DE2408391A1 - Process for the preparation of alkali or alkaline earth metal salts from alkane sulfonic acids - Google Patents

Description

Process for the preparation of alkali or alkaline earth metal salts of alkanesulfonic acids

The invention relates to the production of alkanesulfonates by adding bisulfite to an olefin in a liquid Reaction medium in the presence of a free radical Initiator. So far, two methods for the preparation of alkanesulfonates have been described:

(1) All reaction participants are poured in together, which is referred to below as the "one-pot method" or "one-to-one filling method" is referred to, and

(2) a method in which a prepared sodium bisulfite solution is continuously added to a solution over a period of two to four hours, which an alpha olefin, a cosolvent, and a free radical Contains initiator.

In the prior art, the importance of controlling influencing variables such as the pH value, the reflux conditions, the

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TELEGRAMS: LEATHER P ATENT MONKS

Maintaining no more than two phases of reaction mixture, etc. is described. Contrary to the teachings of the The prior art has now surprisingly found that alkanesulfonates by adding alpha-olefins to a Sodium bisulfite solution, which water and an aliphatic organic, hydroxyl group-containing compound, e.g. B. isopropanol, contains, can be prepared in the presence of a free radical initiator.

In the process according to the invention, the alpha-olefin, |

ι which 'contains, continuously to a solution of sodium bisulfite as' a soluble in the olefin, free radical initiator added ■ reflux for a period of two hours; will. This is surprising because such an addition, e.g. B. from small aliquots of alpha-olefin, a large amount of undesired sulfonate sulfonate and undesired disulfonates could be expected to a large part of the reagent for the sulfite formation reaction. The reaction is to be shown schematically as follows:

,) CH = CH ₀₊ NaHSO, CH ₂ (CE ₀ ) CH ₀ CH ₀ SO ₂ Na (a)

! y d. ο ρ c. y d. d ο

Main product

CH ₃ (CH ₂ ) CHCH ₂ SO ₃ Na '(b) SO ₂ Na

CH ₃ (CH ₂ ) CHCH ₂ SO ₃ Na (c) SO ₃ Na

where y = 7 and 12 and is present in each case with 50%. In other words, it means that those skilled in the art will predominate of the products labeled (b) and (c) would rather be expected than the preponderance of alkanesulfonate, as actually is

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Is found. Analytical data have shown that this process produces a reaction mixture of alkanesulfonates which is similar to that which was prepared by the known sodium bisulfite addition method.

The addition of the olefin, which contains the initiator system, to the sodium bisulfite cosolvent mixture gives several advantages not heretofore achievable in the art were, d. H. (a) continuous addition of the catalyst simultaneously with the olefin addition, (b) depressing one Oxidation of the sodium bisulfite solution before and during the Reaction sequence to a minimum and (c) a product with a lower content of inorganic constituents. the continuous addition of the catalyst gives a significant economic benefit because of cost of peroxide catalyst. This is the result of the fact that the "cage effect" inherent in the reaction, which is the case with the previously known Methods given is greatly minimized so that less initiator is required. the addition of the catalyst according to the invention also results in a noticeable reduction in undesired by-products, z. B. Tetramethylsuccinonitrile, if azo-bis- (isobutyronitrile) ■ (AIBN) is used. In addition, the fact that the Bisulfite is present in the reaction medium from the outset, the need to carry out the reaction under an inert atmosphere, d. H. Nitrogen, avoided. This is because the alcohol vapors from the cosolvent die Prevent air from reaching the bisulfite. The final one The advantage is the reduction in the formation of inorganic material, i.e. H. Sodium sulfate. Another benefit of that too Cost savings means that smaller reaction vessels and equipment are made from carbon steel and not Stainless steel can be used to store the olefin, which is then added to the reaction vessel will.

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The alkanesulfonate is produced in high yield and with high purity and it exhibits a high degree of biodegradability as well as excellent surfactant properties on. It is · of sufficient purity to be in high To be able to use proportions in toilet soap bars.

The invention is particularly applicable to olefinic materials, which have a terminal, olefinic bond, d. H. alpha-olefins, these alpha-monoolefins with im essential acyclic, straight chain or branched chain 1-olefins having 5 to 30 carbon atoms. The branched chain Olefins which can be used in the process according to the invention are those which do not have any branching on the 1- or 2-carbon atom of the vinyl group. Long-chain vinylidene compounds with a methyl or ethyl radical on the 2-carbon atom can also be used. However, vinylidine compounds are substituted with substituents above ethyl as well as either trans isomers or trisubstituted isomers with a straight or branched chain cannot be used in the method according to the invention. The method according to the invention is applicable to individual olefins of the class defined above or to mixtures thereof. The olefin defined above can Contains limited amounts of impurities and other olefins such as internal or secondary olefins. The presence these "other olefins" are not harmful because they react to such a limited extent that they cause the sulfitation reaction Do not interfere with the normal 1-0 lefins described above.

The inventive method is, as will be explained in more detail below, carried out so that initially z. B. Sodium metabisulphite is dissolved in water with stirring and formation of sodium bisulphite. The pH of this solution

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is adjusted to about 5.5 using a base, preferably using NaOH. This solution becomes the organic one Hydroxyl compound, namely the alcohol, together with 25% of the catalyst, e.g. B. t-butyl perbenzoate, added and heated to reflux. The olefin and the Eest of the catalyst to .dem stirred mixture of bisulfite / organic Hydroxyl compound was added over a period of two hours. After adding the olefin / catalyst, the mixture, while the pH is kept at approximately neutral value, by z. B, SOp into the reaction mixture is initiated, refluxed for a further two hours. * The product is then obtained.

The olefin, which contains an oil-soluble, free radical initiator, is added to the refluxing mixture of sodium bisulfite / cosolvent. The mixture comprises sodium bisulfite, water and a polar solvent which is an organic, hydroxyl group-containing compound, e.g. B. contains an alcohol. The term "polar solvent" as used in the description is to be understood as meaning an aliphatic, organic, hydroxyl-containing compound with a low molecular weight and 1 to 6 carbon atoms, ie C 1 -C _6. The preferred and most widely used polar solvents are alcohols such as methanol, ethanol and isopropanol. However, this class of solvents also includes diols, polyols and polyhydroxyl ethers having 1 to 6 carbon atoms.

It can be advantageous to add an additional, enter faster acting initiator to support the rapid formation of free radicals in the reaction mixture. This can be brought about by using so-called co-initiators, which have different half-lives will. This is explained using the following: benzoyl peroxide = 2.1 hours, t-butyl perbenzoate = 150 hours, di- (t-butyl peroxide) =

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10000 hours, t-butylperoxymaleic acid = 12 hours, 2,2'-azo-bis (isobutyronitrile) = 0.53 hours, the specified half-lives being based on 85 ^° C. An initiator with a shorter half-life drives the reaction forward so that the residence time of the reactants is reduced if a single catalyst is used. In addition, this ensures a smoother reaction because after the faster initiator has disappeared, the slower initiator has been activated in the meantime and in this way ensures that the reaction will continue to the end. Some types of reaction initiating agents that can be used for this reaction are molecular oxygen, NaOCl, inorganic oxidizing compounds such as inorganic peroxides, e.g. B. H ^ Op, Na ^ Oo * organic peroxides such as benzoyl peroxide and peracetic acid. The preferred peroxides are organic peroxides in which the peroxy radical is attached to at least one tertiary carbon atom, e.g. B. tert-butyl perbenzoate, tert-butyl pertoluate, 2,2-bis- (t-butylperoxy) -butane, di-tert-butyl peroxide, tert-butyl perphthalate (ortho compound) and t-butylperoxymaleic acid. In addition to the aforementioned compounds, it has been found that azo-bisisobutyronitrile (AIBN) is effective both alone and in combination with other initiators. The above-mentioned peroxides can be used individually or in combination if an accelerating effect is desired.

As previously described, the best source of the bisulfite ion is sodium bisulfite. However, other sources of bisulfite ion can also be used. These include sodium metabisulfite, ammonium bisulfite, calcium bisulfite, potassium bisulfite and magnesium bisulfite. In the specification, the definition of "alkali metal bisulfite" also includes ammonium bisulfite.

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Although the pH is not critical to the process according to the invention and it has been found that various pH ranges are favorable for the formation of alkanesulfonate, it has nonetheless been found that maintaining the pH in the aqueous phase during the reaction is advantageous and a represents an essential improvement feature of the invention. In particular, it has been found that maintaining a pH of from about 4 to about 9, preferably a pH range of about 6 to about 8, and more preferably a pH range of 6.9-0.2, results in high purity alkanesulfonates in excellent yields . This pH value can be adjusted either by (a) rinsing with SO «, (b) adding mineral acids (such as sulfuric acid, phosphoric acid, nitric acid and hydrochloric acid), (c) adding organic acids such as fatty acids containing 8 to 12 carbon atoms and (d) Addition of combinations of the above to the bisulfite solution can be maintained during the reaction. SO ₂ is particularly preferred because, in addition to maintaining the pH, it also serves to replenish used bisulfite ions. The reason for keeping the pH below 9 is that above this pH the desired bisulfite ion is largely neutralized to sulfite, which is not reactive, while below a pH of about 4 the bisulfite becomes sulfurous acid which decomposes into SOp and water. Fewer bifunctional sulfur compounds are formed within the specified pH range. It may also be necessary to use alkaline reagents to maintain the pH. Virtually any alkaline reagent can be used, e.g. B. basic metal oxides, basic metal hydroxides, basic nitrogen compounds, e.g. B. CaO, MgO, NaOH, KOH, Mg (OH) ₂ , UH ,, amines, etc. The amount used must exactly correspond to the amount required to achieve and maintain the desired pH. A more detailed explanation of the pH effects can be found in the article by Norton et al, J. Org. Chem., 33 No. Nov. 11, 1968, pp. 4158-4165.

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The applied during the reaction temperature can greatly from a value as low as about 50 ⁰ C up to such a high value vary as about 200 ⁰ C. Temperatures are advantageously in the range of about 75 ° C to 100 ⁰ C for the preferred organic peroxide and AIBN.

Furthermore, it is often advantageous to carry out the reaction in the presence of a small amount of an alkanesulfonate, e.g. H. a remaining amount, z. B. from a previous approach, which can be up to about 15 mol% to be carried out.

The molar ratio of alkali or alkaline earth metal bisulfite to olefin varies from about 0.1 / 1.6 to about 1.0 / 1.6 mol. For example, the reaction starts at an amount of about 0.1 / 1.6 mol of olefin to bisulfite in the bisulfite reaction mixture, and olefin is continuously added over a period of 1.5 to 2 hours until the final molar ratio is about Is 1.0 / 1.6. A preferred ratio is 1.0 mole olefin to 1.2 mole bisulfite ion.

The amount of present in the bisulfite reaction mixture Initiator can be from 0% to 100% of the total initiator to be used. Ideally, around 1 to 25% of the catalyst to be used in the bisulfite reaction mixture prior to the addition of the olefin. Although the reaction also with As 0% catalyst advances in the bisulfite mixture, the rate of alkanesulfonate formation is very slow. Ideally, there should be about 20 to about 25% catalyst in the bisulfite reaction mixture, with the remainder of the catalyst is to be added at the same time as the olefin.

In each case the ratio of total moles of catalyst to total moles of olefin is from 0.005 to 0.10; H. of 0.5 to 10 mol%, preferably from 0.008 "to 0.030 and especially

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preferably from 0.011 to 0.025 · It has also been found that the
Reaction is promoted through the use of fresh catalyst. This promotion is shown in the use of smaller amounts of catalyst and also in the shorter reaction times.

The ratio of organic compound containing hydroxyl groups to water can vary from about 4: 1 to 1: 9 and preferably from 3 '· 2 to 7 ' · 3 .

If the reaction proceeds to completion, will
a white monophasic aqueous liquid
educated. Before the end, depending on the type of catalyst addition, two or three phases can be present. Contains the water-white liquid present in one phase
the alkanesulfonate, which was produced according to the invention, and also the bisulfonate and sulfinate sulfonate product,
unconverted olefin, which is referred to below as "non-cleaning, organic substance" = (NDOM)
are, furthermore, inorganic salts which are not soluble in dimethyl sulfoxide (DMSO), these being referred to below as DMSO-insolubles. The amount of alkanesulfonate is
by determining the amount of unreacted olefins
(NDOM) and total solids determined. The total solids
include both the inorganic material (DMSO insolubles) and sulfonate products. The difference between total solids and DMSO solids gives the amount of sulfonates, ie the active material. The yields of active material, based on the amount of unreacted olefin, range from 65 to 95% depending on how the alkanesulfonate is used
is processed.

As previously described, one of the main uses is for the product produced according to the invention, its use as a component in a fine soap bar. A short

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Explanation of this application is given below: Normally, alkanesulfonates, which are obtained by addition from SO, to an alpha olefin, although they were Much harder than alkylbenzenesulfonates are, very sticky when small percentages of water are in a molded detergent bar · As a result, pieces made from these materials are also very difficult to pick up to process the usual soap making equipment, and in addition, they have a sticky after-effect on the hands and also have a rate of wear and tear is extremely high, so that it is unfavorable in spite of the fact that the developed foam is of excellent quality are.

The alkanesulfonates, especially in the molecular weight range from Cg-C.Q are also for use in detergent compositions has been proposed. These materials are hard, at least as mild as soap and allow up to 25% Water too without getting sticky.

Using the alkanesulfonates prepared in accordance with the present invention, an inexpensive toilet soap bar can be made with synthetic Detergents or detergents are manufactured which have "better foaming properties under all water conditions which is both mild and has a soap-like feel on the skin after washing, which does not become slimy under conditions of use and in a simple manner with conventional soap making equipment can be, with an alkanesulfonate, the 8 to 18 Contains carbon atoms in the alkyl chain, or a mixture of alkanesulfonates, which contain an average of 8 to 18 carbon atoms in the alkyl chain, and a superfatting, agents containing natural or synthetic fatty acids can be used. Has a bar of soap made in this way a composition which, based on the existing

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active ingredients, about 10 to about 90% by weight and preferably about 40 "to 80% by weight of the alkanesulfonate, preferably in the form of the alkali metal or magnesium salt, about 5 to about 35 % of a natural or synthetic fatty acid and 5" contains up to about 30 % of a suds booster, and, based on the total weight of the bar, contains 5 % to about 25% water.

Another feature that goes into making toilet soap bars can be used from the alkanesulfonates prepared according to the invention consists in mixing others Substances such as fragrances, dyes or coloring agents, germicides, softening substances, possibly inorganic ones Detergent builders, opacifying agents and Hardeners with these alkanesulfonates. After mixing all of the ingredients, the water-solvent system becomes inherently known working methods removed, z. B. by vacuum drying, distillation, flash drying or drying in the drum.

Though merely toilet soap bars as one of the end uses of the alkanesulfonates prepared according to the invention have been described, the product prepared according to the invention can also as a cleaning substance, as a foam booster, as a dispersant for lime soap foam and as a hydrotrope can be used.

The invention is explained in more detail by means of the following examples:

example Λ

A sodium bisulfite solution was obtained by dissolving 4.2 mol Sodium metabisulfite prepared in 201.8 mol of distilled water while stirring with a magnetic stirrer. The pH of the Solution was adjusted with 50% sodium hydroxide solution,

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until a pH of 5 »5 was reached (about 1.3 ^ mol). The so Sodium bisulfite solution prepared was in the reaction vessel together with 40.0 mol of isopropyl alcohol and 0.05 mol entered tert-butyl perbenzoate catalyst. The mixture was heated to reflux.

To the stirred mixture of sodium bisulfite / alcohol / water was added 6.9 moles of a 1: 1 CQ-C 1-4 alpha olefin containing 0.15 moles of tertiary butyl perbenzoate catalyst over a period of two hours. After the addition of olefin catalyst the mixture under reflux (about 82 ⁰ C) boiled for a further two hours while the pH to 6.9 - 0.2 was maintained by bubbling sulfur dioxide into the reaction mixture. The resulting mixture after completion of the reaction contained 1.1% NDOM, 26.3% total solids, 8.0% DMSO insolubles. The conversion based on olefin consumed was found to be 95 +%.

Example 2

The procedure of Example 1 was repeated with the exception that 0.07 mol of azo-bis-isobutyronitrile catalyst to were added to the sodium bisulfite cosolvent mixture prior to refluxing and olefin addition. The rest of the Catalyst, 0.15 moles of tert-butyl perbenzoate, was added to the Added olefin. After the addition of olefin catalyst over a period of two hours, the mixture became an additional two hours boiled under reflux, the pH value being kept at 6.9-0.2 by means of sulfur dioxide. The resulting mixture after completion of the reaction contained 2.0% NDOM, 26.2% Total solids and 11.8% DMSO insolubles. The conversion based on olefin consumed was 89 +%.

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The procedure of Example 1 was repeated except that 0.06 moles of azo-bis-isobutyronitrile catalyst was added to the sodium bisulfite cosolvent mixture prior to reflux and olefin addition. The remainder of the catalyst, 0.16 moles of azo-bis-isobutyronitrile, was periodically during the two. Added hours of olefin addition. As in Example 1, the reactants were refluxed for a further two hours at a pH of 6.9-0.2. The resulting mixture when the reaction was complete contained 2.2 % NDOM, 26.1% total solids, and 7.3 % DMSO insolubles.

Example 4

The procedure of Example 1 was repeated with the exception that 0.04 mol ITaOCl were used as a catalyst and that tetradecene-d) was used as olefin. The transformation was 94 - +%, based on consumed olefin.

Examples 5 to 9

The examples shown in Table I below illustrate the preparation of alkanesulfonates according to the invention Process wherein olefins with varying chain lengths, varying reaction times and varying catalyst concentrations were applied. However, the catalyst used was not a fresh catalyst.

From the following examples it can be readily seen that there is a direct relationship between the total consumed, catalyst (regardless of whether it is mixed or not), the reaction time, the total solids, the NDOM value and gives the value for the DMSO-insoluble. Whenever an aged one Catalyst is used in low amounts, i.e. H. 0.07 mol, this corresponds to about 1 mol% based on the olefin longer reaction times of about 4 to about 5 hours are required, um.die optimal yields of total solids and

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24U8391

Obtain acceptable values for NDOM and DMSO insolubles . There is no real upper limit to the amount of total catalyst that can be used other than that. the cost must be taken into account.

Ideally, the total reaction time should be at least two hours, ie one hour as the addition time and one hour as the reflux time. When using fresh catalyst as shown in the following examples or can be obtained to 9 comparable results in this period, with the examples. 5 In any case, however, the person skilled in the art is not restricted to the use of fresh catalyst, but can also use an aged catalyst. The exact values for the individual parameters and the conditions can be determined in a simple manner by means of preliminary tests. The corrected percentage for active ingredients is obtained by calculating the amount of DMSO in total solids relative to the percentage of NDOM, and subtracting this from total solids. Or perhaps only C 1-4 and C 1-4 olefins are shown in the examples, similar results were also obtained when using Cj-- and C, ₀ -01efinen by the method according to the invention.

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Table I.

At- olefin- addition- catalyst- reflux-% NDOM total clearance chain time system time (h) fixed length (h) fabrics

DMSO active
Insoluble ^Stock ) part3 - ^e v _{0 /} N corr., (%)

5 ° 10 2 0.07M
0.11M AIBNCa)
TBP Cb) 2 2.1 6th ^C 10 1.5 0.07M
0.04M AIBN (a)
TBP Cb) 2 2.0 CD
CX> 7th ° 14 2 0.08M
O, 11M TBP (a)
TBP (b) 2 2.3 CO 8th ^C 10- ^C 14 2 0.04M
0.08M TBP (a)
TBP (b) 2 1.6 to 9 ^C 10- ° 14 2 0.02M
0.08M TBP (a)
TBP (b) 2 1.0

24.2 11.2 21.5 "2373 (theor.) 25.6 16.8 19.6 25.9 (theor.) 26.0 -9.8 23.4

28.4 (theor.)

25.5 19.4 20.4

26.6 (theor.)

25.7 8.2 23.6 26.6 (theor.)

(a) Amount of catalyst initially charged to the reaction vessel

(b) Amount of catalyst added simultaneously with the olefin
(theor. J »theoretical yield

(AIBN) «Azo-bis (isobutyronitrile) (TBP) - tert-butyl perbenzoate

OC GJ CD

114 U 8 3

Examples 10 to 17

The following examples shown in Table II show the process according to the invention using fresh catalyst. The procedure, with a few minor modifications, was as follows: 4.2 moles of sodium metabisulfite were dissolved in 3630 g of water, 1.34 moles of 50% NaOH were added to the solution, resulting in a pH of 5> 5 - 5> 65 resulted. 2400 g of isopropanol and 0.031 mol of AIBN catalyst were added to the reaction vessel containing this solution. The reaction mixture was heated to reflux (82 ° - 83 ⁶ C). 3.4-5 moles of CQ, C 1-4, C QC- alpha olefin (where applicable) were added over a one hour period, containing 0.026 moles of t-butyl perbenzoate catalyst. At the end of the one hour addition, 0.012 moles of AIBN was added to the reaction mixture. The addition was continued for an additional hour with a further 3 * 4-5 moles of the olefin containing 0.010 moles of t-butyl perbenzoate. The pH was maintained at 6.8-7.0 by adding SO4. The reaction mixture was then refluxed for an additional two hours. After this time, the reaction mixture was emptied and analyzed. The usual hyamine titration was used for the analysis. The corrected percentage for the active ingredients was obtained by calculating the amount of DMSO in total solids based on percent NDOM and subtracting this from total solids.

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Table II

At- olefin- addition- reflux catalyst-% NDOM total clearance chain time according to the system fixed length (h) adding substances

DMSO active hyamin insol. Stock active

share,

corr., (%)

10 ^C 10 " ^C 14 2 1 0.043M
0.036M AIBN
TBP 1.6 25.1 8.4 23.0 *) 11 ° 10- ^C 14 2 2 0.043M
0.036M AIBN
TBP 1.1 25.3 8.9 23.0 23.0 12th ^C 10- ^C 14 2 1 0.043M
O, O36M AIBN
TBP 1.6 25.4 10.3 22.8 *) 13th ° 10- ^C 14 2 2 0J036M AIBN
TBP 1.1. 25.9 8.5 23.7 23.2 14th ^C 10- ^C 14 2 2 0.043M
0.036M AIBN
TBP 0.5 27.5 11.4 24.4 23.2 15th ^C 10 2 2 0.043M
0.036M AIBN
TBP 2.3 24.2. 8.4 22.2 20.9 at
MG 265 16 ^C 14 2 2 0J036M AIBN
TBP 1.7 27.2 8.3 24.9 *) 17th ^C 14 2 3 0.043M
0.036M AIBN.
TBP 1.4 27.6 7.5 25.5 *)

*) ," not determined

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Examples 18 and 19

The examples shown in Table III below were made carried out by the method according to the invention, wherein. a single catalyst system instead of a mixed one Catalyst system was applied. In the approach with AIBN, a total amount of 0.07 mol of catalyst was used in partial amounts of 0.018 moles and 0.052 moles were used. In the approach with t-butyl perbenzoate, a total of 0.072 mol in Allocations of 0.026 moles, 0.026 moles, 0.010 moles and 0.010 moles were used. The analysis methods were the same as for the previous examples, d. H. of Table II.

At the beginning of the addition of oil, the pH of the reaction mixture was 6.15-6.2. After the addition of the olefin, over an hour and 25 minutes, the pH rose to 7 »0-7» 10 and an aqueous white solution was obtained. At this point, SOp should be in a slow, steady stream be introduced to keep the pH at approximately neutral.

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Table III

With- olefin- addition- return- catalyst-% NDOM total- DMSO- active hyamin

game chain time flow system fixed insol. Stock active

length (h) by fabric (%) parts,

the (%) corr. , (%)

. Encore

C ₁₀ -C ₁₄ 2 2 0.07 MAIBN 1.3 25.3 9.1 23.0 21.8
_1O - ^C 14-

^C _1O - ^{C 14-2 3} 0.072 MTBP 2.4 25.0 10.0. 22.5 *) '

*) " not determined

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Example 20

In the following Table IV is the use of alpha olefins with varying chain lengths as well as explained by different solvents. The working method used corresponded to that of Example 1. The reflux times and temperatures will, of course, vary with the particular solvent used. However, the setting of each of these parameters is within the scope of general knowledge.

Olefin chain length

solvent

Table IV

temperature

% Yield (based on olefin consumed)

Ethylene glycol

60-63 C

n-butanol 118 ° C

85

Values for total solids, DHSO-insolubles, and NDOMs that were comparable to those of the previous examples.

(a) alpha-olefins der

-Fraction (GuIf Development Chemical)

Distribution of carbon atoms as determined by chromatography

'18
'20
'22
'24

C,

C.

C.

in% by weight

0.2

5.1

33.3

26.1

13.4

7.6

'32

'34

38
J40

44

3.2 2.2 1.7

1.1 0.8 0.5 0.1

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Claims (11)

Claims 1. A process for the preparation of an alkali or alkaline earth metal salt of an alkanesulfonic acid, characterized in that a reaction mixture under reflux which (1) is a cosolvent of water and an aliphatic, hydroxyl-containing compound with 1 to 6 carbon atoms, the ratio of this organic compound to water is from 4: 1 to 1: 9, (2) an alkali or alkaline earth metal sulfite and (3) a free radical initiator, which makes up to 25% of the total .initiator, contains an acyclic, alphamonoolefinic compound which has a terminal double bond and has from 5 to 30 carbon atoms and contains the remaining part of the free radical initiator mixed in, the ratio of this alpha-monoolefin to the bisulfite varying from 0.1 / 1.6 to 1.0 / 1.6, and that after the addition of olefin and initiator has been completed, the reaction mixture is refluxed while maintaining the pH-We rtes between 4 and 9 by adding an acid or an acid-forming compound continues until the reaction is complete. 2. The method according to claim 1, characterized marked eichn e t that as a free radical initiator Op, HpOo, NapOp »NaOCl, benzoyl peroxide, peracetic acid, t-butyl perbenzoate, 2,2-bis- (t-butylperoxy) -butane, di- (t-butylperoxide), orthot-butyl perphthalate, t-butyIperoxymaleic acid or azo-bisisobutyronitrile used. 409834/1 121 24G3391 3. The method according to claim 1 or 2, characterized in that the alkali metal or alkaline earth metal bisulfite is used Sodium bisulfite, potassium bisulfite, ammonium bisulfite, Calcium bisulfite or magnesium bisulfite is used. 4 ·. Method according to claim 3, characterized in that that the pH is maintained between about 6 and about 8. 5- The method according to claim 4-, characterized in that that the pH is kept at about 6.9-0.2. 6. The method according to any one of the preceding claims, characterized in that the reaction is carried out at a temperature of approximately 50 ^° C. to approximately 200 ^° C. 7. Method according to one of the preceding claims, characterized in that the ratio of the alphamonoolefinic Compound to the bisulfite is 1.0 mol of olefin to about 1.2 mol of bisulfite ion. 8. The method according to any one of the preceding claims, characterized in that the pH value by treatment of the reaction mixture with sulfuric acid, phosphoric acid, nitric acid or hydrochloric acid as inorganic acids or organic fatty acids with 8 to 16 carbon atoms are maintained as organic acids. 9. The method according to any one of the preceding claims, characterized in that the acid-forming compound SOp is used. 10. The method according to any one of the preceding claims, characterized It is shown that the free radical initiator in the reaction mixture has a shorter half-life as the free radical initiator added with the olefin. 409834/1121 11. The method according to any one of the preceding claims, characterized in that the olefinic compound is a branched-chain, alpha-monoolefinic
Compound is used which has a terminal double bond and no branching on the 1- or 2-carbon atom of the vinyl grouping. 4 0 9 8 3 A / 1 1 2 1