CZ79693A3 - Improvement of surface-active sintered products color by adding a solid bleaching agent - Google Patents

Abstract

The present invention relates to a process for manufacturing improved color surfactant agglomerates, particularly comprising methyl ester sulfonates, for use in detergent compositions, said process comprising sulfonation of methyl ester, digestion of the sulfonation product, esterification of said sulfonated product to produce an acid product and agglomeration of said acid product, characterized in that said acid product is exposed to a solid bleaching agent immediately prior to or during agglomeration of said acid product.

Description

Improvement of the surface color of the running agent

Area, techniques

The present invention is based on a method for the preparation of surfactants.

The present invention includes a novel process for preparing from surface to active agglomerates; whose color is by the addition of a solid bleaching agent. These agglomerates form part of detergent compositions. in particular, the present invention relates to the preparation of surfactant agglomerates. one component of which is the ester sulfonate (R18). The preparation of the alkali salts of the alpha-sulfonic acid fatty acid ester (ester sulfonate) by sulfonation of the fatty acid rethyl esters with gaseous SO3 and subsequent neutralization of the formed salts with aqueous alkali hydroxides, e.g. sodium hydroxide, has been known for some time. The resulting products of this method, i.

the alkali salts of the corresponding .alpha.-sulfonic acid fatty acid esters are predominantly nourished in detergent and cleaning detergent compositions.

However, all known processes for their preparation are, however, light colored end products suitable for direct cetergents, but the yields of the step are low. If the conditions of the preparation result in unsatisfactory use, the yield in the yield is higher.

causes the coloring of the acids and their esters in the sulphonation to give a dark color from Dor enriched brownish-black raw products, which are for direct use in car washes. t m a v v h h č st st pros pros pros pros pros pros pros í pros í í í í i x x

C č cl i 11 ci er i ·. at ύ ajfa ^- suj: o »ic '· <. II rt t O h OV yp 1 VV bleach and Li operation

. f O nev hod hod hod - - - - - - - - - - - - k - k k k k k k k k k k k k k k k i 'r \. In particular, methyl esters of sulfonates are used in washing and cleaning detergent compositions. as natural surfactants - i.e.

tallow active substances. coconut e: palm, fabric is, in addition to many detergents.

in many superficial U these problem it.

Other disadvantages, in particular that when mixing NES with inorganic dust to form agglomerates, the resulting NES agglomerates are dark colored and therefore unacceptable to consumers of detergent products.

A further problem with the preparation of aqueous esters-SLitonates is that during preparation, the product accumulates in the form of an aqueous paste which, in turn, contains a considerable proportion of the active ingredient. Particular recent attempts to obtain an acceptably colored NES-containing detergent product have resulted in a highly viscous fist even when other methods are used. These pastes can no longer be pumped; Highly viscous ester sulfonate pastes always carry the risk of blocking the apparatus and tubes. Accordingly, there is a long-felt need not to find such a process for preparing alkali salts of alpha-sulfonic acid alkyl esters that would avoid or at least reduce the high viscosity of the products.

A third problem frequently encountered with ester sulfates, particularly NES-containing detergents, is the addition of hypochlorite or hydrogen peroxide to the acidic composition to improve color. In addition to forming highly viscous pastes, these compounds tend to c-vat esters to form double salts in alkaline medium. These salts are already too hydrophilic for general use in detergents.

Japanese Patent Application Publication No. 84-16870 discloses a process for preparing an alpha .alpha.-sulfonic fatty acid alkyl ester salt according to which the alpha .alpha.-sulfonic fatty acid esters formed in the sulfonation step are bleached with H2O2 in the presence of a polycarboxylic acid or one of its salts. Subsequent neutralization converts alpha-sulfonic fatty acid esters into the corresponding salts. Although the salts thus prepared are very suitable for use in detergent detergent compositions, the bleaching step requires a reaction time of the order of 1 hour, not counting the time for subsequent neutralization.

US-A-4,547 SIS describes a method for preparing color stable.

world lyc h Acids stained in suitonecnim

a fist of aqueous salts of alpha-sulfonate esters with a cleaning effect. According to this process, the dark alpha-sulfonic fatty acid esters resulting from the step are bleached with alkaline in a neutral or mildly alkaline aqueous medium, the step being bleached by a conventional procedure with hydrogen peroxide in a slightly acidic aqueous medium. The whole bleaching operation takes several hours, including the change of pH in the reaction medium in ser: χ

.. o ι ί o pi inside i i

Its' / ýslc-dkeni <? Ci 1Ίi salt paste containing 20 to 60¾% of active substance. As the active ingredient content increases, the viscosity of the paste increases. as described above. leads to certain difficulties.

US-ft-3 sulfone light-colored derivatives. In particular, the sulfonic fatty acids have strong oxidizing properties

142 691 discloses the preparation of fatty acids and describes a process for bleaching dark colored acids and their derivatives using their salts or anhydrides, which effect.

US-A-4,874,552 discloses a process for preparing solid, anhydrous alkali metal salts of alkyl esters of alpha .alpha.-sulfonic fatty acids continuously mixing esters with aqueous solution. This process results in an alkali metal containing drug within a certain temperature range by which hydrogen peroxide, solid carbonate or in the presence of aqueous alkaline hydroxide.

C h a r t e r i s e c t i n s comprising a two-step bleaching process.

deteriorated and the method of bleaching paint agglomerates. According to which the reagents can optionally be further described in water. aqueous

The present invention seeks to provide a way to improve the color of surfactant agglomerates, especially hESE agglomerates. Looking for a way longer. How to Simplify Without Visibly Over Time The present invention is omitted by adding solutions containing additional bleach

Reagents. This will reduce the problems associated with high viscosity of the paste and / or formation of foams of acidic products, which are caused by the high water content, as mentioned above. Finally, the present invention proposes an advantageous process for preparing agglomerates with reduced water content. which reduces the need for drying. The present invention is directed to a process for the preparation of color-improved ester-sulfonate-containing surfactant agglomerates, in particular methylsulfonate (MES). Commonly used preparation methods leave undesirable color properties for many surfactant agglomerates, especially when they contain MES. This in turn limits their use in detergent products. For this reason, for most NES-containing detergents, NES granules are bleached by the action of an aqueous bleaching agent. between the esterification and neutralization step.

It has now surprisingly been found that anhydrous alkyl esters of solid alpha-sulfonic fatty acids of good color properties, in particular NES-containing agglomerates, can be prepared using solid bleaching agents in bleaching and preferably also at neutralization (particularly dry neutralization) of sulfonation step products, i.e. dark colored alkyl esters of alpha-sulfonic fatty acids (eg, MES). In the process of the present invention, by avoiding the early bleaching step or neutralizing the product prior to granulation agglomeration, the formation of high viscosity pastes can be avoided. Thus, the present invention enables the unexpectedly simple formation of color-acceptable products. The present invention also reduces the problem of forming a hydrovariate paste which exhibits an increased tendency to form double salts.

The present invention reduces the problem of formation of a hydrated paste by omitting the step of adding hypochlorite or hydrogen peroxide to the acidic mixture and the subsequent ester hydrolysis step in an alkaline medium, resulting in the formation of double salts. Any of the alkali metal carbonates can be used alone or in a mixture, in the presence and absence of an alkali hydroxide solution. Sodium carbonate is preferred because it is cheap and readily available.

The products thus obtained contain a high proportion of solid active substances, which facilitates further operations. Their use as part of detergents in detergents and cleaning agents is more advantageous than the products available so far. Alkaline alpha-sulfonic acid fatty acid esters prepared by neutralizing alpha-sulfonic acid fatty acid esters and optionally bleaching. in each case they contain a certain proportion of the double alkali pigments of the corresponding alpha-sulfonic fatty acids. These double salts are formed in part by the alkaline hydrolysis of mixed alpha-sulfonic fatty acid ester anhydrides with the sulfuric acid methyl ester present in the crude sulfonation product. The double salts are also formed by undesired alkaline hydrolysis of alpha-sulfonic acid fatty acid methyl ester at elevated temperature and pH values of 9 and higher. Therefore, these steps must be carried out very carefully in order to limit the formation of the salt salts.

Surprisingly, it has been found that the process for preparing the alkali salts of alpha-sulfonic fatty acids of the present invention substantially reduces the formation of double pigs without being its original purpose.

DETAILED DESCRIPTION OF THE INVENTION The formulations comprise sulfation

The present invention relates to a process for the preparation of surfactant agglomerates used as part of detergent compositions with improved color properties of methyl esters of sulfonates. The process comprises methyl ester, boiling off the sulfonation product, esterifying it to an acid product, and agglomerating the acid product. The latter step is carried out by reacting the acid product with a solid bleaching agent immediately before or during agglomeration. The formed agglomerates useful in detergent compositions have a particle size suitable for detergents, especially powder formulations (preferred diameter 100 to 1400 µm) and exhibit good free flow characteristics.

According to this method, it is preferred that the acid product is neutralized simultaneously with or after bleaching with a solid bleaching agent. It is even more preferred to perform neutralization after bleaching. The most preferred neutralization method is dry neutralization, whether after, concurrently or preferably before the formation of agglomerates containing mES.

The technical pogms used herein are areas. Some of the initial steps of the present invention are also well known in the art.

In this*. According to the invention, it is related to the sulfoester of an alpha acid. The sulfonator must be adjusted so that the product effluent mixture contains a maximum of the alpha-suifonic fatty acid ester. This can be ensured by maintaining the reaction time (at a given temperature) sufficiently long to allow the resulting kinetically advantageously sulfo fatty acid ester of the alpha * sulfonic acid to convert to a thermodynamically more stable alpha sulfonic acid fatty acid ester. Another step known in the art is esterification.

α-sulfone bridges

An example is to process the acid mixture of the product for a time and at certain to maximize the formation following to allow the reaction to evolve, in which methanol is reacted after a certain temperature. The purpose of this procedure is to alpha-sulfonic acid fatty acid ester and to reduce the formation of double salts. Additional steps such as the addition of perfumes, coating agents, solubilizing agents, etc. can be found in the general agglomeration methods. In describing the characteristics of detergent agglomerates, one of ordinary skill in the art will recognize that the good free flow property includes low tendency to caking, tackiness, low static friction angle and the like. The percentages are by weight, unless otherwise indicated.

Any solid bleaching agent can be used in the method of the present invention, for example: sodium perborate in different hydrated form (monohydrate, tetrahydrate, etc.), sodium percarbonate, urea peroxide (such as calcium pyrophosphate peroxyhycirate, lithium hypochlorite, chlorinated sodium chloride, Potassium bleach, sodium or potassium bisulfite, sodium or zinc dithionite, and sodium borohydride are more preferred Solid bleaching agents Peroxyborates, percarbonates and organic peroxyacids, most preferably sodium or potassium are preferred, and finely ground in the form of dust Preferably, the average solid bleaching agent is less than 600 µm than 200 µm.

The solid bleaching agent of the present invention is used in various amounts and in specified proportions relative to the acidic product for bleaching detergent granules. The amount of solid bleach (i) (sodium peroxyhydrate) phosphate trisodium hypophosphate.

The peroxycarbonate bleaching agent has a particle size of more preferably a lower surfactant and refers to the acid product.

The proportion of reagent is from 1 to 200% by weight of the acid to the acid product, more preferably 100% by weight. A suitable temperature for bleaching the acid product with a solid bleaching agent is 60-90 ° C.

The most preferred preparation process of the present invention comprises the steps of:

1) mixing the acidic MES with the desired amount of solid bleaching agent in the form of fine dust;

2) immediately reacting the above mixture with a dry neutralizing ciriol in a suitable mixer / agiomeric device;

3) processing of NES agglomerates with good free flow properties in the sinter plant:

thereby completing the preparation of NES-containing isomers having improved color properties.

Steps i and 2 can also be performed simultaneously. The acidic NES is reacted with the appropriate powders premixed in a mixer / agglomerator. This procedure yields the expected product. but its color properties are worse than the previous one.

Agiomerates prepared according to the present invention may initially have a poor coloration, but the color will gradually improve during storage.

The present invention relates to a process for preparing alkali salts of alpha-sulfonic acid fatty acid alkyl esters, especially NES-containing agglomerates. The preparation involves bleaching and neutralization of the methyl ester of the sulfo acids carried out in the corresponding apparatus. NES is continuously blending at a temperature from 20 to 120 ^D ex C. preferably to 120 ° C, preferably 60 to 90 ° C with a solid bleaching agent or H2O2-releasing compound as a solid alkali metal carbonate. The weight ratio of the ester to the solid bleaching agent is in the range of 0.5 to 25, more preferably 1.5 to 5. The product obtained has the character of particles (agglomerates) of such properties that it can be added to the detergent granules in the dry state. The resulting solids are mixed according to known methods.

The process according to the invention can be carried out in a suitable apparatus or a production plant equipped with a sulfonation reactor, for example. boiling tank, esterite reactor, etc. Any mixer / agglomeration apparatus may be used for mixing / agglomeration. Fukee ** FS ~ G mixers from Fukee Powtech Kogvo Co. are very suitable. . Japan. This mixer has the shape of a base accessible from above, is placed by a mixer with a vertical axis and mounted controllable.

on the walls.

The knife beater 1 is a drum, the blades are independent of each other at different speeds. The mixer can be supplemented with a cooling jacket, if necessary with a cryogenic unit.

a lazy mixer suitable for use in wind turbines is D i, R

V of series made in Dierks & Sohne, Germany; and Pharma Matrix ^R of TK Fielder Ltd., England. Other suitable mixers are Fuji ^R and Rot. o ^R

VG-C of a series manufactured by Fuji Sangyo Co., Japan: from a series manufactured in Zanchetta & Co srl, Italy.

Other suitable devices include: Eirich ^R of the RV series manufactured by Gusc.au Exrich Kardheini, Germany; Lodige ^R , from the FM series for series mixing and agglomeration, Paderborn, Germany;

KM designed for continuous Lodige Machinenbau GmbH, with the Baud series from Baud series manufactured in

Drais ^R T160 from the range manufactured by Drais Werke

GmbH, Mannheim. Germany; and Winkworth ^R RT 25 of the series manufactured by Winkworth Machinery Ltd., Bershire, England.

The starting alkyl esters of alpha .alpha.-sulfonic fatty acids are according to commonly used fatty acid sulfonation processes. These esters are obtained from synthetic, semisynthetic or natural oils and / or fats derived from plants. animals or aquatic animals. Fatty acids contain in the acid radical 5 to 22 carbon atoms, more preferably 12 to 18. Most preferred are fatty acids whose acid residues contain 16 to 18 carbon atoms. The ester group of alkyl esters of fatty acids usually contains 1 to 6 carbon atoms, more preferably 1 to 3, methyl esters are particularly preferred.

Esters are usually prepared by saponification of synthetic, semisynthetic or natural oils and / or fat (optionally mixtures thereof) and subsequent reaction of the resulting acids with alcohols containing one hydroxyl group and 1 to 6 carbon atoms. An alternative procedure is direct transesteritization with the corresponding alcohols, especially methanol. The resulting fatty acid ethers are then sulfonated in a conventional manner at elevated temperature by the action of a mixture of gaseous sulfur trioxide and inert olefin in a sulfonation reactor. The resulting product is sulfonated from 90¾ and is more or less dark colored due to the color instability of the fatty acid alkyl esters.

The present invention encompasses a process for preparing neutral to mime alkali alkyl esters of alpha-sulfonic acid fatty acids (ester sulfonate) having less than 10¾ water and K years. in the case of a color value of less than 100. According to the method, the oxidative bleaching and neutralization takes place simultaneously. The raw material used is the crude sulfonation product of an alkyl ester of fatty acids, the acid residue of which contains S and? 22 carbon atoms, more preferably 12 to 18. i.e., alpha-sulfonic acid fatty acid esters.

Bleaching is accomplished by the action of solid bleaching agents or by neutralization with alkali carbonate or sodium bicarbonate, mixtures thereof, metals, particularly with other alkaline solids such as sodium citrate, sodium silicate and the like. The present invention employs a preferred method of simultaneous bleaching and neutralization. The bleaching effect is surprisingly enhanced by the effect of the solid bleaching agent, it is not substantially influenced by side reactions, which are usually

Said prior art process does not require the process products of the two-step process used, the second stage of alkaline bleaching. The resulting simultaneous bleaching and neutralization at temperature. they are neutral, which can be packaged, granulated, are well soluble in water by cooling the apparatus to laboratory to slightly alkaline solids or flocculated by conventional methods and are not sticky. The process of the present invention employs more or less dark colored alkyl esters of alpha-sulfonic acids (prepared by sulfonating anhydrous fatty acid alkyl esters. The starting materials may be solid or alpha-sulfone type alkyl esters having a reaction temperature of 20 to 120 ° C, more preferably at higher temperatures. The fatty acid alkyl esters used), melted depending on the fatty acid and at a predetermined temperature, are generally maintained at 20 to 90 ° C, most preferably 60 to 90 ° C. eg, in the range of 60 to 90 ° C. the alpha-sulfonic fatty acids are present in the molten state. Mostly the bleach or alkali metal bicarbonate are simultaneously added at a given temperature to the starting esters of the sulfosulfic fatty acids. Most preferred are methyl esters prepared as described above by trensesterification with methanol from natural sources such as tallow, coconut or palm kernel oil. The most common solid bleaching agents used in practice as part of detergent compositions are

Sodium peroxyborate and percarbonate. The safety precautions required for working with concentrated hydrogen peroxide solution must also be achieved here.

The agglomeration process itself is well known in the art. For agglomeration, a number of standard dusts can be utilized, such as carporot, zeolite, silicate, and the like.

According to some methods, wherein the alpha-sulfonic fatty acid alkyl esters or mixtures thereof are obtained directly by sulfonating the natural alkyl fatty acid esters, the sulfonated products are mixed with the bleaching and optionally neutralizing agent in a suitable mixer / egglomerator. The reaction begins spontaneously. Its beginning is manifested by the formation of foam (the effect of carbon dioxide release) and gradual lightening of the mixture. According to the present invention foam does not arise which facilitates the preparation of acceptable agglomerates.

Examples Embodiments of the invention

Formulation examples

The following examples illustrate some possible compositions of the composition of the present invention but do not wish to limit its further applications.

In the present examples, the agglomerates comprise the following formulations as solid particles.

Components weight percent

Preparation 2.

Sulfuric acid methyl ester (acidic MES ¹ !

zeolite A 40.0% sodium carbonate 25.0¾ bleaching agent (c-eroxyborate monohydrate) 10.0%

Preparation 2

Sulfuric acid methyl ester 25.0% zeolite A 40.0% peroxybcritene bleaching agent) 3 0.0% other components supplement Preparation 5 Sulfuric acid methyl ester 25.0% zeolite A 50.0% Peroxyboritone Monohydrate 20.0% other components supplement Preparation 4 Sulfuric acid methyl ester 25.0% zeolite. AND 0.0% sodium carbonate 25.0% bleaching agent (perborate monohydrate) 50.0% Preparation 5

100¾

100% Sulfuric acid methyl ester 25.0¾ from Eolite A 45.0¾ Sodium carbonate 25.0¾ Bleaching agent (ceroxyborate monohydrate) 5.0¾

Preparation 6 • Sulfuric acid methyl ester zeolite. A bleaching agent (tic. Horn & dr: another slice to l ox ox vb or i t. A nu)

25.0¾ 4 5.0%

5.0¾

00%] 2 '

Examples of preparation methods

Example. 1

The acidic MES (sulfuric acid methyl ester) is heated in an oven at 60 ° C. At the same time, a mixture of powdered components is prepared comprising a solid bleaching agent (perborate monohydrate), a dry leutralizing agent (sodium carbonate) and a fluidic acid (zeolite A). The powder mixture is placed in an Eirich RVQ2 mixer (from Meschinenfabrik Gustav Eirich) and the machine is turned on. The acidic MES is then slowly poured into the powder mixture until the appropriate aolomerate is formed.

Example 2

The sulfuric acid methyl ester is heated to 60 ° C in a suitable vessel (for example, in a thermostatic bath). The desired amount of solid bleaching agent is then added to the acid and the mixture is stirred until a good dispersion is obtained. This mixture is then poured into an Eirich RV02 mixer which has already contained a mixture of other powder components (dry neutralizing agent, fluid acids, etc.). The mixer is then turned on until suitable agglomerates are formed.

Claims (3)

CLAIMS 1. A process for the preparation of a surface-containing methyl acid ester with color properties, comprising: sulfonating the methyl ester, generating sulfonation. the esterification of said product is acidified to the product and eg is carried out by simultaneously or tightly treating the product with a solid bleaching agent. 2. A process according to claim 1, wherein: The acid product is neutralized simultaneously or after reaction with the solid bleaching agent. 3. A process according to claim 2 wherein said acid product is neutralized by reaction with a solid bleaching agent. 4. A process according to claim 1 5. Method distinguishing 1 or 2, wherein said solid bleaching group is selected from the group consisting of: perborate: percarbonate, preferably sodium or potassium percarbonate; and organic peroxyacids. The composition of claim 2, wherein said acidic product is neutralized by dry neutralization. Process according to any one of the preceding claims, characterized in that the proportion of said bleaching agent is 1 to 200% by weight relative to the fermented product, more preferably 10 to 100% by weight. A preparation according to any one of the foregoing, wherein said acidic 60 to 60% is used 7. The method of claim, the product 90 ° C during the reaction with the color properties of the methyl ester wherein the solid is maintained at a temperature by the solid bleaching agent. 8. A process for the preparation of improved sulphonic acid-containing surfactant agglomerates comprising the following: 1) mixing acidic ME5 with the desired amount of bleaching agent in the form of fine Drach; 2) immediately reacting the above mixture with a dry neutra reagent in a suitable mixer / agglomerator; (3) processing of MES agglomerates of the prior flow characteristics in the sinter plant; this completes the preparation of aalomer ethers containing improved color properties. is free