (superimp. to 558) indicates the considerable
amount of phenolic aromatic carbons linked to a -CH 2-
(methylenic or methylolic). It is then safe to conclude that as
soon as some methylene linkage between phenol and melamine
exists in the liquid resin a certain significant amount of phenol
remains in the resin network, some as simply a pendant
side group of the aminoplastic chain, some bound in the resin
main chain itself and some only as free not-linked monomeric
phenols.
The ~3CNMR spectrum in Fig. 3 in which phenol was first
reacted with formaldehyde to which then urea and melamine
were sequentially added as for a normal MUF resin (thus, the
PMUF with the phenol added at the beginning) shows several
interesting features. The very high amount of ortho-para
and para-para methylene linkages connecting phenolic nuclei is
shown by the now very intense bands at 36.5 ppm and 31 ppm
(which show each a fine structure of three superimposed bands).
This indicates that in this resin the phenolic nuclei have
reacted extensively between each other forming PF resin
segments. The PMUF resin is then a true block copolymer of
PF and MUF. The shift of these bands from 39/33 ppm to
36.5/31 ppm must be mentioned, as it means that a consistant
amount of these PF chains is linked to the aminoplastic polymer.
Very little free ortho, and no free para phenolic sites remain
as shown by the very small 115-116 ppm peak and the absence
of the 120 ppm peak. Single phenols (not in a PF oligomer chain)
attachement to the chain is very small as noticeable by the very
small, almost absent peaks at 55 ppm and in the 124-132 ppm
region of the spectrum. However, equally evident is that the
degree of polymerization of the aminoplastic side of the resin
is lower (note the small aminomethylene peaks in the 45-57
ppm region of the spectrum). It is interesting however, that
phenolic methylol (-CHzOH) groups are present (peak at
60 ppm). This is an important characteristic which indicates
attachement to the hardened network of any methylol phenol
or methylolated phenolic oligomer during hardening of the
resin (it is a redeemimg feature of the resin 2.3 too). The picture
of this resin (Fig. 3) which emerges then is that of a block
copolymer of methylolated PF oligomers linked to the main
chain of the MUF resin. The MUF portion of the PMUF resin
is of lower degree of polymerisation then for the resins in
Figs. 1 and 2. Considerable branching, or potential cross-linking
ability (Tomita, Hatono 1978; Ferg et al. 1993), already exists
on the MUF block of the PMUF resin as testified by the
high relative abundance of-N(-CH2-)-CH2OH groups (peak
at 78 ppm).
In conclusion the preparation method of a PMUF resin
manufactured by single synthesis procedure presents
a fundamental importance both at the resin molecular level and
on its application results. ~3CNMR spectra of PMUF resins
present excellent correspondence with applied tensile strength
results of the plywood prepared with them. PMUF resins
prepared by initial reaction of phenol with formaldehyde
followed by sequential urea and melamine additions according
to a standard preparation procedure for MUF resins (Pizzi 1994)
present better results than resins prepared with the phenol'
either added during or at the end of the reaction. The reasons
for this are due to the reaction procedure ensuring that the great
majority of the phenol is really copolymerised with the MUF
part of the total resin, and that both phenolic and aminoplastic
portions of the resin still present consistant amounts of reactive
methylol groups. Progressive deviation from these molecular
requirements during the course of PMUF preparation also
ensures a progressive deviation from the optimal performance
of the resin, even leading to PMUF resins performing worse then
their corresponding MUF resin to which phenol has not been
added.
References
Breitmaler, E.; Voelter, W. 1987:Carbon-13 NMR Spectroscopy, 3rd
Edition, VCH, Weinheim
Cremonini, C.; Pizzi, A.; Tekely, P. 1996: Improvement of PMUF
adhesives performance for fireproof plywood, Holz Roh Werkstoff, 54:
Dunk-y, M. 1995: private communication
European Norm UNI EN314, pretreatment 5.1.3, Plywood bonding
quality (1993)
Ferg, E. E.; Pizzi, A.; Levendis, D. 1993: A ~3CNMR Analysis method
for urea-formaldehyde resin strength and formaldehyde emission,
J. Appl. Polymer Sci., 50:907-915
Higuchi, M.; Roh; J.-K.; Tajima, S.; Irita, H.; Honda, 1";Sakata, L 1994:
Polymeric structures of Melamine based composite adhesives, in
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429-449
Pizzi, A.; 1983: Wood adhesives Chemistry and Technology, Vol 1,
Dekker, New York
Pizzi, A. 1994:AdvancedWood Adhesives Technology,Dekker, New York
Tomita, B.; Hatono, S. 1993: Urea-formaldehyde resins III:
Constitutional characterization by ~3CFourier transform NMR
spectroscopy, J. Polymer Sci., 16:2509-2517
Van Niekerk, J.; Pizzi, A. 1994: Characteristic industrial technology
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