U.S. patent application number 11/652837 was filed with the patent office on 2007-05-24 for preparation and use of iminodisuccinic acid ammonium metal salts.
Invention is credited to Torsten Groth, Thomas Klein, Thomas Menzel, Alfred Mitschker, Ralf-Johann Moritz, Wolfgang Wirth.
Application Number | 20070118000 11/652837 |
Document ID | / |
Family ID | 28798890 |
Filed Date | 2007-05-24 |
United States Patent
Application |
20070118000 |
Kind Code |
A1 |
Groth; Torsten ; et
al. |
May 24, 2007 |
Preparation and use of iminodisuccinic acid ammonium metal
salts
Abstract
The invention relates to a process for the preparation of
iminodisuccinic acid ammonium metal salts, characterized in that,
in a first stage, maleic anhydride (MA), alkali metal hydroxide and
water are mixed in the molar ratio of 2:0-3:5-30 and then ammonia
is metered in in the ratio MA:ammonia 2:1.5-8, in order to obtain
iminodisuccinic acid ammonium salts which, in a second stage, are
reacted with metal oxides, metal hydroxides (and) or other metal
salts or their mixtures to give iminodisuccinic acid ammonium metal
salts of the formula 8,
IDA(NH.sub.4).sub.x(Na).sub.y(K).sub.z(Me).sub.m.(NH.sub.3).sub.n
Formula 8 in which IDA represents iminodisuccinic acid anion,
x=0.1-3.9 y=0-3 z=0-3 m=0.1-2 n=0-6 and Me represents metals of the
IInd, IIIrd and IVth main groups and of the Ist to VIIIth subgroups
as well as metals of the lanthanide series, of the Periodic Table,
which can occur in the oxidation states 1, 2, 3 or 4, the compounds
themselves and their intermediates, and the use.
Inventors: |
Groth; Torsten; (Odenthal,
DE) ; Mitschker; Alfred; (Odenthal, DE) ;
Moritz; Ralf-Johann; (Neuss, DE) ; Klein; Thomas;
(Koln, DE) ; Menzel; Thomas; (Hilden, DE) ;
Wirth; Wolfgang; (Bergisch Gladbach, DE) |
Correspondence
Address: |
LANXESS CORPORATION
111 RIDC PARK WEST DRIVE
PITTSBURGH
PA
15275-1112
US
|
Family ID: |
28798890 |
Appl. No.: |
11/652837 |
Filed: |
January 12, 2007 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
10423326 |
Apr 25, 2003 |
7183429 |
|
|
11652837 |
Jan 12, 2007 |
|
|
|
Current U.S.
Class: |
562/571 |
Current CPC
Class: |
C07C 229/76 20130101;
C05D 9/02 20130101; C07C 227/08 20130101; A01N 37/44 20130101; C07C
229/24 20130101; C05D 9/02 20130101; C05F 11/00 20130101 |
Class at
Publication: |
562/571 |
International
Class: |
C07C 227/06 20060101
C07C227/06 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 29, 2002 |
DE |
10219037.2 |
Claims
1-9. (canceled)
10. Iminodisuccinic acid ammonium salts of the formula 7,
IDA(NH.sub.4).sub.y(H).sub.y Formula 7 wherein x=2-4 and y=0-2.
11. A Process for the preparation of iminodisuccinic acid ammonium
metal salts, comprising: in a first stage, mixing maleic anhydride
(MA) and water in a molar ratio of 2:5-30 and then metering ammonia
into the resulting reaction mixture in a molar ratio of MA:ammonia
2:1.5-8, in order to obtain iminodisuccinic acid ammonium salts
according to claim 10 in a second stage, reacting the
iminodisuccinic acid ammonium salts with metal oxides, metal
hydroxides or metal salts or their mixtures to give iminodisuccinic
acid ammonium metal salts of the formula 8,
IDA(NH.sub.4).sub.x(Na).sub.y(K).sub.z(Me).sub.m.(NH.sub.3).sub.n
Formula 8 in which x=0.1-3.9 y=0-3 z=0-3 m=0.1-2 n=0-6 and Me
represents metals of the IInd, IIIrd and IVth main groups and of
the Ist to VIIIth subgroups as well as metals of the lanthanide
series of the Periodic Table, which can occur in the oxidation
states 1, 2, 3 or 4.
12. Iminodisuccinic acid ammonium salts of the formula 6
IDA(NH.sub.4).sub.x(Na).sub.y(K).sub.z(H).sub.m Formula 6 wherein
x=0.1-4 y=0-3 z=0-3 m=0-2.
13. A method of increasing the availability of trace elements in an
agricultural product comprising: providing an agricultural product
comprising an iminodisuccinic acid ammonium metal salt according to
formula (8)
IDA(NH.sub.4).sub.x(Na).sub.y(K).sub.z(Me).sub.m.(NH.sub.3).sub.n
Formula 8 in which x=0.1-3.9 y=0-3 z=0-3 m=0.1-2 n=0-6 and Me
represents metals of the IInd, IIIrd and IVth main groups and of
the Ist to VIIIth subgroups as well as metals of the lanthanide
series of the Periodic Table, which can occur in the oxidation
states 1, 2, 3 or 4.
14. The method according to claim 13 wherein the agricultural
product is a fertilizer.
15. The method according to claim 13 wherein the agricultural
product is a slug and snail pellet.
16. An agricultural product comprising: an iminodisuccinic acid
ammonium metal salt according to formula (8)
IDA(NH.sub.4).sub.x(Na).sub.y(K).sub.z(Me).sub.m.(NH.sub.3).sub.n
Formula 8 in which x=0.1-3.9 y=0-3 z=0-3 m=0.1-2 n=0-6 and Me
represents metals of the IInd, IIIrd and IVth main groups and of
the Ist to VIIIth subgroups as well as metals of the lanthanide
series of the Periodic Table, which can occur in the oxidation
states 1, 2, 3, or 4.
17. The agricultural product of claim 16 wherein the agricultural
product is a fertilizer.
18. The agricultural product of claim 16 wherein the agricultural
product is a slug and snail pellet.
19. A solution for use in providing surface coloring to ceramics
comprising: one or more iminodisuccinic acid ammonium salts.
20. The solution according to claim 19 wherein the iminodisuccinic
acid ammonium salts is according to formula 6
IDA(NH.sub.4).sub.x(Na).sub.y(K).sub.z(H).sub.m Formula 6 wherein
x=0.1-4 y=0-3 z=0-3 m=0-2.
21. The solution according to claim 19 wherein the iminodisuccinic
acid ammonium salts is according to formula 7
IDA(NH.sub.4).sub.y(H).sub.y Formula 7 wherein x=2-4 and y=0-2.
22. A solution for use in providing surface coloring to ceramics
comprising: iminodisuccinic acid ammonium salts of the formula 7,
IDA(NH.sub.4).sub.y(H).sub.y Formula 7 wherein x=2-4 and y=0-2.
23. A solution for use in providing surface coloring to ceramics
comprising: iminodisuccinic acid ammonium salts of the formula 6
IDA(NH.sub.4).sub.x(Na).sub.y(K).sub.z(H).sub.m Formula 6 wherein
x=0.1-4 y=0-3 z=0-3 m=0-2.
24. A process for providing surface coloring to ceramics
comprising: providing iminodisuccinic acid ammonium salts to a
ceramic article to be colored.
25. The process of claim 24 wherein the iminodisuccinic acid
ammonium salt is that according to formula 6
IDA(NH.sub.4).sub.x(Na).sub.y(K).sub.z(H).sub.m Formula 6 wherein
x=0.1-4 y=0-3 z=0-3 m=0-2.
26. The process of claim 24 wherein the iminodisuccinic acid
ammonium salt is that according to formula 7 iminodisuccinic acid
ammonium salts of the formula 7, IDA(NH.sub.4).sub.y(H).sub.y
Formula 7 wherein x=2-4 and y=0-2.
27. An agricultural product comprising iminodisuccinic acid
ammonium salts of formula (8) prepared according to the process of
claim 11.
28. The agricultural product of claim 27 wherein the agricultural
product is a fertilizer.
29. The agricultural product of claim 27 wherein the agricultural
product is a slug and snail pellet.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a continuation application
claiming benefit from copending U.S. patent application Ser. No.
10/423,326 having a filing date of Apr. 25, 2003 and entitled
PREPARATION AND USE OF IMINODISUCCINIC ACID AMMONIUM METAL
SALTS.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The invention relates to a process for the preparation of
iminodisuccinic acid ammonium metal salts by reaction of maleic
anhydride, alkali metal hydroxides, ammonia and water in a first
stage to give iminodisuccinic acid ammonium salts and their
subsequent reaction with metal oxides, metal hydroxides or other
metal salts in a second stage. The products resulting therefrom can
be used to increase the availability of metal ions, e.g. in
agriculture, as trace element fertilizers or slug and snail
pellets, or in the ceramics industry, for surface colouring.
[0004] 2. Brief Description of the Prior Art
[0005] Trace element fertilizers are used in agriculture to
increase agricultural yields and to prevent plant diseases, such as
apple spot (brown spots) or tomato fruiting rot (black spots) which
can be traced back to a disrupted supply of calcium.
Illustratively, there is employed specific calcium, magnesium,
manganese, iron, copper or zinc salts of ethylenediaminetetraacetic
acid (EDTA), diethylenetriaminepentaacetic acid (DTPA) or other
complexing agents.
[0006] EDTA and DTPA are two conventional complexing agents which
have been used for years in large amounts. However, many of the
conventional complexing agents, such as EDTA and DTPA and various
phosphonates and the metal complexes resulting therefrom, are not
at all or only partially biodegradable; they remobilize heavy
metals in surface waters and can even enter drinking water
treatment, since they are not adsorbed in sewage sludges or
soils.
[0007] It is therefore an important object to develop complexing
agents which do not have the eco-toxicological disadvantages, such
as described above.
[0008] Iminodisuccinic acid is an art-known complexing agent which
is readily biodegradable and which therefore has an
eco-toxicological advantage with respect to the complexing agents.
Its metal salts, which can be used in agriculture and in the
ceramics industry, are also biodegradable, and the preparation
process is environmentally friendly, since it generates no
significant solid or liquid waste and any ammonia released can be
recycled in chemical processes.
[0009] GB 1 306 331 discloses the preparation of iminodisuccinic
acid from maleic acid and ammonia in a molar ratio of 2:3 to 2:5 at
temperatures of 60 to 155.degree. C. For their work up, either
hydrochloric acid or sodium hydroxide solution can be added. In SU
0 639 863, iminodisuccinic acid is prepared in the presence of
alkali metal hydroxides from maleic acid and ammonia at a molar
ratio of 2:0.8 to 2:1 at temperatures of 110 to 130.degree. C. JP
6/329 606 discloses a three-stage process for the preparation of
iminodisuccinic acid. A maleic acid derivative is first reacted
with ammonia in an aqueous medium. Alkali metal or alkaline earth
metal hydroxides are then added. A "maturing process" follows in
the third process stage. JP 6/329 607 likewise discloses a
three-stage process for the preparation of iminodisuccinic acid. In
the first stage, a maleic acid derivative is again first reacted
with ammonia in aqueous medium. Alkali metal or alkaline earth
metal hydroxides are then added in the second stage. In the third
stage, the reaction is continued after addition of further maleic
acid derivative.
[0010] However, in none of the patents is a process for the
preparation and the use of the iminodisuccinic acid ammonium metal
salts according to the invention disclosed.
[0011] A process for the preparation of iminodisuccinate alkali
metal salts and their suitability as complexing agents are known
from U.S. Pat. No. 6,107,518. It is known, from U.S. 2001/0 044 381
A1, that complexes with calcium, magnesium, barium, strontium,
manganese, zinc, copper and iron can be prepared.
[0012] However, none of the documents discloses a specific process
for the preparation of the iminodisuccinic acid ammonium metal
salts according to the invention in which not all ammonium groups
are replaced with alkali metals, alkaline earth metals or heavy
metals.
SUMMARY OF THE INVENTION
[0013] The present invention consequently relates to a process for
the preparation of iminodisuccinic acid ammonium metal salts,
characterized in that, in a first stage, maleic anhydride (MA),
alkali metal hydroxide and water are mixed in the molar ratio of
2:0-3:5-30 and then ammonia is metered in the reaction mixture, in
the ratio of MA:ammonia 2:1.5-8, in order to obtain iminodisuccinic
acid ammonium salts of the formula 6
IDA(NH.sub.4).sub.x(Na).sub.y(K).sub.z(H).sub.m Formula 6 wherein
IDA represents iminodisuccinic acid anion, with x=0.1-4, y=0-3,
z=0-3 and m=0-2, which, in a second stage, are reacted with metal
oxides, metal hydroxides or other metal salts to give
iminodisuccinic acid ammonium metal salts of the formula 8,
IDA(NH.sub.4).sub.x(Na).sub.y(K).sub.z(Me).sub.m.(NH.sub.3).sub.n
Formula 8 in which x=0.1-3.9 y=0-3 z=0-3 m=0.1-2 n=0-6 and Me
represents metals of the IInd, IIIrd and IVth main groups and of
the Ist to VIIIth subgroups as well as metals of the lanthanide
series of the Periodic Table, which can occur in the oxidation
states 1, 2, 3 or 4.
DETAILED DESCRIPTION OF THE INVENTION
[0014] In the process according to the invention, in the first
stage, water, maleic anhydride (MA), alkali metal hydroxide
(AlkaliOH) and ammonia (NH.sub.3) are metered into a reactor and
the maleic acid salt formed is reacted at the reaction temperatures
(T) and for the reaction times (t) mentioned. In the second stage,
the reaction mixture obtained is then reacted with metal oxides,
metal hydroxides or other metal salts at the reaction temperatures
(T) and for the reaction times (t) mentioned to give
iminodisuccinic acid ammonium metal salts, optionally after
addition of water and distilling off aqueous ammonia, by which
highly concentrated, storage-stable and low-odour iminodisuccinic
acid ammonium salt solutions can be prepared optionally after a
clarifying filtration. The salts presented therein can also, by
drying, be converted to solids.
[0015] The process according to the invention has the advantage
that it can be carried out economically, both batchwise and
continuously. As would be realized, even environmentally friendly
products, in spite of all advantages, are only competitive if they
can be prepared under suitably economic conditions. The process
according to the invention generates virtually no waste since,
after the distillation of the ammonia, this can be recycled or used
in other processes and the remaining product is made use of in its
entirety. Only in the clarifying filtration can small amounts of
material arise, resulting from the filtration. The products
according to the invention are, in addition, biodegradable. In the
process and product, economics and ecology are combined with one
another in a very efficient way.
[0016] In the process according to the invention, in the first
stage, MA, alkali metal hydroxide and water are first mixed
together in the molar ratio of MA:AlkaliOH:water 2:0-3:5-30. The
mixing of the components can be carried out both under continuous
and under batchwise process control. MA and alkali metal hydroxide
are added to the water either simultaneously, in succession or
alternately in portions. In a preferred embodiment, the pH in the
metering is <11, particularly preferably <8. The metering is
preferably carried out at temperatures of 50-150.degree. C.,
particularly preferably at 70-120.degree. C. The metering time
depends on the embodiment. Maleic acid alkali metal salts in
solution or suspension, preferably in solution, particularly
preferably in concentrated solution with solids contents of more
than 30 weight %, preferably more than 40 weight %, particularly
preferably more than 50 weight %, are produced. After the final
metering, the solutions or suspensions can be stirred.
[0017] In a particular embodiment, the molar ratio of
MA:AlkaliOH=2:0. Alkali-free maleic acid solutions are thereby
produced. In a further particular embodiment, the molar ratio of
MA:AlkaliOH=2:0.2-2.8, preferably 2:0.5-2.5, particularly
preferably 2:1.5-2.3. In a preferred embodiment, the molar ratio of
MA:water=2:5.5-25, particularly preferably 2:6-20.
[0018] When the preparation is carried out in accordance with this
invention, only small amounts of byproducts, such as, for example,
fumaric acid and malic acid or their salts, are formed. For this
reason, maleic acid or its salts are obtained with yields of more
than 90%, preferably more than 95%, particularly preferably more
than 98%.
[0019] With regard to a continuous process control, the continuous
and simultaneous metering of a MA melt and alkali metal hydroxide
solutions into a pre-charged maleic acid salt solution has proved
to be particularly advantageous. In this way, even very pure and
also colourless solutions can be obtained, with equally high
yields.
[0020] Ammonia is metered into the suspensions or solutions
comprising maleic acid or maleic acid salts formed in the course of
the first stage. The molar ratio of MA:ammonia is 2:1.5-8,
preferably 2:1.5-6, particularly preferably 2:1.8-5. The addition
can be carried out equally well both under continuous and under
batchwise process control.
[0021] In the process, MA can be used in the form of a melt, flakes
or briquettes, preferably as a melt. Alkali metal hydroxides are
used in bulk or in aqueous solution, e.g. in concentrations of
10-60 weight %, preferably of 20-55 weight % and particularly
preferably of 25-50 weight %. Lithium hydroxide, sodium hydroxide
or potassium hydroxide, and preferably sodium hydroxide or
potassium hydroxide, can be chosen as alkali metal hydroxides.
Ammonia can be metered in as a liquid, as a gas or as an aqueous
solution.
[0022] The maleic acid ammonium salt solutions formed from MA,
AlkaliOH, ammonia and water are reacted at temperatures of
70-170.degree. C., preferably at 75-160.degree. C., particularly
preferably at 80-155.degree. C., very particularly preferably at
85-140.degree. C., and for reaction times of 0.1-100 h, preferably
0.7-70 h, particularly preferably 1-50 h, very particularly
preferably 2-40 h. The reaction can be carried out both in
continuous reactors and in batch reactors. One or more temperature
levels can be introduced in a process for the reaction
temperature.
[0023] The reaction is carried out under autogenous pressure. In
this way, pressures of up to 50 bar, preferably up to 30 bar,
particularly preferably up to 20 bar, can occur. It is possible in
addition to cover the mixture with a blanket of inert gases,
especially in batch reactors, thereby making possible pressures of
up to 80 bar.
[0024] In a particular embodiment, alkali-free maleic acid ammonium
salt solutions can surprisingly be reacted in open reactors at
standard pressure without significant amounts of ammonia
escaping.
[0025] A maleic acid conversion of >93%, preferably >95%,
particularly preferably >98%, of the theoretical conversion is
achieved through the reaction conditions.
[0026] Iminodisuccinic acid ammonium salt solutions are thus
obtained in the first stage of the process according to the
invention, which solutions are either used directly in the second
stage for the formation of the iminodisuccinic acid ammonium metal
salts or are used for the preparation of the iminodisuccinic acid
ammonium metal salts if need be only after a workup.
[0027] The workup step is of considerable advantage if the
preparation of the iminodisuccinic acid ammonium metal salts cannot
be carried out immediately afterwards or cannot be carried out in
the same manufacturing plant. Through the workup, in which the
solids content and the ammonia or ammonium content are reduced
through addition of water and distilling off aqueous ammonia,
success is achieved in preparing highly concentrated,
storage-stable and low-odour iminodisuccinic acid ammonium salt
solutions. Flexible downstream production, essential for the
present day, is thereby made possible.
[0028] In a preferred embodiment, the reaction mixtures obtained
after reaction are thus first of all treated with water and
optionally with alkali metal hydroxide and are converted, by
distilling off aqueous ammonia, adjusting the pH with ammonia or
aqueous ammonia, adjusting the concentration with water and
optionally carrying out a clarifying filtration, to highly
concentrated, storage-stable, weakly coloured and low-odour
iminodisuccinic acid ammonium salt solutions.
[0029] The molar ratio of initially charged MA:AlkaliOH is 2:0-3,
preferably 2:0-2. The aqueous ammonia is distilled off at
temperatures of 50-150.degree. C., preferably at 60-130.degree. C.,
particularly preferably at 70-110.degree. C., very particularly
preferably at 75-105.degree. C., and pressures of 0.1-10 bar,
preferably 0.2-2 bar, over the course of 0.1-50 h, preferably
0.3-30 h, particularly preferably 0.5-25 h, very particularly
preferably 0.9-20 h.
[0030] The workup can on the other hand be carried out as component
of a continuous or batchwise overall process. The introduction of
steam has proved to be particularly advantageous for distilling off
aqueous ammonia. After workup, the solids contents are more than 20
weight %, preferably more than 30 weight %, particularly preferably
more than 40 weight %. The solutions are storage-stable under the
usual temperature conditions for transportation and storage, e.g.
from 0-50.degree. C., preferably 1-40.degree. C., particularly
preferably from 2-35.degree. C.
[0031] The iminodisuccinic acid ammonium salt solutions prepared in
the first stage according to the invention exhibit the following
composition: iminodisuccinic acid and its salts (formula I) as a
mixture of the stereoisomers (S,S-IDA, R,R-IDA and R,S-IDA) in
yields of >65%, preferably >70%, particularly preferably
>74%, of the theoretical yield. The combined byproducts and
their salts are present in amounts of <35%, preferably <30%,
particularly preferably <26%, of the theoretical amounts, in
which maleic acid and its salts (formula 2) are present with
<7%, preferably <5%, particularly preferably <2%, of the
theoretical amount, fumaric acid and its salts (formula 3) are
present with <20%, preferably <15%, particularly preferably
<10%, of the theoretical amount, malic acid, as a mixture of the
stereoisomers (R- and S-malic acid), and its salts (formula 4) are
present with <7%, preferably <5%, particularly preferably
<3%, of the theoretical amount and aspartic acid, as a mixture
of the stereoisomers (R- and S-aspartic acid), and its salts
(formula 5) are present with <25%, preferably <20%,
particularly preferably <15%, of the theoretical amount.
##STR1##
[0032] Overall, product solutions are obtained in which the stated
components of the formulae 1-5 are present in overall yields of
>93%, preferably >96%, particularly preferably >98%, of
the theoretical yield. According to the OECD 301 E test, the
biodegradation of the products after 28 days is more than 70%,
generally more than 72%, frequently more than 74%. Thus, e.g., the
IDA(NH.sub.4).sub.3 salt is 90% degraded after just 28 days. In the
OECD 302 B test, the IDAK.sub.2NH.sub.4 salt is 99% degraded after
just 14 days and the IDA(NH.sub.4).sub.3 salt is 97% degraded after
14 days.
[0033] According to the invention, the carboxyl groups of the
iminodisuccinic acid and of its byproducts are, depending on the
amount of ammonia introduced, particularly preferably in the
ammonium salt form. According to the amount of the alkali metal
hydroxide introduced in the first stage, iminodisuccinic acid
ammonium salts with sodium, lithium or potassium components are
obtained, for example. The preferred intermediates of the first
stage according to the invention are iminodisuccinic acid ammonium
salts of the formula 1 ##STR2## in which X represents OLi, ONa, OK,
OH or ONH.sub.4, preferably ONa, OK, OH or ONH.sub.4. In the
preferred form, the groups have the following molar ratio with
respect to one another: ONa:OK:OH:ONH.sub.4=0-3:0-3:0-2:0.1-4,
preferably 0-2.5:0-2.5:0-1.5:0.5-3.5, particularly preferably
0-2.2:0-2.2:0-1.2:0.8-3.2. For the byproducts according to the
invention, the molar ratios ensue corresponding to the number of
their carboxyl groups.
[0034] If the iminodisuccinic acid anion is denoted by IDA, the
iminodisuccinic acid ammonium salts according to the invention in
the preferred form can also be described by the formula 6:
IDA(NH.sub.4).sub.x(Na).sub.y(K).sub.z(H).sub.m Formula 6 with
x=0.1-4, y=0-3, z=0-3 and m=0-2, preferably x=0.5-3.5, y=0-2.5,
z=0-2.5 and m=0-1.5, particularly preferably x=0.8-3.2, y=0-2.2,
z=0-2.2 and m=0-1.2.
[0035] In particular embodiments, the particularly preferred
intermediates according to the invention or their mixtures are
obtained:
[0036] IDA(NH.sub.4).sub.3K, IDA(NH.sub.4).sub.2K.sub.2,
IDA(NH.sub.4)K.sub.2H, IDA(NH.sub.4).sub.2 KH and
IDA(NH.sub.4)K.sub.3 or IDA(NH.sub.4).sub.3Na,
IDA(NH.sub.4).sub.2Na.sub.2, IDA(NH.sub.4)Na.sub.2H,
IDA(NH.sub.4).sub.2NaH and IDA(NH.sub.4)Na.sub.3 or
IDA(NH.sub.4).sub.3H and IDA(NH.sub.4).sub.2H.sub.2. In principle,
IDA(NH.sub.4).sub.4 can also be prepared in this way. These
intermediates of formula 6 which can be prepared according to the
present invention can be applied in the area of photography.
Alkali-free iminodisuccinic acid ammonium salts are preferably
used, particularly preferably IDA(NH.sub.4).sub.3H,
IDA(NH.sub.4).sub.2H.sub.2 and IDA(NH.sub.4).sub.4.
[0037] Alkali-free iminodisuccinic acid ammonium salts of the
formula 7 IDA(NH.sub.4).sub.x(H).sub.y Formula 7 with x=2-4 and
y=0-2, preferably with x=2.5-3.5 and y=0.5-1.5, particularly
preferably with x=2.75-3.25 and y=0.75-1.25, are particularly
preferred according to the invention for the reaction in the second
stage. The iminodisuccinic acid triammonium salt according to
formula 7 with x=3 and y=1 is very particularly preferred according
to the invention.
[0038] In the second stage of the process according to the
invention, the iminodisuccinic acid ammonium salts of formula 6 or
formula 7, prepared with or without workup, are reacted with metal
oxides, metal hydroxides or other metal salts in aqueous solution
to give the iminodisuccinic acid ammonium metal salts according to
the invention of formula 8
IDA(NH.sub.4).sub.x(Na).sub.y(K).sub.z(Me).sub.m.(NH.sub.3).sub.n
Formula 8 in which x=0.1-3.9, y=0-3, z=0-3, m=0.1-2 and n=0-6,
preferably with x=0.1-3, y=0-2.5, z=0-2.5, m=0.4-1.8 and n=0-4,
particularly preferably with x=0.1-2, y=0-2.2, z=0-2.2, m=0.43-1.7
and n=0-3 and very particularly preferably with x=0.5-2, y=0, z=0
or 2, m=0.43-1.6 and n=0-2.5, and Me represents metals of the IInd,
IIIrd and IVth main groups and of the Ist to VIIIth subgroups as
well as metals of the lanthanide series of the Periodic Table,
which can occur in the oxidation states 1, 2, 3 or 4 and are
preferably in the oxidation states 2 and 3, with the exception of
the S,S isomers of the Mg and Ca iminodisuccinic acid ammonium
metal salts. Me preferably represents the metals Mg, Ca, Sr, Ba,
Ti, Zr, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Ag, Zn, Cd, Al, Sn, Pb, La
or Ce and particularly preferably the metals Mg, Ca, Ti, Zr, Cr,
Mo, Mn, Fe, Co, Ni, Cu, Zn, Cd, Al, Pb and Ce. In a very
particularly preferable way, Me represents the metals Ti, Zr, Cr,
Mo, Co, Ni, Cd, Al, Pb and Ce.
[0039] The ammonia represented in the formula 8 with
(NH.sub.3).sub.n can exist in the free form, in the complexed form
or as ammonium salt with the anions which are introduced into the
product solution when using metal salts.
[0040] In a practical embodiment, the iminodisuccinic acid ammonium
salt solutions prepared in the first stage are converted with metal
oxides, metal hydroxides or other metal salts or their mixtures, as
well as with the addition of further water and optionally with the
removal by distillation of aqueous ammonia, to the iminodisuccinic
acid ammonium metal salts according to the invention. The addition
can be carried out continuously or portion-wise at temperatures of
10-140.degree. C., preferably at 15-120.degree. C. and particularly
preferably at 20-100.degree. C., over the course of 0.1-100 h,
preferably 0.2-50 h, particularly preferably over the course of
0.5-25 h. The rate of addition is limited by the ability of the
reaction mixture to be stirred.
[0041] The metal oxides, metal hydroxides or other metal salts or
their mixtures can be added as solids, suspensions, dispersions,
slurries or solutions. Auxiliaries, such as, e.g., polycarboxylic
acids or polysulphonic acids, which can function as dispersing
agents or threshold inhibitors, can be used with them.
[0042] Environmentally friendly, biodegradable polycarboxylic
acids, such as, e.g., polyamino acids, are preferred; polyaspartic
acids are particularly preferred.
[0043] Alkyl- and arylamines can be added in the second reaction
stage as auxiliaries for additional complexing of the metal ions.
Alkylamines in which the amino group can be mono-, di- or
trisubstituted are preferably used. Mono-, di-, tri- and polyamines
can be used as alkylamines. Ethanolamine, diethanolamine,
triethanolamine, ethylenediamine or aminosaccharides are examples.
Biodegradable amines are preferably used. Alcohols, e.g. alkanols,
diols, triols or polyols, can be used as additional auxiliaries.
Biodegradable alcohols, e.g. ethylene glycol, can preferably be
used.
[0044] Metal oxides to be used according to the invention in stage
2 of the process are, e.g., MgO, CaO, TiO, Ti.sub.2O.sub.3,
TiO.sub.2, ZrO.sub.2, chromium(III) oxide, MnO, Mn.sub.2O.sub.3,
MnO.sub.2, iron(II) oxide, iron(III) oxide, cobalt(II) oxide,
copper(II) oxide, zinc oxide, cadmium oxide and cerium(IV) oxide.
Use may be made of metal hydroxides, such as Mg(OH).sub.2,
Ca(OH).sub.2, Zr(OH).sub.4, freshly precipitated basic iron oxide,
cobalt(II) hydroxide, nickel(II) hydroxide, basic copper(II)
carbonate, copper(II) hydroxide, basic copper(II) phosphate, basic
zinc carbonate, cadmium hydroxide, aluminium hydroxide,
lanthanum(III) hydroxide and cerium(IV) hydroxide. The other metal
salts are salts of inorganic and organic acids, such as, e.g.,
halides, sulphates, nitrates, phosphates, chlorates, perchlorates,
carbonates, acetates, formates, gluconates, oxalates, sulphonates
and citrates. Use is preferably made of MgCl.sub.2, CaCl.sub.2,
zirconium acetate, basic zirconium (IV) acetate, zirconium(IV)
citrate, zirconium(IV) hydrogenphosphate, chromium(II) acetate
hydrate, basic chromium(III) acetate, chromium(III) chloride,
chromium(III) nitrate, chromium(III) sulphate, manganese(II)
acetate, manganese(II) chloride, manganese(II) nitrate,
manganese(II) sulphate, iron(II) acetate, iron(II) chloride,
iron(III) chloride, iron(III) citrate, iron(III) pyrophosphate
hydrate, iron(III) nitrate, iron(III) oxalate, iron(II)
D-gluconate, iron(III) perchlorate, iron(III) phosphate, iron(II)
sulphate, iron(III) sulphate, iron(III) p-toluenesulphonate,
cobalt(II) acetate, cobalt(II) carbonate, cobalt(II) chloride,
cobalt(II) nitrate, cobalt(II) oxalate, cobalt(II) sulphate,
nickel(II) acetate, nickel(II) chloride, nickel(II) nitrate,
nickel(II) oxalate, nickel(II) perchlorate, nickel(II) sulphate,
copper(I) acetate, copper(II) acetate, copper(I) chloride,
copper(II) chloride, copper(II) nitrate, copper(II) perchlorate,
copper(II) sulphate, silver acetate, silver nitrate, silver
perchlorate, zinc acetate, zinc chloride, zinc citrate, zinc
nitrate, zinc perchlorate, zinc sulphate, cadmium acetate, cadmium
carbonate, cadmium chloride, cadmium nitrate, cadmium perchlorate,
cadmium sulphate, basic aluminium acetate, aluminium chloride,
aluminium nitrate, aluminium sulphate, tin(II) acetate, tin(II)
chloride, tin(II) methanesulphonate, tin(II) sulphate, tin(IV)
sulphate, basic lead(II) acetate, basic lead(II) carbonate,
lead(II) nitrate, lead(II) perchlorate, lanthanum(III) acetate,
lanthanum(III) carbonate, lanthanum(III) chloride, lanthanum(III)
nitrate, lanthanum(III) sulphate, lanthanum(III) perchlorate,
lanthanum(III) triflate, cerium(IV) ammonium sulphate, cerium(IV)
ammonium nitrate, cerium(IV) perchlorate and cerium(IV) sulphate.
All compounds mentioned can be used separately or as mixtures.
[0045] After the addition of the oxides, hydroxides or salts,
stirring is carried out at temperatures of 10-140.degree. C.,
preferably at 15-120.degree. C. and particularly preferably at
20-100.degree. C., over the course of 0.1-100 h, preferably 0.2-50
h, particularly preferably over the course of 0.5-25 h. Aqueous
ammonia can be distilled off during the addition or during the
stirring period. Adjustment to a suitable concentration of, e.g.,
more than 10 weight %, preferably more than 20 weight %,
particularly preferably more than 30 weight %, or to a suitable pH
is achieved through addition of water or aqueous ammonia. If
undissolved components have remained, these can be filtered off.
Use is preferably made of metal oxides, metal hydroxides or other
metal salts or their mixtures for which only a clarifying
filtration is necessary in this process stage. The solutions
prepared according to the invention, which can also include free
ammonia, can subsequently be dried, for example spray-dried.
Products with a solids content of more than 75 weight %, preferably
more than 80 weight %, particularly preferably more than 85 weight
%, are thereby produced.
[0046] The present invention also relates to the iminodisuccinic
acid ammonium metal salts of the formula 8
IDA(NH.sub.4).sub.x(Na).sub.y(K).sub.z(Me).sub.m.(NH.sub.3).sub.n
Formula 8 in which x=0.1-3.9, y=0-3, z=0-3, m=0.1-2 and n=0-6,
preferably with x=0.1-3, y=0-2.5, z=0-2.5, m=0.4-1.8 and n=0-4,
particularly preferably with x=0.1-2, y=0-2.2, z=0-2.2, m=0.43-1.7
and n=0-3 and very particularly preferably with x=0.5-2, y=0, z=0
or 2, m=0.43-1.6 and n=0-2.5, and Me represents metals of the IInd,
IIIrd and IVth main groups and of the Ist to VIIIth subgroups as
well as metals of the lanthanide series of the Periodic Table,
which can occur in the oxidation states 1, 2, 3 or 4 and are
preferably in the oxidation states 2 and 3, with the exception of
the S,S isomers of the Mg and Ca iminodisuccinic acid ammonium
metal salts.
[0047] The invention relates preferably to compounds of the formula
8 in which x, y, z, m and n have the above-mentioned meanings and
Me represents the metals Mg, Ca, Sr, Ba, Ti, Zr, Cr, Mo, W, Mn, Fe,
Co, Ni, Cu, Ag, Zn, Cd, Al, Sn, Pb, La or Ce and particularly
preferably the metals Mg, Ca, Ti, Zr, Cr, Mo, Mn, Fe, Co, Ni, Cu,
Zn, Cd, Al, Pb and Ce, with the exception of the S,S isomers of the
Mg and Ca iminodisuccinic acid ammonium metal salts. In a very
particularly preferred embodiment, Me represents the metals Ti, Zr,
Cr, Mo, Ni, Cd, Al and Pb.
[0048] The iminodisuccinic acid ammonium metal salt solutions or
solids prepared according to the invention in the second stage are
of the following composition: iminodisuccinic acid ammonium metal
salts (formula 8) as a mixture of the stereoisomers (S,S-IDA,
R,R-IDA and R,S-IDA) in yields of >65%, preferably >70%,
particularly preferably >74%, of the theoretical yield. The
combined byproducts and their salts are present in amounts of
<35%, preferably <30%, particularly preferably <26%, of
the theoretical amounts, in which maleic acid and its salts are
present with <7%, preferably <5%, particularly preferably
<2%, of the theoretical amount, fumaric acid and its salts are
present with <20%, preferably <15%, particularly preferably
<10%, of the theoretical amount, malic acid, as a mixture of the
stereoisomers (R- and S-malic acid), and its salts are present with
<7%, preferably <5%, particularly preferably <3%, of the
theoretical amount and aspartic acid, as a mixture of the
stereoisomers (R- and S-aspartic acid), and its salts are present
with <25%, preferably <20%, particularly preferably <15%,
of the theoretical amount.
[0049] The products are surprisingly also biodegradable and for
that reason highly advantageous environmentally. In the
Zahn-Wellens test, OECD 302 B, the
IDAK.sub.2Zn.sub.0.5(NH.sub.4).sub.0.5 salt (Example 23) was 98%
degraded after just 14 days and the
IDAK.sub.2Cu.sub.0.43(NH.sub.4).sub.0.58 salt (Example 24) was 99%
degraded after 28 days.
[0050] The products described can be used in all fields of
application in which it is necessary to increase the availability
of trace elements or metal ions, e.g. in agriculture or gardening,
as trace element fertilizers or slug and snail pellets, or in the
ceramics industry, for surface colouring.
[0051] In fields of application in which water represents a
fundamental medium, a great many metal ions form insoluble metal
salts and are thus in reality unavailable for use. Upn addition of
simple inorganic or organic water-soluble salts, the metal ions
would in this way not reach their intended site of action. For
example, it would not be possible to use the trace elements for
plants and the chromophoric metal ions would not be able to
penetrate deeply enough into ceramic material.
[0052] With the help of complexing agents, success is now achieved
in preventing the formation of insoluble metal salts and in
bringing the required metal ions to their site of action. The
compounds used to date are predominantly strong complexing agents
which are not biodegradable or are biodegradable with difficulty,
which complexing agents, on the one hand, actually almost
completely prevent the formation of insoluble metal salts but, on
the other hand, also partially limit the availability, e.g. of
trace elements, through the strong complexing.
[0053] The availability of metal ions, for example of the trace
elements Mg, Ca, Mn, Cu, Fe and Zn as trace element fertilizers, is
now increased through the use of the iminodisuccinic acid ammonium
metal salts according to the invention. These salts are now also
available for use in the field of ceramics as metal ion carriers in
the preparation of ceramics or glazings. In addition, the new salts
are biodegradable and accordingly more environmentally friendly
than the products to date. In biological applications, the anion
can even serve additionally as nutrient source, partially as a
result of the degradation. An additional advantage is that the
intermediate degradation products are aspartic acid and fumaric
acid, two naturally occurring compounds.
[0054] Sodium-poor mixed salts are suitable as particularly
preferred trace element fertilizers based on the iminodisuccinic
acid ammonium salts.
[0055] In the last decade, the colouring of tile fragments made of
gres porcellanato with concentrated aqueous solutions of heavy
metals has increased in importance. In the course of this, the
fragments are sprayed or coated on the surface with the metal salt
solution or the entire body is dipped in the solution, subsequently
dried and fired. As a result of the firing, the metal complexes are
converted to the corresponding coloured oxides.
[0056] The preparation of the most concentrated possible,
sulphate-, nitrate- and chloride-free, solutions is important for
the process-(no corrosive discharge gases during the firing). A
further requirement is the high capability of penetration of the
metal salt solutions, which shows this in particular for gres
porcellanato tiles, since these are polished after firing (marble
effect). The iminodisuccinic acid metal salts according to the
invention make available in solution satisfactory amounts of heavy
metal down into the relatively deep layers of these tiles.
[0057] The iminodisuccinic acid ammonium salts according to the
invention of the formulae 6 and 7, in particular the
iminodisuccinic acid triammonium salts, surprisingly prove to be
essentially ideal for this application, since chromophoric heavy
metals (cobalt, nickel, iron, copper, chromium) can be held well
complexed and in high concentration in solution, without chloride,
nitrate and the like having to be available as counterion.
[0058] The invention is further illustrated but is not intended to
be limited by the following examples in which all parts and
percentages are by weight unless otherwise specified.
EXAMPLES
[0059] Preparation of Iminodisuccinic Acid Ammonium Salts
Example 1
[0060] MA:NH.sub.3:H.sub.2O molar ratio=2:4:9, 90.degree. C., 30
h
[0061] 1 782 g=99 mol of water are introduced and heated to
80.degree. C. 2 157.3 g=22 mol of maleic anhydride are added at
80-100.degree. C. with stirring and cooling. After the maleic
anhydride has gone into solution, the mixture is stirred for a
further 0.5 h approximately. Subsequently, 748 g=44 mol of ammonia
are introduced at >90.degree. C. After the introduction of
ammonia has ended, the reaction mixture is stirred at 90.degree. C.
for more than 30 h, diluted with 1 312.7 g=72.93 mol of water and
cooled to ambient temperature. After a clarifying filtration, which
is optionally carried out, 6 000 g of product solution are obtained
with the following yields: 80.0% of theory iminodisuccinic acid
ammonium salt, 14.6% of theory aspartic acid ammonium salt, 2.5% of
theory fumaric acid ammonium salt, 0.6% of theory malic acid
ammonium salt and 0.4% of theory maleic acid ammonium salt. The
solids content (=.SIGMA. ammonium salts) is 55 weight %. The clear
light-yellow solution has a density of 1.242 kg/litre and a pH of
7.3.
Example 2
[0062] MA:NH.sub.3:H.sub.2O molar ratio=2:4:9, 90.degree. C., 24
h
[0063] Implementation and amounts of this example correspond to
those of Example 1. The reaction time is 24 h. The following yields
are obtained: 77.9% of theory iminodisuccinic acid ammonium salt,
12.8% of theory aspartic acid ammonium salt, 3.0% of theory fumaric
acid ammonium salt, 1.0% of theory malic acid ammonium salt and
3.4% of theory maleic acid ammonium salt.
Example 3
[0064] MA:NH.sub.3:H.sub.2O molar ratio=2:4:9, 90.degree. C., 36
h
[0065] Implementation and amounts of this example correspond to
those of Example 1. The reaction time is 36 h. The following yields
are obtained: 80.1% of theory iminodisuccinic acid ammonium salt,
15.0% of theory aspartic acid ammonium salt, 3.3% of theory fumaric
acid ammonium salt, 1.1% of theory malic acid ammonium salt and
0.6% of theory maleic acid ammonium salt. The solids content
(=.SIGMA. ammonium salts) is 55 weight %. The clear light-yellow
solution has a density of 1.243 kg/litre and a pH of 7.03.
Example 4
[0066] MA:NH.sub.3:H.sub.2O molar ratio=2:4:10, 80.degree. C., 96
h
[0067] Water, maleic anhydride and ammonia are mixed together in
the molar ratio 10:2:4, as in Example 1. The reaction time is 96 h
at 80.degree. C. After diluting and optionally carrying out a
clarifying filtration, iminodisuccinic acid ammonium salt is
obtained with a yield of 82.5% of theory.
Example 5
[0068] MA:NH.sub.3:H.sub.2O molar ratio=2:4:10, 100.degree. C., 9
h
[0069] Water, maleic anhydride and ammonia are mixed together in
the molar ratio 10:2:4, as in Example 1. The reaction time is 9 h
at 100.degree. C. After diluting and optionally carrying out a
clarifying filtration, iminodisuccinic acid ammonium salt is
obtained with a yield of 77.8% of theory.
Example 6
[0070] MA:NH.sub.3:H.sub.2O molar ratio=2:4:10, 110.degree. C., 4
h
[0071] Water, maleic anhydride and ammonia are mixed together in
the molar ratio 10:2:4, as in Example 1. The reaction time is 4 h
at 110.degree. C. After diluting and optionally carrying out a
clarifying filtration, iminodisuccinic acid ammonium salt is
obtained with a yield of 76.9% of theory.
Example 7
[0072] MA:NH.sub.3:H.sub.2O molar ratio=2:4:10, 120.degree. C., 2
h
[0073] Water, maleic anhydride and ammonia are mixed together in
the molar ratio 10:2:4, as in Example 1. The reaction time is 2 h
at 120.degree. C. After diluting and optionally carrying out a
clarifying filtration, iminodisuccinic acid ammonium salt is
obtained with a yield of 67.9% of theory.
Example 8
[0074] MA:NH.sub.3:H.sub.2O molar ratio=2:4:8, 80.degree. C., 72
h
[0075] Water, maleic anhydride and ammonia are mixed together in
the molar ratio 8:2:4, as in Example 1. The reaction time is 72 h
at 80.degree. C. After diluting and optionally carrying out a
clarifying filtration, iminodisuccinic acid ammonium salt is
obtained with a yield of 82.7% of theory.
Example 9
[0076] MA:NH.sub.3:H.sub.2O molar ratio=2:4:6, 80.degree. C., 60
h
[0077] Water, maleic anhydride and ammonia are mixed together in
the molar ratio 6:2:4, as in Example 1. The reaction time is 60 h
at 80.degree. C. After diluting and optionally carrying out a
clarifying filtration, iminodisuccinic acid ammonium salt is
obtained with a yield of 82.2% of theory.
Example 10
[0078] MA:NH.sub.3:H.sub.2O molar ratio=2:4:6, 120.degree. C., 1
h
[0079] Water, maleic anhydride and ammonia are mixed together in
the molar ratio 6:2:4, as in Example 1. The reaction time is 1 h at
120.degree. C. After diluting and optionally carrying out a
clarifying filtration, iminodisuccinic acid ammonium salt is
obtained with a yield of 71.9% of theory.
Example 11
[0080] MA:NH.sub.3:H.sub.2O molar ratio=2:6:10, 80.degree. C., 54
h
[0081] Water, maleic anhydride and ammonia are mixed together in
the molar ratio 10:2:6, as in Example 1. The reaction time is 54 h
at 80.degree. C. After diluting and optionally carrying out a
clarifying filtration, iminodisuccinic acid ammonium salt is
obtained with a yield of 79.0% of theory.
Example 12
[0082] MA:NH.sub.3:H.sub.2O molar ratio=2:6:10, 110.degree. C., 2
h
[0083] Water, maleic anhydride and ammonia are mixed together in
the molar ratio 10:2:6, as in Example 1. The reaction time is 2 h
at 110.degree. C. After diluting and optionally carrying out a
clarifying filtration, iminodisuccinic acid ammonium salt is
obtained with a yield of 69.1% of theory.
Example 13
[0084] MA:NH.sub.3:H.sub.2O molar ratio=2:6:8, 80.degree. C., 42
h
[0085] Water, maleic anhydride and ammonia are mixed together in
the molar ratio 8:2:6, as in Example 1. The reaction time is 42 h
at 80.degree. C. After diluting and optionally carrying out a
clarifying filtration, iminodisuccinic acid ammonium salt is
obtained with a yield of 77.3% of theory.
Example 14
[0086] MA:NH.sub.3:H.sub.2O molar ratio=2:6:6, 120.degree. C., 1
h.
[0087] Water, maleic anhydride and ammonia are mixed together in
the molar ratio 6:2:6, as in Example 1. The reaction time is 1 h at
120.degree. C. After diluting and optionally carrying out a
clarifying filtration, iminodisuccinic acid ammonium salt is
obtained with a yield of 61.0% of theory.
Example 15
[0088] MA:KOH:NH.sub.3:H.sub.2O molar ratio=2:2:2.3:10, 110.degree.
C., 8 h.
[0089] 679.8 g=37.73 mol of water are introduced and heated to
80.degree. C. Subsequently, 1 961.2 g=20 mol of MA, as a melt, and
2 244.4 g=20 mol of KOH, as a 50% solution, are metered in
simultaneously at 95-105.degree. C. over the course of 4 h. After
the addition of 391.7 g=23 mol of ammonia, which is carried out at
90-105.degree. C., the reaction mixture is stirred at 110.degree.
C. under pressure for 8 h. 5 277.1 g of reaction mixture are
obtained, which can be used directly for the formation of the
iminodisuccinic acid ammonium metal salts.
Example 16
[0090] 200 g of water are added to the 5 277.1 g of reaction
mixture from Example 15 and 230 g of aqueous ammonia are distilled
off at 95-112.degree. C. Subsequently, the mixture is adjusted to
pH 7.5 with aqueous ammonia and made up with water to 5 863 g=4
248.6 ml. After a clarifying filtration at 20-40.degree. C., an
iminodisuccinic acid K.sub.2 NH.sub.4 salt solution with a solids
content of 58.4 weight % is obtained. The following yields were
found: 79.7% of theory IDAK.sub.2NH.sub.4 salt, 14.5% of theory
aspartic acid potassium ammonium salt, 4.4% of theory fumaric acid
potassium ammonium salt, 0.7% of theory maleic acid potassium
ammonium salt and 0.2% of theory malic acid potassium ammonium
salt.
Conversion to Iminodisuccinic Acid Ammonium Metal Salts
Example 17
[0091] Preparation of Iminodisuccinic Acid Zn NH.sub.4 Salt
[0092] 545.5 g of product solution from Example 1 are introduced
and heated to 60.degree. C. 81.4 g of 100% ZnO=1 mol of zinc oxide
are added in 10 portions each of 8.14 g. After a total of 2.5 h,
all the zinc oxide has dissolved. 626.9 g of a clear light-yellow
solution are obtained, which solution is also stable on storage at
1.degree. C. The following values are determined: pH=7.8 at
23.degree. C. TABLE-US-00001 Calculated Found C 15.3% 15.5% N 8.93%
9.0% Zn 10.4% 9.9%
[0093] This corresponds to a compound of the formula
IDA(NH.sub.4).sub.2Na.sub.0K.sub.0Zn.sub.1.(NH.sub.3).sub.1.
[0094] Drying this solution at 40-80.degree. C. yielded a solid
with the following values: C.sub.fd=22.6 weight %, N.sub.fd=12.4
weight %. This corresponds to a compound of the formula
IDA(NH.sub.4).sub.2Na.sub.0K.sub.0Zn.sub.1.(NH.sub.3).sub.0.76.
Example 18
[0095] Preparation of Iminodisuccinic Acid Cu NH.sub.4 Salt
[0096] 545.5 g of the product solution from Example 1 are
introduced and heated to 35.degree. C. 113.5 g of 86%
Cu(OH).sub.2=1 mol of copper hydroxide are added in 10 portions of
11.35 g at 35-50.degree. C. After 1 h, all the copper hydroxide has
dissolved. 659 g of a deep-blue solution are obtained, which
solution is stable on storage at 1.degree. C. The following values
are determined: pH=7.1 at 23.degree. C. TABLE-US-00002 Calculated
Found C 14.6% 14.5% N 8.5% 8.3% Cu 9.6% 9.8%
[0097] This corresponds to a compound of the formula
IDA(NH.sub.4).sub.2Na.sub.0K.sub.0Cu.sub.1.(NH.sub.3).sub.1. The
solution can be dried at 40-80.degree. C. A solid is obtained with
the following values: C.sub.fd=22.5 weight %, N.sub.fd=12.5 weight
%. This corresponds to a compound of the formula
IDA(NH.sub.4).sub.2Na.sub.0K.sub.0Cu.sub.1.(NH.sub.3).sub.0.8.
Example 19
[0098] Preparation of Iminodisuccinic Acid Mg NH.sub.4 Salt
[0099] 545.5 g of product solution from Example 1 are introduced
and heated to 40.degree. C. 61.4 g of 95% Mg(OH).sub.2=1 mol of
magnesium hydroxide are added in 10 portions of 6.14 g at
40-80.degree. C. After 4 h, the magnesium hydroxide has almost
completely dissolved with slight evolution of ammonia. The slightly
cloudy solution is stirred for a further approximately 4 h at
80.degree. C. and 1 h at 90.degree. C. After a clarifying
filtration, 590 g of an almost colourless solution are obtained,
which solution is stable on storage at 20.degree. C. The following
values are determined: pH=9.2 at 24.degree. C. TABLE-US-00003
Calculated Found C 15.8% 16.4% N 9.2% 7.9% Mg 4.0% 3.9%
[0100] This corresponds to a compound of the formula
IDA(NH.sub.4).sub.2Na.sub.0K.sub.0Mg.sub.1.(NH.sub.3).sub.1. The
solution can be dried at 40-80.degree. C. A solid is obtained with
the following values: C.sub.fd=26.4 weight %, N.sub.fd=10.7 weight
%. This corresponds to a compound of the formula
IDA(NH.sub.4).sub.1.78Na.sub.0K.sub.0Mg.sub.1.(NH.sub.3).sub.0.
Example 20
[0101] Preparation of Iminodisuccinic Acid Ca NH.sub.4 Salt
[0102] 545.5 g of product solution from Example 1 are introduced
and heated to 60.degree. C. 77.2 g of 96% Ca(OH).sub.2=1 mol of
calcium hydroxide are added in 10 portions of 7.72 g at
approximately 60-65.degree. C. After 8 portions and approximately
2.5 h, an almost clear solution is present. After a further 2
portions and approximately 3 h, a cloudy solution is obtained.
After a clarifying filtration, 605 g of an almost colourless
solution are obtained, which solution is stable on storage at
20.degree. C. The following values are determined. pH=9.7 at
24.degree. C. TABLE-US-00004 Calculated Found C 15.4% 15.8% N 9.0%
8.1% Ca 6.4% 6.2%
[0103] This corresponds to a compound of the formula
IDA(NH.sub.4).sub.2Na.sub.0K.sub.0Ca.sub.1.(NH.sub.3).sub.1. The
solution can be dried at 40-80.degree. C. A solid is obtained with
the following values: C.sub.fd=26.6 weight %, N.sub.fd=10.0 weight
%. This corresponds to a compound of the formula
IDA(NH.sub.4).sub.1.58Na.sub.0K.sub.0Ca.sub.1.(NH.sub.3).sub.0.
Example 21
[0104] Preparation of Iminodisuccinic Acid Mn NH.sub.4 Salt
[0105] 545.5 g of product solution from Example 1 are introduced
and heated to 60.degree. C. 258 g of (CH.sub.3CO.sub.2).sub.2
Mn.2H.sub.2O=1 mol of manganese acetate dihydrate are added in 2
portions of 129 g at 60.degree. C. After approximately 3 h, the
manganese acetate dihydrate has dissolved. After a clarifying
filtration, 785 g of a clear solution are obtained, which solution
is stable on storage at 20.degree. C. The following values are
determined: pH=5.5 at 24.degree. C. TABLE-US-00005 Calculated Found
C 18.3% 18.5% N 7.0% 7.0% Mn 6.8% 6.7%
[0106] This corresponds to a compound of the formula
IDA(NH.sub.4).sub.2Na.sub.0K.sub.0Mn.sub.1.(NH.sub.3).sub.1. The
solution can be dried at 40-80.degree. C. A solid is obtained with
the following values: C.sub.fd=25.4 weight %, N.sub.fd=9.9 weight
%. This corresponds to a compound of the formula
IDA(NH.sub.4).sub.2Na.sub.0K.sub.0Mn.sub.1.(NH.sub.3).sub.1. The
excess ammonia is present in this case as ammonium acetate.
Example 22
[0107] Preparation of Iminodisuccinic Acid Zn NH.sub.4 Salt
[0108] 545.5 g of product solution from Example 1 are introduced
and heated to 60.degree. C. 130.24 g of ZnO=1.6 mol of zinc oxide
are added in 16 portions of 8.14 g at 60-70.degree. C. After
approximately 4.5 h, the zinc oxide has dissolved, after the
temperature had been briefly raised to 80.degree. C. After a
clarifying filtration, 663 g of a clear solution are obtained,
which solution is stable on storage at 20.degree. C. The following
values are determined: TABLE-US-00006 Calculated Found C 14.2%
14.6% N 8.3% 8.3% Zn 15.5% 15.0%
[0109] This corresponds to a compound of the formula
IDA(NH.sub.4).sub.0.8Na.sub.0K.sub.0Zn.sub.1.6.(NH.sub.3).sub.2.2.
The solution can be dried at 40-80.degree. C. A solid is obtained
with the following values: C.sub.fd=21.3 weight %, N.sub.fd=11.9
weight %. This corresponds to a compound of the formula
IDA(NH.sub.4).sub.0.8Na.sub.0K.sub.0Zn.sub.1.6.(NH.sub.3).sub.2.03.
Example 23
[0110] Preparation of
IDA(NH.sub.4).sub.0.5Na.sub.0K.sub.2Zn.sub.0.5.(NH.sub.3).sub.0
Salt
[0111] 527.7 g=1 mol of iminodisuccinic acid K.sub.2
(NH.sub.4).sub.1.3 crude product from Example 15 are introduced and
heated to 50.degree. C. 40.7 g=0.5 mol of zinc oxide are added
portionwise. A total of 500 g of aqueous ammonia, comprising 13.6 g
of ammonia, are distilled off at 80-115.degree. C. from the cloudy
yellow solution comprising the
IDA(NH.sub.4).sub.1Na.sub.0K.sub.2Zn.sub.0.5.(NH.sub.3).sub.0.3.
During the distillation, a corresponding amount of water is
readded. After the distillation, the mixture is made up to 595.2 g
with water. After a clarifying filtration, a clear solution is
obtained, which solution is stable on storage at 1.degree. C. over
several weeks.
Example 24
[0112] Preparation of
IDA(NH.sub.4).sub.0.58Na.sub.0K.sub.2Cu.sub.0.43.(NH.sub.3).sub.0
Salt
[0113] 527.7 g=1 mol of iminodisuccinic acid K.sub.2
(NH.sub.4).sub.1.3 crude product from Example 15 are introduced and
heated to 60.degree. C. 48.8 g of 86% Cu(OH).sub.2=0.43 mol of
copper hydroxide are added in 5 portions of 9.76 g at 60.degree. C.
A total of 300 g of aqueous ammonia, comprising 12.17 g of ammonia,
are distilled off at 80-115.degree. C. from the cloudy blue
solution comprising the
IDA(NH.sub.4).sub.1.14Na.sub.0K.sub.2Cu.sub.0.43.(NH.sub.3).sub.0.16
salt. During the distillation, a corresponding amount of water is
readded. After the distillation, the mixture is made up to 593.6 g
with water. After a clarifying filtration, a clear solution is
obtained, which solution is stable on storage.
Further Examples
[0114] The following additional products can be prepared
analogously to formula
8=IDA(NH.sub.4).sub.x(Na).sub.y(K).sub.z(Me).sub.m.(NH.sub.3).sub-
.n: TABLE-US-00007 Example Me x y z m n 25 Al 1 0 0 1 2 26 Al 2.5 0
0 0.5 0.5 27 Cr 1 0 0 1 2 28 Cr 2.5 0 0 0.5 0.5 29 Fe.sup.II 2 0 0
1 1 30 Fe.sup.II 3 0 0 0.5 0 31 Fe.sup.III 1 0 0 1 2 32 Fe.sup.III
2.5 0 0 0.5 0.5 33 Co 2 0 0 1 1 34 Co 3 0 0 0.5 0 35 Ni 2 0 0 1 1
36 Ni 3 0 0 0.5 0 37 Ag 3 0 0 1 0 38 Ag 2 0 0 2 1 39 Cd 2 0 0 1 1
40 Cd 3 0 0 0.5 0 41 Pb 2 0 0 1 1 42 Pb 3 0 0 0.5 0 43 La 2 0 0 1 1
44 La 3 0 0 0.5 0
[0115] Although the invention has been described in detail in the
foregoing for the purpose of illustration, it is to be understood
that such detail is solely for that purpose and that variations can
be made therein by those skilled in the art without departing from
the spirit and scope of the invention except as it may be limited
by claims.
* * * * *