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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a novel catalyst system for the
preparation of cellular foams characterized by carbodiimide and
isocyanurate linkages. More particularly the invention relates to the use
of a catalyst system comprising (a) an alkanolaminotriazine, (b) a
hexahydrotriazine, and (c) phenol or a substituted phenol in the
preparation of cellular foams characterized by carbodiimide and
isocyanurate linkages.
2. Prior Art
The preparation of foams containing carbodiimide and isocyanurate linkages
is well known in the art. The art teaches that foams containing both
linkages can be prepared by condensing an organic polyisocyanate with a
catalyst which promotes both carbodiimide and isocyanurate linkages or
with a co-catalyst system, one catalyst promoting carbodiimide linkages
and one catalyst promoting isocyanurate linkages. Representative of such
teachings are the disclosures found in U.S. Pat. Nos. 3,645,923;
3,657,161; 3,717,596; 3,723,366; 3,746,709, and 3,806,475.
SUMMARY OF THE INVENTION
The present invention relates to an improved process for the preparation of
carbodiimide-isocyanurate foams employing a catalytically sufficient
amount of a catalyst system comprising (a) an alkanolaminotriazine, (b) a
hexahydrotriazine, and (c) phenol or a substituted phenol. The
polymerization times of organic polyisocyanates are significantly reduced
when a phenol is employed along with the aforementioned triazine
co-catalysts. In addition, because of the higher reactivity of the
catalyst system the amount of catalysts required to polymerize the
polyisocyanates is considerably reduced.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In accordance with the present invention rigid cellular foams are prepared
by the catalytic condensation of an organic polyisocyanate in the presence
of the aforementioned catalyst systems. The products which are produced in
accordance herewith are rigid cellular foam plastics containing
carbodiimide linkages and isocyanurate linkages. It is the carbodiimide
linkages whose formation provides the carbon dioxide blowing agent and
which together with the isocyanurate linkages imparts the excellent flame
properties to the products.
As mentioned above, there are three essential ingredients which comprise
the catalyst system of the present invention. One ingredient is an
alkanolaminotriazine. Representative alkanolaminotriazine catalysts which
are of use in the present invention include:
2,4,6-tris(diethanolamino)-s-triazine,
2,4,6-tris(diisopropanolamino)-s-triazine,
2,4,6-tris(dibutanolamino)-s-triazine,
2,4,6-tris(N-methylethanolamino)-s-triazine, and unsymmetrically
substituted triazines of the formula:
##SPC1##
wherein R is hydrogen or lower alkyl of from 1 to 10 carbon atoms, R.sup.1
is CR.sub.2 CR.sub.2 OH or lower alkyl of from 1 to 12 carbon atoms, X is
NR.sub.2, alkoxy of from 1 to 12 carbon atoms, phenoxy, alkyl of from 1 to
12 carbon atoms, phenyl, hydroxyl, halogen, aziridyl, pyrrolidyl,
piperidyl, or N-alkylpiperazyl. Since the triazines are unsymmetrically
substituted, it is apparent that each X cannot concurrently be
##EQU1##
wherein each R and R.sup.1 is the same.
Representative compounds from the above generic formula include:
2-amino-4,6-bis(N-methyl-2-hydroxyethylamino)-1,3,5-triazine,
2,4-bis(N-methyl-2-hydroxyethylamino)-6-methoxy-1,3,5-triazine,
2,4-bis(di-2-hydroxyethylamino)-6-chloro-1,3,5-triazine,
2,4-bis(N-methyl-2-hydroxyethylamino)-6-chloro-1,3,5-triazine,
2,4-bis(N-methyl-2-hydroxyethylamino)-6-phenyl-1,3,5-triazine,
2,4-bis(N-methyl-2-hydroxyethylamino)-6-diethylamino-1,3,5-triazine,
2,4-bis(N-methyl-2-hydroxyethylamino)-6-dimethylamino-1,3,5-triazine,
2,4-bis(di-2-hydroxyethylamino)-6-diethylamino-1,3,5-triazine,
2,4-bis(di-2-hydroxyethylamino)-6-phenoxy-1,3,5-triazine,
2,4-bis(N-methyl-2-hydroxyethylamino)-6-phenoxy-1,3,5-triazine,
2,4-bis(N-methyl-2-hydroxyethylamino)-6-methyl-1,3,5-triazine,
2,4-bis(di-2-hydroxyethylamino)-6-methyl-1,3,5-triazine,
2,4-bis(N-methyl-2-hydroxyethylamino)-6-hydroxy-1,3,5-triazine,
2,4-bis(diethylamino)-6-(N-methyl-2-hydroxyethylamino)-1,3,5-triazine,
2,4-dimethoxy-6-(N-methyl-2-hydroxyethylamino)-1,3,5-triazine,
2,4-bis(dimethylamino)-6-(N-methyl-2-hydroxyethylamino)-1,3,5-triazine,
2,4-diphenoxy-6-(N-methyl-2-hydroxyethylamino)-1,3,5-triazine, and
2,4-diphenoxy-6-(di-2-hydroxyethylamino)-1,3,5-triazine.
Generally, the amount of s-triazine catalyst employed in the process of the
subject invention will be from 0.1 part to 10 parts per 100 parts of
organic polyisocyanate.
The preparation of the triazine catalyst generally comprises condensing
cyanuric chloride with the selected amine in the presence of a
neutralizing amount of sodium hydroxide. Thus, for example,
2,4,6-tris(diethanolamino)-s-triazine is prepared from the condensation of
diethanolamine and cyanuric chloride in the presence of a neutralizing
amount of sodium hydroxide. The triazine compounds and their methods of
preparation are known in the art and are more fully described by Kaiser et
al., Journal Of The American Chemical Society, V. 73, p. 2984 (1951), as
well as in U.S. Pat. No. 3,806,475.
The second ingredient of the catalyst system employed in the process of the
present invention is a
1,3,5-tris(N,N-dialkylaminoalkyl)-s-hexahydrotriazine or the alkylene
oxide and water adducts thereof.
1,3,5-Tris(N,N-dialkylaminoalkyl)-s-hexahydrotriazines are generally
prepared by reacting equimolar amounts of a dialkylaminoalkylamine and a
37% aqueous solution of formaldehyde (formalin) at a temperature ranging
from about 0.degree.C. to 20.degree.C., and at atmospheric pressure. More
particularly, the amine and the formaldehyde are mixed together with
gentle stirring at about 0.degree.C. Thereafter, and with continuous
gentle stirring the resulting mixture is allowed to heat up to room
temperature. The hexahydrotriazine compound is then recovered by first
salting out the hexahydrotriazine from the reaction mixture with a strong
base, such as potassium hydroxide, and then purifying by distillation.
These hexahydrotriazine compounds and their methods of preparation are
more particularly described by Nicholas et al., Journal of Cellular
Plastics, 1(1), 85 (1965), and Graymore, Journal of the Chemical Society,
1493 (1931).
Representative of the
1,3,5-tris(N,N-dialkylaminoalkyl)-s-hexahydrotriazines useful herein
include, for example,
1,3,5-tris(N,N-dimethyl-2-aminoethyl)-s-hexahydrotriazine,
1,3,5-tris(N,N-dimethyl-2-aminopropyl)-s-hexahydrotriazine, and the like;
1,3,5-tris(N,N-diethyl-2-aminoethyl)-s-hexahydrotriazine, and the like;
1,3,5-tris(N,N-dipropyl-2-aminoethyl)-s-hexahydrotriazine, and the like;
and so forth. The preferred compound is
1,3,5-tris(N,N-dimethyl-3-aminopropyl)-s-hexahydrotriazine which can also
be designated as 1,3,5-tris(3-dimethylaminopropyl)-s-hexahydrotriazine.
Other preferred isocyanate trimerization catalysts, as noted, are the
alkylene oxide and water adducts of the hereinbefore described
1,3,5-tris(N,N-dialkylaminoalkyl)-s-hexahydrotriazines. The alkylene
oxides which may be used to prepare the adducts are, preferably, linear
alkylene oxides, such as ethylene oxide, propylene oxide, the butylene
oxides, and the pentylene oxides. Although not preferred, alicyclic
oxides, such as cyclopentylene oxide, cyclohexylene oxide, and the like,
can be used herein. Also, substituted alkylene oxides such as styrene
oxide can be used herein. The preferred alkylene oxide, though, is
propylene oxide. For a more comprehensive discussion of these adducts,
reference is made to U.S. Pat. No. 3,746,709. Generally, from about 1 part
to 6 parts by weight of catalyst based on 100 parts of polyisocyanate will
be employed in the present invention.
The third ingredient of the catalyst system is phenol or a substituted
phenol. Representative phenols which may be employed in the catalyst
system of the present invention include phenol, monosubstituted phenols
such as the o-, p- and m-substituted methylphenols, chlorophenols,
bromophenols, fluorophenols, nitrophenols, methoxyphenols,
hydroxyacetophenones, hydroxydiphenyls, hydroxybenzophenones, and
hydroxydiphenylmethanes; disubstituted phenols such as the
dichlorophenols, dibromophenols, dimethylphenols and dimethoxyphenols;
trisubstituted phenols such as the trichlorophenols, tribromophenols and
trimethylphenols; pentasubstituted phenols such as pentachlorophenol,
pentabromophenol and pentafluorophenol; and polyhydric phenols such as
catechol, resorcinol, hydroquinone, pyrogallol, hydroxyhydroquinone and
phloroglucinol. Generally from about 0.01 part to 5.0 parts, preferably
0.5 part to 2.0 parts by weight of a phenol based on 100 parts of
polyisocyanate will be employed in the process of the subject invention.
The organic polyisocyanate used to prepare the carabodiimide foam
corresponds to the formula:
R"(NCO).sub.z
wherein R" is a polyvalent organic radical which is either aliphatic,
aralkyl, alkaryl, aromatic or mixtures thereof, and z is an integer which
corresponds to the valence of R" and is at least 2. Representative of the
organic polyisocyanates contemplated herein includes, for example, the
aromatic diisocyanates, such as 2,4-toluene diisocyanate, 2,6-toluene
diisocyanate, mixtures of 2,4- and 2,6-toluene diisocyanate, crude toluene
diisocyanate, methylene diphenyl diisocyanate, crude methylene diphenyl
diisocyanate and the like; the aromatic triisocyanates such as
4,4',4"-triphenylmethane triisocyanate, 2,4,6-toluene triisocyanates; the
aromatic tetraisocyanates, such as
4,4'-dimethyldiphenylmethane-2,2'-5,5'-tetraisocyanate, and the like;
arylalkyl polyisocyanates, such as xylylene diisocyanate; aliphatic
polyisocyanates, such as hexamethylene-1,6-diisocyanate, lysine
diisocyanate methylester and the like; and mixtures thereof. Other organic
polyisocyanates include polymethylene polyphenylisocyanate, hydrogenated
methylene diphenylisocyanate, m-phenylene diisocyanate,
naphthylene-1,5-diisocyanate, 1-methoxyphenyl-2,4-diisocyanate,
4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate,
3,3'-dimethyl-4,4'-biphenyl diisocyanate, and
3,3'-dimethyldiphenylmethane-4,4'-diisocyanate.
These polyisocyanates are prepared by conventional methods known in the art
such as the phosgenation of the corresponding organic amine.
Still another class of organic polyisocyanates contemplated for use herein
are the so-called "quasi-prepolymers". These quasi-prepolymers are
prepared by reacting an excess of organic polyisocyanate or mixtures
thereof with a minor amount of an active hydrogen containing compound as
determined by the well-known Zerewitinoff test, as described by Kohler in
Journal Of The American Chemical Society, 49, 3181 (1927). These compounds
and their methods of preparation are well known in the art. The use of any
one specific active hydrogen compound is not critical hereto, rather any
such compound can be employed herein.
Suitable active hydrogen-containing groups as determined by the
Zerewitinoff method which are reactive with an isocyanate group include
--OH, --NH--, --COOH, and --SH. Examples of suitable types of organic
compounds containing at least two active hydrogen-containing groups which
are reactive with an isocyanate group are hydroxy-terminated polyesters,
polyalkylene ether polyols, hydroxy-terminated polyurethane polymers,
polyhydric polythioethers, alkylene oxide adducts of phosphorus-containing
acids, polyacetals, aliphatic polyols, aliphatic thiols including alkane,
alkene and alkyne thiols having two or more --SH groups; diamines
including both aromatic, aliphatic and heterocyclic diamines, as well as
mixtures thereof. Compounds which contain two or more different groups
within the above-defined classes may also be used in accordance with the
process of the present invention such as, for example, amino alcohols
which contain an amino group and a hydroxyl group. Also, compounds may be
used which contain one --SH group and one --OH group as well as those
which contain an amino group and a --SH group.
Any suitable hydroxy-terminated polyester may be used such as are obtained,
for example, from polycarboxylic acids and polyhydric alcohols. Any
suitable polycarboxylic acid may be used such as oxalic acid, malonic
acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic
acid, azelaic acid, sebacic acid, brassylic acid, thapsic acid, maleic
acid, fumaric acid, glutaconic acid, .alpha.-hydromuconic acid,
.beta.-hydromuconic acid, .alpha.-butyl-.alpha.-ethyl-glutaric acid,
.alpha.,.beta.-diethylsuccinic acid, isophthalic acid, terephthalic acid,
hemimellitic acid, and 1,4-cyclohexane-dicarboxylic acid. Any suitable
polyhydric alcohol, including both aliphatic and aromatic, may be used
such as ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol,
1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol,
1,5-pentanediol, 1,4-pentanediol, 1,3-pentanediol, 1,6-hexanediol,
1,7-heptanediol, glycerol, 1,1,1-trimethylolpropane,
1,1,1-trimethylolethane, hexane1,2,6-triol, .alpha.-methyl glucoside,
pentaerythritol, and sorbitol. Also included within the term "polyhydric
alcohol" are compounds derived from phenol such as
2,2-bis(4-hydroxyphenyl)propane, commonly known as Bisphenol A.
The hydroxy-terminated polyester may also be a polyester amide such as is
obtained by including some amine or amino alcohol in the reactants for the
preparation of the polyesters. Thus, polyester amides may be obtained by
condensing an amino alcohol such as ethanolamine with the polycarboxylic
acids set forth above, or they may be made using the same components that
make up the hydroxy-terminated polyester with only a portion of the
components being a diamine such as ethylene diamine.
Any suitable polyalkylene ether polyol may be used such as the
polymerization product of an alkylene oxide or of an alkylene oxide with a
polyhydric alcohol. Any suitable polyhydric alcohol may be used such as
those disclosed above for use in the preparation of the hydroxy-terminated
polyesters. Any suitable alkylene oxide may be used such as ethylene
oxide, propylene oxide, butylene oxide, amylene oxide, and heteric or
block copolymers of these oxides. The polyalkylene polyether polyols may
be prepared from other starting materials such as tetrahydrofuran and
alkylene oxide-tetrahydrofuran copolymers; epihalohydrins such as
epichlorohydrin; as well as aralkylene oxides such as styrene oxide. The
polyalkylene polyether polyols may have either primary or secondary
hydroxyl groups and, preferably, are polyethers prepared from alkylene
oxides having from two to six carbon atoms such as polyethylene ether
glycols, polypropylene ether glycols, and polybutylene ether glycols. The
polyalkylene polyether polyols may be prepared by any known process such
as, for example, the process disclosed by Wurtz in 1859 and Encyclopedia
Of Chemical Technology, Vol. 7, pp. 257-262, published by Interscience
Publishers, Inc. (1951) or in U.S. Pat. No. 1,922,459. Alkylene oxide
adducts of Mannich condensation products are also useful in the invention.
Alkylene oxide adducts of acids of phosphorus which may be used include
those neutral adducts prepared from the alkylene oxides disclosed above
for use in the preparation of polyalkylene polyether polyols. Acids of
phosphorus which may be used are acids having a P.sub.2 O.sub.5
equivalency of from about 72% to about 95%. The phosphoric acids are
preferred.
Any suitable hydroxy-terminated polyacetal may be used such as, for
example, the reaction product of formaldehyde or other suitable aldehyde
with a dihydric alcohol or an alkylene oxide such as those disclosed
above.
Any suitable aliphatic thiol including alkane thiols containing at least
two --SH groups may be used such as 1,2-ethanedithiol, 1,2-propanedithiol,
1,3-propanedithiol, and 1,6-hexanedithiol; alkenethiols such as
2-butene-1,4-dithol, and alkynethiols such as 3-hexyne-1,6-dithiol.
Any suitable polyamine may be used including aromatic polyamines such as
p-aminoaniline, 1,5-diaminonaphthalene, and 2,4-diaminotoluene; aliphatic
polyamines such as ethylenediamine, 1,3-propylenediamine,
1,4-butylenediamine, and 1,3-butylenediamine, as well as substituted
secondary derivatives thereof.
In addition to the above hydroxy-containing compounds, other compounds
which may be employed include graft polyols. These polyols are prepared by
the in situ polymerization product of a vinyl monomer in a reactive polyol
medium and in the presence of a free radical initiator. The reaction is
generally carried out at a temperature ranging from about 40.degree.C. to
150.degree.C.
The reactive polyol medium generally has a molecular weight of at least
about 500 and a hydroxyl number ranging from about 30 to about 600. The
graft polyol has a molecular weight of at least about 1500 and a viscosity
of less than 40,000 cps. at 10% polymer concentration.
A more comprehensive discussion of the graft polyols and their method of
preparation can be found in U.S. Pat. Nos. 3,383,351; 3,304,273; 3,652,639
and 3,823,201.
Also, polyols containing ester groups can be employed in the subject
invention. These polyols are prepared by the reaction of an alkylene oxide
with an organic dicarboxylic acid anhydride and a compound containing a
reactive hydrogen atom. A more comprehensive discussion of these polyols
and their method of preparation can be found in U.S. Pat. Nos. 3,585,185;
3,639,541, and 3,639,542.
The foams of the present invention are prepared by mixing together the
organic polyisocyanate and the catalysts at an initiating temperature
which, depending on the catalysts will range from about 0.degree.C. to
150.degree.C. Under such conditions, carbon dioxide is generated, foam
formation begins, and almost immediately an exotherm is developed within
the reaction system.
The present invention also contemplates the incorporation of additional
ingredients in the foam formulation to tailor the properties thereof.
Thus, plasticizers such as tris(2-chloroethyl) phosphate and surfactants
such as the silicone surfactants, e.g., alkylpolysiloxanes and polyalkyl
siloxanes, may be employed in the invention. Further additional
ingredients include auxiliary or supplemental blowing agents, such as
water or halohydrocarbons, and inorganic fillers, pigments and the like
can be used. In addition, polyols such as those described above in
connection with the preparation of quasiprepolymers may be employed in the
process of the subject invention. If a polyol is employed, a
urethane-promoting catalyst may also be added to the formulation.
Preferred urethane-promoting catalysts are the tin salts of carboxylic
acids such as dibutyltin dilaurate and acetate.
It should also be pointed out that in certain instances the triazine is a
solid at ambient conditions. Thus, it can be first dissolved in an
ingredient such as a plasticizer, a surfactant or blowing agent, thereby
providing an easy means for introducing the ingredients into the system.
In any event, the carbodiimide foams prepared in accordance herewith are
rigid cellular products having a density of from about 1 pound to 40
pounds per cubic foot which exhibit excellent flame properties, such as
fire resistance, low smoke evolution and excellent weight retention.
Following are specific, non-limiting examples which are provided to
illustrate the enumerated principles described herein. All parts are by
weight unless otherwise indicated. In the examples, the compressive
strength properties of the foams were determined in accordance with
ASTM-1621 and the friability properties by ASTMC-421. The flame retardant
properties were determined by the Butler Chimney Test as described by
Krueger et al, SPE 25th Antec., Vol. XIII, Detroit, Mich. 1967, pp.
1052-1057.
EXAMPLES 1-40
A series of foams was prepared by simultaneously adding a catalyst system
to a reaction vessel equipped with a high speed stirrer to which had been
charged a polyisocyanate and in certain cases a foam stabilizer, a
plasticizer and/or a blowing agent. An exotherm was generated and foam
formation followed soon after. Table I, below, illustrates the details of
the preparations. Infrared spectroscopic analyses indicate that the foams
exhibit carbodiimide and isocyanurate linkages. In the Tables, the
following abbreviations are employed:
Tdi -- a mixture of 80/20 by weight 2,4-, 2,6-tolylene diisocyanate
Papi -- polymethylene polyphenyl isocyanate
Tdh -- 1,3,5-tris(N,N-dimethylaminopropyl)hexahydrotriazine
Dmt -- 2,4-bis(diethylamino)-6-N-methylethanolamino-s-triazine
Tmt -- 2,4,6-tris(N-methylethanolamino)-s-triazine
Fyrol cef -- tris(2-chloroethyl) phosphate
Dc-193 -- polyalkyl siloxane-polyoxyalkylene copolymer, a foam stabilizer
F-113 -- 1,1,2-trichloro-1,2,2-trifluoroethane
pbw. -- parts by weight
TABLE I
__________________________________________________________________________
Isocyanate Catalyst Blend, pbw. Cream
Rise
Max.
Exam-
Blend, pbw. FYROL
DC- F-113
Time,
Time,
Temp.
ple PAPI
TDI DMT TMT TDH Phenol
CEF 193 pbw. sec.
sec.
.degree.C.
__________________________________________________________________________
1 100 -- 2.8 -- 1.4 -- 1.9 0.93
15 200 255 116
2 100 -- 2.3 --1.2
1.2 1.6 0.77 15 105 165 124
3 100 -- -- 2.8 1.4 -- 1.9 0.93
15 125 240 125
4 100 -- -- 2.3 1.2 1.2 1.6 0.77
15 60 120 138
5 90 10 2.6 -- 1.3 -- 1.7 0.86
15 145 230 136
6 90 10 2.2 -- 1.1 1.1 1.5 0.72
15 63 105 141
7 90 10 -- 2.6 1.3 -- 1.7 0.86
15 92 195 132
8 90 10 -- 2.2 1.1 1.1 1.5 0.72
15 47 95 145
9 80 20 2.4 -- 1.2 -- 1.6 0.80
15 120 205 143
10 80 20 2.0 -- 1.0 1.0 1.3 0.67
15 55 90 155
11 80 20 -- 2.4 1.2 -- 1.6 0.80
15 76 160 138
12 80 20 -- 2.0 1.0 1.0 1.3 0.67
15 40 75 147
13 70 30 2.2 -- 1.1 -- 1.5 0.74
15 100 170 147
14 70 30 1.8 -- 0.9 0.9 1.2 0.61
15 55 90 155
15 70 30 -- 2.2 1.1 -- 1.5 0.74
15 65 130 143
16 70 30 -- 1.8 0.9 0.9 1.2 0.61
15 36 65 164
17 100 -- 5.3 -- 2.7 -- -- -- 15 210 280 125
18 100 -- 5.1 -- 2.5 0.4 -- -- 15 128 165 139
19 100 -- 3.6 -- 1.8 0.6 -- -- 15 132 165 142
20 100 -- 4.0 -- 2.0 2.0 -- -- 15 78 100 148
21 90 10 5.3 -- 2.7 -- -- -- 15 135 185 143
22 90 10 5.1 -- 2.5 0.4 -- -- 15 88 110 152
23 90 10 3.6 -- 1.8 0.6 -- -- 15 95 120 153
24 90 10 4.0 -- 2.0 2.0 -- -- 15 53 70 150
25 80 20 5.3 -- 2.7 -- -- -- 15 105 140 155
26 80 20 4.4 -- 2.2 0.4 -- -- 15 85 93 162
27 80 20 3.6 -- 1.8 0.6 -- -- 15 73 85 171
28 80 20 4.0 -- 2.0 2.0 -- -- 15 44 55 177
29 70 30 5.3 -- 2.7 -- -- -- 15 90 120 172
30 70 30 4.4 -- 2.2 0.4 -- -- 15 67 80 177
31 70 30 3.0 -- 1.5 0.5 -- -- 15 75 90 174
32 70 30 3.5 -- 1.8 1.8 -- -- 15 43 50 181
33 50 50 5.3 -- 2.7 -- -- -- 15 72 90 178
34 50 50 3.2 -- 1.6 0.3 -- -- 15 62 80 193
35 50 50 2.4 -- 1.2 0.4 -- -- 15 67 75 195
36 50 50 3.5 -- 1.8 1.8 -- -- 15 37 43 198
37 -- 100 5.3 -- 2.7 -- -- -- -- 20 25 182
38 -- 100 1.9 -- 1.0 0.2 -- -- -- 30 -- 217
39 -- 100 1.8 -- 0.9 0.3 -- -- -- 20 -- --
40 -- 100 2.0 -- 1.0 1.0 -- -- -- 15 -- --
__________________________________________________________________________
EXAMPLES 41-52
A series of foams was prepared by simultaneously adding a catalyst system
to a reaction vessel equipped with a high speed stirrer to which had been
charged a polyisocyanate and in certain cases a foam stabilizer, a
plasticizer and/or a blowing agent. An exotherm was generated and foam
formation followed soon after. Table II, below, illustrates the details of
the preparations. Infrared spectroscopic analyses indicate that the foams
exhibit carbodiimide and isocyanurate linkages.
TABLE II
__________________________________________________________________________
Isocyanate
Catalyst Blend, Cream
Rise
Max.
Exam-
Blend, pbw.
pbw. F-113
Time,
Time,
Temp.
ple PAPI
TDI DMT TDH Phenol
pbw. sec.
sec.
.degree.C.
__________________________________________________________________________
41 100 -- 5.3 2.7 -- 15 210 280 125
42 100 -- 5.1 2.5 0.40
15 150 200 131
43 90 10 5.3 2.7 -- 15 135 185 143
44 90 10 5.1 2.5 0.40
15 100 135 146
45 80 20 5.3 2.7 -- 15 105 140 155
46 80 20 4.4 2.2 0.35
15 83 110 161
47 70 30 5.3 2.7 -- 15 90 120 172
48 70 30 4.4 2.2 0.35
15 70 92 168
49 50 50 5.3 2.7 -- 15 72 90 178
50 50 50 3.8 1.9 0.30
15 60 75 179
51 -- 100 5.3 2.7 -- -- 20 25 182
52 -- 100 2.6 1.3 0.20
-- 20 25 203
__________________________________________________________________________
EXAMPLES 53-58
A series of foams was prepared by simultaneously adding a catalyst system
to a reaction vessel equipped with a high speed stirrer to which had been
charged a polyisocyanate and in certain cases a foam stabilizer, a
plasticizer and/or a blowing agent. An exotherm was generated and foam
formation followed soon after. Table III, below, illustrates the details
of the preparations as well as some of the physical properties of the
resulting foams. Infrared spectroscopic analyses indicate that the foams
exhibit carbodiimide and isocyanurate linkages.
TABLE III
__________________________________________________________________________
Butler
Iso- Comp. Chimney Test
cyanate Str.
Tumb. Time
Blend Catalyst Blend, pbw. Den-
10% Friab.
Closed Flame
to
Exam-
pbw. FYROL
DC- F-113
sity
Defl.
% Wt.
Cells
% Wt.
Ht. SX
ple PAPI
TDI
DMT TDH Phenol
CEF 193 pbw. pcf.
psi.
Loss
% Ret.
in. sec.
__________________________________________________________________________
53 300
-- 10.8 5.4 0.9 8.6 4.3 90 1.96
24.3
71.5
98.7
94.0
3 10
54 300
-- 8.6 4.3 1.4 7.1 3.6 90 1.96
30.2
71.9
99.9
96.6
4 10
55 270
30 9.1 4.5 0.7 7.1 3.6 75 2.19
39.0
64.8
101.2
95.7
3 10
56 270
30 8.6 4.3 1.4 7.1 3.6 75 2.20
36.4
66.7
100.6
96.1
3 10
57 240
60 7.2 3.6 0.6 5.7 2.9 75 1.89
30.2
83.1
102.8
96.2
3 10
58 240
60 6.9 3.4 1.1 5.7 2.9 75 2.14
34.9
73.0
100.5
95.9
3 10
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EXAMPLE 59
A carbodiimide-isocyanurate foam was prepared in the manner described in
the previous examples. The ingredients employed and amounts thereof as
well as the physical properties of the resulting foam are as follows:
Foam Formulation
Ingredients Parts by Weight
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Polymethylene polyphenyl-
isocyanate 100
Polyol prepared by reaction of
propylene oxide with Mannich
condensation product of form-
aldehyde, phenol and diethanol-
amine (hydroxyl number of 530,
nitrogen content of 4.17% by
weight) 20
DMT 1.0
TDH 1.0
Phenol 1.0
Silicone surfactant 1.0
Trichlorofluoromethane
25.0
Physical Properties Of Foam
Density, core, pcf. 1.86
Compressive strength, psi.
at yield point 21
at 10% defl. 21
Tensile strength, psi.
27
K factor, BTU/(hr.)(ft..sup.2)(.degree.F./in.)
initial 0.118
after 10 days at 140.degree.F.
0.151
Friability
Taber, cycles/in. 268
Tumbling, % wt. loss 16
Flammability
Butler Chimney test
% wt. retained 86
flame ht., in. 7-8
Bureau of Mines
sec. to burn-through
1209
Simulated Service Conditions
158.degree.F., 100% R.H., % volume change
1 day 2.6
2 days 3.0
7 days 3.8
14 days 4.1
28 days 4.6
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