DE2114115A1 - Discontinued alkanesulfonate detergent composition and method of making the same - Google Patents

Description

PATENTANWALT D-1 BERLIN 33 March 17th, 1θ7ΐ

FALKENRIED 4

MANFRED MIEHE τ «ωοη.

Chemist Tetegramme = PATOCHEM BERLIN

Docket 670047-A-WGY US / 07/1131

MARATHON OIL COMPANY 539 South Main Street, Findlay, Ohio 45840, USA

Discontinued alkanesulfonate detergent composition and method for

Making the same ™

According to the invention, a method for adjusting the composition of an alkyl sulfonate product is provided, by reacting an inorganic bisulfite with an α-olefin in the presence of gaseous Oxygen is produced. By means of adjusting the contact value of the oxygen with the Implementation mix and the contact time for implementation an alkyl sulfonate product can be tailored to suit consumption requirements.

U.S. Patent 3,479,397 relates to the general field of the subject invention and teaches a method for suI-phoning of unsaturated organic compounds using a soluble and not adversely affecting the reaction Bisulfites in the presence of molecular oxygen and a catalyst. The US patent specification (US patent application SN 520 632) relates to the general field of the subject invention and teaches the sulfonation of unsaturated organic compounds with an inorganic bisulfite, the unsaturated organic Compounds have been pre-aerated prior to sulfonation. US patent specification (US patent application SN 763,929) relates to the general field of the subject invention and teaches the sulfonation of unsaturated organic compounds with inorganic ones Bisulfites, where the ρ value during the implementation

is adjusted by means of a chemical buffer.

109849/1961

The invention relates to the field of those carried out in the liquid phase Sulphonation of unsaturated organic compounds with inorganic bisulphites in the presence of molecular oxygen. The invention finds utility in the manufacture of detergents and can especially be used for scheduling the suIfonierungs implementation be applied in such a way that specific detergent products are obtained.

The implementation of olefins, especially α-olefins, with inorganic ones Bisulfites in the presence of molecular oxygen Production of an alkyl sulfonate is well known. A corresponding one The state of the art results from the US patent " Writings 3 306 931, 3 231 606, 3 084 186 and 2 653 970, as well as British Patent 995,376. These patents teach various processes for making organic Sulfonates. So far, however, there has been no successful method for that Adjusting the composition of the organic sulfonate product known by setting the specific implementation parameters become.

According to the invention a process for adjusting the bisulfite addition to olefinic ones carried out in the liquid phase Compounds in the presence of molecular oxygen created in such a way that a specific alkyl sulfate product is obtained will.

™ It has been found that the bisulfite addition carried out in the liquid phase an α-01efine leads to the formation of a mixture of sulfonated olefins. This mixture apparently contains 3 alkyl sulfonates, referred to herein as alkyl monosulfonate, alkyl disulfonate and alkyl hydroxymonosulfonate. Each of these Sulphonate has certain useful properties. For example, the alkyl monosulfonate is and is relatively insoluble in water therefore useful as a detergent for making laundry soaps. On the other hand, the alkyl disulfonate is very much in water soluble relative to the alkyl monosulfonate. The alkyl disulfonate is suitable for the production of liquid cleaning agents,

109849 / 19S1

The alkyl hydroxysulfonate is very soluble in water relative to that Alkyl sulfonate and alkyl disulfonate. The alkyl hydroxysulfonate also leads to form a relatively persistent foam when mixed with water. That is why the alkyl hydroxysulfonate useful for forming foam and may be useful as an ore flotation agent. Furthermore, all of these show alkyl sulfonates superior properties in terms of biodegradation.

Since the market for each of these 'products is subject to fluctuations, it is advantageous for the manufacturer to be able to adjust this process so that the product is obtained which is in demand on the market right now. According to the invention, a method for such an adjustment is now created.

An embodiment of the invention is shown in the drawing and is described in more detail below. Show it:

Fig. 1 is a graph showing the relationship between olefin conversion and molar ratio oxygen to olefin contacted per contact time for pre-aerated olefin feed and pretreated olefin feed;

Figure 2 graphically shows the relationship between the monosulfonate to disulfonate ratio in the sulfonate product and the molar ratio oxygen to olefin contacted per contact time for pre-aerated olefin feed and pretreated olefin feed;

Fig. 3 is a graph showing the relationship between olefin conversion and contact time;

Figure 4 graphically shows the relationship between the monosulfonate and the Disulfonate ratio in the sulfonate product and the contact time for both pre-aerated olefin feed and pre-treated olefin feed.

The subject of the invention is based on the knowledge that the implementation of olefins with bisulfite ions can be adjusted in the presence of a suitable solvent and molecular oxygen can by means of adjustment to form certain alkyl sulfonates

- 3 109849/1961

the contact of the implementation participants with oxygen, the contact time the implementation participant and the special olefin feed. It has been found that both alkyl monosulfonates and alkyl disulfonates are formed in the sulfonation reaction will. In accordance with the invention, the ratio of monosulfonate to disulfonate in the sulfonate product can be varied up to at least a multiple of six.

The olefin of the present invention can be selected from an olefin group having from about 6 to about 24 carbon atoms, more preferably from about 10 to about 20 carbon atoms, and especially preferably about 10 to about 14 carbon atoms for the

W applications in the liquid detergent field and from about 14 to about 18 carbon atoms for laundry or conventional household soap applications. Such olefins are particularly preferably straight-chain olefins, but such olefins can contain up to 5% branched-chain olefins. The olefins are preferably terminal olefins or α-olefins. These olefins can be subjected to a pretreatment, for example silica gel or alumina, to remove peroxides and hydroperoxides, as taught in US Pat. No. 3,306,931. Such olefins are referred to below as pretreated olefins. More preferably, such olefins are subjected to a pre-aeration by means of

t blowing oxygen, as described in US patent specification (US patent application SN 520 632) is taught. Such olefins are referred to below as pre-aerated olefins.

Alkali metal bisulfite or ammonium bisulfite can be used as the source for the bisulfite ion. Furthermore, the bisulfite in situ by contacting gaseous sulfur dioxide with the reaction mixture, which is an alkali metal hydroxide or contains ammonium hydroxide. Preferably, from 0.5 to about 5.0 moles of bisulfite per mole of olefin are used. Optimal Results are generally obtained with 1.0 to about 2.5 moles of bisulfite per mole of olefins.

109849/1961

The reaction is carried out in the presence of an organic solvent. The solvent can be selected from the group of monohydroxy alcohols, Glycols and amino alcohols having 1 to 5 carbon atoms can be selected. The monohydroxy alcohols are preferred. Optimal results are generally obtained with straight chain alcohols, out of economic considerations however, branched chain alcohols may be preferred. The weight ratio of alcohol to olefin is preferably 1 to 0.3 to 2.8, more preferably to 0.6 to 2.0, and particularly preferably to 0.8 to 1.5.

The reaction is carried out in the presence of water, which is a solvent for the inorganic bisulfite. Preferably the weight ratio of water to olefin ranges from 0.5 to 3.5, more preferably from 0.7 to about 2.8, and most preferably from 0.9 to about 2.4.

The reaction is carried out in the presence of gaseous elemental oxygen. The source of oxygen can be any be oxygen-containing gas that is at least 2 vol.% 0 ~ contains, which does not have any constituents that intervene adversely in the implementation, but represents for reasons of economy Air is the preferred source of oxygen. Olefin conversion in the sulfonate product is a function of the amount in contact with the olefin during a time of contact brought oxygen. This relationship is illustrated in FIG. 1. Line L gives an apparent limit on olefin conversion again. While the mechanism of implementation is not fully understood, this limitation appears to be one Function of the contact time. The relationship between olefin conversion and contact time is shown in FIG. 3 and explained further below. It was found that the olefin conversion and the composition of the sulfonate product is a function of the amount of oxygen shared with the reactants are brought into contact during the contact time. This is shown on the basis of FIG. 1.

- ET »

109849/1961

In general, increased exposure to oxygen results increases the formation of alkyl monosulfonate and reduces the formation of alkyl disulfonate. This is based on shown in FIG. Thus, within the specific area of contact with oxygen is that with the reaction participants during a specific contact time The amount of oxygen brought into contact is a function of the olefin- charging and the desired conversion product.

Regarding the olefin which is disclosed in US patent specification (US patent application SN 520 632) is pre-aerated, preferably 0.02 to about 2.0 moles of gaseous oxygen per mole of olefin charge are used per hour, more preferably about 0.025 to about 1.600, and particularly preferably about 0.035 to about 1.400 of implementation. With respect to pretreated olefins, there is preferably about 0.02 to about 2.00 moles of gaseous oxygen per mole of purified olefin per hour, more preferably about 0.03 to about 1.600, and most preferably about 0.04 up to about 1,400 together with the implementation participants. Again, the specific amount of oxygen contacted with the reactants depends on the olefin feed and the desired suflonate product.

To achieve optimal results it is necessary to use the p "value ^ preferably to hold at 5.0 to 9.0, more preferably at 5.5 to 8.0 and particularly preferably at 6.0 to 7.5.

It was also found that the conversion amount of olefin to alkyl sulfonate is a function of contact time and that the optimum contact time for sulfonation of the olefins is 1.0 to 3.0 hours. This is shown in FIG. 3 shown. It is illustrated in the examples that the optimum value of 0 »approaches the desired value of olefin contact to less for the pre-aerated olefin feed than for the pretreated olefin feed amounts. Mach 3.0 hours takes under the working conditions of the exemplary embodiments, the amount of alkyl monosulfonate formed increases, but the amount increases Total alkyl sulfonate. The specific one in use Contact time during implementation depends on what is sought

109849/1961

21 U115

Product and the efficiency of the implementation.

It has been found that the composition of the sulfonate product is a function of touch time. This is based on the figure explained. Therefore, the specific contact time selected for the reaction will depend on the sulfonate product sought. The contact time in the reaction is preferably from 0.2 to about 6.0 hours, more preferably from 0.3 to 5.0 Hours and particularly preferably from 0.5 to about 4.5 hours.

The temperature of the Sulfonierungsumsetzung is preferably at 2O ° to 200 ° C, more preferably 30 to about IQO ⁰ C and most preferably at about 4O to about 80 ° C. Even if the temperature is not critical, the highest temperature depends roughly on the boiling point of the water, the alcohol solvent and the pressure under which the reaction is carried out.

The sulfonation reaction is carried out under a pressure of preferably 0.4 to 100 atmospheres, more preferably 0.6 to about 50 atmospheres, and most preferably 0.8 to about 20 atmospheres executed. Since the pressure in the narrower sense is not a critical factor, normal pressure can be the most economical Prove pressure value. It goes without saying that pressure and temperature interact with one another in such a way that that you can use low-boiling alcohol solvents at temperatures higher than their boiling point if the pressures are higher than normal pressure.

The sulfonation reaction can either be batchwise or continuously be performed. However, the continuous working method can prove to be more economical.

Even if the implementation mechanism of the implementation is not flawless is clarified, it goes without saying that the product formed by the sulfonation reaction and the efficiency of the reaction is a function of many interacting variables and those shown in the figures mutual relationships are created by changing these

109849/1981

21U115

Variables changed a bit. So it can be expected that the Formation of the alkyl sulfonate by increasing the molar ratio of the inorganic bisulfite to the olefin in the Reaction mixture can be increased. One can use preliminary tests without further ado to determine the correct working conditions, which are necessary for the creation of the desired product and the efficiency of the implementation.

The invention is further explained below with the aid of a number of exemplary embodiments.

example 1

An overflow tube is placed in a 500 ml four-neck Morton flask for continuous operation. The conversion flask is equipped with a heating jacket, high-speed stirrer, reflux condenser, thermometer and inlet for the measured supply of air and: or SO ₃ , olefin-isopropanol solvent mixture, NaHSO ₃ solution and p "value adjustment solution (H ₂ SO ₄ or NaOH) equipped. The p "value is monitored with a pi-value control device.

n ri

which is located on the pumps that are used for pumping the setting solution for the ρ value. The temperature the conversion mixture is measured with a standard temperature control device monitored, which is arranged on the thermometer. After measuring by the gas flow meter, the air is below the surface of the conversion mixture introduced. There are metering pumps for the Introducing the implementation solution applied. A metering pump becomes "for the olefin-isopropanol mixture and another metering pump for the NaHSO_ solution applied. Air and / or SO is in the reaction mixture bubbled under the surface of the same.

The olefin-isopropanol mixture consists of 572 parts by weight of olefin and 672 parts by weight of isopropanol. The olefin is a primary olefin with an average molecular weight of 228.

The NaHSO ₃ solution consists of 321 parts by weight of NaHSO ₃ , 5.0 parts by weight of NaOH and 875 _{parts by weight of H 3} O.

- 8th -

109849/1961

Table I shows the operating parameters for Example 1. In this example, the olefin is adjusted to a hydroperoxide number of 423 and a polymeric peroxide number of 1098 according to the procedure of the US patent specification (US patent application SN 520 632).

Table I. Implementation conditions:

continuous flow contact time temperature

P _H value

Implementation participants:

Olefin (pre-aerated) NaHSO ₃

solvent

0.5 h

O ⁰ C

7.0

70 ° C

Isopropyl alcohol ^H 2 °

Molar ratio of O ₂ to olefin per hour

Molar ratio of the reactants to olefin:

1.00 1.24

Solvent weight ratio to olefin

1.17 1.53

Mol% olefin converted to sulfonate

Ratio of alkyl monosulfonate to alkyl disulfonate in the product

0.000
0.092
0.168

48.1
68.7
69.8

1.11 1.38 1.49

The sulfonate content in the reaction product is determined by means of Analyzing a sample for unreacted olefin, water and inorganic salts and calculating the sulfonate content based on the mass balance of the sample. Specifically, 5 g of the product in 100 ml of a Dissolved 20% isopropanol in water solution. The isopropanol solution is shaken three times in succession with 15 ml batches of diethyl ether in a separating funnel. The three ether volumes

9/1961

211 Al M

Minas are then combined and then the ether is evaporated until a constant weight is achieved. It remains a residue consisting of unreacted olefin. The olefin is then weighed. The water is definitely distributed Shake a 20 g sample of the product with 50 ml of anhydrous methanol and the water in the methanol is mediated determined by the Karl Fisher method. The inorganic salts are determined by means of the simmering of a 0.5 g sample of the Sulfonate product with 5150 ml of anhydrous methanol, separate the salts of methanol by filtering and weighing the salts.

A routine method of analysis for the purpose of determining the content of monosuffonate and disulfonate in the product is based on the chromatographic separation of the methyl esters of the sulfonates. The inorganic salts are first separated from the sulfonates by keeping 0.5 g of the sulfonate product boiling with 150 ml of anhydrous methanol. The salts are separated from the sulfonates by filtration and weighed. The methanol solution of the sulfonates is then passed through an ion exchange column 2.5 cm wide and 30 cm high containing Dower 50-8X resin in the hydrogen ion form. This converts the sulfonates from the sodium salt to form the sulfonic acid form. The methanol is then removed from the sulfonic acids by evaporation by blowing dry air over the methanol solution - no heat is applied as some of the sulfonic acids decompose easily. The sulfonic acids are then dissolved in Diäthylather and with a slight excess of diazomethane dissolved in Diäthylather, to implement brought by means of slow addition of diazomethane-ether solution to which the sulfonic acids containing ivbherlösung _g and indeed until the Umsetzungsgemiseh opposite ρ -paper neutral. The ether is evaporated and the sulfonic acid ester is dissolved in 1 ml of toluene. 0.5 ml of this solution is introduced into a glass column. ^ which has a width of 2.6 cm and a height of 33 cm and is loaded with silica gel with a particle size of 0.147 to 0.104 m.

- 10 -

109849/1961

211A115

The column is washed with hexane-toluene-diethyl ether solvent eluted at a rate of 3 ml per minute. The hexane-toluene-diethyl ether solvent consists of 12 parts by volume of hexane, 7 parts by volume of toluene and 1 part by volume of diethyl ether. The first 100 ml of the eluted hexane-toluene-diethyl ether solvent are discarded. The next 110 ml of the eluted hexane-toluene-diethyl ether solvent are collected in a tared beaker. The solvent is evaporated and that Weight of the residue given as alkyl monosulfonate. The remaining sulfonates are eluted from the column by first adding 1OO ml of diethyl ether and then 100 ml of hexane rapidly the pillar are guided. These eluted solvent solutions are combined and the solvent is removed from the sulfonates by means of Evaporation is separated by passing dry air over the solution - again, the solutions are not heated to avoid decomposition -. The residue remaining after the evaporation of the diethyl ether and hexane is stated as alkyl disulfonate, even if the residue is actually a mixture of alkyl disulfonate and alkyl hydroxysulfonate contains.

Example 2

The implementation vessel and implementer solutions are the same as in Example 1 except that the olefin is pretreated by the method of U.S. Patent 3,306,931 will. The conversion parameters for this example 2 are given in Table II. The analytical working methods are the same as in Example 1.

Table II Implementation conditions

continuous flow

Contact time temperature P _H value

0.5 h

70 ° C 7.0

- 11 -

109849/1961

Implementation participants Pick-up ratio of the implementation participants to olefin

Olefin (pretreated) 1.00

NaHSO ₃ 1.24 -

Solvent weight ratio solvent

to olefin

Isopropy alcohol 1 * 17

H ₂ O 1.53

Molar ratio of O ₂ mol% olefin ratio of alkyl to olefin per hour conversion to monosulfonate to alkyl

Sulfonates disulfonate in the product

0.168 65.2 0.82

0.336 69.8 2.38

Example 3

The conversion vessel here is the same as the one after Example 1.

The olefin-isopropanol mixture contains 563 parts by weight of pre-aerated Olefin and 630 parts by weight isopropanol. The olefin is the same as the olefin according to Example 1.

The NaHSO ₃ solution contains 1.517 parts by weight of Na ₃ S ₃ O ₅ , 115 parts by weight of NaOH and 4.374 parts by weight of H ₃ O.

The conversion parameters of Example 3 are in Table III reproduced. The analytical procedures are the same as in Example 1.

Table III Implementation Conditions
continuous flow

Temperature 7OC.

P _H value 6.5

Translation participants Molar ratio of translation participants

to olefin

Olefin (pre-aerated) 1.00

NaHSO ₃ 1.48

- 12 -

109849/1961

211 Al 15

/ i

solvent

Isopropyl alcohol H ₂ O

Molar ratio of 0 to olefin per hour

Solvent to olefin weight ratio

1.12
1.93

Contact mole% olefin time, h conversion to Su If on at

Ratio of Alk.y.1-monosulfonate to alkyl disulfonate in the product

0.324 0.324

2 3

95.2 88.6

1.05
3.18

Example 4

The reaction vessel and the reaction participants are the same as in Example 3 with the exception that the olefin is pretreated. The implementation parameters of this Example 4 are shown in Table IV. The analytical procedures are the same as in Example 1.

Conversion conditions continuous flow temperature ρ value

Implementation participant

Table IV

7O ° C
6.5

Molar ratio of reactants to olefin

Olefin (pretreated) 1.00 NaHSO ₃ 1.48 solvent Solvent to olefin weight ratio Isopropyl alcohol 1.12 H ₀ O 1.93

- 13 -

10984 9/1961

Molar ratio of 0 "contact mole percent olefin ratio of to olefin per hour time, h conversion to alkyl monosulfonate

Sulfonate to alkyl disulfonate

in the product

0.324 2 99.1 0.53

0.324 3 88.6 0.98

- 14 -

1: 09848 / 10-1

Claims (14)

Patent claims Process for the addition of bisulfite in the liquid phase a-01efine selected from the group of pre-aerated and pretreated a-01efine having from about 6 to about 24 carbon atoms, by treating the α-01efine with an inorganic bisulfite selected from the group of alkali metal bisulfites and ammonium bisulfite is selected, in the presence of water, an organic solvent in the form of alcohols, glycols and amino alcohols, all of which have 1 to about 5 carbon atoms, as well as one oxygen-containing gas with no disadvantageous in the reaction engaging ingredients, at a practically constant temperature over a predetermined contact time at a practically constant ρ value, characterized in that the percentage of alkyl non-hydroxylated monosulfonate in the product, based on the total weight of the sulfonate in the product, is increased merely by increasing the number of Moles of oxygen per mole of olefin that are brought into contact with one another during the contact time. 2. The method according to claim 1, characterized in that an oxygen-containing gas is used, which is about 2 to contains about 100 percent oxygen by volume. 3. The method according to claim 1, characterized in that essentially air is used as the oxygen-containing gas will. 4. The method according to claim 1, characterized in that that the oxygen-containing gas with the olefins in an amount from about 0.020 to about 2.00 moles of gaseous oxygen per mole of olefin per hour for about 0.2 to about 6.0 hours is brought. 5. Process for the addition of bisulfite in the liquid phase to ot-olefins selected from the group of pre-aerated and pre-treated α-olefins having 6 to about 24 carbon atoms, by contacting the ot-olefins simultaneously with an inorganic one Bisulfite from the group consisting of alkali metal bisulfite and ammonium bisulfite, the bisulfite having a concentration of - 15 109849/1961 has about 0.5 to about 5.0 moles of bisulfite per sol of olefin, wherein the addition reaction in the presence of water in an amount equivalent to about 0.5 to about 3.5 times by weight of the olefin carried out in the presence of an orgasmic solvent is selected from the group of alcohols, glycols and amino alcohols, all of which have 1 to about 5 carbon atoms, the organic solvent is present in amounts by weight from about 0.3 to about 2.8 times the weight of the oil fine, . as well as in the presence of an oxygen-containing gas that does not contain any Has constituents which adversely affect the reaction, as well as about 2 to about 100 volumes by weight of gaseous oxygen contains, the addition conversion at practically constant P temperature within a range of about 20 to about 200 ° C and at a practically constant p "value of about 5.0 to about 9.0 is carried out, as well as the implementation participants via a predetermined contact time within the range of about 0.2 to about 6.0 hours, thereby characterized in that the percentage of alkyl non-hydroxylated Monosulfonate in the product based on the total weight of the sulfonates in the product, merely thereby is increased that only the number of moles of oxygen per mole of olefin which are brought into contact with the olefin during the contact time, as well as the number of Moles of oxygen per mole of olefin in contact with the olefin k tion can be brought to about 0.02 to about 2.00 moles of gaseous form Oxygen per mole of olefin feed per hour. 6. The method according to claim 1 and 5, characterized in that the percentage of alkyl non-hydroxylated Monosulfonate in the product, based on the total weight of the sulfonates in the product, is merely increased in that only the period of time during which oxygen is brought into contact with the transfer participants is increased. - 16 - 109849/1961 21U115 7. The method according to claim 6, characterized in that that the contact time is from about 0.2 to about 6.0 hours. 8. A process for the addition of bisulfite in the liquid phase to α-olefins selected from the group consisting of pre-aerated and pretreated α-olefins having from about 6 to about 24 carbon atoms, by means of contacting the ot-olefins with inorganic bisulfite, which is selected from the group consisting of is selected from alkali metal bisulfites and ammonium bisulfite, the inorganic bisulfites have a concentration of about 0.5 to about 5.0 moles of bisulfite per mole of olefin, the addition is carried out in the presence of water, the water has a concentration by weight of about 0.5 to about 3.5 times the weight of the olefin, in the presence of an organic solvent selected from the group of monohydroxy alcohols having 1 to about 5 carbon atoms, the organic solvents in concentrations with respect to the dish in amounts of about 0.3 to about 2.8 times the olefin weight, in the presence of an oxygen-containing gas that does not hastily intervening in the reaction components and contains about 2 to about 100% gaseous oxygen, wherein the oxygen-containing gas is bubbled into the olefins in an amount of about 0.02 to about 2.00 moles of gaseous oxygen per mole of olefin per hour, and the addition is carried out at a practically constant temperature of about 20 to about 200 ^° C., at a practically constant p "value of about 5.0 to about 9.0, and the addition is carried out during a predetermined contact time, characterized in that, that the percentage of 'alkyl non-hydroxylated monosulfonate in the product, based on the total weight of sulfonates in the product, is increased only by increasing the amount of time in which oxygen is contacted with the reactants and the amount of time is increased to about zero .2 to about 6.0 hours. - 17 - 10 9 8 4 9/1 961 9. The method according to claim 1, characterized in that that the percentage of alkyl non-hydroxylated monosulfonate in the product based on the total weight of the Sulfonates in the product is increased by increasing the number of moles of oxygen per mole of olefin used during the Contact time are brought into contact and by means of lengthening the period of time within which oxygen is with the Implementation participants is brought into contact. 10. The method according to claim 5, characterized in that the oxygen-containing gas is about 2 to about fc has volume percent oxygen. 11. The method according to claim 5, characterized in that the oxygen-containing gas ± m essentially consists of air. 12. The method according to claim 5, characterized in that the oxygen-containing gas with the olefins in an amount of about 0 _r 020 to about 2.00 moles of gaseous oxygen per mole of olefin per hour for about 0.2 to about 6.0 hours in Is brought into contact. 13. The method according to claim 6, characterized in that that the contact time is from about 0.2 to about 6.0 Hours. 14. The method according to any one of the preceding claims, characterized gekennzeic hn et that the percentage of alkyl non-hydroxylated Monosulfonate in the product, based on the total weight of the sulfonate in the product, thereby increased is that the number of moles of oxygen per mole of olefin which is brought into contact with the olefin during the contact time is increased by means of lengthening the Time span within which oxygen is brought into contact with the reactants, as well as the time span - 18 - 109849/1961 ranges from about 0.2 to about 6.0 hours, as well as the number the moles of oxygen per mole of olefin that is brought into contact with the olefin within this period of time to about 0.02 to about 2.0O gaseous oxygen per mole of the Olefin feed per hour. - 19 - 1098A9 / 1961