JPS6340414B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an improved process for producing high purity cobalt or zirconium soaps in high yields. Cobalt soap is used as a drying accelerator for oil-based paints, alkyd paints, etc., as a drying agent for printing inks, and as a bond strengthening agent between the steel and rubber components of radial tires.Zirconium soap is used as a drying accelerator for the above paints and as a dye imparting agent. etc. Cobalt or zirconium soap (hereinafter referred to as Co or Zr soap) has conventionally been produced by subjecting an alkaline soap and a cobalt or zirconium salt to a double decomposition reaction in an aqueous solution at 90 to 100°C, and separating the resulting grease-like or powdered soap by standing. It has been produced by separating the soap from the aqueous phase using a method such as washing, washing with water to remove impurities such as sodium soap and sodium sulfate, and then dehydrating it by heating. However, the above method tends to contain impurities and is difficult to remove even by washing with water. As a method to overcome the drawbacks of the above-mentioned methods, a new method is disclosed in JP-A-53-137857, in which an alkali soap and a cobalt salt are subjected to a double decomposition reaction in an aqueous solution in the presence of an organic solvent. That is, the method described in the above publication uses a system in which an aqueous solution and an organic solvent coexist, and the produced cobalt soap is transferred to the organic solvent phase for separation and recovery, thereby facilitating the operation and further improving the purity. However, since the above technology is a technology for producing metal soap in a coexistence system of an aqueous solution and an organic solvent, depending on the type of metal soap, especially the type of organic acid group, that is, organic carboxylic acid group, in the reaction system. When the concentration of metal soap in the emulsion phase exceeds a certain value, an emulsion phase may be formed between the aqueous phase and the organic phase, or in some cases, the entire phase may become an emulsion. contains metal soap, which is a product.
There is a drawback that the yield tends to decrease. In particular, the above-mentioned emulsion contains fatty acids with 12 or more carbon atoms.
This phenomenon is likely to occur in the production of Co or Zr soaps, particularly when the reaction is carried out in a relatively concentrated reaction system, and a similar phenomenon may also occur depending on the conditions in the production of naphthenic acid Co or Zr soaps. To prevent this, it is possible to increase the amount of organic solvent and relatively lower the concentration of Co or Zr soap in the solvent, but operations such as distillation that are performed when separating Co or Zr soap from the solvent are This becomes complicated and is not desirable from the viewpoint of productivity. The present invention is based on the results of intensive studies to solve the above problems, and according to the method of the present invention, high purity Co or Zr soaps of saturated or unsaturated fatty acids or alicyclic carboxylic acids can be obtained. You can produce things efficiently. That is, the method of the present invention uses an alkali soap and a cobalt or zirconium salt as raw materials and the corresponding Co or Zr
A method for producing Co or Zr soap, characterized in that the production of soap is carried out in the presence of an organic solvent phase and a compound represented by the general formula R-(R'-O-) _o OH in an aqueous liquid phase. It is something. The content of the present invention will be explained in detail below. The alkaline soap used in the present invention is an alkali metal salt of an organic acid, and the organic acid has a carbon number of 12 to
22 saturated or unsaturated fatty acids or cycloaliphatic carboxylic acids. Specifically, examples of organic acids include:
Saturated fatty acids include lauric acid, tridecanoic acid,
myristic acid, pentadecyl acid, palmitic acid,
Margaric acid, stearic acid, arachidic acid, behenic acid, 2-methyltetradecanoic acid, 2-methylpentadecanoic acid, 2-methylheptadecanoic acid, and unsaturated fatty acids include lindelic acid, matskoic acid, oleic acid, elaidic acid, and linoleic acid. Acids, linolenic acid is exemplified, depending on the target Co or Zr soap,
One type or a mixture of two or more types is selected. The above-mentioned fatty acids may be either synthetic, vegetable oils or animal fats separated from plants or animals, or those obtained by chemically treating natural raw materials such as tall oil. Examples of alicyclic carboxylic acids include naphthenic acid, which is the main component of petroleum acids. Examples of the cobalt salt or zirconium salt as a raw material used in the present invention include salts having a sulfuric acid group, a nitric acid group, a hydrochloric acid group, a carbonic acid group, and an acetic acid group, and these are collectively referred to as Co or Zr salts. Therefore, the Co or Zr soap referred to in the present invention is a salt formed by bonding cobalt or zirconium to the above-mentioned organic acid, such as cobalt stearate, zirconium stearate, cobalt naphthenate, zirconium naphthenate, cobalt oleate, Examples include zirconium oleate alone or in mixtures. The organic solvent used in the present invention is not particularly limited as long as it dissolves Co or Zr soap, and suitable examples include mineral turpentine, toluene, xylene, modified naphtha, and naphthenic solvents. In the production of Co or Zr soap, as the reaction of raw materials progresses, they are eventually dissolved and transferred to the organic solvent phase, which increases the specific gravity of the organic solvent phase, reducing its separability from the aqueous phase and causing reaction products. From the viewpoint of ease of distillation separation from the organic solvent, a solvent with a low specific gravity, low boiling point, and excellent solubility is preferred. The main feature of the present invention is that the reaction is carried out in the presence of a compound represented by the general formula RO-(R'O-) _o H in the reaction system. Here, R is an alkyl group having 1 to 6 carbon atoms or a phenyl group, and R' is -CH ₂ -CH ₂ - or -
Hydrocarbon group represented by CH(CH ₃ )—CH ₂ —, n
is an integer of 1 or 2. Specifically, methyl cellosolve, ethyl cellosolve, n-propyl or
iso-propyl cellosolve, n-butyl cellosolve, sec-butyl cellosolve, t-butyl cellosolve, n-hexyl cellosolve, phenyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether,
Examples include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, and diethylene glycol monophenyl ether. One or more of the compounds represented by the above general formula may be added to the reaction system in an appropriate amount before the reaction starts, during the reaction progress, or after the reaction ends. The amount added is determined depending on the degree of suppression of emulsion generation at the reaction completion stage. In other words, whether to completely suppress or partially allow generation is related to the required purity of the Co or Zr soap to be produced, and the amount added should be determined accordingly, and from an economic standpoint, the amount added should be reduced as much as possible. It is preferable to let The amount of organic solvent used in the reaction system is relatively large,
If the concentration of Co or Zr soap is to be relatively reduced, the amount added can be reduced, but in order to simplify the organic solvent separation process in the subsequent process, it is preferable to use a system as concentrated as possible, so in this case, the amount added should be reduced. What is necessary is to relatively increase . Taking the production of cobalt stearate soap as an example, in a system where the cobalt concentration in the organic solvent is about 0.5 to 1.5 wt%, butyl cellosolve is 1.0 to 2.0 wt% or more relative to the organic solvent, and the cobalt concentration is 2.0 to 3.0 wt%. 5.0~ if wt%
By adding about 10.0wt%, generation of emulsion can be prevented. The content of the present invention will be specifically explained below with reference to Examples and Comparative Examples. Example 1 Stearic acid (acid value 197 mg
After adding 90g of KOH/g) and stirring at 80℃ for 30 minutes, add 26g of n-butyl cellosolve to 350g of xylene.
A solution in which was dissolved was mixed with the above aqueous solution, and while stirring, 142 g of an aqueous cobalt sulfate solution (containing 6.42 wt% as cobalt content) was added, and the mixture was stirred at 80° C. for 30 minutes. After the stirring was completed, the mixture was transferred to a glass column (inner diameter 30 mm, height 2500 m/m) having a pot at the bottom, kept at 80° C., and allowed to stand for 30 minutes. During this time, the rate of rise of the aqueous phase and xylene phase interface in the column was measured over time. Immediately after transferring to the column, the interface rapidly continued to rise (ie, separated), and after 20 minutes, complete separation (100% separation) was achieved. The xylene phase was also transparent. The water content in the xylene phase was 0.30 vol%, and the n-butyl cellosolve content in the aqueous phase was 0.53 wt%. Comparative Example 1 Stearic acid (acid value 197 mg
After adding 50g of KOH/g) and stirring at 80℃ for 30 minutes, 453g of xylene was mixed with the above aqueous solution, and while stirring, 79g of cobalt sulfate aqueous solution (as cobalt content) was added.
6.42wt%) was added and stirred at 80°C for 30 minutes. After stirring, the mixture was transferred to a glass column in order to measure the rate of interface rise, etc. using the method described in Example 1.
I left it still. In this case, all phases remained in an emulsified state and no separation occurred even after 3 hours. Example 2, Comparative Example 2 Cobalt salt (cobalt sulfate) or zirconium salt (zirconium sulfate) was reacted with stearic acid, lauric acid, naphthenic acid (acid value 200 mgKOH/g), or tall oil fatty acid, and various compounds (additives ) and the results of investigating the additive concentration in the aqueous phase after reaction are shown in the table.

【table】

【table】

Claims (1)

[Claims] 1. When producing cobalt soap or zirconium soap by reacting an alkali soap and cobalt salts or zirconium salts in an aqueous liquid phase,
An organic solvent is added to the aqueous liquid phase and the following general formula: RO-(R'O-) _o H (where R is an alkyl group having 1 to 6 carbon atoms or a phenyl group, and R' is -CH ₂ -CH ₂ -or-CH
Hydrocarbon group represented by (CH ₃ )—CH ₂ —, n
is an integer of 1 or 2. 1.) A method for producing cobalt soap or zirconium soap, characterized in that the method is carried out in the presence of one or more selected from the group of compounds represented by: