U.S. patent number 3,929,875 [Application Number 05/488,382] was granted by the patent office on 1975-12-30 for ethanetetracarboxylate perhydrates.
This patent grant is currently assigned to Monsanto Company. Invention is credited to Marvin M. Crutchfield, John N. Rapko.
United States Patent |
3,929,875 |
Rapko , et al. |
December 30, 1975 |
Ethanetetracarboxylate perhydrates
Abstract
Ethane tetracarboxylate perhydrates represented by the formula
##EQU1## wherein M is alkali metal or ammonium are useful as
complexing agents and as sources of hydrogen peroxide. The
compounds are particularly useful as ingredients of detergent
formulations wherein they provide detergency building, bleaching,
and disinfectant functionality.
Inventors: |
Rapko; John N. (St. Louis,
MO), Crutchfield; Marvin M. (Creve Coeur, MO) |
Assignee: |
Monsanto Company (St. Louis,
MO)
|
Family
ID: |
23939519 |
Appl.
No.: |
05/488,382 |
Filed: |
July 15, 1974 |
Current U.S.
Class: |
562/590;
252/186.44; 252/181; 510/229; 510/318; 510/375; 510/477; 510/309;
510/220 |
Current CPC
Class: |
C07C
55/24 (20130101) |
Current International
Class: |
C07C
55/24 (20060101); C07C 55/00 (20060101); C07C
055/24 () |
Field of
Search: |
;260/537R |
Other References
chem. Abstracts, 19:1249-1250. .
Chem. Abstracts, 77:128511Z..
|
Primary Examiner: Garner; Vivian
Attorney, Agent or Firm: Willis; Neal E. Maurer; J. E.
Wallin; Thomas N.
Claims
What is claimed is:
1. A compound represented by the formula ##EQU4## wherein M is
alkali metal or ammonium.
2. A compound of claim 1 wherein M is sodium.
Description
BACKGROUND OF THE INVENTION
This invention relates to novel ethane tetracarboxylate perhydrates
useful as complexing agents for various metal and alkaline earth
metal ions (particularly ions such as calcium and magnesium which
contribute to "hardness" of water) and which serve as sources of
hydrogen peroxide to provide oxidizing, bleaching and disinfectant
functionality.
The utility of compounds characterized by the ability to complex
ions in aqueous media which contribute to hardness thereof e.g.,
calcium and magnesium and/or provide in combination with various
detergent surfactants, detergent formulations of enhanced cleansing
ability is well recognized by those skilled in the art. Such
compounds are used in water treating applications to "soften" water
and/or inhibit scale formation and/or as detergency builders.
Further, the utility of hydrogen peroxide and compounds serving as
a source of this material which exhibit bleaching and disinfectant
functionality is well understood.
In detergent formulations both detergency building and bleaching
and disinfectant functionality are often desired. Since detergency
building and bleaching functionality are not generally found in a
single compound having acceptable stability, the preparation of a
formulation having both functionalities normally requires the use
of a plurality of components with attendant problems related to
chemical compatibility, the formulation of uniform mixtures,
etc.
It is apparent, therefore, that a single stable compound possessing
both detergency builder and bleaching function would constitute a
substantial advance in the detergent art as well as being useful in
those applications in which the independent functionalities are
desired.
SUMMARY OF THE INVENTION
It is an object of this invention to provide novel compounds useful
as complexing agents and/or detergency builders and which also
serve as sources of hydrogen peroxide to provide the recognized
functionality associated with this material.
The compounds of this invention are ethane tetracarboxylate
perhydrates whose structure, synthesis, and use will be understood
from the following description of the preferred embodiments.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The compounds of the present invention are represented by the
formula ##EQU2## wherein M is alkali metal or ammonium. The
compound wherein M is sodium is particularly preferred.
The compounds of the present invention are conveniently prepared by
reacting tetra alkali metal or ammonium ethane tetracarboxylate
with aqueous hydrogen peroxide. Reaction conditions such as
concentration, temperature, pressure, etc. do not appear to be
critical. For example, the reaction can conveniently be conducted
using anhydrous or hydrated ethane tetracarboxylate and 30-50% by
weight aqueous hydrogen peroxide at ambient temperature (about
25.degree.C.) and atmospheric pressure. Product is isolated by
drying the mixture (preferably at ambient temperature).
The ethane tetracarboxylate employed in the synthesis of the
compound of the present invention is a well known material whose
preparation is described in the literature.
The ethane tetracarboxylate perhydrates of this invention are
useful as agents for complexing metal and/or alkaline earth metal
ions in aqueous media. The amount of tetracarboxylate required to
effectively complex the ions in a given system will depend, to some
extent, on the particular polycarboxylate salt being used and the
particular metal or alkaline earth metal ions in the aqueous media.
Generally, complexing is more effective in basic solution. Optimum
conditions and amounts of complexing agent can readily be
determined by routine experimentation.
As sources of hydrogen peroxide, the compounds of this invention
are utilized in substantially the same manner as sodium perborate.
Since the ethane carboxylate moiety associated with the hydrogen
peroxide provides building functionality, the compound offers
particular advantages as contrasted to perborates wherein the boron
moiety is relatively inert with regard to detergency
functionality.
The ethane tetracarboxylate perhydrates are particularly useful as
bleaching agents and as builders in detergent formulations.
Generally, the use of the alkali metal salts, particularly the
sodium salt, is preferred.
The detergent formulations will contain at least 1% by weight and
preferably at least 5% by weight of the ethane tetracarboxylate
perhydrate of this invention. In order to obtain the maximum
advantages, the use of from 5 to 75% is particularly preferred. If
the detergent formulation contains nitrogen containing compounds
capable of forming N.fwdarw.O adducts it may be desirable to limit
the amount of perhydrate present in order to inhibit the formation
of such adducts. Suitable quantities can be determined by routine
testing. The ethane tetracarboxylate perhydrate compound can be the
sole detergency builder of the formulation or can be utilized in
combination with other detergency builders which may constitute
from 0 to 95% by weight of the total builders in the formulation.
By way of example, builders which can be employed in combination
with the novel compounds of this invention include water soluble
inorganic builder salts such as alkali metal polyphosphates, i.e.,
the tripolyphosphates and pyrophosphates, alkali metal carbonates,
borates, bicarbonates and silicates and water soluble organic
builders including amino polycarboxylic acids and salts such as
alkali metal nitrilotriacetates, cycloalkane polycarboxylic acids
and salts, ether polycarboxylates, alkyl polycarboxylates, epoxy
polycarboxylates, tetrahydrofuran polycarboxylates such as 1,2,3,4
or 2,2,5,5 tetrahydrofuran tetracarboxylates, benzene
polycarboxylates, oxidized starches, amino (trimethylene phosphonic
acid) and its salts, diphosphonic acids and salts (e.g., methylene
diphosphonic acid; 1-hydroxy ethylidene diphosphonic acid) and the
like.
The detergent formulations will generally contain from 5 to 95% by
weight total builder (although greater or lesser quantities may be
employed if desired) which, as indicated above, may be solely the
ethane tetracarboxylate perhydrate compounds of this invention or
mixtures of such compounds with other builders. The total amount of
builder employed will be dependent on the intended use of the
detergent formulation, other ingredients of the formulation, pH
conditions and the like. For example, general laundry powder
formulations will usually contain 20 to 60% builder; liquid
dishwashing formulations 11 to 12% builder; machine dishwashing
formulations 60 to 90% builder. Optimum levels of builder content
as well as optimum mixtures of builders of this invention with
other builders for various uses can be determined by routine tests
in accordance with conventional detergent formulation practice.
The detergent formulations will also contain a water soluble
detergent surfactant. Any water soluble anionic, nonionic,
zwitterionic or amphoteric surfactant can be employed.
Examples of suitable anionic surfactants include soaps such as the
salts of fatty acids containing about 9 to 20 carbon atoms, e.g.,
salts of fatty acids derived from coconut oil and tallow; alkyl
benzene sulfonates--particularly linear alkyl benzene sulfonates in
which the alkyl group contains from 10 to 16 carbon atoms; alcohol
sulfates; ethoxylates alcohol sulfates; hydroxy alkyl sulfonates;
alkyl sulfates and sulfonates monoglyceride sulfates; acid
condensates of fatty acid chlorides with hydroxy alkyl sulfonates
and the like.
Examples of suitable nonionic surfactants include alkylene oxide
(e.g., ethylene oxide) condensates of mono and polyhydroxy
alcohols, alkyl phenols, fatty acid amides, and fatty amines; amine
oxides; sugar derivatives such as sucrose monopalmitate; long chain
tertiary phosphine oxides; dialkyl sulfoxides; fatty acid amides,
(e.g., mono or diethanol amides of fatty acids containing 10 to 18
carbon atoms), and the like.
Examples of suitable zwitterionic surfactants include derivatives
of aliphatic quaternary ammonium compounds such as
3-(N,N-dimethyl-N-hexadecylammonio) propane-1-sulfonate and
3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxy
propane-1-sulfonate.
Examples of suitable amphoteric surfactants include betains,
sulfobetains and fatty acid imidazole carboxylates and
sulfonates.
It will be understood that the above examples of surfactants are by
no means comprehensive and that numerous other surfactants are
known to those skilled in the art. It will be further understood
that the choice and use of surfactants will be in accordance with
well understood practices of detergent formulation. For example,
anionic surfactants, particularly linear alkyl benzene sulfonate
are preferred for use in general laundry formulations, whereas low
foaming nonionic surfactants are preferred for use in machine
dishwashing formulations.
The quantity of surfactant employed in the detergent formulations
will depend on the surfactant chosen and the end use of the
formulation. In general, the formulations will contain from 5 to
50% surfactant by weight, although as much as 95% or more
surfactant may be employed if desired. For example, general laundry
powder formulations normally contain 5 to 50%, preferably 15 to 25%
surfactant; machine dishwashing formulations 0.5 to 5%; liquid
dishwashing formulations 20 to 45%. The weight ratio of surfactant
to builder will generally be in the range of from 1:12 to 2:1.
In addition to builder and surfactant components, detergent
formulations may contain fillers such as sodium sulfate and minor
amounts of dyes, optical brighteners, soil anti-redeposition
agents, perfumes and the like.
If desired, the formulation may contain other bleaching agents to
supplement the ethane tetracarboxylate perhydrate.
Bleach activators such as tetraacetylethylenediamine, sodium
p-acetoxybenzene sulfonate, or tetraacetylglycouril may be
advantageously employed to promote release of hydrogen peroxide by
ethane tetracarboxylate.
The invention is further illustrated by the following examples (all
parts and percentages are by weight unless otherwise
indicated):
EXAMPLE I
Ten grams anhydrous tetrasodium-1,1,2,2-ethane tetracarboxylate are
dissolved in 15 ml. of 50% aqueous hydrogen peroxide. The mixture
is evaporated to yield a solid which is further dried over a
desiccant at a temperature of about 25.degree.C. The resulting
tetrasodium ethane-1,1,2,2-tetracarboxylate perhydrate ##EQU3## is
a crystalline material exhibiting the following Cu K-.alpha. X-ray
diffraction pattern.
______________________________________ 2.THETA. d-spacing relative
intensity ______________________________________ 15.65 2.8553 100
14.28 3.1227 100 18.30 2.4531 90 14.05 3.1728 50 11.55 3.8470 40
16.85 2.6572 40 16.38 2.7313 35 22.60 2.0043 35
______________________________________
EXAMPLE II
Detergent formulations are prepared containing about 17 parts
linear sodium alkylbenzene sulfonate having an average molecular
weight of about 230; 8.5 parts silicate having a 1:2 ratio of
Na.sub.2 O:SiO.sub.2 ; 24.5 parts sodium sulfate and 50 parts tetra
sodium ethane-1,1,2,2-tetracarboxylate perhydrate. This composition
is compared in cleaning effectiveness on polyester/cotton and
cotton fabrics with an otherwise identical composition containing
no tetra sodium ethane-1,1,2,2-tetracarboxylate perhydrate.
Detergency performance of the formulations containing the builder
as determined by measurement of the difference in reflectance of
washed and unwashed samples averages twice that of the formulation
containing no tetra sodium ethane-1,1,2,2-tetracarboxylate
perhydrate. Similar results are obtained with formulations
containing 25 parts and 38 parts tetra sodium
ethane-1,1,2,2-tetracarboxylate perhydrate. The formulations are
also found to provide effective bleaching of the fabrics at wash
temperatures above 90.degree.C. in absence of bleach activators and
at lower temperatures (50.degree.-60.degree.C.) if activators such
as these previously referred to are employed.
* * * * *