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8 Principles of Polymer Networking and Gel Theory in Thermosetting

Adhesive Formulations

Article · August 2003

DOI: 10.1201/9780203912225.ch8

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 8
Principles of Polymer Networking and
Gel Theory in Thermosetting
Adhesive Formulations
A. Pizzi
Ecole Nationale Supérieure des Technologies et Industries du Bois,
Université de Nancy I, Epinal, France

I. INTRODUCTION

The study of adhesion and adhesives involves many scientific approaches and in parti-
cular many different scientific disciplines. From physics to applied engineering, from
surface science to chemistry, be it analytical, organic, or physical, all have, and would
have a contribution to make to the fields of adhesives and adhesion. Polymer science
is, among others, one of the important ways to approach several fields of the science of
adhesives. However, while polymer physics and perhaps the physical chemistry of
polymers are extensively used in this field, not much work is found that reports the
use of the principles of polymer chemistry and, in particular, of polymer networking
and gelation theory in the applied formulation of adhesives, i.e. on how adhesives are
made to achieve particular effects. While in many other fields this branch of science is
used extensively, in adhesive formulation a variety of factors have contributed to the
lack of its extensive use. The main cause of this is the relative unwillingness of this
industry to abandon empirical research, this being an approach often successful in
solving some applied adhesive problems. Notwithstanding this, important applicable
results can be rapidly achieved from polymer gel theory if this science is properly
applied to adhesive formulation, and these results are obtainable much more readily
and with much less effort than by empirical research.
So, in this chapter the interest and importance of the polymer gel theory
approach to the formulation of adhesives will be briefly shown and, in particular,
we will limit this to thermosetting wood adhesives obtained by polycondensation
such as phenol–formaldehyde-, urea–formaldehyde-, melamine–formaldehyde- and
resorcinol–formaldehyde-based adhesives. The same approach is, however, very valid
for other polycondensation resins, and also for adhesives obtained by routes other than
polycondensation.

Copyright © 2003 by Taylor & Francis Group, LLC

 II. SOME PRINCIPLES OF POLYMER NETWORKING AND GEL THEORY
OF IMPORTANCE TO THERMOSETTING ADHESIVES

Several theories and methods defining and modeling the formation of polymer networks
exist [1–3]. The most useful of such theories, purely from an applied everyday use, are
often the simpler and older ones [4,5]. More complex theories, although often excellent at
describing to a much greater and thorough extent the molecular reality of gelation, suffer
also from being rather difficult to use and unyielding for everyday practice. Thus, they
often remain rather unapprochable to those who could benefit most from their application
for the easy resolution of applied problems.
Many such theories concentrate on the determination, by different mathematical
approaches and different physicochemical approximations, of the degree of conversion
and hence of the advancement of polymerization at the point of gel formation and on the
calculation of basic polymer parameters derived from the determination of the gel point.
Two main approaches are used: statistical methods and kinetic methods. Combinations of
the two have also been presented [1].

A. Statistical Methods
These methods generate structures by random combinations of reacting functional groups.
This approach is thorough and the results are good when dealing with equilibrium-
controlled reactions. The results are often a good approximation in kinetic-controlled
reactions. Most of the formaldehyde-based polycondensations are equilibrium-controlled
reactions, this being particularly true for urea–formaldehyde, melamine–urea–
formaldehyde, phenol–formaldehyde and phenol–resorcinol–formaldehyde adhesive
resins. Statistical methods are then ideal to describe these adhesive systems at the
moment of gel formation and during formation of the hardened network.
Among the statistical method dealing with polymer networking and gelation in the
field of polycondensation must be considered:
(1) The gel theory of Carothers [4] in which the critical degree of conversion at the
gel point ( pgel) is defined as pgel ¼ 2/f, with f being the average functionality of
the monomers in the system.
(2) The probabilistic gel theory of Flory [5]–Stockmayer [6,7] in which pgel is
defined through the coefficient of branching  ¼ 1/( f  1). In this theory f is
taken as the functionality of the monomer of greater functionality. The main
expression of this theory is the equation  ¼ rp2
/[1  rp2(1 
)] where p is both
the degree of conversion and the probability that a certain reactive group type
has in fact reacted,
is the proportion of such a reactive group type belonging
to branching units, and r is the ratio of the types of reactive groups of the two
monomers participating in the polycondensation.
(3) The cascade process theory of Gordon [8,9] based on more complex functions
than the two preceding ones but also offering some further advantages over
them.
(4) The Miller–Macosko [10] recursive method.
(5) The stochastic graphes theory of Bruneau [11] which is a more complete theory
but very complex and complicated to use.
Even more complex theories can be found in the review literature [2,3]. Of the above
theories the first two are of such a simplicity to be constantly used and the third and fourth

Copyright © 2003 by Taylor & Francis Group, LLC

 ones are also used sometimes. They all suffer from some drawback: the Carothers theory,
for instance, overestimates the numerical value of pgel while Flory’s theory underestimates
it, but they are nonetheless extremely useful in solving applied problems. Furthermore,
they do not describe what happens in the system between reaching the gel point and
complete hardening of the network.
Percolation is another technique that is also used for structure growth simulation.
Percolation techniques are only statistical methods of a slightly differently nuanced
approach, and they appear not to be very suitable general methods to correlate structure
and structure growth parameters but seem to be useful in examining structure growth near
the gel point.

B. Kinetic Methods
Kinetic or coagulation theories develop all chemical species by the use of an infinite set
of kinetic differential equations [1]. The resulting chemical species distribution can be
obtained analytically only in the simplest case of random reactions; in some other cases
distributions can be obtained numerically; and lastly the solution of the set of equa-
tions can also be obtained by Monte Carlo simulation methods. The application of
kinetic methods has severe disadvantages: the gel is considered as one giant molecule,
and hence cannot generate parts of the structures which are characteristic of the gel;
and the equations and methods used are long, unyielding, and not very handy or
practical to use. Combination of statistical and kinetic theories in some rare cases
solves the problems inherent to the kinetic approach alone. Combination of statistical
and kinetic theories also results in systems even more complex and unyielding that
kinetic theory treatments alone. This field is not a very successful one. However, it is
also in this field that the trend to ever more unwieldy mathematical treatment systems
has led to approaches bordering on meaninglessness [12–14]. These are exercises
removed from reality [12–14]. These have been developed for many years by groups
[12–14] which have not understood that the aim of theories in this field is not to render
more difficult but rather to solve everyday applied problems. Not only it is inconve-
nient to carry around equations half a page or longer as advocated by these groups,
but their results cannot be believed either. Thus, these unwieldy methods are not worth
further mention here.

C. Simple Statistical Gel Theories

The branching coefficient as defined by Flory is  ¼ the probability that a certain branched
unit will be joined to a second branched unit rather than to a terminal group. For example,
for a trifunctional monomer if  ¼ 1=2 the molecule is a continuous chain equivalent in
theory to a gel. In this case  ¼ 1=2 is the critical condition defining the start of the
formation of an infinite tridimensional network.
When the monomer has functionality greater than or equal to 3 the system will gel
when ( f  1) > 1. The critical value of  is then
1
¼ ð1Þ
f 1
where in Flory’s statistical gel theory  is ¼ the functionality of the monomer of higher
functionality when there are only two monomers taking part in the polycondensation
reaction. So if f ¼ 3 then  ¼ 0.5. If f ¼ 4 then  ¼ 0.33, etc. When  ¼ 0 there is no reaction
and when   1 the system never gels. The gel point of a thermosetting resin, hence of an

Copyright © 2003 by Taylor & Francis Group, LLC

 adhesive based on a thermosetting resin, depends on
1. the functionality of the monomers
2. the degree of conversion reached by the reaction
3. the ratio of the two monomers, or more exactly of the reactive sites/groups of the
two monomers.

1. Case 1: Case of Reaction of a Trifunctional Monomer with a

Bifunctional Monomer
In the polycondensation of a trifunctional monomer with a bifunctional monomer

the limiting condition to gelling is then that a bifunctional B–B monomer must be
linked to two branched monomers, hence bound to two trifunctional monomers. Thus,
if the proportion of B–B is limited, the extent of branching is also limited. The limiting
condition to start branching, hence for the start of gelling, depends on the probability that
segments –AB–BA– do indeed exist. In the theory all groups are considered as they cannot
react with groups of the same kind (thus A can only react with B) and all groups have the
same reactivity: the probability that the first group A (the one on the left) has then reacted
with a group B is pA, namely the fraction of all the groups A which have reacted. The
probability that the second group B (the one on the right) has reacted with a group A is
then pB. The probability then that the segment –AB–BA– occurs is
pA pB
therefore
 ¼ pA pB ð2Þ
which is the probability of a joint between two branching sites. As the functionality of the
monomer of higher functionality in this example has been taken as f ¼ 3 then  ¼ 0.5. this
means that at the gel point
ðpA pB Þgel ¼  ð3Þ
As the initial concentrations of reactive groups A and B are considered here to be the
same, then pA ¼ pB ¼ p and hence
p2gel ¼  and pgel ¼ 1=2 ð4Þ
Which gives
pgel ¼ 0:707 ð5Þ

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 Where pgel is the degree of conversion at the gel point which means that 70.7% of the
reactive groups/sites of the system have reacted at the gel point.

2. Case 2: Case of Two Trifunctional Monomers

The polycondensation of two trifunctional monomers

In this case it is necessary that an –AB– joined segment exists between branching
sites. This is equivalent to saying that
 ¼ pA or pB (depending which one is less) ð6Þ

when A and B are at the same initial concentration. Thus, pA ¼ pB ¼ p, and the limiting
condition for a gel to form will be
¼p ð7Þ

Because here too f ¼ 3 and  ¼ 0.5, the limiting condition for a gel to form will then be
pgel ¼ 0:5 ð8Þ

Where pgel is the degree of conversion at the gel point which means that 50% of all the
reactive groups/sites of the system have reacted at the gel point.
These two cases are valid also for monomers of higher functionality with the provi-
sion that higher functionality means a different value of f, hence a different value of .
Thus, in the case of polycondensations based only on two monomers there are only two
possible cases to consider, one in which a bifunctional monomer is also present, and the
other in which only monomers of functionality greater than or equal to 3 are present in the
reaction medium. To take into account the cases in which the reactive sites of the two
molecules are not equimolar one can define a ratio r as the ratio of the number of reactive
sites A and B, with the proviso that r must always be smaller than or equal to 1 (so, if
A > B r ¼ B/A and vice versa if A < B r ¼ A/B; If r is greater than 1, absurd results are
obtained and the theory cannot be used) [15]. The simpler form of the equations defined by
Flory to describe the two cases above are then
 1=2 N
pgel ¼ with r¼ A
r NB
and

pgel ¼ ð9Þ
r
These equations are in their simplest usable form. The original equations of Flory took
into account also the density of the hardened polymer. It has been disregarded here as it is
of no consequence in the formulation of thermosetting adhesives discussed later.

Copyright © 2003 by Taylor & Francis Group, LLC

 3. Case 3: Case of Many Mono-, Bi-, Tri-, and Multifunctional Monomers
The equations described in the previous two cases are not applicable to polycondensation
systems in which either monofunctional monomers are present or a great number of
branching monomers of a number of different functionalities of both type A and B are
present. If one considers the most general case of a polycondensation system as
A þ A2 þ A3 þ þ Ai þ B þ B2 þ B3 þ Bj ! polymer network
in which are present: (1) monomers the functionality of which is between 1 and i for the
reactive groups A, and (2) monomers the functionality of which is between 1 and j for the
reactive groups B, the degree of conversion and advancement of the polycondensation
reaction at the gel point is given by the following equation [15–17]:
1
pgel ¼ ð10Þ
½rð fA  1Þð fB  1Þ 1=2
where fA and fB are the weighted average functionalities of the reactive molecules A and B
respectively, and where r is the same as above and represents the difference in stochio-
metric proportions of the reactive sites. fA and fB are defined as
fAi2 NAi fBj2 NBj
fA ¼ and fB ¼ ð11Þ
fAi NAi fBj NBj
where NAi are the number of moles of Ai containing fAi functional groups for each A-type
molecule. The use of these equations is better shown by an example. Thus, for the follow-
ing complex system of reagents
4 mol A 2 mol B
51 mol A2 50 mol B2
2 mol A3 3 mol B3
3 mol A4 3 mol B5

1ð4Þ þ 2ð51Þ þ 3ð2Þ þ 4ð3Þ

r¼ ¼ 0:9841
1ð2Þ þ 2ð50Þ þ 3ð3Þ þ 5ð3Þ
½12 ð4Þ þ 22 ð51Þ þ 32 ð2Þ þ 42 ð3Þ
fA ¼ ¼ 2:2097
½1ð4Þ þ 2ð51Þ þ 3ð2Þ þ 4ð3Þ
½12 ð2Þ þ 22 ð50Þ þ 32 ð3Þ þ 52 ð3Þ
fB ¼ ¼ 2:4127
½1ð2Þ þ 2ð50Þ þ 3ð3Þ þ 5ð3Þ
1
pgel ¼ ¼ 0:7711
½0:9841ð1:2097Þð1:4127Þ 1=2
This indicates that in such a complex polycondensation system gelling occurs when
77.11% of the reagents have in fact reacted. Equation (10) is then particularly useful
when using Flory’s statistical theory of gelation. Owing to its simplicity and ease of use,
Flory’s theory of gelation is the most useful theory to use for the formulation of thermo-
setting polycondensation adhesives. Flory’s theory presents, however, a problem: it under-
estimates the degree of conversion at the gel point by around 10%. This means that
an experimental value of pgel ¼ 0.770 corresponds to a calculated value of
pgel(Flory) ¼ 0.700–0.710. This is due to not being able to take into consideration cycli-
zation reactions, a fact established by Stockmayer, so this theory is often known today as
the Flory–Stockmayer gelation theory.

Copyright © 2003 by Taylor & Francis Group, LLC

 Other theories, however, do exist, but the majority of these were published well after
Flory’s. These theories became increasingly complex and notwithstanding that they
allowed perhaps a somewhat better precision in the determination of pgel, the equations
derived from them are so complex that in practice they are never used. This unnecessary
complexity trend has gotten out of hand in certain cases to the level of a purely mathe-
matical exercise rather removed from reality [12–14].
However, a second theory, older than Flory’s, does indeed exist. This is the theory of
Carothers. According to Carothers
2
DPn ¼ ð12Þ
2  fp
where DPn is the number-average degree of polymerization and f is the average function-
ality of the system (a concept different from that of Flory’s) which is equal to
½NA fA þ NB fB
f ¼ ð13Þ
½NA þ NB
where NA and NB are the numbers of moles of monomers A and B, and fA and fB are the
functionalities, respectively, of monomers A and B. The degree of conversion in this theory
is defined by the equation of Carothers



2 1
p¼ 1 ð14Þ
f DPn
Because DPn becomes very large at the gel point as p tends to 2/f, the critical condition for
gelling is defined in the Carothers equation as


2
pgel ¼ ð15Þ
f

While the theory of Flory underestimates the gel point, the theory of Carothers over-
estimates it. For example, for the case of a trifunctional and bifunctional reaction system
presented above, at equimolar reactive groups, while Flory’s theory forecasts pgel ¼ 0.707,
Carothers theory forecasts a value of pgel ¼ 0.833, while the experimental pgel is
0.765–0.775. Recently, however [18,19], thermodynamic reasons why the two formulas
should be combined came to light. This led to the proposal of a very simple equation
affording much higher precision than each theory alone. This simple equation also gave
much better precision of all the very complex and difficult to use theories devised and
presented since Flory’s 1942 one:
ð2=f Þ þ ð=rÞ1=2
pgel ¼
2
or
1 1  1=2
pgel ¼ þ ð16Þ
f 2 r
This equation is nothing other than the average of the equations of Carothers and Flory,
and for instance yields a pgel ¼ 0.770, while the most exact of the complex theories yields a
pgel ¼ 0.800 [18,19] for the simple case just shown above. The 1/2 operator is not there (but
/r is) in the case where no bifunctional monomer is present. This is valid also for the
generalized Eqs. (17) and (18) which follow and which have been developed from Eq. (16)
above. For two monomers, Eq. (16) can be developed to eliminate the presence in the

Copyright © 2003 by Taylor & Francis Group, LLC

 equation of two different ways of expressing functionality [Carothers’ average function-
ality of the system in the same equation in which appears (hiding in ) Flory’s function-
ality]. Equation (16) can then be expressed in the same functionality, so as to eliminate
such a discrepancy.

1=2
nA þ nB 1 f B nB
pgel ¼ þ ð17Þ
fA nA þ fB nB 2 fA nA ðfA  1Þ
In the case of a system of more than two monomers where each monomer can react with
the other but not with itself the general formula becomes

1=2
nx 1 
pgel ¼ þ ð18Þ
nx fx 2 rx þ rx y
In the most common case in thermosetting polycondensation adhesives, namely a reaction
system composed of three monomers in which two can both react with the third one but
where the former two cannot react with each other (and no monomer can react with itself),
the equation for higher precision determination of the degree of conversion at the gel point
becomes


f n  1=2
pgel ¼ x x þ ð19Þ
nx rx
It is easy to see from these equations that these higher precision equations become rapidly
more difficult to use and to handle as the polycondensation system becomes more com-
plex. Thus, Eq. (16) for two-reagent systems is used very easily, and Eq. (19) for three-
reagent systems is still relatively easy to use, but for more complex systems Eq. (10) [15–17]
is easier to use notwithstanding the 10% lower value it gives.

III. EXAMPLES OF APPLICATIONS TO THERMOSETTING

WOOD ADHESIVES

A. Formulation of Phenol–Resorcinol–Formaldehyde
Cold–Set Adhesives
Resorcinol-based adhesives are used extensively to bond structural grade, exterior lami-
nated beams for building construction (see Chap. 29 on Resorcinol Adhesives). The cold-
setting adhesives which dominate this field are based on phenol–resorcinol–formaldehyde
(PRF) resins. The adhesive itself is composed of the PRF resin and a hardener that
includes formaldehyde, often in the form of paraformaldehyde mixed with inert fillers.
The performance of the resin is resorcinol dependent. The cost of the resin is also resorci-
nol dependent as this is a very expensive chemical produced industrially in only three
locations in the world. The research work on these resins from their inception has then
been based on the optimization of their bonding performance coupled with the decrease in
the relative percentages of resorcinol used. It has the been a long and successful work of
empirical research and development which still continues.
It is, however, simpler to calculate from basic principles of polycondensation gel
theory, hence using polymer chemistry, the relative amount of resorcinol which needs to be
used in the preparation of a certain PRF resin to optimize its performance. As a simplified
real example of the approach, let us propose the following problem.

Copyright © 2003 by Taylor & Francis Group, LLC

 Let us assume that we have prepared a linear phenol–formaldehyde (PF) resol resin
of number average degree of polymerization DPn ¼ 2 and average content of hydroxyben-
zyl alcohol (methylol) –CH2OH groups of 2. If one wants to prepare a PRF cold-set
adhesive for wood laminated beams or fingerjointing, how can one determine the mini-
mum quantity of expensive resorcinol which is needed to make sure that the addition does
not gel the resin? Such a problem in short asks what is the minimum amount of resorcinol
one needs to have a good performance resin which does not gel on resorcinol addition to
the reaction. A resin that is taken as hardening only on addition of further formaldehyde
hardener, but only in the glue mix.
According to Eqs. (1)–(4) to assure that the resin system does not gel on addition of
resorcinol one imposes the limiting condition
pgel ðexperimentalÞ  1 ð20Þ
As Flory’s version of the polycondensation gel theory, which we will use for this problem,
underestimates by approximately 10% the degree of conversion p at the gel point this means
that the limiting condition expressed by Eq. (20) can be written using Flory’s theory as
pgel ðFlory’sÞ  0:9 ð21Þ
As the functionality of resorcinol is 3 (three potential reactive sites) and of the PF resol
resin is 2 (namely two reactive –CH2OH groups) this means that Flory’s branching coeffi-
cient  ¼ 1/( f  1) ¼ 1 (3  1) ¼ 0.5, and because from Eq. (9) p2gel ¼ /r one can write
numerically the limiting condition defined by the problem as:

0:5
ð0:9Þ2 ¼ ð22Þ
r
one obtains from this a value of r ¼ 0.617. Consequently, because 1 mol PF ¼ 2 mol
–CH2OH and 1 mol resorcinol ¼ 3 mol reactive sites:


2
x¼r ð23Þ
3

hence (2/3)x ¼ 0.617 and the unknown variable x ¼ 0.93. This means then that 0.93 moles
of PF are needed for each mole of resorcinol, which is the equivalent to saying that the
PF: resorcinol molar ratio  1:1.07 is needed.
However, (3/2)x ¼ r ¼ 0.617 is an equally valid situation (as r is still maintained lower
than 1). Solving this equation one obtains x ¼ 0.411. This means that there will be no
gelling of the resin system when adding less than 0.411 mol resorcinol to each mol PF
resin, thus when the PF:resorcinol molar ratio is  0.411.
This means then

It is then easy to determine by polymer chemistry calculations what should be the

most adequate amount of resorcinol which needs to be added to a PF resin to obtain a

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 PRF. Three types of back-checks are, however, needed, namely:
(i) To check mathematically that the assumption that has been imposed at the
beginning, pgel (Flory’s)  0.9, is indeed correct. The 1.07 mol resorcinol is
equal to 1.07
3 ¼ 3.21 mol resorcinol reactive sites. According to Flory’s
Theory in the most simple form pgel ¼ (/r)1/2, and as  ¼ 0.5 and
r ¼ 2/3.21 ¼ 0.623, pgel ¼ 0.896. This is sufficiently close to the value of 0.9
which was imposed on the system at the beginning. It is then not necessary
to repeat the calculation. Had this value been further from the initial 0.9
assumption a second iteration could have been done by imposing as a new
starting hypothesis pgel(Flory’s)  the new value found (here 0.896), until a
sufficiently stable value and condition has been found by iteration.
(ii) Visual check: what does it really mean that amounts of resorcinol lower than
0.411 mol and greater than 1.07 mol stop the system from gelling (until a hard-
ener is added), and how can this be visualized? When the amount of resorcinol
is between 0.411 mol and 1.07 mol there is sufficient resorcinol for two or more
–CH2OH methylol groups from separate PF resol chains to condense on the
resorcinol nuclei. This leads to the formation of a three-dimensional network
sufficiently large to yield a gel: the resorcinol functions then as the ‘‘hardener’’
for the PF resol resin, as shown by the following schematic figure:
CH2ðPhenolCH2 Þn RCH2 ðPhenolCH2 Þn 

CH2 ðPhenolCH2 Þn 
When instead the amount of resorcinol  1.07 mol the majority of –CH2OH
methylol groups have each mainly (but not only) reacted with one resorcinol
molecule. Thus, there are no more methylol groups available for reaction, if one
had nearer to 2 mol resorcinol to 1 mol for the particular PF at hand. At best
one methylol group reacts with one resorcinol, for example
RCH2 ðPhenolCH2 Þn R and RCH2 ðPhenolCH2 Þn R
In reality the situation that presents itself is as follows
CH2 ðPhenolCH2 Þn RCH2 ðPhenolCH2 Þn R
and
RCH2 ðPhenolCH2 Þn RCH2 ðPhenolCH2 Þn
This is closer to the real situation, in which PRF oligomers are formed but there
is enough resorcinol present to stop the oligomers growing to too long a poly-
mer, hence to gel. If viscosity is too high, some unreacted resorcinol is added to
decrease the average molecular mass of the system. This brings the system
viscosity down to a more acceptable level. No interactions are possible unless
a hardener (generally additional formaldehyde) is added. This means that, in
the absence of a hardener, bridges between two resorcinol nuclei grafted onto
PF chains cannot form. Equally, the proportion of resorcinol is not sufficiently
low for resorcinol to function as a bridge between two methylol groups of
separate PF chains. In both cases formation of a very long, continuous polymer
chain (the Flory equivalent of a gel) is severely inhibited. Thus, the system
cannot gel unless additional formaldehyde hardener is added (which is only
added in the glue mix just before use of the adhesive).

Copyright © 2003 by Taylor & Francis Group, LLC

 When instead the amount of resorcinol is  0.411 mol of PF there are not
sufficient molecules of resorcinol to function as a bridge between two or
three methylol groups of different PF chains. The proportion of resorcinol
molecules to achieve this is then insufficient for the gel portion of the system
to predominate. Only short linear structures of the type

HOCH2 ðPhenolCH2 Þn RCH2 ðPhenolCH2 Þn OH

are formed. Since the sol fraction is still in the majority, the resin system
cannot gel.
(iii) Industrial formulation check: how much resorcinol is used in the best indus-
trial PRF cold-setting adhesive formulations (most of which present a
number average degree of polymerization of the original PF resol of approxi-
mately 2, and two reactive methylols)? It is interesting that the majority of
the industrial PRF adhesives of this type use a PF : resorcinol : molar ratio of
1 : 1.15–1 : 1.17. This is an excess of just 0.08–0.1 mol resorcinol, thus just a
small safety margin on what is really necessary to minimize the amount of
resorcinol, maintain the adhesive’s performance, and avoid gelling. This
value has also been obtained over many years by empirical research. For
different PRF adhesive formulations one can redo this calculation to account
for the different characteristics of the formulation and arrive at an equally
correct answer without spending years of empirical research to arrive at an
optimized solution.
Exactly the same type of approach can be used for the formulation of other poly-
condensation adhesives. For example, the formulation of melamine–urea–formaldehyde
adhesive resins for wood panel products can also be successfully approached in the same
way as has been shown above for the cold-setting PRF adhesives.

B. Determining the Gel Point of an Adhesive Based on a

Polycondensation Resin
In the case of the formulation of mixed resins for adhesives for which extensive formula-
tion experience does not exist, the gel theory approach is also particularly useful. Le us
examine, as an example, what would be the degree of conversion at the gel point of a resin
based on the reaction of resorcinol (R) with acetaldehyde (A) and formaldehyde (F) in
relative molar proportions of, respectively, R:A:F ¼ 1:1:0.5. The two aldehydes can react
and do react with resorcinol; while under the conditions used they are considered as not
being able to react with each other (aldol condensation is indeed minimal under the
conditions used to prepare adhesive resins). In short to avoid any gelling of our prereacted
resin in the reactor, during manufacture, we want to know at what degree of conversion
we can advance reaction of the resin without gelling it.
As the system is relatively complex and presents more than two reagents the simpler
approach is to use the formula of Durand and Bruneau (Eq. (10)). This will tell us then
that the functionality of resorcinol is 3; the functionality of the two aldehydes in the
proportions given is 2 (they are both bifunctional, which simplifies matters), and thus
fA ¼ 3 and fB ¼ 2, while r ¼ (1
3)/(1
2 þ 0.5
2) ¼ 1, to yield according to Eq. (10)
pgel  1/[1(3  1)(2  1)]1/2 ¼ 0.707 so according to Flory, gel intervenes at 70.7% of the
reagent having in fact reacted.

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 As we know that Flory’s and derived formulas such as Eq. (10) underestimate by
approximately 10% the degree of conversion at the gel point one could also use the more
exact but more complex Eqs. (18) and (19). In this case Eq. (19) is the one suitable to use.
We will then have that pgel ¼ [(1 þ 1 þ 0.5)/(1
3 þ 1
2 þ 0.5
2)] þ 1/2(0.5/1)1/2 ¼ 0.770.
This indicates that the gel of the system intervenes when 77.0% of the reagents have in fact
participated in the reaction, the latter formula yielding a precision of 99.5% while the
previous one yields a precision of 91% only.

IV. CONCLUSION

In conclusion, the use of the simpler polymer networking and gel theories constitutes a
very useful approach to focus more rapidly and within narrower limits applied formula-
tion research for any polycondensation adhesive resin. This allows much faster adhesive
formulation than just the empirical scan research approach still the favorite today for
some of these resins. Final experimental verification and adjustments will, however, always
be required.

REFERENCES

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