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Патент USA US2406692

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Patented Aug. 27, 1946
" 2,406,692
UNITED STATES PATENT OFFICE
2,406,692
SOLID COIVIPLEX METAL AMMINE SALTS
AND METHOD FOR THE PREPARATION
THEREOF
Grirmell Jones and Walter Juda, Cambridge,
Mass., assignors to Albi Chemical Corporation,
New York, N. Y., a corporation of New York
' No Drawing. Application June 17, 1942,
Serial No. 447,470
5 ‘Claims. (cl. 167-46)
plex’metal ammine salt and to methods for the
preparation thereof.
2
multaneously. The product may
The present invention relates to a solid com
be ground to
' any desired particle size.
In some cases it is desirable to heat the mix
'
By the term "ammine” it is intended to in
clude only ammonia and amines.
Complex metal ammine salts very widely in
chemical structure and also in physical proper
solubility,
ties, particularly
depending
withupon
regard
thetonature
stability
of and
_the -
ture to start the reaction. The heat is prefer
ably moderate, of the order of 70-80" 0., although
considerable variation in this temperature is
permissible according to the ingredients and the
?nal product involved.
-. Drying can be accelerated by the application of
metal (and in some cases its state of oxidation) , 10 a vacuum.
For a better understanding of our invention,
the anion, the conditions of preparation and '
other factors. For these and other reasons, it
is dif?cult to generalize in this ?eld and to deter
mine in advance either the nature of the ?nal
product or the essential or optimum ingredients
or procedures to be employed.
Many complex metal ammine salts are ex
tremely soluble in water and for this reason it
is di?icult to prepare them in the solid state, in
the following speci?c examples of its application
may be given, it being understood that these
are illustrative only and are not to be construed
- in a limiting sense.
The proportions are by
weight.
Example 1.-45 parts of copper sulfate, 50 parts
of ammonium carbonate and 16 parts of sodium
?uoride are mixed in dry form in a mortar and
view of the dif?culty of precipitating them from 20 the mixture is agitated, as by stirring. The re
action starts almost immediately and proceeds
the solutions in which they are formed. Attempts
with the liberation of carbon dioxide and water.
to prepare these soluble salts in the solid state by
After the reaction has gone to completion (as
chilling the solutions are often ineffective and
indicated by the fact that carbon dioxide is no
give poor yields. Attempts to recover the salt
by evaporation of the- liquid commonly result in 25 longer given off), the product may, if desired,
be dried by spreading it in thin layers. It may
loss of ammonia or of a volatile amine by volatili
then be ground if desired.
zation. Other complex metal ammine salts which
The mixing and drying may be simultaneously
are sparingly soluble are not subject to these
accomplished. For instance, the reaction may be
dimculties but involve other difficulties in precip
itation, ?ltering, washing and drying.
30 carried out in a closed vessel to which a vac
It is an object of our invention to provide an
uum is applied during the reaction, the vessel
improved product comprising a solid complex
being heated in a water bath or otherwise. Evo
lution of carbon dioxide and water vapor will
reduce the ‘.acuum during the progress of the
metal ammine salt and an improved method for
the manufacture thereof.
Our products are, for the most part, soluble in 35 reaction and completion of the reaction and
formation of the desired dry product will be in
water or in dilute aqueous ammonia solutions,
dicated by decrease in and stabilization of the
but, ‘upon evaporation of the solution and vola
pressure.
tilization of the, ammonia or volatile amine, in
For example, in one experiment it was found
soluble metal salts are deposited.
-In general, our improved method comprises 40 that when 1 lb. of the product was formed in a
?ve litre, three-neck Pyrex ?ask, under a vacuum
the dry mixing and agitation of a solid metal
which ?nally went to about 22 millimeters of .'
. compound (which may for purposes of identi?ca
mercury, the ?ask being heated in a water bath
tion be referred to as the primary metal com
to approximately 100° C., the reaction was com
pound or salt) which is soluble in water, with a
source of ammine, preferably a solid ammine 45 plete in less than one hour.
The exact nature of the ?nal produce is sub
compound which is relatively unstable and which
will form, with the primary metal compound, a
ject to some speculation.
,
It is possible that the sodium fluoride‘ appears
complex metal ammine salt, and also with a sec
as such in the ?nal product, mixed with copper
ond salt or salts, soluble in water and contain
ing an anion which is capable of forming an in— 50 ammonia sulfate. Or there may be a double de
composition reaction which results in the forma
soluble salt with the primary metal compound.
tion of copper ammonia ?uoride and also the
When a source of ammonia such as ammonium
formation of sodium sulfate simultaneously with
carbonate, ammonium carbamate, or the like, is
the formation of the complex copper ammonia
used, carbon dioxide is liberated during the mix
ing and agitation. In some cases‘color changes 55 salt.v A third possibility is that both of these re
actions may take place to some extent; the ?nal
characteristic of the metal appear. The mixture
product maybe intermediate between the two
becomes, Wet and in some cases pasty, almost
?rst indicated. comprising a mixture of copper
?uid. The solid complex metal compound may
ammonia sulfate, copper ammonia ?uoride, so
be dried after the reaction is complete, or the
agitation and drying may be accomplished si 60 dium sulfate and sodium ?uoride.‘
2,406,692
4
Example 4
in most cases it is immaterial which of these
conditions prevails, since in any event the ?nal
product will contain ions which, when dissolved,
Silver nitrate_
deposited upon a base material such as a fabric
Ammonium carbonate ____________________ __ 40
and the ammonia volatilized, will leave an insolu
Disodium hydrogen arsenate
ble metal compound.
Parts
(Na2HASO4.7H20)
50
____________________ .._ 35
If we assume the ?nal product to be a mixture
When preparing unstable complex metal am
of copper ammonia sulfate and sodium fluoride,
monia salts as in Examples 3 and 4, it may be
the theoretical amounts of copper, ammonia and
necessary to take precautions to prevent decom
?uorine present will be: Cu, 19%, NHz', 20.3% and 10 position of the complex salt during and after its
F, 12%, based on the original amounts of copper
formation.
sulfate, ammonium carbonate and sodium ?u
Example 5.—45 parts of copper sulfate and 16
oride given in Example 1. If complete double
parts of sodium ?uoride are mixed together and,
decomposition takes place and the ?nal product
while being agitated, ammonia gas in amount
consists of copper ammonia ?uoride and sodium 15 of the order of 12-15 parts is passed through the
sulfate, the relative amounts of copper, am
mass.
monia and ?uoride in?the, product still would not
If avacuum is applied to the mixture of Ex
be signi?cantly changed from the percentages
ample 5, it should not be applied until the am
just given.
monia gas has reacted with the salts, since other“
If the number of molecules of water of crys 20 wise the ammonia gas might be drawn oil? with
talli'zation per molecule of copper ammonia ?u
out reacting.
oride should be high, the above theoretical per
While ammonia gas will react with soluble
centages of copper, ammonia and?uorine would
metal salts such as copper sulfate, to form com
‘no longer hold. This, however, seem unlikely,
plex copper ammonia salts, it will not so react
since water is obviously liberated during the re 25 with insoluble salts such as copper ?uoride, cop
action.
'
per phosphate and copper arsenite.
Analysis of our product prepared in accord
Both the speci?c ingredients and the relative
ance with Example 1 has given ?gures closely
amounts thereof given in the foregoing examples
comparable to the theoretical percentages just
are subject to wide variation.
given.
30 ‘ As primary metal salts, salts of cobalt, nickel,
The complex ?nal product is quite stable.
silver, zinc, cadmium and others capable of
Only one-?fth of the ammonia is lost when the
forming complex ammine salts, or mixtures of
powder ‘is dried for thirty minutes at a temper
such metal salts, may be used. One or more of
ature of 106° C. If the product is to be used in
such compounds may be used.
solution, the loss of ammonia during drying (if 35
In the appended claim we use the term “am
any) does not render the product useless, since
mine complexogen metal” to designate metals
a small addition of ammonia to the solution will
which are- capable of forming complex metal
dissolve any residue.
1
The ?nal composition which contains the the
oretical proportions within the limits given above
is soluble in water, giving a deep blue solution
characteristic of copper ammonia complex com
amine salts or metal ammonia salts, when mixed
in the solid state with a solid source of ammine.
In Place of ammonium carbonate there may be
used ammonium bicarbonate, ammonium car
bamate, urea, amine compounds, such as car
pounds. If an excess of water is added, the solu
bonates, for example guanidine carbonate, and
tion turns to a lighter blue and a turbidity ap
the like. Ammonia gas may be used with cop
pears which may be due to hydrolysis. A small 45 per sulfate and like soluble salts.
addition of ammonia, however, clears the solu
For the secondary metal salt there may be used
tion again and causes the deepv blue color to re-'
appear.
This indicates that an excess of am
essentially neutral, water soluble salts, the anion
of which will form, with the metal of the pri
monia is required to obtain stable dilute solu
mary compound or salt, a compound which is
50 relatively insoluble in water. One or more of
tions of copper ammonia compounds.
Since the copper ammonia compound is a fairly
such salts may be used.
,
stable compound, the product can be dried by
It is to be noted that salts which are strongly
heat. A short exposure to,a temperature of
basic or acid are not suitable for admixture with
about 105° C. will dry the product if it is exposed
the primary metal salt and the source of ammine
to the heat in thin layers, without decomposing 55 prior to reaction between these ingredients to
the copper ammonia complex. A continued ex
form the complex metal ammine salt, because the
posure, however, will slowly decompose the com
strong alkalinity or acidity imparted thereby
plex, ammonia being given off and the deep blue
would prevent the formation of the complex salt.
to violet color of the powder becoming lighter.
The ammonia will be driven off from strongly
Additional examples of operative ingredients 60 basic mixtures and the complex formation can
and proportions of ingredients are given below.
not take place in strongly acid media. The com
The mixing and agitation may be carried out
' pound selected as a secondary salt should, there
as in Example 1.
'
fore, be one which is substantially neutral,
As previously indicated, the proportions of in
Example 2
65 gredients usable inour process are subject to
Parts
considerable variation. If it is desired to effect
Copper sulfate
45
complex conversion of the metal salt to the com
Ammonium carbonate _______________ _l______ 60
plex metal ammine compound, sufficient ammine
Monoammonium phosphate _________ __,-______ 20
must obviously be supplied for this purpose.
Our product comprises a solid water-soluble
70
Example 3
complex‘metal ammine salt, in combination with
‘
Zinc chloride
_
Parts
another soluble salt, said combination being
25
either chemical or mechanical. This product is
adapted to a variety of uses. For instance, it may
75 be dissolved in water and applied to a fabric.
Ammonium carbonate ____________________ __ 50
Monoammonium phosphate _______________ __ 20
2,406,692
6
5
Upon drying and volatilizing the ammonia or
volatile amine, there will be deposited upon the
fabric a relatively insoluble metal salt which may
have desirable preservative and/or other proper
ties.
'
contains an anion capable of forming a water
insoluble compound with the metal or the said
first salt, and continuing said agitation until the
formation of a complex metal salt is substantially
complete.
Products or highly
2. The process for forming solid compositions
containing a complex metal salt, which process
comprises mixing together a water-soluble salt
will clear the solution immediately instead .of
carbonate, ammonium bicarbonate, ammonium
plexogen metals.
The stability of the metal ammonia complex
salt depends upon the metal of the primary salt
?nely divided state a solid complexogen metal '
Products of varying degrees of stability may
be prepared by our process. Thus the product of
Example 1 is quite stable.
of a metal selected from the group consisting of
unstable character can also be prepared by our
method, as in Examples 3 and 4. These prod 10 copper, cobalt, nickel, silver, zinc, and cadmium,
a second solid substantially neutral salt which
ucts may contain so low an ammonia content as
is soluble in water and which contains an anion
to necessitate their solution in dilute aqueous
capable of forming an insoluble compound with
ammonia rather than in water. However, even in
the metal of the said ?rst salt, and a substance
these cases a small amount of ammonia added to
selected from the group consisting of ammonium
a turbid aqueous solution of the unstable product
carbamate and non-aqueous ammonia, and agi
causing ?rst a temporary precipitate of metal
tating said mixture until the formation of a com
hydroxide (soluble only in an excess of ammo
plex metal salt is substantially complete.
nia) which is obtained in the case of aqueous
3. The method which comprises reacting in a
solutions of non-complex salts of ammine com 20
salt which is soluble in water, a second solid wa
ter-soluble salt which is substantially neutral and
which contains an anion capable of forming a
and upon the anion of the essentially neutral
secondary salt. Thus the product of Example 3 25 water-insoluble salt with the metal of the said
?rst solid salt, and passing ammonia gas through
is relatively unstable because it contains the un
said mixture while agitating the same.
stable zinc ammonia complex ion which gives
4. The method which comprises reacting in a
salts having a comparatively high vapor pressure
?nely divided state a primary solid complexogen
of ammonia, and the product of Example 4 is
unstable because there is a'strong tendency to 30 metal salt which is soluble in water, a non-aque
ous source of ammonia and a second solid salt
form the highly insoluble silver arsenate (solu
which is soluble in water and substantially neu
bility: 0.00085 g. in 100 cc. water at 20° 0.).
tral and which contains an anion capable of form
Obviously, the more unstable the product, the
ing a water-insoluble salt with the metal of the
more dimcult it is to give exact figures of its am
monia content. Thus the products of Examples 35 primary salt, thereby forming a composition con
taining a solid water-soluble complex metal am
3 and 4 may contain varying amounts of ammo
monia salt, dissolving the composition in water,
nia according to the precautions taken in their
applying the dissolved salts to a fabric and then
preparation, and they may therefore be more or
treating the fabric to volatilize the ammonia,
less soluble in water.
‘
It will thus be seen that by our invention there 40 whereby a water-insoluble metal compound is
deposited on the fabric.
is provided a novel and improved product hav
5. A solid composition of matter comprising the
ing a wide ?eld of utility and also a novel proc
complex copper ammonia ion, an anion which will
ess for the formation of products comprising com
form a sparingly soluble salt with the copper of
plex metal ammine salts.
45 said complex ion upon decomposition of the com
We claim:
plex, and ions which will combine to form a wa
1. The process of forming solid compositions
ter-soluble secondary salt, said composition con
containing a complex metal salt, which process
taining copper and ammonia in approximately
comprises mixing and agitating together a wa
equal quantities.
ter-soluble solid complexogen metal salt, a non
GRDINELL JONES.
aqueous source of ammine, and a second solid, 60
WALTER JUDA.
water-soluble and substantially neutral salt which
Certi?cate of‘ Correction
Patent No. 2,406,692.
GRINNELL JONES ET AL.
August 27, 1946.
_
It is hereby certi?ed that errors appear in the printed speci?cation of the above
numbered patent requiring correction as follows: Column 1, line
_ 6, for “very” read
vary ; column 2, line 46, for “produce” read product; column 4, hue 67 for “complex”
read com lete ; and that the said Letters Patent should be read with t ese corrections
therein at the same may conform to the record of the case in the Patent O?ice.
Signed and sealed this 22nd day of October, A. D. 1946.
[ml
First Assistant Uommz'asiomr of Patents.
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