GB1566655A

GB1566655A - Process for making ether sulphonates

Info

Publication number: GB1566655A
Application number: GB5052077A
Authority: GB
Original assignee: Texaco Development Corp
Current assignee: Texaco Development Corp
Priority date: 1977-03-03
Filing date: 1977-12-05
Publication date: 1980-05-08
Also published as: CA1095929A; AU3156277A; BE862554A; BR7801046A; NL7714573A; DE2748722A1; JPS53108925A; FR2382495A1; AU513737B2; FR2382495B1

Description

(54) PROCESS FOR MAKING ETHER SULFONATES (71) We, TEXACO DEVELOPMENT CORPORATION, a Corporation organized and existing under the laws of the State of Delaware, United States of America, of 135 East 42nd Street, New York, New York 10017, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: This invention relates to an improvement of preparing ether sulfonates from alcohols.

The sulfonate products are useful as detergents and as surfactants for enhanced oil re covery processes.

Organic sulfonic acids and organic sulfonates are becoming increasingly important due to their use in the preparation of liquid detergents, particularly in the preparation of relatively salt-free detergents having good solubility characteristics. Even more recently, compounds of this general type have been found to be useful materials when employed as surfactants for enhanced oil recovery processes. In one general scheme sulfonated materials are prepared by sulfonation processes employing concentrated sulfuric acid or oleum. However, using such strong acids leads to the obvious problems of corrosion and/or salt disposal and separation following neutralization of the final reaction mixture to produce salt by-products. In most instances, products containing substantial amounts of the salt cannot be usefully employed, and such salt must be removed.

To obviate the above problems, another method of preparing organic sulfonates involves reacting an organic alcohol containing at least one hydroxyl group with a hydroxycontaining alkyl sulfonic acid salt. Under appropriate conditions. the two compounds are condensed with formation of by-product water to produce an ether sulfonate. A typical sulfonating (more properly sulfoalkylating) reagent here is sodium isethionate, also named as the sodium salt of 2-hydroxyethane sulfonic acid.

In many instances, use of hvdroxy-containing alkyl sulfonic acids or salts such as 2hydroxyethane sulfonic acid salt or other sulfonating reagents of this type, involves one or more process difficulties. For examples in some instances, the organic alcohol to be sulfonated and the sulfonating reagent of this type are not mutually soluble one in another.

As one example, the hydroxy compounds may be liquids at reaction temperatures but are not solvents for the solid, crystalline sulfonic acid salts. Hence, one is faced with a reaction system consisting of both liquid and solid phases with attendant obvious problems.

In still other instances, reactions of the above type are difficult to control or are even uncontrollable in many instances. Thus, for example, excessive foaming may occur which cannot be practically controlled or eliminated.

It is important in controlling foaming to remove water by-product during the course of the reaction as such water is formed. However, resort to such well-known expedients as azeotropic distillation of said by-product water has been found to be unsuccessful or minimally useful.

In yet other processes involving the just described classes of reactants, prior art efforts were unsuccessful in that highly colored products were obtained. Yellow, brown or other colored products when used for detergent use, for example, are unsatisfactory. - The discolored product requires bleaching in order to compete with like generally colorless products, which bleaching step adds considerably to the cost of production. In still other instances, sulfonation processes of this type involving the above reactants cannot be or are difficulty temperature controlled. Lastly, in some situations the proposed prior art sulfonating process cannot be adapted to batch, continuous, or semi-continuous processes, which latitude of choice is extremely desirable.

In its broadest aspects, the present invention comprises a method of preparing ether sulfonates having the following structural formula:

where R is ClK3 , alkyl, C,-C alkenyl, C1-C,0 substituted alkyl, C2-C30 substituted alkenyl, alkaryl containing one or more C1-C18 alkyl groups substituted on said aryl group, aralkyl containing 7-28 carbon atoms, or substituted aralkyl containing 7-28 carbon atoms, R1 is H or CH,, z is a number from 140 and A is an alkali metal cation, which comprises reacting an allyl ether having the formula:

where R, R1 and z are as above with an alkali metal bisulfite, such as sodium or potassium bisulfite. Preferably the allyl ether is prepared by reacting an alkoxylated alcohol having the formula:

where R, Rl, and z are as above with an allyl halide having the formula: XCH2CR1=CH2 where X is halogen and R1 is H or CH3 in presence of a strong base.

In more detail, a preferred method of preparing ether sulfonates involves preparing materials of the type having the formula:

where R is a C1-C22 alkyl group, more preferably C12C22, and most preferably mixed C16C20, R1 is H or CH3 and z is a number from 1v0, more preferably 1-10, which comprises the step of reacting an alkoxylated alcohol of the formula:

where R, R1 and z are as just noted with an allyl halide having the formula XCH2CR1 = CH2 where X is halo and R1 is H or CH3 in the presence of a strong base to produce an allyt ether having the formula:

and reacting said allyl ether with sodium bisulfite to produce said ether sulfonate.

Both allyl halides themselves and the methyl substituted allyl halides .fmethallyl halides) may be used as reactants, and thus by use of the term "an allyl halide" as used herein is meant a reactant to include both allyl halide and methallyl halide.

Another preferred method of preparing ether sulfonates involves preparation of materials of the type having the following structural formula:

where R' is a C1422 alkyl group, n is an integer of 1-3, R1 is H or CH3, and z is a number from 1v0, which comprises the steps of reacting an alkoxylated alcohol having the formula:

where R', Rl, n and z are as above with an allyl halide in presence of a base to produce an allyl ether having the formula:

where R', Rl, n and z are as above, and reacting said allyl ether with sodium bisulfite to produce said ether sulfonate, z more preferably is 1-10, and most preferably is 26.

More preferably R is CACAO and most preferably is CsCi2.

Other alcohols which can be alkoxylated and then used as starting materials are arylalkanols, preferably containing a total of from 7 to 28 carbon atoms. These may be represented by the following formula:

where R2 is an alkylene group containing 1-22 carbon atoms, R' is a C1-C22 alkyl group and n is an integer of 1-3. Polyether derivatives of these compounds may then be made by appropriate alkoxylation.

Thus, preferred alcohols which may be employed as reactants in preparing alcohol alkoxylate materials are those having the general formula ROH, where R is a radical selected from the group consisting of C1,2 alkyl, C2 C22 alkenyl, substituted derivatives of these alkyl or alkenyl compounds, alkaryl radicals containing one or more C1C22, preferably Chic18 alkyl groups substituted on said aryl group, and aralkyl or substituted aralkyl radicals containing 7-28 carbon atoms.

When the alkyl or alkenyl groups contain further substituents, it is preferred that these be halo, nitro, cyano or lower alkyl (1 carbon atoms) groups which are non-interfering in the reaction sequence of the invention.

The starting alcohols which are alkoxylated by known procedures to produce the starting materials of the invention may be chosen from a wide variety of other readily available alcohols. Thus, for example, fatty alcohols preferably containing from 8 to 20 carbon atoms may be used and include such as lauryl alcohol, cetyl alcohol, tallow alcohol, octadecyl alcohol, and eicosyl alcohol and mixtures of these.

Still other useful alcohols here include the so-called Oxo alcohols from the oxo process, vinylidene alcohols, Ziegler-type primary linear alcohols prepared from trialkylaluminum mixtures made by way of ethylene polymerization, subsequent oxidation, and hydrolysis of the resultant aluminum alkoxides as set out in U.S. Patent No. 3,598,747 and other alcohols of this type. Typical vinylidene alcohols are set out in U.S. Patent 3,952,068 and have the general structure:

wherein individually, x and y are numbers from 1 to 15 and the sum of x and y is in the range of 6 to 16.

Phenols and alkyl substituted phenols may also be employed here. Thus, for example, exemplary phenolic reactants include nonylphenol, dinonylphenol and cresol. Particularly preferred are alkyl substituted phenolic compounds falling within the following structural formula:

where R' is preferably an alkyl group con taining from 6 to 20 carbon atoms or a halo, nitro, or hydroxyalkyl substituted group of the same chain length (non-interfering group), and n is an integer of 1, 2, or 3. Most typic ally R' in the above formula is a C81 alkyl group.

The starting materials used here then as reactant alcohols are those prepared by alkoxylating any of the above classes of alcohols or others. Thus, the above compounds may be reacted with ethylene oxide or propylene oxide or mixtures thereof. When mixed oxides are used, they may be added to the hydroxy compound either sequentially to form block polyether compounds, or may be mixed and reacted simultaneously to form a random, or heteric oxyalkylene chain. The reaction of an alkylene oxide and a hydroxy compound is well-known to those skilled in the art, and the base-catalyzed reaction is particularly described in U.S. Patents 3,655,590; 3,535,307 and 3,194,773. These polyether alcohols are well-known and may be prepared by any known process such as, for example, the processes described in Encyclopedia of Chemical Technology, Vol. 7, pages 257-262, published by Interscience Publishers, Inc.

The preferred first step of the process of the invention involves reacting an alkoxylated alcohol of the type described above with an allyl halide. Preferred are allyl chloride, allyl bromide, methallyl chloride and methallyl bromide. This step is carried out in the presence of a strong base such as an alkali metal hydroxide. Preferred are sodium hydroxide and potassium hydroxide. Generally the allyl halide and alkoxylated alcohol are reacted on a mole per mole basis, though an excess of one reagent or the other may also be employed. The amount of base employed is also preferably used in a substantially equivalent amount, and said amount usually ranges from 0.85 equivalents to 1.2 equivalents per equivalent weight of the alcohol employed.

The formation of the allyl ether compound may be carried out over a wide range of process variables of time, temperature, and pressure. Usually, this step of the reaction is carried out at a temperature ranging from room temperature up to 250"C. More often, the temperature reaction is 25--200"C and most often ranges from 50"C to 1500C. The time of reaction likewise may be considerably varied from say 1/4 to 24 hours. More often the reaction is complete in 1-10 hours. Again, the process may be run at atmospheric, superatmospheric or autogenous pressures. Thus, for example, an autoclave may be used. Usually the pressure ranges from 5 to 500 psig. More often the pressure is 5--100 psig.

The allyl ether then in turn is reacted with sodium bisulfite to produce the desired ether sulfonate. Oxygen is preferably present here to carry out the reaction, and most conveniently is furnished via air as a vehicle. The same conditions of time, temperature and pressure applicable to the formation of the allyl ether are also applicable here. This reaction of the allyl ether with alkali metal bisulfite is preferably carried out in presence of an aqueous media wherein preferably at least 50 percent of the solvent is composed of water on a weight basis. Most preferably water itself may be employed. However, a co-solvent system involving a water miscible organic solvent such as methanol, ethanol, isopropanol, methylethyl ketone, dimethyl formamide, and other solvents of this type mixed with water may also be employed.

The following examples typically illustrate the process of the invention. It is understood, of course, these examples are merely illustrative and that the invention is not to be limited thereto.

EXAMPLE 1 A mixture of 400 g of a 4 mole ethylene oxide adduct of nonylphenol, allyl chloride (76 g) and sodium hydroxide (40 g) was heated in a one-liter autoclave to 100"C and held at that temperature for four hours. The crude reaction mixture was first filtered to remove solids, then heated to 70"C under 25 mm pressure to yield a pale straw colored mobile liquid containing about 86% of the desired allyl ether.

EXAMPLE 2 A mixture of the allyl ether from Example 1 (75 g), sodium bisulfite (35.4 g), isopropanol (150 ml), water '150 ml) and potassium nitrate (2 g) was heated for one hour at 100"C and one hour at 1200C under 20-37 psig of air.

Analysis indicated an 82% yield of the desired ether sulfonate.

EXAMPLE 3 A crude 3 mole ethylene oxide adduct of a mixed C1, C18, C,, linear alcohol (400 g) was charged to a one-liter stirred autoclave along with allyl chloride (95 g) and sodium hydroxide (60 g). After heating for four hours at 100"C, the crude material was filtered and then vacuum stripped to yield a low melting solid. The solid was identified as the desired allyl ether and was isolated in 89% yield.

EXAMPLE 4 The allyl ether of the 3 mole ethylene oxide adduct of the mixed C,0-C18-C10 linear alcohol prepared in Example 3 (75 g) was mixed with sodium bisulfite (35.5 g), isopropanol (150 ml), water (150 ml) and potassium nitrate (2 g) in a one-liter autoclave and heated to 100"C for one hour under 21 psig of air. The temperature was then increased to 122or for another hour. Analysis showed a 81.6 yield of desired ether sulfonate.

EXAMPLE 5 The ether sulfonate derived from the four mole ethylene oxide adduct of nonylphenol (Example 2) -was tested for effectiveness in re covering oil beyond that recoverable by con ventional techniques by the following core flood experiment.

Core: A 2 inch diameter by 6 inch long linear Berea sandstone core which had been fired to prevent clay swelling.

Brine: A produced oil-field brine having a total dissolved solids content of 90,000 ppm, which included about 7,000 ppm calcium and magnesium ions.

Oil: A West Texas crude oil diluted with n-heptane to achieve reservoir viscosity.

Surfactant Solution: 0.83% (w/v) of ether sulfonate plus 1.86% (w/v) of a 360 equivalent weight petroleum sulfonate in the above brine.

Polymer Solution: 1,000 ppm Xanflood biopolymer in fresh water.

The core was prepared by first saturating it with the brine and then flooding the core with oil to the irreducible water saturation. It was then placed in an oven maintained at 109"C and water flooded to a residual oil saturation of 31.8% pore volume. A 30% pore volume slug of the surfactant was then injected and followed by continuous injection of polymer solution. This reduced the oil saturation to 12.10/,, which corresponds to a tertiary oil recovery of 62.1%.

EXAMPLE 6 A mixture of the product of Example 1 (20 gms), water-60 ml, isopropanol-20 ml, NaHSO,10 gms, and KNO,-1/2 gm, was charged to a glass reaction vessel, heated at reflux for 5 hours under a constant air purge and then allowed to cool. Analysis of the resulting product indicated the active ingredient, i.e., the sulfonate salt, was present to the extent of 0.034 meq/gm.

EXAMPLE 7 The preceding example was repeated in all detail except that no isopropanol was added as a solvent. Instead, the amount of charged water was increased to 80 ml to insure the same reactant concentrations. Again, analysis of the reaction product indicated the presence of the desired active ingredient-0.038 meq/gm.

EXAMPLE 8 In a somewhat similar manner to the experiments described in Examples 6 and 7, a mixture of an allvlated-alkoxylated nonvlphenol (75 gms), NaHSO3 (35.4 gms), KNO, (4 gms), and H,O (300 ml) was charged to an autoclave, pressured to 20 psig with air after heating to 100"C. Following a reaction time of 1 hour, the temperature was increased to 1300C and the air pressure increased to approximately 80 psig. After 2 hours, subsequent analysis indicated the concentration of active ingredient to be 0.153 meq/gm.

EXAMPLE 9 It has been noted here that the above ether sulfonates involving use of an allyl halide itself are oftentimes contaminated by minor amounts of impurities believed to be bis-sulfonates or sulfinate-sulfonate mixtures. In an effort to minimize their formation, resort was made to use a more highly sterically hindered allylic halide, namely a methallyl halide to produce the corresponding more hindered ether sulfonate.

Specifically, the product of Example 1 was reacted as follows. Under reaction conditions similar to those employed in Example 1 methallyl chloride (83.9 g, 0.93 mole), product of Example 1(400.0 gm, 1.0 mole) and sodium hydroxide (48.0 gm, 1.2 moles) were allowed to interact in an autoclave for 2 hrs. at 100"C.

The crude reaction mixture was first filtered and the resulting filtrate stripped under reduced pressure thereby yielding a low viscosity (80 cp at 25"C) slightly colored (Gardner color 7-8) material which exhibited a hydroxyl No. of 35.0 and possessed a water content of 0.2 wt %. NMR and IR spectroscopic data confirmed this material to be predominantly the desired methallylated derivative.

Conversion of the derivative described above to the desired sulfonate salt was readily accomplished via the sodium bisulfite addition technique. Thus, heating a mixture of methallylated alcohol (75.0 gm, 0.166 mole), sodium bisulfite (35.4 gm, 0.34 mole) isopropanol (150 ml), potassium nitrate (2.0 gm), and water (150 ml) under a positive pressure of air for 2 hrs. at temperatures between 100 1200C gave rise to a crude reaction mixture which contained active ingredient corresponding to a 78.2% yield. Analysis indicated that a material of higher purity was made compared to the runs of the previous examples.

WHAT WE CLAIM IS: 1. A method of preparing ether sulfonates having the formula:

wherein R is C1C,0 alkyl, C,C,0 alkenyl, C1 C,, substituted alkyl, C2-C,0 substituted alkenyl, alkaryl containing one or more C1-C1, alkyl groups substituted on said aryl group, aralkyl containing 7-28 carbon atoms, or substituted aralkyl containing 7-28 carbon atoms, R1 is hydrogen or methyl, z is a number from 1 to 40 and A is an alkali metal cation, which comprises reacting an allyl ether having the formula:

wherein R, R, and z are as defined above with an alkali metal bisulfite.

2. A method as claimed in Claim 1 wherein the allyl ether is prepared by reacting an alkoxylated alcohol having the formula:

with an allyl halide having the formula XCH2CR1 = CH1 where X is halogen in the presence of a strong base.

3. A method as claimed in Claim 2 wherein the allyl halide is allyl chloride or methallyl chloride.

4. A method as claimed in any preceding Claim wherein said allyl ether is reacted with sodium bisulfite in the presence of an aqueous medium.

5. A method as claimed in Claim 4 wherein said aqueous medium contains at least 50% by weight of water.

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **. reflux for 5 hours under a constant air purge and then allowed to cool. Analysis of the resulting product indicated the active ingredient, i.e., the sulfonate salt, was present to the extent of 0.034 meq/gm. EXAMPLE 7 The preceding example was repeated in all detail except that no isopropanol was added as a solvent. Instead, the amount of charged water was increased to 80 ml to insure the same reactant concentrations. Again, analysis of the reaction product indicated the presence of the desired active ingredient-0.038 meq/gm. EXAMPLE 8 In a somewhat similar manner to the experiments described in Examples 6 and 7, a mixture of an allvlated-alkoxylated nonvlphenol (75 gms), NaHSO3 (35.4 gms), KNO, (4 gms), and H,O (300 ml) was charged to an autoclave, pressured to 20 psig with air after heating to 100"C. Following a reaction time of 1 hour, the temperature was increased to 1300C and the air pressure increased to approximately 80 psig. After 2 hours, subsequent analysis indicated the concentration of active ingredient to be 0.153 meq/gm. EXAMPLE 9 It has been noted here that the above ether sulfonates involving use of an allyl halide itself are oftentimes contaminated by minor amounts of impurities believed to be bis-sulfonates or sulfinate-sulfonate mixtures. In an effort to minimize their formation, resort was made to use a more highly sterically hindered allylic halide, namely a methallyl halide to produce the corresponding more hindered ether sulfonate. Specifically, the product of Example 1 was reacted as follows. Under reaction conditions similar to those employed in Example 1 methallyl chloride (83.9 g, 0.93 mole), product of Example 1(400.0 gm, 1.0 mole) and sodium hydroxide (48.0 gm, 1.2 moles) were allowed to interact in an autoclave for 2 hrs. at 100"C. The crude reaction mixture was first filtered and the resulting filtrate stripped under reduced pressure thereby yielding a low viscosity (80 cp at 25"C) slightly colored (Gardner color 7-8) material which exhibited a hydroxyl No. of 35.0 and possessed a water content of 0.2 wt %. NMR and IR spectroscopic data confirmed this material to be predominantly the desired methallylated derivative. Conversion of the derivative described above to the desired sulfonate salt was readily accomplished via the sodium bisulfite addition technique. Thus, heating a mixture of methallylated alcohol (75.0 gm, 0.166 mole), sodium bisulfite (35.4 gm, 0.34 mole) isopropanol (150 ml), potassium nitrate (2.0 gm), and water (150 ml) under a positive pressure of air for 2 hrs. at temperatures between 100 1200C gave rise to a crude reaction mixture which contained active ingredient corresponding to a 78.2% yield. Analysis indicated that a material of higher purity was made compared to the runs of the previous examples. WHAT WE CLAIM IS:

1. A method of preparing ether sulfonates having the formula:

wherein R, R, and z are as defined above with an alkali metal bisulfite.

6. A method as claimed in Claim 4 or 5

wherein the aqueous medium is water.

7. A method as claimed in Claim 4 or 5 wherein the aqueous medium is water mixed with a water-miscible organic solvent.

8. A method as claimed in any preceding Claim wherein R is a mixed C1.-C20 alkyl group.

9. A method as claimed in any of Claims 1 to 7 wherein R represents a group of the formula

in which R' is a C1C22 alkyl group and n is 1, 2 or 3.

10. A method as claimed in any of Claims 1 to 7 wherein R represents a group of the formula

in which R' is a C1-C12 alkyl group, R2 is a C1-Ca alkylene group, and n is 1, 2 or 3.

11. A method as claimed in any of Claims 1 to 7 wherein R. represents a group of the formula:

in which x and y are numbers from 1 to 15, the sum of x and y being from 6 to 16.

12. A method as claimed in Claim 1 and substantially as hereinbefore described with reference to any of Examples 2, 4 and 6 to 9.

13. Ether sulfonates when prepared by a method as claimed in any of the preceding Claims.