JPS6014009B2 - Manufacturing method of granular metal soap - Google Patents

Description

[Detailed Description of the Invention] The present invention relates to a method for producing granular metal soap,
The aim is to create a revolutionary manufacturing method that allows for the production of granular metal soap of the same quality as conventional products, the ability to control the particle size, and the process of making munification and double decomposition in one step. The point is to provide the following.

Metal soaps are used for a wide range of purposes depending on the properties of the compound, such as mold release agents, waterproofing agents, stabilizers for polyvinyl chloride, desiccants, viscosity modifiers, and vulcanization accelerators, and are manufactured using conventional manufacturing methods. Typical methods include a method in which alkaline soap is produced from a fatty acid and a caustic alkali, and a metathesis precipitation reaction between this and a metal salt, or a melting method in which a fatty acid and a metal oxide or metal hydroxide are directly reacted by heating. However, these conventional methods yielded only powder products.

In order to obtain granular products, a method is used in which granular metal soaps are heated and mixed in a powder mixer to form granules, as in the case of composite stabilizers for polyvinyl chloride. As a result of intensive research into manufacturing conditions under which the reaction product of metal soap itself becomes granular, the present inventors found that the reaction between fatty acids and inorganic salts and caustic alkali, or the reaction between fatty acids and hydroxides was carried out at the melting point of the fatty acid. They found that granular metallic soap can be produced by the following procedure, and that it is also possible to control the particle size of the granular metallic soap by changing the amount of fatty acid reacted below the melting point.

That is, the present invention provides a reaction in which a caustic alkali is added to a mixture of a fatty acid and an aqueous inorganic salt solution, or a reaction in which a fatty acid and a hydroxide are added to an aqueous medium and mixed with heat, in which a certain amount or more of the fatty acid to be reacted is added. is reacted at a temperature below the melting point of the fatty acid, and the remainder is reacted at a temperature above the melting point of the fatty acid.

The above-mentioned amount of fatty acids or more means 40% or more of the total amount of fatty acids to be reacted, and may even be 100%, and it goes without saying that if it is 100%, the reaction at a temperature above the melting point in the second stage can be omitted. stomach.

In the above reaction below the melting point, the temperature range is preferably from the viewpoint of reactivity to a temperature below the melting point (transparent) of the fatty acid or 1 picoC lower than the melting point, and the reaction temperature above the melting point is preferably within the temperature range from the melting point of the fatty acid to 100 do. be.

The fatty acids that can be used are solid at room temperature and have a melting point (
Specific examples include saturated fatty acids having 12 to 29 carbon atoms, unsaturated fatty acids such as crotonic acid, ellaidic acid, brassic acid, and stearolic acid, or fatty acid mixtures such as beef tallow fatty acid. The mixture may have an overall melting point (transparent) of 9,000 or less and a solid state at room temperature (25° C.). Inorganic salts include calcium chloride, barium chloride,
Examples include zinc chloride, cadmium sulfate, magnesium sulfate, and other water-soluble inorganic salts, and hydroxides include calcium hydroxide, barium hydroxide, lithium hydroxide, strontium hydroxide, zinc hydroxide, magnesium hydroxide, etc. Can be mentioned.

These inorganic salts or hydroxides may be used as a mixture of two or more, in which case the product will be a granular composite metal soap, for example a stabilizer for resins, etc.
Suitable for applications using more than one kind of metal soap. In the reaction of adding caustic alkali to a mixture of fatty acids and an aqueous inorganic salt solution, first, a mixture of a predetermined amount of fatty acids of 40% or more and the entire amount of an aqueous inorganic salt solution is heated at a temperature below the melting point of the fatty acids to reduce the amount of the fatty acids present. After completing the reaction by dropping approximately an equivalent amount of a caustic alkali such as caustic soda, the remaining fatty acid is added, and the temperature is raised to above the melting point of the fatty acid to form an approximately equivalent amount of the fatty acid added later. The reaction is caused by dropping caustic alkali.

At this time, the larger the amount of fatty acid added later, that is, the amount of fatty acid reacted above the melting point, the larger the particle size of the granular metal soap produced. Therefore, when the entire amount of fatty acids is reacted below the melting point, granular metal soap with the smallest particle size can be obtained. During the reaction below the melting point, the inorganic salt may be present in an amount equivalent to the fatty acid, and the remainder may be added together with the addition of the remainder of the fatty acid. The above reaction method has the advantage that the two steps of saponification and metathesis precipitation, which were conventionally carried out, can be carried out in one step, since the fatty acids are directly reacted without being made into an alkali soap in advance.

In the reaction in which fatty acids and hydroxides are added to water and heated, similar to the reaction method described above, a set amount of fatty acids and hydroxides of 40% or more are added to water, and the temperature is below the melting point of the fatty acids. The remaining fatty acids are then added and heated above the melting point of the fatty acids to cause a reaction.

Similar to the reaction method described above, the particle size of the granular metallic soap to be produced increases as the amount of fatty acids reacted above the melting point increases. Therefore, when the entire amount of fatty acids is reacted below the melting point, the granular metallic soap with the smallest particle size is obtained. It will be done. The hydroxide is
Water-releasing substances such as zinc hydroxide and magnesium hydroxide can also be used, producing granular metal soaps, but these have relatively low solubility such as barium hydroxide, calcium hydroxide, and lithium hydroxide. Compared to those with high levels, there is a tendency for the response rate to be slightly lower.

The mechanism of particle growth of granular metal soap is not clear, but experimental observations show that metal soap particles generated in a reaction below the melting point become seeds, and fatty acids added later dissolve in a reaction above the melting point and react rapidly. It is presumed that the particles are deposited on the seeds and the particles grow.

Operationally, it is possible to control the particle structure by adding fatty acids to the reaction system during the reaction above the melting point. For example, by making the entire amount of fatty acids exist in the reaction system from the beginning and changing only the temperature conditions, the melting point of the fatty acids can be adjusted. A case where the following reaction is carried out at a temperature above the melting point is also one form of the present invention, and granular metal soap can be obtained, but the particle size is not much different from that when the whole amount of fatty acids is reacted at a temperature below the melting point. Adjustments cannot be made.
The present invention will be illustrated below with examples.

Example 1 50°C hot water]. 5 Calcium chloride (CaC12)
To this was added commercially available stearic acid powder (New Japan Chemical Industrial Powder Stearic Acid #150).
, melting point (transparent) 58°C) for 200 minutes, and then, while maintaining the liquid temperature at 50 to 55 qo, add 132 hours of 22% sodium hydroxide aqueous solution for 20 minutes while keeping the liquid temperature at 50 to 55 qo. After the reaction was completed, the liquid temperature was further raised to 70 to 75 qo and clarification was carried out for 3 minutes to avoid residual reactants.

The resulting reaction slurry was filtered, bulb-washed twice with warm water, and dried to obtain granular calcium stearate (containing about 28% calcium palmitate). The FFA analysis value (free fatty acid content) of this product is 0.2%, 2
The amount remaining through the 0 mesh filter was 2%, and the amount passing through the 100 mesh filter was 15%. Example 2 46 tons of calcium chloride was added and dissolved in 1.5 tons of 50 qo of warm water, 100 tons of commercially available stearic acid powder (same as Example 1) was added thereto, thoroughly stirred, and then the liquid was dissolved. While maintaining the temperature at 50 to 55 °C, 66% of a 22% aqueous sodium hydroxide solution was added dropwise to Takaazusa over 10 minutes to react. After the reaction, the liquid level was raised to 60 to 65 qo, and 100
Add commercially available stearic acid powder, add 22% aqueous sodium hydroxide solution over 10 minutes while stirring to react, and after the reaction is complete, further raise the temperature to 70 to 75 degrees Celsius and heat for 30 minutes. I worshiped it.

When the obtained reaction slurry was treated in the same manner as in Example 1, the PFA analysis value was 0.3%, and the 20 mesh filtration residue was 6.
Granular calcium stearate was obtained with a content of 2% and a content of 0.2% passing through a 100 mesh filtration. Example 3 In place of calcium chloride in Example 1, barium chloride
When the reaction and post-treatment were carried out using a 20-day (20) 96-day filter and all other conditions were the same as in Example 1, the FFA analysis value was 0.1%, the 20-mesh filtration residue was 2%, and the 100-mesh filtration amount was 2%. Granular barium stearate was obtained with a content of 16%.

Example 4 When barium chloride 96 was used instead of calcium chloride in Example 2 and the reaction and post-treatment were carried out under the same conditions as in Example 2, the FFA analysis value was 0.2%.
, granular barium stearisolate was obtained with a 20 mesh filtration residue of 66% and a 100 mesh filtration fraction of 0.1%.

Example 5 The amount of stearic acid powder added at the beginning in Example 4 was changed to 160 ml, and the 22% sodium hydroxide aqueous solution was added dropwise to 10 M in each stream. After heating to 60 to 65 ml, the amount of stearic acid powder added was 40 minutes, a 22% aqueous sodium hydroxide solution was added dropwise for 5 minutes to make it 2M, and the others were Example 4.
When the reaction and post-treatment were carried out under the same conditions as
FFA analysis value 0.1%, 20 mesh filtration residual 8%,
Granular barium stearate with a content of 5% passing through a 100 mesh filtration was obtained.

Example 6 In place of calcium chloride in Example 1, Zn was used as Zn 137.5 / its zinc chloride aqueous solution was used, and all other conditions were the same as in Example 1. When the reaction and post-treatment were carried out, FFA Granular zinc stearate with an analysis value of 0.8%, 1% remaining through a 20 mesh sieve, and 18% passing through a 100 mesh sieve was obtained.

Example 7 In place of calcium chloride in Example 1, 96% of magnesium sulfate (MgS04.7 ratio ○) was used, and all other conditions were the same as in Example 1. Reactions and post-treatments were carried out, resulting in FFA analysis. Granular magnesium stearate was obtained with a value of 8.2%, a 20 mesh filtration residue of 4% and a 100 mesh filtration fraction of 15%.

Example 8 50 qo of warm water 1.5 qo of calcium hydroxide (Ca(O
H) Add 2) 31g and 100g of stearic acid powder (same product as in Example 1) and react for 15 minutes while maintaining the liquid temperature at 50 to 55q0 and stirring thoroughly, and then reduce the liquid temperature. The temperature was raised to 60-65q 0, and 100 g of stearic acid powder was added and reacted for 1 minute under a light lamp.Then, the temperature was further raised to 70-75°C and reacted for 30 minutes to avoid unreacted components remaining. I did a rope frame.

When the obtained reaction slurry was treated in the same manner as in Example 1, the FFA analysis value was 0.2%, and the 20 mesh filtration residue was 68.
%, granular calcium stearate with a content of 0.2% passing through a 100 mesh filtration was obtained. Example 9 Add 31 g of calcium hydroxide and 2009 g of stearic acid powder to 1.5 g of hot water of 5,000 ml to bring the liquid temperature to 50 - 50 g.
While maintaining the temperature at 55q C, react for 25 minutes while thoroughly controlling the temperature, and then raise the liquid temperature to 70-75 oo and incubate for 3 minutes.
Performed a 0 minute fly worship.

When the obtained reaction slurry was treated in the same manner as in Example 1, the FFA analysis value was 0.3%, and the residue on the 20 mesh sieve was 5.
%, granular calcium stearate with a content of 12% passing through a 100 mesh filtration was obtained. Example 10 When barium hydroxide (Ba(OH)2/mother LO) 124 was used instead of calcium hydroxide in Example 8 and all other conditions were the same, the FFA analysis value was 0.3%.
, granular barium stearate was obtained with a 20 mesh filtration residue of 65% and a 100 mesh filtration fraction of 0.1%.

Example 11 When barium hydroxide 124 was used instead of calcium hydroxide in Example 9 and all other conditions were the same, FFA analysis value was 0.2%, 20 mesh filtration residue was 5.
%, granular barium stearate with a content of 10% passing through a 100 mesh filtration was obtained.

Example 12 To 55 q○ of warm water, add 32 ml of calcium hydroxide and 200 ml of pure palmitic acid powder to bring the liquid temperature to 55 ml.
While maintaining the temperature at ~60q0, let the reaction take place for 25 minutes with sufficient care, and then raise the liquid temperature to 70~75oo for 3 minutes.
I performed a female azusa for a long time.

When the obtained reaction slurry was treated in the same manner as in Example 1, the FFA analysis value was 0.1%, and the 20 mesh filtration residue was 2.
%, granular calcium palmitate with a content of 14% passing through a 100 mesh filtration was obtained.

Example 13 When lithium hydroxide (LjOH, raw ○) was used instead of calcium hydroxide in Example 9, and all other conditions were the same, the FFA analysis value was 0.1%, and the 20 mesh filtration remained. min 3%, 100 mesh filtration min 15
% of granular lithium stearate was obtained.

Example 14 When zinc hydroxide (Zn(OH)2) was used instead of calcium hydroxide in Example 9 and all other conditions were the same, the FFA analysis value was 1.5% and the 20 mesh filtration was Remaining 15%, 100 mesh filtration 20%
of granular zinc stearate was obtained.

Comparative example 1 (2 of the total amount of fatty acids at a temperature below the melting point of fatty acids)
(When reacting 0%) Calcium chloride (CaCI) was added to 1.5 liters of 5,000 ml of warm water and dissolved.
Add 40 minutes of commercially available stearic acid powder (same as in Example 1) to this, stir thoroughly, and then lower the liquid temperature to 50 to 5500.
While maintaining the temperature at
Raise the temperature to 0 to 6,500, add commercially available stearic acid powder, and add 105% pine% sodium hydroxide aqueous solution while performing prayer.
It was added dropwise for 8 minutes to react.

The temperature was further raised to 70 to 7yo, and the mixture was incubated for 30 minutes. The reaction products obtained were irregular in size and shape, ranging from the size of a thumb to the size of a red bean. As a result of processing the reaction slurry in the same machine as in Example 1, the amount remaining through the 28 mesh filtration was 94%, the amount passing through the 100 mesh filtration was 0.2%, and the FFA analysis value was 4.8%. This is because the absolute amount of calcium stearate produced in the first stage reaction is small, that is, a small amount of calcium stearate forms a core, and a large amount of calcium stearate produced later adheres to the surroundings, resulting in coarse particles. Seem. Comparative Example 2 (When all of the fatty acids were reacted at a temperature above their melting point, that is, when 0% of the total amount of fatty acids was reacted at a temperature below the melting point of the fatty acids) 65
Add 46 tons of calcium chloride to 1.5 tons of q0 warm water and dissolve it, add 200 tons of commercially available stearic acid to it, perform sufficient prayer, and add 132 tons of 22% sodium hydroxide aqueous solution under mock worship. The mixture was added dropwise for 20 minutes to react.

After 3 days of heating, the resulting slurry was treated in the same manner as in Example 1.
Mesh filtration amount: 0.1%, FFA analysis value: 2.7%
of calcium stearate was obtained.

This product is produced by reacting stearic acid in the form of oil droplets formed by being poured into an aqueous calcium chloride solution, and the FFA analysis value is high because unreacted stearic acid remains inside the particles. It is estimated to be. Method: Examples 1-1
4. The commercially available stearic acid powder used in Comparative Examples 1 and 2 has a melting point of 55 to 6000.

Claims (1)

[Claims] 1. In a reaction in which caustic alkali is added to a mixture of a fatty acid that is solid at room temperature and has a melting point of 90°C or lower and an aqueous solution of an inorganic metal salt, the total amount of fatty acids is reduced at a temperature lower than the melting point of the fatty acid. A method for producing granular metal soap, which comprises reacting 40 to 100% of the fatty acid, and then reacting the remainder at a temperature higher than the melting point of the fatty acid. 2. A method in which a fatty acid that is solid at room temperature and has a melting point of 90°C or less and a metal hydroxide powder are reacted in water, in which 40 to 100% of the total amount of fatty acids is reacted at a temperature below the melting point of the fatty acid. 1. A method for producing granular metal soap, which comprises reacting at a temperature above the melting point of residual fatty acids.