Note: Descriptions are shown in the official language in which they were submitted.
- CA 0223027~ 1998-02-24
W O 97/08287 PCTAUS96/13939
POLYAMINO MONOSUCCINIC ACID DERIVATIVE DEGRADABLE
CHELANTS, USES AND COMPOSITIONS THEREOF
This invention relates to chelants, particularly uses of certain
s degradable chelants.
.
Chelants or chelating agents are compounds which form
coordinate covalent bonds with a metal ion to form chelates. Chelates are
coordination compounds in which a central metal atom is bonded to two or
0 more other atoms in at least one other molecule (called ligand) such that at
least one heterocyclic ring is formed with the metal atom as part of each
ring.
Chelants are used in a variety of applications including food
1~ processing, soaps, detergents, cleaning products, personal care products,
pharmaceuticals, pulp and paper processing, gas conditioning, water
treatment, metalworking and metal plating solutions, textile processing
solutions, fertilizers, animal feeds, herbicides, rubber and polymer
chemistry, photofinishing, and oil field chemistry. Some of these activities
20 result in chelants entering the environment. For instance, agricultural uses
or detergent uses may result in measurable quantities of the chelants being
present in water. It is, therefore, desirable that chelants degrade after use.
Biodegradability, that is susceptibility to degradation by
2s microbes, is particularly useful because the microbes are generally naturallypresent in environments into which the chelants may be introduced.
Commonly used chelants like EDTA (ethylenediamine tetraacetic acid) are
biodegradable, but at rates somewhat slower and under conditions
considered by some to be less than optimum. (See, Tiedje, "Microbial
Degradation of Ethylenediaminetetraacetate in Soils and Sediments,"
Applied Microbiology, Aug. 1975, pp. 327-329.)
It would be desirable to have a chelant useful in areas such as
those mentioned above wherein such chelant is greater than about 60
35 percent biodegradable within less than 28 days according to the OECD
301 B Modified Sturm Test or greater than about 80 percent biodegraclable
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within less than 28 days according to the Semicontinuous Activated Sludge .
Test (ASTM D 2667 89).
It has been found that certain polyamino monosuccinic acid
5 compounds are excellent chelating agents for a variety of applications.
In one aspect, the invention includes methods of electroless
plating using various metals (especially copper) complexed with a mixture
of chelants comprising at least polyamino monosuccinic acids, or salts
0 thereof. The invention includes a method of electroless deposition of
copper upon a non-metallic surface receptive to the deposited copper
including a step of conlaclillg the non-metallic surface with an aqueous
solution comprising a soluble copper salt and a polyamino monosuccinic
acid. Also included is a method of electroless copper plating which
5 comprises immersing a receptive surface to be plated in an alkaline,
autocatalytic copper bath comprising water, a water soluble copper salt,
and a polyamino monosuccinic acid complexing agent for cupric ion.
Additionally, there is an improvement in a process for plating copper on
non-metallic surfaces, only selected portions of which have been pretreated
20 for the reception of electroless copper, by immersing the surface in an
autocatalytic alkaline aqueous solution comprising, in proportions capable
of effecting electroless deposition of copper, a water soluble copper salt, a
complexing agent for cupric ion, and a reducing agent for cupric ion, the
improvement comprising using as the complexing agent for cupric ion, a
2s polyamino monosuccinic acid. The invention includes a bath for the
electroless plating of copper which comprises water, a water soluble
copper salt, a polyamino monosuccinic acid complexing agent for cupric
ions, sufficient alkali metal hydroxide to result in a pH of from 10 to 14,
and a reducing agent.
Another aspect of the invention includes a method for
removing iron oxide deposits or organic stains from a surface including a
step of contacting the deposits or stains with a solution comprising a
polyamino monosuccinic acid.
3s
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WO 97/08287 PCT/US96/13939
Yet another aspect of the invention involves gas conditioning.
In this aspect the invention includes a process of removing H2S from a
fluid comprising contacting said fluid with an aqueous solution at a pH
suitable for removing H2S wherein said solution contains at least one
s higher valence polyvalent metal chelate of a polyamino monosuccinic acid.
Another aspect of the gas conditioning invention includes a process of
removing N0x from a fluid comprising contacting the fluid with an aqueous
solution of at least one lower valence state polyvalent metal chelate of a
polyamino monosuccinic acid.
The present invention is also to a laundry detergent
composition comprising (a) from 1% to 80% by weight of a detergent
surfactant selected from nonionic, anionic, cationic, zwitterionic, and
ampholytic surfactants and mixtures thereof; (b) from 5% to 80% by
1S weight of at least one detergent builder; and (c) from 0.1% to 15% by
weight of at least one polyamino monosuccinic acid or salt thereof.
The laundry detergent of the present invention may be a liquid
laundry detergent composition comprising (a) from 10% to 50% by weight
20 of a detergent surfactant selected from nonionic, anionic, cationic,
zwitterionic, and ampholytic surfactants and mixtures thereof; (b) from
10% to 40% by weight of at least one detergent builder; and (c) from
0.1 % to 10% by weight of at least one polyamino monosuccinic acid or
salt thereof.
2s
The laundry detergent of the present invention may also be a
granular laundry composition comprising comprising (a) from 5% to 50%
by weight of a detergent surfactant selected from nonionic, anionic,
cationic, zwitterionic, and ampholytic surfactants and mixtures thereof; (b)
30 from 10% to 40% by weight of at least one detergency builder; and (c)
from 0.1 % to 10% by weight of at least one polyamino monosuccinic acid
or salt thereof.
The above laundry compositions may be used in a process for
35 laundering fabrics comprising contacting the fabric with an aqueous
solution of any of the above laundry detergent compositions.
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In still another aspect, the present invention is to an automatic
dishwashing composition comprising (a) as least one polyamino
monosuccinic acid, or salt thereof; and (b~ a bleach active salt.
The present invention is also to a chelate composition
comprising a chelating agent and a metal wherein the chelating agent is a
polyamino monosuccinic acid and the metal is iron.
It has been unexpectedly found that polyamino monosuccinic
acids are excellent for use in electroless plating of metals, in removing iron
oxide stains, in removing organic stains from fabrics, in removing H2S from
fluids, and in removing N0x from fluids. The compounds are also
biodegradable as measured by the 301 B Modified Sturm Test or the
15 Semicontinuous Activated Sludge Test (ASTM D 2667 89).
Polyamino monosuccinic acids are compounds having at least
two nitrogen atoms to which a succinic acid (or salt) moiety is attached to
one of the nitrogen atoms. As used herein the term succinic acid includes
20 salts thereof. The compounds have at least 2 nitrogen atoms, and due to
the commercial availability of the amine, preferably have no more than
about 10 nitrogen atoms, more preferably no more than about 6, most
preferably 2 nitrogen atoms. The remaining nitrogen atoms may be
substituted with hydrogen, an alkyl, an alkylaryl, or an arylalkyl moiety.
2s The alkyl moiety may be linear or branched, saturated or unsaturated and
generally contains from 1 to 30 carbon atoms, preferably from 1 to 20
carbon atoms, and more preferably from 1 to 12 carbon atoms. The
arylalkyl or alkylaryl moiety generally contains from 6 to 18 carbon atoms
and preferably contains from 6 to 12 carbon atoms. The alkyl, arylalkyl, or
30 alkylaryl moieties may also be substituted with from 0 to 12 atoms other
than carbon, such as oxygen, sulfur, phosphorus, nitrogen, fluorine,
chlorine, bromine, iodine, hydrogen, or combinations thereof. Such
substitutions include carboxyalkyl, hydroxyalkyl, sulfonoalkyl,
phosphonoalkyl or alkylene hydroxamate groups.
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Although the succinic acid moiety may be attached to any of
the nitrogens, preferably the succinic acid group is attached to a terminal
nitrogen atom. By terminal it is meant the first or last nitrogen which is
present in the compound, irrespective of other substituents. The remaining
s bonds on the nitrogen having a succinic acid group are preferably bonded
to a second nitrogen through an alkyl or alkylene group and the remaining
bond of the nitrogen containing the succinic acid moiety is preferentially
filled by a hydrogen or an alkyl group, but most preferably hydrogen.
Generally the nitrogen atoms are linked by alkyl or alkylene groups, each of
from 2 to 12 carbon atoms, preferably from 2 to 10 carbon atoms, more
preferably from 2 to 8, and most preferabiy from 2 to 6 carbon atoms.
The polyamino monosuccinic acid compound preferably has at least about
6 carbon atoms and preferably has at most about 50, more preferably at
most about 40, and most preferably at most about 30 carbon atoms.
In one aspect of the present invention, when it is desired for
the polyamino monosuccinic acid to contain a metal ion binding moiety in
addition to the carboxyl groups of the succinic acid, it is desirable to place
such a functional group on a nitrogen atom to which the succinic acid
moiety is not bound. For example, when the polyamino monosuccinic acid
contains two nitrogen atoms which are joined by an ethylene moiety, it is
preferred that the nitrogen atom which is not bound to the succinic acid
moiety is substituted with at least one metal ion binding moiety. In another
aspect of the present invention, depending on the molecule to be made, for
ease of synthesis, the nitrogen atom or nitrogen atoms to which the
succinic acid moiety is not bound are generally substituted with hydrogen.
For example, when the polyamino monosuccinic acid contains two nitrogen
atoms joined by an ethylene moiety, it is preferred that the nitrogen atom
which is not bound to the succinic acid moiety is substituted with two
hydrogen atoms.
~ Polyamino monosuccinic acids useful in the present invention
include ethylenediamine-N-monosuccinic acid, diethylenetriamine-N-
monosuccinic acid, triethylenetell~nline-N-monosuccinic acid, 1,6-
hexamethylenediamine-N-monosuccinic acid, 2-hydroxypropylene-1,3-
diamine-N-monosuccinic acid, 1,2-propylenediamine-N-monosuccinic acid,
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W O 97/08287 PCTnJS96/13939
1,3-propylenediamine-N-monosuccinic acid, cis-cyclohexanediamine-N-
monosuccinic acid, trans-cyclohexanediamine-N-monosuccinic acid,
ethylene-bis(oxyethylenenitrilo)-N-monosuccinic acid, N-carboxymethyl-
ethylenediamine-N'-monosuccinic acid, N-carboxyethyl-ethylenediamine-N'-
s monosuccinic acid, N-methyl-ethylenediamine-N'-monosuccinic acid, N-
methyl-ethylenediamine-N-monosuccinic acid, N-phosphonomethyl-
ethylenediamine-N'-monosuccinic acid, N-sulfonomethyl-ethylenediamine-
N'-monosuccinic acid, N-hydroxyethyl-ethylenediamine-N'-monosuccinic
acid, N-hydroxypropyl-ethylenediamine-N'-monosuccinic acid, N-
o hydroxybutyl-ethylenediamine-N'-monosuccinic acid, N-sulfonomethyl-
ethylenediamine-N'-monosuccinic acid, N-2-hydroxy-3-sulfopropyl-
ethylenediamine-N'-monosuccinic acid, ethylenediamine-N-methylene
hydroxamate-N'-monosuccinic acid, N-carboxymethyl-diethylenetriamine-
N"-monosuccinic acid, N-hydroxyethyl-diethylenetriamine-N"-monosuccinic
acid, N-hydroxypropyl-diethylenetriamine-N"-monosuccinic acid, N-
carboxyethyl-diethylenetriamine-N"-monosuccinic acid, N-methyl-
diethylenetriamine-N"-monosuccinic acid, N-phosphonomethyl-
diethylenetriamine-N"-monosuccinic acid, N-sulfonomethyl-
diethylenetriamine-N "-monosuccinic acid, N-carboxymethyl- 1, 6-
hexamethylenediamine-N'-monosuccinic acid, N-carboxyethyl-1,6-
hexamethylenediamine-N '-monosuccinic acid, N-hydroxyethyl- 1, 6-
hexamethylenediamine-N '-monosuccinic acid, N-hydroxypropyl- 1, 6-
hexamethylenediamine-N'-monosuccinic acid, N-methyl-1 ,6-
hexamethylenediamine-N '-monosuccinic acid, N-phosphonomethyl- 1, 6-
hexamethylenediamine-N '-monosuccinic acid, N-sulfonomethyl- 1, 6-
hexamethylenediamine-N'-monosuccinic acid, N-carboxymethyl-2-
hydroxypropylene-1,3-diamino-N'-monosuccinic acid, N-carboxyethyl-2-
hydroxypropylene- 1, 3-diamino-N '-monosuccinic acid, N-hydroxyethyl-2-
hydroxypropylene-1,3-diamino-N'-monosuccinic acid, N-hydroxypropyl-2-
hydroxypropylene-1,3-diamino-N'-monosuccinic acid, N-methyl-2-
hydroxypropylene-1,3-diamino-N'-monosuccinic acid, N-phosphonomethyl-
2-hydroxypropylene- 1, 3-diamino-N ' -monosuccinic acid, N-sulfonomethyl-2-
hydroxypropylene- 1, 3-diamino-N '-monosuccinic acid, N-carboxymethyl- 1, 2-
propylenediamine-N'-monosuccinic acid, N-carboxyethyl-1,2-
propylenediamine-N'-monosuccinic acid, N-methyl-1,2-propylenediamine-N'-
monosuccinic acid, N-hydroxyethyl-1,2-propylenediamine-N'-monosuccinic
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W O 97/08287 PCT~US96/13939
acid, N-hydroxypropyl-1,2-propylenediamine-N'-monosuccinic acid, N-
phosphonomethyl-1 ,2-propylenediamine-N'-monosuccinic acid, N-
sulfonomethyl-1,2-propylenediamine-N'-monosuccinic acid, N-
carboxymethyl-1,3-propylenediamine-N'-monosuccinic acid, N-
s carboxyethyl-1 ,3-propylenediamine-N '-monosuccinic acid, N-methyl-1,3-
propylenediamine-N'-monosuccinic acid, N-hydroxyethyl-1,3-
propylenediamine-N '-monosuccinic acid, N-hydroxypropyl- 1 ,3-
propylenediamine-N'-monosuccinic acid, N-phosphonomethyl-1 ,3-
propylenediamine-N'-monosuccinic acid, N-sulfonomethyl-1,3-
o propylenediamine-N'-monosuccinic acid, N-carboxymethyl-cis-
cyclohexanediamine-N'-monosuccinic acid, N-carboxymethyl-trans-
cyclohexanediamine-N'-monosuccinic acid, N-carboxyethyl-cis-
cyclohexanediamine-N'-monosuccinic acid, N-carboxyethyl-trans-
cyclohexanediamine-N'-monosuccinic acid, N-methyl-cis-
5 cyclohexanediamine-N'-monosuccinic acid, N-methyl-trans-
cyclohexanediamine-N'-monosuccinic acid, N-hydroxyethyl-cis-
cyclohexanediamine-N'-monosuccinic acid, N-hydroxyethyl-trans-
cyclohexanediamine-N'-monosuccinic acid, N-hydroxypropyl-cis-
cyclohexanediamine-N'-monosuccinic acid, N-hydroxypropyl-trans-
20 cyclohexanediamine-N'-monosuccinic acid, N-phosphonomethyl-cis-
cyclohexanediamine-N'-monosuccinic acid, N-phosphonomethyl-trans-
cyclohexanediamine-N'-monosuccinic acid, N-sulfonomethyl-cis-
cyclohexanediamine-N'-monosuccinic acid, N-sulfonomethyl-trans-
cyclohexanediamine-N'-monosuccinic acid, N-carboxymethyl-ethylene-
2s bis(oxyethylenenitrilo)-N'-monosuccinic acid, N-carboxyethyl-ethylene-
bis(oxyethylenenitrilo)-N'-monosuccinic acid, N-methyl-ethylene-
bis(oxyethylenenitrilo)-N'-monosuccinic acid, N-hydroxyethyl-ethylene-
bis(oxyethylenenitrilo)-N'-monosuccinic acid, N-hydroxypropyl-ethylene-
bis(oxyethylenenitrilo)-N'-monosuccinic acid, N-phosphonomethyl-ethylene-
30 bis(oxyethylenenitrilo)-N'-monosuccinic acid, N-sulfonomethyl-ethylene-
bis(oxyethylenenitrilo)-N'-monosuccinic acid, N-carboxymethyl-
triethylenetetramine-N"'-monosuccinic acid, N-carboxyethyl-
triethylenetetramine-N"'-monosuccinic acid, N-methyl-triethylenetetramine-
N"'-monosuccinic acid, N-hydroxyethyl-triethylenetetramine-N"'-
3s monosuccinic acid, N-hydroxypropyl-triethylenetetramine-N'"-monosuccinic
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acid, N-phosphonomethyl-triethylenetetramine-N"'-monosuccinic acid, and
N-sulfonomethyl-triethyleneletl~rnine-N"'-monosuccinic acid.
Preferred polyamino monosuccinic acids are those that contain
s two nitrogen atoms and wherein the nitrogen atom which is bound to the
succinic acid moiety is substituted with hydrogen and the nitrogen atom
which is not bound to the succinic acid moiety is substituted with at least
one hydrogen atom.
o Polyamino monosuccinic acids can be prepared, for example,
by the process of Bersworth et al. in U.S. Patent 2,761,874, the disclosure
of which is incorporated herein by reference, and as disclosed in Jpn. Kokai
Tokkyo Koho JP 57,116,031. In general, Bersworth et al. disclose reacting
alkylene diamines and diaikylene triamines with maleic acid esters under
mild conditions in an alcohol to yield polyamino monosuccinic acid esters
which are then hydrolyzed to the corresponding acids. The reaction yields
a mixture of the R and S isomers.
Polyamino monosuccinic acids with carboxyalkyl groups can
be prepared by reacting the unsubstituted polyamino monosuccinic acids or
their esters with the appropriate haloalkyl carboxylic acid or ester followed
by hydrolysis of the ester. Polyamino monosuccinic acids with
carboxyalkyl groups may also be prepared utilizing the reaction of the
unsubstituted polyamino monosuccinic acids or their esters with the
2s appropriate aldehydes and cyanide followed by hydrolysis of the nitrile and
ester to the corresponding carboxyalkyl groups. Polyamino monosuccinic
acids containing a hydroxyalkyl group may be prepared by reacting the
unsubstituted polyamino monosuccinic acids or their esters with the
appropriate alkyl oxide followed by the hydrolysis of the ester. Polyamino
monosuccinic acids containing hydroxyalkyl or alkyl groups may also be
prepared by reaction of the appropriate hydroxyalkylamine or alkylamine
with a maleic acid ester followed by hydrolysis of the ester or by reaction
of the amine with maleic acid and an alkali metal hydroxide such as sodium
hydroxide. Polyamino monosuccinic acids containing phosphonoalkyl
3s groups or sulfonoalkyl groups can be prepared by reacting the
unsubstituted polyamino monosuccinic acids or their esters with the
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W O 97/0~287 PCTAUS96/13939
appropriate haloalkyl phosphonate or haloalkyl sulfonate, respectively
foliowed by hydrolysis of the ester. Phosphonoalkyl groups may also be
introduced by reacting the unsubstituted polyamino monosuccinic acids
with the appropriate aldehyde and phosphorous acid. Certain sulfonoalkyl
s groups may be introduced by reacting the appropriate aldehyde and a
bisulfite with the unsubstituted polyamino monosuccinic acids.
Hydroxamate groups can be introduced by reacting the appropriate
aminocarboxylic acid ester or anhydride with a hydroxylamine compound as
described in U.S. 5,256,531.
The invention includes use of iron complexes of polyamino
monosuccinic acids such as ethylenediamine-N-monosuccinic acid (EDMS)
in abatement of hydrogen sulfide and other acid gases and as a source of
iron in plant nutrition. Similarly other metal complexes such as the copper,
15 zinc and manganese complexes supply those trace metals in plant nutrition.
The ferrous complexes are also useful in nitrogen oxide abatement.
Iron complexes used in the present invention are conveniently
formed by mixing an iron compound with an aqueous solution of the
20 monosuccinic acid (or salt). The pH values of the resulting iron chelate
solutions are preferably adjusted with an alkaline material such as ammonia
solution, sodium carbonate, or dilute caustic (NaOH). Water soluble iron
compounds are conveniently used. Exemplary iron compounds include iron
nitrate, iron sulfate, and iron chloride. The final pH values of the iron
2s chelate solutions are preferably in the range of 4 to 9, more preferably in
the range of 5 to 8. When an insoluble iron source, such as iron oxide, is
used, the succinic acid compounds are preferably heated with the insoluble
iron source in an aqueous medium at an acidic pH. The use of ammoniated
amino succinic acid solutions is particularly effective. Ammoniated amino
30 succinic acid chelants are conveniently formed by combining aqueous
ammonia solutions and aqueous solutions or slurries of amino succinic
~ acids in the acid (rather than salt) form.
Polyamino monosuccinic acids are effective as chelants
3s especially for metals such as iron and copper. Effectiveness as a chelant is
conveniently measured by complexing the chelant with a metal such as
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copper such as by mixing an aqueous solution of known concentration of
the chelant with an aqueous solution containing copper (Il) ions of known
concentration and measuring chelation capacity by titrating the chelant
with copper in the presence of an indicator dye.
s
The polyamino monosuccinic acid compounds, such as
ethylenediamine-N-monosuccinic acid, are biodegradable by standardized
tests, such as the OECD 301 B Modified Sturm Test or the Semicontinuous
Activated Sludge Test (ASTM D 2667 89).
The polyamino monosuccinic acid compounds are preferably
employed in the form of water-soluble salts, notably alkali metal salts,
ammonium salts, or alkyl ammonium salts. The alkali metal salts can
involve one or a mixture of alkali metal salts although the potassium or
5 sodium salts, especially the partial or complete sodium salts of the acids
are preferred.
Polyamino monosuccinic acids are also useful, for instance, in
food products vulnerable to metal-catalyzed spoilage or discoloration; in
20 cleaning products for removing metal ions, that may reduce the
effectiveness, appearance, stability, rinsibility, bleaching effectiveness,
germicidal effectiveness or other property of the cleaning agents; in
personal care products like creams, lotions, deodorants and ointments to
avoid metal-catalyzed oxidation and rancidity, turbidity, reduced shelf-life;
25 in pulp and paper processing to enhance or maintain bleaching
effectiveness; in pipes, vessels, heat exchangers, evaporators, filters to
avoid or remove scaling, in pharmaceuticals; in metal working; in textile
preparation, desizing, scouring, bleaching, dyeing; in agriculture as in
chelated micronutrients or herbicides; in polymerization or stabilization of
30 polymers; in the oil field such as for drilling, production, recovery, hydrogen
sulfide abatement.
The chelants can be used in industrial processes whenever
metal ions such as iron or copper are a nuisance and are to be prevented.
3s
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The polyamino monosuccinic acids in the present application
may be used in a variety of applications, as is disclosed for the use of
disuccinic acid compounds in W0 94/05674 published May 20, 1994.
These uses include the use of succinic acid mixtures for the electroless
s deposition of metals such as nickel and copper; in the polymerization of
rubber; in the textile industry; in agriculture to supply micronutrients; and ingas conditioning to remove H2S, nitrous oxides (NO") and SO2.
The use of chelating agents in removal of H2S is further
o exemplified by United States Patents 4,421,733; 4,614,644; 4,629,608;
4,683,076; 4,696,802; 4,774,071; 4,816,238 and 4,830,838. Gas
conditioning for removal of N0X or S02 compounds is further described in
United States Patents 4,732,744; 4,612,175; 4,708,854; 4,615,780;
4,126,529; 4,820,391 and 4,957,716.
The polyamino monosuccinic acids are also useful in laundry
detergents, particularly laundry detergents containing a detergent
surfactant and builder. The polyamino monosuccinic acids facilitate the
removal of organic stains such as tea stains, grape juice stains and various
food stains from fabrics during laundering operations. The stains are
believed to contain metals such as copper and iron. The polyamino
monosuccinic acids are very effective in chelating these metals and thus
aid in the removal of the troublesome stain. The compositions comprise
from 1 % to 80% by weight of a detergent surfactant, preferably from 10%
2s to 50%, selected from nonionic surfactants, anionic surfactants, cationic
surfactants, zwitterionic surfactants, ampholytic surfactants and mixtures
thereof; from 5% to 80% by weight of a detergent builder, preferably from
10% to 50%; and from 0.1% to 15% by weight of a polyamino
monosuccinic acid, preferably from 1 % to 10%, or alkali metal, alkaline
earth, ammonium or substituted ammonium salt thereof, or mixtures
thereof .
Nonionic surfactants that are suitable for use in the present
invention include those that are disclosed in U.S. 3,929,678 (Laughlin et
3s al.), incorporated herein by reference. Included are the condensation
products of ethylene oxide with aliphatic alcohols, the condensation of
11
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W O 97/08287 PCT~US96/13939
ethylene oxide with the base formed by the condensation of propylene
oxide and propylene glycol or the product formed by the condensation of
propylene oxide and ethylendiamine. Also included are the various
polyethylene oxide condensates of alkyl phenols and various amine oxide
5 surfactants.
Anionic surfactants that are suitable for use are described in
U.S. 3,929,678. These include sodium and potassium alkyl sulfates;
various salts of higher fatty acids, and alkyl-polyethoxylate sulfates.
Cationic surfactants that may be used are described in U.S.
4,228,044 (Cambre), incorporated herein by reference. Especially
preferred cationic surfactants are the quaternary ammonium surfactants.
In addition, ampholytic and zwitterionic surfactants such as
those taught in U.S. 3,929,678 can be used in the present invention.
Suitable builder substances are for example: wash alkalis,
such as sodium carbonate and sodium silicate, or complexing agents, such
20 as phosphates, or ion exchangers, such as zeolites, and mixtures thereof.
These builder substances have as their function to eliminate the hardness
ions, which come partially from the water, partially from dirt or textile
material, and to support the surfactant action. In addition to the above
mentioned builder substances, the builder component may further contain
2s cobuilders. In modern detergents, it is the function of cobuilders to
undertake some of the functions of phosphates, for example sequestration,
soil antiredeposition and primary and secondary washing action.
The builder components may contain for example
30 water-insoluble silicates, as described for example in German Laid-Open
Application DE-OS No. 2,412,837, and/or phosphates. As phosphate it is
possible to use pyrophosphates, triphosphates, higher polyphosphates and
metaphosphates. Similarly, phosphorus-containing organic complexing
agents such as alkanepolyphosphonic acids, amino- and
3s hydroxy-alkanepolyphosphonic acids and phosphonocarboxylic acids, are
suitable for use as further detergent ingredients generally referred to as
12
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W O 97/08287 PCTrUS96/13939
stabilizers or phosphonates. Examples of such detergent additives are the
following compounds: methanediphosphonic acid,
propane-1,2,3-triphosphonic acid, butane-1,2,3,4-tetraphosphonic acid,
polyvinylphosphonic acid, 1-aminoethane,-1,1-diphosphonic acid,
5 aminotrismethylenetriphosphonic acid, methylamino- or
ethylamino-bismethylenediphosphonic acid,
ethylenediaminetetramethylenephosphonic acid,
diethylenetriaminopentamethylenephosphonic acid,
1-hydroxyethane-1,1-diphosphonic acid, phosphonoacetic and
0 phosphonopropionic acid, copolymers of vinylphosphonic acid and acrylic
and/or maleic acid and also partially or completely neutralized salts thereof.
Further organic compounds which act as chelants that may be
present in detergent formulations are polycarboxylic acids,
15 hydroxycarboxylic acids and aminocarboxylic acids which are usually used
in the form of their water-soluble salts.
Examples of polycarboxylic acids are dicarboxylic acids of the
general formula HOOC-(CH ) -COOH where m is 0-8, maleic acid,
20 methylenemalonic acid, citraconic acid, mesaconic acid, itaconic acid,
noncyclic polycarboxylic acids having 3 or more carboxyl groups in the
molecule, for example tricarballylic acid, aconitic acid,
ethylenetetracarboxylic acid, 1,1,3- propanetricarboxylic acid,
1,1,3,3,5,5-pentanehexacarboxylic acid, hexanehexacarboxylic acid, cyclic
25 di- or poly-carboxylic acids (e.g. cyclopentanetetracarboxylic acid,
cyclohexanehexacarboxylic acid, tetrahydrofu~antet~acarboxylic acid,
phthalic acid, terephthalic acid, benzene-tricarboxylic, -tetra-carboxylic or
-pentacarboxylic acid) and mellitic acid.
Examples of hydroxymonocarboxylic and
hydroxypolycarboxylic acids are glycollic acid, lactic acid, malic acid,
tartronic acid, methyltartronic acid, gluconic acid, glyceric acid, citric acid,tartaric acid and salicylic acid.
Examples of aminocarboxylic acids are glycine, glycylglycine,
alanine, asparagine, glutamic acid, aminobenzoic acid, iminodiacetic acid,
13
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iminotriacetic acid, hydroxyethyliminodiacetic acid,
ethylenediaminetetraacetic acid, ethylenediaminedisuccinic acid,
hydroxyethylethylenediaminetriacetic acid, 2-hydroxypropylene-1,3-
diaminedisuccinic acid, diethylenetriaminepentaacetic acid and higher
5 homologues which are prepared by polymerization of an N-aziridylcarboxylic
acid derivative, for example of acetic acid, succinic acid or tricarballylic
acid, and subsequent hydrolysis, or by condensation of polyamines having
a molecular weight of from 500 to 10,000 with salts of chloroacetic or
bromoacetic acid.
Preferred cobuilder substances are polymeric carboxylates.
These polymeric carboxylic acids include the carboxymethyl ethers of
sugars, of starch and of cellulose. Zeolites and phosphates are also useful.
Particulariy important polymeric carboxylic acids are for
example the polymers of acrylic acid, maleic acid, itaconic acid, mesaconic
acid, aconitic acid, methylenemalonic acid, citraconic acid, the copolymers
between the aforementioned carboxylic acids, for example a copolymer of
acrylic acid and maleic acid in a ration of 70:30 and having a molecular
weight of 70,000, or copolymers thereof with ethylenically unsaturated
compounds, such as ethylene, propylene, isobutylene, vinyl methyl ether,
furan, acrolein, vinyl acetate, acrylamide, acrylonitrile methacrylic acid,
crotonic acid, for example the 1:1 copolymers of maleic anhydride and
methyl vinyl ether having a molecular weight of 70,000 or the copolymers
2s of maleic anhydride and ethylene and/or propylene and/or furan.
The cobuilders may further contain soil antiredeposition agents
which keep the dirt detached from the fiber in suspension in the liquid and
thus inhibit graying. Suitable for this purpose are water-soluble colloids
usually of an organic nature for example the water-soluble salts of
polymeric carboxylic acids, glue, gelatin, salts of ethercarboxylic acids or
ethersulfonic acids of starch and of cellulose or salts of acid sulfates of
cellulose and of starch. Even water-soluble polyamides containing acid
groups are suitable for this purpose. It is also possible to use soluble
starch products and starch products other than those mentioned above, for
14
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W O 97/08287 PCTAJS96/13939
example degraded starch, aldehyde starches. Polyvinylpyrrolidone is also
usable.
Bleaching agents that can be used are in particular hydrogen
s peroxide and derivatives thereof or available chlorine compounds. Of the
bleaching agent compounds which provide H202 in water, sodium
perborate hydrates, such as NaB02.H2O2.3H20 and NaBO .H O and
percarbonates such as 2 Na2C03.3H202, are of particular importance.
These compounds can be replaced in part or in full by other sources of
0 active oxygen, in particular by peroxyhydrates, such as,
peroxyphosphonates, citrate perhydrates, urea, H202-providing peracid
salts, for example caroates, perbenzoates or peroxyphthalates or other
peroxy compounds.
Aside from those according to the invention, customary
water-soluble and/or water-insoluble stabilizers for peroxy compounds can
be incorporated together with the former in amounts from 0.25 to 10
percent by weight, based on the peroxy compound. Suitable
water-insoluble stabilizers are the magnesium silicates MgO:SiO2 from 4:1
to 1:4, preferably from 2:1 to 1:2, in particular 1:1, in composition, usually
obtained by precipitation from aqueous solutions. Other alkaline earth
metals of corresponding composition are also suitably used.
To obtain a satisfactory bleaching action even in washing at
2s below 80~C, in particular in the range from 60~C to 40~C, it is
advantageous to incorporate bleach activators in the detergent,
advantageously in an amount from 5 to 30 percent by weight, based on
the H202-providing Compound.
Activators for peroxy compounds which provide H202 in
water are certain N-acyl and O-acyl compounds, in particular acetyl,
propionyl or benzyl compounds, which form organic peracids with H2O2
and also carbonic and pyrocarbonic esters. Useful compounds are inter
- alia:
N-diacylated and N,N'-tetraacylated amines, for example
N,N,N',N'-tetraacetyl-methylenediamine or-ethylenediamine,
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N,N-diacetylaniline and N,N-diacetyl-p-toluidine, and 1,3-diacylated
hydantoins, alkyl-N-sulfonyl-carboxamides, N-acylated hydrazides, acylated
triazoles or urazoles, for example monoacetylmaleohydrazide,
O,N,N-trisubstituted hydroxylamines, for example
5 O-benzoyl-N,N-succinylhydroxylamine,
O-acetyl-N, N-succinyl-hydroxylamine,
O-p-methoxybenzoyl-N, N-succinyl-hydroxylamine,
O-p-nitrobenzoyl-N,N-succinylhydroxylamine and
O,N,N-triacetylhydroxylamine, carboxylic anhydrides, for example benzoic
0 anhydride, m-chlorobenzoic anhydride, phthalic anhydride and
4-chlorophthalic anhydride, sugar esters, for example glucose pentaacetate,
imidazolidine derivatives, such as 1,3 -diformyl -4,5-diacetoxyimidazolidine,
1 ,3-diacetyl-4,5-diacetoxyimidazoline and
1,3-diacetyl-4,5-dipropionyloxyimidazolidine, acylated glycolurils, for
5 example tetrapropionylglycoluril or diacetyldibenzoylglycoluril, dialkylated
2,5-diketopiperazines, for example 1,4-dipropionyl-2,5-diketopiperazine and
1,4-dipropionyl-3,6-dimethyl-2,5-diketopiperazine and
1,4-dipropionyl-3,6-2,5-diketopiperazine, acetylation and benzoylation
products of propylenediurea or 2,2-dimethylpropylenediurea.
The bleaching agents used can also be active chlorine
compounds of the inorganic or organic type. Inorganic active chlorine
compounds include alkali metal hypochlorites which can be used in
particular in the form of their mixed salts and adducts on orthophosphates
2s or condensed phosphates, for example on pyrophosphates and
polyphosphates or on alkali metal silicates. If the detergent contains
monopersulfates and chlorides, active chlorine will form in aqueous
solution .
Organic active chlorine compounds are in particular the
N-chlorine compounds where one or two chlorine atoms are bonded to a
nitrogen atom and where preferably the third valence of the nitrogen atom
leads to a negative group, in particular to a CO or SO2 group. These
compounds include dichlorocyanuric and trichlorocyanuric acid and their
3s salts, chlorinated alkylguanides or alkylbiguanides, chlorinated hydantoins
and chlorinated melamines.
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Examples of additional assistants are: suitable foam
regulants, in particular if surfactants of the sulfonate or sulfate type are
used, are surface-active carboxybetaines or sulfobetaines and also the
s above mentioned nonionics of the alkylolamide type. Also suitable for this
purpose are fatty alcohols or higher terminal diols.
Reduced foaming, which is desirable in particular for machine
washing, is frequently obtained by combining various types of surfactants,
10 for example sulfates and/or sulfonates, with nonionics and/or with soaps.
In the case of soaps, the foam inhibition increases with the degree of
saturation and the number of carbon atoms of the fatty acid ester; soaps of
saturated C2Q-C24-fatty acids, therefore, are particularly suitable for use
as foam inhibltors.
The nonsurfactant-like foam inhibitors include optionally
chlorine-containing N-alkylated aminotriazines which are obtained by
reacting 1 mole of cyanuric chloride with from 2 to 3 moles of a mono-
and/or dialkylamine having 6 to 20, preferably 8 to 18, carbon atoms in the
20 alkyl. A similar effect is possessed by propoxylated and/or butoxylated
aminotriazines, for example, products obtained by addition of from 5 to 10
moles of propylene oxide onto 1 mole of melamine and further addition of
from 10 to 50 moles of butylene oxide onto this propylene oxide derivative.
2s Other suitable nonsurfactant-like foam inhibitors are
water-soluble organic compounds, such as paraffins or haloparaffins having
melting points below 1 00~C, aliphatic C1 8- to C40-ketones and also
aliphatic carboxylic esters which, in the acid or in the alcohol moiety,
possibly even both these moieties, contain not less than 18 carbon atoms
30 (for example triglycerides or fatty acid fatty alcohol esters); they can be
used in particular in combinations of surfactants of the sulfate and/or
sulfonate type with soaps for foam inhibition.
- The detergents may contain optical brighteners for cotton, for
3s polyamide, for polyacrylonitrile or for polyester fabrics. Examples of
suitable optical brighteners are derivatives of diaminostilbenedisulfonic acid
17
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for cotton, derivatives of 1,3-diarylpyrazolines for polyamide, quaternary
salts of 7-methoxy-2-benzimidazol-2'-ylbenzofuran or of derivatives form
the class of the 7-[1',2',5'-triazol-1'-yl]-3-[1",2",4"-triazol-1"-y] coumarins
for polyacrylonitrile. Examples of brighteners suitable for polyester are
s products of the class of the substituted styryls, ethylenes, thiophenes,
naphthalenedicarboxylic acids or derivatives thereof, stilbenes, coumarins
and naphthalimides.
It is preferred that laundry compositions herein also contain
lo enzymes to enhance their through-the-wash cleaning performance on a
variety of soils and stains. Amylase and protease enzymes suitable for use
in detergents are well known in the art and in commercially available liquid
and granular detergents. Commercial detersive enzymes (preferably a
mixture of amylase and protease) are typically used at levels of from 0.001
5 to 2 weight percent, and higher, in the present cleaning compositions.
Detergent formulations of this invention may contain minor
amounts of other commonly used materials in order to enhance the
effectiveness or attractiveness of the product. Exemplary of such materials
20 are soluble sodium carboxymethyl cellulose or other soil redeposition
inhibitors; benzotriazole, ethylene thiourea, or other tarnish inhibitors;
perfume; fluorescers; dyes or pigments; brightening agents; enzymes;
water; alcohols; other builder additives, such as the water soluble salts of
ethylenediaminetetraacetic acid,
2s N-(2-hydroxyethyl)-ethylenediaminetriacetic acid; and pH adjusters, such as
sodium hydroxide and potassium hydroxide. Other optional ingredients
include pH regulants, polyester soil release agents, hydrotropes and
gel-control agents, freeze-thaw stabilizers, bactericides, preservatives, suds
control agents, fabric softeners especially clays and mixtures of clays with
30 various amines and quaternary ammonium compounds. In the built liquid
detergent formulations of this invention, the use of hydrotropic agents may
be found efficacious. Suitable hydrotropes include the water-soluble alkali
metal salts of toluene sulfonic acid, benzene sulfonic acid, and xylene
sulfonic acid. Potassium toluene sulfonate and sodium toluene sulfonate
35 are preferred for this use and will normally be employed in concentrates
ranging up to 10 or 12 percent by weight based on the total composition.
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It will be apparent from the foregoing that the compositions of
this invention may be formulated according to any of the various
commercially desirable forms. For example, the formulations of this
s invention may be provided in granular form, in liquid form, in tablet form of
flakes or powders.
Use of these ingredients is within the skill in the art.
Compositions are prepared using techniques within the skill in the art.
The invention will be further clarified by a consideration of the
following examples, which are intended to be purely exemplary of the
present invention.
EXAMPLE 1:
One mole (60.01 9) of dry ethylenediamine was mixed into 500 ml
of tertiary butanol and stirred under a dry atmosphere. One mole (144.13
g) of dimethyl maleate was slowly added while keeping the temperature
below 30~C and the mixture then stirred for five days. The mixing of the
ethylenediamine with dimethyl maleate resulted in the formation of a white
precipitate which was filtered from the solution (87.15 9, 0.427 mole).
After vacuum evaporation of the remaining liquid, additional white solid
was obtained and washed with toluene. An NMR confirmed that both
samples of white material were the dimethyl ester of 2-aminoethyl-N-
2s aspartic acid. The solids were combined, weighed, (107.57 9, 0.527
mole), and dissoived in water. Sodium hydroxide as a 50 percent by
weight solution (1.5 moles) was added to the aqueous solution of dimethyl
2-aminoethyl-N-aspartate. The resulting solution was then refluxed for
three to four hours. Conversion of the resulting disodium 2-aminoethyl-N-
aspartate to the acid form was accomplished by passing the solution
through a cationic exchange resin (e.g., MSC-1-H obtained from The Dow
Chemical Company) in the acid form. Vacuum evaporation removed the
water to result in solid 2-aminoethyl-N-aspartic acid (i.e., ethylenediamine-
N-monosuccinic acid). A second method for preparing the acid form of 2-
3s aminoethyl-N-aspartic acid from the disodium salt was performed by
addition of hydrobromic acid to the disodium 2-aminoethyl-N-aspartate
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solution until the pH fell to 4. The resulting solution was added to dry
methanol which precipitated the 2-aminoethyl-N-aspartic acid. Filtration
under a dry nitrogen blanket yielded solid 2-aminoethyl-N-aspartic acid (i.e.,
ethylenediamine-N-monosuccinic acid).
EXAMPLE 2:
In 50 ml of dry tertiary butanol, 1.75 9 (0.0236 mole) N-
methylethylenediamine was dissolved and stirred under a dry atmosphere.
Dimethyl maleate (3.40 9, 0.0236 mole) was slowly added while keeping
0 the temperature of the solution below 30~C. The solution was stirred for
five days followed by vacuum evaporation of the liquid. The resultant
product was weighed (4.27 9, 0.0196 mole) and dissolved in water. NMR
studies revealed the presence of two geometric isomers of the product, the
dimethyl ester of N'-methyl-2-aminoethyl-N-aspartate and the dimethyl
ester of N-methyl-2-aminoethyl-N-aspartate. Sodium hydroxide (0.045
mole) was added and the solution was refluxed for three hours. The
resulting disodium salt was converted to the acid form by passage through
a cationic exchange resin (MSC-1-H) in the acid form. By collecting and
concentrating appropriate fractions from the column, the two geometric
isomers, N'-methyl-2-aminoethyl-N-aspartic acid (i.e., ethylenediamine-N-
methyl-N'-monosuccinic acid) and N-methyl-2-aminoethyl-N-aspartic acid
(i.e., ethylenediamine-N-methyl-N-monosuccinic acid), were separated.
EXAMPLE 3:
The diethyl ester of 2-aminoethyl-N-aspartic acid (23.23 9, 0.1 mole
of diethyl 2-aminoethyl-N-aspartate) was dissolved in water and adjusted
with sodium hydroxide to a pH above 12 in a stainless steel vessel and
kept above 50~C for one hour. The solution was cooled with an ice bath.
An equal molar amount of glycolonitrile (14.33 9 of 38.9% solution, 0.1
mole) was slowly added to the solution while maintaining the temperature
below 20~C and the pH above 12. After 12 hours at room temperature,
the sodium hydroxide concentration was increased to 25% and the solution
was refluxed for two to four hours. The acid form(s) of
monocarboxymethyl 2-aminoethyl-N-aspartic acid were obtained by either
3~ adjusting the pH to 4 by the addition of HBr followed by precipitation in
methanol or by passage through a cationic exchange resin (MSC-1-H) in the
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acid form. A product was obtained consisting of approximately 85%
ethylenediamine-N-carboxymethyl-N-monosuccinic acid and about 15%
ethylenediamine-N-carboxymethyl-N'-monosuccinic acid. '
s EXAMPLE 4:
Dimethyl ester of ethylenediamine-N-monosuccinic acid was
prepared as in Example 1. A quantity of 33.29 9 (0.22 mole) methyl
bromoacetate was dissolved in acetonitrile or toluene. Anhydrous sodium
carbonate (36.20 9, 0.34 mole) was added to the solution. With vigorous
o stirring, 45.02 9 of dimethyl ester of ethylenediamine-N-monosuccinic acid
was added. The reaction mixture was refluxed for an hour and allowed to
cool. The solids were removed by filtration. The solvent was removed by
evaporation under a vacuum resulting in 38.9 9 of a thick, pale yellow
liquid. A carbon NMR spectrum was consistent with the trimethyl ester of
5 ethylenediamine-N-carboxymethyl-N'-monosuccinic acid. Nanopure water
(50 ml) and 10 M NaOH (50 ml) were mixed together and added to the
38.9 9 of liquid. The solution was stirred overnight at room temperature.
A carbon NMR was consistent with the trisodium salt of ethylenediamine-
N-carboxymethyl-N'-monosuccinic acid. The solution was adjusted to pH 5
20 with HBr. Addition of the solution to a large quantity of dry methanol
produced a white precipitate. Filtration of the precipitate beneath a
nitrogen blanket resulted in 97.39 9 of a white powder. A carbon NMR
spectrum was consistent with ethylenediamine-N-carboxymethyl-N'-
monosuccinic acid and methanol. The powder was placed into a vacuum
2s oven at 40~C. After 4 days, the material was a dry, slightly yellow powder
with a weight of 37.24 9 (overall yield 73%).
EXAMPLE 5:
In 100 ml of dry tertiary butanol, 10.32 9 (0.1 mole) of dry
30 diethylenetriamine were dissolved, and the resulting solution was sparged
with dry nitrogen. After cooling to 10~C, 14.41 9 (0.1 mole) dimethyl
maleate was slowly added while maintaining the solution temperature
below 20~C. The solution then was maintained at room temperature for
three days. Although no precipitate formed, NMR analysis indicated
3s completion of the reaction by the disappearance of the methine carbons of
maleate. The solvent was removed by vacuum evaporation resulting in a
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viscous, clear liquid. This liquid was dissolved in 30 milliliters of water and
mixed with 30 milliliters of 10 M sodium hydroxide. The resulting solution
was then refluxed for about four hours. After refluxing, the solution was
passed through a cationic exchange column (MSC-1-H) in the acid form.
s Fractions from the column were collected and concentrated by vacuum
evaporation of the water. A total of 13.30 9 (0.061 mole) of product was
recovered and confirmed by NMR analysis to be (2-aminoethyl)-N'-2-
aminoethyl-N-aspartic acid (i.e., diethylenetriamine-N-monosuccinic acid).
lo EXAMPLE 6:
About 75.1 9 of water and 64.0 9 of 50% (by weight) sodium
hydroxide (0.8 mole) were placed into a stainless steel reactor equipped
with a reflux condenser, thermometer, magnetic stirrer bar, and heating
mantle. Maleic acid (44.5 9, 0.38 mole) was dissolved in the solution with
lS five minutes of stirring. Over a 10 minute period, 2-(2-aminoethyl)-
aminoethanol (42.1 9, 0.40 mole) was added. The reaction mixture was
refluxed for two days and then cooled to room temperature. Half of this
solution was then placed in a beaker in an ice-water bath and hydrobromic
acid (65.9 9 of 49% solution, 0.4 mole) added while stirring and
20 maintaining the temperature below 25~C. The resulting solution had a pH
of 5.2 and precipitated some fumaric acid after standing for three hours.
The fumaric acid was removed by maintained at room temperature for
three days. Although no precipitate formed, NMR analysis indicated
completion of the reaction by the disappearance of the methine carbons of
2s maleate. The solvent was removed by vacuum evaporation resulting in a
viscous, clear liquid. This liquid was dissolved in 30 milliliters of water and
mixed with 30 milliliters of 10 M sodium hydroxide. The resulting solution
was then refluxed for four hours. After refluxing, the solution was passed
through a cationic exchange column (MSC-1-H) in the acid form. Fractions
30 from the column were collected and concentrated by vacuum evaporation
of the water. A total of 13.30 9 (0.061 mole) of product was recovered
and confirmed by NMR analysis to be (2-aminoethyl)-N'-2-aminoethyl-N-
aspartic acid (i.e., diethylenetriamine-N-monosuccinic acid).filtration and the
filtrate was stirred into 1130 9 of methanol. After 30 minutes of stirring,
3s the slurry was filtered and rinsed with 400 ml of methanol. The material
was dried in a vacuum oven at 75~C for several hours. After drying, 31.5
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9 (0.14 mole) of product was produced and confirmed by NMR analysis to
be (2-hydroxyethyl)-N'-(2-aminoethyl)-N-aspartic acid (i.e., ethylenediamine-
N-hydroxyethyl-N'-monosuccinic acid).
s EXAMPLE 7:
A 1.95 9 (0.011 mole) quantity of ethylenediamine-l\l-monosuccinic
acid prepared in Example 1 was dissolved in 200 g deionized water. The
pH was adjusted from 5.3 to 7.1 by addition of an aqueous ammonium
hydroxide solution. Iron nitrate ~2.4 g, 0.00507 mole) was then added to
lO the solution with stirring. The resulting pH of 3.1 was adjusted to about
5.0 with aqueous ammonium hydroxide, and the solution was diluted to a
final volume of 500 milliliters. Fifty gram aliquots were placed in separate
vessels and adjusted to pH 5.0, 6.0, 7.0, 8.0, 9.0, and 10.0 with
ammonium hydroxide. After 21 days, the solutions were filtered and
5 analyzed by inductively coupled plasma spectroscopy for soluble iron. The
results were as follows:
DH pPm Fe % Fe in solution
555 100
6 545 98
7 534 96
8 540 97
9 528 95
9 1.7
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EXAMPLE 8:
A 1.02 gram (0.0058 moles) quantity of ethylenediamine-N-
monosuccinic acid from Example 1 and 200 grams of deionized water were
placed in a beaker. The solution was stirred with a magnetic stirrer bar and
s approximately 2.4 grams of iron nitrate solution (11.8% iron) was added
with stirring. The iron chelate solution (pH = 2.1) was diluted in a
volumetric flask to a final volume of 500 milliliters. Fifty gram aliquots of
the above solution were placed in 2 ounce bottles and the pH adjusted to
5.0, 6.0, 7.0, 8.0, 9.0 and 10.0 by the addition of a few drops of aqueous
o ammonia solution. After the samples stood for 6 weeks, they were filtered
and analyzed for soluble iron by inductively coupled plasma spectroscopy.
The results were as follows:
~ ppm Fe% Fe in solution
500 99.2
6 529 99.2
7 533 100
8 520 97.2
9 3 <1
0.9 <1
EXAMPLE 9:
A 1.35 9 (0.0061 mole) quantity of the material from Example 6
was dissolved in 200 milliliters of deionized water and stirred. Iron nitrate
2s (2.35 g, 0.0050 mole) was added to the solution which was then diluted
to 500 ml. Fifty gram aliquots were placed in separate vessels and
adjusted to pH values of 6.0, 7.0, 8.0, 9.0, and 10.0 with the addition of
aqueous ammonium hydroxide. After 16 days, the solutions were filtered
and the filtrates were analyzed by inductively coupled plasma spectroscopy
for soluble iron. The results were as follows:
E~ ppm Fe% Fe in solution
6 544 100
7 536 99
8 538 99
3s 9 530 97
21 4
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EXAMPLE 10:
The reduction potential of the material prepared in Example 6 was
determined by making the ferric complex. The ferric complex was 0.001
molar iron and 0.0011 molar ethylenediamine-N-hydroxyethyl-N'-
s monosuccinic acid in 0.1 molar NaClO4 adjusted to pH 5 with NaOH and
HCI04. The half cell potentials were measured by normal pulse
polarography as detailed in Electrochemical Methods, Fundamentals and
Ar~Plications by A. J. Bard and L. F. Faulkner, 1980, Wiley. Correcting the
results to the standard Ag/AgCI electrode gives the half cell potential of Fe
0 EDTA as -150 mV and of Fe ethylenediamine-N-hydroxyethyl-N'-
monosuccinic acid as -55 mV. This redox potential indicates that the ferric
complex of ethylenediamine-N-hydroxyethyl-N'-monosuccinic acid was
suitable for use in certain redox applications, such as in hydrogen sulfide
abatement.
EXAMPLE 11:
The reduction potential of the material prepared in Example 1 was
measured by the same method as in Example 10. The half cell potential of
Fe ethylenediamine-N-monosuccinic acid was -140 mV. This redox
potential indicates that the ferric complex of ethylenediamine-N-
monosuccinic acid was suitable for use in redox applications such as in
hydrogen sulfide abatement.
EXAMPLE 12:
2s The biodegradability of the material prepared in Example 1 was
measured by both the ASTM D 2667-89 (SemiContinuous Activated
Sludge) test and the OECD 301 B Modified Sturm test. The ASTM D 2667-
89 test exposes the organisms in sludge to about 33 ppm of the test
compound each day for 28 days. After 23 hours of contact with the
sludge, the remaining compound was analyzed. in order to pass the test, a
minimum of 80% of a compound must be degraded during each 23 hour
period for at least 7 consecutive days during the 28 day period. The
ethylenediamine-N-monosuccinic acid was more than 80% degraded within
the prescribed time for passing the ASTM D 2667-89 test. The OECD
3s 301 B Modified Sturm test measures the CO2 produced by the test
compound or standard, which was used as the sole carbon source for the
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microorganisms. The ethylenediamine-N-monosuccinic acid was tested at a .
20 ppm dose level. In addition to a vessel containing the test compound, a
vessel containing acetate as a standard compound, and a vessel containing
innoculum as a blank were used as controls. The seed innoculum was
s obtained from microorganisms previously exposed to ethylenediamine-N-
monosuccinic acid in a semi-continuous activated sludge test. To confirm
the viability of each seed innoculum, acetic acid was used as the standard
at a concentration of 20 ppm. The blank vessel was used to determine the
inherent C02 evolved from each respective innoculum. Carbon dioxide
o captured in the respective barium hydroxide taps was measured at various
times during the 28-day test period. The results from this test indicated
that the material was over 75 percent biodegraded within the prescribed
time. A value of greater than 60% of the theoretical amount of C ~2
produced in this test indicates that a compound was readily biodegradable.
EXAMPLE 13:
The material prepared in Example 3 was subjected to biodegradability
testing in the ASTM D 2667-89 test as described in Example 12. Results
from this test show that the material was greater than 80% biodegraded
20 within the prescribed time.
EXAMPLE 14:
The material prepared in Example 1 was titrated with 0.01 M copper
solution using murexide as the indicator. The material complexed 1.0 mole
2s of copper per mole of ethylenediamine-N-monosuccinic acid.
EXAMPLE 15:
The material prepared in Example 4 was titrated with 0.01 M copper
solution using murexide as the indicator. Each mole of the material
30 complexed one mole of copper.
EXAMPLE 16:
The material prepared in Example 6 was titrated with 0.01 M copper
solution using murexide as the indicator. Each mole of the material
35 complexed 1.0 mole of copper.
26
