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Publication numberUS3228979 A
Publication typeGrant
Publication dateJan 11, 1966
Filing dateFeb 12, 1962
Priority dateSep 30, 1959
Publication numberUS 3228979 A, US 3228979A, US-A-3228979, US3228979 A, US3228979A
InventorsVan R Gaertner
Original AssigneeMonsanto Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Hydroxypropane sulfonates
US 3228979 A
Abstract  available in
Images(9)
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Claims  available in
Description  (OCR text may contain errors)

, alkenoxy-,

United States Patent 3,228,979 HYDROXYPROPANE SULFGNATES Van R. Gaertner, ll'iallwin, Mo., assignor to Monsanto Company, a corporation of Delaware N0 Drawing. Original application Sept. 30, 1959, Ser. No. 843,353, new Patent No. 3,102,893, dated Sept. 3, 1963. Divided and this application Feb. 12, 1962, Ser. No. 172,750

4 Claims. (Cl. 260512) This application is a division of copending application Serial No. 843,353, filed September 30, 1959, now Patent No. 3,102,893.

This invention relates to the ether-substituted glycidyl ethers. In one aspect, this invention relates to alkoxyalkenoxyand alkaroxyalkenoXy-, as well as alkoxypolyalkenoxyand alkaroxyalkenoXy-, hydroxypropanesulfcnates as new compounds. In another aspect, this invention relates to new surfactant compositions which are highly resistant to curd-forming metal cations of hard water. In another aspect, this invention relates to methods for increasing the lime soap dispersant efficiency of detergent compositions.

It is generally well known that soaps, e.g., the sodium, potassium and ammonium salts of fatty acids, precipitate as insoluble fatty acid salts, more commonly referred to as lime soaps, in hard water or other water containing polyvalent metal ions such as calcium and magnesium ions. Such precipitated lime soaps have a tendency to coagulate and form undesirable curds, scums, films or deposits which are observed in the wash stand and bathtub and which stick to the clothes during the rinsing operation, thereby giving the clothes an unsight- 1y, dingy appearance and a rancid odor. The formation of insoluble lime soaps also destroys or reduces the foaming and cleansing power of the soap.

It is also generally well known that surfactant compositions are useful in dispersing lime soap and thereby preventing the formation of undesirable curds, scums and the like. Such surfactant compounds usually comprise a molecule having hydrophobic as well as hydrophilic groups. Although a few compounds are fairly insoluble in water are known to have good lime soap dispersant properties, very soluble compounds usually do not possess good surface active properties and are not good surfactants. Therefore, it is necessary to develop compounds which have the proper balance of hydrophobic and hydrophilic groups in order to prepare improved surfactants.

An object of this invention is to provide alkoxyand alkaroXyalkenoXy-, including alkoxypolyalkenoxy-, and alkaroxypolyalkenoxyhydroxypropanesulfonates as new compounds.

Another object of this invention is to provide new allpurpose soap compositions which form little or no insoluble lime soap curd when used with hard water.

Another object of this invention is to provide new surfactant compositions which are highly resistant to curdforming ingredients of hard water.

Another object of this invention is to provide a method for increasing the lime soap dispersant eificiency of soap-containing detergent compositions to reduce the coagulation of precipitated lime soap in hard water and thereby prevent the formation of curd, scums, deposits, films and the like.

Other aspects, objects and advantages of this invention will be apparent from a consideration of the accompanying disclosure and the appended claims.

In accordance with this invention, a long-chain monohydric alcohol is (alkenoxylated) in a two step process with at least an equimolar amount, and preferably an excess of an epoxyalkane and then with a substantially equimolar amount of epichlorohydrin to form a polyether-substituted chlorohydrin as illustrated by the following equttions:

noH+$(R'onon2 R0[oHzon0]irr RO-[CHQCHO]XH+CH2CHCHZCI RO[OHZCHOIX-CH2CHCHZCI wherein R is a radical selected from the group consisting of alkyl and alkaryl radicals having from 8 to 24 carbon atoms, R is a radical selected from the group consisting of hydrogen and lower alkyl radicals, each of said R being the same or different when x is greater than 1, and x is a whole number of from 1 to 10. The polyether-substituted chlorohydrin is then dehydrochlorinated to a polyether-substituted glycidyl ether as illustrated by the following equation:

The polyether-substituted glycidyl ether is then reacted with an alkali metal or an alkaline earth metal sulfite to form a polyether-substituted hydroxypropanesulfonate as illustrated by the following equation:

wherein Z is a salt forming group selected from the group consisting of alkali metal and alkaline earth metal. Further, in accordance with the present invention, there are provided, as new compounds, polyether-substituted hydroxypropanesulfonates of the formula wherein R, R, x and Z are as above defined.

Further, in accordance with the present invention, there are provided new surface active compositions comprising, as the active ingredient, a polyether-substituted hydroxypropanesulfonate of the formula given above.

Further, in accordance with the present invention, there are provided new all-purpose detergent compositions comprising a sodium, potassium or ammonium salt of a long-chain fatty acid, and, as an essential ingredient, a polyether-substituted hydroxypropanesulfonate of the formula given above.

Further, in accordance with the present invention, there are provided methods for increasing the lime soap dispersant efiiciency of soap-containing detergent compositions by adding a polyether-susbtituted hydroxypropanesulfonate of the formula given above to a sodium, potassium or ammonium long-chain fatty acid soap.

The monohydric alcohols used in the reaction of the present invention are preferably the long-chain alcohols and alkylphenols having at least a total of 8 carbon atoms per molecule. These alcohols may contain as many as 24 carbon atoms per molecule in either a straight-chain or a branched-chain arrangement and may be unsaturated. The alkylphenols may also include the monoalkylated as well as the polyalkylated aryl radicals.

Illustrative examples of some alcohols which can be used include the Z-ethylhexyl, isononyl, n-dodecyl, tertdodecyl, 2 propylheptyl, 5 ethylnonyl,.2 butyloctyl,

3 n-tetradecyl, n-pentadecyl, tert-octadecyl, 2,6,8-trimcthylnonyl, and 7-ethyl-2-methyl-4-undecyl alcohols.

An especially valuable class of alcohols which are useful for the preparation of the presently provided new compounds of my invention include the branched-chain alcohols wherein the alkyl radical is derived from an alefin monomer, dimer, trime'r, tetramer, pentamer, or the like, carbon monoxide, and hydrogen according to the Oxo process. Such alcohols include the branched-chain tridecyl alcohol derived from propylene tetramer or butylene trimer, carbon monoxide and hydrogen; branchedchain decyl alcohol prepared from propylene trimer, carbonmonoxide and hydrogen; branched-chain hexadecyl alcohol prepared from propylene pentamer, carbon monoxide and hydrogen; and branched-chain nonyl alcohol prepared from diisobutylene, carbon monoxide and hydrogen. I

Illustrative examples of some alkylphenols which can be employed as reactants in'this invention include tertoctylphenol, nonylphenol, (2-ethylheptyl)phenol, decylphenol, 4-tert-dodecy-lphenol, Z-tridecylphenol, 3-tertoctadecylphenol, 2-nonyl-1-naphthol, 1-(2-butyloctyl)-2- naphthol, 2,4-dimethylphenol, 3-butylphenol, and 2,4- din-onylpheno'l. p e

The epoxyalkane reactant used in the reaction of this invention can be any epoxyalkane having a terminal group; i.c., an epoxyalkyane having the structure wherein R is selected from the group consisting of hydrogen and lower alkyl radicals. Preferably, the alkyl radical contains less than 6 carbon atoms and may have either straight chain or branched-chain configuration. Such alkyl radicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, isohexyl, tert-butyl, Z-methylbutyl, 2,2-dimethylpropyl, and Z-methylpentyl.

Illustrative examples of some epoxyalkanes which can be used in the process of this invention include ethylene oxide, 1,2-epoxypropane (propylene oxide), 1,2-epoxybutane, 1,2-epoxypentane, 1,2 epoxyhexane, 1,2- epoxy heptane, 1,2-epoxyoctane, 3-methyl-1,2-epoxybutane, 4- methyl-1,2-epoxypentane, and 4,4-dimethyl 1,2 epoxypentane.

The product of the first alkenoxylation step is an alkoxyalkenoxya-lkanol or an alkaroxyalkenoxyalkanol, including an alkoxypolyalkenoxyalkanol or an alkaroxypolyalkenoxyalkanol, having from 1 to as many as 10. alkenoxy groups in the molecule depending upon the number of moles of the epoxyalkane reactant used. Thus, using 1 mole of the epoxyalkane reactant and an alcohol, the product is an alkoxymonoalkenoxyalkanol whereas using 2 moles of the epoxyalkane and 1 mole of the alkyl alcohol gives a product of alkoxydi(a-lkenoxy)alkanol. Ordinarily, the major product of the alkenoxylation step has the structure shown in Equation 1 with the alkyl group identified by R attached to the carbon atom adjacent the oxygen atom of the alkenoxy group. However, this reaction usually results in the formation of some alkoxyalkenoxyalkanol or some alkaroxyalkenoxyalkanol products of the structure RO- ononzo -11 wherein the alkyl group identified by R is attached to the carbon atom separated from the oxygen atom of the alkenoxy group by a methylene group. Although the predominant product is one in which the alkyl radical is attached to the carbon atom in the 1 position, as shown in Equation 1, it is also intended to include products wherein the alkyl group is attached to the carbon atom in the 2 position and it is intended that the alkenoxy group cover both isomers.

The first alkenoxylation step is preferably conducted in the presence of a catalyst which can be either an alkaline type catalyst or'an acid type catalyst. Suitable alkaline type catalysts include the alkali metal oxides, hydroxides, carbonates, borates, and the like which are alkaline reacting. Such catalysts include sodium oxide, potassium oxide, lithium oxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, sodium bicarbonate, sodium borate, potassium borate, and the like. Suitable acid type catalysts include sulfuric acid, alkanesulfonic acids, arylsu-lfonic acids, and Lewis acids. The Lewis type acids include aluminum chloride, boron trifluoride, stannic chloride, ferric chloride, and the like. Boron trifiuorideetherate is a preferred catalyst of this type. Although either the alkaline or the acid type catalyst can be used in the first alkenoxylation step, it is usually preferred to use the alkaline type catalyst.

The amount of the catalyst present in the first alkenoxylation step can be varied. over wide limits as determined by the particular epoxyalkane reactant used, by the temperature desired, and by the reaction time selected. Ordinarily, the amount of catalyst will be between about 0.1% and 5.0% by weight of the amount of the alcohol reactant present.

Ordinarily, the first alkenoxylation reaction is carried out at a temperature in the range of from 50 C. to 160 C.; however, the temperature selected depends to a considerable extent upon the nature of the catalyst employed. Thus, it is usually suflicient to use a temperature in the range of from 50 C. to 'C. when using an acid-type catalyst whereas a temperature in the range of from 100 C. to C. will usually be employed With an alkaline type catalyst. Alkenoxylation of the alcohol with the lower molecular weight epoxyalkanes usually requires the use of the alkaline-type catalyst and, therefore, a temperature in the range of 100160 C. In comparison, alkenoxylation of the alcohol with the higher molecular weight epoxyalkanes may require the use of an acidtype catalyst, and therefore a temperature below 100 C. Alkenoxylation using the lower molecular epoxyalkanes can also be conducted using the acid-type catalyst; however, a temperature in the lower portion of the range must be used in order to minimize "the formation of byproducts.

The first alkenoxylation reaction may be carried out at substantially atmospheric pressure although elevated pressures can also be used advantageously.

The reaction of the alcohol with the epoxyalkane is primarily an addition-type reaction resulting in the formation of a single product. But some reaction conditions may result in the formation of byproducts, necessitating a separation step. Thus, some ketone by-products may be formed in the reaction requiring removal by distillation. The presence of water in the alkenoxylation step results in the formation of glycol but the formation of this by-product can be reduced by dehydrating the alcohol reactant before conducting the reaction. If an alkalinetype catalyst is used in the first alkenoxylation step, this catalyst must be removed before conducting the second alkenoxylation step using epichlorohydrin. This alkaline catalyst is best removed from the alkoxyalkenoxyalkanol product by washing with water. It is not necessary to remove an acid-type catalyst used in the first step of the alkenoxylation reaction since this same catalyst can be used in the second alkenoxylation step with epichlorohydrin. V

The second alkenoxylation reaction step using epichlorohydrin is conducted using substantially only 1 mole of epichlorohydrin per mole'of the alcohol reactant used in the first alkenoxylation step. The use of more than 1 mole of epichlorohydrin results in the formation of a polyglyceryl ether substituted with a number of chloromethyl groups which would then be converted into polysulfonate groups in the subsequent sulfonation. This second alkenoxylation step differs from the first alkenoxylation step in that the alkenoxylating reactant is a chloro-substituted epoxyalkane instead of an alkyl-substituted epoxyalkane as in the first step and substantially only 1 mole of the epoxyalkane per mole of alcohol is used in the second step whereas more than 1 mole of the epoxyalkane can be used in the first step. As used in this specification, substantially 1 mole is defined as being one or slightly more than 1 mole and always less than 2 moles; that is, substantially 1 mole can be as much as 1.25 or 1.3 moles. In conducting the second alkenoxylation reaction, it is preferred to use at least 1 mole of the epichlorohydrin per mole of the alcohol reactant, and very often as much as 1.2 moles, in order to insure complete chloroalkenoxylation of the alkoxyalkenoxyalkanol product produced in the first alkenoxylation step. The presence of unreacted alkoxyalkenoxyalkanol in the final product is not desirable since it is detrimental to surfac tancy and not readily separated from the desired product.

The second alkenoxylation step using epichlorohydrin is conducted in the presence of a catalyst. This catalyst can be any of the acid-type catalysts used in the first alkenoxylation step but the alkaline-type catalyst can not be used. A preferred catalyst is boron trifluoride. As in the first alkenoxylation step, the amount of catalyst used will usually amount to 0.1% to 5% by weight of the amount of alcohol reactant used. As noted previously, if an acid catalyst is used in the first alkenoxylation step, additional catalyst will not be necessary in the second allrenoxylation step except to replace any catalyst'which may have been lost.

The second alkenoxylation step can be carried out at room temperature; however, usually elevated temperatures are employed in order to shorten reaction times. Ordinarily, the temperature will be maintained at less than 140 C. A preferred temperature range is from 60 to 120 C. The temperature is dependent so some extent upon the nature of the catalyst used; less active catalysts requiring higher temperatures. Thus, boron trifiuoride acts as a very reactive catalyst in this step so that usually the temperature is maintained below 100 C.

As in the first alkenoxylation step, the pressure is ordinarily maintained at substantially atmospheric pressure in the second step although elevated pressures can be employed.

The product from the second alkenoxylation step is primarily a polyether-substituted chlorohydrin, more specifically =a 1-alkoxyalkenoxy-3-chloro-2-propanol, 1 alkaroxyalkenoxy-3-chloro-2-propanol, l-alkoxylpolyalkenoxy-3-chloro-2-propanol, or l-alkaroxypolyalkenoxy- 3-chloro-2-propanol, as shown in reaction 2.

The second alkenoxylation reaction is primarily one of addition so that usually there are very few other products to be found in the reaction product.

Formation of the glycidyl ethers as shown in equation 3 above, takes place readily by contacting the polyethersubstituted chlorohydrin produced in the second alkenoxylation step with an aqueous alkaline solution. This reaction involves dehydrochlorination of the chlorohydrin to form the epoxy group. The alkaline solution may be an aqueous solution of an alkali metal hydroxide or a basically reacting salt thereof, e.g., sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, sodium acetate and the like. Ammonium hydroxide or ammonium salts can not be used. Advantageously, the dehydrochlorination reaction is carried out in a solvent media in order to obtain suitable reaction times and complete dehydrochlorination. The solvent should be one which is soluble in water and suitable solvents may include aliphatic and aromatic hydrocarbons such as toluene or hexane, ethers such as isopropyl ether or dioxane and the dialkyl sulfoxides. The dialkyl sulfoxides are preferred solvents and those in which there are present from 1 to 5 carbon atoms in each alkyl radical e.g., dimethyl sulfoxide, diethyl sulfoxide, dipropyl sulfoxide, di-n-butyl sulfoxide, di-tertamyl sulfoxide, ethylmethyl sulfoxide, n-amyl-n-propyl sulfoxide, and the like. The quantity of diluent employed depends somewhat upon the nature of the individual chlorohydrin and upon the amount of the alkali hydroxide present. With respect to the quantity of sulfoxide, there should be present a quantity of sulfoxide which is at least 10% by weight of the amount of the chlorohydrin and preferably from 25 to by weight of the amount of the chlorohydrin. Advantageously, substantially equal amounts of the sulfoxide and the chlorohydrin are employed. A molecular equivalent of the alkali metal hydroxide with respect to the chlorohydrin should be present and the best results are obtained by employing a slight excess of the hydroxide.

The dehydrochlorination step takes place by contacting the chlorohydrin with the aqueous alkali hydroxide in the presence of the diluent at ordinary or moderately increased temperatures, e.g., at temperatures of from roomtemperature to C. External heating need not generally be employed, although under certain conditions, e.g., when the reaction is effected in the presence of a dilute aqueous alkali metal hydroxide, external heating may be used.

When the dehydrochlorination reaction has been completed, which can be noted by cessation in changes of refractive index, the glycidyl ether is separated from the reaction mixture by customary isolation procedures. Byproduct salt may be removed by filtration. Preferably, the ether product is recovered by solvent extraction, whereby the upper layer is separated, water washed to remove any residual salt and diluent, and finally distilled. The lower layer, which comprises most of the sulfoxide and excess alkali can be recycled in a continuous process. Generally good results are obtained by simply filtering the crude reaction mixture to remove the salt and allowing the filtrate to stratify, whereby the ether product is recovered as the upper layer. Water Washing of the upper layer generally gives a satisfactory ether product without further purification.

The product of the dehydrochlorination step is a glycidyl ether, more specifically, 3-alkoxyalkenoxy-1,2- epoxypropane, 3 alkaroxyalkenoxy 1,2-epoxypropane, 3-alkaroxypolyalkenoxy-1-,2-epoxypropane, or 3-alkoxypolyalkenoxy-1,2-epoxypropane. There can be several lower alkyl radicals identified by R in the formulas when x is greater than 1; such as, when x is 2, there are two R groups in the formula. These lower alkyl groups can be the same or different, including hydrogen. For example, when x is 2, one R can be methyl and the other ethyl, or one can be methyl and the other hydrogen or both can be methyl. These products are generally mobile to viscous liquids which vary in color from water-white to amber. Illustrative examples of some of these glycidyl others are as follows:

3- Z-tert-octadecyloxyethoxy) -1,2-epoxypropane 3-(2-nonylphenoxyethoxy)-1,2-epoxypropane 3-[1-(2-propylheptyloxy)-2-propoxy]-1,2-epoxypropane 3 l- (n-hexadecyloxy) -2-propoxy] -1,2-epoxypr0pane 3-[ 1-( 2,4-dinonylphenoxy) -2-butoxy] -l,2-epoxypropane 3 1- n-hexadecyloxy) 2-butoxy] -1,2-epoxypropane 3-[1-(n-octadecyloxy)-2-butoxy]-1,2-epoxypropane 3 {2- [2-butyloctyloxyethoxy] ethoxy}-1,2-epoxypropane 3-{2- [2- (decylphenoxy) ethoxy] ethoxy}l ,2-epoxypropane 3-{1-[ 1-(tridecyloxy) -2-propoxy] -2-propoxy}- 1,2-

epoxypropane 3-{1- 1- (n-hexadecyloxy) -2-propoxy] -2-propoxy}- 1 ,2-

epoxyprop ane 3-{1-{ l- (Z-ethylheptyl) phenoxy] -2-hexoxy}-2-hexoxy}- 1,2-epoxypropane 3-{ 1- 1- (lauryloxy) -2-butoxy] -2-butoxy}-1,2-epoxypropane 3-{2-{2- [2- (Z-ethylhexyloxy) ethoxy] ethoxy}ethoxy}- 1,2-epoxypropane 3-{2-{2- [2- (4-tert-dodecylphenoxy) ]ethoxy}ethoxy}- 1,2-epoxypropane 3- 1-tert-dodecyloxytri-Z-propenoxy) -1 ,Z-epoxypropane 3- l-tert-dodecyloxytri-Z-butenoxy) -1,2-epoxypropane 3- 1-isononyloxyhexa-Z-ethenoxy) -1,2-epoxypropane 3- 1-( Z-tridecylphenoxy) hexa-Z-ethenoxy] 1,2-epoxypropane 3-( 1-n-pentadecyloxyhexa-Z-pentenoxy) 1 ,Z-epoxypropane 3-[ 1- 3-butylphenoxy) hexa-Z-propenoxy] 1 ,2-epoxypr-opane 3- l-isodecyloxyhexa-2-propenoxy)-1,Z-epoxypropane 3-{ 1-[ 1- (nonyloxy) -2-propoxy] -2-butoxy}- 1,2-epoxypropane 3-{1-[ l-tert-octadecyloxy) -2-propoxy] -2-ethoxy}- 1,2-epoxypropane As disclosed hereinafter, these glycidyl ethers are readily converted upon reaction with an alkali metal sulfite into exceptionally valuable surfactants having good lime soap dispersion properties.

As shown in Equation 4, the glycidyl ether can be reacted with an alkali metal sulfite or bisulfite to form an alkali metal salt, of the polyether-substituted 2-hydroxy-l-propanesulfonate and, an alkali metal hydroxide as a by-product. The alkali metal can be .selected from the group consisting of sodium, potassium, and lithium. lf desired, an alkaline earth metal sulfite or bisulfite can be used in place of the alkali metal sulfite and when using this reactant, the alkaline earth metal can be selected from the group consisting of calcium, strontium, barium and magnesium. The reaction of the glycidyl ether with the alkali metal or alkaline earth metal sulfite or bisulfite is advantageously effected while substantially neutralizing the alkali metal or alkaline earth metal hydroxide as it is formed in the reaction. Thus, to get good yields of the propanesulfonate it is preferred to neutralize the hydroxide as it is formed by the continuous addition of an acid, such as hydrochloric or sulfuric acid, at a rate so as to maintain the pH of the reaction mixture at from approximately pH 6-8 anddefinitely below 10 when using preferred solvents. It is also advantageous to conduct this reaction step in the presence of a diluent or, solvent, e.g., Water, ethanol, isopropanol, hexane, or the like. Although water can be used without admixture with one of the other solvents, it is usually preferred to admix the Water with ethanol in approximately equal amounts for use as a solvent. The use of Water as a solvent without admixture with ethanol requires more elevated tempera-- tures in order to effect the reaction. Furthermore, the use of Water without admixture with ethanol generally requires the use of elevated pressures.

The sulfonation reaction can be carried out at temperatures within the range of from 50 C..120 C. using a water-ethanol solvent The reaction can also be carried out at a temperature'within the same range using water as a single solvent but a reaction time of from 2 to 3 days will be required unless a temperature of 190 C. is used when the reaction time will be 1- to 2 hours.

The sulfonation reaction can be carried out at atmospheric pressure or substantially atmospheric pressure when using a water-ethanol'solvent. However, if water is used as a single solvent super-atmospheric pressurewill be required-in order to effect thereactionin reasonable periods.

When the addition reaction has been completed, the

sulfonate. product is readily recovered 'by customarily;

employed isolating procedures. A product of good purity is obtained by removing the water in the reaction mixture by azeotropic distillation using a suitable azeotrope-v The inorganic salts present a former .such as isopropanol. in the reaction mixture arerinsoluble in hot isopropanol and, since the sulfonate'is. substantially soluble therein, the salts may be removed by filtration. It is usually desirable to have a small amount of water'present in the mixture to be filtered, particularly with the higher molecular weight sulfonate products, in order to prevent any of the sulfonate product from precipitating out of solution.

The sulfonate product is then recovered from the -iso-,

propanol solution by volatilization of the solvent.

An alternative method for forming the polyether-substituted Z-hydroxy-l-propanesulfonate product of this invention involves treatment of the polyether-substituted chlorohydrin obtained from the second alkenoxylation step with epichlorohydrin directly with the alkali metal sulfite or bisulfite. This method requires the use of elevated pressures and temperatures, usually in the range of -2l0 C., and somewhat longer reaction times in order to efiect conversion to the alkali metal sulfonate. This method is less preferred than the method involving formation of the glycidyl ether.

The sulfonate product of this invention, as shown in Equation 4, is an 3-(alkoxyalkenoxy)-2-hydroxy-l-propanesul'fonate salt or an 3-(alkaroxyalkenoxy)-2-hydroxy-l-propanesulfonate salt and, where an excess of the epoxyalkane Was employed. in the first alkenoxylation step, the product is an 3-(alkoxypolyalkenoxy)-2-hy droXy-l-propanesulfonate salt or a 3-(alkaroxypolyalkenoxy)-2-hydroxy-l-propanesulfonate salt. Illustrative examples of some of the sulfonate products of this invention are as follows:

Sodium, potassium or lithium 3-(2-tert-octadecyloxyethoxy)-2-hydroxy-l-propanesulfonate Sodium, potassium or. lithium 3-(2-nonylphenoxyethoxy)- Z-hydroxy-l-propanesulfonate Sodium, potassium or lithium 3-[l-(2propylheptyloxy)- 2-propoxy] -2-hydroxyl-propanesulfonate Sodium, potassium or lithium 3-[l-'(nhexadecyloXy)-2- propoxy]-2-hydroxy-1-propanesulfonate Sodium, potassium or lithium 3-[1-(2,4-dinonylphenoxy)- 2-butoxy] -2-hydroxy-l -propanesulfonate Sodium, potassium, or lithium 3-[1-(n-hexa-decyl0xy)-2- butoxy] -2-hydroxy-1-propanesulfonate Sodium, potassium or lithium 3-[l'-(n-octaclecyloxy)-2- butoxy] -2-hydroxyl -propanesulfonate Sodium, potassium or lithium 3-{2-[2-(2-butyloctyloxy)- ethoxy] ethoxy}-2-hydroxyl-prop'anesulfonate Sodium, potassium or lithium 3-{2-[2-(decylphenoxy)- ethoxy] ethoxy}-2-hydrox -l--propanesulfonate Sodium, potassium or lithium 3-{l-[l-(tridecyloxy)-2- propoxy] -2-propoxy}-2-hydroxyl -propanesulfonate Sodium, potassium or lithium 3-{1-[l-(n-hexadecyl;0xy)- 2-propoxy] -2-propoXy}'-2-hydroxyl-propanesulfonate Sodium, potassiumror lithium 3-{l-{l-[(2-ethylheptyl)- phenoxy] Z-hexoxy}-2-hexoxy}-2-hydroxy-l-propanesulfonate Sodium, potassium or lithium 3-{l-[1-(lauryloxy)-2-butoxy]-2-butoxy}-2-hydroxyl-propanesulfonate Sodium, potassium or lithium 3-{2-{2-[2-(2-ethylhexyloxy) ethoxy] ethoxy}eth0xy} -2-hydroxyl-prop anesulfonate Sodium, potassium or lithium 3-{2-{2-[2-(4-tert-dodecylphenoxy)]ethoxy}ethoxy} 2 hydroxy-l-propanesulonate' Sodium, potassium or lithium 3-{l-[l-(nonyloxy-2-propoxy] -2'-butoxy}-2'-hydroxyl -propanesulfonate Sodium, potassium or lithium 3-(l-tert-dodecyloxytri-Z- propenoxy -2-hydr-oxyl-prop anesulfonate Sodium, potassium or lithium 3.-(l-tert-dodecyloxytri-Z- butenoxy)-2-hydroxy-l-propanesulfonate Sodium, potassium or lithium 3-( l-isononyloxy-hexa-Z- ethenoxy) -2'-hydroxy--l -propanesulfon-ate Sodium, potassium or lithium 3-[1r(2-tridecylphenoxy)- hexa-Z-ethenoxy] -2'-hyd'roxy-l-propanesulfonate Sodium, potassium or lithium 3-(l-n-pentadecyloxyhexaagents, They can: be. used asiwettin'g, fret hing or washing agents in the treatment and processing of textiles, for dyeing, for pasting of dyestuffs, fulling, sizing, impregnating and bleaching, and the like. In addition, these compounds are useful for preparing foam in fire extinguishers, for use as froth flotation agents, as air entraining agents for concrete or cement, and as aids in the preparation of other articles of commerce. These sulfonate compounds are particularly useful in soap and synthetic detergent compositions as lime soap dispersants.

The advantages, the desirability and usefulness of the present invention will be illustrated by the following examples.

Example 1 In this example, 3-[l-(n-hexadecyloxy)-2-propoxy]- 1,2-epoxypropane, and sodium 3-[1-(n-hexadecyloxy)-2- propoxy]-2-hydroxypropanesulfonate were prepared from substantially 1 mole of propylene oxide and 1.2 moles of epichlorohydrin. Cetyl alcohol was dried by heating and stirring in a suitable vessel 242 g. (1.0 mole) of cetyl alcohol for a period of 2 hours at a temperature of approximately 60 C. in a nitrogen stream. Then 2.3 g. of potassium metal was added. After dissolution of the potassium in the cetyl alcohol, 87 g. moles) of propylene oxide was added dropwise during a period of two hours, during which time the temperature was increased from 90 C. to 150 C. After completion of the reaction, the reaction mixture was cooled to approximately 100 C. and the catalyst neutralized using Dry Ice and water. Thereafter, the reaction product was dried over anhydrous sodium sulfate. After standing overnight, the drying agent was filtered off and the filter cake washed with hexane. The filtrate was distilled to obtain a 114.9 g. fraction boiling at 0.3 mm. between 144 C. and 161 C. This product is mainly 1-n-hexadecyloxy-Z-propanol and was found to have a carbon and hydrogen analysis of 75.70 wt. percent carbon and 13.39 Wt. percent hydrogen as compared with calculated values of 76.0 wt. percent carbon and 13.4 wt. percent hydrogen.

The second alkenoxylation step was carried out by heating 113 g. (0.376 mole) of the 1-n-hexadecyloxy-2- propanol with 41.6 g. (0.45 mole) of epichlorohydrin using 1.01 ml. boron trifluoridediethyl ether complex (47% BF as a catalyst. The reaction temperature was maintained at 85-90" C. by regulating the rate of addition of the epichlorohydrin. After the addition of epichlorohydrin was completed, the reaction mixture was heated for an additional one hour while maintaining the temperature :at 90 C. The product of this reaction, 1-(1-n-hexadecyloxy-Z-propoxy)-3-chloro-2-propanol, was not separated from the reaction mixture but was dehydrochlorinated in the next step to form the glycidyl ether.

In the dehydrochlorinating step, 50 g. (0.50 mole) of 40% sodium hydroxide and 50 ml. of water were added to the above reaction mixture to which was also added 100 ml. of dimethyl sulfoxide. This mixture was then heated at a temperature of 90 C. for a period of 1.5 hours. 'The hot reaction mixture was then filtered to remove the sodium chloride formed in the reaction and the oily layer was washed twice with hot saturated aqueous sodium chloride solution in the presence of hexane. The oil was dried over sodium sulfate and the hexane was removed by evaporation under reduced pressure to obtain a faintly yellow oil which is the glycidyl ether, 3-[1-(n-hexadecyloxy)-2-propoxy]-1,2-epoxypropane.

The sodium hydroxy sulfonate product was formed by heating 53.5 g. (0.15 mole) of the glycidyl ether obtained in the above dehydrochlorination step with 25.2 g. (0.20 mole) of sodium sulfite in 100 ml. of ethanol mixed with 100 ml. of water. The pH of the solution was maintained at pH 7-9 by the periodic addition of 6 N hydrochloric acid. The heating was continued for a period of 10.5 hours while maintaining the temper- 10 ature at C. At the end of this time, the reaction mixture was dried by stripping oil the water under reduced pressure while replacing it with isopropanol. The hot isopropanol solution was then filtered to remove insoluble material and the hot filtrate cooled to crystallize out the sulfonate product which was recovered by filtration. The recovered product was dried in an oven at a temperature of 45 C. to obtain 39 g. of the desired sodium 3- l-(n-hex-adecyloxy) -2-propoxy] -2-hydroxy-1- propanesulfonate which is substantially white in color.

Example 2 In Example 1 a fraction boiling from 166 C. to 205 C. at 0.3 mm. (mainly from 182 to 197 C.) is the product resulting from the reaction of 1 mole of the cetyl alcohol with 2 moles of propylene oxide, identified as 1-(1-n-hexadecyloxy-2-propoxy)-2-propanol. It contained 73.67% C and 13.10% H; the calculated values are 73.7 and 12.9, respectively. Then, in the second alkenoxylation step, 95.5 g. (0.266 mole) of the above reaction product was heated with 29.6 g. (0.319

mole) of epichlorohydrin using 1.0 ml. of boron trifluoridediethyl ether complex as a catalyst. The epichlorohydrin was added over a period of 30 minutes at a rate to maintain the temperature at approximately C. After the addition of all the epichlorohydrin, the heating was continued for a period of 1 hour at 8590 C. The reaction product, l-{l-[l-(n-hexadecyloxy) 2 propoxy] -2-propo-xy}-3-chloro-2-propanol, was not separated but was treated directly in the next dehydrochlorination step.

In the dehydrochlorination step, 40 g. of 40% sodium hydroxide solution, 40 ml. of water, and 80 ml. of dimethyl sulfoxide were added to the above reaction mixture which was then heated for a period of 2 hours while maintaining the temperature at 80-85 C. The reaction mixture was cooled overnight and the sodium chloride formed in the reaction was then removed by filtration. Hexane was used to wash the residue on the filter paper and the filtrate was separated; the oily layer was washed with saturated sodium chloride solution and dried over sodium sulfate-magnesium sulfate and distilled to remove the hexane and to obtain as residue 106.3 g. of the glycidyl ether, 3-{ 1 1- (n-hexadecyloxy -2-propoxy] -2-propoxy}- 1,2-epoxypropane, which is a light yellow oil.

The sulfonate was formed by heating 62.2 g. (0.150 mole) of the glycidyl ether obtained above with 25.2 g. (0.20 mole) of sodium sulfite in a mixture of 80 ml. each of water and ethanol. The mixture was heated at a temperature of 82 C. for a period of 19 hours while maintaining the pH of the solution at 79 by the dropwise additionof 6 N hydrochloric acid as required. At the end of this time, the solution was dried by stripping off water at reduced pressure while replacing it with isopropanol. The hot isopropanol solution was then filtered to remove the insoluble salts and the filtrate then cooled to permit crystallization of the sulfonate product. The sulfonate product was separated by filtration and washed 3 times with isopropanol before being dried in a vacuum oven at a temperature of 50 C. to obtain 55.2 g. of the sodium 3 {1-[1-(n-hexadecyloxy)-2-propoxy]-2-propoxy}-2-hydroxy-1-propanesulfonate which is a white solid.

Example 3 In this example, 1-(1-isodecyloxypenta-2-propenoxy)- 2-propanol was prepared as in Example 1 from decyl alcohol and approximately 6 moles of propylene oxide. This material was then alkenoxylated in a second alkenoxylation step using 101.4 g. (0.20 mole) of the l-(l-isodecyloxypenta-Z-propenoxy) -2-propanol and 1 ml. of boron trifluoride-diethyl ether as a catalyst. The epichlorohydrin in an amount of 22.2 g. (0.24 mole) was added to the mixture at a rate so as to maintain the temperature at 8595 C. After addition of the epichlorohydrin during a period of 30 minutes, the reaction mixture was heated for an additional 90 minutes while maintaining the temperature at 8085 C. The product, 1-(1- isodecyloxyhexa 2-propenoxy)-3-chloro-2-propanol, was not separated from the reaction mixture but was treated in the dehydrochlorination to form the glycidyl ether.

In the dehydrochlorination step, 40 g. (0.4 mole) of 40% sodium hydroxide solution, 30 ml. of water and 60 ml. of dimethyl sulfoxide were added to the reaction mixture obtained above and the mixture was heated for a period of 1 hour while maintaining the temperature at 8590 C. At the end of this time, the sodium chloride formed in the reaction was separated by filtration of the hot reaction mixture using hexane to improve the separation. The oily layer was washed with saturated sodium chloride solution and'then dried over magnesium sulfate. The dried filtrate was distilled to remove the hexane and to obtain 105.5 g. of the glycidyl ether, 3-(1-isodecyloxyhexa-Z-propenoxy)-1,2-epoxypropane, which is a light yellow oil.

The sulfonate was then prepared by heating 58.1 g. of the glycidyl ether (0.1 mole) with 18.9 g. of sodium sulfite (0.15 mole) using 100 ml. each of water and ethanol. The heating of the reaction mixture was continued for a period of 4.75 hours while maintaining the temperature at 82 C. and using 6 N hydrochloric acid to maintain the pH in the range of 79. The sulfonate product was dried by stripping off the water at reduced pressure while replacing it with isopropanol. The sulfonate product was permitted to crystallize from the isopropanol solution by cooling overnight and was recovered by filtration using a filter aid. The filtrate was concentrated to dryness under reduced pressure to obtain a light yellow oil in an amount of 52.0 g. which is the desired sodium 3-(1-isodecyloxyhexa-2-propenoxy) -2-hydroxy-l-propanesulfonate.

Example 4 In this example, a mixture of saturated fatty alcohols having an average molecular weight of about 258, corresponding to a mixture of C and C saturated fatty alcohols, marketed by Archer-Daniels-Midland Company as Adol 65, was used to prepare a glycidyl ether and sulfonate product thereof using approximately 1 mole each of butylene oxide and epichlorohydrin.

In the first alkenoxylation step, 258 g. (approximately 1.0 mole) of Adol 65 was dried and then heated with 108 g. (1.5 moles) of butylene oxide using 3 ml. of boron trifluoride-diethyl ether as a catalyst. The addition of the butylene oxide was done at a temperature of 90 C. and the exothermic heat of reaction caused the temperature to rise to 110 C. After completing the addition of the butylene oxide, the reaction mixture was heated for an additional 2 hours while maintaining the temperature at 90 C. At the end of this time, the reaction mixture obtained was filtered at 80 C. using SuperFiltrol and Hyflo Supercel to improve the filtration. The filter cake was washed with hexane and the filtrate was aspirated at 150 C. to obtain 343 g. of the alkenoxylated product.

The second alkenoxylatio-n step was performed by adding 111 g. (1.20 moles) of epichlorohydrin slowly over a period of 40 minutes to the product obtained in the first alken-oxylation step using 2.0 ml. of boron trifiuoridediethyl ether as a catalyst. During the epichlorohydrin addition, the temperature was maintained in the range of 8090 C. by external cooling and after the addition of the epichlorohydrin, the reaction mixture was heated for an additional 2 hours while maintaining the temperature a at 8590 C.

The reaction product from the second alkenoxylation step was .dehydrochlorinated directly using 150 g. (1.5 moles) of 40% sodium hydroxide solution, 150 ml. of water, and 100 m1. of dimethyl sulfoxide. This mixture was heated in a period of 1 hour While maintaining the temperature at 100105 C. At the end of this time, the sodium chloride formed in the reaction was removed by filtration, using hexane to promote separation. The oily layer was washed with saturated sodium chloride solution and dried over magnesium sulfate then distilled to remove the hexane. The glycidyl ether product Was obtained as an amber material in an amount of 346.2 g.

The sulfonate product was formed by heating 62.6 g. of the glycidyl ether with 26.2 g. (0.20 mole) of sodium sulfite using 100 ml. each of ethanol and water. The reaction mixture was heated for a period of 9.25 hours while maintaining the temperature at 82 C. and the pH at 7-9 by the periodic addition of 6 N hydrochloric acid. The reaction mixture was then dried by stripping oif the water at reduced pressure while replacing it with isopropanol. The hot isopropanol solution was then filtered to remove salts and the filtrate permitted to cool. The sulfonate product was recovered by evaporating the solution to dryness at 100 C./l3 mm. to obtain 70.2 g. of the sulfonate which is a light amber colored gum.

Example 5 In this example, a mixture of saturated fatty alcohols of which boiled at 264322 C. at 760 mm. corresponding to 61.0% lauryl alcohol, 23.0% myristyl alcohol and 11.2% cetyl alcohol, marketed by E. I. du Font and Company as Lorol No. 5, was used to prepare corresponding glycidyl ethers and sulfonates thereof.

In the first alkenoxylation step, 186.3 g. (approximately 1.0 mole) Lorol No. 5 was treated with 216 g. (3.0 moles) of butylene oxide using 1.0 ml. of boron trifiuoride as a catalyst. The butylene oxide was added dropwise to the Lorol No. 5 with cooling to maintain a temperature of 8590 C. After heating the mixture for a period of 1.5 hours, the temperature was raised to 133 C. to distill over 81 g. of volatile materials, principally methyl ethyl ketone. The product from the distillation is an ether alcohol derived from 2 moles of the butylene oxide per mole of the original alcohol.

The product from the first alkenoxylation step was alkenoxylated in a second step using 111 g. (1.2 moles) of epichlorohydrin and 1.0 ml. of boron triflu'oride-diethyl ether as a catalyst. After addition of he epichlorohydrin the reaction mixture was heated for a period of 2 hours while maintaining the temperature at 8590 C. The product of this reaction was the chlorohydrin substituted with an alkoxydialkenoxy group.

The chlorohydrin obtained in the above step was then dehydrochlorinated directly by the addition thereto of 150 g. (1.5 moles) of 40% sodium hydroxide, ml. of water and 200 nil. of dimethyl sulfoxide. This mixture was heated at a temperature of l05110 C. for a period of 2 hours. After this time the sodium chloride formed was separated by filtration at an elevated temperature and the oily layer washed with saturated sodium chloride solution, using hexane to effect the separation. The wet oil was dried over magnesium sulfate-sodium sulfate and then distilled to remove the hexane, leaving 359 g. of the glycidyl ether, which is a very faint yellow colored oil. I

The sulfonate product was made by heating 81.0 g. (0.20 mole) of the glycidyl ether with 37.8 g. (0.30 mole) of sodium sulfiite in 100 ml. each of water and ethanol. The mixture was heated for a period of 6.5 hours while maintaining the temperature at 82'83 C. and using 6 N hydrochloric acid, as needed, to maintain the pH at approximately 9. At'the end of this time, the salts present in the reaction mixture were removed by filtration and the filtrate was dried by stripping olf the water at reduced pressure while replacing it with isopropanol. The isopropanol was removed from the sulfonate solution thereof by evaporation at C./ 13 mm. leaving 104.5 g. of the sodium sulfonate. This sulfonate is a translucent gum having a very light yellow color and is very viscous when cool.

Example 6 In this example, the sulfonate of the glycidyl ether, 3-{1-['1-(dodecylphenoxy)-2 butoxy] 2 'butoxy} 1,2-

13 epoxypropane, was prepared by heating 48.1 g. (0.10 mole) of the glycidyl ether with 18.9 g. (0.15 mole) .of sodium sulfite using 100 ml. each of water and ethanol. The reaction mixture was heated for a period of 25 hours while maintaining the temperature at 82 C. and using 6 N hydrochloric acid to maintain the pH in the range of 89. At the end of this time, the sulfonate product was dried by stripping off the water at reduced pressure while replacing it with isopropanol. The isopropanol solution was filtered hot to remove inorganic salts. The filtrate was then concentrated to dryness under reduced pressure at a temperature of 90 C.100 C. to leave 53.5 g. of the sodium 3-{1-[ 1- (dodecylphenoxy) -2-butoxy] -2-butoxy}-2- hydroxy-l-propanesulfonate which is a light yellow gum.

Example 7 In this example, the sulfonate of the glycidyl ether, 3-{1-{l-[1-(dodecylphenoxy)-2-butoxy] 2 butoxy} 2- propoxy}-1,2-epoxypropane, was prepared from 57.7 g. (0.10 mole) of the glycidyl ether, 11.4 g. of sodium metabisulfite, 30 ml. water, and 3 g. (0.03 mole) of 40% sodium hydroxide. The above reactants were placed in a 300 ml. pressure bomb which was pressure sealed and heated for approximately 2 hours at a temperature in the range of 175 C. to 195 C. At the end of this time, the reaction mixture was washed out of the bomb using 100 ml. of ethanol. The insoluble inorganic salts were removed by filtration. The filtrate was then dried by stripping off the water at reduced pressure while replacing it with isopropanol. The isopropanol solution was again filtered to remove insoluble salts. The filtrate was then concentrated to dryness under reduced pressure at a temperature of 100 C. to leave 61.6 g. of the sodium 3-{1-{1-[1-(dodecylphenoxy)-2 butoxy] 2- butoxy}-2-propoxy}-2-hydroxy-l-propanesulfonate which is a hard, amber colored gum.

Example 8 In this example, the sulfonate of the glycidyl ether, 3-(1-tridecyloxyhexa-Z-propenoxy) 1,2 epoxypropane, was prepared from 62.3 g. (0.10 mole) of the glycidyl ether, 3.0 g. of 40% sodium hydroxide, 11.4 g. sodium metabisulfite, and 30 ml. water. The above reactants were placed in a 300 ml. pressure bomb which was pressure sealed and heated for approximately 2 hours at a temperature in the range of 175 C. to 195 C. At the end of this time, the reaction products were removed from the bomb using 100 ml. of ethanol. The ethanol solution was dried by stripping off the water at reduced pressure while replacing it with isopropanol. The insoluble salts were removed from the isopropanol solution by filtration. The filtrate was then concentrated to dryness under reduced pressure at elevated temperature to leave 60.4 g. of sodium 3-(1-tridecyloxyhexa-2-propenoxy)-2 hydroxy-1-propanesulfonate which is a light amber colored oil.

Example 9 In this example, the sulfonate of the glycidyl ether, 3- (1-tridecyloxytetra-Z-propenoxy) -l ,2-epoxypropane, was prepared from 51.1 g. (0.10 mole) of the glycidyl ether, 11. r g. of sodium metabisulfite, 3 g. of 40% sodium hydroxide, and 30 ml. of water. The above reactants were placed in a 300 ml. pressure bomb which was pressure sealed and heated for approximately 1.75 hours at a temperature in the range of 175 C. to 195 C. At the end of this time, the reaction mixture was taken out of the bomb with 100 ml. of ethanol. The ethanol solution was dried by stripping off the water at reduced pressure while replacing it with isopropanol. The insoluble salts were then removed from the isopropanol solution by filtration. The filtrate was concentrated to dryness under reduced pressure at elevated temperature to leave 57.1 g. of the sodium 3-(1-tridecyloxytetra-Z-propenoxy)-2- hydroxy-l-propanesulfonate which is an amber colored viscous gum.

Example. 10

Time in Seconds Compound Product of Example 3 l Inst. 3. 4 8. 2 27. 5 +180 Product of Example 5 18.7 27.8 46.5 110.5 +180 1 Inst.=instantaneous.

Example 11 In this example the lime soap dispersion efficiencies of a number of the new sodium sulfonates of this invention were determined using the procedure described by I. C. Harris in ASTM Bulletin 140, pp. 1-13, May 1946. These results are reported in the table below wherein the dispersion number is equal to ten times the milliliters of the test compound required to disperse 45.5 mg. of calcium oleate formed.

Dispersion Compound: number Sodium 3 1- (n-hexadecyloxy) -2-propoxy] -2- hydroxy-l-propanesulfonate 20 Sodium 3-{1-[ l-n-hexadecyloxy) -2-propoxy] 2-propoxy-2-hydroxy-l-propanesulfonate 20 The sodium sulfonate product of Example 5 20 3-{1-[ l-dodecylphenoxy) -2-butoxy] -2-butoxy}- 2-hydroxy-l-propanesulfonate 3-{1-{1-[l-(dodecylphenoxy)-2 butoxy] 2 butoxy}-2-propoxy}-2-hydroxy- 1 propanesulfonate 10 3 1-tridecyloxyhexa-Z-propenoxy -2-hydroxyl-propanesulfonate 80 3 1-tridecyloxytetra-2-prop enoxy) -2-hydroxyl-propanesulfonate 80 Example 12 50 ppm. 300 p.p.m. Product water water hardness hardness Sodium 3-[1-(n-hexadecy1oxy)-2-propoxy]-2- hydroxy-l-propanesulfonate 101 104 Sodium 3-l1-[1-(n-hexadecyloxy)-2-propoxy]- 2-propoxy -2-hydroxy-Lpropanesulionate- 80 109 Sodium 3-(1-isodecyloxyhexa-2-propenoxy)- 2-hydroxy-l-propanesulfonate 133 113 Using the detergency evaluation procedure noted above, the detergency of built materials using sodium 3-[1-(nhexadecyloxy) -2-propoxy] -2-hydroxy-1-propanesulfonate and sodium 3-{1-[l-(n-hexadecyloxy)-2-propoxy]-2-propoxy}-2hydroxy-l-propanesulfonate were determined. The products were formulated by using 15% of the active surfactant with the balance of the formulation being composed of sodium tripolyphosphate, sodium tetrapyroi phosphate, sodium silicate and soda ash. The following results were obtained: Y

As surface active compositions, the alkali metal polyether-substituted Z-hydroxy-l-propanesulfonates of this invention comprise either the pure compounds or an admixture of the pure compounds'with an adjuvant material or a diluent. Ordinarily, the compounds of this invention are employed in surface active applications in a diluted form where the compound is dissolved or suspended in some liquid medium such as Water. The compounds of this invention can also be admixed with adjuvant materials, particularly when used in soap or synthetic detergent compositions, such as common inorganic builders of the type of carbonates, phosphates, silicates, and fillers such as starch.

The new alkali metal sulfonates of this invention are particularly useful in soap and synthetic detergent compositions because these compounds possess unusually high lime soap dispersion properties. The relative proportions of the alkali metal sulfonate of this invention and the soap and/or synthetic detergent in the new compositions may vary greatly, depending upon the use intended for the composition. Although useful, detergent compositions can be formed by mixing small proportions of soap with large proportions of the alkali metal sulfonates of this invention, usually the. greatest value of soap compositions of the present invention lie in compositions having less than 75% by weight of the alkali metal sulfonate. In general, it is preferred to incorporate in the soap composition about 5-50% by weight of the soap and the alkali metal sulfonate. Of course, other materials such as perfumes, fillers, and inorganic builders of the type such as carbonates, phosphates and silicates, can also be present in the compositions.

The soaps which are useful in the novel compositions of this invention are the so-called water soluble soaps of the soap-making art and include sodium, potassium ammonium and amine salts of the higher fatty acids, that is, those having about 8 to 20 carbon atoms per molecule,

These soaps are normally prepared from such naturallyoccurring esters as coconut oil, palm oil, olive oil, cottonseed oil, tung' oil, corn oil, castor oil, soybean oil, wood fat, tallow, whale oil, menhaden oil, and the like, as well as mixtures of these.

Reasonable variation and modification of the invention as described are possible, the essence of'which is that there have been provided (1) methods for preparing alkali metal sulfonates of polyether derivatives of glycidyl ethers,'(2). said alkali metal sulfonates of said polyether derivatives of glycidyl ethers as new compounds, (3) said alkali metal sulfonate polyether derivatives of glycidyl ethers as new surface active compositions, (4')v detergent compositions comprising a sodium, potassium, or ammonium long chain fatty acid soap and said alkali metal sulfonate polyether derivatives of glycidyl ethers, and (5) methods for increasing the lime soap dispersion efficiency of soap-containing detergent compositions by incorporating an alkali metal sulfonate of a polyether derivative of glycidyl ether therein.

1 claim:

1. The sodium salt of 3-[l-(n-hexadecyloxy)-2-propoxy] -2-hydroxyl -propanesulfonate.

2. The sodium salt of 3-{1.-[1-(n-heXadecyloxy)-2- propoxy]-2-propoXy}-2-hydroxy-1-propanesulfonate.

3. The sodium salt of 3-(l-isodecyloxyhexa-2-propenoxy) -2-hydroxyl-propanesulfonate.

4. The sodium salt of 3-{l-{l-[l-dodecylphenoxy)-2- butoxy] -2-butoxy} -2-propoxy -2-hydroxy- 1 -propanesulfonate.

References Cited by the Examiner UNITED STATES PATENTS 2,094,489 9/1937 Hueter 61511 260513 2,115,192 4/1938 Bruson 260 512 2,535,678 12/1950 Hollander et al. V 2605l2. 2,677,700 5/1954 Jackson et al. 260-513 2,991,253 7/1961 Sheely et al. 252 121 3,030,310 4/1962 Turck 252-121 3,036,130 5/1962 Jackson a a1. 260-513 FOREIGN PATENTS 486,909 6/1938 Great Britain.

' LORRAINE A. WEI'NBERGERPrimary Examiner.

JULIUS G-REENWALD, Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,228,979 January ll, 1966 Van R. Gaertner It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:

Column 3, lines 6 and 7, "alefin" should read l ne 27, "epoxyalkyane" should read epoxyalkane l lh mn 5 line 34, "so" should read to line 46, "l-alkoxylpolyab" should read l-alkoxypolyal- Column 9, line 43 "1.01 ml sholallg read 1.0 ml. Column 12, line 39, "he" should read Signed and sealed this 23rd day of September 1969.

(SEAL) Attest: 1

WILLIAM E. SCHUYLER, JR.

Commissioner of Patents Edward M. Fletcher, Jr.

Attesting Officer

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Classifications
U.S. Classification562/42, 562/110
International ClassificationC11D1/29, C07D303/24, C08G59/02, C11D1/16, C11D10/04, C07C309/10
Cooperative ClassificationC11D1/29, C07C309/10, C11D10/042, C08G59/02, C11D1/16, C07D303/24
European ClassificationC07D303/24, C07C309/10, C11D1/16, C11D10/04B, C08G59/02