Technical Field
[0001] The present invention relates to cleaning compositions which contain a mixture of
succinate builders.
Background to the Invention
[0002] The literature is replete with reference to the ongoing search for new detergency
builders, particularly those which are phosphorus-free. See, for example "Organic
Builder: A review of Worldwise Efforts to Find Organic Replacements for Detergents
Phosphates" Crutchfield JAOCS
55 58-65 (1978).
[0003] Polycarboxylated materials of various types have been suggested for use as detergency
builders, and citric acid is currently used in some liquid laundry products. Other
carboxylates are disclosed, for example in Stubbs et al; U.S. Patent 4,017,541; Issued
April 12, 1977; Pearson et al; U.S. Patent 3,776,850; Issued December 4, 1973; Berg:
U.S. Patent 3,120,207; Issued April 7, 1964 and Lamberti et al; U.S. Patent 3,635,830;
Issued January 18, 1972.
[0004] The patent literature describes the use of alkyl- and alkenyl succinates as surfactants:
US 2,283,214; detenency boosters UK 1,293,753; in various liquid cleaners UK 1,528171,
US 4,277,378; builders US 2,462,758 and the like. See also US 3,784,486.
[0005] A variety of substituted succinates and "sulfur-succinates" are described for various
similar uses: US 3,912,663, US 4,152,515 and US 3,725,286.
[0006] The use of ingredients succinates in combination with certain detergency ingredients
is also known; see EPO 79191 and EPO 70190, as well as German 32 05 791 and German
33 17 337.
[0007] Indeed, the use of carboxylate materials of various types in solid and liquid cleaners,
is well-known; see UK 1,514,276 for amine soap mixture; UK 1,429,143 for zeolite/polycarboxylate
mixtures: US 2,264,103 for citrate and other carboxylate plus soap mixtures; US 3,634,392
for polysaccharidic carboxylate detergency builders; US 3,898,187 for various sulfur-succinates
in dish-washing detergents; and UK 1,400,898 for use with clay softeners.
[0008] Despite the heavy commitment of research towards the development of new detergency
builders, there is a continuing search for improved technology in this area.
[0009] It is an object of this invention to provide detergency builders which are an improvement
over the carboxylate builders of the literature.
[0010] It is another object to provide detergent compositions, especially liquid laundry
detergents, containing said improved builders.
Summary of the Invention
[0011] The present invention encompasses detergency builder compositions comprising:
(a) a tartrate succinate component which is a member select ed from the group
consisting of:
wherein each X is H or a salt-forming cation;
wherein each X is H or a salt-forming cation; and iii) mixtures therof;
and
(b) a hydrocarbyl succinate component of the formula:
wherein R is a hydrocarbyl group and each X is H or a salt-forming cation.
[0012] Preferred compositions are those wherein substituent R in the hydrocarbyl succinate
component (b) is C₈-C₁₈, more preferably C₁₂-C₁₆, alkyl or alkenyl. 2-Dodecenyl succinic
acid, or water-soluble salts thereof, is most preferred for use as component (b).
[0013] Typical compositions herein are those wherein the weight ratio of component (a):(b)
is in the range of 15:1 to 1:15, more preferably 2:1 to 1:3.
[0014] This invention also encompasses detergent compositions comprising conventional detersive
surfactants and detersive ingredients, and a detergency builder composition which
comprises a mixture of:
(a) a tartrate succinate component w hich is a member select ed from the
group consisting of:
wherein each X is H or a salt-forming cation;
wherein each X is H or a salt-forming cation; and iii) mixtures therof;
and
(b) a hydrocarbyl succinate component of the formula:
wherein R is a hydrocarbyl group and each X is H or a salt-forming cation.
[0015] Fully-formulated detergent compositions herein typically contain from 1% to 50% by
weight of detersive surfactants and from 5% to 45% by weight of the detergency builder
composition, the balance comprising conventional detergency ingredients or carriers.
Conventional anionic, cationic, and nonionic detersive surfactants may be used in
such compositions, as may other detersive surfactants as described more fully, hereinafter.
[0016] For laundry or hard-surface cleaning operations, such detergent compositions typically
comprise:
I. A. from 0% to 30% by weight of an anionic detersive surfactant selected from
the group consisting of conventional detersive alkyl benzene sulfonates, alkyl
sulfates, alkyl ether sulfates soaps, and mixtures thereof; and
B. from 0% to 30% by weight of a nonionic detersive surfactant selected
from the group consisting of conventional detersive ethoxylated alcohols, ethoxylated
alkyl phenols, and mixtures thereof;
C. mixtures of A and B, with the proviso that the composition contains
at least 5% by weight of detersive surfactant;
II. at least 10% by weight of a detergency builder component comprising:
(a) i) a tartrate succinate component which is a member selected from the group
consisting of:
wherein each X is H or a salt-forming cation; and
wherein each X is H or a salt-forming cation; iii) mixtures therof; and
(b) a hydrocarbyl succinate component of the formula:
wherein R is a hydrocarbyl group and each X is H or a salt-forming cation;
preferably, the weight ratio of (a) to (b) in the range of 2:1 to 1:3; and
III. the balance of the composition comprising conventional detergent ingredients.
[0017] Preferred for laundry detergents are compositions wherein the hydrocarbyl succinate
component of the builder is a C₁₂-C₁₆ alkyl or alkenyl succinate; the compound 2-dodecenyl
succinic acid, or water-soluble salts thereof, is most preferred.
[0018] The compositions herein may be formulated as liquids; or formulated to be releasably
carried on a sheet or other carrier substrate, or releasably contained in pouches;
or formulated as bars, powders, granules, tablets, flowable gels, or the like.
[0019] All percentages, ratios or proportions herein are on a weight basis, unless otherwise
specified.
Detailed Description of the Invention
[0020] The essential components of the builder compositions herein are the tartrate succinates
and also the hydrocarbyl succinates, all as more fully described hereinafter. The
detersive surfactants, optional detersive adjunct ingredients, as well as the carriers
fillers, etc., used in the detergent compositions of this invention are all well-known
to workers in this field.
[0021] (a) Tartrate Succinate Components: The tartrate succinate compounds used herein may be generically classified as "ether
carboxylates." These include tartrate monosuccinic acid, or salts thereof, having
the structural formula:
wherein each X is H or a salt-forming cation. This tartrate monosuccinic acid or salt
thereof is hereinafter designated as "TMS." "TMS" is used to designate both the acid
and salt forms of this material.
[0022] The tartrate monosuccinic acid component can be employed in the compositions herein
in its free acid form, i.e., wherein X in the structural formula is H. Alternatively,
and preferably this material may be partially or fully neutralized to a tartrate monosuccinate
salt. Preferred salt-forming cations useful in forming the neutralized materials are
those which yield substantially water-soluble salts of tartrate monosuccinic acid.
Examples of such preferred salt-forming cations include alkali metal, e.g., sodium,
potassium, lithium, ammonium, C₁-C₄ alkyl substituted ammonium and C₁-C₄ alkanolamine.
The most preferred salt-forming cations are sodium, potassium, monoethanolamine and
triethanolamine.
[0023] The tartrate monosuccinic component can be used in the builder compositions of this
invention in an amount ranging from about 10% to 85% by weight of the builder. More
preferably, the tartrate monosuccinate component will comprise from about 15% to 75%
by weight of the builder compositions herein. Most preferably, this component is present
to the extent of from about 50% to 65% by weight of the builder composition.
[0024] The second ether carboxylate composition which can be used in this invention is the
particular novel polycarboxylate, tartrate disuccinic acid, or a salt thereof, having
the structural formula:
wherein each X is H or a salt-forming cation. Tartrate disuccinic acid, or a salt
thereof, is hereinafter designated as "TDS.".
[0025] As with TMS component, the TDS component can be utuilzed in either its free acid
form or in its partially or fully neutralized form in the builder compositions herein.
Neutralizing cations are likewise those which provide TDS in the form of its substantially
water-soluble salt. Examples of suitable salt-forming cations include the same cations
hereinbefore described for formation of the tartrate monosuccinate material. For convenience
both the acid and salt forms of the TDS material will hereinafter be referred to as
the "tartrate disuccinate" or "TDS" component.
[0026] The TDS component can be used in the builder compositions of this invention in an
amount ranging from about 10% to 85% by weight of the builder. More preferably, the
TDS component will comprise from about 15% to 75% by weight of the builder compositions
herein. Most preferably, TDS is present to the extent of from about 50% to 65% by
weight.
[0027] Mixtures of TMS and TDS can also be used; indeed, mixtures are generally obtained
in the method of manufacture disclosed hereinafter. Typically, such mixtures comprise
TMS:TDS in ratios ranging from 97:3 to 20:80. Preferred ratios TMS:TDS are 95:5 to
40:60. These are used at the same levels as mentioned above for the single components
to provide the builder compositions of this invention.
[0028] (b)
Hydrocarbyl Succinate Component: This component is of the general formual R-CH(COOH)CH₂(COOH) i.e., derivatives of
succinic acid, wherein R is hydrocarbyl, e.g., C₁₀-C₂₀ alkyl or alkenyl, preferably
C₁₂-C₁₆ or wherein R may be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents,
all as described in the above-mentioned patents.
[0029] These succinate builders are preferably used in the form of their water-soluble salts,
including the sodium, potassium, ammonium and alkanolammonium salts, at levels of
15% to 90%, more preferably 35% to 50%, of the present builder compositions.
[0030] Specific examples of succinate builders include: lauryl succinate, myristyl succinate,
palmityl succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate, and
the like.
[0031] (c)
Detersive Surfactants: The detergent compositions of this invention will contain organic surface-active
agents ("surfactants") to provide the usual cleaning benefits associated with the
use of such materials.
[0032] Detersive surfactants useful herein include well-known synthetic anonic, nonionic
, amphoteric and zwitterionic surfactants. Typical of these are the alkyl benzene
sulfonates, alkyland alkylether sulfates, paraffin sulfonates, olefin sulfonates,
amine oxides, alpha-sulfonates of fatty acids and of fatty acid esters, ethoxylated
alcohols and ethoxylated alkyl phenols, and the like, which are well-known from the
detergency art. In general, such detersive surfactants contain an alkyl group in the
C₉-C₁₀ range; the anionic detersive surfactants can be used in the form of their sodium,
potassium or triethanolammonium salts. Standard texts such as the McCutcheon's Index
contain detailed listings of such typical detersive surfactants. C₁₁-C₁₄ alkyl benzene
sulfonates, C₁₂-C₁₈ paraffin-sulfonates and C₁₁-C₁₈ alkyl sulfates are especially
preferred in the compositions of the present type.
[0033] Aslo useful herein are the water-soluble soaps, e.g. the common sodium and potassium
coconut or tallow soaps well-known in the art.
[0034] The surfactant component can comprise as little as 1% of the detergent compositions
herein, but generally the compositions will contain 5% to 40%, preferably 6% to 30%,
of surfactant. Mixtures of the anionics, such as the alkyl benzene sulfonates, alkyl
sulfates and paraffin sulfonates, with C₉-C₁₆ ethoxylated alcohol surfactants are
preferred for through-the-wash cleansing of a broad spectrum of soils and stains from
fabric.
[0035] (d)
Detersive Adjuncts: The compositions herein can contain other ingredients which aid in their cleaning
performance. For example, it is highly preferred that the laundry compositions herein
also contain 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 mixtures of amylase and protease) are typically
used at levels of 0.001% to 2%, and higher, in the present compositions.
[0036] Moreover, the compositions herein can contain, in addition to ingredients already
mentioned, various other optional ingredients typically used in commerical produces
to provide aesthetic or additional product performance benefits. Typical ingredients
include pH regulants, perfumes, dyes, bleaches, optical brighteners, soil suspending
agents, hydrotropes and gel-control agents, freeze-thaw stabilizers, bactericides,
preservatives, suds control agents, bleach activators and the like.
[0037] In a through-the-wash fabric laundry mode, the compositions are typically used at
a concentration of 500 ppm, preferably 0.10% to 2.5%, in an aqueous laundry bath,
typically at pH 7-11 to launder fabrics. The laundering can be carried out by agitating
fabrics with the present compositions over then range from 5°C to the boil, with excellent
results.
Preparation of TMS/TDS
[0038] The TMS and TDS compounds used in the practice of this invention are not believed
to be described in the literature, so their preparation will be described in detail.
[0039] The first step of the preparation process herein involves the formation a of an aqueous
reaction mixture containing particular amounts of a maleate reactant comprising both
monovalent cation and calcium salts of maleic acid and a tartrate reactant comprising
both monovalent cation and calcium salts of tartaric acid. The total amount of maleate
plus tartrate reactants in the reaction mixture will generally range from about 20%
to 60% by weight of the mixture, more preferably from about 40% to 55% by weight.
Materials which yield these reactants in solution can be dissolved in water to form
the reaction mixture used in this process.
[0040] Usually both the maleate and tartrate reactants in requisite mixed salt form and
amounts can be generated in the reaction mixture in situ. This can be done by combining
in aqueous solution certain amounts of maleic acid or maleic anhydride, tartaric
acid, a source of calcium cations and, as a neutralizing agent, an hydroxide of a
monovalent cation in certain amounts. the molar ratio of maleic acid to tartaric acid
in such solutions will generally range from about 0.5:1 to 8:1, more preferably from
about 0.9:1 to 1.2:1. The ratio of maleic and tartaric acids which is used will depend
upon the relative amounts of tartrate monosuccinate and tartrate disuccinate desired
in the builder composition to be prepared.
[0041] A souce of calcium cations, which acts as a catalyst for the tartrate succinate-forming
reaction, is generally added to such aqueous solutions in an amount such that the
ratio of calcium cations to tartaric acid ranges from about 0.1:1 to about 2.0:1,
more preferably from about 0.8:1 to 1.5:1. However, within this ratio range, the amount
of calcium added should be such that the ratio of moles of calcium cations to total
moles of maleic and tartaric acids in solution is less than 1. Any compound which
yields calcium cations in solution can be employed as the calcium cation source. Such
compounds inlude calcium hydroxide and water-soluble calcium salts. Calcium hydroxide
is highly preferred since it acts as both a calcium cation source and a neutralizing
agent.
[0042] An hydroxide of a monovalent cation is also essentially added to the reactant mixture
as a neutralizing agent. This neutralizing agent is usually aded in an amount such
that the ratio of moles of monovalent cations to total moles of tartaric acid plus
the moles of maleic acid minus the mole of calcium cations ranges from about 2.1:1
to about 3.8:1. More preferably this ratio ranges from about 2.2:1 to about 3:1. The
monovalent cation-containing neutralizing agent can be any hydroxide which upon addition
to water yields monovalent neutralizing cations in solution. Such neutralizing agents
include, for example, alkali metal, ammonium or substituted ammonium hydroxide. Sodium
hydroxide is highly preferred.
[0043] Enough neutralizing base (e.g. calcium hydroxide and monovalent cation hydroxide)
should be added to the reaction mixture to ensure that the reaction mixture is over-neutralized.
Thus the reaction mixtures of this invention will generally have a pH within the range
of about 8.5 to 13, more preferably from 9.5 to 12.5.
[0044] In forming the reaction mixture of the present process, it is possible to employ
of the essential reaction mixture components. Precursors of the tartrate and maleate
mixed salt reactants in solution can take a variety of forms. For example, tartaric
acid in either its D-, L- or DL- stereoisomer form is suitable for use as the precursor
of the tartrate reactant. It is also possible to generate tartaric acid in situ by
reaction of maleic acid and hydrogen peroxide using, for example, a tungstate catalyst.
The maleate reactant can be derived from maleic acid. Maleic acid itself can be formed
in aqueous solution by the addition of maleic anhydride to water.
[0045] It is, of course, also possible to form the reaction mixture used in the process
appropriate by adding the tartrate and maleate reactants in their appropriate salt
forms to water and to thereby prepared the reaction mixture without the step of in
situ neutralization. If the reaction mixture is formed in this manner, amounts of
the tartrate, maleate and calcium materials, as well as added neutralizing agents,
should be selected so that the resulting solution corresponds in composition to the
hereinbefore described reaction mixtures formed by situ generation of the essential
reaction mixture components.
[0046] As indicated hereinbefore, the preferred process of the present invention employing
reactant molar ratios of maleate to tartrate within the range of 0.9:1 to 1.2:1 is
especially advantageous from the reactant converion and reaction kinetis standpoint.
A reactant ratios within this range, total reactant conversion levels as high as 84%
can be realized in comparison with the much lower conversion percentages reported
for & <DPA N=11>preparation of such materials as oxydisuccinate using a maleic
anhydride reactant. Without being bound by theory, the improved conversion percentages
which can be realized using the preferred process embodiments of the present reaction
may be in part due to the inherently greater stability of TMS in the reaction mixture
in comparison with oxydisuccinate (ODS) under similar conditions. TMS under conditions
used for its formation does not appear to decompose as readily as oxydisuccinate to
unreactive by-products such as fumarate, thereby enhancing both TMS formation and
subsequent TDS formation from TMS. It should also be noted that irrespective of conversion
percentage, production of TMS/TDS mixtures in general can be realized in a relatively
short reaction time compared with the extended reaction times which are reported to
be required for preaparation of other ether carboxylates such as oxydisuccinate.
[0047] It should also be noted that use of the hereinbefore described particular amounts
of he calcium cation source is likewise believed to play a role in realizing the improved
conversion levels achieved with the process of the present invention. In direct contrast
to prior art teaching regarding ether carboxylate preparation (See, for example, U.S.
Patent 3,635,830), the amount of calcium in the reaction mixture of the present process
should be kept within the hereinbefore described concentration limits in order to
avoid formation of a large amount of insoluble or sparingly soluble calcium salts
of the maleate and tartrate reactants. Utilization of these reactants in their soluble,
mixed salt, e.g. sodium/calcium, form may facilitate the kinetics of the ether carboxylate-forming
reaction and accordingly improve product yield.
[0048] After the aqueous reaction mixture hereinbefore described has been formed by combining
the separate reactants and catalyst, or precursors thereof, in the required concentrations,
the TMS/TDS composition forming reaction is carried out by maintaining the aqueous
reaction mixture at a temperature of from about 20°C to 120°C, preferably from about
50°C to 80°C, for a period of time sufficient to form a reaction product mixture which
contains the desired amounts of the tartrate monosuccinate and tartrate disuccinate
compounds of the compositios herein. Reaction times of from about 0.5 to to hours,
more preferably from about 1 to 4 hours will generally be suitable for realizing acceptable
yields of the compounds used in the builder composition herein.
[0049] Since the TMS/ TDS are to be used as detergent builders, it is especially important
that such compositions contain especially low levels of alkaline earth metals such
as calcium. The builder compositions of this invention should generally contain no
more than about 10 mole percent of calcium based on the total moles of TMS and TDS
present.
[0050] After the ether carboxylate-forming reaction has been completed to the desired extent,
the calcium content of the aqueous reaction must be reduced. Removal of calcium to
effect this reduction can be carried out in a number of ways known in the art. Frequently,
calcium can be removed from the product mixture by adding thereto a calcium precipitating
material having a greater affinity for reaction with calcium than do the tartrate
monosuccinate and tartrate disuccinate reaction products. Such materials can include,
for example, precipitating chelating agents such as ethanehydroxydiphosphonic acid,
or salts thereof (EHDP), or calcium precipitating materials such as alkali metal carbonate,
pyrophosphate, bicarbonate and/or alkali metal silicate. The resulting calcium precipitate
can thereafter be removed from the aqueous reaction product mixture by filtration.
An alternate means for removing calcium from the aqueous reaction product mixture
involves treatment of the reaction product mixture with an appropriate insoluble ion
exchange resin. No matter what technique is employed, calcium content of the aqueous
reaction mixture should be reduced to th xtent that the ratio of moles
of calcium to total moles of tartrate monosuccinate and tartrate disuccinate is less
than about 1:10, preferably less than about 1:20.
[0051] Preferably, in addition to such calcium reduction processing, the reaction product
mixture of the present process may also optionally be treated to remove excess reactants
or reaction by-products such as maleates, malates, tartrates and fumarates. This can
be accomplished by conventional salt separation procedures using a solvent such as
methanol in which these excess reactants and reaction by-products are relatively soluble
and in which the desired tartrate monosuccinate and tartrate disuccinate are relatively
insoluble.
[0052] After the calcium content of the aqueous reaction product mixture has been reduced
to the requisite levels, and, if desired, after excess reactants and reaction by-products
have been removed, the reaction product mixture may be concentrated by a removal of
water to the desired extent. Water removal may, for example, involve substantially
complete drying of the reaction product mixture, e.g., by spray drying, so that the
TMS/TDS mixture is recovered in solid, e.g., granular, form. Alternatively, the TMS/TDS
mixture in the form of an aqueous liquid may be utilized directly in the preparation
of builder, detergent compositions or laundry additive products of the types more
fully described hereinafter.
[0053] After reduction of the calcium content in the reaction product mixture, it is possible,
if desired, to acidify the product mixture using conventional acidification or ion
exchange techniques to convert the TMS/TDS products therein to their free acid form.
Normally, however, the tartrate monosuccinate and tartrate disuccinate materials can
be used as builders in their water-soluble salt form, and such acidification is therefore
not usually necessary or desirable.
[0054] It is also possible, if desired, to separate the individual components of the resulting
builder mixture and recover such compounds as substantially pure TMS and TDS materials.
Such component separation cab be effected, for example, using conventional liquid
chromatographic techniques. For use in some types of detergent compositions, it may
be desirable to use either TMS or TDS as substantially pure materials. More frequently,
however, recovery of the individual TMS and TDS components as substantially pure materials
is neither necessary nor particularly advantageous.
Reaction Sequence I
[0055] In this sequence, a mixture of tartrate monosuccinate (TMS) and tartrate disuccinate
(TDS) is prepared by a procedure which involves the reaction of maleate salts and
tartrate salts. In such a procedure, maleic anhydride (2205g, 22.5 moles) is heated
in 2000g of distilled water until dissolved. The resultant solution of maleic acid
is cooled to 85 ± 5°C and 2250 g L-(+)-tartaric acid (15.0 moles) is added with stirring
at 85 ± 5°C until a homogeneous clear acid solution is obtained.
[0056] Separately, 1111g of calcium hydroxide (15.0 moles) is slowly added to a mixture
of 4440g of 50% sodium hydroxide solution (55.5 moles) and 1000g distilled water while
stirring at a moderate rate such that only a small fraction of unwetted calcium hydroxide
is upon the surface of the solution at a time. Stirring is continued until an essentially
uniform base mixture is obtained.
[0057] The base mixture is then added at a uniform rate over 0.5 hour to the moderately
stirred acid solution which is at 70-85°C. The resulting reaction mixture is cooled
with warm (ca. 60°C) water in order to maintain a reaction temperature of 90 ± 5°C
most of the time. The reaction mixture may, however, boil briefly from time to time.
The object is to prevent major losses of water vapor and also to limit the amount
of insoluble salt which crystallizes upon the cool reaction vessel walls. As the last
10% of base is added, the reaction temperature is held at 85°C. The reaction mixture
is quickly weighed and b rought to 13,020g, i.e., 50% active,
with 200g of distilled water. (Active is defined here as total weight of organics
taken as their sodium salts i.e., sodium maleate and sodium tartrate or 160 x 22.5
moles + 194 x 15.0 moles = 6510g.)
[0058] The reaction mixture is immediately heated with steam, stirred moderately in a covered
reactor, and a 0.40g sample taken with time arbitrarily set at zero. The reaction
mixture, which is a white suspension, is brough to 90-100°C within 10 minutes. Within
15 to 20 minutes of time zero, the reaction mixture clears. Samples (0.40 + 0.04 g)
of the reaction solution are taken every half hour to be dissolved in 100 ml 0.1N
sulfuric acid solution and immediately submitted for high pressure liquid chromatography
(HPLC) analysis in order to monitor the course of the reaction.
[0059] The results of HPLC analysis of the 1.5 hour sample indicate that the reaction is
to be quenched at the 2.0 hour point. Quenching consists of cooling the reaction product
mixture to 50°C within 10 minutes. The homogeneous, almost colorless quenched reaction
product solution is reweighed and is made up again to 13,020g with 327g of distilled
water to give a reaction product solution containing 50% active.
[0060] HPLC analysis indicates that the composition of the organic portion of the reaction
product solution is 11.1% tartrate. 1.7% malate, 12.6% maleate, 10.9% fumarate, 35.0%
peak 2A, 19.6% peak 2B, 3.3% peak 3A, and 5.9% peak 3B. Peaks 2A and 2B are isomers
of sodium tartrate monosuccinate (TMS) and peaks 3A and 3B are isomers of sodium tartrate
disuccinate (TDS). Therefore, the HPLC estimated yield of TMS + TDS based upon all
peak areas is 63.7%. The approximate weight ratio of TMS:TDS is 86:14. All yields
are based upon HPLC refractive index raw data, i.e., are not corrected to mole%. Calculated
yield of this reaction based on tartrate is 4.139g.
[0061] A second reaction product batch of the same size is made using similar procedures.
HPLC analysis indicates that the composition of this second reaction product solution
is 9.8% tartrate, 1.7% malate, 12.4% maleate, 10.1% fumarate, 35.0% peak 2A, 18.1%
peak 2B, 5.1% peak 3A, and 7.9% peak 3B. Again peaks 2A and 2B are isomers of sodium
tartrate monosuccinate (TMS) and peaks 3A and 3B are isomers of sodium tartrate disuccinate
(TDS). Therefore, the HPLC-estimated yield of TMS + TDS based upon all peak areas
is 66.1%. The approximate weight ratio of TMS:TDS is 80:20. Yield is 4400g based on
calculation.
[0062] Both reaction product batches are combined to give 26,040g of solution which is calculated
to contain 8539g of TMS/TDS and 30 moles of calcium ion. This solution is then diluted
with 26,040g of water. While this solution is at 26°C and stirred vigorously, a 28%
solution of 7500g (30 mole) of ethanehydroxydiphosphonate disodium salt dissolved
in 18,750g of water is added followed by 3178g of 50% sodium hydroxide solution to
give a pH of 10.5. Stirring is continued for 18 hours; the final pH is eleven. The
resulting precipitate (EHDP-calcium complex) is then removed by filtration using suction
filtration equipment with a paper filter, and the filtrate is washed with 4 liters
of water. The resulting supernatant, 56 liters, is filtered again through a glass
frit to remove any remaining fine particles. This clear solution is then evaporated
in a steam heated vat with a compressed air stream blown above the surface to give
a solution of 32,550g.
[0063] This solution is then poured into 80 liters of vigorously stirred methanol. This
is done to help separate the less soluble TMS and TDS from the more soluble maleic
and fumaric acid salts. The stirring is continued for 15 minutes followed by a 1/2
hour settling period. Then the liquid is decanted from the gummy solid by siphon.
This solid is dissolved in 13,500g of distilled water to give 26,685g of solution
which is than poured into 68 liters of methanol, essentially repeating the above.
The resulting solid is dissolved in 6 liters of distilled water (pH = 8.4),
and the vat is heated with steam. Methanol is removed with a stream of nitrogen directed
on the surface of the solution which is well stirred. This is continued until ʹH-NMR
analysis indicates that the methanol is removed. The resulting solution is 16,380g.
To reduce viscosity, 2 liters of water are added, and the mixture is filtered to give
18,887g of solution. This solution is analyzed and found to have the following composition
by high pressure liquid chromatography using a refractive index detector: 43.6% TMS/TDS
(8,235g or 96.4% recovery by workup), 2.1% tartrate, 0.5% malate, 0.9% maleate, and
1.1% fumarate. The TMS/TDS ratio is 78.2:21.8. The calcium ion level of the solution
si 0.048 weight % as determined by atomic absorption.
Reaction Sequence II
[0064] A TMS/TDS reaction product mixture is prepared using procedures similar to those
set forth in Reaction Sequence I except that the reactants used to form the reaction
mixture are maleic anhydride, tartaric acid, sodium hydroxide and calcium hydroxide
in a 1.3:1.0:3.93:0.5 molar ratio. The resulting reaction product mixture is determined
by high pressure liquid chromatography to contain 17.2% tartrate, 1.5% malate, 9.9%
maleate, 10.3% fumarate, TMS (2A 36.2%, 2B 13.4%) and TDS 3A 5.3%, 3B 6.2%). The rest
of the sample is a mixture of water and calcium salts.
[0065] Calcium is then removed from this mixture by a precipitation procedure using a combination
of carbonate salts. In such a procedure 26.5 grams of sodium carbonate and 21.0 grams
of sodium bicarbonate (0.25 mole of each salt) are dissolved in 204 grams of water.
This solution is then added to 250 grams of the above-described reaction product mixture
which contains 0.125 moles of calcium. The resulting mixture is placed in a 1 liter
flask equipped with a thermometer and stirrer. This mixture is then heated to 80°C
and stirred for 3 hours. After cooling to 25°C while stirring is continued, this mixture
is filtered through a sintered glass filter. The resulting filter cake is washed with
20ml of water twice. The filtrate is adjusted to a weight of 1000 grams with the addition
of water and then is analyzed. The filtrate is found to contain tartrate - 1.48%;
malate - 0.14%; maleate - 1.02%; fumarate - 0.83%; TMS (2A 3.3%, 2B 1.3%); TDS -(3A
0.5%, 3B 0.5%); and calcium - 0.009%. The maleate and fumarate salts are then removed
using a methanol precipitation procedure as in Reaction Sequence I.
[0066] The following examples illustrate the practice of this invention, but are not intended
to be limiting thereof.
EXAMPLE I
[0067] A water-softening builder composition is as follows:
Ingredients Percent (wt.)
TMS/TDS Mixture* 50
2-Dodecenyl Succinate (Na Salt) 50
*Prepared as in Reaction I.
[0068] The composition of Example I is added to an aqueous laundry bath at a concentration
of 500ppm to reduce water hardness and to enhance the fabric cleaning performance
of commercial laundry detergents.
EXAMPLE II
[0069] A composition of the type described in Example I is prepared as pre-measured, 50-gram
sachets, using water-permeable non-woven cloth as the sachet material. The sachets
are simply placed in an aqueous bath to provide water softening and detergency builder
activity.
EXAMPLE III
[0070] The present development allows the formation of highly built liquid detergents. Previous
formulations used high levels of precipitating builders, such as fatty acids or alkylsuccinic
acid, but in some conditions these materials may deposit onto fabrics and machine
parts. Other soluble builders, such as polycarboyxlate, cannot be incorporated at
high levels into liquid detergent formulations.
[0071] A heavy-duty, liquid laundry detergent or hard surface cleaner is as follows:
TMS/TDS Mixture 9.2
2-Dodecenyl succinic acid 5.8
Dodecylbenzene sulfonic acid 8.5
C
10-15 alcohl 7 ethoxylated 9.7
Triethanolamine coconut alcohol sulfate 3.2
Oleic acid 3.2
Triethanolamine 3.5
Sodium hydroxide 2.6
Propanediol 1.7
Ethanol 3.3
Cu ene sulfonic acid 5.4
Citric acid .8
Water 40
DTPMPA* 0.85
Miscellaneous - minors inclusive of enzyme balance to 100
*Diethylene triamine pentamethylene phosphonic acid.
[0072] The above composition has a pH, (1% in water; 20°C,) of 7.8. The liquid composition
of the example is homogeneous, and stable on storage at room temperature.
[0073] The following examples illustrate additional executions of this invention. The abbreviations
used are:
C₁₂HLAS linear dodecyl benzene sulfonic acid
TEACnAS triethanolamine alcohol sulfate
C
x-yEO
n C
x-y alcohol ethoxylated with n moles of ethylene oxide
DTPMPA diethylene triamine penta(methylene phosphonic acid
S(soil) (poly(terephthalate propylene glycol ester)
R(elease) (ethoxylated with about 30 moles of ethylene
P(olymer) (oxide
DSA 2-decenylsuccinic acid
DDSA 2-dodecenyl succinic acid
TSA 2-tetradecenyl succinic acid
HSA 2-hexadecenyl succinic acid
C
12-14FA coconut fatty acid
TFA triethanolamine
NaCs sodium cumene sulfonate
S(oil) (Tetraethylene penta-amine .15EO.
D(ispersant)
[0074] The liquid compositions are prepared by admixing the ingredients, and adjusting pH
(1% aqueous solution; 20°C) to the desired level, generally 6.5 to 9.
[0075] In the compositions herein, the levels of tartrate succinate typically range from
2-15%, preferably 2-10%, most preferably 3-7%. The level of hydrocarbyl succinate
is typically 3-20%, preferably 5-15%. The total of the two components is typically
5-35%, preferably 7-25%. The weight ratios of the tartrated succinate: hydrocarbyl
succinate range from 3:1 to 1:6, preferably 2:1 to 1:3.
[0076] The composition of Example V was tested in a washing machine in a 60°C cycle and
compared to VIZIR
R, a liquid detergent containing fatty acid builder. The comparative performance on
various types of soil on cotton fabrics are reported below. Product concentration
during wash was 1.0%.
[0077] The comparative stain removal performance readings represnt the average of the evaluations
by two expert judges.
EXAMPLE XIII
[0078] A granular detergent composition comprises the following ingredients:
[0079] An aqueous crutcher mix is prepared and spray-dried. The Enzyme Mix and TAED bleach
activator and dry-mixed with the resulting granules.