U.S. patent number 3,923,679 [Application Number 05/476,825] was granted by the patent office on 1975-12-02 for salts of tetrahydrofuran polycarboxylic acids as detergent builders and complexing agents.
This patent grant is currently assigned to Monsanto Company. Invention is credited to John N. Rapko.
United States Patent |
3,923,679 |
Rapko |
December 2, 1975 |
**Please see images for:
( Certificate of Correction ) ** |
Salts of tetrahydrofuran polycarboxylic acids as detergent builders
and complexing agents
Abstract
Salts of tetrahydrofuran polycarboxylic acids represented by the
formula ##EQU1## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4 and
R.sub.5 are hydrogen or carboxylic acid groups, at least one of
R.sub.1, R.sub.2, R.sub.3 and R.sub.4 being a carboxylic acid group
when R.sub.5 is a carboxylic acid group are useful as complexing
agents and/or detergency builders. The ester forms of such
compounds, as well as the acids are useful as intermediates for
production of the salts.
Inventors: |
Rapko; John N. (St. Louis,
MO) |
Assignee: |
Monsanto Company (St. Louis,
MO)
|
Family
ID: |
27010897 |
Appl.
No.: |
05/476,825 |
Filed: |
June 6, 1974 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
385131 |
Aug 2, 1973 |
3835163 |
|
|
|
Current U.S.
Class: |
510/229; 252/180;
510/351; 510/361; 510/379; 510/381; 510/533; 510/479; 510/356 |
Current CPC
Class: |
C11D
3/2096 (20130101); C02F 5/10 (20130101); C07D
307/24 (20130101) |
Current International
Class: |
C11D
3/00 (20060101); C07D 307/00 (20060101); C02F
5/10 (20060101); C07D 307/24 (20060101); C11D
3/20 (20060101); C11D 007/54 () |
Field of
Search: |
;252/89,97,99,132,135,180,DIG.11 ;260/347.3,347.5 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Herbert, Jr.; Thomas J.
Assistant Examiner: Hess; Bruce H.
Attorney, Agent or Firm: Willis; Neal E. Maurer; John E.
Wallin; Thomas N.
Parent Case Text
This is a division of application Ser. No. 385,131, filed Aug. 2,
1973, now U.S. Pat. No 3,835,163.
Claims
What is claimed is:
1. A detergent formulation comprising (a) from 1 to 95% by weight
of an alkali metal, ammonium or alkanol ammonium salt of a compound
represented by the formula ##EQU12## wherein R.sub.a, R.sub.b,
R.sub.c, R.sub.d, and R.sub.e are selected from the group
consisting of hydrogen and COOH, at least one of R.sub.a, R.sub.b,
R.sub.c and R.sub.d being COOH when R.sub.e is COOH and (b) from
0.5 to 95% by weight of a surfactant selected form the group
consisting of water soluble anionic, nonionic, amphoteric and
zwitterionic surfactants.
2. A formulation according to claim 1 containing from 5 to 75% of
said salt.
3. A formulation according to claim 1 wherein R.sub.a, R.sub.d and
R.sub.e are COOH and R.sub.b and R.sub.c are hydrogen.
4. The formulation of claim 1 wherein said salt is pentasodium
monohydrogen tetrahydrofuran 2,2,3,4,5,5-hexacarboxylate.
5. The formulation of claim 1 wherein said salt is pentasodium
monohydrogen tetrahydrofuran 2,2-trans-3,4,5,5-hexacarboxylate.
6. The formulation of claim 1 wherein said salt is hexasodium
tetrahydrofuran 2,2-trans-3,4,5,5-hexacarboxylate.
7. The formulation of claim 1 wherein said salt is hexasodium
tetrahydrofuran 2,2-trans-3,4,5,5-hexacarboxylate.
8. A machine dishwashing composition comprising (a) from 0 to 5% by
weight of a surfactant selected from the group consisting of
low-foaming anionic and non-ionic surfactants and mixtures thereof,
(b) a chlorine providing material selected from the group
consisting of potassium dichlorocyanurate; sodium
dichlorocyanurate; [(mono-trichloro) tetra-(monopotassium
dichloro)] penta-isocyanurate; (mono-trichlor) (mono-potassium
dichloro) diisocyanurate; chlorinated trisodium phosphate, said
chlorine providing material being present in an amount sufficient
to provide from 0.5 to 2% by weight available chlorine, (c) from 5
to 30% by weight soluble sodium silicate having an SiO.sub.2 to
Na.sub.2 O mole ratio of from 1:1 to 3.2:1 and (d) from 5 to 90% by
weight of an alkali metal, ammonium or alkanol ammonium salt of a
compound represented by the formula ##EQU13## wherein R.sub.a,
R.sub.b, R.sub.c, R.sub.d and R.sub.e are selected from the group
consisting of hydrogen and COOH, at least one of R.sub.a, R.sub.b,
R.sub.c and R.sub.d being COOH when R.sub.e is COOM.
9. A formulation according to claim 8 containing from 20 to 75% of
said salt.
10. A formulation according to claim 8 wherein R.sub.a, R.sub.d and
R.sub.e are COOH and R.sub.b and R.sub.c are hydrogen.
11. The formulation of claim 8 wherein said salt is pentasodium
monohydrogen tetrahydrofuran 2,2,3,4,5,5-hexacarboxylate.
12. The formulation of claim 8 wherein said salt is pentasodium
monohydrogen tetrahydrofuran
2,2,-trans-3,4,5,5-hexacarboxylate.
13. The formulation of claim 8 wherein said salt is hexasodium
tetrahydrofuran 2,2,3,4,5,5-hexacarboxylate.
14. The formulation of claim 8 wherein said salt is hexasodium
tetrahydrofuran 2,2-trans-3,4,5,5-hexacarboxylate.
15. A formulation according to claim 8 containing at least 0.5%
surfactant.
16. A method of complexing ions selected from the group consisting
of metal ions and alkaline earth metal ions in an aqueous medium
containing said ions by providing in said aqueous medium a quantity
of an alkali metal, ammonium or alkanol ammonium salt of a compound
represented by the formula ##EQU14## wherein R.sub.a, R.sub.b,
R.sub.c, R.sub.d and R.sub.e are selected from the group consisting
of hydrogen and COOH, at least one of R.sub.a, R.sub.b, R.sub.c and
R.sub.d being COOH when R.sub.e is COOH, sufficient to form
complexes with said ions.
Description
BACKGROUND OF THE INVENTION
This invention relates to novel tetrahydrofuran polycarboxylic
acids and salts useful as complexing agents and detergency
builders; to detergent formulations containing such compounds and
to ester forms of such compounds useful, inter alia, as
intermediates for preparation of the salts and acids.
The utility of compounds characterized by the ability to complex
various metal and alkaline earth metal ions (particularly ions such
as calcium ions which contribute to "hardness" of water) in aqueous
media 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 (e.g. to "soften" water) and/or
as detergency builders.
Although many compounds having complexing and/or detergency builder
functionality are known the provision of novel compounds composed
of only carbon, hydrogen and oxygen and having such functionality
is desirable.
Since most known complexing agents form complexes with water
hardness ions on a 1:1 mole basis, novel compounds having the
ability to complex greater quantities of such ions are particularly
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 intermediates
for the synthesis of such compounds. A further object of the
invention is to provide novel detergent formulations containing the
builder compounds of this invention.
The compounds of this invention are tetrahydrofuran polycarboxylic
acids, their salts and esters 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 X is hydrogen, alkali metal, ammonium,
alkanol ammonium, (wherein the alkyl group contains from 1 to 4
carbon atoms) or an alkyl group containing from 1 to 20 carbon
atoms (it is not necessary that all X groups in the compound be
identical) and R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are
hydrogen or --COOX. At least one of the R.sub.1, R.sub.2, R.sub.3
and R.sub.4 groups must be --COOX when R.sub.5 is COOX. Thus, the
formula is seen to encompass acid, salt and ester compounds. It is
further apparent that certain of the compounds, for example, those
in which R.sub.1 and R.sub.4 are --COOX and R.sub.2 and R.sub.3 are
hydrogen include both cis and trans configurations.
The salt forms of the compounds of this invention are useful as
complexing agents and/or as detergency builders.
Tetrahydrofuran-2,2,3,4,5,5-hexacarboxylate salts, especially in
the trans configurations and preferably the pentasodium salts, are
preferred compounds of the invention in view of their ability to
complex more than one mole of calcium ion per mole of
hexacarboxylate salt.
The ester forms of the compounds of this invention are useful as
intermediates for preparation of the salt forms as will be apparent
from the subsequent description of methods of preparing compounds
of this invention. In addition, certain of the esters (particularly
those having more than 4 carbon atoms in the ester alkyl groups)
will be found to exhibit plasticizer properties or, in the case of
the higher alkyl (9 to 20 carbon atoms) esters, surfactant
properties.
The ester forms of the compounds of this invention can be prepared
by reactions represented by the equations: ##EQU3## In the formulae
of the above equations Y is hydrogen or CN, R.sub.1 ', R.sub.2 ',
R.sub.3 ', R.sub.4 ' and R.sub.5 ' are hydrogen or COOR, at least
one of R.sub.1 ', R.sub.2 ', R.sub.3 ' and R.sub.4 ' being COOR
when R.sub.5 ' is COOR and R and R' are alkyl groups containing
from 1 to 20 carbon atoms.
The number and position of carboxylate groups in the ester product
is determined by the choice of the ##EQU4## compound.
For example: the use of dimethyl maleate will yield a mixture of
the cis and trans configurations of ##EQU5## whereas the use of
dimethyl fumarate will yield the trans form of this compound.
The use of methyl acrylate will yield ##EQU6##
The use of methylene malonic ester CH.sub.2 = C (COO
CH.sub.3).sub.2 will yield ##EQU7##
The use of ethene 1,1,2 trimethylcarboxylate will yield
##EQU8##
The use of ethene 1,1,2,2 tetramethylcarboxylate yields
##EQU9##
Higher esters are obtained by use of higher alkyl carboxylate
esters in the reaction or by transesterifying the lower esters with
the appropriate alcohol. The R' in the COOR' groups occupying the
2,2,5,5 positions corresponds to the R' in the alcohol (R'OH) used
in the second reaction.
The reaction shown in the first equation can be conveniently
conducted in an inert solvent, e.g., 1,2-dibromoethane, at a
temperature sufficiently high to promote a reasonable rate of
reaction, e.g. about 120.degree.C in the case of dimethyl fumarate.
Preferably, the reaction is conducted under reflux and a nitrogen
blanket to prevent volatilization or oxidation of the reactants.
The product is recovered by conventional crystallization and
filtration techniques. Reactions of this general type are fully
understood by those skilled in the art, and are discussed, for
example, in U.S. Pat. No. 3,317,567.
The alcoholysis reaction shown in the second equation is preferably
conducted by mixing the product of the first reaction with the
requisite amount of water and alcohol cooling to about 0.degree. to
40.degree.C; adding gaseous HCl; filtering to remove NH.sub.4 Cl;
adding concentrated sulfuric acid as a catalyst and refluxing to
complete the reaction.
The corresponding alkali metal salts are readily obtained by
conventional saponification techniques (using less than
stoichimetric amounts of alkali metal hydroxide if a partial salt
such as the preferred pentasodium tetrahydrofuran
2,2,3,4,5,5-hexacarboxylate is desired). The corresponding ammonium
and alkanol ammonium salts are more easily obtained by
neutralization of the acid forms of the compounds of this
invention.
Acidulation of the salt with a strong acid, e.g., HCl, H.sub.2
SO.sub.4, or a strong acid ion exchange resin, will yield the acid
forms of the compounds of this invention.
The tetrahydrofuran polycarboxylate salts of this invention are
useful as agents for complexing metal and/or alkaline earth metal
ions in aqueous media. The amount of polycarboxylate 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.
The tetrahydrofuran polycarboxylate salts are also useful as
builders in detergent formulations. Generally, the use of the
alkali metal salts, particularly the sodium salt is preferred.
However, in some formulations (such as liquid formulations where
greater builder solubility is required) the use of ammonium or
alkanol ammonium salts may be desirable.
The detergent formulations of this invention will contain at least
1% by weight and preferably at least 5% by weight of the
polycarboxylate salts of this invention. In order to obtain the
maximum advantages of the builder compositions of this invention,
the use of from 5 to 75% of these polycarboxylate salts is
particularly preferred. The tetrahydrofurna polycarboxylic salt
compounds of this invention can be the sole detergency builder or
these compounds 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 builder
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, other 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 of this invention will generally contain
from 5 to 95% by weight total builder (although greater or lesser
quentities may be employed if desired) which, as indicated above,
may be solely the tetrahydrofuran polycarboxylic acids and/or salts
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 power 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 of this invention will generally contain
a water soluble detergent surfactant although the surfactant
ingredient may be omitted from machine dishwashing formulations.
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; ethoxylated 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-hexadecyl ammonio) 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
of this invention 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 bleaches, dyes, optical brightners, soil
anti-redeposition agents, perfumes and the like.
In machine dishwashing compositions the surfactant will be a
low-foaming anionic surfactant which will constitute 0 to 5% of the
formulation.
The term "low-foaming" surfactant connotes a surfactant which, in
the foaming test described below, reduces the revolutions of the
washer jet-spray arm during the wash and rinse cycles less than
15%, preferably less than 10%.
In the foaming test, 1.5 grams of surfactant is added to a 1969
Kitchen-Aid Home Dishwasher, Model No. KOS-16, manufactured by
Hobart Manufacturing Company which is provided with means for
counting revolutions of the washer jet-spray arm during wash and
rinse cycles. The machine is operated using distilled water feed at
a machine entrance temperature of 40.degree.C. The number of
revolutions of the jet-spray arm during the wash and rinse cycles
is counted. The results are compared with those obtained by
operation of the machine using no surfactant charge and percentage
decrease in number of revolutions is determined.
The surfactant should, of course, be compatible with the chlorine
containing component hereinafter discussed. Examples of suitable
nonionic surfactants include ethoxylated alkyl phenols, ethoxylated
alcohols (both mono- and di-hydroxy alcohols), polyoxyalkylene
glycols, aliphatic polyethers and the like. The widely commercially
utilized condensates of polyoxypropylene glycols having molecular
weights of from about 1,400 to 2,200 with ethylene oxide (the
ethylene oxide constituting 5 to 35 weight percent of the
condensate) are, for example, advantageously used in the machine
dishwashing formulations of this invention.
Suitable low-foaming anionic surfactants include alkyldiphenyl
ether sulfonates such as sodium dodecyl diphenyl ether disulfonates
and alkyl naphthalene sulfonates.
Mixtures of suitable low-foaming surfactants can be utilized if
desired.
In addition, machine dishwashing formulations will contain
sufficient chlorine providing compound to provide 0.5 to 2%
available chlorine. For example, the formulation may contain from
0.5 to 5%, preferably 1 to 3% of a chlorocyanurate or from 10 to
30% chlorinated trisodium phosphate. Suitable chlorocyanurates are
sodium and potassium dichlorocyanurate; [(monotrichloro)
tetra-(mono potassium dichloro)] penta-isocyanurate;
(mono-trichloro) (monopotassium dichloro) di-isocyanurate.
Machine dishwashing compositions should additionally contain from 5
to 30% soluble sodium silicate having an SiO.sub.2 to Na.sub.2 O
mole ratio of from 1:1 to 3.2:1 preferably about 2.4:1 to inhibit
corrosion of metal parts of dishwashing machines and provide
over-glaze protection to fine china.
Machine dishwashing compositions will generally contain at least
10%, preferably at least 20% builder, up to a maximum of about 90%
builder. The new builder compounds of this invention should
constitute at least 5% of the weight of the machine dishwashing
formulation in order to obtain the full effects of their inherent
characteristics.
The invention is further illustrated by the following examples
which deal with the preparation and use of the particularly
preferred tetrahydrofuran 2,2-trans-3,4,5,5-hexacarboxylate
compounds. It will be recognized by those skilled in the art that
other compounds of this invention can be prepared and utilized in a
similar manner pursuant to the preceding discussion. In the
examples, all parts and percentages are by weight unless otherwise
indicated.
EXAMPLE I
Tetracyanoethylene oxide (56.6 grams); dimethyl fumarate (56.6
grams); ethylene dibromide solvent (450 ml.) are maintained at
about 120.degree.C with stirring for about 22 hours under nitrogen
atmosphere in a glass flask fitted with a reflux condenser. A dark
brown solution forms which is filtered while hot to remove minor
amounts of unidentified solid impurities. The filtrate is dried on
a rotary evaporator and the residue washed with diethylether and
dried under nitrogen. The residue product is purified by
dissolution in and crystallization from methyl alcohol followed by
vacuum drying. The identity of the product as dimethyl
tetrahydrofuran-trans-3,4-dicarboxylate-2,2,5,5,-tetranitrile is
confirmed by elemental analysis and a H nuclear magnetic resonance
spectrum in deuterated acetone in which the 3 and 4 protons appear
as a singlet at 5.45 ppm; the ester CH.sub.3 protons as a singlet
at 4.10 ppm vs. TMS (relative areas 1:3).
Ninety grams of the dimethyl tetrahydrofuran-trans-3,4
-dicarboxylate-2,2,5,5-tetranitrile; 21 grams water; 1,000 ml.
methyl alcohol are charged to a glass flask and the temperature of
the mixture is held between 0.degree. to 40.degree.C while 50 grams
of hydrogen chloride gas is bubbled into the mixture. The reaction
mxiture is filtered to remove ammonium chloride; 1.5 ml.
concentrated sulfuric acid is added as catalyst to the filtrate
which is then refluxed for about 30 hours. Upon cooling, solid
product separates from the solution and is removed by filtration.
The solid is dissolved in chloroform; washed with 5% sodium
bicarbonate and water. The chloroform solution is dried over
magnesium sulfate and the chloroform evaporated to leave an oily
residue. Dissolution of the residue in methanol followed by
crystallization yields a pure crystalline product. The identity of
the product as hexamethyl tetrahydrofuran 2,2-trans-3,4,5,5
hexacarboxylate is confirmed by elemental analysis and a H nuclear
magnetic resonance spectrum in deuterated chloroform which exhibits
a singlet at 4.50 ppm corresponding to the 3 and 4 protons; a
singlet at 4.02 ppm corresponding to the two CH.sub.3 ester groups
at the 3 and 4 positions; a singlet at 3.88 ppm corresponding to
the four ester CH.sub.3 groups at the 2 and 5 positions (relative
areas 1:3:4).
EXAMPLE II
A mixture of 55.4 grams 50% sodium hydroxide; 100 ml. water; 48.5
grams hexamethyl tetrahydrofuran 2,2-trans-3,4,5,5 hexacarboxylate
is heated under reflux at 90.degree.C for 24 hours in a glass
flask. The solution is concentrated by distillation of methanol and
water from the flask. The reaction mixture is cooled to room
temperature and product precipitated by addition of 1,000 ml.
methanol. The identity of the product as pentasodium monohydrogen
tetrahydrofuran 2,2-trans-3,4,5,5 hexacarboxylate is confirmed by
chemical analysis and a H nuclear magnetic resonance spectrum in
deuterium oxide exhibiting a singlet at 4.1 ppm.
EXAMPLE III
Pentasodium monohydrogen tetrahydrofuran 2,2-trans-3,4,5,5
hexacarboxylate (289.2 mg.) is dissolved in 10 ml. deionized water
and passed through a column packed with a strong acid ion exchange
resin (sulfonated polystyrene marketed by Fisher Scientific Company
under the trademark Rexyn 101). This procedure yields
tetrahydrofuran 2,2-trans-3,4,5,5 hexacarboxylic acid. The
titration curve of the acid with sodium hydroxide exhibits three
breaks and indicates that four protons are highly acidic (apparent
pKa's equal to or less than 5.7); a fifth proton is less acidic
(apparent pKa of about 6.8); and the sixth proton has an apparent
pKa of about 9.1.
EXAMPLE IV
Pentasodium monohydrogen tetrahydrofuran 2,2-trans-3,4,5,5
hexacarboxylate is tested for sequestration function using the
procedures described by Matzner et al, "Organic Builder Salts as
Replacements for Sodium Tripolyphosphate" Tenside Detergents, 10,
Heft 3, pages 119 through 125 (1973). In this test, the divalent
ion electrode shows two separate end points for titration of
calcium ion with a solution of the hexacarboxylate salt. This is
due to the formation of 2:1 and 1:1 (Ca++/ligand) complexes. The
average sequestration values (intensity multiplied by capacity
expressed as a percentage of sodium tripolyphosphate sequestration
value are in the range of 138 to 188% depending upon the complex
formed.
EXAMPLE V
Detergent formulations containing the percent builder shown in
Table I below; 17% linear alkylbenzene sulfonate having an average
molecular weight of about 230; 12% sodium silicate; remainder,
sodium sulfate are prepared. The formulations are tested by washing
identically soiled fabric swatches (indicated in the table) in
water of 200 ppm hardness at 40.degree.C containing 0.15% detergent
formulation using identical washing techniques. The reflectivity of
the soiled swatches before and after washing is measured
instrumentally and the difference reported in Table I as .DELTA.
Rd. High .DELTA. Rd values are indicative of correspondingly high
detergency effectiveness.
TABLE I
__________________________________________________________________________
Cotton Fabric -- .DELTA. Rd Polyester/Cotton Fabric -- Rd 50% 37.5%
25% 50% 37.5% 25% Builder Builder Builder Builder Builder Builder
Builder
__________________________________________________________________________
Pentasodium monohydrogen tetrahydrofuran
2,2-trans-3,4,5,5-hexacarboxylate 1 28.7 27.1 21.3 13.5 10.1 9.8
Sodium Tripolyphosphate 26.2 19.0 14.5 12.0 8.7 5.7
__________________________________________________________________________
EXAMPLE VI
Three pentasodium monohydrogen tetrahydrofuran
2,2-trans-3,4,5,5-hexacarboxylate built detergent formulations
corresponding to those shown in Example V except that linear
alkylbenzene sulfonate surfactant is replaced with:
1. a nonionic surfactant - a condensate of 7 molecular proportions
of ethylene oxide with linear secondary alcohols containing 11 to
15 carbon atoms
2. an amphoteric surfactant - sodium hydroxyalkyl (alkyl group
contains an average of 15 carbon atoms) N-methyl taurate
3. a zwitterionic surfactant -cocodimethylsulfopropylbetaine
are prepared and tested. All three formulations exhibit effective
detergency.
EXAMPLE VII
A machine dishwashing formulation containing 50% pentasodium
monohydrogen tetrahydrofuran 2,2-trans-3,4,5,5-hexacarboxylate; 35%
of an aqueous solution containing 47% sodium silicate having an
SiO.sub.2 to Na.sub.2 O mole ratio of 2.4; 3% of a condensate of
ethylene oxide with polyoxypropylene glycol marketed by Wyandotte
Chemical Corporation as Pluronic L-62; 1.2% potassium
dichlorocyanurate; 10.8% sodium sulfate is prepared. The
formulation is used to wash soiled dishes and glassware in a
conventional automatic home dishwashing machine. Excellent cleaning
is obtained and, in particular, the glassware is found
substantially free from filming and spotting.
EXAMPLE VIII
Three machine dishwashing formulations are prepared which are
identical to that of Example VII except that the following
surfactants are substituted for the ethylene oxide-polyoxypropylene
glycol:
1. condensate of an internal, vicinal, linear diol having an
average chain length of 16 carbon atoms with 3 molecular
proportions of ethylene oxide
2. condensate of N-decanol with 2-1/2 molecular proportions
ethylene oxide
3. sodium decydiphenyl ether disulfonate.
All three formulations provide excellent performance in cleaning
dishes and glassware in a conventional automatic home dishwashing
machine.
Other compounds of this invention can be prepared by techniques
similar to those disclosed in Example I.
For example, Table II, below, indicates the esters which are
obtained by reaction of various ##EQU10## compounds with various
##EQU11## compounds followed by alcoholysis with methanol.
TABLE II
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CNOCN R.sub.1 R.sub.3 Product .angle. .angle.CC.angle.
.angle.C=C.angle. CNY R.sub.2 R.sub.4
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tetracyano ethylene oxide dimethyl malonate mixtures of hexamethyl
tetrahydrofuran 2,2-cis-3,4,5,5 hexacarboxylate and hexamethyl
2,2-cis-3,4,5,5 hexacarboxylate tetracyano ethylene oxide methyl
acrylate pentamethyl tetrahydrofuran-2,2,3,5,5-penta carboxylate
tetracyano ethylene oxide dimethyl/methylene malonate hexamethyl
tetrahydrofuran-2,2,3,3,5,5-hexa carboxylate tetracyano ethylene
oxide trimethyl ethene-1,1,2-tricarboxylate heptamethyl
tetrahydrofuran-2,2,3,3,4,5,5-h eptacarboxylate tetracyano ethylene
oxide tetramethyl ethene-1,1,2,2-tetracarboxylate
octamethyl-tetrahydrofuran-2,2,3,3,4,4,5,5- octacarboxylate
tricyano ethylene oxide ethylene
trimethyl-tetrahydrofuran-2,2,5-tricarboxyl ate tricyano ethylene
oxide methyl acrylate mixture of cis and trans tetramethyl
tetrahydrofuran-2,2,3,5 and 2,2,4,5 tetracarboxylates tricyano
ethylene oxide dimethyl methylene malonate mixture of penta methyl
tetrahydrofuran-2,2 ,3,3,5 and 2,2,4,4,5 penta carboxylate tricyano
ethylene oxide dimethyl fumarate mixture of pentamethyl
tetrahydrofuran-2,2, -trans-3-cis-4,5 and 2,2-cis-3,5-trans-4
pentacarboxylate tricyano ethylene oxide dimethyl maleate mixture
of pentamethyl tetrahydrofuran-cis- 2,2,3,4,5 and
2,2-cis-3,4-trans-5 pentacarboxylate tricyano ethylene oxide
trimethyl ethene-1,1,2-tricarboxylate mixture of cis and
trans-hexamethyl tetrahydrofuran-2,2,3,3,4,5 and 2,2,3,4,4,5
hexacarboxylate tricyano ethylene oxide tetramethyl
ethene-1,1,2,2-tetracarboxylate heptamethyl
tetrahydrofuran-2,2,3,3,4,4,5 heptacarboxylate
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Acids corresponding to the esters shown in Table II, above, and
their corresponding totally or partially neutralized salts can be
prepared by saponification and acidulation techniques comparable to
those exemplified in Examples II and III.
* * * * *