Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
Back~ of the Invention
1. E`ield oE the Invention
The present invention pertains to compositions of
matter and particularly to novel reaction products of certain
tertiary amines, alkylene oxides and carboxylic acids. More
particularly the present invention concerns the use of these
compounds in the preparation of rigid and flexible foams
characterized by polyisocyanurate, polyurethane and poly-
(urethane-isocyanurate) linkages.
2. Prior Art
In U.S. Patent No. 3,954,684 there is taught a
catalyst comprising a tertiary amine trimerization catalyst
and a quaternary ammonium salt of an alkanoic acid. This
catalyst is used to prepare polyisocyanurate foams.
In U.S. Patent No. 3,892,687 there is the teaching
of the preparation of cellular polyurethanes and polyurethane
modified polyisocyanurate employing catalysts composed of a
tertiary amine and a quaternary hydroxyalkyl tertiary amine
base.
In U.S. Patent No. 3,746,709 there is taught an
isocyanurate promoting catalyst comprising adducts oE a
tertiary amine and alkylene oxide and water.
In U.S. Paten~ No. 4,040,992 there is taught the
use of N-hydroxyalkyl quaternary ammonium carboxylate salts
~k
~ .
~ . .
~316~
as catalysts for the preparation of polyisocyanurates and
polyurethanes.
Summary of the Invention
The present lnvention relates to an lmproved
process for the preparation of polyisocyanurates, polyisocyanu-
rate foams, polyurethane foams and poly (urethane-isocyanurate)
foams employlng a catalytically sufficient amount of the reaction
product of a tertiary amine selecte~ from the gro~p consisting
of 1,3,5-tris(N,N-dlalkylaminoalkyl)-s~hexahydrotr~azines, pyridine
and bis (~,N-diaIkylaminoalkyl) ethers, an alkylene oxide and a
carboxylic acid. It was suprising and unexpected to find tha~
the use of these amines, al~ylene oxide and carboxylic acid
products provides for foa~s characterized by polyisocyanuxate
and polyurethane and poly(urethane~isocyanurate) linkages.
In particular the present invention p~ovides a
composition which is the xeaction product of
(a) a tertiary amine se~ected fro~ the group
consis~ing o~ 1~3,5 tris(N,N~diaikylamino-
. alkyl~-s-hexahydrotriazines, pyridine and
bis (N,N-dialkyla~inoalkyl) e~hers~
(b) an alkylene oxide containing f~om 2 to 18
carbon atoms, and
(c) a carboxylic acid-
employing a mole ratio of (a~ to (b) to (c) of fro~ 1:0.5:1
to 1:6:6.
In another aspect the present ~nvention provides
a process for the preparation of a cellular foam chaxacterized
by polyisocyanurate linkages ~hich comp~iSes reacting an organic
polyisocyanate in the presence of a ca~al~tically sufficient
amount of a catalys~ ~hich i5 the reaction product of
~ .
~J - 3 -
(a) a ter-tiary amine, sel~cted from the group
consisting of 1,3,5-tris(N,N-dialkylaminoalkyl)-
s-hexahydrotriazines, pyridine and bis (N,N-
dialkylaminoalkyl) ethers,
(b) an alkylene oxide containing from 2 to 18 carbon
atoms, and
(c) a carboxylic acid
employing a mole ratio of (a) to (b) to (c) of from l:O.S:l to
1:6:6.
The present invention also provides a process for the
preparation of a cellular foam characte~ized by polyisocyanurate
and polyurethane linkages which comprises reacting one equiva-
lent of an organic polyisocyanate and from 0.01 to O.S equiva-
lents of a polyol in the presence of a catalytically sufficient
amount of a catalyst which is the reaction product of
(a) a tertiary amine selected from the group
consisting of 1,3,5 tris(N,N-dialkylaminoalkyl)-
s-hexahydrotriazines, pyridine and bis (N,N-
dialkylaminoalkyl) ethers,
(b) an alkylene oxide containing from 2 to 18 carbon
atoms, and
(c) a carboxylic acid
employing a mole ratio of (a) to (b) to (c) of from 1:0..5:1
to 1:6:6.
The present invention additionally provides a process
for the preparation of a cellular foam characterized by poly-
urethane linkages which comprises reacting an organic polyiso-
cyanate and a polyol, on an essentially 1:1 e~uivalent basis,
in the presence of a catalytically sufficient amount of a
catalyst which is the reaction product of
(a) a tertiary amine selected from the group
consisting of 1,3,5-tris(N,N-dialkylaminoalkyl)-
- 3a -
~,~
~.3~09
s-hexahydrotriazines, pyridine and bis(N,N-
dialkylaminoalkyl) ethers,
~b) an alkylene oxide containing.from 2 to 18 carbon
atoms, and
(c) a carboxylic acld
employing a mole ratio of (a) to (b) to (c) of from 1:0.5:1
to 1:6:6.
Description of the Preferred Embodiments
In accordance with the present invention rigid and
flexible cellular foams are prepared by.the catalytic reaction
of an organic polyisocyanate in the presence of a catalytically
sufficient amount of the reaction product of a tertiary amine
selected from the group consisting of 1,3/5-tris(N,N-dialkyl-
aminoalkyl)-s-hexahydrotriazines, pyridine and bis(N,N-dialkyl-
aminoalkyl)ethers, an alkylene oxide and a carboxylic acid as
hereinafter defined. The products which are produced in
accordance herewith are rigid and cellular foam plastics con-
taining isocyanurate linkages. Furthermore, cellular foams
prepared by the catalytic condensation of an organic polylso-
cyanate with a polyol in the presence of a catalytically
sufficient of an adduct of tertiary amine, - -
/
~ 3b -
~3~
alkylene oxide and carboxylic acid produce rigid or flexible
cellular foam plastics containing both polyisocyanurate and
polyurethane linkages. The catalysts display superior
activity to prior art catalysts and furthermore are more
economically attractive since lesser amounts of catalyst
compared to prior art catalysts may be employed.
The new catalyst compositions which are useful in
the preparation of polyisocyanurate and polyurethane are
provided by reacting the amine, alkylene oxide and a carboxylic
acid in a molar ratio of amine to oxide to acid of from
1:0.5:1 to 1:6:6.
Specific examples of the tertiary amines include
1,3,5-tris(N,N-dimethylaminoethyl)-s-hexahydrotriazine,
1,3,5-tris(N,N-dimethylaminopropyl)-s-hexahydrotriazine,
1,3,5~tris(N,N-diethylaminoethyl)-s-hexahydrotriazine,
1,3,5-tris(N,N-diethylaminopropyl)-s-hexahydrotriazine,
1,3,5-tris(N,N-dimethylamino-l-methylbutyl)-s-hexahydra-
triazine, pyridine, bis(N,N-dimethylaminoethyl)ether, and
.bis(N,N-diethylaminoethyl)eth~r.
Suitable alkylene oxides are those which contain
to lg carbon atoms, and include ethylene oxide, propylene
oxide, 1,2-butylene oxide, 1,2-pentane oxide, styrene oxide,
phenylglycidylether, butadiene oxide, glycidyl ethers of
substituted phenols, diglycidyl ethers of bisphenols, glycidyl
ether of resorcinol, glycidyl ethers of novolaks, and glycidyl
ethers of aliphatic alcohols. Preferred are propylene oxide
and diglycidyl ether of bisphenol A.
Among the acids which may be employed are those
alkyl acids containing from 1 to 18 carbon atoms and aryl
acids having 7 to 14 carbon atoms, aralkyl and alkylaryl
acids having 8 to 16 carbon atoms and heterocyclic carboxylic
acids containing 6 to 10 carbon atoms. Representative acids
include aliphatic acids such as formic acid, acetic acid,
butanoic acid, pentanoic acid, nonanoic acid; N,N-dimethyl-
aminoacetic acid, acetoacetic acid, pyruvic acid, cyclo-
propanecarboxylic acid, cyclobutanecarboxylic acid, cyclo-
pentanecarboxylic acid, cyclohexanecarboxylic acid; unsaturated
acids such as acrylic acid, methacrylic acid, furylacrylic
acid; acids having electron withdrawing groups such as mono,
di and trichloroacetic acids, cyanoacetic acid; aryl acids
such as benzoic acid, naphthoic acid, diphenylcarboxylic
acid; alkaryl acids such as ortho and paratoluic acids;
N,N-dimethylaminobenzoic acid, methylnaphthoic acid; aralkyl
acids such as phenylacetic acid, cinnamic acid, phenyl
propionic acid and heterocyclic acids such as furancarboxylic
acid, thiophenecarboxylic acid, pyridinecarboxylic acid,
pyrazinecarboxylic acid.
The general procedure employed for the preparation
of the catalysts is as follows: The desired amount of
tertiary amine and solvent, if used, is added to a reaction
vessel. Alkylene oxide is ~hen added dropwise. If any
~xotherm occurs, the reaction mixture is allowed to reach a
maximum temperature. The carboxylic acid is then added
dropwise. After the addition has been completed, the reaction
temperature is increased to 75C and maintained at that
temperature for a period of from 5 minutes to 5 hours preferabl-
from 30 minutes to 2 hours. The resulting products are then
employed as catalysts. The temperature may range from lO~C
to 200C, preferably from 20C to 150C.
The oryanic polyisocyanate used in the preparation
of foams in accordance with the present invention include
aromatic, aliphatic and cycloaliphatic polyisocyanates and
combinations thereof. Representative of these types are the
diisocyanates such as m-phenylene diisocyanate, toluene-2,4-
diisocyanate, toluene-2,6-diisocyanate, mixtures of 2,~- and
2,6-toluene diisocyanate, hexamethylene~l,6-diisocyanate,
tetramethylene-1,4-diisocyanate, cyclohexane-1,4-diisocyanate,
hexahydrotoluene 2,4- and 2,6-diisocyanate, naphthalene-1,5-
diisocyanate, diphenylmethane-4,4'-diisocyanate, 4,4'-di-
phenylenediisocyanate, 3,3'-dimethoxy-4,4'-biphenyldiisocyanate
3,3'-dimethyl-d,4'-biphenyldiisocyanate, and 3,3'-dimethyl-
diphenylmethane-4,4'-diisocyanate; the triisocyanates such
as 4,4',4"-triphenylmethanetriisocyanate, polymethylene-
polyphenyl isocyanate, toluene-2,4,6-triisocyanate; and the
tetraisocyanates such as 4,4'-dimethyldiphenylmethane-
2,2',5,5'-tetraisocyanate. Especially useful are the toluene
diisocyanates, diphenylmethane-4,4'-diisocyanate, and poly-
methylenepolyphenyl isocyanate. These isocyanates are
prepared by conventional methods known in the art such as
the phosgenation of the corresponding organic amine.
Crude polyisocyanate may also be used in the
compositions of the present invention such as crude toluene
diisocyanate, obtained by the phosgenation of a mixture of
~3~9
toluene diamines or crude diphenylmethane diisocyanate
obtained by the phosgenation of crude diphenylmethanediamine.
The polyols which are employed in the preparation
of the foamed compositions include for example the oxyalkylene
adducts of polyol bases wherein the oxyalkylene portion is
derived from a monomeric unit which has ethylene oxide,
propylene oxide, butylene oxide and mixtures thereof. The
polyol initiators include ethylene glycol, 1,2-propylene
glycol, 1,3-propylene glycol, 1,2-butanediol, 1,4-butanediol,
hexanetriol, glycerol, trimethylolpropane, triethylolpropane,
pentaerythritol, sorbitol, sucrose, toluene diamine and
bisphenol A, polyethers such as polyethylene ether glycols,
polypropylene ether glycols, polytetramethylene ether glycols,
and alkylene oxide adducts of polyhydric alcohols including
those listed above; hydroxy terminated tertiary amines of
the formula:
HE EH
/N - R - N
HE EH
wherein. R is an alkylene radical containing at least 2 to 6
carbon atoms and E is a polyoxyalkylene chain; amine based
poly~thers of the formula:
HE~
N - Y
HE
wherein E is a polyoxyalkylene chain and Y is selected from
the group consisting of alkyl, hydroxyalkyl and EH; alkylene
oxide adducts of acids of phosphorus such as the adducts
prepared by the reAction o~ phosphoric acid and ethylene
oxide, phosphoric acid and propylene oxide, phosphorus acid
and propylene oxide, phosphonic acid and ethylene oxide,
phosphinic acid and butylene oxide, polyphosphoric acid and
propylene oxide and phosphonic acid and styrene oxide.
Typical polyether polyols include polyoxyethylene
glycol, polyoxypropylene glycol, polyoxybutylene glycol,
polytetramethylene glycol, block copolymers, for example,
combinations of polyoxypropylene and polyoxyethylene glycols,
poly-1,2-oxybutylene and polyoxyethylene glycols, and poly-
1,4-oxybutylene and polyoxyethylene glycols, and random
copolymer glycols prepared from blends or sequential addition
of two or more alkylene oxides. Also adducts of the above
with trimethylolpropane, glycerine and hexanetriol as well
as the polyoxypropylene adducts of higher polyols such as
pentaerythritol and sorbitol may be employed. Thus the
polyether polyols which can be employed in this process are
oxyalkylene polymers which have an oxygen/carbon ratio from
about 1:2 to 1:4 and preferably an oxygen carbon atom ratio
from about 1:2.8 to 1:4 and from about 2 to 6 terminal
hydroxyl groups preferably about 2 to 4 terminal hydroxyl
groups. The polyether polyols generally have an average
equivalent weight from about 150 to lO,000 and preferably
have an average equivalent weight from about 200 to about
6000, polyoxypropylene glycols having molecular weights from
abut 400 to about 4000 corresponding to equivalent weights
from about 200 to 1000 and mixtures thereof are particularly
useful as polyol reactants. Polyol blends such as a mixture
of high molecular weight polyether polyols with lower molecular
weight polyether polyols or monomeric polyols can also be
employed.
Any suitable hydroxy terminated polyester may also
be used. These can be obtained from the reaction of poly-
carboxylic acids and polyhydric alcohols. Such suitable
polycarboxylic acid may be oxalic acid, malonic acid, succinic
acid, glutaric acid, adipic acid, pimelic acid, suberic
acid, azelaic acid, sebacic acid, basillic acid, thapsic
acid, maleic acid, fumeric acid, glutaconic acid, isophthalic
acid and terphthalic acid. Suitable polyhydric alcohols
include the following: ethylene glycol, 1,2-propylene
glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,3-butylene
glycol, 1,4-butylene glycol, 1,3-pentanediol, 1,4-pentanediol,
1,5-pentanediol, 1,6-hexanediol, 1,7-hexanediol, glycerol,
trimethylolpropane, trimethylolethane, hexane 1,2,6-triol,
a-methylglucoside, pentaerythritol, sorbitol, sucrose, and
compounds derived from phenols such as 2,2-bis(4-hydroxyphenol~-
propane.
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
40C to 150C.
The reactive polyol medium generally has a molecular
weight of at least about 500 and a hydroxyl number ranging
_g_
3~9
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 percent polymer concentration.
A more comprehensive discussion of the graft
polyols and their method of preparation can be found in U.S.
Patents Nos. 3,383,351; 3,30~,273, and 3,652,629.
Blowing agents which are employed in the present
invention are well known to those skilled in the art.
Representative blowing agents include water, fluorocarbons
such as tetrafluoromethane, bromotrifluoromethane, chloro-
trifluoromethane, dibromodifluoromethane, trichlorethylene,
chloroform, carbon tetrachloride and low boiling hydrocarbons
such as butane, pentane and hexane. Included are the blowing
agents disclosed in U.S. Patent No. 3,922,238.
The polyisocyanurate foams of the present invention
are prepared by mixing together the organic polyisocyanate,
the catalyst and the blowing agent at initiating temperatures
ranging from 0C to 150C. In the event that polyurethane
foams or mixed polyisocyanurate-polyurethane foams are
desired, these are prepared by mixing together the organic
polyisocyanate with the desired polyol, catalyst and a
blowing agent, also at temperatures ranging from 0C to
150C.
The poly(isocyanurate-urethane).foams are prepared
by reacting 0.01 to 0.5 equivalents of polyol with one
equivalent of polyisocyanate said polyol having an average
--10--
.~
.~w,.,
~3~
functionality of 2 to 3 and an average hydroxyl number
equivalent weight of l00 to 3000.
The polyurethane foams are prepared by reacting
the polyol and polyisocyanate on an essentially l:l equivalent
basis.
Other additives may also be included in the foam
formulations. Included are surfactants such as the silicone
surfactants, e.g., alkylpolysiloxanes and polyalkyl siloxanes,
flame retardants such as tris(2-chloroethyl)phosphate.
Additional optional catalysts may also be employed.
Included are such catalysts as dibutyltin dilaurate, di-
butyltin diacetate, stannous octoate, lead octoate, and
cobalt naphthenate.
The densities of the foams which may be produced
incorporating the novel catalysts of the instant invention
range from l to 60 lbs. per cubic foot.
The test methods empl~yed to determine the proper-
ties of the foams are tabulated below:
Density ~ ASTM D 1622-23 (1970)
K-factor ASTM C 513-177-~5
Compression strength ASTM D 1621-73
Tumbling friability ASTM C 421
Flame retardancy ASTM D 3014
Smoke density N~S Chambex
The foams were characterized by infra-red spectroscopy.
Thus the foams exhibited isocyanurate, urethane and combined
urethane-isocyanurate linkages.
The examples below illustrate the preparation of
the catalysts of the present invention and their use in the
preparation of polyisocyanurate and polyurethane foams.
In the Tables below, the following abbreviations
are employed:
BDAE = bis(N,N-dimethylaminoethyl)ether
DC-1~3l = polyoxyethylene-polyalkylsiloxane copolymer
surfactant
DGEBPA = diglycidyl ether of bisphenol A
DMAE = N,N-dimethylaminoethanol
DMCHA = N,N-dimethylcyclohexylamine
DPG = dipropylene glycol
EHA = 2-ethylhexanoic acid
FREON~_l-B2 = monofluorotrichloromethane
FYROL CEF3 = tris(2-chlroethyl)phosphate
L-53034 = silicone surfactant
L 5340 5 = silicone surfactànt
NEM = N-ethylmorpholine
PO = propylene oxide
Polyol A = polyoxyethylated trimethylolpropane having a
hydroxyl number equivalent weight of 250
Polyol B = polyoxypropylated trimethylolpropane having a
hydroxyl number equivalent weight of 250
Polyol C = reaction product of tetrabromophthalic
anhydride and an oxypropylated pentaerythritol
having a hydroxyl number equivalent weight of
100 to which sufficient propylene oxide is
added to give a hydroxyl number equivalent
weight of 2~6
m~ R ~ -12-
~3~L~V~
Polyol D = polyoxyethylated, polyoxypropylated tri-
methylolpropane having a molecular weight of
6000 and containing about 10 weight percent
ethylene oxide
Polyol E = polyoxypropylated toluene diamine having a
molecular weight of about 400
Polyol F = polyoxypropylated pentaerythritol having a
molecular weight o about 425
RUBINATE M5 = polymethylene polyphenyl polyisocyanate,
equivalent weight ca. 137
TAC = tertiary amine, alkylene oxide and carboxylic
acid reaction product
TDH = 1,3,5-tris(N,N-dimethylaminopropyl)-s-hexa-
hydrotriazine
TDI = 2,1- and 2,6-toluene diisocyanate blend 80/20
ratio
TEA = triethylamine
TEDA = triethylenediamine
1 manufactured by Dow Corning
manufactured by du Pont
3 manufactured by Stauffer Chemical
manufactured by Union Carbide Corporation
manufactured by Union Carbide Corporation
6 manufactured by Rubicon Inc.
Example 1
This example illustrates the process employed for
the preparation of the reaction products of tertiary amine-
alkylene oxide-carboxylic acid in accordance with the present
DP ~kA~ -13-
~3~ 9
invention. Into a 250 ml reaction flask equipped with a
thermometer, dry-ice condenser, mechanical stirrer, addition
funnel and a heating mantle, 34.2 grams of TDH was placed.
Stirring was commenced and 34.8 grams of propylene oxide was
added drop-wise at a temperature of 25C over a period of 25
minutes. Upon completing the addition of the propylene
oxide, 86.4 grams of EHA dissolved in 77.7 grams of DPG was
added drop-wise over a period of 1 hour and 15 minutes with
the tempexature rising to 43C. The reaction mixture was
then heated to 74C and maintained at that temperature for 2
hours. Examination by infra~red spectroscopy disclosed the
appearance of the carboxyl absorption and absence of
absorptions attributable to propylene oxide. The reaction
products 2-23 were prepared in a similar manner employing
the reactants and concentrations as designated in Table I
below.
-14-
~3~
k o o ~ o o o o o o o o o
t~ ~D CO ~ ~V ~ ~r ~ c~ co ~ r
o~ C~
o ~ U ~ o U
rl ~1 0 ~J r~ rl rl
X rl ~ ~
O ~ :r~ m m ~
P~ Q 4~
U~
r~ ~
O oooooooooooo
h
. C4 ~D N
~ ~ ~r r-i ~ ~ ~ ~1 ~ ~J ~ ~r ~ t~
O ~ ~ ~ r~ ~ ~ ~ ,1 ~ ~) ~1 ,~
.g Q) râ
H 11) ~ Il)
a) K ~ .~1 O O O O O O O O O O O O
Q O ~ X G P~
~ -~ O
~ O
O ~/ r~ C`;J ~ N ~ C~ 1 C~
~ ~1 OOOOOOOOOOOO
rl
~ .
CO CO 0~ CO CO OD CO CO CO CO
D ~ W ~ ~D ~ W ~'~
q~
S~ ~ .'
~ ~ m m m m m m m m m m m
a) ~
E~
r~ ~ ~ ~ ~ N ~D O ~ eZ~
~ r- o o o ~ 1~ In co
O
~1 ~ ~ ~ u~ ~ o
~ O
K P~
~l3~
~1
~ ~ ; Cl~ C~ C~ ~
t,
~-0 U U U
R ~'C ~1:~ ~1 ~ W ~1 4 1 ~ IH
U~
O O O' O O O O O O O O
h
~ ~ N N ~ ~ ~ ~r t`~ ~ O O
~: ~ ~ r~
S:
a
~ ~ G) ~ ~
o P; ~1 ~ o o o o o o o o o P: m
H ~j ~-oX
a~ ~
R .-1 ¦ . ~ ~ ~ ~ ~) ~ ~ ~ In
E~ O ~ I o o o o o o o o o o
.~
t~ I ~~D c4 ~ o o o ~ r O
ou~ O ~ D CO ~ CO ~r
Q) a.
rl- ~
S~ E~ m z m ~ m
I ~D ~ CC\
P~ O CO ~ ~D ~r ~ o ~D CO
a ~ w ~4
O
U) I~ CO cr~ O
~I r~
--16--
Example 2
This series of polyisocyanurate foams was prepared
by the addition of the designated catalyst to a reaction
vessel which contained 100 parts by weight (pbw) RUBINATE M,
25 pbw FREON ll-B and 1 pbw DC-193. The above mixture was
stirred at a high speed until foam generation began. The
reactivities were determined by measuring the cream time,
gel time,-tack free time and final rise time for all formu-
lations. The procedures employed for these determinations
are well known to those skilled in the art. In the following
formulations of the catalysts, all concentrations are parts
by weight (pbw).
Catalyst 1 - TDH (5).
Catalyst 2 - TDH (5), DPG (2).
Catalyst 3 - TDH (5), 3PG (2) and Po (2).
Catalyst 4 - TDH (3.3), PO (0.6), H20 (0.2) in DPG (1.9).
Catalyst 5 - TEDA (1.2), PO (0.32), phenol (0.50) in DPG
(2.8).
Catalyst 6 - TEDA (1.2), PO `.(1.6~), EHA (1.53) in DPG
(1.6~).
Catalyst 7 - TDH (1.57), PO (0.27), EHA (0.66), DPG (2.5).
Catalyst B - DMAE (1.02), PO (0.66), EHA (1.65) in DPG
(1.67).
6~
Table II
Catalyst Cream Time Gel Time Tack Free Final Rise
Type Sec. Sec. Time/Sec. Time/Sec.
.
1 170 300 300 360
2 40 120 120 180
3 40 120 135 180
4 15 ~5 100 110
not curing even after 6 minutes
6 510 20 25
7 3< 10 < 10 < 10
8 425 50 35
These results indicate that the catalyst of the
present invention, number 7 has a superior reactivity to
those of the prior art in the formation of polyisocyanurates.
Example 3
The TAC products of Example 1 were evaluated as
polyisocyanurate foam catalysts. Into a suitable vessel was
added 100 parts by weight (pbw) RUBINATE M, 25 pbw FREON ll-B,
1 pbw DC-193 and 5 pbw of the lndicated reaction products.
The mixture was vigorously stirred and the foams were allowed
to develop. The reactivities of the various products were
determined by measuring the cream time, gel time, tack free
time and rise time. The results tabulated in Table III
indicate the suitability of these products as catalysts for
the formation of polyisocyanurate foams.
-18-
-
~3~
Table III
TAC Reaction Reactivity in Seconds
Product No. Cream Gel Rise Tack Free
1 12 25 35 70
2 3 <10 <10 <10
3 3 ~10 <10 ~10
4 3 10 10 10
7 15 20 60
7 10 12 25 35
~ 15 45 110 110
9 20 30 50 100
~0 75 120 240
11 3 -- 20 ~0
12 5 10 20 25
13 7 12 20 20
14 14 25 35 50
-- 10 15
16 3 -- 10 10
17 4 -- 12 12
la 20 50 70 70
19 14 20 35 35
14 25 35 60
21 90 120 150 240
22 10 15 25 30
23 ~145165 190 i85
--19--
Example 4
The TAC reaction products of Example 1 were
evaluated as poly(urethane-isocyanurate) foam catalysts.
Into a suitable vessel was added 100 pbw RUBINATE M, 25 pbw
FREON ll-B. Then a mixture of 1 pbw DC-193, 20 pbw Polyol A
and the amount of products as indicated was added. The
mixture was stirred and in a few seconds the foam developed.
The reactivities of the various products were determined by
measuring the cream time, gel time, tack free time and rise
time. The results of Table I~ indicate that these products
are suitable catalysts for the preparation of poly(urethane-
isocyanurate) foams.
-20-
~3~L6~9
Table IV
TAC Reaction Amount Reactivity in Seconds
Product No. g. Cream Gel Rise Tack Free
1 2 10 30 ~5 90
2 2 6 14 30 50
3 2 5 10 15 35
4 2 4 10 20 30
2 S 14 30 90
6 2 6 15 30 95
7 2 8 20 35 120
8 2 5 60 120 160
9 2 8 12 30 40
2 8 12 30 30
11 2 7 14 45 55
12 2 6 25 ~0 120
13 2 10 30 50 150
14 2 8 15 30 45
2 11 36 60 140
16 2 10 25 40 110
17 2 6 15 35 60
18 5 12 30 50 150
1~ 2 10 20 35 35
2 11 16 30 30
21 2 12 20 40 40
22 2 10 25 50 160
23 3 10 25 45 150
-
Example_5
The TAC products of Example 1 were evaluated
employing Polyol B instead of Polyol A and the designated
concentrations of TAC reaction product. The results as
obtained and tablulated in Table V below indicate the
suitability of the products as poly(urethane-isocyanurate)
foam catalysts.
~L3~6~
Table V
TAC Reaction Amount Reactivity in Seconds
Product No. g. Cream Gel Rise Tack Free
1 3 20 45 65 90
2 2 15 30 60 75
3 2 12 25 40 65
4 2 1~ 30 55 gO
2 14 30 70 120
6 ` 2 20 30 40 60
7 2 40 65 105 150
8 2 40 130 240 180
9 2 25 45 70 120
2 45 90 130 190
11 2 20 35 75 gO
12 3 10 14 30 30
13 3 20 50 80 130
1~ ~ 18 35 50 70
2 12 45 70 120
16 3 9 20 35 35
17 2 12 40 65 95
13 5 25 70 90 360
19 2 20 45 70 70
2 lg 30 40 40
21 3 ~0 65 90 110
22 4 14 30 40 55
23 5 23 45 70 70
-23-
~3~
Example 6
The activity of the TAC reaction products as
"cold-cure" flexible polyurethane foam catalysts is
determined in the following manner.
FORMULATION
Polyol D 150.00 g.
Distilled water ~.05 ml.
L5303 surfactant 3.00 mlO
TAC Reaction Product See Table VI
Dibutyltin dilaurate 0.05 ml.
TI~I/RUBINATE M ( 80/20; w/w/) 51.00 g.
Polyol D, distilled water, L5303 and the TAC
reaction product were mixed for 30 seconds using a ~IGHTIN
Model V-7 stirrer e~uipped with a 1-1/2" shrouded mixing
blade. Dibutyltin dilaurate was then added and mixed for
another 15 seconds. Thereafter, the TDI/RUBINATE M mixture
was added, mixed for 5 seconds, poured into a one-gallon
"cake-box" and the foam was allowed to rise therein. There-
after, the foam was cured in an oven for 8 minutes at 120C.
The cream, gel and rise time was determined and is shown in
the table.
--24--
~3~
Table VI
TAC Reaction Reactivity in Seconds
Product_No. Amount, ~. Cream Gel Rise
2 1.0515 130 170
2 2.1010 85 120
1.0511 70 125
2.10 7 40 80
6 1.0517 155 210
6 2.1012 105 160
7 1.0518 145 200
7 2.1014 110 165
8 1.0511 60 115
-8 2.10 9 55 95
12 ~.0518 1~0 180
12 ~.1014 '07 155
13 1.0522 240 360
13 2.1017 160 200
14 1.05 9 170 240
14 2.1010 110 175
Example 7
A series of poly(urethane-isocyanurate~ foams was
prepared employing representative reaction products of the
instant invention. The indicated quantities of RUBINATE M
and FREON ll-B were mixed in a suitable container. The
indicated amounts of polyol blend, TAC reaction product and
DC-193 were mixed together in a separate container. While
stirring the isocyanate blend, the polyol mixture was rapidly
added to it. When the foaming process began, the entire
~3~
mixture was poured into 10" x 10" x 2" molds. After allowing
the foam to stay in the mold for 15 minutes, the foam was
removed and stored for two days before some of the foam
properties were determined.
Table VII
Foam No. 1 2 3 4
Isocyanate Component
RUBINATE M, g. 200 200 200 200
FREON ll-B, g. 50 50 50 50
Resin Component
Polyol A, g. 30 30 30 30
Polyol C, g. 10 10 10 10
TAC Reaction Product 1 14 17 19
TAC amount, g. 5 5 5 5
DC-1~3, g. 2 2 2 2
Foam Properties
Density, pcf. 2.1 2.0 1.7 1.6
Compressive strength,
psi. 10% deflection 19 22 22 22
K factor, initial0.1090.1080.121 0.120
aged 10 days at 140F0. 13a0.144 0.165 0.167
Friability, % wt. loss 6 6 16 14
Butler Chimney Test
wt. retained, ~ 88 88 90 86
flame ht., inches 7 7 7 7
time to SX, sec.10 10 10 10
NBS smoke density, Dm 69 63 52 57
-26-
