DE2032635C2 - Oil-soluble, anionic, surface-active agent - Google Patents

Description

R '

C = C

R "

R "

10

15th

in which R is a straight-chain or branched, saturated alkyl radical, R ', R "and R'" are a Represent hydrogen atom or a straight-chain or branched saturated alkyl radical, among provided that R ', R "and R'" are not all hydrogen atoms, and the total number of R, R ', R ", and R'" carbon atoms range from 22 to 38 carbon atoms

2. Oil-soluble, anionic, surface-active agent according to claim 1, characterized in that 2s that the sulfonation product in an alkaline medium and / or - in the case of the presence of Sultons - treated with sulton-splitting agents in a manner known per se

3. Oil-soluble, surface-active agent according to claim 1, characterized in that the Monoolefins in the form of a thin film in continuous contact with gaseous sulfur trioxide brings

35

oil-soluble sulfonic acid-type surfactants, which were previously made from petroleum, such as the salts of mahogany acid or alkylbenzenesulfonate, are well known These surfactants are commonly used as detergents for Dry cleaning, as an emulsifier, dispersant, lubricant additive, anti-corrosion agent and as a general Detergent used.

The salts of mahogany acid consist mainly of alkyl aryl sulfonate and can be used as a by-product sulfuric acid refining of petroleum. But because it comes from different sources Hydrocarbons of unknown constitution and contains many impurities that lead to a If the product is discolored, it will be necessary to use the product be refined by, for example, active clay. The quality of the product obtained is accordingly different, especially if the product is in emulsifiers or detergents for dry cleaning, in which it is to be incorporated as an ingredient, and when a product of high quality is required, it is accompanied by such severe impurities that the mixing speed of the other ingredients to be mixed because of the lack of uniformity of the produced Mahogany acid salt needs to be changed.

Furthermore, the salt of mahogany acid has the disadvantage <> 5 which can be attributed to the origin of the substance that it contains so much non-sulfonated substances that A de-oiling pressing of the unreacted oil is necessary to reduce the content of the mahogany acid Increase in salt. However, this leads to an increase in manufacturing costs, the commercially available products contain 60 to 70% mahogany acid salt, the presence of relatively large amounts of non-sulfonated Products is the reason for the lack of uniformity of previous products.

In addition, the mahogany acid salt is very troublesome to handle because of its high viscosity So far it has only been used after extensive heating for the purpose of softening. What that Dialkyl aryl sulfonate with alkyl radicals with 10-15 carbon atoms is concerned, its viscosity - although it is is free from the above-mentioned disadvantages - as high as that of the above-mentioned mahogany acid salt. This makes handling of this substance equally difficult. In the case of the long chain Alkylarylsulfonate, which is described in US Pat. No. 3,410,925, is its method of manufacture Quite complicated in that the as The starting substance of the hydrocarbon to be used makes two process stages necessary, namely the dimerization and alkylation of the alkyl radical.

DE-AS 12 76 634 deals with a method for the preparation of mixtures of surface-active compounds, after which one in a manner known per se Sulphonation mixtures obtained by sulphonating certain olefins with 1 to 1.7 mol of sulfur trioxide have been obtained, neutralized and treated with halides, amines, alcoholates, phenolates:!, carboxylic acid salts and salts of compounds containing SH groups. However, these known products are said to be good be soluble in water, which thus largely rules out oil solubility

In the present invention, an oil-soluble anionic surfactant becomes more aliphatic by sulfonation Monoolefins obtained by means of sulfur trioxide, which can be obtained by sulfonating a monoolefin the general formula

R "

R '

R '"

in which R is a straight-chain or branched saturated alkyl radical, R ', R "and R'" a hydrogen atom or represent a straight-chain or branched saturated alkyl radical, with the proviso that R ', R "and R '" are not all hydrogen atoms and are the total number of carbon atoms of R, R', R "and R '"is in the range from 22 to 38, and by optionally subsequent treatment in alkaline Medium and / or - if sultones are present - treatment with sultone-splitting agents in in a manner known per se.

As for the starting material of the agent of the present invention, monoolefins are 24-40 C atoms obtained by oligomerization of monoolefins that are not -olefins, or of corresponding low molecular weight monoolefins were obtained (dimerization or trimerization), usable.

With regard to the former monoolefins, either branched or straight chain ones are used; particularly however, straight-chain monoolefins are suitable.

In the case of the latter monoolefins, oligomerized material is also used, either branched or straight chain; straight chain olefins however, they are preferred

The latter material can be used in high yield, for example in the case of dimerization be obtained that either olefins with 12-20 C-atoms reacts with one another or monoolefins with 2-18 C-atoms with olefins with 22 or more Reacts carbon atoms in the presence of a catalyst

In addition, the oligomers of C3-Cn-OIeR-nen and, preferably, of Ce-Cu olefins which are important Are starting materials for the purposes of the invention.

The former material, namely monoolefins with 24-40 carbon atoms, can be produced by paraffin cracking, Ethylene polymerization, hydrogen chloride removal from chlorinated paraffins or dehydrogenation of Paraffins, are obtained; the latter material oligomerized olefins can also according to one of the above method can be obtained.

Organometallic compounds, such as organoaluminum, are used as a catalyst for the oligomerization Compounds, metal oxides, alkali salts or boron fluorides are suitable

The composition changes according to the constitution of the oligomerized starting material, the properties or the polymerization conditions (such as temperature, time pressure, etc.) of the low molecular weight, straight-chain olefins. In the case where, for example, the dimerization under Use of a straight chain C ^ -CM olefin is carried out, high molecular weight monoolefins are mainly of the following constitution or get their mixtures.

(vii) R ₁ CH ₂ CH

CH ₂

R, CH ₂ CH ₂ CHCH ₂ CH - = CHR,
(ii) R ₁ R ₁

Ί I

CH ₂ CH ₂

RiCH ₂ CH ₂ CH-CHCH = CHR ₁
(iii) R ₁ CH ₂ CH ₂ CH ₂ CH ₂ Ch = CHR ₁
(iv) CH ₃

40

R ₁ CH ₂ CHCH ₂ CH = CH-R ₁

(ν) R ₁

C = CH ₂

Ri

(vi) R ₁ CH = CH (CH ₂ ) B

CH-CH ₃

R ₁

-CH ₃

Ri

(in which Ri is an alkyl radical with a carbon chain, whose total number of carbon atoms in each molecule is in the range of 24-40).

Occasionally, however, isomerization of the starting material takes place before dimerization, which of depends on the type of catalyst used. It can be assumed that the compounds of the formulas (i) and (ii) more than the compounds of formulas (iii) and (iv) are obtained. In addition, there are other constitutions both from the point of view of the transition point for the double bond and from the point of view the combinations of alkyl chain lengths conceivable. As for the trimeric or tetrameric product, so Various constitutions other than those mentioned above can be obtained.

The facts can be summarized as follows:

It is sufficient if the high molecular weight monoolefins which can be used according to the invention have 24-40 carbon atoms, preferably Have 25-36 carbon atoms. Because many of these monoolefins have a branched chain or double bond have inside, even in the case of a straight-chain internal monoolefin of formula (iii), they show a low flocculation point and a low pour point compared to a straight chain «-Olefin with the same number of carbon atoms and despite the high molecular weight such excellent properties that they are generally colorless at room temperature Liquid. The following table shows the properties of mixtures of typical high molecular weight Monoolefins put together:

Dimerized number of In ⁰ C In ° C Olefin Carbon atoms Flocculation Pour point Point 45
Dimerized Olefin 28 -1 -3 Dimerized Olefin 32 1 -1 ⁵⁰ dimerized Olefin 36 5 2

where η = 0-21

The agent according to the invention is produced by sulfonating the above-mentioned starting materials. The sulfonated product thus obtained is usable as it is. But it is preferably initially neutralized and then used, using it as such or only after hydrolysis. To the A sulton-splitting agent is also added to the sulfonation product. The ones used on this occasion Processes of sulfonation, neutralization and cleavage of sultones are the same as those used for conventional water-soluble olefin sulfonates, for example, in GB-PS 10 72 601 and 1139 158 can be used. In other words, the agent according to the invention can be obtained by placing the initial oiefin in the form of a

thin film continuously with gaseous sulfur trioxide brought into contact and the reaction product is subjected to neutralization and then the sultones contained therein are subjected to a ring cleavage reaction by hydrocracking or by implementing them with one-sulton splitting agents.

During the sulfonation, the starting olefin, which is naturally liquid at room temperature, can contribute Room temperature can be added. In sulfonation Neither expensive press heating nor the use of a solvent is necessary.

The sulfonation plant can either be a continuous powered falling film reactor or a forced film reactor can be used, which is constructed in the manner are that a thin film starting material is brought into contact with gaseous sulfur trioxide can. The dimensions of the system are »not subject to any particular restrictions; there are Systems for the laboratory up to large-scale systems are possible. A suitable reaction device for the production of the agent according to the invention consists in a continuous sulfonation device in one high level sulfonation can be performed. A sulfonation device of this type is preferably with a Provide the largest possible heat exchanger surface. The sulfonation device used here can of course also be equipped with a thermocouple with which the internal temperature can be controlled. It it is also practical to have one with an attached reactor to complete the reaction Use sulfonation device.

The sulfonating agent used for the sulfonation reaction is either sulfur trioxide obtained by oxidation of sulfur dioxide or stabilized sulfuric acid anhydride (liquid sulfur trioxide). The SO ₃ gas concentration suitable for use in the reactor is between 1 - 10 percent by volume, based on the inert gas. Air is usually used as the inert gas; but it can also be replaced by nitrogen, carbon dioxide or sulfur dioxide. The temperature of the sulfur trioxide gas to be introduced should be between 30 and 100 ^° C. (preferably between 40 and 50 ^° C.). The molar ratio of sulfur trioxide gas to the starting olefin is between 0.5 - 1.5, preferably between 0.8 -13-

Furthermore, the previous production of mahogany acid salt is made more difficult by the fact that the conversion of the petroleum fraction to be sulfonated increases very rapidly, which is associated with a sudden increase in viscosity Conversion exceeds 90%, no such increase in viscosity (which could make handling of the product difficult). This fact is characteristic of the invention. Since the starting olefin has a low viscosity although its molecular weight is very high as mentioned above, it can be sulfonated without the use of high temperatures. Even in the case of a mixture of dimeric olefins having 36 carbon atoms, it is well at about 5O ⁰ C sulfonated Moreover, the Sulfonsäuregemisch obtained does not solidify at a temperature above 40 ⁰ C, and has a low viscosity so that the Sulfonierungsreak- *> 5 tion can be done easily. The suitable reaction temperature is by 5 ° C or more higher than the solidification point of the starting olefin, but does not exceed 100 ⁰ C and is preferably between 30 and 70 ⁰ C.

The sulfonated substance (acid) obtained in this way generally consists of 30-95% of a monoalkene sulfonic acid with a high molecular weight, 0-50% from a hydroxymonoalkanesulfonic acid, 0-30% from a di- and polysulphonic acid, 10-75% from a 13- and 1,4-sultone and 0-60% from none converted substances.

The neutralization of these mixtures is achieved by adding alkali hydroxide, such as LiOH, NaOH, KOH, etc., carbonate, such as Na ₂ CO ₃ , (NH ₄ I ₂ CO _3, etc., NH ₄ OH, organic amines, namely primary, secondary and tertiary amipes or Alkanolamines ^ in an amount of 0.6-1.0 equivalents, based on the amount of SO _{3 introduced} (in moles) by adding alkaline earth metal hydroxides and dgL or alkali metal hydroxides with subsequent double bond cleavage.

Hydrocracking turns the sultones contained in the above mixture into hydroxyalkane sulfonates Since the hydroxyl group in this sulfonate is hydrophilic in nature, there are cases in which do not require the sulfonate to make a useful oil-soluble surfactant In such a case, it is therefore sufficient to control the formation of the hydroxyl group, initially by neutralizing the sulfonic acid with alkali hydroxides and then adding a sulton-splitting one Means in such an amount that the equivalent of the following ring opening of the residual sulton is exceeded will. As sulton-splitting agents that are used for this purpose, for example, alcohols, Phenols, especially sodium phenolate, carboxylic acids, primary or secondary amines, imines, or amides Imides of carboxylic acids or sulfonic acids, active hydrogen containing compounds such as mercaptans or thiourea or its N-substitution products, as well as compounds that do not have active hydrogen contain, such as aminesulfonates, suitable. In addition, tertiary amines, thioethers or tertiary amines are also suitable Phosphines suitable Of these sulton-splitting agents, those that have active hydrogen are said to be contain, in the presence of a salt or a residue that binds with the sulfonic acid residue able to be used. The substitution group can be an aliphatic group, an alicyclic group aromatic group, etc., or a single group or multi-functional groups. For this purpose the salt of an inorganic acid, thiocyanic acid, thiosulfuric acid or hydrogen sulfide comes as the salt in question. Such sulton-splitting agents which do not contain active hydrogen require one such salt or neutralizing agent does not.

Especially noteworthy is the fact that despite the high molecular weight, the viscosity of the olefin sulfonic about a maximum of 1000 according to the invention cp is with regard to the neutralization in the process described is at 50 ⁰ C, which is even true when the present olefinsulfonic rapidly to the basic aqueous neutralizing solution is added and stirred so that it therefore does not become a

solid mass solidifies, but is generally already neutralized without the use of a solvent. This solidification is possible during the neutralization in the course of the production of a water-soluble, surface-active agent, even in the case in which an α-olefin sulfonate with a chain length in the range of 20-24 carbon atoms is used. If not, either the temperature is maintained at about 8O ⁰ C in this case, or a suitable solvent is added, the neutralization does not proceed. In the invention, small amounts of solvents can also be used in the neutralization if deemed necessary.

The pulp which is obtained in this way and which contains alkali or sulton-splitting agents is then held at a certain temperature for a certain time while stirring. Included the opening of the Sulton ring takes place. The cleavage temperature and the cleavage time depend on one another; than ever the higher the temperature, the shorter the time required. The one required to split the Sulton Temperature and time requirements are 100-200 ° C and 7 Hours to 1 minute. The sulton's ring has already been opened if this Bedv.f has been met has been.

In this connection there can be no question of the need to keep the pulp alkaline by controlling the amount of alkali or the amount of sultone-splitting agent.

The sultone thus split is first subjected to the following aftertreatment: The resulting cleavage product of the sultone usually contains a mixture of non-converted oil, water, some inorganic salt or alkali in addition to the olefin sulfonate, so that this product can be used as an oil-soluble, surface-active agent under these conditions ; however, there are many cases where the effective components (including the unreacted oil) must be separated for use. It is then necessary to remove the impurities such as the inorganic salt or water from the mixture. A petroleum-based solvent or a chlorinated hydrocarbon- based solvent is used to separate the impurities from the active components of the cleavage product. This means that the active components, which consist essentially of olefin sulfonates, are already soluble in the solvent and are extracted in this way, while the impurities remain as a residue. Petroleum-based solvents suitable for this purpose are pentane, hexane, ligroin, octane, gasoline, or kerosene; while solvents based on a chlorinated hydrocarbon for the

ίο same purposes trichlorethylene, tetrachlorethylene or carbon tetrachloride. In the case where there is also a simultaneous separation of polysulfonates is intended, a lower alcohol based solvent such as ethanol or Isopropanol, is used. When performing the extraction by evaporation of the solvent under atmospheric or reduced pressure, an olefin sulfonate having a high molecular weight can be used can be obtained containing unreacted oil. That Olefin sulfonate does not suffer any loss of effectiveness because it only contains the unreacted oil in to a small extent and accordingly there is no need to bother with the unreacted oil by extraction by use generation of additional solvents, by distribution or Separate absorption; rather, the unreacted oil contained in the olefin sulfonate has a beneficial effect aimed at reducing the viscosity. The oil-soluble surfactant that is im consists essentially of the inventive olefin sulfonate, is rich in sulfonate and in terms of Hue, anti-corrosion property and oil solubility compared to conventional mahogany acid salts and the like, and has that The advantage is that it is easy to process because of its low viscosity and that it is optimal To obtain products with almost uniform properties. From the standpoint of effectiveness, that is surfactants present when you use it compares the conventional mahogany acid salts, in terms of lubricating effect, anti-corrosion effect, emulsifying effect and hydrating effect, such as them are required by detergents for dry cleaning, consider.

example 1

3000 g of an -olefin with 16 carbon atoms, which consisted of 93% of a -olefin, 6.6% of vinylidene paraffin and 0.4% of an internal olefin and which was produced by ethylene polymerization, and 600 g a nickel catalyst, which consists of 6.2% NiO. 84.4% SiO: and 9.4% Al ₂ O ₃ were placed in a 4-necked flask and reacted for eight hours at 35 ° C under nitrogen with vigorous stirring. mainly an isomerized internal olefin) was evacuated under reduced pressure, whereby a dimerized olefin containing somewhat higher polymerized olefin was obtained in 50% yield.

The IR spectrum of the dimerized olefin thus obtained showed almost no terminal double bond at 910 cm ^-1 . Rather, a peak was observed at 965 cm ^-1 which was attributable to the trans form of the inner double bond, as well as another peak - albeit weak and indistinct - at 800-900 cm ^-1 . This proves that the present olefin contains much of those components which have three substituents and one double bond. This high molecular weight mixture of olefins was sulfonated using an apparatus to produce a continuous, thin, sulfonated film on a laboratory scale

The apparatus consisted of Pyrex glass, which was equipped with a reactor 5 mm in diameter and 120 mm in length and constructed in such a way that the olefin and SO3 gas flow down in parallel and in this way was achieved that the components in one another Contact kamea as regards the reaction conditions so the SOrTemperatur was 50 ⁰ C, the SO3 concentration 23 mol% (diluted with nitrogen gas), see the contact time 30 Olefineinleitungsgeschwindigkeit 6 g / min and the Olefintemperatur 25 ° C the molar ratio of sO ₃ to olefin and the reaction temperature used are shown in Table I.

Table I.

Relationship between the ratio of SCV high molecular weight C ₃₂ oils, reaction temperature and properties of the olefin sulfonate produced

10

No. Molar ratio Temperature of % Sales coloring Solubility) Tetrachlor Dry cleans Spindle oil S0 ₃ / high- Sulfonation the (Velcro value)?) CCI ₄ ethylene agent number 1 molecular Product ( ⁰ C) Reaction!) petroleum based Olefin O O O 1 0.5 40 45 10 O O O O 2 0.8 50 73 13th O O O O 3 1.0 50 90 50 O O O O 4th - 90 90 70 O O O O 5 1.2 50 93 70 O O O O 6th _ 90 92 90 O O O O 7th 1.5 50 95 110 O

') Analysis method: Estimated on the basis of the sulfur content in the high molecular weight olefin sulfonate.

² ) The Klett value in the case of a 5% isooctane solution.

³ ) In the case of a 30% strength by weight solution at 25 ° C .; the sign O means "good".

30th

35

40

Different as prepared above sulfonic acids with a 10% aqueous sodium hydroxide solution were neutralized in an amount which is introduced during the sulfonation SCH amount in mole of the same, and then C for 20 minutes subjected to hydrolysis at 160 ^0, while the sodium salt obtained from the olefin sulfonic acid.

This sodium salt of olefin sulfonic acid separates into two layers when mixed with ethanol and is subjected to extraction using petroleum ether. The upper petroleum ether layer consists of olefin sulphonate and extracted, unreacted olefin, while the excess alkali, disulphates and Glauber's salt are separated, the lower one from water and ethanol form existing layer. By removing the solvent from the petroleum ether layer, the obtained olefin sulfonate according to the invention. Simple extraction is sufficient to practically complete the To remove excess alkali and Glauber's salt and to get a light color and low viscosity.

The loss of the olefin sulfonate mixture in the course of the refining is less than 3%.

The by sulfonation at a molar ratio of SO3 to high molecular weight olefin of 1.0 and a reaction temperature of 50 ⁰ C (as seen from Table I is) sodium sulfonate obtained was in place as an active ingredient of a dry cleaning agent of a conventional mahogany acid sodium salt used The content of the olefin sulfonate (sodium salt ) in the dry cleaning agent was between 5 and 30% in the present example. The present olefin sulfonates, both those obtained using a petroleum-based solvent and those obtained using a tetrachlorethylene-based solvent, withstand a comparison with the conventionally prepared products in every respect, such as detergency, hydration power, finishing effect, the Softness of the finish, the smell and the influence on the fiber. They can therefore be used for the same purposes.

Especially when using the inventive

50

55

65 Olefin sulfonates are their hydration properties superior to conventional agents in that they dissolve one and a half times as much water able.

The viscosity of the present sodium olefin sulfonate was as follows:

No. 2 No. 3 No. 7 mahogany acid sodium salt

300 cp (25 ° C)

450 cp (25 ° C)

600 cp (25 ° C)

3000cp (25 ° C)

Example 2

3000 g of an α-olefin with 12 carbon atoms, consisting of 98% of an α-olefin, 1.5% each of vinylidene paraffin and 0.5% of an internal olefin and produced by ethylene polymerization, were used in a nitrogen atmosphere dimerized by 1 mol% of triethylaluminum as a catalyst at 200 ° C. and stirring for 5 hours, and an olefin of the vinylidene type with 24 carbon atoms and a yield of 85% are obtained. This olefin was first sulfonated using the same apparatus and the conditions of Example 1. The molar ratio SO ₃ ZC ₂₄ -OIefin was 1.0: 1.2 and the reaction temperature was 40.degree

500 g of the sulfonic acid obtained in this way were mixed analogously to Example 1 with an aqueous sodium hydroxide solution in an amount which was equivalent to the amount of SOr introduced. On the other hand, a part of the sulfonic acid with sodium hydroxide to pH was neutralized 7 and then mixed with sodium phenolate in an amount of 120 equivalent% (333 g) of 20% Restsulton and stirred Subsequently, the sulfonic acids thus obtained at 160 ⁰ C-15 minutes, the Phenoryse were subjected and then treated analogously to Example 1, whereby various translucent sulfonates of light color were obtained. The properties of the sulfonates obtained in this way are summarized in Table Π

The above olefin with 24 carbon atoms contained about 8% of a straight chain internal olefin, 1% of an α-olefin and a tertiary olefin.

Table II

Properties of C ₂₄ olefin sulfonate

Molar ratio of neutralization and conversion (in%) Coloring SO ₃ / C24-olefin sulton-splitting (KJett value)

middle

solubility

para (lined
lubricant

Tetrachlorethylene spindle oil No. 1

just well oh

NaOH and
Na phenolate

96.7
97.0

50 100

50 100 Δ
Δ

O O

O O

Δ
Δ

O O

Note: The sign O means "good"; the sign Δ means "worse".

From the results in Table II it can be seen that the solubility for hydrophobic base oil des obtained sulfonates can be increased by controlling the formation of the hydroxyl group and by using a sultone reaction accelerator.

Example 3

1000 g of an -olefin with 8 C-atoms, 92% of a -olefin, 6% of a diolefin, 1.2% of a paraffin, 0.5 of an internal olefin and 03% consists of a branched or cyclic olefin and which was produced by paraffin cracking, was _{mixed with 1000 ml of BF 3} -GaS and stirred for 24 hours at 160 ⁰ C, a high molecular weight olefin was obtained, which was obtained from a mixture of trimeric and tetrameric Cg- Consisted of olefins.

This high molecular olefin was subjected to sulfonation by using the same apparatus and applying the same conditions as in Example 1. The average molecular weight of this Olefines, calculated on the basis of the iodine value was 400. This olefin was then sulfonated at a reaction temperature of 6O ⁰ C and at a molar ratio of SO3: olefin of 1.2.

300 g each of the sulfonation product obtained were mixed with sodium hydroxide solution, Ca (OH) ₂ and octylamine in an amount corresponding to 95% of the amount of SO3 introduced into the olefin and kept at 130 ° for 1 hour with stirring. The mixture was then taken out and treated in the same way as in Example 1, whereby 3 kinds of sulfonates were obtained. These three sulfonates and the sodium salt of mahogany acid were dissolved in No. 1 spindle oil (a desulfurized product) in an amount of 4 equivalent% based on the oil to prepare various anti-corrosion oils

When these anti-corrosion oils are tested for their wet strength in accordance with JIS-Z-0228 (Japanese Industrial Standard Regulation) are examined, the anti-corrosion oil, which contains the sodium salt of mahogany acid, in 24 hours rust, the anti-corrosion oils, the sulfonate according to these examples, will rust after 43 hours if they contain a sodium salt, rust after 72 hours if they contain a calcium salt and rust after 120 hours if they contain a Contain octylamine salt. The agents according to the invention are therefore with respect to the conventional products superior in anti-corrosion effectiveness.

Example 4

A material consisting of one part by weight of an -olefin with 15-18 carbon atoms, obtained by paraffin cracking, as well as one part by weight of an λ-olefin with JS carbon atoms, produced by ethylene polymerization, would contain 5% BFrätherat (with a BFj Content of 46%) was subjected to dimerization at 120 ° C. for 6 hours, an olefin having 33-56 carbon atoms being obtained with a yield of 80%. The starting olefin thus produced was then introduced into a sulfonation apparatus, which is described in Japanese Patent Gazette Sho-42-252 , and the sulfonation was carried out by using sulfuric anhydride in an iron Motverfalhnis of SO ₃ to iplf of 1.15, diluted with dry air and at a building temperature of 50 or 8O ⁰ C, uiHHnüilÜl nobti ifm types of sulfonation pro- doätn ΛWB (JgUiI of 100 kg / hour received wattice. The coatfect time averaged 25 sea

The apparatus used in the present example had a main reaction zone 120 cm long which are also provided in three places (above, unien and in

the middle) had a thermometer.

The reaction products obtained (acids) were, as above, neutralized with 10% strength aqueous sodium hydroxide solution in such an amount that these 95% of the SO ₃ - introduced during the sulfonation reaction

Amount corresponded, and then the hydrolysis at

subjected to a temperature of 150 ° C / 45 minutes.

Then the oil-soluble, surface-active

High molecular weight agents by refining

of the above olefin sulfonate prepared analogously to Example 1

The properties of the agent are summarized in Table III which shows that a sulfonate can be obtained on an industrial scale of the same quality as on a laboratory scale.

Table ΠΙ

Properties of a C ₃₃ _ ₃₈ olefin sulfonate in an industrial scale

sample Temperature of
Sulfonation
reaction Sales (in%) coloring
(Velcro value) solubility
CCl ₄ Tetrachlor
ethylene Dry cleans
agent
petroleum based Spindle oil
number 1 1
2 50
80 91.5
91.3 80
100 O
O O
O O
O O
O

Sample 1 was double digested to degrade it to the calcium salt and to put it in spindle oil No. 1 to solve. The effectiveness of additives for lubricants prepared in this way was compared to that of the calcium salt of Mahogany acid compared. The results are summarized in Table IV:

Table IV
Anti-corrosion test Wet strength ')
(Time in h, during
that does not rust) Corrosion of the
Steel blue?) Frictional
coefficient ³ ) composition
after load ⁴ )
(kg / cm2) sample <10
48 1
2 0.304
0.223 2.5
3 1 spindle oil only
Spindle Oil No. 1 97%

Calcium salt of
Mahogany acid 3%

Spindle oil No. 1 97% 72 1 0.198 4

Ca salt of the sulfonate
from example 4 3%

Note: ') According to J1S-Z-O223, JIS-Z-2912.

2) According to JIS-K-2513.

³ ) With the aid of the soda oil tester of the pendulum type (25 ° C; 65% rel. Humidity).

⁴ ) According to JIS-K-2519 (Japanese Industry Standard Regulation).

Table V shows the solubilities of various olefin sulfonates having 15-24 carbon atoms for various solvents listed for comparison. In addition, the difficulties in the production are compared and the solubility for Solvent of the agent according to the invention is shown in Table VI by comparing an α-olefin with 24-40 carbon atoms with the mahogany salt.

Table V

Solubility of C ₁₅ . ₂ i olefin sulfonates (sodium salts) for various solvents

Olefin number of Solubility for various solvents of a 3% strength * BuOH Petrol lubricant Solution at 25 ⁰ C Tetrachlor Carbon atoms of solvent ether on parassin ethylene Alkyl radical Water EtOH Base spindle Dry cleans O oil No. 1 agent O Δ X X petroleum based X α-olefin straight chain O O X X X C 16 O O Δ X X X X X ClO Δ O O Δ Δ X X Δ Vinylidene C 16 O O Δ X X X X X paraffin C 20 Δ O Δ Δ Δ Δ Δ Dimerized C 16 O O X X Olefin C20 Δ Δ X X Δ Δ X Trimerized O Olefin C 15 O Δ Δ Δ X X Δ Trimerized Olefin C 21 Δ Δ Δ

The sulfonization of the above olefins is always carried out to the end, except in the case of an α-olefin with 20 carbon atoms. The neutralization and hydrolysis can also be carried out easily.

In the case of an a-olefin having 20 carbon atoms is derSclimelzpunkt 29 ⁰ C; this olefin must therefore be heat treated. In addition, it tends to build up clots during neutralization, so that it either has to be heated to a high temperature or a solvent has to be added.

Table VI 230 235/17 of C ₂₄ -4o-01 ^e fi ^nsul ' ^onates U ¹¹ ^ their solubility for various solvents Difficulty with the
Sulfonation Difficulty with the
Aftercare solubility
water for different solvents (in the case of a 30% solution at 25 ⁰ C)
BuOH petroleum spindle oil lubricant CCl ₄ tetrachlor
ether no. 1 on paraffin ethylene
Base X X X X X K) cn Difficulty in manufacturing salt Heating the output
materials or loosening
of the solvent
necessary Neutralization is
difficult; Heat
at high temperature
and thinning
of the solvent
is required X O X X X X X I 32 635 Output number
material of carbon atoms
of the alkyl radical N / A Heating the output
materials or loosening
of the solvent
necessary Neutralization is
difficult; Heat
at high temperature
and thinning
of the solvent
is required Δ X X X X X X «• -olefins C ₂₄ Approx Heating the output
materials or loosening
of the solvent
necessary Neutralization is
difficult; Heat
at high temperature
and thinning
of the solvent
is required Δ X X X X X X C ₂₄ N / A Heating the output
materials or loosening
of the solvent
necessary Neutralization is
difficult; Heat
at high temperature
and thinning
of the solvent
is required Δ X X X X X X C ₂ * N / A Heating the output
materials or loosening
of the solvent
necessary Neutralization is
difficult; Heat
at high temperature
and thinning
of the solvent
is required Δ X X X X X X C ₃₂ N / A Heating the output
materials or loosening
of the solvent
necessary Neutralization is
difficult; Heat
at high temperature
and thinning
of the solvent
is required Δ X C ₃₆ N / A

continuation amount of salt Difficulty with the Difficulty with the Solubility for various solvents (im BuOH Petrol Spindle oil Case of a 30% solution at 25 ⁰ C) CCl ₄ Tetrachloride ro IN THE*
00 Starting Carbon atoms Sulfonation Aftercare water ether number 1 lubricant athyler; O material of the alkyl radical on paraffin Base lsi example 1 X O O O O Examples of the C ₃₂ SO ₃ molar ratio N / A Well Well Δ O U) invention 1.00 reaction cn temperature 50 ⁰ C Example 2 O O X O O C ₂₄ vinylidine N / A- Well Well Δ X Phenates O O O O O SO ₃ molver ratio 1.00 N / A- Well Well Δ O Phenates Example 3 X O O O O Examples of the C ₂₄ and C ₃₂ N / A Well Well Δ X O O O O O invention SO ₃ molar ratio 1.20 Approx Well Well Δ O Reaction O O O O O temp. 60 ⁰ C Octylamine Well Well Δ O Example 4 X O O O O C ₃₃ . ₃₆ olefin N / A Well Well Δ O SO ₃ molar ratio 1.15 Reaction temp. X O O O O 50 ° C-80 ° C Approx Well Well Δ O O O O O O C ₂₅ H ₄₀ SO ₃ Na N / A _ extraction Δ X mahogany and refining X O O O O sour salt C ₂₅ H ₄₀ SO ₃ ^ Approx Approx - is done Δ O means "insoluble", x means "partially soluble" and 0 means »translucent and soluble". Note: Δ

Claims (1)

Patent claims: 1. Oil-soluble, anionic surfactant Means obtained by sulfonation of aliphatic monoolefins using sulfur trioxide, thereby characterized in that one has a monoolefin general formula