PT94099A - Process for the preparation of alkyl ethoxycarboxylate surfactants - Google Patents

Abstract

An improved process for the preparation of alkyl ethoxycarboxylate surfactants characterized in that ethoxylated fatty acids are caused to react with a selectively retarded base and anhydrous chloroacetic acid or a salt thereof is described. The reagents can be caused to react simultaneously or, initially, the retarded base may be caused to react with the ethoxylated fatty alcohol and the resultant product subsequently reacts with the anhydrous chloroacetic acid or salt thereof.

Description

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Mod. 71-10000 ex. -89/07 20 25 30 62 238 Casei 39 ^ 7

This invention relates to a process for the preparation of alkyl ethoxycarbonic acid surfactants of the type disclosed in U.S. Patent Nos. 2,183,853; 2,653 * 972; 3,003,954; 3,038,862; 3,741,911; and 3,941,710; British Patent No.s. 456,917 and 1,169 * 496; Canadian Patent No. 912,395; French Patent nos. 2.014 * 082 *. and 2,042,793; and Patent Application Ser. 7,201,735-Q and 7,406,336; and Japanese Patent Application Ser. 96,579 / 71 and 99,331 / 71. The invention also relates to laundry compositions, such as shampoos, laundry detergents, and, preferably, liquid dishwashing detergent compositions containing such alkyl ethoxy carboxylates surfactants.

Alkyl ethoxycarbonyl-xylates surfactants are usually prepared from nonionic alkyl polyether surfactants. Specifically, the alkyl ethertaxicarboxylate surfactants are initially formed by reacting ethoxylated fatty alcohol with a hydroxide base to deprotonize the alcohol and create the corresponding alkoxide base. The alkoxy is then reacted with a chloroacetic acid salt to produce the alkyl ethoxy carboxylate. However, the chloroacetic acid salt also tends to react with the hydroxide base in an undesired parallel reaction to form a glycolate salt. In order to obtain a high conversion of the ethoxylated alcohol to alkyl ethoxy carboxylate, the reaction must proceed at elevated temperature and under low pressure to bring the equilibrium of the deprotonation reaction to the alkoxide base and avoid undesirable parallel reaction. Alternatively, the reaction may be carried out by an excess of hydroxide base and an excess of chloroacetic acid and subsequently by removing the contaminant which is insoluble in water. 3967

1 formed by hydroxide and chloroacetic acid salt. It is an object of the present invention to provide a process for the preparation of alkylethoxycarboxylate surfactants using a selective delayed base in place of a hydroxide base in order to avoid undesirable side reactions and eliminate the need for removal of conidia. indesedables. 10 15

Mod. 71-10000 ex. It is a further object of this invention to provide a process for the preparation of allyl ethoxycarbonic surfactants so that a minimum amount of anhydrous chloroacetic acid or a salt thereof used in the conversion of ethoxylated alcohol into alkylethoxycarboxylate product. The present invention encompasses processes for the preparation of alkylethoxycarboxylates surfactants of the formula ## STR3 ## wherein R @ 2 is a C1-6 alkyl group, x is an average number of about 1 to 15 (A) an ethoxylated fatty alcohol of the formula ROCG H (CH₂)!), Wherein R á is a C a to C gex al alkyl group and is a number about 1 to 15; (b) a delayed base of the formula R 0 -M + wherein R 2 is a secondary or tertiary alkoxy, R 2 is a C 12 non-linear alkyl group with at least one branching site at 3 carbon atoms of the oxygen atom , and M is an alkali metal or alkaline earth metal cation; and -2.35 1 5 10 15

Mod. 71 -10000 ex. 89/07 20 25 62,233 Gas: 3967

(c) anhydrous chloroacetic acid, a molar ratio of the delayed base to the anhydrous chloroacetic acid of 2: 1, or an alkali metal salt or an alkali metal salt of anhydrous chloroacetic acid at a molar ratio of the delayed salt base alkali metal or alkaline earth metal salt of chloroacetic acid of 1: 1; wherein the molar ratio of the ethoxylated fatty alcohol to the anhydrous chloroacetic acid or the alkali metal salt or alkaline earth metal salt thereof is from about 1: 0.7 to about 1: 1.25 at the temperature is about 20 to 14 ° C, and the pressure is about 1 to 760 mm Hg. The alkyl ether oxycarbocarboxylates of this invention are of the formula RO (GH2 GH20) xGH2 G00-M + wherein R is a C1-6 alkyl group, x is an average number of about 1 to 15 and M is alkali metal or an alkaline earth metal cation. The alkyl chain having about 8 to about 18 carbon atoms may be obtained from fatty alcohols, olefins, and the like. Usually and prexerentially the alkyl chain will be a mixture of alkyl chains. Pure alkyl chains can be used. The alkyl chain is desirably a saturated alkyl chain in a mixture, but may also be a disulphated and / or unsaturated alkyl chain. Suitable alcohol precursors of the surfactant alkyl ethoxy ethoxy carboxylates of this invention are the primary aliphatic alcohols containing 8 to 18 carbon atoms. Other suitable primary aliphatic alcohols are the linear primary alcohols obtained from the hydrogenation of vegetable or animal fatty acids, such as,

Case; 3967 5 10 15

Mod. 71-10000 ex. Such as coconut, palm kernel, and tallow fatty acids or reactions formed by ethylene and subsequent hydrolysis as in the Ziegler type processes. Preferred alcohols are; n-octylic, n-nonylic, n-nonadecyl, n-nonadecyl, n-decadyl, n-decadecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl and n-octadecyl. Other suitable alcohol precursors include primary alcohols having a derivation ratio in the beta or 2 carbon atoms in which the alkyl derivation contains 1 to 4 carbon atoms. In such alcohols at least 30% of the alcohol of each specific chain length is desirably linear and the derivative preferably comprises about 50% of methyl groups with small amounts of ethyl, propylic, and butyl. These alcohols are conveniently produced by reacting linear olefins having from about 11 to 17 carbon atoms with carbon monoxide and hydrogen. Both the linear and the derivative alcohol chain are formed by these processes and the blends can be used as such or can be separated into individual components and then further compounded to give the desired combination. 25

Typical processes for preparing alcohols which are then used to prepare alcohols are disclosed in U.S. Pat. 2,564,456 and 2,587,858 and the direct hydroformylation of olefins to give alcohols is disclosed in U.S. Pat. 2,504,682 and 1,581,988. All these patents are hereby incorporated by reference.

Equivalent secondary alcohols may also be used. It will be apparent that by using a single olefin chain length as the starting material, a corresponding single strand of alcohol will result, but it is generally more economical to use blends of olefins having a carbon chain length extension of 35 around the desired medium. Of course, this provides -4-

Ml. 19¾¾ 52,238 Oase: 396? 1 will show a mixture of alcohols having the same distribution of chain lengths around the medium. Primary aliphatic alcohols, obtained from vegetable oils and fats and other petroleum-providing products, having alkyl groups or alkyl groups as part of their structure, will also contain a series of chain extensions. Since the area of chain extensions is Gg-C20 and higher, it is common practice to separate the product from such supplier products into different series of chain extensions which are chosen based on the purposes of their use. 15

Mod. 71-10000 ex. The ethoxy portion of the operating force corresponding to the ethoxy portion of the ethoxylated reactant alloy is desirably containing a chain length in the range of from 1 to 15 · Kais preferably, the average length of the ethoxy chain is from about 2 to 6. The desirable average length of the ethoxy chain in the ethoxylated fatty alcohol may be obtained using a catalyzed ethoxylation process wherein the molecular amount of ethylene oxide reacted with each equivalent of fatty alcohol will correspond to the average number of ethoxy groups in the ethoxylated alcohol. It is known that the addition of ethylene oxide to alkanols is promoted by a catalyst, more conventionally, a strongly acidic or strongly basic catalyst. Suitable basic catalyses are the basic alkali metal salts of Group I of the Periodic Table, such as sodium, potassium, rubidium and cesium; and the basic salts of certain alkaline earth metals of Group II of the Periodic Table, such as calcium, strontium, barium and in some cases magnesium. Suitable acid catalysts include, broadly, lewis acid from Friedel-Graft catalysts. Specific examples of such catalysts are the fluorides, chlorides and bromides of boron, antigen, tungsten, iron, -5-35 10 15

Mod. 71 -10000 ex. 89/07 20 25 30 35 62.238Gase: 3967

Jl.Mainn

nickel, zinc, tin, aluminum, titanium, and molybdenum. The use of compounds of such halides with, for example, alcohols, ethers, carboxylic acids, and amines has also been reported. Still further examples of known acidic and alkoxylation catalysts are sulfuric and phosphoric acids; perchloric acid or perchlorates of magnesium, calcium, manganese, nickel and zinc; metals oxalates, sulphates, phosphatides, carboxylates and acetates; alkali metal fluoroborates; zinc titanate; and metal salts of benzene sulphonic acid. The type of catalyst used will determine the distribution of the arrangement of the ethoxy groups. Stronger catalysts will result in a wider distribution. Conventional methods for the preparation of alkyl ethoxy ethoxy carboxylate surfactants use hydroxides to react with the ethoxylated fatty alcohols. The hydroxide deprotonates the alcohol and converts it to the corresponding alkoxide. A chloroacetic acid salt is added to the reaction mixture and reacted with the alkoxide to form the alkyl ethoxy carboxylate. A problem with this method is that the hydroxide, in addition to deprotonating the alcohol , also reacts with the chloroacetic acid salt to form a glycolate salt, a very undesirable byproduct. It is therefore necessary that this reaction takes place at elevated temperatures and at low pressures to bring the deprotonating reaction towards the alkoxide so as to leave a minimal amount of hydroxide in the reaction mixture to react with the chloroacetic acid salt. An alternative or complementary method involves the use of excess hydroxide and excess chloroacetic acid salt, removing the contaminant, the glycol salt, from the alcohols upon completion of the reaction. An alternative to the use of the hydroxide to deprotonize the fatty alcohol has therefore been investigated and herein proposed. It has been found that the pKa base (measure of the reactivity of a molecule) has to be large enough to enable it to deprotonize the fatty alcohol, leaving it in a form to react with the chloroacetate. I) and likewise, the base must have sufficient complements attached to the reacting oxygen atom to prevent any reaction with the chloroacetyl ion. 10 15

Mod. 71 -10000 ex. The delayed base of this invention is represented by the formula R 0 -M +, generally constituting an alkyl group, a reactant oxygen center, and a cation. The structure of this delayed base is either secondary or tertiary. The base contains a non-linolenic alkyl group with at least one branching site at 3 carbon atoms from the reactive center, the oxygen atom, and an alkali metal or complementary alkaline earth metal. The preferred delayed base is a tertiary material containing less than 6 carbon atoms. More preferred is the terti-butyxide, which is sufficiently reactive to remove a hydrogen atom from the fatty alcohol, but contains a tertiary alkyl attached to the reactant oxygen atom which prevents it from reacting with the chloroacetate ion. Instead, the t-butoxide combines with the hydrogen of the alcohol to form t-butanol, which is easily removed from the resulting mixture. Anhydrous chloroacetic acid may be used to combine with the alkoxide to form the alkylethoxycarboxylate, but aqueous chloroacetic acid can not be used. The reason for this is that the aqueous chloroacetic acid contains water which, under the reaction conditions, generates hydrate ions. This necessarily re-establishes the complications associated with the method described above, i.e. the formation of undesirable parallel product, glioolated salt, of the hydroxide reaction with chloroacetate. Thus, chloroacetic acid has

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Mod. 71 -10000 ex. - 89/07 20 62.236 Case? 3967 to be used in the anhydrous state, but this requires the use of 2 equivalents of the delayed base for each equivalent of anhydrous chloroacetic acid. This ratio of 2 to 1 is necessary because, in addition to deprotonating the fatty alcohol, the base must also deprotonize the chloroacetic acid to form the chloroacetate anion which is required to react with the alkoxide and form the alkylethoxycarboxylate. The preferred form of chloroacetic acid is its alkali metal salt or alkaline earth metal salt. Most preferred among these are sodium chloroacetate, potassium chloroacetate, or a combination thereof. These acetates require only one equivalent of the delayed base for each equivalent of the chloroacetate. The ethoxylated fatty alcohol has to be put into the reaction mixture at a molar ratio of the alcohol to the anhydrous chloroacetic acid or alkali metal salt or alkaline earth metal salt made therefrom of from about 1: 0.7 to 1: 1.25, preferably from about 1: 1 to about 1: 15. The temperature and pressure control in the process of this invention increases the degree of reaction. For example, the reaction of the present invention may be in the range of 20 DEG to 140 DEG and under a pressure of 1 to 760 mm Hg, preferably 60 to 120 ° C and under a pressure of 15 to 350 mm Hg, if a increased degree of reaction. In comparison conventional methods for making alkylkethoxycarboxylic surfactants have to be carried out at elevated temperatures and at low pressures so as to avoid the undesirable parallel glycol reaction.

In addition, the process of this invention can achieve very specific conversion levels of the alcohol

Mod. 71 -10000 ex. 62,238 Case: 3967 ethoxylated on alkyl ethoxy carboxylate from about 70% to 1000% without tight control of the reaction temperature and / or pressure and without large excesses of the reactants. Conventional methods for laser surfactants or alkyl ethoxy carboxylates generally require excess hydroxyl and chloroacetic acid in addition to the aforementioned requirement of elevated temperatures and low pressures. This advantage over conventional methods for making alkylkethoxycarboxylate surfactants becomes very prominent when the desired conversion of the alcohol to alkylethoxycarboxylate is above 90%. Under this parameter, conventional methods require excess of hydroxide and chloroacetic acid (sometimes above 100%) and / or 15 1 s X <D Rigorous temperature and pressure control. By using the Î ± -butoxide, the process of this invention requires only minimal temperature and pressure control (only for the purpose of accelerating the degree of reaction) and, at most, terti-butoxide and chloroacetate excesses of about 10% to 25%. The resulting product may be subjected to an improvement process depending on the purpose for which it is used. For certain uses, such as for example the voltage flow, it is possible to directly use the resulting crude product. In this case it is unnecessary to separate the sodium chloride or potassium chloride formed as a by-product. If such separation is desired, it is possible to do so by adding the reaction mixture to a sufficiently strong aqueous solution of sulfuric or hydrochloric acid, such that the final pli is cooled, at room temperature, to an upper organic phase containing the free acid which may be readily separated from the lower aqueous phase containing any unreacted chloroacetate and inorganic salts in dissolved form (Pat., U.S. Patent 3,002,443). column 4, lines 6-11). A greater degree of separation in a markedly shorter time period will occur if the mixture is heated. Then the alkyl ethoxy carboxylate acid can be neutralized by adding the higher phase mixture to a sufficiently strong aqueous solution of sodium hydroxide, potassium hydroxide or ammonium hydroxide so that the final pH is about 7 to 10 .

Mod. 71-10000 ex. - 89/07

The alkylethoxycarboxylate surfactants produced by the present invention may be used in any compositions known in the art because they contain such surfactants. They are preferably used in laundry compositions, such as shampoos, laundry detergents and liquid detergent compositions for dishwashing. Such compositions are disclosed, for example, in U.S. Patent 4,486,338 and (Ootani et al) and 3,941,710 (Gilbert et al) and Japanese Patent Application 48-60706 and 48-64102 (both patents Kao) , all incorporated herein by reference *

Preferred compositions of household dishwashing liquid detergent comprise from about 5% to 50% of a surfactant blend comprising: (a) from about 80% to 100% of alkyl ethoxy -carboxylates of the formula R 2 (OH) 2 O 2 wherein R 2 is a C 1-6 alkyl group, x ranges from 0 to about 10 and the ethoxylated distribution and such that, based on weight, the amount of material wherein x is 0 is less than about 20% and the amount of the material. wherein x is greater than 7 and less than about 25%, the median x is about 2 to 4 when the mean of R is 0-40 or less, and the mean is 10-15.

Mod. 71 -10000 ex. - 89/07 62,233 Gase *. M x J7 x is about 3 a. 6 when the mean R is greater than 0 · 4, and M is a 0 to about 10% alcohol ethoxylates of the formula: wherein R is a C 1-12 alkyl group â € ƒâ € ƒâ € ƒ16 ex ranges from 0 to about 10 and the mean x and less than about 6 and (c) from 0% to about 10% of soaps of formula: wherein R is And M is a cation; said composition having a pH of about 7 to 11.

The above-mentioned liquid dishwashing detergent compositions contain a surfactant blend comprising a higher amount of alkyl ethoxy ethoxy carboxylate surfactant and little or no alcohol ethoxylate and counterbalance soap by-products. These and other optional and complementary ingredients usually found in liquid 25-fold dishwashing compositions are given below. The foregoing composition contains from about 5% to 50% by weight, preferably from about 10% to 40%, preferably from about 12% to about 30%, of a mixture of surfactant restricted in mine account levels. The surfactant blend contains from about 80% to 100%, preferably from about 85% to 95%, most preferably from about 90% to 95%, of alkane: 3967

2-methoxycarboxylates of the general formula RO ## STR7 ## in which R 1 and a C 2 to C 3 alkyl group, x ranges from 0 to about 10, and the ethoxylated distribution is such that, based on weight, the amount of material in which x is 0 is less than about 20%, preferably less than about 15%, more preferably less than about 10%, and the amount of material in which x is greater than 7%, is less than about 25%, preferably less than about 15%, even more preferably less than about 10%, the mean x is from about 2 to 4 when the average of R 2 is or less, and the mean x is from about 3 to 6 when the average R is greater than G 1, and M is a cation, of choice selected from alkali metal, alkaline earth metal, ammonium, mono-, di-, and triethane-1-ammonium, still more preferably sodium, potassium, ammonium, and mixtures of the same magnesium ions. Preferred alkyl ethoxy carboxylates are those in which R is a C12 to C12 alkyl group. The surfactant blend also contains from 0% to about 10%, preferably less than about 20%, even more preferably less than about 5%, of alcohol ethoxylates of the formula ROECR? C? wherein R is a C1-4 alkoxycarbonyl group ranges from 0 to about 10 and the mean x is less than 6. The surfactant mixture also contains 0% to about 10%, preferably less than about 10% more preferably less than about 5% of soaps of the formula RC00-M +, wherein R is a C1 to C6 alkyl group and G is a cation as described above. 30

The a-dotted non-carboxylated alcohol ethoxylates are detrimental to the mixture of alkyl ethoxy ethoxy carboxylate surfactants. Therefore, it is decisive that the alkyl ethoxy carboxylate surfactant blend used in this invention contains less than 10% by weight of the ethoxylates of the alcohol from which it is derived. 35 62,238 Oasei 3967

The above compositions have a pH of about 7 to 11, determined as the pH of the composition undiluted with a pH meter. The preferred detergent composition has a pH of about 8 to 10.5 and still more preferably of about 8.5 to 10. Traditionally, with liquid dishwashing positions have a pH of about 7. for detergent compositions such as these that a more alkaline pH of about 9 considerably improves fat cleaning compared to a product having a pH of 7. This cleaning benefit appears to be unique in compositions containing the present alkyl ethoxy carboxylates. Surprisingly, these compositions are nevertheless very gentle to the hands at an alkaline pH. 15

Mod. 71 -10000 ex. - 89/07 20 25

If a composition having a pfi greater than 7 is more effective in improving performance it should contain a buffering agent capable of maintaining the alkaline pH in the composition in dilute solutions of the composition. This buffering agent may be an active detergent in its own sense, or may be a low molecular weight, organic or inorganic material which is used in this composition only to maintain an alkaline pH. Preferred buffers for compositions of this invention are nitrogen containing materials. Some examples are gliein or other lower amino acids or amines of the alcohol such as mono-, di-, and tri-ethanolamine. These buffering agents are usually present at a level of about 0.1% to 10% by weight, preferably from about 1% to 1%, still more preferably from about 1.5% to 5%

The cations for the alkylethoxycarboxylates may be alkali metals, alkaline earth metals, ammonium, and lower alkanol and ammonium ions. It has been found that for the present alkylethoxycarboxylates the presence of bivalent cations greatly improves the cleaning of fatty surfaces.

Mod. 71-10000 βχ.-89/07 20 25 30 62,238 Case; 3967

harsh This is especially true when the compositions are used in purified water containing few bivalent ions. Liquid dishwashing compositions containing alkyl ethoxy carboxylates which do not conform to the narrow definition referred to above will be less favored by the addition of bivalent ions, and in many cases will actually inhibit a reduced cleaning action on the addition of actives bivalents. Bivalent ions are believed to increase the volume of the present alkylethoxycarboxylates within the oil / water, thereby reducing the inner tension and improving the cleaning of the fat. Preferably, the bivalent ions are added with a salt chloride or sodium sulfate compositions containing an alkali metal or ammonium salt of the alkylethoxycarboxylate, even more preferably the sodium salt, after the composition has been neutralized with a strong base. The level of divalent ion in the composition is from 0% to about 1.5%, preferably from about 0.2% to 1%, even more preferably from about 0.3% to 0.8% by weight. Particularly preferred divalent ions are the magnesium ions. When both the divalent ions and the alloal pH are combined with the surfactant blend, a fat cleaning is achieved which is greater than. which is obtained either by the alkaline pH or by the divalent ions in the quiescent state. Preferably the divalent ion is magnesium present in the composition at a level of about 0.1% to 1%, even more preferably about 0.3% to 0.8% by weight, while the pH is Preferably about 8 to 9.5 and still more preferably about 8.5 to 9.5. Compositions containing high levels of magnesium and having a pH well above about 9.5 are not preferred because of a tendency to form precipitates · -14- 35 1 62.238 Qase: 3967 21 m 189?

Co-Iensio-Active Agents

The compositions disclosed herein preferably contain certain cosurfactant agents to aid in the formation of foam, solvent action and / or mildness. 5 10

Included in this category are various anionic surfactants commonly used in liquid dishwashing detergents. The cations associated with these anionic surfactants may be the same as the ions described previously for the alkyl ethoxy carboxylates. Examples of the anionic cosurfactants available for use herein are the following classes:

Mod. 71-10000 ex. (1) Alkyl benzene sulfonates in which the alkyl group contains from 9 to 15 carbon atoms, preferably 11 to 14 carbon atoms, in a straight or branched chain configuration. A particularly preferred linear alkyl benzene sulfonate contains about 12 carbon atoms. U.S. Patent 2,220,099 and 2,477,333 describe these surfactants in detail. (2) Alkyl sulphates obtained by sulphating an alcohol having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms. The alkyl sulphates have the formula ROSO-Mh-, wherein R is the C1-4 alkyl group and M is a mono- and / or bivalent cation. (3) Paraffin sulfonates having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms, in the alkyl moiety. These surfactants are commercially available as Hostapur SAS from Hoechst Oela-nese. (4) Olefin sulphonates having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms. -15- 35 '3' 3 21.MAI.iS80 fil 62.238

Case? U.S. Patent 3,332,880 contains a description of usable olefin sulphonates. (5) Alkyl ether sulfates obtained from the toxination of an alcohol having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms, less than 30, preferably less than 12, ethylene oxide molecules. The sulfates of alkyl ether has the formula: R0 (C2 H40) xs3-M + 10 wherein R1 is C1-22 alkyl, x is 1-30, and M is a mono- or divalent cation. (6) Alkyl gillceryl ether sulfonates having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms in the alkyl moiety.

Mod. 71 -10000 ex. (7) Bialkyl sulfosuccinates of the formula: wherein each of R 2, which may be the same or different, represents a straight-chain alkyl group or branched chain having from about 4 to 10 carbon atoms and more preferably from about 6 to 8 carbon atoms, and M + represents a mono- or divalent cation. A more complete description of usable bialkyl sulfosuccinates can be found in GB 2,105,325 and GB 2,104,913,30 (8) Fatty acid ester sulphonates of the formula: â € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒ- linear or branched alkyl of from about 1 g to about 1 g, preferably from 1 to 28, a linear or branched alkyl of from about 0 to 1 g, preferably from 1 to 2, , And M + represents a mono or bivalent catheter. 5 10 15

Mod. 71 -10000 ex. (9) Mixtures thereof. The above-described anionic surfactants are all commercially available. It should be noted that although both the bialkyl sulfosuccinates and the fatty acid ester sulfonates function well at a neutral or slightly alkaline pH, they are not chemically stable in a composition having a pH much greater than about 8.5. Other cosurfactants suitable for use in the compositions are the nonionic fatty alkyl polyglycosides. These surface active agents contain straight chain or branched chain alkyl groups, preferably about G to G, and an average of about 1 to 5 glucose units, with a mean of 1 to 2 units of glucose more preferably. U.S. Patent 4, 393, 203 and 4-732,704 incorporated by reference, describe these surfactants. The foregoing agents for the compositions described herein may also contain mixtures of anionic surfactants with alkyl polyglycosides. The coacting forces are present in the composition at a level of from 0% to about 35% by weight, preferably from about 3% to about 25%, most preferably from about 7% to about 20%

Another component that may be included in the compositions is a foam stabilizer surfactant (foam enhancer) at a level of less than about 15%, preferably about 0.5% to about 12%, preferably about from 1% to 10%. Optional surfactants foam stabilizers operable in the instant composition are of five basic types - betaines, condensates of gaseous: ethylene oxide, fatty acid amides, non-semipolar oxide ions amine and cationic surfactants.

The compositions may contain bethanolic detergent surfactants having the general formula (+) (-) R -

Mod. 71-10000 ex. - wherein R is a hydrophobic group selected from the group consisting of alkyl groups containing from about 10 to about 10 carbon atoms, preferably from about 12 to about 18 carbon atoms, alkyl aryl and aryl al-alkyl containing a similar number of atoms with a ring of benzene treated as equivalent to about 2 carbon atoms, and similar structures interrupted by starch or ether groups and an alkyl group containing 1 to about 3 carbon atoms and R is an alkylene group containing from 1 to about 6 carbon atoms.

Examples of preferred betaines are: dodecylcarbodiimide, betaine, cetyl dimethyl betaine, dodecylamido-propyldimethyl betaine, tetradecyldimethyl betaine, tetradecylamidopropyldimethyl betaine and dodecyldimethylammonium hexanoate

Other usable amidoalkyl betaines are disclosed in U.S. Patent 3,950,417; 4,137,191; 4, 375, 421; and British Patent 2,103,236, all of which are hereby incorporated by reference.

It will be recognized that the alkyl (and acyl) alkyl groups for the aforesaid betaine surfactants can be obtained from both natural and synthetic sources, for example can be obtained from naturally occurring fatty acids? olefins such as those prepared by Ziegler or by Oxo? or separated oil olefins with or without &quot; popping &quot;. 1 62 238

Case: 396? 5

Ethylene oxide condensates are broadly defined as compounds produced by the condensation of ethylene oxide (hydrophilic in nature) groups with an organic hydrophobic compound, which may be aliphatic or aromatic aliphatic by weight. The extent of the hydrophilic or polyoxyalkylene radical which is condensed with any of its own hydrophobic groups can be easily adjusted to give rise to a water soluble compound having the desired balance between hydrophilic and hydrophobic elements. 10 15

Mod. 71 -10000 ex. 89/07 20

Examples of such ethylene oxide condensates usable as foam stabilizers are the condensation products of aliphatic alcohols with ethylene oxide. The aliphatic alcohol alkyl chain may either be linear or branched and generally contain from about 8 to about 18, preferably from about 8 to about 14 carbon atoms for the best performance as foam stabilizers, the ethylene oxide being present in amounts of about 8 molecules to about 30, of about 8 to about 14 oxide molecules ethylene per molecule of alcohol. 25

Examples of the amide surfactants usable herein include ammonia, monoethane, diatanol fatty acid amides having an acyl moiety containing from about 8 to about 18 carbon atoms and represented by the general formula: Wherein R is a saturated or unsaturated aliphatic hydrocarbon radical having from about 7 to 21, preferably from about 11 to about 17 carbon atoms, represents a methylene or ethylene group of 1, 2 or 3, preferably 1. Specific examples of said amides are monoethanol amine, coconut fatty acid amide and di-amine fatty acid amide. These acyl halides may be obtained from naturally occurring glycerides, for example: coconut oil,

Mod. 71 -10000 ex. - 89/07 20 25 30 62,233 Case: 3937

palm oil, soybean oil and tallow, but may be obtained synthetically, for example, by the oxidation of petroleum or by hydrogenation of carbon monoxide by the Fischer-Tropscb process. Non-ionic and nonionic amine oxide surface active agents comprise compounds and mixtures of compounds having a formula wherein R 2, R 2, R 3, R 4, is an alkyl, 2-hydroxyalkyl, 3-hydroxy-xyalkyl or 3 "alkoxy-2-hydroxypropyl radical, wherein alkyl and alkoxy respectively contain from about 8 to about 18 carbon atoms, Rg and each of which is methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, or 3-hydroxypropyl, ranging from 0 to about 10. Particularly preferred are the amine oxides of the formula: The ethylene oxide condensates mentioned above, amides and amine oxides are more fully described in U.S. Patent 4,166,824, which is incorporated herein by reference in its entirety. (Pancherl), incorporated herein by reference. having certain cationic quaternary ammonium surfactants of the formula: ??????????????????????????????????????

or amine surfactants of the formula wherein A is a benzylic alkyl or alkyl group having from 6 to 16 carbon atoms and n is 1 or 2; alkyl group and each of R2 and R3 is selected from the group consisting of hydrogen, and mixtures of the same or different moieties selected from the group consisting of C1-4 alkyl, C1-6 alkoxycarbonyl, C1-6 alkoxycarbonyl, C1-6 alkoxycarbonyl, Benzyl hydroxyalkyl and hydrogen when y is not O 2 is the moiety that R 2 is an alkyl chain in which the total number of carbon atoms in R 3 is from about 8 to about 16% each and is from 0 to about 10, and only those values are from 0 to about 15% by any compatible anion. Quaternary ammonium surfactants are preferred over those mentioned above, especially the monolongic chain of alkyl surfactants described in the above formula wherein R5 is selected from the same groups as R1, More preferred quaternary ammonium surfactants are chloride, bromide, and trimethylammonium alkylsulfate sulfate salts, C_ g galkyl di (hydroxyethyl) -methylammonium alkyl salts, C ^ g alquiloalkylammonium salts of hydroxy- ethylhexylammonium salts, alkyloxypropyl trimethylammonium salts, 8-16, and allyl-9β, 10β, 11β, 11β, 11-dihydroxyethylmethylammonium salts. Of the above-mentioned, the alkyl, trialkyl, hydroxyalkyl, trialkylammonium, and trialkylammonium salts are preferred, for example: decyl trimethylammonium methylsulfate, lauryl trimetylammonium chloride, trimetylammonium myristyl bromide and trimethochloride ylammonium, and methyl sulfate. The enhancer enhancers used were: 3967

1 in the composition may contain any one or a mixture of the foam intensifiers listed above.

Additional Facultative Ingredients In addition to the above-described ingredients, the compositions may contain other conventional ingredients suitable for use in liquid dishwashing compositions. 10 15

Mod. 71-10000 ex. - 89/07 20 25 30

Optional ingredients include drainage promoting nonionic ethoxylated surfactants of the type disclosed in U.S. Patent 4,116,824, Paneheri (February 23, 1982), incorporated herein by reference. Others include builders of solvent actions, both organic and inorganic. Examples of water-soluble inorganic builders which may be used separately or in a mixture made with themselves or with alkaline organic builder salts are the alkali metal carbonates, phosphates, polyphosphates and silicates. Specific examples of such salts are sodium tripolyphosphate, potassium pyrophosphate, potassium tripolyphosphate and sodium hexametaphosphate. Examples of organic builder salts which may be used separately or in a mixture with each or with the foregoing alkaline inorganic builder salts are the alkali metal polycarboxylates, for example; water-soluble citrates such as sodium and potassium citrate, sodium and potassium tartrate, sodium and potassium ethylenediamine tetraacetate, sodium and potassium N- (2-hydroxyethyl) ethylene diamine triacetates, sodium and potassium diisocyanates (NTA), sodium and potassium N- (2-hydroxyethyl) nitrile biacetates, sodium and potassium oxidisuccinates, and sodium and potassium tartrate mono- and di-succinates as described in U.S. Patent 4,663,071 (Bush et al., filed May 5, 1987), 35 10 15

Mod. 71 -10000 ex. - 89/07 20 25 30 62 238 Gas: 396?

incorporated herein by reference. Other builders of organic solvent action such as water-soluble phosphonates may be used in the compositions of the invention. However, and in general the solvent builders have limited the value of the above-mentioned conventional dishwashing detergent compositions and use of about 10% may restrict the preparation of flexibility in the liquid compositions presented herein due to solubility issues and phase stability. Alcohols, such as ethyl alcohol and propylene glycol, and hydrotropes, such as sodium and potassium sulfonate toluene, sodium and potassium xylene sulfonate, trisodium sulfosuccinate and related compounds (as disclosed in U.S. Patent 3,915,903, incorporated herein by reference), and urea, may be used to achieve a desired stability phase and viscosity of the product. Alcohols, such as ethyl alcohol and propylene glycol, at a level of from 0% to about 15% toluene of potassium sodium, xylene, or cumene sulfonate, at a level of from 0% to about 10% and urea to one from 0% to about 10%, are particularly useful in the compositions. Other desirable ingredients include diols and solvents. The diluents may be inorganic salts, such as sodium sulfate, ammonium chloride, sodium chloride, sodium bicarbonate, etc., and the solvents include water, low molecular weight alcohols such as ethyl alcohol, isopropyl, etc. The compositions will typically contain about 80%, preferably from about 30% to about 70%, still more preferably from about 40% to about 65%, of water. All percentages, parts and ratios used are in terms of weight unless otherwise indicated.

Mod. 71 -10000 ex. - 89/07 20 25 30 62 238 Case: 3967 trario.

The following examples illustrate the processes of the invention and facilitate their understanding. EXAMPLE I An alkylethoxycarboxylate surfactant of the formula RO (OHgO¾O) COO-M + wherein R is an alkyl &amp; 2.2-13 * a ra and sodium is synthesized by performing the following procedure. 1.1 moles of potassium tert-butoxide are reacted with an alkyl ethoxylate molecule of 2 to 3 carbon atoms in three ethoxy groups (iodine 23-3) at 45 ° C per hour by stirring at the same time under low pressure of about 17 mm Hg. Tertiary butanol which is withdrawn and collected in a dry ice / acetone separator. After one hour, 1.1 moles of sodium chloroacetate is added to the iodine 23-3 / potassium t-butoxide mixture. The reaction temperature is raised to 9Â ° C and the pressure reduced again to about 17 mm Hg. The reaction mixture is stirred under these conditions overnight. The alkylethoxycarboxylate I is isolated when the reaction mixture is added to an aqueous solution of HCl, such that the pH is about 3, by supplying the mixture to 90 ° C and collecting the upper layer of the two-phase system. Based on the analysis, the% conversion of alkyl ethoxylate to alkylethoxycarboxylate is greater than 90%. This mixture of the top phase is added to an aqueous solution of sodium hydroxide so that the pH is about 8. EXAMPLE II An alkylethoxycarboxylate surfactant of the formula ROCCI (OH) O, In which R is an alkyl, the average x is 5.4% and K is sodium, is carried out following the procedure of Example I, but substituting the alkyl ethoxylate 0-2-13 (Neodol 23-3) for an alkyl ethoxylate

62,238

The average conversion of ethoxylate into ethoxy is 1, 10, 10, 10, 10, 10, 15, than 90%.

EXAMPLE III 10

A similar alkyl ethoxyethoxycarbonyle surfactant &amp; carried out in Example I is obtained when the procedure of Example I is repeated with the alkyl ethoxylate, potassium tert-butoxide and sodium chloroacetate added simultaneously at the start of the reaction. The reaction temperature is slowly increased to about 90 ° C and the reaction pressure is gradually reduced to about 17 mm Hg. The remaining procedure and the results are similar to the data in Example I.

Mod. 71-10000 ex. - 89/07

Other processes of the present invention are obtained when the potassium tert-butoxide in the preceding examples is replaced by tertiary pentyl or allyloxy-alkyloxy. 20

Other processes of the present invention are obtained when the sodium chloroacetate in the preceding examples is replaced with anhydrous chloroacetic acid at a molar ratio of the delayed base to 2-chloroacetic acid. 25

EXAMPLE IV

The following three liquid dishwashing detergent compositions contain alkyl acrylate ethoxy carboxylates produced by a process of this invention. Preparation S is produced by adding ethanol, sodium chloride and sodium xylene sulfonate to the mixture of alkyl ethoxy carboxylate surfactants. The surfactants that remain are then adioen-2-carboxylic acid. Alternatively, they may be mixed together. Glycine is then added and the pH is adjusted to about 10 with sodium hydroxide. Finally, magnesium chloride is added, which reduces the pH to about 9.5. The final viscosity and pH adjustments can be produced at this point followed by addition of color and charcoal. The balancing agent and the mare. Preparation B is produced by adding ethanol, sodium chloride and sodium sulfonate xylene to sodium allyl kethoxycarboxylate. The remaining components of the formula are added in the order given in the table.

Mod. 71 -10000 ex. Preparation 0 is produced by the addition of ethanol, sodium chloride and xylene of sodium sulfonate to the alkylethoxycarboxylate sodium salt. The alkyl glucoside is mixed together and the temperature of the mixture is increased to about 40 ° C. The amide coconut monoethanolamine is stirred at about 65 ° C and mixed together. Small adjustments of pH and viscosity are made at this point, if the addition of the color and perfume and water are added to bring the preparation to 100 ° C. 25 30 -26- 35 62,238 Case: 3967 2i ma

Mod. 71 -10000 ex. - 89/07 1% oestrone Preparation Preparation Preparation Components AB 0 5 Alkylet oxycarboxylate (2.8 average) sodium 2-13% 15 15 15 Alkylethoxycarboxylate (2.3 med) 0.97 0.97 0.97 10 Alkylethoxycarboxylate (0.8 gm) sodium β2-13 15β-Acetic acid Î ± (sodium methyl ester sulfoxide O -IL 03 15 15 Polyglucoside (1.4 m) G-alkyl Alkyl dimethyl betaine G12-12, -16 A, 0-Dimethyl amine oxide, alkyl, 14 -14-16 ° C, 4.0%, 20% monoethanolamine fatty acid cycloalkyl 4.0 g Magnesium ion added as MgClâ,ƒHgO) 0.76 0.76 mm 25 Glycine 10 - - Sodium xylene sulfonate 2.0 2.2 2.0 Et anol 7.5 7.0 7.0 Sodium chloride 1.5 &lt; 1 2.25 30 Product pH 9.5 7.53 7.05 Perfume & color 0.13 0.15 0.15

X rigua

balance

Equilibrium Balance

35 10 15

Mod. 71-10000 ex. - 89/07 20 25 30 62 238 Case: 3967

The mixture of sodium-alkyl ethoxy carboxylate and alkyl-alkoxy alcohol-containing surfactants is prepared according to the process outlined below. 1. A alkylthioalcohol (3.0 m) 0] 2-13 Γθδ β β with potassium tert-butoxide and sodium chloroacetate in the ratio of 1: 1 → 1: 1 by first mixing the alkylethoxylate with t -potassium butoxide at about βΟΘΟ and about 20 mm Hg of pressure for about 1 hour. Then the t-butanol is continuously removed from the reaction mixture by distillation. The vacuum is then broken and sodium chloroacetate is stirred together. The pressure is restored to about 18-20 mm Hg and the reaction can continue for about 3 hours. Then the reaction pressure is brought to the atmospheric level with nitrogen and the steam heating coils are turned off. The reaction is left in this state overnight. The next day the temperature of the reaction mixture is increased and the pressure reduced to remove t-butane from the system. The reaction mixture is then added to an aqueous solution of hydrochloric acid containing 105% of the theoretical amount necessary to neutralize the initially added potassium t-butoxide. The aqueous acid reagent product is heated to force a phase of separation of the organic and aqueous materials. The organic phase is collected. 2. The above-mentioned phase 1 is repeated using an alkyl ethoxyalcohol (2.7 m) and a ratio of this ethoxyl alcohol to potassium t -butoxide and sodium chloroacetate of 1: 1, 3: 1. The potassium t-butoxide is added to the alkyl ethoxylate, which is at a temperature of about 32.2 ° C and the reaction mixture is then increased to about 104.420, and the t-butanol is withdrawn and collected over a period of about of 30 mi- 28-35 1 62,238

Gase; 3967 5

nutes. The sodium chloroacetate is then added to. The reaction mixture was cooled slightly to about 66 ° C. The reaction is mixed for about 1.5 hours, cooled and added to an aqueous solution of sufficient hydrochloric acid to reach a pH of 3.4. Water is added to increase the volume of the reaction mixture to about 50% and the mixture is then heated to about 49 ° C. The organic matter at the top is collected and the washing process is repeated. 10 3.

The mixtures of the requisite surfactants in the above-mentioned steps 1 and 2 are mixed at a ratio of 40.4 to 59> 6. A portion of this broad mixture of compound surfactants is neutralized with

Mod. 71-10000 ex. Of sodium hydroxide at a pH of about 8 and diluted by about 50% with a mixture of water and ethanol for 25/75 volume. The resulting solution is further extracted at room temperature with hexanes for about four days. The aqueous phase is further collected and some ethanol and water are removed by heating to give a slurry containing the alkyl ethoxy carboxylate containing the mixture of surfactants described below. In what has been previously stated the part of surfactants of the abovementioned mixture contains about 93% of alkylethoxycarboxylates of the formula in which R¹ is C,-alkyl, on average 12 , 5; x ranges from 0 to about 10 and the ethoxy · 30 lata distribution and such that the amount of material where x is 0 is about 2.8 $ and the amount of material where x is greater than 7 is less than about 2% by weight of the alkylethoxycarboxylates. The mean x in the distribution is 2.8. The surfactant mixture also contains about 6.1% of alcohol ethoxylates of the formula ## STR6 ## with an alkyl being 12-13 in that of 3967

day of 12.5 and the mean χ = 2.8. The mixture of surfactants: contains 0% of soap materials.

The above preparations provide 5æm. excellent combination of fat cleaning and mildness benefits * By using the alkylethoxycarboxylate containing the surfactant blend as a building block, and achieving a degree of good fat cleaning with the order of degree being prepared. Preparation B> Preparation A, 10 15

Mod. 71-10000 ex. EXAMPLE VA The following preparation, containing the surfactant mixture used in Example 1, comprising the same alkylethoxycarboxylates, provides an exceptional limescale and softness of the hands with a foam formation somewhat less than Preparations A, B and 0.

Components Alkylethoxycarboxylate (2.8 gm) sodium 12-13 Alkylethoxyalcohol (2.8 gm) and 12-13 Magnesium ion (added as MgCl2 .61 g. G-licine Sodium xylene sulfonate Ethanol Sodium chloride pH of product Perfume and color Water

Preparation D Weight% 281,80.6 4.0 2.0 7.5 1.5 9.0 0.15 Balance -30- 35

Claims (1)

1 10 15 Mod. 71 -10 000 ex. - 89/07 20 25 62 * 238 Case: 3967 Claims 1. A process for the preparation of an alkyl ethoxy carboxylate surfactant of the formula R0 (G H2 H2 O) â € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒwherein R1 is an alkyl group, 15 and M and an alkali metal or alkaline earth metal cation, characterized in that it is reacted; (a) an ethoxylated fatty alcohol of the formula wherein R is a C 18 to C 18 alkyl group and an average number of 1 to 15 (b) a delayed base of the formula RO-M +, wherein RO- is a secondary or tertiary alkoxide, R is a non-linear G 1 to 0 12 alkyl group with at least one branching site at 3 carbon atoms of the oxygen atom, and K is an alkali metal or an alkaline earth metal cation; and (c) anhydrous chloroacetic acid at a molar ratio of the delayed base to anhydrous chloroacetic acid of 2.1, or an alkali metal salt or alkaline earth metal salt of anhydrous chloroacetic acid, at a molar ratio of bs-se retarded for the alkali metal salt 01; alkaline earth metal salt of 1: 1 co-roactic acid; wherein the molar ratio of the ethoxylated fatty alcohol to the anhydrous chloroacetic acid or the alkali metal salt or alkaline earth metal salt thereof is from 1: 0.7 to 1: 1.25, the temperature is 20 to 14060 and the pressure is 1 to 760 mm Hg. 2. A process according to claim 1, wherein the ethoxylated fatty alcohol R 2 is a C 1 to C 2 alkyl group and is calculated from 2 to 6. -31- 35 A process according to claim 1 or 2, characterized in that the delayed base is tertiary butoxide salt. 4. A process according to any one of the preceding claims, wherein in reaction (c) is potassium chloroacetate, sodium chloroacetonate, or a combination thereof. A process according to any one of the preceding claims characterized in that in the ethoxylated fatty alcohol R is a C1-6 alkyl group, the C1-6 alkyl is calculated from 2 to 6, and the delayed base is a butoxide salt tertiary. A process according to any one of the preceding claims, characterized in that the ethoxylated fatty acid R 2 is a C 2 to C 5 alkyl group and is calculated from 2 to 6, and in reaction (c) is potassium chloroacetate, sodium chloroacetate, or a combination of the weeds. 7. A process according to any one of the preceding claims, wherein the delayed base is a tertiary butyl salt and in the reaction (c) is potassium chloroacetate, sodium chloroacetate, or a combination thereof. 8. A process according to any of the preceding claims characterized in that the reaction temperature is 60 to 120 ° C and the reaction pressure is 15 to 350 mm Hg. 9. A process according to any one of the preceding claims, characterized in that: Converting more than 855% of the ethoxylated fatty alcohol to the alkyl ethoxy carboxylate surfactant. A process according to any one of the preceding claims characterized in that the ethoxylated fatty alcohol is reacted with the delayed base and subsequently the resulting product is reacted with anhydrous chloroacetic acid or the alkali metal salt or alkaline earth metal salt thereof. GAMBLE COMPANY ^ OFFICIAL AGENT / Uu 4klÇO MARQUES JJ3TE and / / Official Agent of the Industrial Preroration Ibtíó rio-Arco da Conceição, 3, 1.ΜΜΘ 35