Novel polyol composition and the use thereof in the preparation of rigid polyurethane foams

The present invention is directed to a novel polyol composition and the use thereof in the preparation of a rigid polyurethane foam. More particularly the polyol composition is a blend of specific amounts of two polyols, one based on ortho-toluene diamine and the other based on a non-ortho-toluene diamine.

BACKGROUND OF THE INVENTION 
Reaction products of ortho-toluene diamine and alkylene oxides have been 
described in the art (note British Patent No. 1,311,095). Also described 
in the art is the propoxylated product of a mixture of 51% by weight of 
ortho-toluene diamine and 49% by weight of meta-toluene diamine (see 
Example 3 of the above identified British patent). 
Toluene diamine initiated polyols derived from ethylene and propylene oxide 
are also known and described in the art (see U.S. Pat. Nos. 4,209,609 and 
4,243,759). Alkylene oxide adducts of ortho-toluene diamine are also 
known. U.S. Pat. No. 4,562,290 describes adducts prepared by first 
reacting one to three moles of ethylene oxide with ortho-toluene diamine, 
and then reacting the resultant product with from four to eight moles of 
propylene oxide. The resultant products are described as being useful in 
the production of rigid polyurethane foams. The `290 patent suggests that 
the adducts described therein can be blended with a variety of different 
polyols. Among the polyols suggested as being useful are alkylene oxide 
adducts of a variety of different aromatic amines including 
2,4-diaminotoluene. 
Finally, a variety of different adducts of ortho-toluene diamines and 
alkylene oxides are described in U.S. Pat. Nos. 4,397,966, 4,410,641, 
4,421,871, 4,469,822, and 4,767,795. 
While all these various adducts based on ortho-toluene diamine have been 
known for some time, they have not met with any substantial commercial 
success primarily because when substituted for more conventional polyols, 
the resultant foams will vary in k-factor, and various physical properties 
with variations in product density.

DESCRIPTION OF THE INVENTION 
The present invention is directed to a novel polyol composition and its use 
in the production of rigid polyurethane foams to be used in the appliance 
industry. The novel polyol composition of the present invention provides 
foams at varying densities having comparable thermal properties (i.e. 
k-factor) while maintaining physical properties and having good processing 
and excellent demold properties. Molded core densities in foams used in 
the appliance industry typically range from 1.45 pounds per cubic foot to 
2.00 pounds per cubic foot. More particularly, the present invention is 
directed to a polyol composition comprising: 
(a) an adduct obtained by sequentially reacting 2,4- and/or 2,6-toluene 
diamine with from 3 to 5 moles of ethylene oxide and then with from 1 to 
5.1 moles of propylene oxide, the total number of moles of ethylene oxide 
plus propylene oxide being at least 5 and no more than 8.1, and 
(b) an adduct obtained by sequentially reacting 2,3- and/or 3,4-toluene 
diamine with from 1 to 5 moles of ethylene oxide and then with from 1 to 6 
moles of propylene oxide, the total number of moles of ethylene oxide plus 
propylene oxide being at least 5 and no more than 9, the weight ratio of 
component (a) to component (b) being from 35:65 to 70:30, and preferably 
from 50:50 to 70:30, and most preferably 50:50. 
The adducts used herein are known in the art. Thus, adducts based on 2,4- 
and/or 2,6-toluene diamine and their method of manufacture are described 
in U.S. Pat. Nos. 4,209,609 and 4,243,759, the disclosures of which are 
herein incorporated by reference. The adducts based on 2,3- and/or 
3,4-toluene diamine and their methods of manufacture are described in U.S. 
Pat. Nos. 4,562,290, and 4,767,795, the disclosures of which are herein 
incorporated by reference. 
The novel polyol compositions herein are used to prepare polyurethane 
foams. 
The various methods for the preparation of polyurethane foams are well 
known in the art and do not require detailed discussion; see, for example, 
Dombrow, "Polyurethanes," Reinhold Publishing Corporation, New York, pages 
1-105 (1957); Saunders et al, "Polyurethanes", Part I, Interscience 
Publishers, New York (1962). One common procedure consists in reacting a 
polyol, for example, a polyester or polyether, with an organic 
polyisocyanate and with a blowing agent, if necessary in the presence of 
catalysts, surface active agents or other auxiliary agents, whereby 
simultaneous interaction between the isocyanate, blowing agent and the 
polyol occurs to give the required foam product. This is the so-called 
"one-shot" procedure. Alternatively, the polyol may be reacted with 
sufficient polyisocyanate to give an intermediate reaction product 
containing free isocyanate groups and this product, known as prepolymer, 
may then be reacted with water, if desired in the presence of catalyst, 
surface active agents or other auxiliary agents, in order to produce the 
final foamed product. This latter is the so-called "prepolymer" process. 
Many variations in the method of carrying out these basic processes are 
known. 
Any of the prior art polyisocyanates conventionally used in the preparation 
of rigid polyurethane foams can be employed in the process of the present 
invention. Illustrative of such isocyanates are 2,4-tolylene diisocyanate, 
2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, dianisidine 
diisocyanate, tolidine diisocyanate, hexamethylene diisocyanate, 
m-xylylene diisocyanate, 1,5-naphthalene diisocyanate, and other di- and 
higher polyisocyanates such as those listed in the tables of Siefken, Ann. 
562, 122-135 (1949). Mixtures of two or more of the above isocyanates can 
be used if desired. Preferred polyisocyanates are products obtained by 
phosgenation of mixtures of methylene-bridged polyphenyl polyamines 
obtained by the interaction of formaldehyde, hydrochloric acid, and 
primary aromatic amine, for example, aniline, o-chloroaniline, 
o-toluidine, or mixtures thereof. Such polyisocyanates are known in the 
art, e.g., U.S. Pat. Nos. 2,683,730, 2,950,263 and 3,012,008; Canadian 
Patent No. 665,495; and German Patent No. 1,131,877. A particularly 
preferred polyisocyanate of this type is the polymethylene 
poly(phenylisocyanate) available commercially as Mondur MR, from Mobay 
Corporation. 
In preparing polyurethane foams according to the invention, it is 
desirable, in accordance with conventional procedures, to employ a 
catalyst in the reaction of the polyisocyanate and polyol. Any of the 
catalysts conventionally employed in the art to catalyze the reaction of 
an isocyanate with reactive hydrogen containing compounds can be employed 
for this purpose; see, for example, Saunders et al., Ibid, Volume I, pages 
228-232; see, also Britain et al., "J. Applied Polymer Science," 
4,207-4,211, 1960. Such catalysts include organic and inorganic acid salts 
of and organometalic derivatives of, bismuth, lead, tin, iron, antimony, 
uranium, cadmium, cobalt, thorium, aluminum, mercury, zinc, nickel, 
cerium, molybdenum, vanadium, copper, manganese, and zirconium, as well as 
phosphines and tertiary organic amines. The preferred catalysts for use in 
the process and compositions of the invention are the tertiary organic 
amines of which the following are representative: triethylamine, 
triethylenediamine, N,N,N',N'-tetramethylethylenediamine, 
N,N,N',N'-tetraethylethylene diamine, N-methylmorpholine, 
N-ethylmorpholine, N,N,N',N'-tetramethylguanidine, 
N,N,N',N'-tetramethyl-1,3-butanediamine, N,N-dimethylethanolamine, 
N,N-diethylethanolamine, and the like, or mixtures of two or more such 
amines. The amount of catalyst employed is generally within the range of 
about 0.1 to about 2.0% by weight based on total weight of reactants in 
the polyurethane forming reaction mixture. 
The ratio of isocyanate groups to active hydrogen containing groups in the 
foam mixtures of the invention is within the normal limits employed in the 
production of polyurethane foams. This ratio is advantageously within the 
range of from 1.50 to 0.65:1 and preferably within the range of 1.20:1 to 
1:1, whether the isocyanate and polyol are employed separately in the 
one-shot process or whether the two components have been reacted to form a 
prepolymer. 
The final foam density of the products produced by the process of the 
invention can be controlled in accordance with methods well known in the 
art. For example, this control can be accomplished by regulating the 
amount of water present in the foam mixture or by using a combination of 
water and a conventional blowing agent having a boiling point below about 
110.degree. C. and preferably below about 50.degree. C., such as a 
volatile aliphatic hydrocarbon or a volatile highly halogenated 
hydrocarbon, for example, trichloromonofluoromethane, 
chlorotrifluoromethane, 1,1-dichloro-1-fluoroethane, 
1-chloro-1,1-difluoro-2,2-dichloroethane and 
1,1,1-trifluoro-2-chloro-2-fluorobutane or mixtures thereof. 
Optional additives such as dispersing agents, cell stabilizers, 
surfactants, flame retardants, and the like which are commonly employed in 
the fabrication of rigid polyurethane foams, can be employed in the 
process of the invention. Thus, a finer cell structure may be obtained if 
water-soluble organosilicone polymers are used as surfactants. 
Organosilicone polymers obtained by condensing a polyalkoxy polysilane 
with the monoether of a polyalkyleneether glycol in the presence of an 
acid catalyst are representative of those surfactants which can be used 
for this purpose. The organosilicone copolymer available under the trade 
name L5420 is typical of such polymers. Other surfactants such as ethylene 
oxide modified sorbitan monopalmitate or ethylene oxide modified 
polypropyleneether glycol may be used, if desired, to obtain better 
dispersion of the components of the foam mixture. 
Other additives such as dyes, pigments, soaps and metallic powders and 
other inert fillers may be added to the foam mixture to obtain special 
foam properties in accordance with practices well-known in the art. 
The polyurethane foams produced using the novel polyols of the instant 
invention are useful in a variety of commercial and industrial 
applications including for example, the production of foam-insulation, 
structural foam sporting goods, and the like. 
The following examples are provided to illustrate the present invention. 
Unless otherwise specified, all parts are by weight. 
EXAMPLES 
In the examples, the following materials were used: 
POLYOL A: a 460 OH number polyol prepared by sequentially reacting 1 mole 
of a 80/20 mixture of 2,4- and 2,6-toluene diamine with about 3.7 moles of 
ethylene oxide and then with about 3.3 moles of propylene oxide. 
POLYOL B: a 395 OH number polyol prepared by sequentially reacting 1 mole 
of a mixture of 2,3- and 3,4-toluene diamine with about 3.5 moles of 
ethylene oxide and then with about 4.5 moles of propylene oxide. 
POLYOL C: a 380 OH number polyol prepared by sequentially reacting 1 mole 
of the diamine mixture used in POLYOL B with about 4.3 moles of ethylene 
oxide and then with about 3.7 moles of propylene oxide. 
POLYOL D: a 420 OH number polyol prepared by sequentially reacting 1 mole 
of the diamine mixture used in POLYOL B with about 4.6 moles of ethylene 
oxide and then with about 3.6 moles of propylene oxide. 
Y-10325: a polyalkyleneoxide/methyl siloxane copolymer surfactant available 
from Union Carbide. 
PV: Desmorapid PV, a pentamethyldiethylenetriamine available from 
Rhein-Chemie. 
PC-8: Polycat 8, a dimethylcyclohexylamine available from Air Products. 
R-11: trichlorofluoromethane. 
WATER 
ISO: Mondur MR, a polymethylenepoly(phenylisocyanate) having an isocyanate 
content of about 31.5%, commercially available from Mobay Corporation. 
A handmixing technique was used to measure reactivity and foaming 
performance of high and low density rigid foams. The temperature of the 
raw materials was kept at 20.degree. C..+-.0.2.degree. C. The B-side was 
prepared by weighing the polyol, surfactant, catalysts and R-11, in that 
order, into a previously weighed mixing container. After mixing 
thoroughly, the mixing container was reweighed and the evaporated R-11 was 
replaced. To another container was added the required amount of 
isocyanate. The contents of both containers were adjusted to 20.degree. 
C..+-.0.2.degree. C. The isocyanate was then added to the B-side. The 
timer was started and the components were mixed at 1000 rpm. The mixture 
was stirred for about 3 seconds. After mixing was complete, the reaction 
mixture was poured into a large paper container and the reaction times 
were recorded. 
The products were then tested for k-factor (ASTM C-518) and densities (ASTM 
D-1622). The formulations were as indicated in Table 1, while the test 
results were as set forth in Table 2. 
TABLE 1 
__________________________________________________________________________ 
Example # 
1 2 3 4 5 6 7 8 9* 10* 
__________________________________________________________________________ 
Ingredients, 
parts by weight 
B-Side: 
POLYOL A 
35.42 
30.53 
35.42 
30.53 
35.42 
30.53 
49.59 
42.74 
21.25 
18.32 
POLYOL B 
35.42 
30.53 
-- -- -- -- 21.25 
18.32 
49.59 
42.74 
POLYOL C 
-- -- 35.42 
30.53 
-- -- -- -- -- -- 
POLYOL D 
-- -- -- -- 35.42 
30.53 
-- -- -- -- 
PV 0.5 
0.45 
0.5 
0.45 
0.5 0.45 
0.5 0.45 
0.5 
0.45 
PC-8 1.0 
1.35 
1.0 
1.35 
1.0 1.35 
1.0 1.35 
1.0 
1.35 
Y-10325 1.0 
1.0 1.0 
1.0 1.0 1.0 1.0 1.0 1.0 
1.0 
WATER 1.66 
1.14 
1.66 
1.14 
1.66 
1.14 
1.66 
1.14 
1.66 
1.14 
R-11 25 35 25 35 25 35 25 35 25 35 
A-Side 
ISO 98.77 
80.67 
98.67 
80.67 
102.34 
83.75 
101.95 
83.42 
97.25 
79.36 
Wt. Ratio 
Non-vicinal: 
Vicinal TDA 
50:50 
50:50 
50:50 
50:50 
50:50 
50:50 
70:30 
70:30 
30:70 
30:70 
Polyol 
__________________________________________________________________________ 
Example # 
11 12 13 14 15 
16 17 18 19 20 21 22 
__________________________________________________________________________ 
Ingredients, 
parts by weight 
B-Side: 
POLYOL A 
46.05 
39.69 
24.79 
21.37 
42.5 
36.64 
28.32 
24.42 
38.96 
33.58 
31.88 
27.48 
POLYOL B 
24.79 
21.37 
46.05 
39.69 
28.34 
24.42 
42.50 
36.64 
31.88 
27.58 
38.96 
33.58 
POLYOL C 
-- -- -- -- -- -- -- -- -- -- -- -- 
POLYOL D 
-- -- -- -- -- -- -- -- -- -- -- -- 
PV 0.5 0.45 
0.5 
0.45 
0.5 
0.45 
0.5 
0.45 
0.5 
0.45 
0.5 
0.45 
PC-8 1.0 1.35 
1.0 
1.35 
1.0 
1.35 
1.0 
1.35 
1.0 
1.35 
1.0 
1.35 
Y-10325 1.0 1.0 
1.0 
1.0 
1.0 
1.0 
1.0 
1.0 
1.0 
1.0 
1.0 
1.0 
WATER 1.66 
1.14 
1.66 
1.14 
1.66 
1.14 
1.66 
1.14 
1.66 
1.14 
1.66 
1.14 
R-11 25 35 25 35 25 35 25 35 25 35 25 35 
A-Side 
ISO 101.47 
83.0 
97.8 
79.85 
100.7 
82.4 
98.51 
80.4 
101.8 
83.25 
100.6 
82.2 
Wt. Ratio 
Non-vicinal: 
Vicinal TDA 
65:35 
65:35 
35:65 
35:65 
60:40 
60:40 
40:60 
40:60 
55:45 
55:45 
45:55 
45:55 
polyol 
__________________________________________________________________________ 
*9 and 10 are comparative examples 
TABLE 2 
__________________________________________________________________________ 
Example # 1 2 3 4 5 6 7 8 9 10 11 
__________________________________________________________________________ 
Test 
Reactivity Times 
Cream (sec) 8 7 8 8 7 7-8 10 7-8 6 6 7 
Gel (sec) 39 37 37 40 36 38 39 37 37 37 38 
Flow (sec) 119 140 119 
140 
118 
140 121 
140 124 
143 120 
Densities (pcf) 
Free Rise 1.35 
1.08 
1.37 
1.09 
1.36 
1.08 
1.30 
1.11 
1.28 
1.12 
1.34 
Molded Core 1.67 
1.49 
1.68 
1.55 
1.67 
1.56 
0.64 
1.64 
1.70 
1.62 
1.68 
Freeze Stable 
1.92 
1.74 
1.93 
1.77 
1.99 
1.75 
1.86 
1.86 
1.87 
1.86 
1.86 
K-Factor (molded core) 
(BTU in/ft.sup.2 HR .degree.F.) 
0.128 
0.125 
0.126 
0.126 
0.123 
0.121 
0.125 
0.122 
0.122 
0.127 
0.121 
% Difference of 
K-factor between 
densities -2.3% 0 -1.6% -2.4% +4.1% 
__________________________________________________________________________ 
Example # 12 13 14 15 16 17 18 19 20 21 22 
__________________________________________________________________________ 
Test 
Reactivity Times 
Cream (sec) 7 7-8 
6 7-8 
7 6 6 8 7 8 6 
Gel (sec) 36-37 
37 36 37 36 37 37 37 36 36 36 
Flow (sec) 139 121 
138 118 
138 120 
138 121 
140 121 
140 
Densities (pcf) 
Free Rise 1.11 
1.34 
1.13 
1.33 
1.10 
1.33 
1.10 
1.34 
1.12 
1.31 
1.10 
Molded Core 1.59 
1.65 
1.62 
1.69 
1.60 
1.68 
1.66 
1.65 
1.63 
1.66 
1.64 
Freeze Stable 
1.84 
1.85 
1.84 
1.86 
1.84 
1.86 
1.90 
1.86 
1.86 
1.86 
1.86 
K-Factor (molded core) 
(BTU in/ft.sup.2 HR .degree.F.) 
0.123 
0.123 
0.124 
0.121 
0.122 
0.124 
0.123 
0.125 
0.126 
0.125 
0.126 
% Difference 
+1.7% +1.0% +1.0% -1.0% +1.0% +1.0% 
__________________________________________________________________________