Process of making a cured resole foam and product produced therefrom

Phenolic foams are disclosed which are obtained by conventional procedures from phenol-aldehyde resole resins and novel premixed catalyst combinations comprising (a) a phosphonate compound ##STR1## wherein R, R.sub.1 and R.sub.2 are independently selected from the class consisting of alkyl having from 1 to 8 carbon atoms, inclusive, aryl having from 6 to 12 carbon atoms, inclusive, and aralkyl having from 7 to 13 carbon atoms, inclusive; and (b) an aromatic sulfonic acid. The foams are characterized as non-punking, fire resistant, and fine celled foams which can be prepared at room temperature (about 20.degree. C) in thick sections without splitting or cracking. Furthermore, the foams do not require a heat curing treatment in order to achieve a thermoset state.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
This invention relates to phenolic foams and is more particularly concerned 
with a novel process for producing non-punking phenolic foams. 
2. Description of the Prior Art 
Phenolic foams, and their various modes of preparation beginning with a 
resole or a novolac resin, are well known in the art; see, for example, 
Plastic Foams Part II, pp 639 - 673, edited by K. C. Frisch and J. H. 
Saunders, 1973, Marcel Dekker Inc., New York, N. Y. Phenolic foams are 
most commonly produced by the acid curing of a resole resin, and, 
generally speaking, strong mineral acids have been found to be the most 
efficient catalysts. But, at the same time, the foams tend to overheat 
which causes their distortion, cracking, and splitting, especially when 
formed in anything but small amounts or thin sections so as to allow heat 
dissipation. 
U.S. Pat. No. 2,772,246 discloses the use of combinations of various 
organic phosphorus acid esters with a mineral acid or phosphoric acid as a 
means of controlling foam cell size and uniformity during the foam 
formation. U.S. Pat. No. 3,298,973 teaches the use of boric acid in 
combination with organic hydroxy acids as resole curatives and also as a 
means to reduce punking. U.S. Pat. No. 2,933,461 discloses mixtures of 
phenol sulfonic acid with benzene sulfonic acid or sulfuric acid as useful 
catalysts. Some art teaches the removal of vaporizable acidic catalysts 
from the formed phenolic foams by treatment of the foams at high 
temperatures; see U.S. Pat. No. 3,522,196. U.S. Pat. No. 3,673,130 
discloses the use of various phosphorus compounds in conjunction with 
known acid catalysts to provide non-punking foams. The term "punking" 
refers to the phenomenon observed when a piece of foam which has been 
removed from a flame continues to glow and combust without a visible 
flame. This phenomenon will be discussed in greater detail hereinbelow. 
While the prior art discloses the preparation of phenolic foams which have 
good fire resistance properties including non-punking characteristics and 
which can be produced within desired density ranges with fine uniform 
cells, as typically noted in U.S. Pat. No. 3,673,130, such foams are 
severely limited in the batch size in which they can be prepared. When it 
is desired to scale-up their preparation above the bench scale level, that 
is to say preparations greater than a few pounds of foam contained in a 
thick section, the foams split and crack regardless of what heating cycles 
or curing steps are employed. This is caused by the high and rapid 
exotherm arising from the curing reaction of the resole resin, which 
curing reaction is brought to its peak very rapidly by the prior art 
catalysts. 
U.S. Pat. No. 4,001,148 discloses acid curing agents that call for mixtures 
of a strong inorganic or organic acid, a glycol, and phosphoric acid 
wherein the novelty resides in the inclusion of the glycol in order to 
avoid cracking and bursting of the formed foam block. 
It has now been discovered that non-punking phenolic foams of fine uniform 
cell and controllable densities can be prepared in large mass without 
cracking or splitting. Further, in contrast to the prior art, it has been 
discovered that the foams can be prepared using reactants at room 
temperature. Any heat curing of the resulting foam is purely optional and 
not necessary to achieve a full thermoset condition. 
In a further distinguishing feature over prior art phenolic foams, those of 
the present invention are characterized as being essentially non-corrosive 
in terms of the materials with which they come into contact. 
The advantageous properties of the present foams are achieved without the 
need for employing both the corrosive phosphoric acid and a glycol. 
Although the use of a glycol is not precluded in the present invention. 
SUMMARY OF THE INVENTION 
This invention comprises a process for the preparation of a phenolic foam 
from the reaction of a phenol-aldehyde resole resin, a blowing agent and 
an acidic catalyst wherein the improvement comprises employing a premixed 
catalyst combination comprising: 
(a) an aromatic sulfonic acid; and 
(b) a phosphonate compound having the formula 
##STR2## 
wherein R, R.sub.1 and R.sub.2 are independently selected from the class 
consisting of alkyl having from 1 to 8 carbon atoms, inclusive, aryl 
having from 6 to 12 carbon atoms, inclusive, and aralkyl having from 7 to 
13 carbon atoms, inclusive. 
An aromatic sulfonic acid is inclusive of aryl sulfonic acids, 
hydroxyphenyl sulfonic acids, carboxyphenyl sulfonic acids, and the like. 
The term aryl is defined hereinafter. 
The term "aryl" means the radical obtained by removing one nuclear hydrogen 
atom from an aromatic hydrocarbon having from 6 to 12 carbon atoms and is 
inclusive of phenyl, phenyl substituted by alkyl as defined hereinafter, 
naphthyl, biphenylyl, and the like. 
The term "alkyl from 1 to 8 carbon atoms" means methyl, ethyl, propyl, 
butyl, amyl, hexyl, heptyl, octyl, and isomeric forms thereof. 
The term "aralkyl from 7 to 13 carbon atoms" is inclusive of benzyl, 
p-methylbenzyl, p-ethylbenzyl, .beta.-phenylethyl, naphthylmethyl, 
benzhydryl, and the like. 
The invention also comprises the improved non-punking phenolic foams 
obtained from the novel process. 
DETAILED DESCRIPTION OF THE INVENTION 
The phenolic foams in accordance with the present invention are obtained by 
the acid catalyzed curing of a phenol-aldehyde resole resin using the 
general procedures well known by those skilled in the art in conjunction 
with the novel teachings of the present invention. For general methods for 
the preparation of phenolic foams from resole resins see Plastic Foams 
cited supra. 
The phenol-aldehyde resole resins employed may be any of the known resole 
resins commercially available. Alternatively, the resins can be easily 
prepared according to methods well known in the art, see for example U.S. 
Pat. No. 2,772,246. 
Any of the resole resins which are prepared by carrying out the 
condensation in the ratio of about 1 mole of phenol to from about 1.5 to 
about 3.0 moles of aldehyde are useful in the present invention. Generally 
speaking, the resole resin has a viscosity at 25.degree. C of from about 
200 centipoises to about 300,000 centipoises, and preferably from about 
400 to about 25,000 centipoises. 
Illustrative of the phenols which may be used in the preparation of the 
resole resins are compounds such as phenol, resorcinol, alkyl-substituted 
phenols such as cresols, xylenols, meta and para-tertiary butylphenol, 
isopropylphenol, p-phenylphenol, and the like. Phenol itself is the 
preferred species. 
The aldehydes employed can be aliphatic aldehydes, cycloaliphatic 
aldehydes, aromatic aldehydes, polyaldehydes, and aldehyde liberating 
compounds. Typical examples include formaldehyde, acetaldehyde, 
furfuraldehyde, propionaldehyde, butyraldehyde, benzaldehyde, and the 
like. Typical examples of aldehyde liberating compounds are 
paraformaldehyde, formalin solution, and the like. A preferred aldehyde is 
formaldehyde. 
Although some resole resins contain minor amounts of dissolved water and 
water is produced in the foam forming polymerization reaction which 
provides some foam "blowing" by its vaporization due to the heat of the 
reaction exotherm, it is preferred to incorporate an organic blowing agent 
in the resole resin in order to obtain fine and uniform cell structure in 
the resulting foam as well as to have the capability of adjusting foam 
density to desired values. U.S. Pat. Nos. 3,298,973, 3,389,094, 3,968,300, 
and Plastic Foams, cited supra, disclose the use of a variety of auxiliary 
blowing agents and the disclosures of these references are specifically 
incorporated herein. 
The amount of blowing agent employed is not critical and depends largely on 
factors such as the desired density of the phenolic foam, the viscosity of 
the resole resin, and, additionally, the type of blowing agent being 
employed. However, the preferred amount of any given formulation can be 
easily determined by simple trial and error. Generally speaking the 
blowing agent is employed within the range of about 2 to about 40 parts 
per 100 parts by weight of resole resin and preferably from about 5 to 
about 30 parts per 100 parts of resole resin. 
A preferred group of blowing agents to be used in the practice of the 
present invention are the polyhalogenated fluorocarbons. Particularly 
preferred are the polyhalogenated fluorocarbons having a boiling point 
between 20.degree. C and 130.degree. C. Included in this range as 
preferred blowing agents are trichloromonofluoromethane and 
trichlorotrifluoroethane, and mixtures of the two. 
The addition of minor amounts of low molecular weight water soluble polyols 
such as ethylene glycol, diethyleneglycol, glycerine, and the like, 
assists in the homogenization of water present in the reaction mixture 
which, in turn, gives rise to more even cell size when and if the water is 
volatilized and can aid in reducing minor splits or cracks in the foam. 
The actual amount of the polyol employed is not critical and can vary from 
about 1 to about 20 parts per 100 parts of resole. 
It has also been found advantageous to employ a surfactant in the foams as 
an additional control over foam cell size and regularity. The choice of 
surfactant is not critical and any one, or mixtures thereof, of the many 
surfactants employed in the art can be employed in the present process; 
see U.S. Pat. No. 3,298,973 whose disclosure with respect to surfactants 
is hereby incorporated in its entirety. 
When a surface active agent is employed it can be present in any amount 
depending on the results desired with respect to foam cell size, shape, 
etc. However, in most applications the surfactant is employed in the range 
of about 0.5 parts to 10 parts by weight per 100 parts of resole resin, 
and preferably from about 1 part to about 5 parts. 
The novelty of the present invention resides in the catalyst employed for 
the curing of the resole resin and in its mode of preparation. The 
catalyst in question consists of a premixed combination of (a) an aryl 
sulfonic acid and (b) a phosphonate compound (I). 
The aromatic sulfonic acid component of the catalyst is defined 
hereinbefore. Illustrative examples of such acids are benzene sulfonic 
acid, p-toluene sulfonic acid, 4-phenol sulfonic acid, xylene sulfonic 
acid, .beta.-naphthalene sulfonic acid, .alpha.-naphthalene sulfonic acid, 
4-sulfophthalic acid, and the like. A preferred acid is p-toluene sulfonic 
acid. Mixtures of aromatic sulfonic acids are contemplated by the present 
invention and a preferred mixture comprises p-toluene sulfonic acid and 
xylene sulfonic acid in equal proportions by weight. 
The aromatic sulfonic acid may be present either in the pure form or as a 
solution in water, glacial acetic acid, phenol, or the like. Generally 
speaking, it is conveniently employed in the form of its solution. 
The phosphonate component (I), whose structure is defined hereinabove, 
belongs to a class of well known and readily available phosphorus 
compounds. 
In a preferred phosphonate compound of the formula (I), R, R.sub.1 and 
R.sub.2 are independently selected from alkyl having from 1 to 8 carbon 
atoms inclusive. 
Illustrative examples of the phosphonate compound (I) are dimethyl 
methylphosphonate, diethyl methylphosphonate, dibutyl methylphosphonate, 
dioctyl methylphosphonate, dimethyl butylphosphonate, dimethyl 
octylphosphonate, dimethyl 2-ethylhexylphosphonate, dimethyl 
phenylphosphonate, dibutyl phenylphosphonate, diphenyl phenylphosphonate, 
diphenyl methylphosphonate, dimethyl benzylphosphonate, dibenzyl 
methylphosphonate, dimethyl .beta.-phenylethylphosphonate, diethyl 
naphthylmethylphosphonate, and the like. 
A preferred group of phosphonate compounds is comprised of dimethyl 
methylphosphonate, diethyl methylphosphonate, dibutyl methylphosphonate, 
dioctyl methylphosphonate, dimethyl butylphosphonate, dimethyl 
octylphosphonate, dimethyl 2-ethylhexylphosphonate. A particularly 
preferred phosphonate compound is dimethyl methylphosphonate. 
The phosphonate compounds as mentioned hereinabove are readily available 
commercially. Alternatively, they are prepared by the well known Arbuzov 
reaction wherein the appropriate halogen compound is reacted with the 
appropriate phosphite to yield the desired phosphonate; see Topics in 
Phosphorous Chemistry, Vol. I, p 65, edited by M. Grayson and E. J. 
Griffith, 1964, Interscience Publishers, New York, N. Y. 
As mentioned hereinbefore the novelty of this invention resides in part in 
the premixing of the aromatic sulfonic acid with the phosphonate compound. 
This refers to the premixing of the catalyst components with each other 
prior to their addition to the resole resin. 
The catalyst components may be blended together using any mixing or 
blending procedure known to those skilled in the art. Heat is evolved 
during the blending. Preferably, the mixing is carried out in the absence 
of significant atmospheric moisture and the absence of conditions of heat. 
In fact, if large batches are to be blended, it is recommended that the 
blending be done in a closed container to exclude atmospheric moisture and 
air but with means for venting and for cooling the container. The duration 
of mixing is not critical and generally speaking is from about 5 minutes 
to about 1 hour. 
It is believed that the heat evolved during the mixing of the sulfonic acid 
with the phosphonate arises from an ester interchange reaction between the 
components. However, it is to be understood that such theoretical 
considerations are offered by way of explanation only and are not to be 
construed as limiting the scope of the present invention which is defined 
solely by the claims appended to this specification. 
In a preferred embodiment of the premixed catalyst combination, the 
phosphonate compound is first blended with a diluent, preferably a 
non-ionic type diluent surfactant prior to its admixture with the sulfonic 
acid. Alternatively, the sulfonic acid is first blended with the diluent 
but no matter which component is chosen the blending operation is 
accompanied by the generation of some heat. The surfactants used for the 
above dilution are not to be confused with the surfactants already 
referred to above for use as cell modifiers and will be distinguished 
therefrom by the term "diluent surfactants". The diluent surfactants are 
employed not only to assist in the mixing of the catalyst components but 
also to modify the heat evolved during the mixing of the two components. 
The choice of non-ionic diluent surfactant is not critical to the present 
invention. The diluent surfactant may be any one of a wide variety of 
surfactants such as alkylene oxide-phenol addition products, fatty acid 
esters, ester phosphatides, alkyl aryl sulfates and sulfonates, alkyl aryl 
polyether alcohols, long chain alkyl polyether alcohols, and the like. 
The proportions of the phosphonate compound to the diluent surfactant in 
parts by weight are in no way critical but, generally speaking, are within 
the range of about 1:2 to about 2:1, and preferably about 1:1. 
The proportions of phosphonate compound (I) to aromatic sulfonic acid in 
parts by weight is advantageously from about 5:1 to about 1:5, preferably 
from about 4:1 to about 1:4, and most preferably from about 3:1 to about 
1:3. 
The weight of the premixed catalyst combination, exclusive of the weight of 
any optional diluent, which is advantageously employed in the process of 
the invention is in the range of about 3 parts to about 30 parts per 100 
parts of resole resin, and preferably from about 5 parts to about 20 
parts. 
In addition to the use of the catalyst combination set forth above it has 
been found that the optional addition of minor amounts of a heavy metal 
organic catalyst, within the range of about 0.5 parts to about 5 parts by 
weight per 100 parts of resin, and preferably from about 0.5 parts to 
about 2 parts, leads to an improvement in foam cell structure. Exemplary 
heavy metal catalysts are calcium naphthenate, cobalt nephthenate, iron 
naphthenate, manganese naphthenate, lead naphthenate, zinc octoate, lead 
octoate, and the like. Particularly preferred is lead octoate. 
Various modifiers, flameproofing agents, additives, and fillers may be 
added to modify the resultant foam properties if desired. For example, the 
addition of polyvinyl alcohol imparts flexibility to the phenolic foam 
while finely divided fillers, such as talc, mica, asbestos, and carbon 
black ordinarily improve foam texture. 
In a preferred embodiment of the present invention the resole resin is 
premixed with the blowing agent and any other optional ingredient 
including surfactants, modifiers, and the like. The catalyst combination 
is then thoroughly stirred into the resin premix and the resulting 
reacting mixture is delivered to a mold, conveyor, surface, or other 
suitable receiving means where it is allowed to rise freely. 
The novel catalyst combination of the present invention allows the 
reactants to be combined at room temperature (about 20.degree. C), and, 
surprisingly, after the foam has risen it can be cured also at room 
temperature to a thermoset state to produce foams of a density of from 
about 0.5 to about 20 pounds per cubic foot (pcf). Foams may be produced 
with higher density, however the heat dissipation problems become a factor 
in controlling the reaction. Contrastingly, the phenolic foams of the 
prior art require heat curing processes after the foam has risen in order 
to provide a completely thermoset product; see for example U.S. Pat. No. 
3,298,973, column 5 line 9-10. 
Although the foams of the invention are obtained with smooth skins and 
little or no shrinkage, even in the absence of a heat curing step, foam 
physical properties are usually maximized when the foam is formed in a 
preheated mold or container and cured at a temperature of from about 
100.degree. F to about 250.degree. F for a period of from about 5 minutes 
to about 1 hour. The preheated mold temperature is not critical and can 
fall within the same range as that used for curing. 
However, it is in the size and thickness of the foams prepared in 
accordance with the present invention wherein the most unexpected results 
lie. In contrast to prior art methods large machine prepared pours of the 
phenolic foams can be formed in large blocks in sizes exceeding those 
capable of preparation heretofore without cracking and splitting. Phenolic 
foams are notorious for the exotherms produced and resultant internal 
pressures produced by water vapor during the curing of the resole. Prior 
art methods have been limited to small bench scale pours. If large amounts 
were prepared the foam had to be formed in thin sections no greater than a 
few inches thick in order that the heat and volatile reaction by-products 
produced could be liberated so as to avoid cracks in the foam. 
The use of the premixed catalyst combination of the present invention 
overcomes the excessive heat production during the resole curing and 
therefore allows the foam to be formed in sections at least 12 inches 
thick without cracking or splitting. 
The foams produced in accordance with the present invention, in addition to 
being classified as non-punking, are further characterized as having 
excellent flame resistance and low smoke generation when subjected to 
flame testing. In fact, the foams when exposed to a flame test which is 
comparable to the ASTM E-84 Test were found to possess Flame Spread 
Ratings as low as 25. 
In a further unexpected advantage to flow from the practice of the present 
invention it has been discovered that the premixed catalyst combinations 
in accordance with the invention, and particularly the foams produced 
thereby, do not possess the high corrosive properties encountered with 
prior art materials including both catalysts and the final foams. 
The phenolic foams of the present invention are utilized in the production 
of preformed thermal insulation panels, such as roof and wall insulation, 
and particularly as the core insulant in prefabricated portable booths, 
kiosks, and the like. Further utility for the foams is found as sound 
insulation to deaden noise transmission through ceilings, floors or 
multi-story buildings, and various acoustical panels. The foams are also 
used in the floral trade in plant potting, as fire barriers in shipping 
and storage of pyrotechnic devices, as electric battery separators, and as 
decorative coatings in the building trade.

The following examples describe the manner and process of making and using 
the invention and set forth the best mode contemplated by the inventor of 
carrying out the invention but are not to be construed as limiting. 
EXAMPLE 1 
The phenolic foams A, B, and C of this example were prepared in accordance 
with the present invention by blending the reactants and proportions 
thereof set forth in Table I at ambient room temperature (about 20.degree. 
C). The blending procedure consisted of first mixing the resole resin 
(BRL-2760) with the surfactant (L-5320) using a high speed drill press 
motor equipped with an efficient agitator blade. The Freon blowing agents 
were blended into the mixture followed by the boric acid anti-punking 
agent, ethylene glycol, and benzyltrimethylammonium chloride, where they 
were called for. 
The premixed catalyst combinations were prepared by mixing in a separate 
container first the dimethyl methylphosphonate (DMMP) with the surfactant 
(TMN-10) followed by the mixed sulfonic acid combination of 
p-toluene-sulfonic acid and xylene sulfonic acid in equal proportions by 
weight which caused an immediate and substantial exotherm accompanied by a 
gradual increase in viscosity. Stirring of catalyst ingredients was 
continued by means of a suitable stirrer for about 15 minutes. The amine 
polyurethane catalyst Niax ES was added last where it was called for. 
The premixed catalyst combination was then thoroughly stirred into the 
resin blend for about 30 - 60 seconds. 
A sufficient amount of the ingredients was employed in each foam 
preparation so that, upon completion of stirring in the catalyst, 
approximately 2000 grams of each reaction mixture was poured into a 12 
inch .times. 12 inch .times. 12 inch cardboard box which had been 
preheated to about 140.degree. F. Each sample was allowed to exotherm and 
rise freely to form a solid block of foam about a cubic foot in volume. 
Post rise curing conditions for the foams are set forth in Table I. The 
foam blocks did not split or crack. 
Foam B contained the art recognized anti-punking agent boric acid. Both 
Foam A and Foam C, which latter also lacked the additional agents 
including the anti-punking agent, were characterized by the same absence 
of punking as Foam B and excellent flame resistance including the lack of 
any smoke formation. Foam C was also characterized by a FSR=25 in a test 
which is comparable to the ASTM E-84 Tunnel Test. 
TABLE I 
______________________________________ 
Foams A B C 
______________________________________ 
Resin ingredients 
(parts by weight): 
BRL-2760.sup.1 
100 100 100 
L-5320.sup.2 
4 4 4 
Freon-11.sup.3 
6 6 6 
Freon-113.sup.4 
6 6 6 
Boric acid -- 15 -- 
Ethylene glycol 
5 5 -- 
Benzyltrimethyl- 
ammonium 
chloride solution.sup.5 
3 3 -- 
Catalyst 
(parts by weight): 
Catalyst I.sup.6 
20 -- -- 
Catalyst II.sup.7 
-- 20 -- 
Catalyst III.sup.8 
-- -- 20 
Foam Rise 
Characteristics 
(minutes:seconds): 
Cream 1:30 &lt;18:00 2:00 
Gel 13:30 -- -- 
Rise 16:00 &lt;30:00 17:00 
Foam Curing 15 minutes 1 hr./150.degree. F 
1 hr./110.degree. F 
Conditions: 130-140.degree. F 
then stand 
overnight 
at room temp. 
Foam Properties: 
Core density, pcf 
1.61 2.38 2.29 
Closed cells (%) 
-- 4.0 3.6 
Flammability 
characteristics.sup.9 : 
Flame resistance 
Excellent Excellent Excellent 
(FR) 
Smoke formation 
None None None 
Punking None None None 
4 ft. Tunnel, 
flame 
spread rating 
38 -- 25 
(FSR) 
______________________________________ 
Footnotes to Table I 
.sup.1 BRL-2760 is a proprietary liquid phenol-formaldehyde resole resin 
supplied by Union Carbide Corp., 270 Park Ave., New York 17, N. Y.; 
viscosity = 2300 - 6500 centipoise at 25.degree. C; pH = 6.0-6.3. 
.sup.2 L-5320 is a proprietary silicone surfactant supplied by Union 
Carbide Corp., 270 Park Ave., New York 17, N. Y. 
.sup.3 Freon-11 is a trichloromonofluoromethane supplied by Union Carbide 
Corp., 270 Park Ave., New York 17, N. Y. 
.sup.4 Freon-113 is trichlorotrifluoroethane supplied by Union Carbide 
Corp., 270 Park Ave., New York 17, N. Y. 
.sup.5 The benzyltrimethylammonium chloride solution is 40 percent by 
weight in methanol. Supplied by Sumner Div. of Miles Laboratories, 
Zeeland, Michigan. 
.sup.6 Catalyst I was a premixed catalyst combination comprising the 
following ingredients and their proportions in parts by weight: 
2 parts of dimethyl methylphosphonate (DMMP). Supplied by Stauffer Chem. 
299 Park Ave., New York, N.Y. 
2 parts of TMN-10, a nonionic surfactant prepared from the reaction of 
about 10 moles of ethylene oxide with trimethylnonanol, supplied by Union 
Carbide Corp., 270 Park Ave., New York 17, N. Y. 
3 parts of a combination of p-toluenesulfonic acid and xylene sulfonic 
acid in equal parts by weight (Ultra TX Acid, supplied by Witco Chemical 
Co., 277 Park Ave., New York, N.Y.) 
1 part of Niax Catalyst ES, a proprietary silicone amine polyurethane 
catalyst supplied by Union Carbide Corp., 270 Park Ave., New York 17, N. 
Y. 
.sup.7 Catalyst II was a premixed catalyst combination comprising the 
following ingredients and their proportions in parts by weight 
2 parts DMMP 
2 parts TMN-10 
6 parts of Ultra TX Acid defined in Footnote 6 above. 
1 part Niax Catalyst ES. 
.sup.8 Catalyst III was a premixed catalyst combination comprising the 
following ingredients and their proportions in parts by weight 
2 parts DMMP 
2 parts TMN-10 
6 parts of Ultra TX Acid defined in Footnote 6 above. 
.sup.9 Flammability characteristics are determined using the following 
procedures: 
(a) Flame resistance (FR) is determined qualitatively by positioning the 
center of a 4" by 4" by 1" piece of the foam sample in the blue oxidizing 
flame of a Meeker burner about 2" above the top of the burner and noting 
the burning characteristics of the sample while at the same time observin 
the smoke which is being generated. 
(b) The test for punking is performed by holding a 6" .times. 6" .times. 
2" sample of the foam above the same blue flame described above and about 
2" above the burner top so that the flame impinges on the middle of one 6 
face of the sample for about 3 minutes. The sample is then removed from 
the flame and its burned side superimposed immediately on the charred fac 
of another similarly sized sample of the same foam which had been allowed 
to cool. The test is considered positive for punking when the heat 
radiation from the hot piece of foam causes both pieces to ignite or glow 
(c) The 4 ft. Tunnel test is a miniaturized adaptation of the ASTM E-84 
Tunnel Test and the FSR values obtained from a calibrated 4 ft. Tunnel ar 
considered comparable to those obtained in the ASTM E-84 test. 
EXAMPLE 2 
Using the procedure set forth in Example 1 and the ingredients and 
proportions set forth in Table II there were prepared the following Foams 
D, and F to H in accordance with the present invention wherein a mixture 
of two different resoles were employed. Foam E which contained 
insufficient catalyst exhibited shrinkage and therefore was not prepared 
in accordance with the present invention. 
The addition of the heavy metal catalyst provided a foam characterized by a 
fine cell structure. 
TABLE II 
______________________________________ 
Foams D E F G H 
______________________________________ 
Resin ingredients 
(parts by weight): 
BRL-2760 100 100 100 100 100 
R-2170.sup.1 
20 40 20 30 20 
L-5320 2 2 2 2 -- 
Tween 40.sup.2 
-- -- -- -- 2 
Glycerine 5 -- -- -- -- 
37% aqueous formal- 
dehyde solution 
-- -- 10 10 10 
Freon-113 10 10 5 5 5 
Catalyst 
(parts by weight): 
Catalyst IV 5 2 4 -- 4 
Catalyst V.sup.4 
-- -- -- 7 -- 
Foam Rise 
Characteristics 
(mins.:secs.): 
Cream 1:10 0:40 0:45 0:60 0:70 
Gel 2:40 -- 3:52 4:00 3:40 
Rise 3:55 -- 4:45 4:45 4:22 
Foam Curing 
Conditions: 
160.degree. F cure for the 
times specified in 
10 10 10 3 10 
minutes 
Shrinkage slight yes very very very 
slight slight 
slight 
Core density, pcf 
-- -- 1.98 1.96 2.93 
Cell structure 
-- -- medium fine medium 
to fine 
Flammability 
characteristics: 
FR Excell- -- Excell- 
Excell- 
Excell- 
ent ent ent ent 
Smoke None -- None None None 
Punking None -- None None None 
______________________________________ 
Footnotes to Table II 
.sup.1 R-2170 is a proprietary liquid resorcinol formaldehyde resin 
supplied by Koppers Co., Inc., Pittsburgh, Pa., (75 + 1% solids, visc. = 
50 poise at 23.degree. C, pH 0.5 - (1.5). 
.sup.2 Tween 40 is a proprietary surfactant supplied by Atlas Powder Co., 
Div. of ICI America and is polysorbate polyoxyethylene sorbitan 
monopalmitate. 
.sup.3 Catalyst IV was a premixed catalyst combination comprising the 
following ingredients and their proportions in parts by weight: 
1 part of Carboxane NW a proprietary surfactant supplied by Textilana 
Ind., Hawthorne, California 
1 part DMMP 
3 parts of Ultra TX Acid defined in Footnote 6 of Table I above. 
.sup.4 Catalyst V was a premixed catalyst combination comprising the 
following ingredients and their proportions in parts by weight: 
4 part of Catalyst IV 
parts of a 24% weight solution of lead octoate in Rule 66 exempt mineral 
spirits supplied by Tenneco Chemical, Nuodex Division, Piscataway, N. J. 
EXAMPLE 3 
Using the procedure set forth in Example 1 and the ingredients and 
proportions set forth in Table III Foam I, not in accordance with the 
present invention, was prepared. The foam punked in spite of the fact that 
it contained boric acid. 
TABLE III 
______________________________________ 
Foam I 
______________________________________ 
Resin ingredients (pts. by wt.): 
BRL-2760 120 
L-5340.sup.1 2 
Freon 11 20 
Boric acid 15 
Catalyst (pts. by wt.): 
Catalyst VI.sup.2 30 
Foam rise characteristics: 
(mins.:secs.): 
Cream 0:60 
Rise &gt;12:00 
Foam cured 15 min./150.degree. F 
Core density 2.96 
Punking Foam Punks 
______________________________________ 
Footnotes to Table III 
.sup.1 L-5340 is a proprietary silicone surfactant supplied by Union 
Carbide Corp., 270 Park Ave., New York 17, N. Y. 
.sup.2 Catalyst VI was a premixed catalyst combination comprising the 
following ingredients and their proportions in parts by weight: 
3 parts of a solution of 60% by weight of phenolsulfonic acid in phenol 
6 parts of ethylene glycol 
21 parts of 85% phosphoric acid. 
EXAMPLE 4 
Using the procedure set forth in Example 1 and the various resole mixtures 
and proportions set forth in Table IV the following room temperature 
(about 20.degree. C) curable phenolic foams (J to O) in accordance with 
the present invention were prepared. Good foam skins were observed in 
spite of the absence of any heat curing. Although good foams were obtained 
at room temperature without any necessity for oven curing, foam strength 
was maximized by curing for 2 hours at about 150.degree. F. 
TABLE IV 
______________________________________ 
Foam J K L M N O 
______________________________________ 
Resin 
ingredients 
(pts. by wt.): 
RN441 
solution.sup.1 
20 20 20 20 40 40 
BRL-2760 60 60 -- -- 80 -- 
RI-5100.sup.2 
-- -- 60 60 -- 80 
WS-3-85.sup.3 
40 -- 40 -- -- -- 
MB-11.sup.4 
-- 40 -- 40 -- -- 
L-5350.sup.5 
2 2 2 2 2 2 
Freon-11 10 10 10 10 10 
Boric acid 
15 15 15 15 15 15 
Catalyst 
(pts. by wt.): 
Catalyst IV 
15 10 10 10 15 15 
Foam rise 
character- 
istics: 
(mins.:secs.) 
Cream 0:10 0:60 0:60 0:30 0:10 ::10 
Gel 5:00 9:00 10:30 9:00 1:30 2:05 
Rise 6:10 12:00 13:00 10:30 2:30 2:55 
Shrinkage 
very very very very very some 
slight slight slight 
slight 
slight 
Cell structure 
fine fine fine fine fine fine 
Core density 
1.73 1.92 2.02 1.92 1.54 1.95 
Flammability 
character- 
istics: 
FR Excell- Excell- Excell- 
Excell- 
Excell- 
Excell- 
ent ent ent ent ent ent 
Smoke None None Slight 
Slight 
None None 
after after 
burn burn 
Punking None None None None None None 
to very 
slight 
Compressive 
str. 
.parallel. to rise 
(psi): 
Room temp. 
-- 11.8 11.5 12.0 -- -- 
cure 
Cured at 
150.degree. F/2 hrs. 
-- 13.1 14.5 13.2 -- -- 
______________________________________ 
Footnotes to Table IV 
.sup.1 RN441 solution is a 60% solution by weight of RN441, a 
resorcinol-formaldehyde resle resin, dissolved in ethylene glycol. The 
RN441 is supplied by Koppers Co. Inc., Pittsburgh, Pa. 
.sup.2 R1-5100 is a resole resin supplied by Monsanto Chemical Corp., 
Pittsburgh, Pa; viscosity at 25.degree. C = 35000 cps, pH 4.6, 85% solids 
content. 
.sup.3 WS-3-85 is a proprietary, in-house, resole resin obtained from 
Borden Chemical Corp., Portland, Oregon. 
.sup.4 MB-11 is a proprietary, in-house, resole resin obtained from Borde 
Chemical Corp., Portland, Oregon. 
.sup.5 L-5350 is a proprietary silicone surfactant supplied by Union 
Carbide Corp., 270 Park Ave., New York 17, N. Y. 
EXAMPLE 5 
Using the procedure set forth in Example 1 and the ingredients and 
proportions set forth in Table V the following room temperature curable 
phenolic foams (P-1 to R-2) in accordance with the present invention were 
prepared. 
When the resin employed was BRL-2760 the density of the product foams could 
be increased by the addition of a brominated aromatic fire retardant 
additive as seen in the comparison of Foam P-1 to P-2 and Q-1 to Q-2. When 
the resin was RI-5100 the addition of the fire retardant had no effect of 
foam density as noted in the comparison of Foam R-1 to R-2. The addition 
of the minor amount of the RN441 resin to the BRL-2760 gave rise to an 
increase in foaming reactivity as noted in the comparison of the rise 
characteristics of Foam Q-1 to P-1 and Foam Q-2 to P-2 
TABLE V 
______________________________________ 
Foam P-1 P-2 Q-1 Q-2 R-1 R-2 
______________________________________ 
Resin ingredients 
(pts. by wt.): 
BRL-2760 120 120 120 120 -- -- 
RN441 solution.sup.1 
-- -- 20 20 -- -- 
RI-5100 -- -- -- -- 120 120 
L-5350 2 2 2 2 2 2 
Freon-11 10 10 10 10 10 10 
UK-60.sup.2 -- 15 -- 15 -- 15 
Catalyst 
(pts. by wt.): 
Catalyst IV 10 10 10 10 10 7.5 
Foam rise 
characteristics: 
(mins.:secs.) 
Cream 0:20 0:20 0:10 0:10 0:10 0:15 
Gel 7:00 10:15 2:00 4:30 4:00 10:45 
Rise 8:30 12:30 2:40 5:30 5:15 12:00 
Foam core density 
pcf 1.18 1.68 0.98 1.51 1.82 1.78 
______________________________________ 
Footnotes to Table V 
.sup.1 See Footnote 1 of Example 4. 
.sup.2 A 50% by weight solution of a brominated aromatic fire retardant 
compound in ethylene glycol supplied by Great Lakes Chemical Corp., and 
consists of: 
tetrabromobisphenol A (46 - 54%), 
2,4,6-tribromophenol (25 - 29%), and 
di and tribromobisphenol A (10 - 17%). 
EXAMPLE 6 
A machine pour preparation of a phenolic foam in accordance with the 
present invention was performed using a resin component mixture which was 
comprised of the following ingredients in the proportions indicated: 
BRL-2760 120 parts, glycerine 10 parts, L-5320 4 parts, Freon 11 10 parts, 
and 10 parts of the premixed catalyst combination identified as Catalyst 
IV in Example 2. The resin component was at 85.degree. F while the 
catalyst component was at ambient room temperature. 
The two components were reacted in a 12 lb. Admiral Foam Machine 
(manufactured by the Admiral Equipment Corporation, Akron, Ohio) employing 
a high speed conical self cleaning head and at the rate of 299 grams of 
resin component with 25.2 grams of catalyst component per 6 seconds, or 
7.14 lbs./minute. The reaction mixture was discharged into 14 inch .times. 
14 inch .times. 18 inch cardboard boxes and allowed to rise freely. The 
foam was characterized by a cream time of 55 seconds; gel of 5 minutes, 10 
seconds, rise of 7 minutes, 30 seconds; and a gel/rise = 0.689. Curing of 
the foam blocks was carried out in an oven at 250.degree. F for 5 minutes 
to eliminate any possibility of shrinkage. 
Because the self cleaning head caused pressure build-up, it was replaced by 
a basket type head and the foam preparation repeated with an additional 2 
parts of methyl formate added to the resin side. The foam was 
characterized by a cream time of 70 seconds; gel of 5 minutes; rise of 6 
minutes, 30 seconds; and a cup foam core density of 1.55 pcf. and a box 
foam core density of 1.29 pcf. The phenolic foams obtained above were 
characterized by excellent flame resistance, no smoke and no punking when 
tested in a Meeker burner in accordance with the test procedures described 
previously. No cracking or splitting of the foam was observed in spite of 
the size of the blocks. 
EXAMPLE 7 
Using the procedure set forth in Example 1 except that the foams were 
prepared in 1 quart cups, and the reagents and proportions set forth in 
Table VI, there were prepared Foams S and T in accordance with the present 
invention. Foam S employed as the premixed catalyst combination the 
premixed Catalyst IV defined in Example 2 in combination with the 
additional acid of 4-sulfophthalic acid. Foam T employed the premixed 
catalyst combination of DMMP with 4-sulfophthalic acid. 
The reaction was carried out with the components at room temperature. The 
foams were cured at room temperature with slight shrinkage observed. When 
foam T was tested in accordance to the flammability test described in 
Example 1 it was characterized by excellent flame resistance, no smoke, 
and no punking. 
TABLE VI 
______________________________________ 
Foam S T 
______________________________________ 
Resin ingredients (pts. by wt.): 
BRL-2760 120 120 
L-5320 2 2 
Freon 11 10 10 
Catalyst (pts. by wt.): 
Catalyst VII.sup.1 20 -- 
Catalyst VIII.sup.2 
-- 40 
Foam rise characteristics: 
(mins.:secs.) 
Cream 1:20 1:10 
Gel 8:00 20:00 
Rise 10:30 &gt;20:00 
Foam core density (pcf.) 
2.02 4.35 
Shrinkage -- slight when 
cured at room 
temperature 
Flammability characteristics: 
Flame rating -- Excellent 
Smoke -- None 
Punking -- None 
______________________________________ 
Footnotes to Table VI 
.sup.1 Catalyst VII was a premixed catalyst combination comprising the 
following ingredients and their proportions in parts by weight: 
10 parts of catalyst IV 
10 parts of a 50% by wt. solution of 4-sulfophthalic acid in water. 
.sup.2 Catalyst VIII was a premixed catalyst combination comprising the 
following ingredients and their proportions in parts by weight: 
20 parts of DMMP 
20 parts of a 50% by wt. solution of 4-sulfophthalic acid in water.