NL8400302A - METHOD FOR PREPARING METAL SOAPS - Google Patents

Description

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Method for preparing metal soaps.

The invention relates to an improved method for preparing water-insoluble alkaline earth metal salts or heavy metal salts of fatty acids by the precipitation method.

Alkaline earth metal salts and heavy metal salts of aliphatic monocarboxylic acids, commonly referred to as metal soaps, are widely used for numerous commercial applications.

They are used, for example, as stabilizers against heat and light and as lubricants for plastics; as drying agents in paints? as fluxes for varnishes and lacquers; as lubricants in the metal-machining; as means to easily remove rubber from a mold; as dispersing and suspending agents, etc. More information on these and numerous other applications is provided by S.B. Elliott in chapter 9 of a text entitled "The Alkaline-Earth and Heavy Metal Soaps", Reinhold Publishing Corp. (1946).

Metal soaps are generally prepared on a commercial scale by the melting method or by the double decomposition or precipitation methods. In the melting process, a fatty acid is directly reacted with the appropriate metal oxide or metal hydroxide at elevated temperature to release water. After all the water of reaction has been removed, the molten mass is cooled and crushed or ground to obtain the final metal soaps. Melted metal soaps are dense powders. Typical methods of preparing metal soaps by the melting method are described in U.S. Pat. Nos. 3,803,188, 4,307,027, and 4,316,852.

Since the melting process is not always entirely acceptable for the preparation of some alkaline earth metal soaps or heavy metal soaps, metal soaps are also prepared using the precipitation method. According to this method, the alkali metal salt of the fatty acid is first prepared by adding an acid to a fatty acid and the soluble salt is then reacted with an aqueous solution of the appropriate alkaline earth metal salt or heavy metal salt.

The insoluble alkaline earth metal soap or heavy metal soap precipitates from the solution and is recovered by filtration followed by washing and drying 8400302 * m * 2 gene. Typical preparations of water-insoluble metal soaps are described in the. U.S. Patents 2,417,071, 2,447,064 and 2,945,051.

There are a number of drawbacks to the precipitation process because of the fine particle size of the precipitated metal soaps. Filters can become clogged, requiring more time to filter and filters often need to be changed or cleaned. This also makes it more difficult to wash the precipitate.

This often leads to higher alkali metal salt contents than desired due to incomplete removal of the soluble alkali metal salts from the precipitate. Yet another problem associated with that process is the larger water content of the filter cake, making subsequent drying difficult and more expensive.

It would be desirable if a method of preparing metal soap by the precipitation method were available, which would overcome these and other problems typically associated with such processes. It would be even more desirable if the metal soaps obtained by such a process were products of fine particle size and of good color.

Surprisingly, an improved process has now been found for preparing alkaline earth metal soaps and heavy metal soaps from aliphatic monocarboxylic acids by the precipitation method, minimizing the problems previously associated with product recovery. The most remarkable thing about the improved method according to the invention is that considerably better filtering speeds are obtained. Higher yields are therefore realized at reduced production costs. As a result of the improvement in the filtration of the metal soaps, the products can be washed more efficiently, making it easier to obtain significantly lower alkali metal salt contents. It has further been noted that the metal soaps obtained on filtration contain less water. This makes drying easier and leads to a significant reduction in energy costs.

The present invention relates to a process for preparing a water-insoluble metal soap from an 8400302 * 3 - aliphatic monocarboxylic acid or mixture of aliphatic monocarboxylic acids having about 5-26 carbon atoms according to the precipitation method. aliphatic monocarboxylic acid is added 1.25-12% by weight of a polymeric fatty acid obtained by polymerization of unsaturated 5C monocarboxylic acids, or 1.25-12% by weight of a C. aliphatic dicarboxylic acid, or 3 - 25 wt% of a by-product acid obtained by ozonizing oleic acid, or 0.01 - 10 wt% of at least one of the following polycarboxylic acids: (1) aliphatic polycarboxylic acids with 2-10 carbon atoms, (2) polyacrylic acid, (3) cycloaliphatic polycarboxylic acids with 5-20 carbon atoms, or (4) aromatic polycarboxylic acids with 8-20 carbon atoms, or anhydrides of such acids.

The present process is suitable for preparing water-insoluble metal soaps of aliphatic monocarboxylic acids with 5-26 carbon atoms, including saturated and unsaturated fatty acids, branched and straight chain fatty acids, as well as hydroxy-substituted fatty acids. Mixed fatty acids derived from natural fats and oils are particularly suitable. Although the method is particularly suitable for the preparation of magnesium, calcium, zinc and aluminum soaps, it can also be successfully used for the preparation of strontium, barium, iron, cobalt, nickel -, copper, cadmium or lead soaps.

From 1.25 to 12% by weight of a polymeric fatty acid or a C11-24 dicarboxylic acid or from 0.1 to about 10% by weight of a polycarboxylic acid is added to the aliphatic monocarboxylic acid to obtain the better results contained herein called. Suitable polycarboxylic acids are aliphatic, cycloaliphatic or aromatic di-, tri- or higher carboxylic acids. Aliphatic dicarboxylic acids with from about 6 to 9 carbon atoms are particularly suitable, especially when they form from 0.25 to 5% of the total amount of acid. According to an embodiment of the invention, use is advantageously made of 3-25% acids which are obtained as a by-product in the ozonation of oleic acid and which typically contain 10-20% c-24 dicarboxylic acids. The process is carried out according to conventional precipitation processes (double decomposition), except that the acids mentioned herein are added together with the aliphatic monocarboxylic acid. The conditions and the device used can be varied according to principles known per se.

The present process relates to an improvement in the preparation of water-insoluble metal soaps of fatty acids by the precipitation method. The process is useful for the preparation of metal soaps of aliphatic monocarboxylic acids with from about 5 to 26 carbon atoms, and preferably from about 8 to 22 carbon atoms. Such acids include caprylic acid, pelargonic acid, caprir. neic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, benzene, lignoceric acid and the like or mixtures thereof.

The invention is useful not only for preparing metal soaps from saturated fatty acids, but also unsaturated monocarboxylic acids such as oleic, linoleic and the like can be advantageously used and converted to useful metal bars according to the method of this invention. It is also possible to use aliphatic monocarboxylic acids, saturated or unsaturated, branched or branched, obtained by synthetic means, such as by oxidation processes. Metal soaps of hydroxy-substituted aliphatic monocarboxylic acids, such as 12-hydroxy-stearic acid and ricinoleic acid, can also be advantageously prepared according to the improved method of this invention.

Commercially available fatty acids derived from animal fats or oils or vegetable oils are commonly used to prepare metal soaps. These commercially available fatty acids are obtained by splitting and fractionating natural fats and oils and usually consist of mixtures of aliphatic monocarboxylic acids, the predominant acids of which contain from about 12 to 18 carbon atoms. The acids can include both saturated and unsaturated acids. Useful commercially available fatty acid products of this type are derived from talc, pork lard oil, fish oil, sperm oil, coconut oil, palm oil, palm kernel oil, groundnut oil, rapeseed oil, cottonseed oil, sunflower seed oil, soybean oil, linseed oil, and the like. Also suitable are hydrogenated versions thereof, for example hydrogenated tallow fatty acids and the like.

The process of the invention is particularly suitable for preparing metal stearates or metal soaps from fatty acid mixtures, the predominant acid being stearic acid. Water-insoluble soaps of stearic acid, for example calcium stearate, 8400302 f * 5 have numerous industrial applications and a better process for their preparation is therefore highly desirable, especially when the metal stearates prepared by that process have a fine particle size as well as excellent whiteness.

The acids mentioned herein to be added to the monocarboxylic acid can be added at the start of the reaction, namely before the formation of the water-soluble alkali metal salt, or after the formation of the water-soluble alkali metal salt, an alkali metal salt of each of those acids is added thereto.

According to the present method, from about 0.1 to about 10% by weight of a polycarboxylic acid is included in the above aliphatic monocarboxylic acids, and more preferably of the invention, the di- or higher polycarboxylic acid forms 0.25-5% by weight. of the total amount of acid. Useful polycarboxylic acids for carrying out the method of the invention include aliphatic carboxylic acids, cycloaliphatic carboxylic acids and aromatic carboxylic acids.

As aliphatic carboxylic acids, di-, tri- or tetra-carboxylic acids with 2-10 carbon atoms can be used. Higher polycarbonic acids, such as polyacrylic acid, can also be used to advantage. Examples of aliphatic carboxylic acids are oxalic, maleic, fumaric, malonic, succinic, glutaric, adipic, pimeline, suberic, azelaic, sebacic, citric, butane tetracarboxylic, and the like. Aliphatic dicarboxylic acids with 6-9 carbon-25 atoms are particularly suitable for carrying out the present process.

Useful cycloaliphatic carboxylic acids contain about 5-20 carbon atoms and include di-, tri- or higher polycarboxylic acids of cyclopropane, cyclobutane, cyclopentane and cyclohexane, which may contain one or more alkyl substituents on the ring. The alkyl substituents can contain 1-8 carbon atoms, but usually contain 1-4 carbon atoms. Preferred cycloaliphatic carboxylic acids for carrying out the present process contain 7-12 carbon atoms. Cyclohexane dicarboxylic acid 35 and C 1-6 alkyl-substituted cyclohexane dicarboxylic acids are particularly suitable.

Aromatic carboxylic acids, which can be used to carry out the present process, contain 8-20 carbon atoms and have 2 or 3 carboxyl groups on the ring. The ring can also be substituted with one or more C 1 alkyl groups. Particularly suitable are 1-4 aromatic di- and tricarboxylic acids with 8-12 carbon atoms, for example phthalic acids and triellitic acid.

It will be understood that when an anhydride of any of the above-mentioned polycarboxylic acids is available, that anhydride can be used in place of the acid in the operation of the process and then comparatively better results are obtained.

According to the present method, from about 1.25 to about 12% by weight of polymeric fatty acid or C 1-24 aliphatic dicarboxylic acid is combined with the above-defined aliphatic mono-carboxylic acids. The polymeric fatty acid or dicarboxylic acid can be combined with the aliphatic monocarboxylic acid at the start of the reaction, namely before the formation of the water-soluble alkali metal soap, or after the formation of the water-soluble alkali metal soap, an alkali metal soap of a polymer fatty acid or an aliphatic dicarboxylic acid are added thereto. Mixtures of aliphatic dicarboxylic acids can be advantageously used in the practice of the process and, according to an embodiment of this invention, acids are used which are obtained as by-products in the ozonation of oleic acid and which typically contain 10-20% aliphatic dicarboxylic acids . . In carrying out the present process, particularly favorable results are obtained when the aliphatic dicarboxylic acids and / or the polymeric fatty acid are used in an amount of 1.5 - 7.5%, based on the total amount of acid.

Polymeric fatty acids useful in the present process are obtained by polymerizing unsaturated carboxylic acids, such as oleic, linoleic, ricinoleic, linolenic, eleostearic acid, and mixtures thereof, by any of the known processes. The polymeric fatty acids can be obtained, for example, by using treated or untreated clay catalysts or acidic catalysts, such as HF, BF 2, AlCl 3, SnCl 3, or by thermal polymerization, such as the method described in U.S. Patent No. 2,482,761. Acids obtained by such processes are generally referred to as polymeric fatty acids or as polymeric acids, and more specifically they are referred to as dimer, trimer, etc. acid, depending on the degree of polymerization 8400302 * 2%. For the method of the invention, the polymeric fatty acid typically contains 50% or more dimer acid.

Polymeric fatty acids containing 65% or more dimer acid and obtained by polymerizing oleic acid, linoleic acid or mixtures thereof, for example tall oil fatty acids, are particularly suitable. Such products are commercially available and are sold under the trade name "EMPOL". If desired, the polymeric fatty acids can be hydrogenated before use.

Aliphatic dicarboxylic acids which can be used in the practice of the present process contain from 11 to about 24 carbon atoms. Examples of aliphatic dicarboxylic acids are undecanedioic acid, dodecanedioic acid, tridecanedioic acid (brassylic acid), tetra-decanedioic acid, hexadecanedio-diutir (thapsic acid), octadecanedioic acid, eicansanedioic acid, heneicosanedioic acid, docosanedioic acid and the like. Aliphatic dicarboxylic acids with 11-18 carbon atoms are particularly suitable for carrying out the present process. Mixtures of aliphatic dicarboxylic acids within the prescribed carbon ranges can also be used.

In addition to the above-mentioned polymeric fatty acids and aliphatic dicarboxylic acids, anhydrides of such acids can also be used, yielding comparable improved results.

According to another embodiment of the invention, use is made of acids obtained as by-products in the preparation of pelargonic acid and azelaic acid by the ozonation of oleic acid. Such an ozonation process is described in U.S. Pat. No. 2,813,113. As described in this patent, the crude product obtained by the ozonation / oxidation consists essentially of pelargonic acid and azelaic acid; other saturated monocarboxylic and dicarboxylic acids. however also present due to impurities in the oleic acid used as the starting material. After separating pelargonic acid and azelaic acid by distillation, the azelaic acid is extracted with hot water. The oil layer, which contains a mixture of water-insoluble Cr monocarboxylic acids (80-90%) o-10 and C11-14 dicarboxylic acids (10-20%), the so-called by-product or waste acid, can be successfully used in the performing the present method. Depending on the extraction efficiency, 8400302 t? <· Δ the acid obtained as a by-product also contains up to a few percent azelaic acid. The acid obtained as a by-product can be used as such or it can be distilled and / or hydrogenated before use. When acid obtained as a by-product in the ozonation of oleic acid is used for the present process, about 3-25%, and most preferably 5-20% thereof, is used to obtain the better filterability and other associated benefits.

Using the above-identified polymeric fatty acids, polycarboxylic acids, aliphatic dicarboxylic acids or acids obtained as a by-product, the present process is carried out according to the conventional methods of preparing metal soaps by the double decomposition or precipitation method. Such processes have been extensively described in the literature, and reference can only be made to chapter 5 of the text of S.B. by way of explanation. Elliot, The Alkaline-Earth and Heavy-Metal Soaps, Reinhold Publishing Corp. (1946), where the precipitation method and the various related steps are described. An article by M.L. Castes and others in "Industrial and Enginee-20 ring Chemistry", vol. 41, No. 10, p. 2084 and 2085, find a detailed description of the preparation of a metal soap according to the precipitation process.

Generally, the process first involves forming the water-soluble salt of the aliphatic monocarboxylic acid, to which the prescribed amount of the polycarboxylic acid, the polymeric fatty acid, the aliphatic dicarboxylic acid or the by-product acid is added. This is usually done by dissolving or dispersing the acids in a sufficient amount of water while heating at about 40-95 ° C, most preferably at 50-85 ° C, while stirring. An aqueous solution of sodium hydroxide, potassium hydroxide, anhydrous soda or the like is then slowly added while maintaining the temperature. Generally, a small excess of the alkali is added, which is generally 2-5 mol%, based on the acid number of the combined acids.

If desired, the water-soluble soap can be obtained by adding the acid to the base.

8400302 '4 *%

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9

When the formation of the soluble alkali metal soap is completed, an aqueous solution of an alkaline earth metal salt or a heavy metal salt is added to precipitate or precipitate the metal soaps. The alkaline earth metal soaps and the heavy metal soaps are insoluble in water and precipitate as fine particles, giving a milky appearance to the solution. As the precipitation takes place, the particles can coalesce depending on the conditions used, namely the addition speed, the stirring speed and the stirring duration, and the temperature. Generally, an excess, usually from about 5 to about 15 mol%, of the alkaline earth metal salt or of the heavy metal salt is used to ensure complete formation of the insoluble soaps.

Earth-alkali metal salts and heavy metal salts which are soluble in water and which form water-insoluble soaps of the fatty acids can be used. These salts are generally salts of magnesium, calcium, strontium, barium, aluminum, iron, cobalt, nickel, copper, zinc, cadmium or lead. Generally, chlorides or sulfates of these metals are used. " The improved process according to the invention is particularly suitable for the preparation of magnesia-20 µm, calcium, zinc and aluminum soaps, because soaps of these metals have previously caused problems during filtration. The alkaline earth metal soaps and the heavy metal soaps can also be precipitated by adding the solution of the alkali metal soap to a solution of the alkaline earth metal salt or the heavy metal salt.

After the precipitate has been digested sufficiently, the metal soap is collected and washed several times to remove residual water-soluble alkali metal salts. The metal soap is then dried, typically to a water content of less than about 2.5 wt%; however, higher moisture contents can be tolerated depending on the eventual use of the metal soap. Wearing can be carried out at ordinary temperature, or, as is more often done, the metal soap is heated at a higher temperature. Temperatures of up to about 150 ° C can be used if products with a very low moisture content are desired.

Although a portionwise mode of operation has been described above, the method of the invention may also be carried out in a continuous manner by modifying the processes and the device appropriately.

The improved method according to the invention is further elucidated by means of the examples below. As will be readily apparent to those skilled in the art, numerous variations can be made which are then within the scope of the present invention. All parts and percentages mentioned in the examples are by weight unless otherwise indicated.

Example I

A calcium soap from commercially available stearic acid was prepared according to the improved method of the present invention. To conduct the reaction, 66.67 g of EMEBSOL 132 US Lily Stearid Acid containing 1.5 wt% dodecanedioic acid was added to a reaction vessel along with 1500 g of water. The mixture was heated to 70 ° C and stirred with a three-blade stirrer at 400-450 rpm. The temperature and stirring were maintained throughout the reaction. A 3% molar excess of sodium hydroxide (10.82 gj, dissolved in 50 g of distilled water, was then added, and after the solution became clear, a solution of calcium chloride (15.67 g of CaClj in 150 g of distilled water - 10) was added. % molar excess CaCl2) The addition was carried out by pouring the calcium chloride solution over the rim of the reaction vessel in 30 seconds After the addition was completed, the mixture was stirred for exactly 1 minute After this mixing period the stirrer was turned off and the mixture was immediately filtered through a 15 cm filter funnel fitted with double filter paper (Fisher Coarse), under a vacuum of 660 mm Hg The calcium soap was completely filtered in 110 seconds.

The filtering time was determined from the time of the first contact with the filter paper until the first cracks appeared in the filter cake or the cake started to peel off the walls of the filter funnel. Species Similar filtration rates were obtained when using brassylic acid or thapsic acid in the reaction described above in place of dodecanedioic acid.

Example II

For comparison, the experiment described above was repeated, except that the dodecanedioic acid was omitted. In this 84 Q 1 & 11 comparative example, 66.67 g of commercial stearic acid was combined with 1500 g of distilled water. The temperature, stirring and stirring time were the same as in Example 1 and the solutions of sodium hydroxide and calcium chloride were prepared using the same amount of distilled water and calculated to give a 3% molar excess of sodium hydroxide and a 10% molar excess of calcium chloride was obtained. It took more than 1000 seconds for the calcium soap obtained according to this test to be completely filtered.

Example III

According to the procedure of Example I, a calcium soap of stearic acid was prepared using a commercially available stearic acid, to which 5% by weight of a commercially available polymeric fatty acid was added. The commercially available polymeric fatty acid (EMPOL 1016) contained 87% dibasic acid. In the calcium soap prepared according to this reaction, the filtering time was 165

seconds. Similar filter times were obtained when EMPOL

1022 dimer acid (75% C, dibasic acid) in the 36 test described above was used.

Example XV

The calcium soap of stearic acid was prepared by the procedure of Example X using a commercially available stearic acid, to which 15% of a mixed acid product obtained as a by-product of the preparation of pelargonic acid and azelaic acid by ozonation of oleic acid was added. The acid obtained as a by-product contained about 7% pelargonic acid, 2% azelaic acid and 12% C18, and O.dibasic acids, while the rest of the mixture consisted of C144 C7 'C8' C10 'C12' C13 'C14 "C15" C16 "C17" and C18 Monocarboxylic Acids. A 40 second filter time was obtained for the calcium soap obtained using the by-products described above as by-products. When the test was repeated using a mixing speed of 950-1000 rpm, a filtering time of 50 seconds was obtained.

Examples 5-8 35 In order to demonstrate that it is possible to vary the ratio of the stearic acid and the by-products acids, a number of tests were carried out according to the procedure of Example I, except that the mixing time after the addition of the calcium chloride solution. 2 minutes. The acid mixture used and the results obtained in the different reactions are as follows:

Example Acid Mixture Filtering Time _ (sec.) V 97% Stearic Acid / 3% By-Product Acids 180 VI 95% Stearic Acid / 5% By-Product Acids 145 VII 90% Stearic Acid / 10% By-Product Acids 45 10 VIII 75% Ste Aric Acid / 25% By-Product Acids 40

Example IX

To demonstrate the versatile applicability of the present improved process as well as the ability to prepare calcium soaps from other aliphatic monocarboxylic acids, especially mixed fatty acids of animal origin, the following experiment was conducted. A mixed fatty acid consisting of 3% myristic acid, 0.5% penta-decanoic acid, 27.5% palmitic acid, 2% margaric acid, 2% oleic acid and 65% stearic acid was used. 15% by weight of the by-product acid of Example IV was mixed with the mixed fatty acid and the calcium soap was prepared according to the procedure of Example 1. The reaction mixture was stirred for 2 minutes after the addition of the calcium chloride solution. The calcium soap obtained had a filtering time of 40 seconds. Analysis of the filter cake indicated that the cake contained 26.4% solids. After washing the cake with 1500 g of water, the chloride content of the cake was found to be 13 ppm. A calcium soap, which was prepared identically from the same mixed fatty acid, but without the addition of the by-product acid, took 130 seconds to filter and the resulting filter cake contained only 20% solid. After the cake was washed with 1500 g of water, the cake was found to contain 240 ppm of chloride. Since the filter cakes obtained using the by-product acids contain less water than the filter cakes prepared in the absence of by-product acids, a proportional reduction in the amount of water-soluble salts in the product prepared from the mixed fatty acids with added by-product acid could be expected.

8400302 r 13

Surprisingly, however, the chloride content of the calcium soap obtained by the method of the invention was found to be considerably lower than could be expected based solely on a reduction in the water content. Sr thus shows that the water-soluble salts used or formed in these reactions have less affinity for the water-insoluble metal salts prepared by the method of the invention, possibly due to a change in the crystal structure of the water-insoluble soap.

Example X.

Similar results were observed when Example IX was repeated using another mixed fatty acid.

The mixed fatty acid used in this experiment contained 3.5% myristic acid, 0.5% pentadecanoic acid, 49.5% palmitic acid, 1.5% margaric acid and 45% stearic acid. The mixed acid calcium soap, obtained with 15% added by-product acid, had a 40 second filter time and analysis of the resulting filter cake indicated 25/2% solids in the wet cake. After the cake was washed with 1500 g of water, the chloride content of the cake was determined to be 31 ppm. The calcium soap of the mixed acid, which was prepared without using the side by-product. 20-acid, had a filter time of 150 seconds and contained 18.9% solids in the filter cake. After washing with 1500 g of water, the cake had a chloride content of 102 ppm.

Example XI

To further illustrate the versatile applicability of the method and the ability to prepare soaps from other metals, the zinc soap from EMERSCL 132 USP Lily Stearic Acid was prepared.

For the reaction, 66.67 g of the stearic acid, which contained 15% by-product acid, was added to 1500 g of distilled water and heated at 70 ° C while stirring with a three-blade stirrer at 400-450 rpm. 3% molar excess of sodium hydroxide dissolved in 50 g of distilled water, then added while maintaining temperature and stirring. When the mixture became clear, a solution of zinc chloride (13.50 g of ZnCl 2 in 150 g of distilled water) was added. - 10% molar excess ZnCl2) poured down the wall of the reaction vessel in 30 seconds. The mixture was then stirred at 70 ° C for exactly 1 minute and filtered. The zinc soap was completely filtered in 25 seconds. An 8400302

"V

Zinc soap prepared in an identical manner, except that the by-product acid was omitted, took 45 seconds to filter-Example XII · ·

A magnesium soap of commercially available stearic acid was prepared in the usual manner. 15% by-product acid was added to the stearic acid, and 66.67 g of the resulting mixture was combined with 1500 g of distilled water under heating (70 °) and stirring (400-450 rpm). The water-soluble sodium soap was prepared by adding a solution obtained by dissolving 10.68 g of sodium hydroxide in 50 g of distilled water (3% molar excess NaOH). To precipitate the insoluble magnesium soap, a solution of 28.57 g of MgCl 4 -OH 2 O in 150 g of distilled water (10% molar excess of MgCl 3) was added and the mixture was stirred for 1 minute before being filtered. The filtering time for the magnesium soap thus obtained was 40 seconds. A magnesium soap prepared identically, except that the by-product acid was omitted, had a filtering time of 500 seconds.

Example XIII

The calcium soap of a commercially available stearic acid was prepared according to the improved precipitation process of the present invention. To conduct the reaction, 66.67 g of EMERSOL 132 USP Lily Stearic Acid containing 0.1% azelaxic acid was added to a vessel containing 1500 g of distilled water. The mixture was heated to 70 ° C while stirring with a three-blade stirrer at a speed of 400-450 rpm. The temperature and stirring were maintained during the reaction. 3% molar excess of sodium hydroxide (10.36 g) was then dissolved in 50 g of distilled water and added to the mixture. When the solution was clear, a solution of calcium chloride (15.14 g CaCl 2 in 150 g distilled water -30% molar excess CaCl 2) was added. The addition was done by pouring down the wall of the beaker over a period of 30 seconds. After the addition was complete, the mixture was stirred for exactly 1 minute, keeping the temperature of the solution at 70 ° C. After the mixing period was completed, the stirrer was turned off and the reaction mixture was immediately filtered through a filter funnel with double filter paper (Fisher Coarse) under a vacuum of 8400302-666 mm Hg. The calcium soap was completely filtered in 160 seconds. The filtering time was measured from the time of the first contact with the filtering paper until the first cracks occurred in the filter cake or until the cake started to peel off the walls of the filter funnel.

For comparison, the experiment was repeated except that the azelaic acid was omitted. For this reaction, 66.67 g of the commercially available stearin product was dissolved in 1500 g of distilled water. The temperature and stirring were the same as in the previous test. The sodium hydroxide and calcium chloride solutions were also prepared using the same amounts of distilled water and were calculated to provide a 3% molar excess of sodium hydroxide and a 10% molar excess of calcium chloride, respectively. Thousand (1000) seconds were needed to filter the calcium soap. When making the comparison, it is clear that a more than fivefold increase in the filtration rate was obtained by adding only 0.1% azelaic acid to the fatty acid.

Example XIV

Example XIII was repeated, except that the amount of azelaic acid was increased and the mixing time was changed. For this reaction, the stearic acid contained 2% azelaic acid and the mixture was stirred for 2 minutes after the addition of the calcium chloride solution. A filtration time of 25 seconds was obtained. When the test was repeated and the azelaic acid was omitted, a filtration time of 275 seconds was obtained. The calcium soaps obtained from both runs were filtered for a total time of 350 seconds and the resulting filter cakes were analyzed to determine the percentage solids and the chloride content. The calcium soap prepared according to the method of the invention contained 32.9% solid and 2.83% chloride, while the calcium soap prepared in the absence of azelaic acid contained 18.7% solid and 6.85% chloride. Since the filter cakes obtained from stearic acid with added azelaic acid contained less water than filter cakes prepared in the absence of azelaic acid, a proportional reduction in the amount of water-soluble salts in the cakes prepared from the stearic acid with added azelaic acid could be expected.

8400302 «V- 16

Surprisingly, however, it was found that the chloride content of the filter cakes obtained by the method of the invention, namely with added dicarboxylic acid, was found to be considerably lower than could only be expected on the basis of a smaller water content. Thus, it appears that the water-soluble salts used or formed in these reactions have a lower affinity for the water-insoluble metal soaps prepared in accordance with the improved process of the invention, perhaps due to a change in the crystal structure of the water-insoluble soaps.

Example XV

Following the procedure of Example XIII, a calcium soap of commercially available stearic acid was prepared. The reaction was identical to that of Example XIII, except that 2% adipic acid was added to the stearic acid and the mixing time after addition of the calls cium chloride solution was extended to 2 minutes. There was a filter! of 30 seconds. The resulting wet filter cake, obtained after 350 seconds of filtration, contained 30.9% solids and had a chloride content of 3.40%. This is a significant improvement over the results obtained in the absence of dicarboxylic acid, namely, a filtration time of 275 seconds and 18.7% solids, as well as a chloride content of 6.85% in the filter cake obtained after 350 seconds of filtration.

Examples XVI - XXI

A number of tests were carried out according to the procedure of Example XIII, except that the commercially available stearic acid contained 1.5% dicarboxylic acid. The following results were obtained in the various reactions:

Example No. Dicarboxylic Acid Filter Time (sec.) XVI Maleic Acid 35 30 XVII Isophthalic Acid 40 XVIII Eyelohexanedioic Acid 50 XIX Malonic Acid 27 XX Adipic Acid 28 XXI Azelaic Acid 35 8400302

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17

All the filter times obtained in the above tests are considerably lower than the filter time (1000 seconds) obtained when the commercially available stearic acid did not contain dicarboxylic acid.

5 Example XXXI

To demonstrate that better results can be obtained when using polycarboxylic acid, Example XIII was repeated, except that 5% citric acid was added to the commercially available stearic acid. A filtering time of 30 seconds was obtained.

Examples XXIII - XXXI

Following the general procedure of Example XIII, a number of tests were conducted to prepare the calcium soaps of different fatty acids and fatty acid mixtures using different dicarboxylic acids and polycarboxylic acids. 66.67 g of the mixture consisting of fatty acid and di- or poly-carbonic acid were used for each reaction. The mixing time, after the calcium chloride solution was added, was 1 minute for all reactions - Details of the various tests, including the fatty acid and the di- or polycarboxylic acid used, as well as the results obtained are shown in Table A.

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g ff 3 3 O 3 3 Η H 3 3 3 N 3

3 P N N H C N

ft (0 (U <U P OH

3 G G OT P> 1

dP P Η Η H ftM

Ti al U U U 3 a σι ft ft> i 0 3

dP 3 3 Ό P S O

- -3 · O O H 3 dP

p O 3 #> O dP

3 * dP dP rtj N CD Ol 01 3 H Ή rH OJ O! M 3 O G P - -

G 3 - - Η H · »3 P P P

3NPP3PP3 333 3d) 3 3H3 3N 333

OG 3- 30 3 3d) NNN

3 Η N N PNGG GHG

* Μ Η H * -h Μ OH O 3! Ö O P

33> i> iCM> iGP M 3 P O '3 POP P CN X Η H 3 H G P 3

CPftft 0PHNP33N

p 03 3 0HP3HPd) GH0 3 ft g- 0 0 00 33 0 ^ 00 3

3 m> i HO,> 3 QO »H

NdPdP P A P> O

P inindPdPdJIdPdPH dPdP3 d) * »σι σ> g cm h» h 3dpror- p> o ό * σι σι w> -i r- p m m cn <u p ’

G

O

H

3

d> H

A Η Η H

PH> HHHX H

0 Η H >>>> HX> <S

ace ba s 8400302 Z · ZU Λ · 19

The filters obtained in all the tests shown in the table are considerably better when compared with identical tests performed in the absence of the di or polycarboxylic acid. For example, the filtering time obtained using EMERSOL 221 Oleic Acid, which did not contain adipic acid at all, was more than 2000 seconds. Similarly, the filtering time obtained for the calcium soap of tallow fatty acids in the absence of phthalic anhydride was 450 seconds.

Example XXXII

To demonstrate the versatile applicability of the present improved process and to demonstrate that it is also possible to prepare soaps from other metals, the aluminum soap of Emersol 132 US? Lily Stearic Acid prepared. For the reaction, 66.67 g of the stearic acid, which contained 10% azelaic acid, was added to 1500 g of distilled water and heated at 70 ° C while stirring with a three-blade stirrer at a speed of 400-450 rpm. A 3% molar excess of sodium hydroxide dissolved in 50 g of distilled water was then added while maintaining the temperature and stirring. When the mixture had become clear, a solution of aluminum sulfate (51.36 g A ^ CSO ^} ^ in 150 g distilled water - 10% molar excess Al (SO ^) was added along the wall of the beaker in a 30 second period The mixture was stirred for exactly 1 minute while maintaining the temperature at 70 ° C, then filtered The aluminum soap was completely filtered in 35 seconds An aluminum soap prepared identically except that the azelaic acid was omitted, took 650 seconds to filter.

Example XXXIII

The magnesium soap of a commercially available hydrogenated stearic acid was prepared in the usual manner. 2% of the stearic acid product, which consisted of a mixture of saturated acids (4% C. 0.5% C, c, 29% C, 1.5% C, and 65% C). aze-14 15 16 17 18 laic acid. The mixture (66.67 g) was then dispersed in 1500 g of distilled water by heating at 70 ° C with stirring (400-450 rpm). The water-soluble sodium soap was prepared by adding a solution obtained by dissolving 10.61 g of sodium hydro-8400302 xyde in 50 g of distilled water (3% excess NaOH). To precipitate the insoluble metal soap, a solution of 28.9 g of magnesium chloride in 150 g of distilled water (10% excess of MgC 2 SiO 2) was added, and the mixture was stirred for 1 minute before filtered. The filtration time for the magnesium soap obtained by the above-described process was 30 seconds, while when the magnesium soap was prepared identically, except that the azelaic acid was omitted, a filtration time of 130 seconds was required.

Example XXXIV

Example XXXIII was repeated using stoichiometric amounts of the sodium hydroxide and zinc chloride solutions. All other conditions were the same. The zinc soap of the stearic acid, containing 2% azelaic acid, was filtered in 30 seconds. When the azelaic acid was omitted from the reaction, the zinc soap obtained took more than 2000 seconds to filter.

/ 8400302

Claims (13)

A process for preparing a water-insoluble metal soap from an aliphatic monocarboxylic acid or a mixture of aliphatic monocarboxylic acids of about 5 to 26 carbon atoms by the precipitation method, characterized in that the aliphatic monocarboxylic acid is added: (a) 1 25-12 wt.% Of a polymeric fatty acid obtained by polymerization of unsaturated carbon monocarboxylic acid 1 or (b) 1.25-12 wt.% Of a c 24 carboxylic aliphatic dicarboxylic acid, or 10 (c ) 3-25% by weight of a by-product acid obtained by ozonizing oleic acid, or (d) 0.1-10% by weight of at least one of the following polycarboxylic acids: (1) aliphatic polycarboxylic acids with 2-10 carbon atoms , (2) .polyacrylic acid, (3) cycloaliphatic polycarboxylic acids with. 5-20 carbon atoms, or (4) aromatic polycarboxylic acids with .8-20 carbon atoms, or anhydrides of those acids. A method according to claim 1, characterized in that the aliphatic monocarboxylic acid is derived from animal fats or oils or vegetable oils. 3. A method according to claim 1 or 2, characterized in that the water-insoluble metal soap is a soap of magnesium, calcium, strontium, barium, aluminum, iron, cobalt, nickel, copper, zinc, cadmium or lead. 4. Process according to claim 3, characterized in that the water-insoluble metal soap is calcium stearate or the calcium soap 30 of a fatty acid mixture 1 of which stearic acid is the main component. Process according to claims 1 to 4, characterized in that the polymeric fatty acid (a) is derived from oleic acid, linoleic acid or 8400302 -Hr * mixtures thereof and contains 65% or more of C 1-4 dimer acid and is used Jo in an amount of 1.5 - 7.5%, based on the total amount of acid. 6. Process according to claims 1-4, characterized in that the aliphatic dicarboxylic acid (b) is a ^-acid, which is used in an amount of 1.5 to 7.5%, based on the total amount of acid. f Process according to claim 6, characterized in that the aliphatic dicarboxylic acid is dodecanedioic acid or brassylic acid. 8. Process according to claims 1-4, characterized in that the by-product acid (c) contains 10-20 wt.% Dicarboxylic acids and is used in an amount of 5-20%, based on the total amount of acid. 9. Process according to claims 1-4, characterized in that the aliphatic polycarboxylic acid (1) is an aliphatic di-, tri- or tetracarboxylic acid, the cycloaliphatic polycarboxylic acid (3) is a di-, tri- or higher carboxylic acid of cyclopropane , cyclobutane, cyclopentane or cyclohexane, and the aromatic polycarboxylic acid (4) contains two or three ring-substituted carboxyl groups. 10. A method according to claim 9, characterized in that the aliphatic polycarboxylic acid (1) is an aliphatic dicarboxylic acid with ". 6-9 carbon atoms, the cycloaliphatic polycarboxylic acid (3) is a cycloaliphatic dicarboxylic acid with 7-12 carbon atoms, and the aromatic polycarboxylic acid (4) is an aromatic di- or tricarboxylic acid with 8-25 carbon atoms. Process according to claim 9 or 10, characterized in that the polycarboxylic acid is present in an amount of 0.5-5% by weight, based on the total amount of acid. 12. A method according to claims 9-11, characterized in that the polycarboxylic acid is adipic acid, azelaic acid, phthalic acid or trimellate acid. Process according to claims 9-11, characterized in that the polycarboxylic acid is cyclohexane dicarboxylic acid or C 1-4 alkyl-substituted cyclohexane dicarboxylic acid. 6400302