Scoopability of triethylene diamine (TEDA) is improved by admixture therewith of a minor quantity (about 0.5 up to 2% by weight) of an additive in liquid form. The types of additives described are liquid glycol compounds selected from among polyethylene glycols, glycol esters, glycol ethers and amino alcohols. Preferred additives are: Carbowax polyethylene glycols having the general formula EQU HOCH.sub.2 (CH.sub.2 OCH.sub.2).sub.x CH.sub.2 OH wherein x is about 3 to about 13, glycol diacetate and triethylene glycol diacetate.

BACKGROUND OF THE INVENTION 
Triethylene diamine (TEDA), also known as 1, 4-diazabicyclo(2.2.2) octane, 
is well known on the commercial market, particularly for use as a catalyst 
or co-catalyst in the production of polyurethane plastics, elastomers and 
foams. A number of methods are known to the art for preparing and 
isolating this compound as a product of commercially acceptable purity. 
The earliest production of TEDA on a commercial scale was by the methods 
disclosed in U.S. Pat. No. 2,937,176, employing as starting material an 
alkylene polyamine. Other patented processes employ as starting material 
for production of TEDA, mono- or bis-hydroxyethyl piperazine (U.S. Pat. 
No. 3,166,558); N-aminoethyl piperazine (U.S. Pat. No. 2,985,658); or 
alkanolamines alone (U.S. Pat. No. 2,977,364) or in admixture with 
ethylene diamine (U.S. Pat. No. 2,977,363). 
By any of the above methods the TEDA is isolated from the reaction mixture 
as a white crystalline hygroscopic product, containing a small amount of 
by-product amine compounds. The TEDA product is generally placed on the 
market for commercial users in fiber drums of about 12 gallon (about 45 
liter or 25 kg.) capacity. 
With improved techniques of purification of the synthesized TEDA product, 
by recrystallization or more precise fractionation, the product is 
recovered having less than about 500 ppm of accompanying by product 
organic amine impurities. It was found, however, that the purified 
commercial product of this desired low content of organic amine 
impurities, when stored in commercial size drum container for even short 
periods, particularly in a moderately warm environment, tended to form a 
crust or agglomerate at the top surface of the closed drum, which crust or 
agglomeration on further standing, penetrated further and further into the 
contents of the drum, rendering it difficult to scoop the product out of 
the drum. Without being bound to any particular explanation for the cause 
of this hardening of the upper layer of the TEDA in the drum, it is 
believed that there occurs a sublimination of the TEDA followed by its 
recrystallization forming a bridge between adjacent particles. This 
condition renders it difficult to remove product from the drum, herein 
referred to as poor "scoopability". 
In initial attempts to avoid such hardening of the TEDA and to improve the 
facility of its removal ("scoopability") from the shipping containers the 
addition of talcs and various other additives were tried of the kinds 
typically employed to improve flow or prevent lumping of crystalline or 
powdered solid products. These substances were not found successful in 
improving scoopability of the TEDA product which had been exposed to 
temperatures above ambient. It was found, for example, that fumed or 
colloidal silica additives, such as Cab-O-Sil.RTM., when admixed and 
dispersed through the TEDA product at levels of 200 to 2000 ppm did obtain 
some improvement in the scoopability if the product remained at ambient 
temperature or lower. Higher levels of the Cab-O-Sil within the stated 
range kept the TEDA scoopable for longer time periods. At somewhat warmer 
temperatures, as in excess of about 35.degree. C., the product hardened in 
about three days, apparently with little dependence on the level of the 
additive therein. 
SUMMARY OF THE INVENTION 
It has now been found, in accordance with the present invention, that the 
scoopability of triethylene diamine can be improved when there is admixed 
therewith a minor amount of an additive in liquid form. Generally 
additives having a vapor pressure approximate to that of triethylene 
diamine over the range of storage temperature generally encountered (i.e., 
10.degree.-50.degree. C.) have been found most effective; however, other 
compounds in the desired classes with lower vapor pressures can be equally 
effective. The proposed additives of the invention comprise respectively 
polyethylene glycols, glycol ethers and esters and amino alcohols, which 
have a water solubility of at least 5 parts per hundred. 
The preferred compounds of the invention are those which obtain good 
scoopability when admixed at levels of about 0.5 to 1.0% (wt/wt); also 
useful are compounds of the kind described which are added at somewhat 
higher quantity levels for desired scoopability, i.e. up to about 2.0%. 
With the proposed additives of the invention at the levels employed, there 
is not obtained the insoluble floc otherwise present when TEDA containing 
a silica type additive is dissolved in water or glycol.

DETAILED DESCRIPTION 
The additive may be admixed with the TEDA in any manner effective to obtain 
good dispersion throughout the mass. The additive employed should have a 
viscosity higher than that of water. The preferred additives are those 
which do not adversely affect the appearance or performance of the TEDA or 
blends of TEDA; such as aqueous solutions thereof or its mixtures with 
dipropylene glycol or with dimethyl ethanolamine. While a certain degree 
of improvement in scoopability is observed when less than about 0.5% of 
the designated preferred additives are used; such lower additive levels 
have not been found to obtain the desired scoopability of the TEDA for 
sufficiently long storage periods. 
Water solubility of the additive is important when the TEDA is employed in 
formulations in which it is dissolved in water, as in formulations for the 
production of water-blown flexible polyurethane foams. Such 
water-solubility is not required where the TEDA is used as catalyst in 
non-aqueous urethane formulations, isocyanate polymerization, or the like, 
provided that the additive is sufficiently soluble in the polyol or other 
solvent or component of the formulations with which the TEDA is to be 
admixed. 
Among the preferred additives which in trial runs showed best results are: 
Carbowax-400 polyethylene glycol, glycol diacetate and triethylene glycol 
diacetate. Other additives that may be employed include: polyethylene 
glycols of lower or higher molecular weight than Carbowax 400, such as in 
the range of about 200 to about 600 average molecular weight, Carbitol 
acetate, butyl Carbitol acetate, and dimethyl ethanolamine. The useful 
glycol esters are those obtained by esterifying the glycol with a lower 
fatty acid of 1 to 3 carbon atoms; i.e. formic, acetic or propionic acid. 
The glycol ethers include compounds corresponding to the formula: 
EQU RO(C.sub.2 H.sub.4 O).sub.n H 
where R is alkyl of 2 to 4 carbon atoms and n is 1 or 2. Among the useful 
amino alcohols are included dimethyl ethanolamine and Quadrol. 
Various additives were subjected to prescreening test to determine their 
use for improving scoopability of plant produced TEDA having a content of 
co-produced amine impurities in the range of about 100 to 500 ppm. The 
designated additives were incorporated in the respective amounts set out 
in Table 1, with 3600 grams of the TEDA, and the product stored for three 
weeks at 120.degree. F. (49.degree. C.) in a quart jar. 
TABLE 1 
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Additive Storage 
Additive wt. grams Test Results 
______________________________________ 
None -- Hard 
.sup.(1) Cab-O-Sil M-5 
1.5 Hard 
.sup.(2) Quadrol 
36 Fair Scoopability - 
yellow product 
1,4-butane diol 
36 Fair Scoopability - 
turbid water solution 
Glycol diacetate 
36 Good scoopability - 
somewhat sweet odor 
.sup.(3) Carbitol.RTM. 
36 Good Scoopability - 
Turbid water solutions 
400p.(4) Carbowax.RTM. 
36 Good scoopability - 
clear water solution 
.sup.(5) Butyl Cellosolve.RTM. 
36 Fair scoopability - 
turbid water solution 
Dimethyl dodecylamine 
36 Poor scoopability - 
turbid water solution 
Dimethyl ethanolamine 
36 Fair scoopability - 
yellow/tan product 
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.sup.(1) Colloidal silica marketed by Cabot Corp. included herein as a 
control. 
.sup.(2) BASF-Wyandotte tradename for N,N,N,`N`-tetrakis (2hydroxy propyl 
ethylene diamine. 
.sup.(3) Union Carbide tradename for diethylene glycol monoethyl ether. 
.sup.(4) Polyethylene glycols of general formula HOCH.sub.2 (CH.sub.2 
OCH.sub.2).sub.x CH.sub.2 OH, marketed by Union Carbide, wherein x ranges 
from about 6 to 10. The numerical designation 400 generally corresponds t 
the average molecular weight. 
.sup.(5) "Cellosolve" is the proprietary designation of Union Carbide for 
glycol alkyl ethers. 
Other commercial polyethylene glycol compounds available include Carbowax 
200, Carbowax 300, Carbowax 600. These correspond to the general formula 
HOCH.sub.2 (CH.sub.2 OCH.sub.2).sub.x CH.sub.2 OH wherein x may average 
from about 3 to about 13. 
The turbidity of the water solutions is believed due to the limited 
solubility of the additive in the system. As indicated above, the 
formation of such water-insoluble material would be of no significance in 
instances where the TEDA is to be employed in non-aqueous systems. Since, 
in many instances, polyurethane producers may employ TEDA catalyst in 
aqueous as well as in non-aqueous systems, preference is had for additives 
obtaining clear water solutions for their admixture with TEDA. Except for 
possible sales resistance, the formation of yellow coloration, is not 
believed to have any significance as to properties of the TEDA composition 
containing this additive, provided such compositon has desired 
scoopability. As to those additives showing only fair scoopability, it is 
believed that scoopability could be improved by using larger proportions 
of the additive. 
The additives which were found to perform best in the screening tests were 
then tried in larger scale runs. One hundred kilograms of plant-produced 
TEDA were added to a six cubic foot ribbon blender, which was operated for 
several minutes to remove lumps. At a designated time the ribbon speed was 
adjusted to 40 rpm and the additives listed in Table 2 were each added 
over a 15-30 second period. The blender was continued to run for ten 
minutes at 40 rpm and the mixed products discharged into 12 gallon fiber 
drums. These drums were stored for a week at 120.degree. F. (49.degree. 
C.) and each tested for scoopability as compared to controls (1) without 
additive and (2) with colloidal silica as additive. 
TABLE 2 
______________________________________ 
Penetration by 
Additive curved metal 
Additive wt. gms. Scoopability 
spatula, inches 
______________________________________ 
None -- None 1 
Cab-O-Sil M-5 
80 None 1 
Glycol diacetate 
1000 Good 6 
Carbowax -400 
1000 Good 6 
______________________________________ 
The glycol diacetate and Carbowax-400 also retained good scoopability when 
stored at 120.degree. F. for several months. 
A set of exploratory runs was carried out with the various additives 
designated in Table 3 in the amounts shown, and scoopability tested 
determined after storage at various temperatures for 8 weeks in half 
filled quart jars. 
TABLE 3 
______________________________________ 
Scoopability when 
Conc. stored at .degree.F. 
Additive wt. % 105 amb. 50 
______________________________________ 
Quadrol 1.2 good good -- 
(yellowish) 
Quadrol 0.75 good fair -- 
None -- rock-like -- -- 
1-butoxyethoxy-2- 
propanol 1.0 good good good 
wet 
appearance 
2-methyl-2,4- 
1.0 good fair/ good 
pentanediol good 
Triethylene glycol 
diacetate 0.5 good good -- 
Triethylene glycol 
0.5 fair poor -- 
______________________________________