JPH04504732A - Surfactant mixture containing α-sulfo fatty acid methyl ester salt, its production method and its uses - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] α-Sulfo fatty acid methyl ester salt-containing surfactant mixture, method for producing the same, and its use Selected α-sulfo fatty acid alkyl ester water-soluble salts provide high quality cleaning and Detergent active surfactant component, for example for laundry and in industrial cleaning It has long been known that it can be used.

Such ingredients include, inter alia, fatty acid triglycerides of plant and/or animal origin. In the first step, the triglyceride is converted into a lower l-functional alcohol. Selected monohydric alcohols of the corresponding fatty acids are subjected to transesterification reaction by Produces esters. In fact, what is important in this regard is methanol and therefore Only the production of the corresponding fatty acid methyl ester.

The methyl ester is sulfonated in the next step. When using saturated fatty acids, the alpha position Sulfonation occurs selectively in The agent actually used in this sulfonation reaction is It is gaseous SOs and is used in excess within a limited range. The conversion rate used More than 90%, preferably at least 95% based on fatty acid methyl ester. Adjust the sulfonation reaction so that Since a dark colored reaction product is obtained first, Post-bleaching is essential.

Bleaching is usually carried out using aqueous systems in the acidic and/or slightly alkaline range. as an example This includes acid bleaching with hydrogen peroxide and complex bleaching, and complex bleaching. , an acidic hydrogen peroxide bleaching step is performed first, followed by a partial bleaching step. The prepared sulfonate is treated with an alkali metal hydroxide, preferably sodium hydroxide. Neutralize and then hydrogen peroxide solution, more preferably with a final solution using hypochlorite. bleaching steps (for example, West German Patents Nos. 1179931 and 12347) (See No. 09). In another method, the dark crude sulfonate is converted into a neutral to weakly First subjected to prebleaching with hypochlorite in a caustic aqueous medium, then bleached. Any hypochlorite present is then removed, and the salt paste is then soaked in a mildly acidic medium. completely bleached with hydrogen peroxide or compounds that produce hydrogen peroxide (West German (See Published Patent No. 3319591).

Achieving the desired high degree of sulfonation (at least 95%) in the sulfonation step Since an excess of SO3 is required for salt) and the corresponding digroups as components of the mixture, It is usually obtained after neutralization and aqueous treatment steps. Initially, the two units themselves had their own It is said that there is no detergency or cleaning power, but recently two and/or or its mixture with monosalts has been recognized as a high-quality surfactant ingredient. (see West German Published Patent Application Nos. 3,726,326 and 3,726,327).

The cleaning and cleaning effects of the monosalt described above depend on the C chain length of the sulfonated fatty acid residue. It has long been recognized that important in terms of performance is C,,/C,. It is a fatty acid residue. In reality, depending on the starting material, it may be shorter. Small amounts of chain or longer chain acid residues may be present in the mixture. However, the range It is important to contain fatty acid residues of Finally, surfactants such as those mentioned above For practical use, primarily the sodium salts are considered. On the one hand, this means that On the other hand, due to the easy availability of the necessary chemicals on an industrial scale, this Such situations are typical of practical laundry and/or industrial detergent and cleaning formulations. It originates from the formulation.

Sodium-salts and di-bleached aqueous pastes of acids such as those described above may be used, e.g. Suitable for combination in active substance formulations of the laundry detergent type, but such Surfactant mixtures are manufactured and processed in substantially anhydrous form. This is desirable for a number of reasons. However, in this regard, the person skilled in the art The following known physical/chemical factors must be considered. α− as mentioned above Monosodium salts of sulfofatty acid methyl esters are characterized by relatively high melting points. I get kicked. For example, the anhydrous sodium salt of α-sulfopalmitic acid methyl ester The melting point of is +8+-3°C. Correspondence of α-sulfostearic acid methyl ester The melting point of the sodium salt is 175-6°C. Produced by ester saponification The corresponding sodium salt of Decomposes with partial carbonization. - in the melting point range slightly below 200°C of the salt. However, there is a considerable risk that the pre-bleached product will undergo undesirable discoloration. Therefore, α-sulfofatty acid ester salts (-salts) and α-sulfofatty acid salts (dibases), especially Anhydrous solids containing such salts derived from valmitic acid and stearic acid Why is the production and/or processing of surfactants or surfactant mixtures so difficult? It is easy to understand why this issue has not been discussed much in the literature.

West German Published Patent Application No. 3620158 describes α-sulfo fatty acid alkyl esters, A method for making solid, substantially anhydrous alkali metal salts is described. This method However, the above problem is solved when hydrogen peroxide or hydrogen peroxide-generating compounds are simultaneously present. By adding alkali metal carbonate, crude α-sulfo fatty acid alkyl ester is overcome by subjecting it to dry neutralization. In this method, the foam is first It is described that it is produced and destroyed mechanically at a temperature of 50 to 70°C under moderate vacuum. The resulting product was then heated under a pressure of 15 to 100 mbar for 5 Thoroughly degas and dehydrate with mechanical stirring at a temperature of 0-80°C. Fluid rough material Bleaching and neutralization of the material (in this known method, the bleaching and neutralization treatments are combined in one step) The production of the desired surfactant mixture that is solid at room temperature by It comes with a big problem. Continuous mixing of reactant mixtures also helps overcome problems caused by foaming. Homogenization also costs a lot of money when the reaction is carried out on an industrial scale.

The teachings of the present invention can be applied to known bleached aqueous alpha-stains, provided the selected composition is maintained. Rupho fatty acid methyl ester salt paste (among other things, easily pumped and stirred) (existing in a known state in a possible form) is destroyed by evaporation of water under the following conditions: Based on the surprising observation that it can be converted into water materials. Highly anhydrous obtained after drying mixtures can be homogenized well even at relatively low temperatures so that there is no substantial loss of color. It is possible to produce a uniform dry product without any damage. Selected according to the invention The selected monosalts and mixtures of the two salts are capable of softening at least to a plastic state and are therefore Processable by shape: In a preferred embodiment, the mixture is heated above 80°C, It can be melted at temperatures above 100°C and below 150°C, which can then be stirred and Can be transported and pumped. Bring such dehydrated surfactant mixture to room temperature. When cooled, it hardens into a solid mass that can be processed, for example, into powder or granules. can be done. However, on the other hand, a stirrable hot paste should preferably be cooled. The mold can be used to shape, e.g. extrude, into needles or granules of any diameter. Ru. Basically, the surfactant mixture is temperature-unstable, both for dehydration and further processing by shaping. without substantially further ester degradation and/or undesirable discoloration of I can do it.

Therefore, the present invention mainly focuses on alpha-sulfo fatty acids derived from C+t-+s fatty acids. Washing and cleaning of tile esters - Correspondence with active salts (-salts) and α-sulfo fatty acids dry, light-colored surfactant mixtures containing (dual) salts that The surface activity The sex agent mixture is a substantially anhydrous mass of - a mixture of salt and two groups, It melts or at least softens to a plastic state at temperatures below ℃ and is suitable for modeling. Therefore, the active substance content (AS content nee salt and sum of two groups) can be processed. is at least 75% by weight, and the mixing ratio of salt and digroup is from 90:10 to 40': within the range of 60 parts by weight to reduce the water content of bleached monosalt and bisalt aqueous pastes. It exists as a mass obtained by evaporating at least a large part of it. It is thus characterized.

AS content is defined as the sum of -field and two groups. The numbers related to the mixing ratio are based on weight. parts, so the upper limit for the monosalt in the mixture is 90 parts by weight, in which case the two groups are It is 10 parts by weight. According to the invention, this mixing ratio is two parts by weight and one part by weight. The mass is expanded to a mixture containing 40 parts by weight.

The AS content of the surfactant mixture according to the invention is preferably at least 80% by weight. Preferably, it does not exceed 0% by weight. - addition of salts and dioxygens and a certain amount of residual water; In addition, the surfactant mixture is suitable for the industrial production of α-sulfo fatty acid methyl ester salts. Contains small amounts of side reaction products produced in the process. Such side reaction products are especially unsulfonated and unsaponified fatty acid methyl esters (so-called “unsulfonated” fatty acid methyl esters) methyl sulfonate), soap produced by saponification of unsulfonated esters, methyl sulfonate Phate salts, especially sodium methyl sulfate, as well as inorganic sulfate salts, especially sulfuric acid. It is sodium.

In a preferred embodiment, the water content of the dry surfactant mixture of the present invention is lower than the total water content of the mixture. Up to 5%, especially up to 2% by weight of the body.

- A particularly suitable mixing ratio of salt and diradical is - 60:4 for the mixture of salt and diradical. It is in the range of 0 to 85:15 parts by weight. For example, an optimally prepared surfactant mixture The active substance content of the compound is 84-85% by weight, in which case the digroup content is 20% by weight. The content of unsulfonated substances and soap in this mixture is , about 1-5% by weight. The degree of sulfonation of the fatty acid methyl ester used was 90. ~98% by weight, preferably 93-96% by weight. Sodium methyl sulfate content is less than 5% by weight and the sodium sulfate content is less than 3% by weight.

In a preferred embodiment, the substantially anhydrous surfactant mixture of the present invention is light colored. (Klett) color value (an aqueous solution containing 5% by weight of active substance, (measured from 400 to 465 nm using a blue filter in a 4 cm cell) is less than 150 less than 100, preferably less than 100.

The fatty acid component of the fatty acid methyl ester used for sulfonation is mainly C+y-+* Consists of fatty acids. Fewer fatty acids with fewer and/or more carbon atoms There can be a large amount.

Particularly suitable starting materials for the production of the light colored surfactant mixtures of the invention are Neutralize the α-sulfo fatty acid methyl ester or ester mixture formed by Mono- and di-salts obtained according to the prior art by tellolysis and bleaching is a pumpable and stirrable paste. At least 20% by weight of water, preferably Preferably a pumpable and stirrable paste containing at least 30% by weight. Particularly appropriate.

The pale mono- and di-salts of α-sulfonated fatty acid methyl esters used are especially , present as a fully saturated starting material before sulfonation, or as an olefin derived from fatty acids or fatty acid methyl esters that have very few double bonds. guide Therefore, the present invention provides for fats having an iodine value of less than 1, preferably up to 0.5. It is characterized by the use of salts of said type derived from fatty acids.

The fatty acids or fatty acid derivatives used for sulfonation are the corresponding synthetic monocarbons. It may be derived from acids, especially fatty acids of natural origin. Particularly preferable C Natural fatty acids or fatty acid mixtures in the If-Ill range are typically more or less prolific mono- or fatty acids. and/or polyolefinically unsaturated compounds. Sulfonation The content of unsaturated compounds in the starting material can be reduced by known methods to achieve the low iodine content required for the present invention. It can be the urinium value. A mixture of fatty acids with a relatively low degree of unsaturation in the above C chain length range The products are derived from, for example, yang oil or palm kernel oil. Even in such cases, Hydrogenation must be performed prior to sulfonation to reduce the iodine value to the desired level. Must be. Starting materials derived from other natural products, such as palm oil, peanut oil, cottonseed oil , fatty acid methyl esters obtained by transesterification and fractionation of linseed oil, etc. fractionation, the extensive hydrogenation required in such cases may be detrimental to the process itself or In principle, it may be considered if it is not considered to be extremely burdensome in terms of cost. animal One example of a suitable starting material derived from hydrogenated tallow fatty acids is the methyl ester of hydrogenated tallow fatty acids.

The present invention melts or at least softens to a plastic state at relatively low temperatures. A process for producing the light-colored surfactant mixture as described above, obtained by known methods and comprising: Before existing as a bleached high-grade aqueous paste that can be pumped and stirred separately α-sulfo fatty acid methyl ester or T2 is α-sulfo fatty acid monosalt and di-group of the aqueous mixture by heating and, if desired, the dehydrated product by shaping. It also relates to a method characterized by processing.

Suitable pasty starting materials include, among others, pumpable and stirrable monosalts and In a preferred embodiment of the invention, this is a 20% by weight paste. Drying at high temperatures ensures homogenization of the mixture even in the water removal phase down to values below dry In this preferred embodiment, the mixture to be dried is dried intermittently during the drying process. Or heat to a temperature that allows continuous uniformity. Therefore, the mixture to be dried Heating to a temperature of 80-100°C may be advantageous. , about 20 for S Particularly preferred surfactant mixtures containing % by weight of digroups and 80% by weight of monosalts typically melts completely at temperatures of only about 100°C, so in such cases drying The necessary homogenization within is easily possible. Melting temperature or plasticity of the surfactant mixture The higher the digroup content in the surfactant mixture, the higher the curing temperature. According to the present invention, one On the one hand, it is proposed to limit the digroup content of the surfactant mixture; on the other hand, A good homogenization of the whole mixture is also achieved during drying due to the increase in drying temperature and therefore , local overheating, which always carries the risk of undesirable darkening, can be avoided.

In one embodiment of the invention, the dehydration is carried out at a pH value in the range of about 3 to 7. The surfactant mixture is heated to temperatures above 100°C, especially up to 150°C. May be heated. Suitable starting materials have a low AS content (in particular less than 35% by weight AS). (full) bleached aqueous surfactant pastes and high AS content, e.g. 75% by weight of the paste, more preferably about 60-75% by weight.

In another embodiment of the method of the invention, a drying step is used to separate the di- and monosalts in the paste. Adjust the ratio to a predetermined value. This is a paper that has been alkalized with a predetermined amount of alkali. By carrying out the drying process using a This is possible by partial saponification. The salts mentioned above are particularly sensitive to the effects of temperature. Below are some effective alkaline compounds that are known to be unstable to aqueous alkaline solutions. It is converted into two corresponding groups in proportion to the amount of potash. This is incorporated into the method of the present invention. It can be used.

On the other hand, α-sulfo fatty acid methyl ester salts are extremely resistant to hydrolysis in acidic regions. Therefore, the mixing ratio of mono- and di-salts, once adjusted in the paste, is The p)l value can then be adjusted before drying and maintained throughout the drying process. used for drying It is particularly suitable in this respect that the value of p) for the aqueous paste is, for example, about 3 to 7. It is.

The present invention provides detergents and cleaners intended for use at room temperature or elevated temperatures up to 45°C. It also relates to the use of surfactant mixtures in cleaning formulations.

In this regard, the following factors must be considered.

The steric configuration of the surfactant mixtures of the invention may be selected substantially as desired. Mixed The compound can be shaped into a fine powder or bulk material in a predetermined manner. The materials are often Finely divided, e.g. powdered, preparations are particularly , by printing with additives, or by later incorporating additives. It is best to ensure that the powder state is maintained under normal storage conditions. this Additives suitable for the purpose are, for example, those commonly used in modern detergent and cleaning formulations. soluble and/or insoluble finely divided inorganic components.

However, the surfactant mixture of the present invention, which can be softened or melted, can be used as a bulk material. It is specifically intended for use in This lumpy material may be, for example, flaky or stale. It can change size like a trundle. The surfactant mixture of the invention is suitable for washing and cleaning. It is particularly suitable to mix it with the other customary components of cleaning active mixtures. Even at room temperature, By pressurizing them together, a sufficiently uniform mixture and, if desired, modeling can be achieved. be able to. The mixing process is very simple when carried out at high temperatures. Books/Inventions surfactant mixtures can be used, for example, in the form of blocks or bars known as so-called soap bars. It is particularly suitable for the production of laundry detergent and cleaning formulations. such kind These agents are now widely used in many parts of the world, especially for cleaning at low temperatures. ing. The surfactant mixtures of the invention may be advantageously used for this purpose, e.g. It can replace conventional petroleum-based surfactants or increase their cleaning power. can.

Aqueous fatty acid methyl ester sulfone was prepared in a heated, double-jacketed stirred tank. paste (manufactured from hydrogenated tallow fatty acid methyl ester: for AS, about 20% by weight of the thorium salt and about 80% by weight of the -sodium salt) (water content 20-2 5% by weight) is heated with stirring to a temperature above about 100°C.

After 3 hours, the water content of the material is 3.5% by weight and the AS content is 85% by weight. child The dehydrated material is stirred and pumped at temperatures above 80°C, e.g. 100°C. It is possible.

Chihoretsu I Aqueous tallow fatty acid methyl ester sulfonate of Example 1 (water content approximately 25% by weight) 400g was placed in porcelain and concentrated by evaporation in a drying oven at 120°C to remove water content. The amount shall be 1%.

The dried material is easily stirrable at approximately 100°C and has an ASS content of 88% by weight. It is.

After cooling to room temperature, the solidified material can be ground into powder in a ball mill. .

Example 3 C+t-+s fatty acid methyl ester sulfonate derived from hydrogenated palm kernel oil fatty acids Thorium paste (Iodine of palm kernel oil fatty acid methyl ester used for sulfonation) 500 kg of water content of this material (less than 0.1) (water content approximately 30-35% by weight) Stir in a heated double-jacketed stirred tank until the amount is less than 2% by weight. while heating to 110-130°C. Throughout the process, the contents of the stirred tank are constantly can be sufficiently homogenized and, at the end of the process, can be melted, stirred and pumped. It becomes a lump.

A portion of the melt to be cooled is formed into a bar-like mass. Another part of the melt is After hardening, mechanically crush. Compress the crushed material at a slightly elevated temperature or at room temperature. Using the apparatus and method described in Example 3 to obtain a bulk material by , Hydrogenated Coconut Oil Fatty Acid Methyl Ester Sodium Sulfonate with Sodium Salt - sodium salt ratio similar to that of Example 1) on a pumpable basis. The melt is converted from a melt into a melt that flows at 110-130°C. The melt solidifies and becomes thin. A colored dry product results, which can be further processed according to Example 3.

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Claims (17)

[Claims] 1. α-Sulfofatty acid methyl derived at least primarily from C12-18 fatty acids Washing of esters - and cleaning active salts (monosalts) and the corresponding α-sulfo fatty acids A dry, light-colored surfactant mixture containing salts (disalts), monosalts and di-salts. The mixture of salts melts or at least softens and becomes plastic at temperatures below 150°C. It becomes a sexual state, can be processed by shaping, and has an active substance content (AS content: - the sum of salts and di-salts) is at least 75% by weight, and the mixing ratio of monosalts and di-salts is 90%. :10 to 40:60 parts by weight, bleached mono- and di-salt aqueous Substance obtained by evaporating at least most of the water in a paste A surfactant mixture characterized by its existence as an anhydrous mass. 2. The active ingredient content is at least 80% by weight and preferably not more than 90% by weight. A surfactant mixture according to claim 1, characterized in that: 3. Claims characterized in that the water content is up to 5% by weight, preferably less than 2% by weight. A surfactant mixture according to claims 1 and 2. 4. Pumps with a water content of at least 20% by weight, preferably at least 30% by weight Transportable and stirrable mono- and di-salt pastes with values less than 20% by weight By dehydrating at such high temperatures that homogenization of the mass is ensured even in the water removal phase. The surfactant mixture according to any one of claims 1 to 3, characterized in that the surfactant mixture is Compound. 5. The iodination before sulfonation is up to 1, especially up to 0.5, preferably Transesterification of fats and oils from natural sources with methanol and From α-sulfonated fatty acid methyl esters obtained by hydrogenation of heavy bonds. Surface activity according to claims 1 to 4, characterized in that the mono-salt and the di-salt are derived. agent mixture. 6. In addition to the mono- and di-salts and a certain amount of residual water, Side reaction products that accumulate during the production of stellate salts, especially unsulfonated substances, soaps, and sulfuric acid Claims 1 to 5 characterized in that it contains small amounts of methyl and sulfate salts. surfactant mixture. 7. The mixing ratio of mono-salt and di-salt in the mixture is 60:40 to 85:15 (parts by weight). A surfactant mixture according to claims 1 to 6, characterized in that: 8. Cret color value (5% AS, 4cm cell) less than 150, preferably less than 100 A surfactant mixture according to claims 1 to 7, characterized in that the surfactant mixture is 9. Mono- and di-salts are alkali metal salts, preferably sodium salts, In other words, if an unsaturated fraction originally existed, the saturated fraction could be saturated by hydrogenation. The interface according to claims 1 to 8, characterized in that it is derived from fatty acids derived from natural substances. Activator mixture. 10. The mono- and di-salts include coconut oil fatty acids and/or palm kernel oil fatty acids and The field according to claims 1 to 9, characterized in that it is derived from tallow fatty acid. Surfactant mixture. 11. α-sulfo fatty acid methane derived at least primarily from C12-18 fatty acids Washing and cleaning of active salts (mono-salts) and α-sulfo fatty acids A dry, light-colored surfactant mixture containing salts (disalts), monosalts and The mixture of two salts melts or at least softens at a temperature below 150°C. It is in a plastic state, can be processed by shaping, and has an active substance content (AS content; the sum of monosalt and disalt) is at least 75% by weight, and the mixing ratio of monosalt and disalt is 9. Present as a substantially anhydrous mass in the range of 0:10 to 40:60 parts by weight. A process for the preparation of surfactant mixtures obtained by known methods, in particular by pumping. and mono- and di-salts present as a stirrable bleached highly concentrated aqueous paste. The aqueous mixture is dehydrated by heating and optionally the dehydrated product is processed by shaping. A method characterized by: 12. The mixture to be dehydrated is maintained at a temperature, preferably at a temperature that can homogenize it intermittently or continuously during drying. A claim characterized in that heating is preferably carried out to a temperature of at least 80 to 100°C. 11. The method described in 11. 13. Dehydration is carried out in a weakly acidic to neutral pH range, preferably at a pH value of 3 to 7. The surfactant mixture to be dehydrated is prepared such that a predetermined amount of the monosalt is converted to the disalt during the dehydration process. Claims 11 and 12, characterized in that it may first be alkalized to such an extent that Method described. 14. Dewatering a bleached aqueous surfactant paste with an AS content of 60-75% by weight The method according to claims 11 to 13, characterized in that. 15. dry material or at least its softened component; In particular, it is possible to process the components by shaping, especially at room temperature or slightly higher temperature or optionally at a temperature exceeding 80°C, such as a temperature in the range of 100 to 130°C, Claims 11-1 characterized in that it is homogeneously mixed with other components of detergent and cleaning formulations. 14. The method described in 14. 16. The surfactant mixture according to claims 1 to 10 or the one according to claims 11 to 15 The use of surfactant mixtures prepared by the method at room temperature or at elevated temperatures up to 45°C is Intended use in detergent and cleaning formulations. 17. The surfactant mixture can be used in bulk detergent and cleaning formulations, especially in so-called right-hand baths. 17. The use according to claim 16, characterized in that it is used in -.