US3842119A

US3842119A - Hydroxypropane sulfonates of c21-cycloaliphatic acids

Info

Publication number: US3842119A
Application number: US00374551A
Authority: US
Inventors: A Bills
Original assignee: Westvaco Corp
Current assignee: Westvaco Corp
Priority date: 1973-06-28
Filing date: 1973-06-28
Publication date: 1974-10-15
Anticipated expiration: 1991-10-15

Abstract

1. BIS-HYDROXYPROPANE SULFONATES OF THE FORMULA 1-(NA-O3S-CH2-CH(-OH)-CH2-OOC-(CH2)Y-),2,3-DI(Z-),

4-(H3C-(CH2)X-)-CYCLOHEX-5-ENE

WHEREIN X AND Y ARE INTEGERS FROM 3 TO 9,X AND Y TOGETHER EQUAL 12, AND ONE Z IS H AND THE OTHER Z IS NA-O3S-CH2-CH(-OH)-CH2-OO

Description

United States Patent 3,842,119 HYDROXYPROPANE SULFONATES 0F C -CYCLOALIPHATIC ACIDS Alan M. Bills, Summerville, S.C., assignor to Westvaco Corporation, New York, NY.

No Drawing. Filed June 28, 1973, Ser. No. 374,551 Int. Cl. C07c 143/22 US. Cl. 260-468 K 2 Claims ABSTRACT OF THE DISCLOSURE There is disclosed hydroxypropane sulfonates of a soap of C -cycl0aliphatic dicarboxylic acid having the following formula wherein x and y are integers from 3 to 9, x and y together equal 12, where Z is a member of the group consisting of H and COOH, with one Z of each moiety. These synthesis products are prepared by reaction of the corresponding alkali metal soaps of the C -dicarboxylic acid with a halide hydroxy sulfonate, preferably 3-chloro- 2-hydroxypropane-l-sulfonate. The synthesis products of the mono-soap are useful as lime soap dispersing agents in a soap-based detergent formulation.

BACKGROUND OF THE INVENTION (1) Field of the Invention This invention relates to new C -dicarboxylic acid surfactants. More particularly, this invention relates to the synthesis product of C -cycl0aliphatic dicarboxylic acid soaps and a halide hydroxy sulfonate, its preparation and its use as a lime soap dispersant.

(2) The Prior Art The hydroxypropane sulfonates of certain C -cycloaliphatic dicarboxylic acid soaps find applicability as limesoap dispersants. The concept of lime-soap dispersion may be described in the following manner. In any detergent system where an alkali metal soap of a fatty acid is the major surfactant, there is a tendency in the presence of water containing hardness (divalent Ca or Mg++) to form the insoluble soaps of the divalent ions. These insoluble soaps are the so-called lime-soap. As long as there is a large excess of alkali-metal soap, as there would be in a normal wash cycle, the lime soap is well dispersed by the alkali-metal soap. However, during the rinse cycle, fresh hard water is added and the concentration of alkali metal soap is considerably reduced causing the immediate precipitation of lime-soap along with occluded soil. This scum adheres to the washing machine and clothes giving a very unsatisfactory wash. The object of a lime soap dispersant is then to maintain' the lime-soap Well dispersed through the rinse cycle so that these insoluble soaps are rinsed away and not deposited in the system. Of course, the same lime-soap dispersion problem arises in other systems besides laundry detergency; particularly any system employing a fatty soap in the presence of hard water.

Various lime-soap dispersants have been proposed for use in a tallow soapbased heavy duty laundry detergent, which include, for example, sulfated ethoxylated fatty alcohols, sulfated N-(Z-hydroxyethyl) fatty amides, methyl esters of u-sulfoethyl fatty acids, and 2-sulfoethyl fatty acid esters.

It is the general object of this invention to provide the hydroxypropane sulfonates of the alkali metal soap ice of a C -cycloaliphatic dicarboxylic acid. Another object of this invention is to provide a process for producing the hydroxypropane sulfonate of C -cycloaliphatic dicarboxylic acids. Still another object of this invention is to provide a new lime-soap dispersing agent.

Other objects, features and advantages of this invention will become apparent from the following detailed description of the invention.

SUMMARY OF THE INVENTION It has been found that new surfactants may be made by forming the hydroxypropane sulfonate of a C -dicarboxylic acid soap having the folowing formula:

wherein x and y are integers from 3 to 9, x and y together equal 12, Z is a member of the group consisting of hydrogen and COOM, with one Z of each moiety, and M and M are selected from the group consisting of sodium, potassium, lithium and ammonium. The monohydroxypropane sulfonate has been found to be an effective lime-soap dispersant.

DETAILED DESCRIPTION OF THE INVENTION The essence of this invention is the discovery that when a mixture of a C -cycloaliphatic dicarboxylic acid soap, which is predominately 5 carboxy-4-hexyl-2 cyclohexenel-octanoic acid soap is reacted with a halide hydroxypropane sulfonate the isomer mixture forms an effective surfactant. The mixture of these two isomers is repre sented by the general formula:

wherein x and y are integers from 3 to 9, x and y together equal 12, where Z is a member of the group consisting of hydrogen and COOM with one Z of each moiety and M and M are selected from the group consisting of sodium, potassium, lithium and ammonium. Although the isomers wherein x is 5 and y is 7 form a preponderance of the composition, there are minor amounts of the C -dicarboxylic acid where cyclohexene ring varies in position along the carbon chain. For the purpose of this specification, compositions of the general formulation shown above are termed C -dicarboxylic acids or C -dicarboxylic acid soaps.

The C -dicarboxylic acids used in this invention are produced from linoleic acid of various animal, vegetal and tall oil sources. The C -dicarboxylic acids may be made by reacting linoleic acid with acrylic acid and catalytic amounts of iodine. One such process for making the C -dicarboxylic acids for use in the esters of this invention is set forth in US. Pat. 3,753,968 entitled Selective Reaction of Fatty Acids and Their Separation. Although any of the conventional soaps of the C -dicarboxylic acid may be used in the process of this invention the potassium or sodium soap is preferred. Additional disclosure of these high solids content soaps may be found in US. Pat 3,734,859 entitled, Dicarboxylic Acid Soaps.

The process for making the synthesis product is to start with the alkali metal soap, e.g., the potassium or sodium soap, of the C -dicarboxylic acid and react it in situ with a stoichiometric amount of sodium bisulfite and epichlorohydrin at a temperature between 60 C. and C. for /2-2 hours and raise the temperature to between about C. and 200 C. for an additional 2 to 4 hours. A small amount, about 1% by weight of sodium sulfite may be added as a catalyst.

(As an alternative procedure, the synthesis product may also be formed by reaction of the soap of the C -dicarboxylic acid with a halide hydroxysulfonate. An alkali metal l-chloro-2-hydroxypropane-3-sulfonate is the preferred reactant. Halide hydroxysulfonate compounds have long been known and may be produced according to the process of Cambre and Theile set forth in US. Pat. 3,239,560 as the first step. Using this process the halide hydroxysulfonate serves as an intermediate and is then reacted with the soap of C -dicarboxylic acid as the second step.

Both the mono-hydroxypropane sulfonates and the bishydroxypropane sulfonate may be prepared. If the starting C -dicarboxylic acid is the half soap the product will be a monoand, of course, if the full soap is the starting material the bis-hydroxypropane sulfonate is formed. The new products of this invention, as prepared by reaction of the corresponding soaps of C -dicarboxylic acid with 1-chloro-2-hydroxypropane-3-sulfonate, are:

cH=oH OH OH-(CH2)y'-CO O CHzAlHCHgS OaNa CH-C mono-hydroxypropane sulfonate CH=CH Ha( 2) r-C OH CH--(OHZ) C O 0 CH C HCH S OaNa CH-C 3 O OCHzCHCI-IzSOaNS bis-hydroxypropane sulfonate The mono-hydroxypropane sulfonates of the C -dicarboxylic acid have excellent lime soap dispersing properties. These materials were tested as lime soap dispersing agents in a soap-based detergent formulation. The laundry detergent formulation typically used had 65% to 80% by weight tallow soap, to by weight sodium silicate, and 10% to of the dispersing agent of this invention along with minor amounts of brighteners and other ingredients. The mono-hydroxypropane sulfonates of C -dicarboxylic acid exhibit excellent lime-soap dispersing power in the detergent formulation used as determined by the percent soil removal of 48.1% compared with a commercial linear alkyl benzene sulfonate-phosphate detergent (53.7% soil removal).

The practice of this invention is illustrated in the following examples.

EXAMPLE 1 One-step in situ method.--In this procedure, the half C. Then 125.0 grams of epichlorohydrin was added through a dropping funnel at such a rate as to maintain the reaction temperature at 85 C. This required about 45-60 minutes. The mixture was then stirred for a further 20 minutes at 80 C. The reaction temperature was then raised to 180 C. over a 1 /2 hour period and allowed to remain there for 2 hours. The final product had an acid number of about 75.

EXAMPLE 2 Two-step procedure-The first step in this procedure was to prepare 1-chloro-2-hydroxypropane-3-sulfonate. This was carried out as described in the patent by Cambre and Theile. This procedure involved the reaction of sodium bisulfite and epichlorohydrin in the presence of a catalytic amount of sodium sulfite. The yield from this reaction was about 83 The product was a white, crystalline solid.

The second step was to form the half soap from the C -dicarboxylic acid and to react the half sodium soap of C -dicarboxylic acid and 1-chloro-2-hydroxypropane- 3-sulfonate. To 212.2 grams of the sodium soap of C dicarboxylic acid (saponification number 156) was added 109.0 grams of 1-chloro-2-hydroxypropane-3-sulfonate that had been dissolved in 109 ml. water. The resultant opalescent mixture was maintained under reflux at C. for 1 hours. The water was then allowed to distill olf keeping the temperature below C. After most of the water had distilled oif, the temperature was raised to C. and maintained there for 2 hours.

The product was a yellow, opaque solid which becomes fluid at 100 C. and is completely water soluble. The IR spectrum of the product shows both ester carbonyl (1735 cm. and free acid carbonyl (1710 cm.- adsorption indicating the desired product. The acid number (after correcting for sodium chloride) was 96.0 compared with a theoretical value of 109.0.

EXAMPLE 3 The mono-hydroxypropane sulfonate of C -dicarboxylic acid of Example 1 was tested in a tallow soap formulation at a level of 20% of the total formulation and compared to tallow soap alone, to a sodium N-methyl-N-(Z- sulfoethyD-tallow amide (Igepon T-77), and to a linear alkyl benzene sulfonate built with sodium tripolyphosphate (Colgate-Palmolive Co.) for better detergency and lime-soap dispersing power. The formulation containing Diacid MHPS-SE means that solvent extraction was used to remove and unreacted salt before testing. The results show, see Treatment No. 1 that compared to tallow soap alone the mono-hydroxypropane sulfonate of C -dicarboxylic acid (Diacid-MHPS) was an effective lime soap dispersant. Only at the highest water hardness (475 p.p.m.) did any scum form with the Diacid-MHPS.

TABLE I.TERGOTOMETER DATA ron r r n E s oar DISPERSANTS IN A TALLOW SOAP Percent soil removal in washing (detergeney) Tallow soap plusl Sodium N-methyl-N-sulioethyl tallow amide (GAF).

b Diacid monohydroxypropane sulionate.

' Diacid monohydroxypropane sulionate (salt free).

6 Linear alkyl benzene sulionate built with sodium tripolyphosphate (Colgate-Palmolive 00.).

8 Indicates scum on rinse water-poor lime-soap dispersion.

soap of Diacid was reacted in situ with 1 chloro-Z-hydroxypropane-3-sulfonate to form the mono-product.

To 500 grams of C -dicarboxylic acid was added 53.7 grams of sodium hydroxide to form the half sodium soap. To 531.75 grams of the sodium soap was added 127.0 grams of sodium bisulfite and 4.04 grams of sodium sulrfite catalyst dissolved in 100 ml. water and heated to 80 The mono-hydroxypropanesulfonate for C -dicarboxylic acid is an eifective lime soap dispersants at a combination of high temperature (120 F.) and high pH (10.0) even at 300 p.p.m. hardness. At lower hardness (47-150 p.p.m.) it was also a good lime soap dispersant. Upon solvent extraction with methanol to remove the sodium chloride, the resulting purified mono-hydroxypropane was not detrimental to the detergency of tallow soap. The mono-hydroxypropanesulfonate of C -dicarboxylic acid was found to be completely biodegradable Laboratory detergency test procedure.The so-called Spangler sebum/Particulate Method as devised by the Colgate-Palmolive Company was employed in testing the various lime soap dispersants. In this method, a standard cotton swatch (4" x 6") is soiled with an artificial soil and then washed under specific conditions The amount of soil removed during washing is determined by reflectance measurements on the cloth before soiling, after soiling, and after washing.

Reflectance measurements-All reflectance measurements were carried out on the Martin-Sweets Brightness Meter using the tristimulus green filter (No. 10). Six readings were taken on the same side of each swatch near the center of the swatch and the average of these six was accepted as the value for that swatch. The swatch was backed with a block of magnesium oxide of constant reflectance while reading the reflectance.

Washing procedure.This procedure is used before soiling 1000 swatches (4" x 6") of 80 x 80 cotton obtained from Testfabrics, Inc. are washed in a standard detergent solution (1.5 g./l.) containing no brightness or anti-redeposition agents in a home washing machine with hot water and a regular wash and rinse cycle. The swatches are then washed twice in Calgon, through two complete regular wash and rinse cycles, to remove any residual detergent. The swatches are then dried in a home dryer and the reflectance is measured as described above.

Soiling procedure.-A two quart Mason jar was half filled with the water emulsion of synthetic sebum plus particulate soil. Forty of the 4" x 6" swatches were added and shaken for 5 minutes on laboratory shaker. The emulsion was decanted off and retained. The swatches were passed through a wringer (the wringer pressure was set so that the swatch retains its own weight of soil). The swatches were returned to the two quart Mason jar with the retained emulsion and the shaking and wringing operations repeated. The swatches (saturated with the sebum/Particulate Emulsion) were then dried in a home dryer for 30 minutes. The reflectance of each of the finished soiled swatches was then determined again by determining the average of six readings near the center of the same side of each swatch.

The concentration of the formulated detergents used in these experiments Was 1.5 g./liter.

A model 7243 Tergotometer (United States Testing Company, Hoboken, NJ.) was employed for all washing tests. This model has four wash buckets, thereby permitting testing of four dilferent detergent solutions at four difierent conditions.

In the normal procedure, one liter of hot tap water is placed in a beaker and the hardness is adjusted to the desired level by addition of standard calcium chloride and magnesium sulfate solutions in a ratio of 60:40: :calcium: magnesium. The detergent formulation is then dissolved in the hot water and then the solution is transferred to the wash bucket. The temperature of the wash solution is then adjusted to the desired level and the bucket is placed in the Tergotometer bath. The pH is then adjusted to the desired level by addition of either dilute sodium hydroxide or dilute sulfuric acid. Ten soiled swatches are then added to the bucket and the wash cycle begun for 10 minutes at an agitator speed of 100 r.p.m. After the washing cycle is complete, the wash solution is poured off and the swatches are squeezed out by hand and replaced in the bucket (do not rinse out the bucket or agitator). One liter of water of the same hardness and temperature is added to the bucket and the swatches are rinsed at r.p.m. for 5 minutes. After the rinse cycle, note is made of any scum on the rinse water or on the walls of the bucket, and then the rinse water is poured off and the swatches squeezed again by hand. The swatches are then separated and placed in the home dryer for 30 minutes.

The final reflectance reading of the clean swatches is then determined and the percent soil removal is calculated from:

R 1 --R Percent soil removal= orizinnl dirt where R =reflectance of washed swatches R =refiectance of soiled swatches R =refiectance of swatches before soiling.

wherein x and y are integers from 3 to 9, x and y together equal 12, and one Z is H and the other Z is C o o OHZOHCHZ s OaNa.

2. Mono-hydroxypropane sulfonates of the formula C H=C H O H OH-(CH2) O o o CHztJHOHz s OaNa COOH wherein x and y are integers from 3 to 9, and x and y together equal 12.

armorial-on References Cited UNITED STATES PATENTS 1,881,172 10/1932 Daimler et al. 260-400 3,097,218 7/1963 Kooijman et al. 260400 3,239,560 3/1966 Cambre et al. 260-513 3,753,968 8/1973 Ward 26097.6

OTHER REFERENCES Mukherjea et al.: Fette, Seifen, Anstrichm, vol. 71 (1969), pp. 53-5.

JAMES A. PATTEN, Primary Examiner M. SHIPPEN, Assistant Examiner US. Cl. X.R. 252-555

Claims

1. BIS-HYDROXYPROPANE SULFONATES OF THE FORMULA 1-(NA-O3S-CH2-CH(-OH)-CH2-OOC-(CH2)Y-),2,3-DI(Z-),