KR102536993B1 - method for tetramine palladium hydrogen carbonate and tetramine palladium hydrogen carbonate manufactured with this - Google Patents

Abstract

The present invention relates to a method for producing tetraamine palladium hydrogen carbonate and tetraamine palladium hydrogen carbonate produced through the same, and more particularly, to a method capable of producing tetraamine palladium hydrogen carbonate in high yield by a simple and easy method. In addition, it relates to a method for producing tetraamine palladium hydrogen carbonate capable of producing tetraamine palladium hydrogen carbonate having a low content of impurities such as dichlorodiamine palladium and tetraamine palladium hydrogen carbonate produced thereby.

Description

Method for producing tetraamine palladium hydrogen carbonate and tetraamine palladium hydrogen carbonate manufactured through the method {method for tetramine palladium hydrogen carbonate and tetramine palladium hydrogen carbonate manufactured with this}

The present invention relates to a method for producing tetraamine palladium hydrogen carbonate and tetraamine palladium hydrogen carbonate produced through the same, and more particularly, to a method capable of producing tetraamine palladium hydrogen carbonate in high yield by a simple and easy method. In addition, it relates to a method for producing tetraamine palladium hydrogen carbonate capable of producing tetraamine palladium hydrogen carbonate having a low content of impurities such as dichlorodiamine palladium and tetraamine palladium hydrogen carbonate produced thereby.

Recently, acceptance of electronic components applied with high-frequency and high-speed communication technologies such as 5G high-frequency mobile communication and autonomous vehicles is rapidly increasing, and nickel plating is limited in surface treatment of package substrates operating in high-frequency bands. In order to solve this problem, surface treatment containing palladium is being newly reviewed, and various palladium compounds are being reviewed for the development of next-generation palladium plating.

Palladium compounds for plating often contain chloride, mainly palladium chloride (PdCl ₂ ), dichlorodiamine palladium ((NH ₃ ) ₂ PdCl ₂ ), tetraamine palladium chloride ([(NH ₃ ) ₄ Pd]Cl ₂ ) has been used, and these chlorine-containing compounds cause allergies to workers and cause corrosion of plant materials.

On the other hand, as a palladium compound for plating that does not contain a chlorine-containing compound, there is tetraamine palladium hydrogen carbonate. Conventionally, it is a method widely known as a method for producing tetraaminepalladium hydrogencarbonate. A solution obtained by reacting an aqueous solution of palladium chloride (PdCl ₂ ) with ammonia is concentrated by evaporation, and then ammonium bicarbonate is added to precipitate, which is then filtered, washed, and dried. can be obtained by

However, the prior art method for producing tetraaminepalladium hydrogencarbonate has a low yield, and tetraaminepalladium hydrogencarbonate prepared through the prior art is likely to have trace amounts of dichlorodiaminepalladium remaining, so that these compounds can reduce chlorine. Since it contains, it does not meet the purpose of using non-chlorine-based compounds.

Therefore, tetraamine palladium hydrogen carbonate can be produced in high yield even by a simple and easy method capable of overcoming such disadvantages, and tetraamine palladium hydrogen carbonate having a low content of impurities such as dichlorodiamine palladium can be produced. A manufacturing method was developed to complete the present invention.

Japanese Patent Registration No. 2773920 (published on May 16, 1991)

The present invention has been made to solve the above problems, and the problem to be solved by the present invention is not only to be able to produce tetraamine palladium hydrogen carbonate in high yield by a simple and easy method, but also to dichlorodiamine palladium, such as It is to provide a method for producing tetraamine palladium hydrogen carbonate capable of producing tetraamine palladium hydrogen carbonate having a low content of impurities and a tetraamine palladium hydrogen carbonate produced through the method.

In order to solve the above problems, the method for producing tetraaminepalladium hydrogencarbonate of the present invention is to prepare a mixed solution by adding tetraaminepalladium chloride ([(NH ₃ ) ₄ Pd]Cl ₂ ) to water and then stirring. A first step of doing, a second step of adding ammonium bicarbonate (NH ₄ HCO ₃ ) to the mixed solution, stirring to obtain a precipitate product, and washing the precipitate product, followed by drying to tetraamine palladium hydrogen carbonate ( A third step of obtaining [(NH ₃ ) ₄ Pd](HCO ₃ ) ₂ ) may be included.

In one preferred embodiment of the present invention, tetraamine palladium chloride introduced in the first step and ammonium bicarbonate introduced in the second step may have a molar equivalent ratio of 1:2 to 10.

In a preferred embodiment of the present invention, the mixed solution may include palladium (Pd) at a concentration of 50 to 200 g/L.

In a preferred embodiment of the present invention, the stirring in the first step may be performed at a temperature of 5 to 85 °C.

In a preferred embodiment of the present invention, the stirring in the second step may be performed at a temperature of 5 to 85 °C.

In a preferred embodiment of the present invention, in the third step, the sediment product may be washed with water at 0 to 15 ° C.

In a preferred embodiment of the present invention, the drying in the third step may be performed at a temperature of 40 to 70 ° C for 6 to 24 hours.

In a preferred embodiment of the present invention, tetraamine palladium chloride is added to palladium (Pd) powder with hydrochloric acid and water, followed by stirring and reaction to produce palladium chloride (PdCl ₂ ) in the first step, the palladium chloride After adding ammonia water (NH ₄ OH), stirring and reacting to the second step of preparing dichlorodiamine palladium (Pd(NH ₃ ) ₂ Cl ₂ ) and the dichlorodiamine palladium and ammonia water are separated and introduced into a closed environment, , It may be prepared including a third step of preparing tetraamine palladium chloride by reacting the dichlorodiamine palladium with ammonia (NH ₃ ) gas generated from ammonia water.

On the other hand, the tetraamine palladium hydrogen carbonate of the present invention may be prepared by the method for producing tetraamine palladium hydrogen carbonate of the present invention.

Furthermore, the plating solution of the present invention may include tetraamine palladium hydrogen carbonate.

The method for producing tetraamine palladium hydrogen carbonate of the present invention and the tetraamine palladium hydrogen carbonate produced through the method can be prepared by a simple and easy method, and tetraamine palladium hydrogen carbonate in high yield.

In addition, the method for producing tetraaminepalladium hydrogencarbonate of the present invention and the tetraaminepalladium hydrogencarbonate produced through the method can produce tetraaminepalladium hydrogencarbonate having a low content of impurities such as dichlorodiaminepalladium.

1 is a table showing the results of analyzing elements for each of the tetraaminepalladium hydrogencarbonate powders prepared in Examples 1 to 5 through inductively coupled plasma mass spectrometry (ICP-MS).
Figure 2 is a view showing a reaction vessel used in the method for producing tetraamine palladium chloride of the present invention.

Hereinafter, with reference to the accompanying drawings, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. This invention may be embodied in many different forms and is not limited to the embodiments set forth herein. In order to clearly describe the present invention in the drawings, parts irrelevant to the description are omitted, and the same reference numerals are added to the same or similar components throughout the specification.

The method for preparing tetraaminepalladium hydrogencarbonate ([(NH ₃ ) ₄ Pd](HCO ₃ ) ₂ ) of the present invention includes first to third steps.

First, in the first step of the method for producing tetraaminepalladium hydrogencarbonate of the present invention, tetraaminepalladium chloride ([(NH ₃ ) ₄ Pd]Cl ₂ ) is added to water, followed by stirring to prepare a mixed solution. there is.

At this time, the mixed solution may contain palladium (Pd) at a concentration of 50 to 200 g/L, preferably at a concentration of 75 to 150 g/L, and if the concentration is less than 50 g/L, bicarbonate is acidified in a second step to be described later. When ammonium (NH ₄ HCO ₃ ) is added, it may be difficult to obtain a sediment product because the mixed solution is too dilute and sedimentation and precipitation reactions do not occur. There may be issues that are difficult to deal with.

In addition, the stirring in the first step may be performed at a temperature of 5 to 85 ° C, preferably 20 to 60 ° C, and if the temperature is less than 5 ° C, the solubility is low, and tetraamine palladium chloride is not completely dissolved in water. If the temperature exceeds 85 ° C., it may be difficult to control the concentration of the mixed solution, and there may be a problem of deteriorating economic feasibility.

Meanwhile, in the mixed solution prepared in the first step, impurities may be removed by filtering the prepared mixed solution under reduced pressure using a membrane filter.

Next, in the second step of the method for producing tetraaminepalladium hydrogencarbonate of the present invention, ammonium bicarbonate (NH ₄ HCO ₃ ) is added to the mixed solution prepared in the first step, preferably the mixed solution from which impurities are removed, and then , can be stirred to obtain a precipitate product.

At this time, the stirring in the second step may be performed at a temperature of 5 to 85 ° C, preferably 20 to 60 ° C, and if the temperature is less than 5 ° C, the solubility is low, so that ammonium bicarbonate is not completely dissolved in the mixed solution. There may be a problem that does not occur, and when the temperature exceeds 85 ° C., ammonium bicarbonate is rapidly decomposed and the reaction does not occur well.

In addition, the stirring in the second step can be performed for 30 to 120 minutes, preferably 45 to 90 minutes, and if the stirring time is less than 30 minutes, ammonium bicarbonate and tetraamine palladium chloride do not completely react, and each reactant There may be a problem of remaining in the mixed solution, and if it exceeds 120 minutes, there may be a problem of deterioration in economic efficiency.

Furthermore, tetraaminepalladium chloride added in the first step and ammonium bicarbonate added in the second step have a molar equivalent ratio of 1:2 to 10, preferably a molar equivalent ratio of 1:3 to 7, more preferably 1:4 to It may have a molar equivalent ratio of 6, more preferably 1: 4.5 to 5.5, and if the molar equivalent ratio is less than 1: 2, the reaction between tetraamine palladium chloride and ammonium bicarbonate does not completely occur, thereby removing unreacted tetraamine palladium chloride. There may be a problem in obtaining tetraamine palladium hydrogen carbonate containing tetraamine, and when the ratio exceeds 1: 10, not only the economic feasibility is reduced due to the use of an excessive amount of ammonium bicarbonate, but also the ammonium bicarbonate salt in the obtained tetraamine palladium hydrogen carbonate There may be residual problems.

Meanwhile, the sediment product obtained in the second step may be filtered under reduced pressure using a membrane filter.

Finally, in the third step of the method for producing tetraaminepalladium hydrogencarbonate of the present invention, the sediment product obtained in the second step is washed, dried, and tetraaminepalladium hydrogencarbonate ([(NH ₃ ) ₄ Pd] (HCO ₃ ) ₂ ) can be obtained.

At this time, the washing may be performed using water of 0 to 15 ° C, preferably 1 to 5 ° C, and if the temperature of the water exceeds 15 ° C, there is a problem that the yield of tetraamine palladium hydrogen carbonate is lowered. can

In addition, washing may be performed 1 to 5 times, preferably 2 to 4 times, and if washing is not performed, there may be a problem that impurities including ammonium bicarbonate are not removed, and if washing exceeds 5 times, There may be a problem that the yield of tetraamine palladium hydrogen carbonate is lowered.

In addition, drying may be performed for 6 to 24 hours at a temperature of 40 to 70 ° C., preferably for 8 to 12 hours at a temperature of 45 to 60 ° C. If the drying time is less than 6 hours, the moisture is not completely dried. There may be a problem that does not occur, and if it exceeds 24 hours, there may be a problem of deteriorating economic feasibility.

On the other hand, tetraamine palladium chloride introduced in the first step of the method for producing tetraamine palladium hydrogen carbonate may be produced including the first to third steps.

Specifically, in the first step of the method for producing tetraaminepalladium chloride of the present invention, hydrochloric acid and water are added to palladium (Pd) powder, and then stirred and reacted to produce palladium chloride (PdCl ₂ ). At this time, the palladium powder may be a palladium sponge or palladium black.

Specifically, the first step of the method for producing tetraaminepalladium chloride of the present invention may include a 1-1 step and a 1-2 step.

In the first-first step of the method for producing tetraaminepalladium chloride of the present invention, hydrochloric acid is added to palladium powder, nitric acid (HNO ₃ ) and water are further added, followed by stirring and reaction to prepare an aqueous solution of palladium chloride. . At this time, hydrochloric acid may use 10N to 14N hydrochloric acid, preferably 11N to 13N hydrochloric acid, and hydrochloric acid to palladium powder is 1: 2 to 10 equivalent ratio, preferably 1: 2 to 8 equivalent ratio, more preferably It can be added to have an equivalence ratio of 1:4 to 7. If the equivalence ratio is less than 1:2, there may be a problem in that palladium powder is not leached, and if it exceeds 1:10, there may be a problem in that economic feasibility is lowered due to the use of excessive hydrochloric acid.

In addition, nitric acid is added to the palladium powder to react with hydrochloric acid to produce aqua regia, and hydrochloric acid and nitric acid may be added to have an equivalent ratio of 1: 2 to 10, preferably hydrochloric acid and nitric acid in a ratio of 1: 2 to 10 It can be added to have a 6 equivalence ratio. If the hydrochloric acid and nitric acid are less than 1: 2 equivalence ratio, there may be a problem in that the palladium powder is not leached because the amount of aqua regia is small, and if the equivalence ratio is greater than 1: 10, nitrate may be generated.

In addition, water is added to the palladium powder to serve as a solvent, and the palladium powder and water may be added to have an equivalent ratio of 1: 1 to 10, and if the palladium powder and water are less than 1: 1 equivalent ratio, the palladium powder There may be a problem of not being leached, and if the equivalence ratio of 1:10 is exceeded, hydrolysis occurs and there may be a problem of oxide formation and a decrease in leaching efficiency.

In addition, stirring and reaction may be performed at a temperature of 70 to 120 ° C, preferably 80 to 100 ° C for 30 to 300 minutes, preferably 120 to 240 minutes, and if the temperature is less than 70 ° C, the problem of lowering leaching is solved. There may be, and if it exceeds 120 ° C., there may be a problem in that oxide is generated due to thermal decomposition.

In step 1-2 of the method for producing tetraaminepalladium chloride of the present invention, a denitrification reaction may be performed on the aqueous solution of palladium chloride prepared in step 1-1.

Specifically, the denitrification reaction is carried out by adding sulfamic acid (H ₃ NSO ₃ ) to an aqueous solution of palladium chloride for 10 to 120 minutes at room temperature, preferably 17 to 30 ° C, more preferably 23 to 27 ° C, preferably It can be performed for 20 to 40 minutes. At this time, sulfamic acid may be added to the palladium chloride aqueous solution to smoothly denitrify, and an appropriate amount may be added compared to the previously introduced nitric acid. Specifically, nitric acid to sulfamic acid may be added to have an equivalent ratio of 1: 0.5 to 2.0, and if the nitric acid to sulfamic acid is less than 1: 0.5 equivalent ratio, there may be a problem that the denitrification reaction does not proceed smoothly, and the 1: 2.0 equivalent ratio If it is exceeded, there may be a problem with sulfate generation.

Additionally, after performing the denitrification reaction, water may be additionally added, water is added to serve as a solvent for controlling and confirming hydrogen ions, and water is added in an appropriate amount compared to the palladium chloride aqueous solution subjected to the denitrification reaction. can do. Specifically, water may be added to have an equivalent ratio of 1: 0.5 to 2.0 compared to the aqueous palladium chloride solution subjected to the denitrification reaction, and if the aqueous palladium chloride solution and water subjected to the denitrification reaction are less than 1: 0.5 equivalent ratio, the concentration of hydrogen ions In addition, when synthesizing dichlorodiamine palladium, there may be a problem of increasing the amount of ammonia used, and when the 1: 2.0 equivalent ratio is exceeded, not only the concentration of hydrogen ions decreases, but also excessive ammonia is injected when synthesizing dichlorodiamine palladium. There may be a problem of declining economic efficiency.

Next, in the second step of the method for producing tetraamine palladium chloride of the present invention, ammonia water (NH ₄ OH) is added to the palladium chloride prepared in the first step, and then stirred and reacted to obtain dichlorodiamine palladium (Pd(NH ₃ ) ₂ Cl ₂ ) can be prepared.

Specifically, the second step of the method for producing tetraaminepalladium chloride of the present invention may include steps 2-1 to 2-4.

In step 2-1 of the method for producing tetraaminepalladium chloride of the present invention, ammonia water may be added to aqueous palladium chloride solution to adjust the pH of the aqueous palladium chloride solution to 6 to 8, preferably 6.5 to 7.5. The reason why the pH of the aqueous palladium chloride solution is adjusted to 6 to 8, preferably 6.5 to 7.5 is to adjust the equivalent amount of ammonia water required for synthesis in the manufacturing step to be described later, and if the pH of the aqueous palladium chloride solution is adjusted When proceeding to the next step without doing so, the step 2-2 described later is performed, but there may be a problem in that the reaction is not all performed with dichlorodiamine palladium. Specifically, the ammonia water used in the 2-1 step may use 15 to 35% by weight of ammonia water, preferably 20 to 30% by weight of ammonia water.

In the 2-2 step of the method for producing tetraaminepalladium chloride of the present invention, ammonia water is added to the palladium chloride aqueous solution whose pH is adjusted to 6-8, preferably 6.5-7.5 in the 2-1 step, followed by stirring and A dichlorodiamine palladium (Pd(NH ₃ )Cl ₂ ) solution may be prepared by reaction. Specifically, the ammonia water used in step 2-2 may use 15 to 35% by weight of ammonia water, preferably 20 to 30% by weight of ammonia water, and adjust the pH to 6 to 8, preferably 6.5 to 7.5. Aqueous ammonia may be added to an aqueous palladium chloride solution in an equivalent ratio of 1:1 to 10, preferably 1:1 to 6 equivalents, and more preferably 1:3 to 6 equivalents. If the equivalence ratio is less than 1: 1, there may be a problem of lowering the production of dichlorodiamine palladium, and if it exceeds 1: 10, there may be a problem of lowering economic feasibility due to the use of excessive ammonia water.

In addition, the stirring and reaction in step 2-2 can be carried out at room temperature, preferably 17 to 30 ° C, more preferably 23 to 27 ° C, for 30 to 120 minutes, preferably 45 to 75 minutes. there is.

On the other hand, before performing step 2-3 of the method for producing tetraaminepalladium chloride of the present invention, it is necessary to remove impurities (heavy metals, organic substances, etc.) that may be included in the dichlorodiamine palladium solution prepared in step 2-2. For this, an additional filtration process may be performed using active carbon.

In step 2-3 of the method for preparing tetraamine palladium chloride of the present invention, hydrochloric acid may be added to the dichlorodiamine palladium solution prepared in step 2-2, and then filtered to obtain a filtrate.

At this time, hydrochloric acid may use 10N to 14N hydrochloric acid, preferably 11N to 13N hydrochloric acid, and dichlorodiaminepalladium included in the dichlorodiaminepalladium solution may be precipitated by adding hydrochloric acid. In addition, the filtration of the second and third steps may be performed by a vacuum filtration method, and a high-purity dichlorodiamine palladium filtrate may be obtained by filtration.

In steps 2-4 of the method for producing tetraaminepalladium chloride of the present invention, dichlorodiaminepalladium powder may be prepared by washing and drying the filtrate obtained in steps 2-3. At this time, washing may be performed until the pH of the filtrate is 6 to 8, preferably 6.5 to 7.5, using purified water at 25 to 70 ° C, preferably 40 to 55 ° C. This is to completely remove free hydrochloric acid that adjusts the pH of the filtrate to 6 to 8, preferably 6.5 to 7.5, and if the pH of the filtrate is not adjusted in this way, hydrochloric acid remains and the yield is lowered. there may be In addition, if the temperature of the pure water used for washing is less than 25 ° C, there may be a problem in that the washing efficiency is lowered, and if it exceeds 70 ° C, there may be a problem in that the yield due to redissolution is lowered.

In addition, drying may be performed at a temperature of 60 to 80 ° C, preferably 65 to 75 ° C for 6 to 24 hours, preferably 10 to 18 hours, and if the drying temperature is less than 60 ° C, the problem of remaining moisture There may be, and if it exceeds 80 ℃, there may be a problem of thermal decomposition.

Finally, in the third step of the method for producing tetraamine palladium chloride of the present invention, dichlorodiamine palladium and ammonia water prepared in the second step are separated and introduced into a sealed environment, and ammonia (NH generated from the dichlorodiamine palladium and ammonia water) ₃ ) Gas can be reacted to produce tetraaminepalladium chloride ([(NH ₃ ) ₄ Pd]Cl ₂ ).

Specifically, the third step of the method for producing tetraaminepalladium chloride of the present invention may include a 3-1 step and a 3-2 step.

In step 3-1 of the method for producing tetraaminepalladium chloride of the present invention, dichlorodiaminepalladium and aqueous ammonia may be separated and introduced into a sealed environment. Specifically, in order to create an airtight environment, dichlorodiaminepalladium powder and ammonia water may be added to the reaction container shown in FIG. 1 and then sealed. At this time, as shown in FIG. 1, dichlorodiaminepalladium powder and ammonia water They may be separated so that they do not come into direct contact with each other. If the dichlorodiamine palladium powder and the ammonia water are in direct contact without being separated inside the reaction vessel, there may be a problem of dissolution and decrease in purity, so they must be separated. On the other hand, the ammonia water used in step 3-1 may use 15 to 35% by weight of ammonia water, preferably 20 to 30% by weight of ammonia water, and dichlorodiamine palladium powder and ammonia water in an equivalent ratio of 1: 1.2 to 10, preferably. Preferably 1: 1.2 ~ 6 equivalence ratio, more preferably 1: 3 ~ 5 may be added to have an equivalence ratio. If the equivalence ratio is less than 1:1.2, there may be a problem of yield reduction and unreacted dichlorodiamine palladium remaining, and if it exceeds 1:10, there may be a problem of economic efficiency.

Step 3-2 of the method for producing tetraamine palladium chloride of the present invention is left in the closed environment of step 3-1 for 5 to 20 hours, preferably 8 to 15 hours, and ammonia generated from dichlorodiamine palladium and ammonia water. Gases can be reacted to produce tetraaminepalladium chloride. That is, the production of tetraamine palladium chloride is produced through the reaction of dichlorodiamine palladium and ammonia gas rather than the reaction of dichlorodiamine palladium and ammonia water. Purity and yield can be increased. On the other hand, if the standing time is less than 5 hours, there may be a problem of yield reduction and unreacted dichlorodiamine palladium remaining, and if it exceeds 20 hours, there may be a problem of deteriorating economic feasibility.

Furthermore, the tetraamine palladium hydrogen carbonate of the present invention may be prepared through the method for preparing tetraamine palladium hydrogen carbonate described above.

In addition, the plating solution of the present invention may include the tetraamine palladium hydrogen carbonate of the present invention, and at this time, the plating solution may be a plating solution used in electronic components to which high-frequency (approximately 30 KHz to 300 GHz) high-speed communication technology is applied. Specifically, the plating solution may be used for surface treatment of a package substrate operating in a high frequency band.

Hereinafter, the present invention will be described through the following examples. At this time, the following examples are only presented to illustrate the invention, and the scope of the present invention is not limited by the following examples.

Preparation Example 1: tetraamine palladium chloride ([(NH ₃ ) ₄ Pd]Cl ₂ ) manufacture of

(1) 122 ml of 12N hydrochloric acid (HCl) was added to 26.6 g of a palladium sponge (= palladium sponge and 12N hydrochloric acid were added in an equivalent ratio of 1: 6), and 40 ml of nitric acid (HNO ₃ ) and 122 ml of water were further added. After the addition, 285 ml of an aqueous solution of palladium chloride (PdCl ₂ ) was prepared by stirring and reacting at 90° C. for 180 minutes.

(2) 7.8 g of sulfamic acid (H ₃ NSO ₃ ) was added to 285 ml of the prepared palladium chloride aqueous solution, denitrification was performed at room temperature (25 ° C) for 30 minutes, and then water was added to palladium chloride. An aqueous solution was prepared in 500 ml.

(3) 110 ml of 25 wt% ammonia water (NH ₄ OH) was added to 500 ml of the prepared palladium chloride aqueous solution to adjust the pH of the palladium chloride aqueous solution to 7, and 145 ml of 25 wt% ammonia water (NH ₄ OH) was further added (pH was added to an aqueous solution of palladium chloride adjusted to 7 and 25% by weight ammonia water added to have an equivalent ratio of 1: 5), followed by stirring and reacting at room temperature (25 ° C) for 60 minutes to obtain dichlorodiamine palladium (Pd (NH ₃ ) ₂ Cl ₂ ) A solution of 750 ml was prepared.

(4) Using activated carbon, the prepared dichlorodiaminepalladium solution was filtered to remove impurities, and 206ml of 12N hydrochloric acid (HCl) was added to 750ml of the dichlorodiaminepalladium solution from which impurities were removed to precipitate dichlorodiaminepalladium. After that, it was filtered under reduced pressure to obtain a filtrate.

(5) The obtained filtrate was washed with purified water at 50° C. until the pH reached 7, and the washed filtrate was dried at 70° C. for 12 hours to prepare 48.3 g of dichlorodiamine palladium powder. At this time, the yield measured by the following relational expression 1 was 91.4%.

[Relationship 1]

(6) Prepare a reaction container (= using a stainless steel sealed locker in FIG. 2), and put 48.3 g of dichlorodiamine palladium powder and 90 ml of 25% by weight ammonia water prepared inside the reaction container (= dichlorodiamine palladium powder and 25 weight % ammonia water was added to have an equivalent ratio of 1: 3.2). At this time, the dichlorodiamine palladium powder and 25% by weight ammonia water were separately added without direct contact, and the reaction vessel into which the dichlorodiamine palladium powder and 25% by weight ammonia water was added was sealed. After leaving the sealed vessel for 12 hours, tetraaminepalladium chloride ([(NH ₃ ) ₄ Pd]Cl ₂ ) prepared by reacting dichlorodiamine palladium powder with ammonia (NH ₃ ) gas generated from ammonia water inside the reaction vessel. 58.8 g of powder was obtained. At this time, the yield measured by the following relational expression 2 was 97.7%.

[Relationship 2]

Example 1: tetraamine palladium hydrogen carbonate ([(NH ₃ ) ₄ Pd](HCO ₃ ) ₂ ) manufacture of

(1) 24.78 g of tetraamine palladium chloride powder prepared in Preparation Example 1 was added to 83 g of ultrapure water and stirred at room temperature (25° C.) until tetraamine palladium chloride was completely dissolved to obtain palladium at a concentration of 100 g/L. A mixed solution containing

(2) Using a membrane filter, the prepared mixed solution was filtered under reduced pressure to remove impurities, and 15.53 g of ammonium bicarbonate (NH ₄ HCO ₃ ) was added to the mixed solution from which impurities were removed (= tetraamine palladium chloride and ammonium bicarbonate 1: 2 to have a molar equivalent ratio), and then stirred at room temperature (25 ° C.) for 60 minutes to perform a sedimentation and precipitation reaction to obtain a sediment product

(3) The obtained sediment product was filtered under reduced pressure using a membrane filter, washed three times with purified water at 3° C., and dried at a temperature of 50° C. for 12 hours, and tetraamine palladium hydrogen carbonate ( 13.47 g of [(NH ₃ ) ₄ Pd](HCO ₃ ) ₂ ) powder was obtained.

Example 2: tetraamine palladium hydrogen carbonate ([(NH ₃ ) ₄ Pd](HCO ₃ ) ₂ ) manufacture of

(1) 24.54 g of tetraamine palladium chloride powder prepared in Preparation Example 1 was added to 83 g of ultrapure water and stirred at room temperature (25° C.) until tetraamine palladium chloride was completely dissolved to obtain palladium at a concentration of 100 g/L. A mixed solution containing

(2) Using a membrane filter, the prepared mixed solution was filtered under reduced pressure to remove impurities, and 23.30 g of ammonium bicarbonate (NH ₄ HCO ₃ ) was added to the mixed solution from which impurities were removed (= tetraamine palladium chloride and ammonium bicarbonate 1: 3 added to have a molar equivalent ratio), and then stirred at room temperature (25 ° C.) for 60 minutes to perform a sedimentation and precipitation reaction to obtain a sediment product

(3) The obtained sediment product was filtered under reduced pressure using a membrane filter, washed three times with purified water at 3° C., and dried at a temperature of 50° C. for 12 hours, and tetraamine palladium hydrogen carbonate ( 18.45 g of [(NH ₃ ) ₄ Pd](HCO ₃ ) ₂ ) powder was obtained.

Example 3: tetraamine palladium hydrogen carbonate ([(NH ₃ ) ₄ Pd](HCO ₃ ) ₂ ) manufacture of

(1) 24.68 g of tetraamine palladium chloride powder prepared in Preparation Example 1 was added to 83 g of ultrapure water and stirred at room temperature (25° C.) until tetraamine palladium chloride was completely dissolved to obtain palladium at a concentration of 100 g/L. A mixed solution containing

(2) Using a membrane filter, the prepared mixed solution was filtered under reduced pressure to remove impurities, and 31.07 g of ammonium bicarbonate (NH ₄ HCO ₃ ) was added to the mixed solution from which impurities were removed (= tetraamine palladium chloride and ammonium bicarbonate 1: 4 added to have a molar equivalent ratio), and then stirred at room temperature (25 ° C.) for 60 minutes to perform a sedimentation and precipitation reaction to obtain a sediment product

(3) The obtained sediment product was filtered under reduced pressure using a membrane filter, washed three times with purified water at 3° C., and dried at a temperature of 50° C. for 12 hours, and tetraamine palladium hydrogen carbonate ( 24.83 g of [(NH ₃ ) ₄ Pd](HCO ₃ ) ₂ ) powder was obtained.

Example 4: tetraamine palladium hydrogen carbonate ([(NH ₃ ) ₄ Pd](HCO ₃ ) ₂ ) manufacture of

(1) 24.60 g of tetraamine palladium chloride powder prepared in Preparation Example 1 was added to 83 g of ultrapure water and stirred at room temperature (25° C.) until tetraamine palladium chloride was completely dissolved to obtain palladium at a concentration of 100 g/L. A mixed solution containing

(2) Using a membrane filter, the prepared mixed solution was filtered under reduced pressure to remove impurities, and 38.84 g of ammonium bicarbonate (NH ₄ HCO ₃ ) was added to the mixed solution from which impurities were removed (= tetraamine palladium chloride and ammonium bicarbonate 1: 5 in a molar equivalent ratio), and then stirred at room temperature (25 ° C) for 60 minutes to perform a sedimentation and precipitation reaction to obtain a sediment product

(3) The obtained sediment product was filtered under reduced pressure using a membrane filter, washed three times with purified water at 3° C., and dried at a temperature of 50° C. for 12 hours, and tetraamine palladium hydrogen carbonate ( 25.46 g of [(NH ₃ ) ₄ Pd](HCO ₃ ) ₂ ) powder was obtained.

Example 5: tetraaminepalladium hydrogencarbonate ([(NH ₃ ) ₄ Pd](HCO ₃ ) ₂ ) manufacture of

(1) 24.60 g of tetraamine palladium chloride powder prepared in Preparation Example 1 was added to 83 g of ultrapure water and stirred at room temperature (25° C.) until tetraamine palladium chloride was completely dissolved to obtain palladium at a concentration of 100 g/L. A mixed solution containing

(2) Using a membrane filter, the prepared mixed solution was filtered under reduced pressure to remove impurities, and 46.61 g of ammonium bicarbonate (NH ₄ HCO ₃ ) was added to the mixed solution from which impurities were removed (= tetraamine palladium chloride and ammonium bicarbonate 1: 6 added to have a molar equivalent ratio), and then stirred at room temperature (25 ° C) for 60 minutes to perform a sedimentation and precipitation reaction to obtain a sediment product

(3) The obtained sediment product was filtered under reduced pressure using a membrane filter, washed three times with purified water at 3° C., and dried at a temperature of 50° C. for 12 hours, and tetraamine palladium hydrogen carbonate ( 25.39 g of [(NH ₃ ) ₄ Pd](HCO ₃ ) ₂ ) powder was obtained.

Experimental Example 1: Yield measurement of the obtained tetraaminepalladium hydrogencarbonate powder

For each of the tetraaminepalladium hydrogencarbonate powders prepared in Examples 1 to 5, yields were calculated using the following relational expression 1 and are shown in Table 1 below.

[Relationship 1]

As can be seen in Table 1, it was confirmed that the yield of tetraamine palladium hydrogen carbonate obtained in Examples 3 to 5 was 80% or more, and the yield of tetraamine palladium hydrogen carbonate obtained in Example 4 was the most excellent. I was able to confirm.

Experimental Example 2: Elemental analysis of the obtained tetraaminepalladium hydrogencarbonate powder

The elements for each of the tetraaminepalladium hydrogencarbonate powders prepared in Examples 1 to 5 were analyzed through inductively coupled plasma mass spectrometry (ICP-MS), and are shown in Table 2 below.

As can be seen in Table 2, it can be seen that the tetraamine palladium hydrogen carbonate obtained in Examples 2 to 5 has no significant difference from the theoretical value calculated by molecular weight, which indicates that tetraamine palladium hydrogen carbonate with fewer impurities is obtained. can be seen to have been If the content of impurities such as dichlorodiamine palladium is high, the ratio of N, C, and H decreases as a result of elemental analysis.

In the case of tetraaminepalladium hydrogencarbonate obtained in Example 1, the content of impurities increased compared to the tetraaminepalladium hydrogencarbonate obtained in Examples 2 to 5, and it can be seen that the values of N, C, and H are small. . In particular, in the case of C, if a large amount of unreacted tetraaminepalladium chloride remains, the ratio may be greatly reduced.

Simple modifications or changes of the present invention can be easily performed by those skilled in the art, and all such modifications or changes can be considered to be included in the scope of the present invention.

Claims (10)

A first step of preparing a mixed solution by adding tetraaminepalladium chloride ([(NH ₃ ) ₄ Pd]Cl ₂ ) to water and stirring;
A second step of adding ammonium bicarbonate (NH ₄ HCO ₃ ) to the mixed solution and then stirring at a temperature of 20 to 60° C. for 45 to 90 minutes to obtain a sediment product; and
A third step of washing the sediment product and then drying to obtain tetraaminepalladium hydrogencarbonate ([(NH ₃ ) ₄ Pd](HCO ₃ ) ₂ ); including,
The washing is performed 2 to 4 times with water at 1 to 5 ° C.
Tetraaminepalladium chloride introduced in the first step and ammonium bicarbonate introduced in the second step have a molar equivalent ratio of 1: 4 to 6. Method for producing tetraaminepalladium hydrogencarbonate.
delete According to claim 1,
The mixed solution is a method for producing tetraamine palladium hydrogen carbonate, characterized in that it contains palladium (Pd) at a concentration of 50 ~ 200g / L.
According to claim 1,
The method for producing tetraamine palladium hydrogen carbonate, characterized in that the stirring of the first step is carried out at a temperature of 5 ~ 85 ℃.
delete delete According to claim 1,
The drying of the third step is a method for producing tetraamine palladium hydrogen carbonate, characterized in that carried out for 6 to 24 hours at a temperature of 40 to 70 ℃.
The method of claim 1, wherein the tetraamine palladium chloride
A first step of preparing palladium chloride (PdCl ₂ ) by adding hydrochloric acid and water to palladium (Pd) powder, stirring and reacting;
A second step of preparing dichlorodiamine palladium (Pd(NH ₃ ) ₂ Cl ₂ ) by adding aqueous ammonia (NH ₄ OH) to the palladium chloride and then stirring and reacting; and
A third step of separately introducing the dichlorodiamine palladium and aqueous ammonia into an airtight environment and reacting the dichlorodiamine palladium with ammonia (NH ₃ ) gas generated from the ammonia water to produce tetraamine palladium chloride;
Method for producing tetraamine palladium hydrogen carbonate, characterized in that produced by including.
delete delete

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