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Патент USA US2406423

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Patented Aug. 27, 1946
' 2,406,423
UNITED STATES PATENT OFFICE
2,406,423
ORGANIC PHOSPHORUS AND NITROGEN
CONTAINING COMPOUNDS
Willard H. Woodstock, Flossmoor, Ill., assignor to
Victor Chemical Work s, a corporation of Illi
nois
No Drawing. Application April 20, 1944,
1
Serial No. 531,999
13 Claims. (Cl. 260—461).
2
This invention relates to organic phosphorus
and nitrogen containing compounds and more
particularly to compounds of the type formula:
su?iciently so to cause the reaction mass to solid
ify. After the metaphosphate ester is completely
added the mixture is agitated for a period of about
one hour or suiliciently long for completion of the
reaction and the product then allowed to cool to
room temperature. As an alternate procedure it
is sometimes desirable to carry out the reaction
in which each of the R's represents an alkyl or
in an inert liquid solvent medium such as carbon
aryl group, or in the case of R’, R2 and R4 may
tetrachloride or toluene. In this case the solvent
represent hydrogen or its equivalent, and in which 10 is evaporated off after the reaction is completed.
either R.3 or R5 contains a straight chain aliphatic
As a speci?c example, one mole of ethyl meta
group or its equivalent.
phosphate was reacted with two moles of com
Products produced by the method herein de
mercial lauryl amine in the manner described
scribed and having the formula above given are of
above. This commercial material contained about
particular value as surface active agents. In the 15 90% of the mono amine. It was melted and held
preferred form R3 contains an alkyl group of 8 or
at a temperature of about 50 to 60° C., while add
more carbon atoms. Compounds of this type have
ing the mole equivalent of ethyl metaphosphate.
strong wetting out properties and are cation ac
This was chosen as the amount required to form
tive, when R5 is a short chain alkyl group of less
a product having a pH of 6.5 to 7.0 in 0.5% aque
than 5 carbon atoms. The aqueous solutions of 20 ous dispersion. The product in this case was the
such materials possess the property of substan
laury1 amine salt of the lauryl amide of ethyl or
tially completely discharging on cotton, silk and
thophosphoric acid. It was a slightly colored oily
paper ?bres.
liquid which solidi?ed at a temperature slightly
This application is a continuation-in-part of
above normal room temperature.
my copending application Serial No. 417,412, ?led 25 When solid the product was tan-colored and
October 31, 1941.
of butter-like consistency, It had an ammonical
The products are preferably prepared by re
odor and a melting range of about 45 to 50° C.
acting neutral esters of metaphosphoric acid with
Its speci?c gravity at 55° C. was 0.91. It had a
ammonia or amines in accordance with the for
Draves sinking time of 19.4 seconds at 0.4% con
30
centration.
In a similar manner a stearyl amine salt of the
stearyl amide of ethyl orthophosphoric acid was
produced.
This product was a tan colored solid
of butter-like consistency with a melting point
35 of 50 to 60° C.
In a jacketed kettle of suitable size equipped
with a stirrer and temperature indicator, 427
parts by weight of a commercial stearyl amine
.Either anhydrous ammonia or organic pri
(86-92% amine) is melted at 55 to 60° C. and 74
mary or secondary amines may be employed. In 40 parts of ethyl metaphosphate (65.8% P205 con~
tent) slowly added at such rate that the heat of
the preferred case, however, two molecular equiv
reaction does not raise the temperature above 80°
alents of the nitrogen bearing material are em
ployed with one molecular equivalent of the meta
C. This takes about 5 hours and the charge is
phosphoric acid ester. It is not necessary to use
held at 70 to 80° C. for three hours longer to
the same nitrogen bearing compound in each of
allow reaction to be completed. The molten prod
the above formulae. The product produced may‘;
duct is then poured into trays and allowed to cool
be a mixed composition as, for example, by using
and solidify. The product is a tan-colored butter~
ammonia for the primary reaction and an amine
like solid, having an ammonical odor with a melt
for the second or vice versa.
ing range of about 50 to 60° C. In 0.5% aqueous
As a typical example of my procedure, two mole 60 dispersion, it has a pH value between 6.7 and 7.2.
equivalents of a long chain aliphatic amine are
It has a speci?c gravity of 0.89 at 55° C. and a
melted in a reaction vessel and vigorously stirred
Draves sinking time of 30 seconds at 1.0% con
while slowly adding one mole equivalent of a neu
centration.
tral organic metaphosphate ester. The heat of
The'above lauryl and stearyl compositions have
' reaction is removed by external cooling, but not 55 characteristics which are quite similar in that
2,406,428
they are both soluble in mostorganic solvents ,
was inert towards calcium and other salts in
such as benzene, alcohol, ether, mineral oil, car- ,
hard waters.
bon tetrachloride, lubricating oil, butyl acetate,
linseed oil, etc.
Both disperse in water giving
opaque togel-like solutions. A 5% aqueous solu
tion of the stearyl compound and a 10% solution
of the lauryl compound are gelatinous starch-like
'
'
In another example where octyl metaphosphate
was reacted with ethylene diamine, the product
was yellow and butter-like. It did not foam in
water andwas much more soluble in organic sol
. vents than in water.
'Two moles of octyl amine were reacted with
ethyl metaphosphate to give an amber colored
10 oil which foamed in, water, but was not a good
emulsifying agent. It was only partially soluble
ly discharging on cotton, silk and paper ?bres.
pastes of equal consistency.
.
‘
Both compounds are cation-active, their aque
ous solutions possessing the property oi! complete
For example, cotton skeins when immersed in a
in oils.
'
1
-
The lauryl amine salt of the lauryl amide or
with distilled water anddried, showed adsorption - methyl orthophosphoric acid prepared by react
equivalent to 3.8% and 2.4% respectively for the 15 ‘mg two moles of the amine with methyl meta
phosphate was found to be an excellent wetting
lauryl and stearyl compounds based on the
and cationic active agent.
I
‘weight 01' the cotton. Both compounds possess
This may be prepared as follows:
wetting out properties and are strong emulsify
In a one-liter ?ask equipped with a bath,
ing agents. For example, eight grams of each
product in 100 cc. of water were agitated with 20 stirrer, and thermometer, 600 g. commercial
lauryl amine (92% amine) is heated to' 50° C.
' 100cc. of mineral oil to produce thick creamy
and 141 g. methyl metaphosphate slowly added
stable emulsions of the water-in-oil type.
while maintaining the temperature at 50 to 70° C. In the two examples above given, the alkyl'
with cooling bath. The charge was then held at
groups in the salt and amide positions of the
80° C. for 2 hours to complete the reaction. The
molecule were the same, but products may be
charge was poured and allowed to solidify forming
made in which the groups are unlike by carrying
a tan-colored, butter-like solid, having an am
out the reaction in two stages employing di?er
monical odor, and a melting range near 45° C.
ent organic amines for the two stages of the re
Its speci?c gravity at 75°v C. was 0.935, and the
action. -For example, one mole of ethyl meta
phosphate may be reacted with one mole of 30 Draves sinking time was 16 seconds at 0.5% con
centration. It has a pH value range of 6.7 to 7.2
lauryl amine, and this reaction product further
in 0.5% aqueous dispersion. In aqueous disper
reacted with one mole of a different organic
sion it hasstrong cationic activity. It is soluble
amine. A compound of this type was prepared
by reacting one mole of ethyl metaphosphate with
in methanol, ether, kerosene, toluene, etc.
one mole of lauryl amine and subsequently ,re-‘ 35 A particularly desirable amine from the stand;
point of economic availability is cocoa amine
acting with one mole of ethylene diamine. The
which contains a mixture of various amines
product was a clear oil of alkaline reaction. It
ranging from 8 to 18 carbon atoms. The reac
would not-disperse in water.- When treated with
tion product of one mole oi! methyl metaphos
concentrated hydrochloric acid a crystalline hy
drochloride of the compound was formed which 40 phate and two moles of the cocoa amine had
wetting out properties and was cation active. It
was dispersible in water giving a foaming solu
may be prepared as follows:
tion. It discharged on cotton and exhibited other‘
In a, two-liter ?ask equipped with stirrer,
cationic active properties.
thermometer, and cooling bath, 187 g. methyl
In another example, lauryl amine is reacted
metaphosphate is slowly added to 671 g. commer
with ethyl metaphosphate, and, the resulting
cial. coco-amine at a temperature not greater
product reacted with one mole of stearyl amine
to produce a product having good wetting and ' than 70° C. ‘After stirring 3 hours at 70 to 75° C.
the charge is poured and allowed to cool. The
excellent cationic active properties.
product is a tan-colored semi-liquid having a
This experiment may be carried out as follows:
In a one-liter 3-necked ?ask equipped with 50 melting range between 25 and50" C. and an am
monical odor. It is a good wetting agent, and is
' cooling bath, stirrer, and thermometer, 108 g.
strongly cation-active. It has a speci?c gravity
ethyl metaphosphate was slowly added to 185 g.
.Of 0.927 at 55° C., a pH of 6.5 in 0.5% aqueous
commercial lauryl amine 'at 50. to 55° C. with
dispersion, and is soluble in methanol, ether,
some cooling, and the productthen heated at
80° C. for 1 hour. This product was then cooled 55 kerosene, toluene, and similar solvents.
Long chain amines in the salt position increase
to_55 to 60° C., 268 g. molten commercial stearyl
the stability and dispersibility oi! the product in
amine added, and the charge heated to 80° C. for
water. They also increase the organic nature
2 hours. After pouring and cooling the product
and oil solubility of‘ the product. Alkyl groups
was a tan-colored semi-liquid having an ammoni
cal odor, and a melting range from 30 to 35° C. 60 of more than 3 carbon atoms in length in the
gsiziet; position appear to decrease the water solu
It had a speci?c gravity of 0.918 at 65° C., and a
pH value of 6.25 in 0.5% aqueousdispersion, a
All of the compounds the preparation of which
Draves sinking time of 12 seconds at 0.5% con
have been specifically described herein are stable
centration, and analysis showed it to' contain
13.5% P205. It was soluble in methanol, ether, 65 against thermal decomposition at temperature
up to at least 175° C.
'
kerosene, toluene, and similar solvents,_ and was
dispersible in water with strong cation-active‘
It is not essential that the esters and amines
employed in our process be pure homogeneous
character.
'
.
compounds, for example, the neutral. metaphos
In another example one mole ofoctyl meta
phate esters may be mixtures 01' several alkyl or
phosphate was reacted with two ,moles- of anhy
aryl groups. The amines may contain mixed
drous ammonia in a toluol reaction medium.
alkyl, alkaryl, or aryl-groups; however, it is es
After completion of the reaction the toluolwas
evaporated off. The product was a light yellow, ' sential that little it any aryl groups be present
- in the amide forming step or the process if wet
friable, non-crystalline solid. It was soluble in
water with roaming. It was a wetting agent and. 75 ting and cationic properties are desired. Alkaryl
0.4% solution of these compounds, then washed
1
.
-
. 2,406,428
amines may be suitable for producing cationic
active compounds where the straight ‘chain group
has sufficient length preferably at least 8 carbon
atoms in length. Aryl amide compositions, how
ever, may be produced by the' reaction if desired. ,
Such compounds may be useful as plasticizers or
oil treating agents.
'
v
The new surface active compounds of this in
vention are compatible with other similar sur
face active compounds and may be used in com
6
an alkyl group of 1 to 4 carbon atoms chain
length.
I
I
~
'
2. A compound as set forth in claim 1, in which
R4 is hydrogen.
‘
3. A compound as set forth in claim 1, in which
R4 and R’ are hydrogemand R.2 is an alkyl group.
4. A compound as set forth in claim 1, in which
RF and R3 are stearyl radicals.
‘
5. A compound as set forth in claim 1, in which
10 R.2 and R3 represent stearyl radicals, R’ and R4
positions containing such compounds. For exam
represent hydrogen, and R5 represents an alkyl
ple, the cation active products may be mixed with
group of 1 tov 4 carbon atoms.
.
other cation active products to give a surface
6. A compound as set forth in claim 1, in which
active composition having the speci?c charac
R5 represents an ethyl radical.
teristic advantages of each type of component.
15
7. The long chain aliphatic amine salt of a
In determining the number of carbon atoms
long chain aliphatic amide of a short’chain alkyl
in any particular chain compound the usual rules
ester of orthophosphoric acid obtained by react
of equivalents apply.
ing one mole proportion of a neutral alkyl ester
The Draves sinking time referred to herein, is‘
of metaphosphoric acid in which the alkyl group
a test carried out in accordance with the “Braves” 20 contains from 1 to 4 carbon atoms with one mole
method described in American Assoc. Textile
proportion of each of two aliphatic amines in .
Chem. Colorists Year-Book, p. 162 (1935-6). The
which at least one of the amines has an aliphatic
test comprises the determination of the time re
radical containing a straight chain of at least 8
quired for a 5.0 g. skein of two-ply unboiled cot
carbon atoms.
ton yarn to sink when weighted with a 1.5 gram 25
8. A compound as set forth in claim "I, in which
sinker and submerged in the wetting agent solu
the metaphosphate is ethyl metaphosphate, and
tion by means of an anchor.
in which an amine is lauryl amine.
9. A compound as set forth in claim 7, in which
The foregoing detailed description has been
given for clearness of understanding only, and no
the metaphosphate is ethyl metaphosphate, and
unnecessary limitations should be understood 30 in which an amine is stearyl amine.
therefrom.
What I claim as new, and desire to secure by
Letters Patent is:
'
-
'
.
10. A salt as set forth in claim "I, in which
at least one of the reacting amines is primary.
11. A surface active composition consisting es-"
1. A surface active composition consisting es-.
sentially of a monostearyl amine salt of the mono- ‘
sentially of a compound of the formula:
35 stearyl amide of ethyl phosphoric acid.
.
12. A surface active composition consisting es
sentially of a monolauryl amine salt of the mono
lauryl amide of ethyl phosphoric acid.
13. A surface active composition consisting es-_
in which R‘. R2 and 34 represent a radical of 40 sentially of a monostearyl amine salt of the mono
the class consisting of hydrogen and an alkyl
stearyl amide of methyl phosphoric acid.
group, I1‘.3 represents an alkyl group of at least.
8 carbon atoms chain length, and RB represents
WILLARD H. woopsrocx.
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