JPS6023339A - Production of metallic soap - Google Patents

Abstract

PURPOSE:To produce a metallic soap, without leaving unreacted raw materials nor producing by-products, by adding one or more kinds of aluminosilicate compounds to the reaction system, and reacting an aliphatic monocarboxylic acid with the oxide or hydroxide of a metal in water. CONSTITUTION:A metallic soap (e.g. calcium stearate) is produced by reacting an aliphatic monocarboxylic acid such as caprylic acid, caproic acid, capric acid, etc. directly with the oxide or hydroxide of a metal such as Li, Mg, Ca, Sr, Ba, etc. (preferably a univalent or bivalent metal) in water. The reaction is carried out in the presence of 0.01-40wt%, preferably 0.1-20wt%, based on the aliphatic monocarboxylic acid, one or more aluminosilicate compounds (preferably A, X, Y or P type zeolite). EFFECT:The water washing step can be eliminated. USE:Additive for plastics, pigment dispersant, wire drawing agent, mold release agent, additive to sand for shell mold process, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application and Prior Art] The present invention relates to a novel method for producing metal soap, and more particularly to a method for producing metal soap using a wet direct precipitation method.

Conventionally, wet metathesis precipitation, dry direct melting, or wet direct precipitation have been used as industrial methods for producing metal soaps.

The metathesis precipitation method is the most common method for producing metal soaps, and most of the metal soaps currently on the market are produced by this method. However, a drawback of this production method is that a large amount of water-soluble impurities is generated as a by-product, and washing with a large amount of water is required to remove all of these impurities. Since the dry direct melting method requires heating to a high temperature to complete the reaction, it has the disadvantage that the produced metal soap is thermally altered. In addition, the wet direct precipitation method is a method in which an aliphatic monocarboxylic acid is diffused in water, and then a metal oxide or hydroxide is added and reacted directly to obtain a precipitate. Compared to the melting method, it does not produce by-product impurities, so no cleaning is required, and compared to the dry direct melting method, it does not require high-temperature heating, so it has advantageous features such as no thermal deterioration. . However, the disadvantage of the conventional wet direct precipitation method is that it is very difficult to complete the direct reaction between the aliphatic monocarboxylic acid and the metal oxide or hydroxide. The monocarbo/acid or the metal oxide or hydroxide must be added in total excess.

In particular, it is common practice to add metal oxides or hydroxides to perJA to eliminate residual free aliphatic monocarboxylic acids. This stipulates that excess unreacted monocarboxylic acids (or oxides or hydroxides of metals in particular) may remain in the final product and, when added to plastics, for example, cause undesired blooming or puncturing. This often causes negative effects such as contamination of molds and poor dispersibility.

In order to prevent the products produced by this wet direct method from having these adverse effects, improvements can be made to promote the direct reaction, such as adding a surfactant, adding hydrogen peroxide during the reaction, and pressurizing the entire reaction system. However, all of these disclosed methods are unsatisfactory and do not lead to a sufficient solution.

[Structure of the invention]

The present inventors have conducted intensive research to improve the manufacturing method of metal soap by a wet direct precipitation method that eliminates these drawbacks, and as a result, we have found that aliphatic monocarboxylic acids and metal oxides or hydroxides are directly reacted in water. When producing metal soap, the reaction is accelerated by adding one or more aluminosilicate compounds to the reaction system in advance, and the reaction is accelerated by adding one or more aluminosilicate compounds to the reaction system, and the reaction is accelerated by adding one or more aluminosilicate compounds to the reaction system. The present invention is achieved in that the reaction can be completely completed without adding an excessive amount of .

[Conditions and effects]

The details of the production method of the present invention are as follows: In hot water, an aliphatic monocarboxylic acid and a small amount of aluminosilicate compound are mixed for a total stirring fraction of 1 or more, and during t, a metal oxide is mixed with water. This is a method to obtain an aliphatic monocarboxylate salt of the metal by adding an oxide and reacting directly at a temperature above the melting temperature of the aliphatic monocarboxylic acid, followed by dehydration and drying without washing. Depending on the reaction temperature and drying conditions. It can be obtained in either powder or granule form.

The metal soap produced by the method of the present invention has less residual unreacted metal oxides or hydroxides than those produced by the conventional wet direct precipitation method, and unlike the conventional double decomposition precipitation method, there is no washing process. can be omitted and no by-product impure contaminant ions remain, making it possible to obtain excellent leather products at extremely low cost.

The metal soap produced by the method of the present invention is mainly used as a plastics additive, a pigment dispersant, a wire drawing agent, a sand additive for fermold, a mold release agent, etc., compared to the metal soap produced by the conventional production method. Demonstrates the same or better performance.

In the production method of the present invention, by selecting the amount of the erialuminosilicate compound added depending on the application, the performance gold LD required depending on the application can be further improved. For example, by increasing the amount of aluminosilicate compound added, it can be added to plastics to exhibit better mold release, thermal stability, and electrical properties than conventional metal soaps.

The production method of the present invention is applicable not only to the production of metal salts of aliphatic monocarboxylic acids, but also to the production of aliphatic polycarboxylic acids, such as maleic acid, fumaric acid, citric acid, cepatic acid, lactic acid, dimer acid, etc. Aromatic carboxylic acid.

For example, it is applied to the production of water-insoluble metal salts of alkylbenzoic acid, oxybenzoic acid, salicylic acid, phthalic acid, terephthalic acid, trimellitic acid, etc., alicyclic carboxylic acids, such as naphthenic acid, abietic acid, resin acid, etc. You can also do that.

[Specific examples of raw materials and additives]

The aliphatic monocarboxylic acid referred to in the present invention has 8 to 30 carbon atoms.
Natural or synthetic even or odd saturated or unsaturated monocarboxylic acids with side chains in the structure.

OH group, ketone group, aldehyde group, or epoxy group), representative examples of which include cabrylic acid, caproic acid, capric acid, lauric acid,
Myristic acid, palmitin dl, stearic acid, alagic acid, hebutadecylic acid, behenic acid, oleic acid, elaidic acid, eruca linoleic acid, riluic acid, ricinol d, hydroxystearic acid, montanic acid, instearic acid, ebok 7 stearin Examples include acids and the like, and some of the carboxylic acids may be substituted with carboxylic acids other than aliphatic monocarboxylic acids.

Aluminosilicate compounds used in the present invention are natural or synthetic aluminosilicates, representative examples of which are aAA4 zeolite, type X zeolite, YIj1
Zeolite, mordenite, clinobutyrolite, analcite, wairakite.

natrolite, menrite, tomphrite, gonaldite, scolecite, rainbow/datonite, gismondite, rheumondite, nigawalite, erionite, ashcroftenite, hyurandite, stilbite, evistilbite, tachyardite, builipsite, damelinite, chabasite, Examples include faujasite and its metal-substituted products, preferably one or more of A4 zeolite, X-type zeolite, Y-type zeolite, and its metal-substituted products.

The aluminosilicate compound used in the present invention may be any metal-substituted aluminosilicate, but preferably an alkinosilicate substituted with the same metal as the metal soap to be produced or an aluminosilicate compound that is easily substituted with the same metal. good. In the latter case, a soluble salt of the same metal as the metal soap to be produced is necessary for metal displacement of the aluminosilicate compound added at the time of diffusion of the aliphatic monocarboxylic acid and the aluminosilicate compound in water. is added to replace the aliphatic monocarboxylic acid with a metal before reacting with the metal oxide or hydroxide.

Addition amount of aluminosilicate compound a is 0.01 to 40% by weight based on the aliphatic monocarboxylic acid, but preferably 0.
．． It is 1 to 20% by weight.

The metal oxide or hydroxide used in the present invention is directly reacted with an aliphatic monocarboxylic acid to form the metal soap. As iLi, Mg, Oa, Sr, Ba, Zn,
Cd, Az, Zr, Ou, Sn, Pb, IS
b, Or.

MOLW, Be, Oe, Mn, Fe1I Co, N1
One or more of the following oxides or hydroxides.

Alternatively, if necessary, a composite metal soap can also be produced using two or more aliphatic carboxylic acids and two or more metal oxides or hydroxides. Furthermore, if necessary, the existing production method of wet direct precipitation method and production method of double decomposition precipitation method may be used in combination.

Depending on the use of the method of the present invention, additives necessary for the use, such as other metal soaps, antioxidants, fillers, pigments, lubricants, etc., may be added beforehand or after the reaction is completed. can.

〔Example〕

The present invention will be explained in detail below using examples.

Example 1 Add 1,500 p of stearic acid ($300 manufactured by Shin Nippon Chemical Co., Ltd.) to 800 ml of water, heat to 80°C for 7 JI] to melt the stearic acid, and add calcium-substituted A4 zeolite (Nippon Chemical Co., Ltd. 1! Add 15'te and stir for 30 minutes, then add 4e of water. Next, gradually add the stirred and dispersed dispersion of calcium hydroxide (Junsei Kagaku #) 208.3ii'e to the 4th volume of water and stir. While stirring, raise the temperature to 90°C, and continue stirring for another 30 minutes after adding the entire amount 1.
Dehydrated and dried and contains Oa! Calcium stearate with an acid value of 6.7ins and an acid value of 0.1 was obtained.

Comparative Example 1 For comparison, stearic acid 15001i"i8.6 was added to water and heated to 80°C to melt the stearic acid, and while stirring, 413 water + C1 TIE was added to water + 208 calcium hydroxide while stirring. .3i was added and the constant dispersion liquid was gradually added, the temperature was raised to 90°C while stirring, the entire amount was added, stirring was continued for another 30 minutes, and the mixture was dehydrated and dried to obtain an Oa content of 6.8% by weight, acid A calcium stearate solution of 1i [1i 3.8 was obtained.

The acid value was 3.7 higher than that of the example.

Example 2 Lauric acid (Lauric acid P manufactured by Shin Nihon Rika) 2001 was
, 6-e water, heated to 65°C with stirring to stir lauric acid financial decomposition, and added to X-type Sl-IJ um zeolite (Nippon Kagaku JR) 4P' and continued stirring for 30 minutes. Then, add 0.62% of water and lower the temperature to 50℃, then add 1.6% of calcium chloride dihydrate. was added to replace the X-type sodium zeolite with the gold X-type calcium zeolite. Next, add calcium hydroxide as 1 to 0.11 water. is added and diffused while stirring, and this diffusion liquid is gradually added to the lauric acid diffusion liquid to directly react with the lauric acid. After the temperature was set to 65°C, stirring was continued for 30 minutes and dehydrated and dried to obtain Oa containing N t 9.1% by weight, acid + 111i 0
．． Calcium laurate No. 7 was obtained.

Example 3 Stearic acid ($300 manufactured by New Japan Chemical Co., Ltd.) 200 Pi
Add to O, 6,, e water and stir and heat from B to 80'C.
Warmed to stearic acid? After melting and diffusing in water, add 4A type sodium zeolite (Nihon Kagaku Shu 4i) and stir for 30 minutes, then add 0.6 n of water to bring the temperature to 50°C. Next, add 1.5 n of magnesium sulfate heptahydrate. 4?t-0,1
,/3 of water and then gradually added to 2i, 5ylo, za of magnesium hydroxide by stirring and dispersing in water. To accelerate the reaction, the temperature was gradually raised to 90° C. and stirring was continued for 60 minutes. Thereafter, a washed precipitate 2 was dehydrated and dried to form a Mg-containing precipitate 4. l nail t%, acid value 0
．． Magnesium stearate No. 6 was obtained.

Comparative Example 2 For comparison, stearic acid 2oOtk was used in the same manner as in Example 3.
Add 0.6-e of water and heat to 8°C while stirring to melt stearic acid and diffuse it into the water, then add 0.6-e of water.
13 and bring the temperature to 50°C.

Next, magnesium hydroxide 21.5y-i0.2J! Stir and disperse in the water and gradually add. In order to promote the reaction, the temperature was gradually raised until the temperature reached 90°C in total, and stirring was continued for 60 minutes. After washing, # was removed and dehydrated to reduce the Mg content to 4.
．． Magnesium/Um stearate, 1% by weight, acid value 3.7
-I got it. The acid value of the magnesium stearate produced in this comparative example was 3.1 higher than that of the magnesium stearate produced in Example 3.

Example 4 Stearic acid 2005' was added to 0.6-8% water and heated to 80°C while stirring, zinc-substituted type A zeolite (Nippon Kagaku #) 10? After stirring for 30 minutes, add zinc oxide (
Mitsui Kinzoku) 29.3Pk 0.1 in advance! Stir and disperse in the water and gradually add. After addition, continue stirring 9.
After heating to 0℃ and stirring for 30 minutes, add water o, 3
-e k 7111 and then lowered the temperature to 70"C, and after stirring for an additional 30 minutes, the precipitate was dehydrated and dried to reduce the Zn content to 1.
Zinc stearate with O07% by weight and an acid value of 0.2 was obtained.

Comparative Example 3 In the same manner as in Comparative Example 4, 200 y of stearic acid was added to 0.62 ml of water and heated to 80°C while stirring, and 0.8 P of zinc oxide (5% excess) was added in advance. 0.
Stir and disperse in the water from Step 11 and gradually add.

After the addition, the mixture was heated to 90°C with continued stirring, stirred for 30 minutes, then 0.3 A k of water was added, the temperature was lowered to 70°C, and after stirring for another 30 minutes, the precipitate was dehydrated and dried. , lead stearate containing Zn, Ti, %, and acid value of 1.5 was obtained. In Comparative Example 3, even though 5 tons of zinc oxide was added in excess compared to the zinc stearate of Example 4, the reaction was not completed and the acid value was as high as 1.5. Salivary lead content was also 3 more.

Example 5 12-hydroxystearic acid (also known as hydrogenated castor fatty acid)
285ii was added to 0.81% of water and heated to 80°C while stirring to melt and disperse. Next, 5A type calcium-substituted zeolite 1517' was added and after stirring for 30 minutes, water was added to 5pt.
- In addition, the temperature was set at 60°C.

Next, after stirring and dispersing 33.45"io of hydroxide in 2-g of water, gradually add it and heat it up to 90℃ while stirring for 30 minutes. Next, add water. The temperature was set to -70°C, and stirring was continued for an additional 60 minutes.The formed precipitate was dehydrated and dried to reduce the Oa content to 6.1.
% fc of calcium 12-hydroxystearate with an acid value of 0.7.

Example 6 Stearic acid was added to 100 kN'f of 25 Q-6 water and heated to 80°C with stirring to melt and diffuse the stearic acid, then 1 kl of A-type sodium zeolite was added and stirred for 30 minutes. 4.5 kt of zinc oxide is pre-suspended in 250 swamps of water and then added gradually. After addition, stirring was continued for 30 minutes, 2oo and 81 grams of water was added, the temperature was lowered to 1 and 60°C, and 9.6 kilograms of calcium hydroxide was added to 1,002 grams of water in advance! 8 while adding the suspension in 1.
Heat the temperature to 5℃. After continuing stirring for another 60 minutes, it was dehydrated and dried to have a Zn content of 3.6% by weight and an Oa content of 4.0% by weight.
8ii-1t%, acid value 0. ; A zinc stearate-calcium co-precipitated composite metal soap was obtained.

In the dehydration and drying steps, the precipitate obtained according to the present invention can be shaped into powder, fM grains, flakes, etc. depending on the process conditions, such as heat melting, spray drying, fluidized drying, etc.

Junjin Nitto Kasei Kogyo Co., Ltd. Kosei Co., Ltd. Agent Sakamoto Sakae − 263-

Claims (1)

[Claims] +l) When producing a metal soap by directly reacting an aliphatic monocarboxylic acid with a metal oxide or hydroxide in water, one or more aluminosilicate compounds are added to the reaction system. 12
A method for producing metal soap, characterized in that more than one species is present. (2) The method according to claim 1, wherein the metal oxide or a-hydroxide is a monovalent or divalent metal oxide or hydroxide. (3) The method according to claim 1, wherein the aluminosilicate is one or more types of A-type, X-type, Y-type or Hp-type zeolite.