JPH0399089A - Synthesis of organoplatinum compound - Google Patents

Abstract

PURPOSE:To obtain the subject compound suitable as a raw material for thin film-forming materials in the electronic industry and having superior preservation stability, etc., when dissolved together with a metal resinate, etc., in a solvent by reacting a platinate with a specific compound, followed by specific treatment of the reaction mixture. CONSTITUTION:First, a camphene mercaptan is added to an aqueous solution of a platinate [example; tetrachloroplatinic acid (II)] and sufficiently agitated and the reaction mixture is extracted with chloroform. Then the chloroform layer is separated and washed with water, which is then separated The chloroform layer is heated to evaporate the chloroform and give an oily substance. Finally the oil substance is added to an alcohol such as methanol to afford a crystal of the objective compound. The amount of the camphene mercaptan to be added to 1mol platinate is preferably 2-4mol and 1-2 times of a stoichiometrical amount.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to pastes and solution metal film forming materials for forming various platinum-containing catalysts, conductors, resistors, and corrosion-resistant films for electronic component materials. The present invention relates to a method for synthesizing platinum camphenmercabutide as an organic platinum compound that is a raw material for.

(Prior art and its problems) Conventionally, platinum as a raw material for paste has been prepared by dissolving inorganic compounds such as chloroplatinates in alcohol etc. as fine metal powder or platinum compounds. Inorganic compounds such as platinum salts generate harmful gases that can damage the base material during thermal decomposition, and when alcohol, etc. evaporates, they precipitate as crystals and are unstable, causing the formation of platinum films. may be lacking.

In addition, what is called water platinum, which is used for decoration, can be made into a thin film of platinum by applying platinum as a solution, drying, and baking, but its synthesis method is based on sulfur balsam and platinum salts. The raw material is an organic platinum compound synthesized from

However, the turpentine used in the synthesis of sulfur balsam is a natural product containing rosin and several types of terpenes.
The platinum content or bulk in the synthesized platinum compound,
When mixing other metal resinates and various resins as binders and dissolving them in an organic solvent, it is necessary to maintain a stable and uniform liquid state by dissolving them in a common organic solvent because they are susceptible to deterioration due to light, moisture, etc. It does not meet the demands of practical use.

(Objective of the Invention) The present invention has been made to solve the conventional drawbacks, and it can be dissolved in an organic solvent with other metal resinates, etc., and maintain a stable state even when stored for a long period of time, even in the form of a solution. The platinum content as a platinum compound is also relatively high and has little variation.
The present invention provides a method for synthesizing an organic platinum compound that does not damage a base material during the process of thermally decomposing it into platinum.

(Means for Solving the Problems) The present invention includes a first step of adding camphene mercabutan to an aqueous solution of an autorate, stirring the mixture thoroughly, and then adding chloroform for extraction, and separating the chloroform layer. a second step of separating water after washing with water, a third step of heating the filtered chloroform layer to evaporate the chloroform to obtain an oily substance, and adding the commercial substance to alcohol. A method for synthesizing an organoplatinum compound characterized by comprising a fourth step of generating crystals and a fifth step of filtering the crystals and drying them under reduced pressure at room temperature, in which light-colored crystals of platinum camphene mercaptide are That's what you get.

The details of the present invention will be explained below.

Aqueous solutions of platinates include tetrachloroplatinic (It) acid, potassium tetrachloroplatinate (II), hexachloroplatinic (IV) acid, sodium hexachloroplatinate (IV),
Either potassium hexagonal platinate (IV) or ammonium hexagonal platinate (IV) is dissolved in a small amount of distilled water and used.

The amount of platinate and camphene mercaptan to be added is preferably 2 to 4 moles of camphene mercaptan per 1 mole of platinate, about 1 to 2 times the chemical theoretical equivalent.

The aqueous solution of the platinum salt and camphene butane are added and stirred, but it is necessary to do this at room temperature for at least 24 hours.

If the stirring and reaction described above are insufficient, the yield of the desired platinum compound will decrease.

Then, an appropriate amount of chloroform is added, stirred, extracted into chloroform, and the chloroform layer is separated.

Since the separated chloroform layer contains impurities, it is washed with distilled water, but the end point of the washing is when the PH of the separated distilled water is 5 to 5 after washing the chloroform layer.
It is necessary to continue until reaching 7.

After thorough washing with distilled water, some water contained in the chloroform layer is left to stand and separated.

In addition, to remove moisture, an appropriate amount of powder such as sodium sulfate (anhydrous) may be added, mixed gently, and then filtered and separated.

Next, the separated chloroform layer is transferred to a distillation device such as an evaporator, and the chloroform is evaporated at 40 to 60°C to obtain an MlJ-like substance.

The oily substance may be used as an alcohol such as methyl alcohol, and when the alcohol is added with stirring, pale yellow crystals are formed.

After filtering the pale yellow crystals produced above, drying in a desiccator under reduced pressure at room temperature resulted in a platinum content of 3.
Crystals of camphuene mercaptide having a concentration of 2 wt% or more are obtained.

Incidentally, the oily substance obtained after evaporating the chloroform obtained in step 2 can also be used as a raw material for the platinum thin film forming material.

Examples related to the present invention will be described below, but the examples are not intended to limit the present invention.

(Example)) Distilled water 7.7 g to 34.7 g of hexachloroplatinic (IV) acid
- and dissolve it, add camphenmercabutan 45
．． 9 g was added and stirred at room temperature for 24 hours, then 55 ml of chloroform was added and stirred to extract into chloroform, left to stand, and the chloroform layer was separated.

200 J of distilled water was added to the separated chloroform layer, stirred, allowed to stand, and the operation of separating the distilled water layer was performed 10 times, and the pH of the separated distilled water was 6.

Add 15 g of sodium sulfate (anhydrous) to the chloroform layer washed with distilled water, stir gently, and filter to remove water in the chloroform layer.Then, the filtrate was transferred to an evaporator and the chloroform was evaporated at 60°C. A substance No. 11 was obtained. The liquid substance was added to 1 liter of methyl alcohol with stirring to produce pale yellow crystals. The crystals were collected by filtration using a glass filter and kept at room temperature in a desiccator under reduced pressure. The dry pale yellow crystals were dried for 6 hours at a temperature of 30.5
When this was obtained and chemically analyzed, the content of platinum was 33.5 wt%.

From the above results, the purity as platinum camphene mercaptide was 93%, and the yield as platinum was 78%.

(Examples 2 to 4) Example 2 was operated in the same manner as Example 1 except that a tetrachloroplatinic (n) acid solution containing 13.1 g of platinum was used.

Example 3 was carried out in the same manner as Example 1, except that 28 g of potassium tetrachloride platinate (n) was dissolved in 250 g of distilled water.

Example 4 is sodium 1 and 3 lithium platinum (IV) oxides.
Distilled water 10rn for 8g! The procedure was the same as in Example 1 except that the solution was added and dissolved.

The above results were as shown in the table below.

〔result〕

(Example 5) Platinum camphenmercabutide obtained in Example 1 (4.
Rhodium resinate (0.03g) and bismuth resinate (0.8g) were used as other metal resinates.
31g), lead resinate (0.09g) and asphalt as an organic binder (0.5g), terpene resin (0.
5g) as an organic solvent and terpineol (3.27g)
was dissolved in benzyl acetate (0.5 g) to obtain a viscous solution.

The viscous solution can be used as glass glaze, quartz, glass, hollow,
Screen printed and coated on a 64 mm x 64 mm x 1 mm thick stainless steel or ceramic substrate at 150°C.
It was dried for 10 minutes at 700° C. and baked for 10 minutes at 700° C. to form a platinum film.

The platinum thin films formed on the surfaces of the bellows, glass glaze, quartz, and glass were shiny, while the platinum thin films formed on the surfaces of hollow, stainless steel, and ceramic were matte.

A beer test was conducted to confirm the adhesion of the platinum thin film described above, and no peeling occurred in any case.

In addition, the prepared drying solution was stored in a brown bottle for 6 months with a tightly stopper, but it remained in a uniform solution state.

(Example 6) Using the crystals obtained in Examples 2 to 4 as other metal resinates, rhodium resinate, bismuth resinate, and lead resinate were each added at 0.0%. 3-5. owt%, asphalt as an organic binder, terpene resin 10wt%, terpineol and benzyl acetate as organic solvents 40wt%
The remaining part was crystallized to prepare a viscous solution, and it was confirmed that it became a homogeneous solution.Similar to Example 5, the storability for 6 months was confirmed, but no abnormalities were observed.

In addition, when the oily substance produced during the process of synthesizing platinum camphene mercaptide crystals was printed on a glass substrate, dried, and burned in the same manner as in Example 5, a thin platinum film was formed in the same way, and the adhesion was preserved. There was no change in the location either.

(Effects of the Invention) As described above, the present invention can synthesize crystals of platinum camphuene mercaptide with stable quality, which have characteristics that cannot be obtained with conventional organic autometal compounds such as water-platinum.
Moreover, by mixing and preparing other metal resinates, organic binders, and organic solvents, a uniform and appropriate viscosity can be prepared.The platinum content is also relatively high, so when forming a thin film, it is difficult to apply, dry, and bake. It has the effect of being able to obtain a suitable thin film thickness even with a small number of repeated operations, making it extremely useful as a raw material for forming thin films for the electronics industry, such as precise thicknesses and thin film widths.

Claims (1)

[Claims] (1) The first step is to add camphene mercaptan to an aqueous solution of platinum salt, stir it thoroughly, and then add chloroform for extraction.The second step is to separate the chloroform layer, wash it with water, and then separate the water. a third step of heating the filtered chloroform layer to evaporate the chloroform to obtain an oily substance, a fourth step of adding the oily substance to alcohol to form crystals, and filtering the crystals. A method for synthesizing an organic platinum compound, comprising a fifth step of drying under reduced pressure at room temperature.