Triazine compositions and their use as catalysts

New triazine compositions having incorporated therewithin both alkanolamino groups and pendent tertiary amino groups are defined herein. The triazines are prepared by the reaction of (1) an intermediate prepared from either alkyl chlorides or alkylene oxides and dialkylaminoalkyl primary amines and (2) cyanuric chloride or a derivative thereof. The triazines hereof exhibit excellent catalytic activity in the preparation of rigid cellular foams characterized by carbodiimide linkages.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The present invention relates to triazine compositions, methods of 
preparation therefor and uses thereof. More particularly, the present 
invention pertains to triazine compositions having incorporated 
therewithin alkanolamino groups and pendent tertiary amino groups, methods 
of preparation therefor and uses thereof. Even more particularly, the 
present invention pertains to the preparation of triazines containing both 
alkanolamino and tertiary amino groups from intermediate secondary amines 
and the use of such triazines as catalysts for the preparation of cellular 
products. 
2. Prior Art 
There has been disclosed heretofore the use of triazine compounds as 
catalysts for the preparation of rigid cellular products characterized by 
carbdiimide linkages. The prior art has taught, inter alia, the use of 
both symmetrical and unsymmetrical triazines in the preparation of such 
cellular products. See, inter alia, U.S. Pat. Nos. 3,645,923 and 
3,806,475. 
Although these prior catalysts are extremely efficacious in their intended 
use, it has, generally, been found that it was essential to incorporate 
isocyanate trimerization catalysts therewith, to generate an exothermic 
reaction at room temperature. The exothermic reaction, in turn, activated 
the triazine catalyst. Thus, in essence, the reactivity of the of the 
prior art catalysts could be improved upon, i.e., exhibit a greater 
catalytic activity in the preparation of such cellular products. 
To this end, it would be most beneficial to provide catalysts which possess 
the features of both carbodimide catalysts, i.e., alkanolamino triazines, 
and isocyanurate catalysts, i.e., hexahydrotriazine. It is to this with 
which the present invention is concerned. 
SUMMARY OF THE INVENTION 
In accordance with the present invention there is provided new triazine 
compositions which incorporate therewithin strongly basic pendent tertiary 
amino groups and alkanolamino groups. The triazines hereof are prepared 
from the reaction of (1) cyanuric chloride or a derivative thereof and (2) 
the reaction product of (a) a dialkylaminoalkyl primary amine with (b) 
either an alkylene oxide or an alkyl halide. 
The triazines hereof are useful as catalysts for the preparation of rigid 
cellular products characterized by carbodiimide linkages. These products 
are generally prepared by the catalytic condensation of an organic 
polyisocyanate in the presence of a catalytically sufficient amount of the 
present triazines. 
The triazines hereof, which are more reactive than heretofore known 
triazines, are enhanced by the conjoint use of an alkanol therewith. 
For a more complete understanding of the present invention reference is 
made to the following detailed description and accompanying drawings. 
DESCRIPTION OF THE PREFERRED EMBODIMENTS 
The present invention, as hereinbefore noted, provides triazine compounds 
or compositions useful as catalysts for the preparation of rigid cellular 
products characterized by carbodiimide linkages. As will subsequently be 
explained in greater detail, the cellular products produced with the 
triazines hereof contain both carbodiimide and isocyanurate groups 
therewithin. However, for purposes of brevity these products shall be 
referred to as carbodiimide products. 
The triazine compositions of the present invention may be represented by 
the following formula: 
##STR1## 
wherein R is either lower alkyl having from about one to six carbon atoms, 
2-hydroxy lower alkyl having from about one to six carbon atoms, or 
(R').sub.2 N--R" wherein R' is lower alkyl having from about one to six 
carbon atoms and R" is alkylene having from about one to ten carbon atoms 
and wherein at least one R must be 2-hydroxy lower alkyl and at least one 
R must be (R').sub.2 N--R", as defined above. 
The triazines hereof are prepared by the reaction of cyanuric chloride or a 
derivative thereof with an intermediate derived from either an alkyl 
halide or alkylene oxide and a dialkylaminoalkyl primary amine. Generally, 
the reaction proceeds at a temperature of from about 0.degree. to about 
110.degree. C for a period of from about one to six hours. The reaction is 
carried out in the presence of a base to neutralize liberated hydrochloric 
acid. 
The cyanuric chloride is employed as a slurry or suspension thereof to 
which the intermediate is slowly added, at a temperature of from about 
-5.degree. to about 35.degree. C depending on the solvent. The base is 
then slowly added thereto. After the base addition is complete the 
reaction is allowed to proceed at the reaction temperatures hereinbefore 
noted. 
Useful basses include, for example, sodium hydroxide, potassium hydroxide, 
lithium hydroxide, sodium carbonate, sodium bicarbonate, and the like. 
Also, tertiary alkylamines, such as tributylamine, as triethylamine, can 
be used herein as a base. 
In carrying out the reaction the cyanuric chloride and intermediate are 
employed in a, respective, molar ratio of from about 1:1 to 1:3, depending 
upon the number of chlorines to be replaced, and, usually, 1:3. 
The base is present in an amount equimolar to the intermediate. 
The triazines hereof range from liquid compositions to viscous oils. 
Representative of the compounds encompassed hereby are, for example, 
2,4,6-tris[3-dimethylamino-N-(2-hydroxyethyl)propylamino]-s-triazine; 
2,4-bis[bis 
(3-dimethylaminopropyl)amino]-6-(N-methyl-2-hydroxyethylamino)-s-triazine; 
2,4-bis 6-[3-dimethylamino-N-(2-hydroxyethyl)propylamino]-s-triazine; and 
2,4-bis(N-methyl-2-diethylaminoethylamino)-6-(N-methyl-2-hydroxyethylamino 
)-s-triazine, and the like. 
As noted, the triazines hereof are, generally, prepared by the reaction of 
cyanuric chloride or a derivative thereof with a new intermediate prepared 
from either an alkyl halide or an alkylene oxide and a dialkylaminoalkyl 
primary amine. The dialkylaminoalkyl primary amine used to prepare the 
intermediate, generally, corresponds to the formula: 
EQU (R').sub.2 N--R"--NH.sub.2 
wherein R' and R" are defined, as above. 
The reaction of the primary amine with the alkyl halide or alkylene oxide 
proceeds in accordance with either of the following equations: 
##STR2## 
As is known to those skilled in the art, the first reaction, generally, 
takes place in the presence of a base, such as, sodium hydroxide, 
potassium hydroxide, lithium hydroxide, sodium bicarbonate, carbonate, 
potassium carbonate and the like. Preferably, where used, the basic 
compound is sodium hydroxide. The reaction generally proceeds at 
50.degree. to 125.degree. C, preferably, 80.degree. to 100.degree. C. 
With alkylene oxide addition, the reaction generally proceeds, under 
conventional oxyalkylation conditions, at a temperature ranging from about 
20.degree. to about 125.degree. C, and usually, at about 60.degree. C to 
about 90.degree. C. Generally, the alkylene oxide and amine are reacted in 
a respective molar ratio ranging from abut 1:1 to about 1:10 and, 
preferably, from about 1:5 to about 1:10, and for a period of from about 
one to three hours. 
Useful alkylene oxides include, for example, ethylene oxide, 1,2-propylene 
oxide, 1,2-butylene oxide, pentylene oxides, hexylene oxides, and the 
like. Generally, the alkylene oxides are those having from two to six 
carbon atoms in the alkylene portion thereof. 
Useful alkyl halides include both substituted and unsubstituted, primary or 
secondary, and having from about one to six carbon atoms in the alkyl 
portin thereof. Useful, unsubstituted alkyl halides include, for example, 
methyl chloride, methyl idodide, ethyl chloride, ethyl bromide, n-propy 
chloride, i-propyl chloride, etc. Useful substituted alkyl halides include 
for example, 2-dimethylaminoethyl chloride, 2-diethylaminoethyl chloride, 
3-dimethylaminopropyl chloride, 3-diethylaminopropyl chloride, 
2-methyl-3-dimethylaminopropyl chloride or bromides or iodides. 
In preparing the intermediate derived from the alkyl halide, the amine and 
akyl halide are reacted in a, respective, molar ratio of from about 20:1 
to about 2:1, and, preferably, from about 15:1 to about 5:1. The reaction, 
generally, proceeds at a temperature ranging from about 50.degree. to 
about 125.degree. C and for a period of about one to ten hours. The times 
and temperatures will vary depending upon the reactants. 
Preferably, the alkyl halide-based intermediate is prepared by adding the 
halide to the amine, after which the base is added thereto to neutralize 
any liberated acid in solution. 
The secondary amine intermediates hereof are, generally, liquids which can 
be readily reacted with cyanuric chloride or a derivative thereof, such 
as, 2-chloro-4,6 bis(dibutylamino)-s-triazine, to provide the triazines 
hereof. 
As hereinbefore noted the triazines hereof exhibit excellent catalytic 
activity in the preparation of rigid cellular products and, in particular, 
rigid cellular compositions characterized by carbodiimide linkages. These 
rigid cellular products, which are discussed in the hereinbefore 
referenced patents are rigid cellular products or foams which have 
isocyanurate and some free isocyanate groups therewithin, as well as, 
substantial amounts of carbodiimide linkages. Thus, the products are 
characteristically referred to as carbodiimide products or foams. 
The foams hereof are generally prepared by the catalytic condensation of an 
organic polyisocyanate in the presence of a catalytically sufficient 
amount of the herein defined triazines. Generally, from about one-half 
part to about ten parts, by weight, of triazine per one hundred parts by 
weight of polyisocyanate is employed, and, preferably, from about one to 
five parts, by weight, of triazine per one hundred parts by weight of 
polyisocyanate. 
It has also been found that by utilizing the triazines hereof conjointly 
with an alkanol that the catalytic activity of the triazine is enhanced. 
This was completely unexpected in that triazine catalytic activity 
enhancement with alkanols was unknown, heretofore, although isocyanurate 
catalysts have been known to be so-enhanced. See, inter alia, British Pat. 
No 824,420. 
The alkanol can be used conjointly with the triazine in an amount ranging 
from about 0.25 to two parts by weight thereof per part by weight of 
triazine. Preferably, from about 0.5 to 1.5 parts of alkanol, by weight, 
per part of triazine is employed. 
Useful alkanols include, for example, methanol, ethanol, n-propanol, 
i-propanol, n-butanol, i-butanol, t-butanol and the like, as well as 
mixtures thereof. 
Any organic polyisocyanate can be efficaciously employed herein. 
Representative of the useful organic polyisocyanates include those 
enumerated in the hereinbefore referenced patents, as well as in U.S. Pat. 
Nos. 3,804,782; 3,732,187; and 3,717,596, etc., the disclosures of which 
are hereby incorporated by reference. 
In preparing the rigid cellular products hereof the triazine or triazine 
and alkanol admixture can be used, alone, or in admixture with an 
isocyanurate or isocyanate trimerization catalyst. Useful isocyanate 
trimerization catalysts include those disclosed in the prior art. 
In preparing rigid cellular products in accordance herewith, additional 
ingredients, such as, surfactants, plasticizers, fillers, active 
hydrogen-containing compounds, and the like can be utilized. 
The foams hereof, it should also be noted, can be prepared by any suitable 
technique including the one-shot process disclosed in the above-referred 
to patents, as well as the quasi-prepolymer and two-stage processes 
disclosed in copending U.S. Patent Application Serial No. 511,111 October 
2, 1974 and entitled "Urethane-Modified Carbdiimide-Isocyanurate Foams 
Prepared From TDI-Rich Iscyanates". In this regard it must be noted that 
in employing the latter two processes, any organic polyisocyanate can be 
utilized herein, not just solely major amounts of distilled toluene 
diisocyanate. 
Also, it has been found that the present triazines are useful in the 
preparation of carbodiimide-isocyanurate resins.

For a more complete understanding of the present invention reference is 
made to the following examples. In the examples, which are not to be 
construed as limitative of the invention, all parts are by weight absent 
indications to the contrary. 
EXAMPLE I 
This example illustrates the preparation of a secondary amine intermediate 
in accordance with the present invention. 
Into a three-liter vessel equipped with a dry ice condenser, agitation 
means, heating means, thermometer and gas inlet was charged 1550 parts (15 
moles) of 3-dimethylaminopropylamine. The charge was gradually heated to 
80.degree. C. Over a period of abut 1.7 hours, 88 parts (2 moles) of 
ethylene oxide was bubbled into the amine, while maintaining the 
temperature in the vessel at about 80.degree. C. 
After the ethylene oxide addition was completed, the temperature in the 
vessel was gradually raised to 137.degree. C over a period of 1.5 hours to 
ensure complete reaction. 
After the reaction was completed, the dry ice condenser was removed and 
replaced with a twelve-inch Vigreaux Column and a fraction cutter. Excess 
dimethylaminopropylamine was stripped until the temperature in the vessel 
reached 160.degree. C. 
The liquid residue in the vessel was, then, transferred to a 500 ml. 
distillation vessel and was distilled under reduced pressure to yield 
187.9 parts (64%) of a product having a boiling point of 
81.degree.-84.degree. C at 0.18 to 0.22 Torr and identified as 
3-dimethylamino-N-(2-hydroxyethyl)propylamine. 
EXAMPLE II 
This example illustrates the preparation of another secondary amine 
intermediate in accordance with the present invention. 
Into a reaction vessel equipped with heating means, agitation means, a 
thermometer, reflux condenser and an addition funnel was charged 306 parts 
(3 moles) of 3-dimethylaminopropylamine. The amine was heated to 
100.degree. C While maintaining the temperature thereat and with stirring 
an aqueous solution of 131.3 parts (0.3 mole) of 
3-dimethylaminopropylchloride hydrochloride, was added thereto through the 
addition funnel over a period of 1.5 hours. 
After the addition was completed and with continuing agitation, the 
contents in the vessel were heated at the reflux temperature, 108.degree. 
C, for 3 hours, and, then, allowed to cool to room temperature. A 50% 
aqueous solution of 72 parts (1.8 moles) of sodium hydroxide was, then, 
added dropwise thereto over a period of 0.5 hours. 
After the sodium hydroxide addition was completed, the contents of the 
vessel was stripped of the dimethylaminopropylamine-water mixture by 
gradually heating the vessel until the temperature therewithin reached 
107.degree. C. 
The residual liquid in the vessel was distilled under reduced pressure to 
yield 68.2 parts (41%) of a product having a boiling point of about 
65.degree.-69.degree. C at 0.3 to 0.4 Torr and identified as 
bis(3-dimethylaminopropyl)amine. 
The following examples illustrate the preparation of triazine compounds in 
accordance with the present invention. 
EXAMPLE III 
Into a reaction vessel equipped with a thermometer, addition funnel, 
agitation means, reflux condenser and a cooling bath was charged 200 parts 
of water. The water was cooled to 0.degree. C, then, 18.5 parts (0.1 mole) 
of cyanuric chloride was added, portionwise, to the water, with stirring. 
While still maintaining the temperature at 0.degree. C, and with stirring, 
48.2 parts (0.33 mole) of 3-dimethylamino-N-(2-hydroxyethyl)propylamine 
was added to the aqueous sooution over a one hour period. After the 
addition was completed the cooling bath was removed and replaced with 
heating means. Then, 13.2 parts (0.33 mole) of sodium hydroxide dissolved 
in 20 parts of water was added to the vessel at a rate such that the pH 
remained between 7 and 8. As the base was being added, the contents of the 
vessel were slowly heated to 100.degree. C. 
After the base addition was completed, the reaction mixture was heated at 
reflux (100.degree.-101.degree. C) for three hours. Water was then 
stripped off under reduced pressure. The residue in the vessel was, then, 
treated with methanol to remove sodium chloride. The methanol solution was 
then evaporated to yield 52.7 parts of a viscous oil product identified as 
2,4,6-tris[3-dimethylamino-N-(2-hydroxyethyl)propylamino] -s-triazine. 
EXAMPLE IV 
Into a reaction vessel, equipped as described in Example III, was charged 
50 parts of water which was cooled to 0.degree. C. To the cooled water was 
added 100 parts (0.05 mole) of cyanuric chloride, portionwise. While 
maintaining the temperature at 0.degree. C, 20.3 parts (0.11 mole) of 
bis(3-dimethylaminopropyl)amine was added dropwise, with stirring, to the 
aqueous solution over a period of 1.25 hours. 
After the addition was completed, the cooling bath was removed and replaced 
with heating means. Then the temperature in the vessel was gradually 
raised to 40.degree. C. Nine and one-tenth parts (0.11 mole) of solid 
sodium bicarbonate was added to the vessel portionwise over a one-half 
hour period. The contents of the vessel was then heated at 45.degree. C 
for 2 hours. A charge of 4.1 parts (0.051 mole) of 
N-methyl-2-hydroxyethylamine was then added to the vessel. This was 
followed by the portionwise addition of 4.6 parts (0.051 mole) of solid 
sodium carbonate over a ten minute period. With stirring the reactants 
were heated at the reflux temperature, 103.degree. C, for 3 hours. Water 
was then stripped off under reduced pressure and the residue was extracted 
with methanol to remove sodium chloride. 
The methanol was then evaporated to yield 26.3 parts of an oil identified 
as 2,4-bis[bis(3-dimethylaminopropyl)amino]-6-(N-methyl-2-hydroxyethylamin 
o)-s-triazine. 
EXAMPLE V 
Into a reaction vessel equipped with a reflux condenser, thermometer, 
heating means and a mechanical stirrer was charged 50 parts of xylene, 5 
parts (0.06 mole) of solid sodium bicarbonate, 8.7 parts (0.06 mole) of 
3-dimethylamino-N-(2-hydroxyethyl)propylamine and 20 parts (0.05 mole) of 
2-chloro-4,6-bis(dibutylamino)-s-triazine, the triazine being a cyanuric 
chloride derivative prepared from 1 mole of cyanuric chloride and 2 moles 
of dibutylamine. 
The reaction mixture was heated, with stirring, at 120.degree. C for 4 
hours. Then, the mixture was filtered hot to remove the inorganic 
material. Xylene was, then, stripped off under reduced pressure and the 
liquid product was purified by distillation. 
There was, thus, obtained 25.6 parts of a product having a boiling point of 
170.degree.-179.degree. C at 0.2 Torr and identified as 
2,4-bis(dibutylamino)-6-[3-dimethylamino-N-(2-hydroxyethyl) 
propylamino]-s-triazine. 
EXAMPLE VI 
Into a reaction vessel, equipped as described in Example III, was charged 
150 parts of water which was cooled to 0.degree. C. To the cooled water 
was added, with stirring, 37 parts (0.2 mole) of cyanuric chloride. With 
continued stirring and at 0.degree. C, 52 parts (0.4 mole) of 
N-methyl-2-diethylaminoethylamine was added thereto over a period of 1.25 
hours. 
After the addition was completed, the cooling bath was removed and replaced 
with heating means. The contents in the vessel was then heated to 
45.degree. C. Contemporaneously with the heating, 34.4 parts (0.41 mole) 
of solid sodium bicarbonate was added to the vessel over a 25 minute 
period. The contents was heated at 45.degree. C for another hour. The 
temperature in the vessel was then raised to 100.degree. C. With the 
temperature at 100.degree. C, 34.4. parts (0.41 mole) of 
N-methyl-2-hydroxyethylamine was added to the vessel dropwise followed by 
the dropwise addition of 8 parts (0.2 mole) of sodium hydroxide, as a 50% 
aqueous solution, over a ten minute period. 
The contents in the vessel was, then, heated at the reflux temperature, 
105.degree. C, for 2 hours. While still hot, the contents in the vessel 
was transferred to a separatory funnel and the organic layer was separated 
and stripped to yield 69.5 parts (85%) of 
2,4-bis(N-methyl-2-diethylaminoethylamino)-6-(N-methyl-2-hydroxyethylamino 
)-s-triazine. The triazine was purified by distillation, and had a boiling 
point of 224.degree. C at 0.4 Torr. 
The following example illustrates the utility of the instant compounds. 
EXAMPLE VII 
Utilizing the triazines of Examples III-VI hereof, a series of cellular and 
resinous products characterized by carbodiimide linkages, as defined in 
the above-referred to patents, were prepared by the following procedure: 
One hundred parts of toluene diisocyanate was admixed with a catalyst in 
accordance herewith. With stirring, the admixture was heated to its 
reaction initiation temperature at which time the reactants were 
transferred to a separate container for foaming. 
Table I, below, shows the nature of the resultant products produced hereby: 
TABLE I 
______________________________________ 
Max. 
Initiation 
Exo- Nature 
Triazine Tempera- 
Sample Type Amt. ture, .degree. C 
.degree. C 
Product 
Peaks 
______________________________________ 
A Ex.III 2.0 95 180 Foam C-I.sup.3 
B Ex.IV 2.0 100 188 Foam C-I 
C Ex.V 1.0 95 197 Resin C-I 
D Ex.VI 1.0 94 140 Resin I 
Control.sup.1 
DMT.sup.2 
1.0 124 185 Foam C-I 
______________________________________ 
.sup.1 A control foam utilizing a known carbodiimide catalyst 
.sup.2 2,4-bis(diethylamino)-6-N-methylethanolamino-s-triazine, a known 
carbodiimide catalyst 
.sup.3 C carbodiimide peaks I isocyanurate peaks 
To test the efficacy of the instant catalysts, samples analogous to samples 
C, D and Control were prepared, but wherein one part of methanol was 
introduced into the catalyst blend. The results of this procedure are 
shown in Table II. 
TABLE II 
______________________________________ 
Nature 
Initiation 
Maximum of 
Sample Temp.,.degree. C 
Exotherm,.degree. C 
Product IR Peaks 
______________________________________ 
C' 25 -- Foam C-I 
D' 25 177 Foam C-I 
Control' 
25 -- No Foam 
______________________________________ 
Thus, the unexpected result attendant the conjoint use of an alkanol with 
the instant triazines becomes evident. 
EXAMPLE VIII 
Following the procedure of Example VII, a series of rigid cellular products 
characterized by carbodiimide linkages were prepared from varying organic 
polyisocyanates, two different catalyst blends and 15 parts of 
1,1,2-trichloro-1,2,2-trifluoroethane blowing agent were utilized. 
The first catalyst blend, Blend A, comprised a 2:1:1.5:0.5 weight ratio 
blend of 2,4-bis(diethylamino)-6-N-methylethanolamino-s-triazine; 
1,3,5-tris(3-dimethylaminopropyl)-s-hexahydrotriazine; 
tris(2-chloroethyl)phosphate, and the polysiloxane surfactant. Blend B was 
the same as Blend A, but utilizing the triazine of Example IV in lieu of 
the known carbodiimide catalyst. 
The following table, Table III, sets forth the ingredients and amounts 
thereof used to prepare the products, as well as observed physical 
properties. 
TABLE III 
__________________________________________________________________________ 
Catalyst 
Cream 
Rise 
Max. .sup.(3) 
Isocyanate, Amt. 
Blend Time 
Time 
Temp Vol. 
IR 
Sample 
TDI.sup.(1) 
CMDI.sup.(2) 
Type 
Amt. 
Sec. 
Sec. 
C. QT Peaks 
__________________________________________________________________________ 
1 0 100 A 10 197 340 111 2.0 C-I Foam 
2 0 100 B 8 188 315 118 1.3 -- 
3 10 90 A 10 145 265 123 1.8 -- 
4 10 90 B 8 145 250 130 1.2 C-I Foam 
__________________________________________________________________________ 
.sup.(1) an 80:20 weight mixture of 2,4- and 2,6-toluene diisocyanate 
.sup.(2) crude methylene diphenyldiisocyanate 
.sup.(3) reaction initiated at 25.degree. C