JPH0132812B2 - - Google Patents

Description

[Detailed description of the invention]

In the present invention, copper dicarboxylate is produced from dicarboxylic acid, alkali metal hydroxide, and inorganic copper salt by double decomposition reaction, and when the produced copper dicarboxylate precipitate is separated by filtration, decantation, etc., the general formula (However, R represents hydrogen or a methyl group.) Concerning a method for producing copper dicarboxylate using a polymer of a monomer represented by the formula or a copolymer of a monomer of the above general formula and acrylamide as a separation aid, The purpose of this is to use a separation aid to turn fine dicarboxylic acid copper precipitates into flocs, thereby increasing the overspeed or sedimentation rate and improving production efficiency. Copper dicarboxylate, such as copper salts such as terephthalic acid and fumaric acid, retain copper ions with strong bactericidal power in a stable state as a dicarboxylate, and their bactericidal action is sustained over a long period of time.
It has a high protective fungicidal effect and is extremely useful as an agricultural fungicide. In addition, contamination by mold and other microorganisms that occur on the paint film when mixed with paint,
Damage can be prevented. Conventionally known manufacturing methods, such as the method described in US Pat. No. 3,623,896 or Ind.Eng.
Chem.Prod.Res.Develop., Vol.9, No.3, 1970,
In the method described on pg.408, copper dicarboxylate is first completely dissolved in an aqueous solution of alkali metal hydroxide such as caustic soda to create an aqueous solution of alkali metal dicarboxylate; A copper dicarboxylate is obtained by dissolving a water-soluble inorganic copper salt in water to form an aqueous solution, and adding and mixing one of the two with the other. However, the precipitate of copper dicarboxylate produced as a result of the double decomposition reaction is extremely fine, and it cannot be removed using conventional industrial filtration techniques such as a vacuum filtration machine or pressure filtration machine, or separation techniques such as a centrifugal separator. Even using technology, it is virtually impossible to separate the precipitate from the water within a short time after its formation. Therefore, in the conventional method, after the copper terephthalate precipitate is formed, it is left as is for 8 to 12 hours.
The crystals of the copper dicarboxylate hydrate are allowed to grow for a period of time, and separation is carried out by waiting for the crystal grains to grow to a size that allows the precipitate to be easily separated from the water using techniques such as suction filtration. It's on. In such conventional methods, it takes a long time from the time the copper dicarboxylate precipitate is formed to the next step, which is separation of the precipitate by filtration, which impairs the continuity of the operation. This point has been a problem in terms of manufacturing efficiency. The present invention involves producing a precipitate of copper dicarboxylate through a double decomposition reaction between an aqueous solution of an alkali metal salt of a dicarboxylate and an aqueous solution of a water-soluble inorganic copper salt, and immediately separating this precipitate from a reaction solution without stagnation by an advanced technique. As a method, an aqueous solution of a homopolymer of the monomer represented by the general formula () or a copolymer of this and acrylamide is added to the reaction solution after precipitation, and the precipitate of copper dicarboxylate is made into a floc-like form. Immediately after formation, the precipitate can be separated from the aqueous layer of the reaction solution very easily and in a short time by separation techniques such as filtration or decanting. Cationic flocculants such as polymers of monomers represented by the general formula ( It has been considered inappropriate since then. However, the present inventor has discovered that a polymer of the monomer represented by the general formula (), such as a quaternized salt of dimethylaminoethyl methacrylate, is extremely effective in small amounts in forming a floc of copper dicarboxylate precipitate. We have discovered that this is the case and have completed the present invention. Furthermore, copper dicarboxylate exhibits excellent effects against many diseases as an agricultural fungicide, etc., but the separation aid of the present invention, that is, a homopolymer of vinyl monomers represented by the general formula (), or a combination of this and acrylamide According to Japanese Patent Application Laid-Open No. 54-32624, which describes the separation aid itself, the copolymer is described to have an excellent control effect against mosaic viruses of tobacco, cucumber, and tomato, and is used as an agricultural fungicide. The separation aid of the present invention is suitable as an auxiliary agent used in the production of copper dicarboxylate. In the method for producing copper dicarboxylate by metathesis reaction from an aqueous solution of an alkali metal dicarboxylate and an aqueous inorganic copper salt, the precipitate of copper dicarboxylate is separated from the aqueous layer of the reaction solution, and then the precipitate is washed with water, reslurried, It is common to go through the steps of drying with a spray dryer and pulverizing with a micronizer, but the separation aid used must not cause any hindrance during these steps. The separation aid used in the present invention, for example, a polymer such as a quaternized salt of dimethylaminoethyl methacrylate, does not pose any hindrance to the process after copper dicarboxylic acid precipitation and separation. The particle size of the copper terephthalate powder finely pulverized with a small micronizer was 1.90 microns for the product obtained by a manufacturing method that does not use a separation aid, whereas the particle size of the copper terephthalate powder, which is a separation aid used in the present invention, was 1.90 microns. The product using the polymer of the quaternized salt of the rate was 1.35 microns. Copper dicarboxylate is also highly effective as an agricultural fungicide in preventing many diseases, but when copper dicarboxylate is used as a hydrating agent,
The dispersibility of a product in water also affects its medicinal efficacy and drug damage. When we tested the dispersibility in water of copper terephthalate powder finely pulverized using the micronizer mentioned above and adding sodium ligninsulfonate (trade name: Sun-Etsukiss) as a dispersant, we found that dimethylaminoethyl methacrylate quaternized The dispersibility of products obtained using polymers such as salts was superior to that of products obtained without the use of polymers. Furthermore, this copper terephthalate product was actually used as an agricultural fungicide, and a test was conducted to control scab disease on cucumbers. As a result, a product obtained using a polymer of dimethylaminoethyl methacrylate quaternary salt as a separation aid showed an effect equal to or better than a product obtained without using it. Separation aid used in the present invention,
For example, a homopolymer such as dimethylaminoethyl methacrylate quaternized salt or a copolymer of this monomer and acrylamide is a product obtained by ordinary radical polymerization and can be obtained as a flocculating precipitant. The amount of these separation aids used in the present invention may be from 0.1 to 5.0% by weight based on the calculated yield of copper dicarboxylate obtained per batch. The separation aid is added as an aqueous solution of about 0.1 to 5.0% by weight to the reaction solution after the copper dicarboxylate precipitate is formed, and is stirred to form a precipitate floc. Specific examples of the separation aid used in the present invention include methyl chloride quaternary salts of polymers of dimethylaminoethyl (meth)acrylate or copolymers of these and acrylamide. Dicarboxylic acids include terephthalic acid, isophthalic acid,
Phthalic acid, fumaric acid, maleic acid, marzipic acid,
It refers to glutamic acid, aspartic acid, etc.; inorganic copper salts include copper sulfate, cupric sulfate, cupric chloride, etc., and their hydrated salts; alkali metals include:
Refers to caustic soda, caustic potash, etc. Next, examples of the present invention will be shown. Example 1 43 g (1 mol) of caustic soda with a purity of 93% is dissolved in water to make a total volume of 1 liter, and 83 g (0.5 mol) of terephthalic acid is dissolved in this. Except for 99% purity
Dissolve 252g (1 mol) of copper sulfate pentahydrate in water,
The total volume is 1 liter. 50ml of this copper sulfate aqueous solution
While stirring, add sodium terephthalate aqueous solution.
Add 100 ml to form a precipitate of copper terephthalate. After continuing to stir for 5 minutes, 50 ml of a 0.1% by weight aqueous solution of coagulation precipitant A listed in Table 1 was added and stirred for 5 minutes. Transfer this suspension onto a 7.6 cm diameter Buthunerto plate covered with Toyo Paper No. 2 (7 cm diameter).
Suction was performed using an aspirator for 5 minutes. After 5 minutes, suction was stopped, the liquid in the suction bottle was transferred to a graduated cylinder, and the amount of liquid was read. Similar tests were conducted on other flocculating precipitants shown in Table 1. The results are shown in Table 1.

【table】

[Table] Example 2 100 ml of the sodium terephthalate aqueous solution prepared in Example 1 was taken and stirred, and 50 ml of the copper sulfate aqueous solution also prepared in Example 1 was added thereto to form a precipitate of copper terephthalate. After continuing stirring for 5 minutes, 60 ml of a 0.1% by weight aqueous solution of coagulation precipitant A listed in Table 2 was added and stirred for 5 minutes. Thereafter, this suspension was transferred to a 1 liter measuring cylinder, water was added to bring the total volume to 1 liter, the suspension was well stirred with a glass rod, and then left to stand. After 5 minutes, the volume of the precipitate that had settled to the bottom of the graduated cylinder was read from the scale of the graduated cylinder. Similar tests were conducted on other flocculating precipitants shown in Table 2. The results are shown in Table 2.

【table】

[Table] *Product names are the same as in Table 1 **Sedimentation volume after 30 minutes The composition of the separation aid of the present invention used in Examples 1 and 2 is shown. Coagulation precipitant A Coagulating precipitant B Same as above A Coagulating precipitating agent C Test Example Copper terephthalate produced using the coagulation precipitant A of Example 1 was washed with water, dried, and crushed in a mortar. This copper terephthalate was further finely ground using a micronizer "Micron Master" model 02-505 manufactured by The Jet Pulverizer Co., Ltd.
Particle size was measured using a Fisher Subsieve Sizer manufactured by Fisher Scientific. The average particle size of copper terephthalate produced using coagulation precipitating agent A was 1.35 microns, and the average particle size of copper terephthalate produced without using coagulating precipitant A was 1.90 microns. Using this finely pulverized copper terephthalate, a control test for scab disease of cucumbers was conducted. Aqueous suspensions of copper terephthalate prepared at copper concentrations of 360 ppm and 540 ppm were sprayed onto potted cucumbers using a glass sprayer, and air-dried. The next day, the seeds were spray-inoculated with scoliosis fungi and left in a heat iron house under humid conditions of 17-23°C for 5 days after contact to form lesions. In a pot test of four consecutive plots, the number of leaves with lesion formation was examined and the rate of inhibition of lesion formation was determined. Ta.

Claims (1)

[Claims] 1. When copper dicarboxylate is produced from a dicarboxylic acid, an alkali metal hydroxide, and an inorganic copper salt by a metathesis reaction, and then the precipitate of the copper dicarboxylate produced is separated from the aqueous layer, the general formula (However, R represents hydrogen or a methyl group.) Copper dicarboxylate, characterized in that a polymer of the monomer represented by the formula or a copolymer of the monomer of the above general formula and acrylamide is used as a separation aid. Production method.