JPS6360014B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention produces copper dicarboxylate from dicarboxylic acid, alkali metal hydroxide, and inorganic copper salt by double decomposition reaction, and separates the resulting copper dicarboxylate precipitate by filtration, decantation, etc. It is involved in the production process of copper dicarboxylate as an auxiliary agent, and its purpose is to increase overspeed, sedimentation rate, etc. by making the precipitate floc-like, thereby 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 also has a high protective and bactericidal effect, making it extremely useful as an agricultural fungicide. It can also be added to paints to prevent contamination and damage caused by mold and other microorganisms that occur in paint films. 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, dicarboxylic acid is first completely dissolved in an aqueous solution of an alkali metal hydroxide such as caustic soda to create an aqueous solution of an alkali metal dicarboxylic acid salt; A copper dicarboxylate is obtained by dissolving the 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 allowed to stand for 8 to 12 hours to grow crystals of copper dicarboxylate hydrate, and then the precipitate can be easily removed by techniques such as suction filtration. Wait for the crystal grains to grow to a size that allows them to separate from the water.
Separation is taking place. In this way, in the conventional method, it takes a long time to produce a precipitate of copper dicarboxylate through a double decomposition reaction and then move on to the next step, which is separation of the precipitate by filtration, resulting in poor continuity of operation. This caused a problem in manufacturing efficiency. The present invention involves producing a precipitate of copper dicarboxylate through a double decomposition reaction from an aqueous solution of an alkali metal dicarboxylate and an aqueous solution of a water-soluble inorganic copper salt, and immediately separating this precipitate from the reaction solution without stagnation by an advanced technique. As a method, an aqueous solution of a polyacrylamide-based coagulating precipitant is added to the reaction solution after the precipitate is formed, and the precipitate of copper dicarboxylate is made into a floc. The precipitate is separated from the aqueous layer of the reaction solution in a short period of time. In the production method for precipitating copper dicarboxylate by mixing an aqueous solution of alkali metal dicarboxylate and an aqueous solution of inorganic copper salt, the final reaction solution is
The pH depends on the liquid properties of the inorganic copper salt aqueous solution used, and when using an aqueous solution of copper sulfate or copper nitrate, which are the most commonly used inorganic copper salts, the pH of the reaction solution after copper dicarboxylate precipitate is Liquidity is pH4-
It becomes a weak acidity of 5. However, inorganic flocculants are said to be effective in the weakly acidic to neutral range.
For example, polyaluminum chloride or ferric chloride were ineffective in promoting precipitation of copper dicarboxylate. The inventors have discovered that a polyacrylamide-based coagulating precipitant is extremely effective in forming flocs of copper dicarboxylate precipitates in small amounts. In addition, this polyacrylamide-based coagulating precipitant shows an excellent flocculating effect, but when copper dicarboxylate is used as a hydrating agent in the agricultural and industrial fields, the dispersibility of the product in water affects the medicinal efficacy and drug damage. It is also important to consider the situation thoroughly. When a surfactant, specifically, sodium ligninsulfonate (trade name: Sunextract) was added as a dispersant to the above-mentioned copper terephthalate powder finely pulverized with a micronizer, the dispersibility in water was tested. The dispersibility of the product using the polyacrylamide coagulation precipitant of the present invention was superior to that of the product not using it. Furthermore, this copper terephthalate product was actually used as an agricultural fungicide, and tests were conducted to control late blight on tomatoes and scab on cucumbers. As a result, no adverse effects were found in the products obtained using the polyacrylamide flocculant as a separation aid compared to the products without the use. Examples of the polyacrylamide coagulation and precipitant used in the present invention include polyacrylamide, a partial hydrolyzate of polyacrylamide, and a copolymer of acrylamide and an acrylate. These are products obtained by ordinary radical polymerization, and are available as coagulation and precipitating agents. The partially hydrolyzed product of polyacrylamide is obtained by partially hydrolyzing the amide group of polyacrylamide, and is represented by the following structural formula. It is also called modified polyacrylamide. The polyacrylamide coagulation precipitant of the present invention is
It is possible and convenient to use commercially available products. Although some of these specific products are illustrated, the present invention is not limited to these only. As a polyacrylamide coagulation precipitant, Sunfloc N-
OP and 50P (Sanyo Chemical Industries, Ltd.), Aron Flock N
Series (Toagosei Chemical Industry Co., Ltd.), Highset 613
Ya66 (Daiichi Kogyo Seiyaku Co., Ltd.), Cliff Lock LN-111
and P-111 (Kurita Industries, Ltd.), Sumifloc FN series (Sumitomo Chemical Industries, Ltd.), Himoroku (Kyoritsu Organic Industrial Research Institute, Ltd.), etc., which are polyacrylamide partial hydrolyzate coagulation precipitants. Examples include Hiset P-711 and 67 (Daiichi Kogyo Seiyaku Co., Ltd.), Kurifrock PA series (Kurita Industries, Ltd.), and Sunfrost P-711 and 67 (Daiichi Kogyo Seiyaku Co., Ltd.).
AH200P and AB-100P (Sanyo Chemical Industries, Ltd.), Separan AP-30 and PG-2 (Dow Chemical), Diafloc AP335 (Nitto Chemical Co., Ltd.), Sumifloc FA
series (Sumitomo Chemical Industries, Ltd.), etc. In addition, as a copolymer coagulation precipitant of acrylamide and acrylate, Aronfloc A-101 (Toagosei Kagaku Kogyo Co., Ltd.), Flock Ace A-200 (Hamano Kogyo Co., Ltd.), and Arafloc (Arakawa Chemical Co., Ltd.) ), Kayafrock (Nippon Kayaku Co., Ltd.), etc. The amount of these separation aids to be used in the present invention is about the same as that of a polyacrylamide coagulation precipitant, even if it is a coagulation precipitant such as polyacrylamide partial hydrolyzate. 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 undergo the steps of drying with a spray dryer and pulverization with a micronizer, but the separation aid used must not pose any hindrance during these steps. The polyacrylamide flocculant does not cause any trouble in the process after copper dicarboxylate precipitation and separation. For example, the particle size of copper terephthalate powder that is finely pulverized with a small micronizer after drying is similar to that without using a separation aid. The size of the product obtained using the manufacturing method was 1.90 microns, while the product obtained using a polyacrylamide flocculant was 1.25 microns, and the product using a polyacrylamide partial hydrolyzate flocculant was also 1.25 microns. .
Further, copper dicarboxylate is used as an agricultural fungicide to prevent many diseases, and is preferably used in an amount of 0.1 to 5.0% by weight based on the calculated yield per batch of copper dicarboxylate.
The separation aid can be used as an aqueous solution of 0.1 to 5.0% by weight.
It is added to the reaction solution after the copper dicarboxylic acid precipitate has been formed and stirred to form a floc of precipitate.
There is no problem with the timing of addition, even if it is added to the reaction solution before the formation of the precipitate. The separation aid used in the present invention refers to polyacrylamide, a partial hydrolyzate of polyacrylamide, or a copolymer copolymer of polyacrylamide and acrylate as described above, and the dicarboxylic acid refers to terephthalic acid. , isophthalic acid, phthalic acid,
Refers to fumaric acid, maleic acid, adipic acid, glutamic acid, aspartic acid, etc., and inorganic copper salts include copper sulfate (pentahydrate), cupric nitrate (trihydrate), and cupric chloride (dihydrate). Alkali metals refer to caustic soda and caustic potash. 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. Separately, dissolve 252 g (1 mol) of copper sulfate pentahydrate with a purity of 99% in water to make a total volume of 1 liter. While stirring 50ml of this copper sulfate aqueous solution, 100ml of sodium terephthalate aqueous solution was added.
is added to form a precipitate of copper terephthalate. 5
After continuing stirring for a minute, 25 ml of a 0.1% by weight aqueous solution of coagulation precipitant A listed in Table 1 was added and stirred for 5 minutes. This suspension was transferred onto a Buchner bowl with a diameter of 7.6 cm covered with Toyo paper No. 2 (7 cm in diameter), and suctioned with 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. The coagulating and precipitating agents B, C, D and E in Table 1 were also tested in the same manner. The results are shown in Table 1.

[Table] Example 2 Take 100 ml of the sodium terephthalate aqueous solution prepared in Example 1, and add 25 ml of the 0.1% by weight aqueous solution of coagulant A used in Example 1. The copper sulfate aqueous solution prepared in Example 1 while stirring this solution.
50 ml was added to form a precipitate of copper terephthalate. Since the precipitant solution was added before the precipitate was formed, the precipitate grew into a floc as it formed. Thereafter, this floc was suctioned off in the same manner as in Example 1. Liquid volume after 5 minutes of suction is 150ml
It was hot. Example 3 100 ml of the sodium terephthalate aqueous solution prepared in Example 1 is taken and stirred, and 50 ml of the copper sulfate aqueous solution also prepared in Example 1 is added thereto to form a precipitate of copper terephthalate. After continuing stirring for 5 minutes, 25 ml of a 0.1% by weight aqueous solution of coagulation precipitant A listed in Table 2 was added and stirred for 5 minutes. After this, transfer this suspension to a 1 liter graduated cylinder,
Water was added to bring the total volume to 1 liter, and the suspension was well stirred with a glass rod and then allowed to stand still. The time was measured using a stopwatch, and 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. Coagulation precipitant B in Table 2,
Table 2 shows the results of similar tests for C, D and E.

[Table] Test Example Copper terephthalate produced using coagulation precipitants A to E of Example 1 was washed with water, dried, and coarsely ground in a mortar. This copper terephthalate is further added to the
The particles were finely pulverized using a micronizer "Micron Master" model 02-505 manufactured by Jet Pulverizer, and the particle size was measured using a Fisher Servsieve Sizer manufactured by Fisher Scientific. Coagulation precipitating agents A to B and C
The average particle size of copper terephthalate produced using ~E is 1.25 microns, respectively, and the average particle size of copper terephthalate produced without using a flocculating precipitant is
It was 1.90 microns. The finely ground copper terephthalate was used to test the control effect of the copper terephthalate produced by the production method of the present invention against scabrous blight on cucumbers. The results are shown in Table 3.

[Table] *Product names are the same as in Table 1.

Claims (1)

[Claims] 1. When producing copper dicarboxylate from dicarboxylic acid, alkali metal hydroxide, and inorganic copper salt by metathesis reaction, and separating the produced copper dicarboxylate precipitate from the aqueous layer, polyacrylamide, a partial hydrolyzate of polyacrylamide, or acrylamide is used. - A method for producing copper dicarboxylate, characterized by using a copolymer of acrylate as a separation aid.