JPS62205041A - Production of hydroxyalkyletherified substance of 1,4-butynediol and nickel plating treating solution using same - Google Patents

Abstract

PURPOSE:In obtaining the titled substance by adding an alkylene oxide to 1,4- butynediol in the presence of an alkali hydroxide, to use the 1,4-butynediol as an aqueous solution with a specific concentration. CONSTITUTION:In adding 1.0-3.0mol alkylene oxide (e.g. ethylene oxide or propylene oxide) to 1mol 1,4-butynediol in the presence of an alkali metal hydroxide at 40-60 deg.C, 30-60wt% aqueous solution of 1,4-butynediol is used in the reaction. In the operation, a catalyst is added to the aqueous solution of 1,4-butynediol and then the alkylene oxide is gradually added to the solution. EFFECT:1,4-Butynediol on the market is directly used as a raw material and the aimed substance is obtained without producing undesirable by-products. USE:An improver for Ni plating gloss.

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to an improved method for producing a hydroxyalkyl ether of 1,4-butynediol and a nickel plating solution using the same.

``Prior Art'' As is well known, it is common practice to electrolytically plate metals such as iron, zinc, and brass in a plating process.

Various improved techniques are being implemented. Among these improved technologies, without polishing the surface of the plated object after plating,
There is a technique to improve the surface gloss of a plated object by improving the plating method itself.

On the other hand, methods of adding various additives to improve the gloss during plating have been implemented. Taking nickel plating as an example, in addition to sulfur compounds such as sulfonic acid and surfactants, 1,4 -butynediol (hereinafter referred to as 1
．． It is abbreviated as 4-BD. ) are used as gloss improvers.

The 1,4-nD hydroxyalkyl ether compound itself can be produced by a known alkylene oxide addition method, but its use is limited to the nickel plating gloss improver as described above.

Widely used methods are inadequate.

That is, if a hydroxyalkyl ether of 1,4-BD is used as a nickel plating gloss improver using an alkali metal hydroxide or alcolade as a catalyst according to the method described above, a high-molecular-weight secondary product is used during the production of the ether. There is a drawback that living organisms coexist and are insoluble in the plating bath, which actually reduces the gloss of the surface after plating. Furthermore, when a tertiary amine is used as the catalyst, the catalytic activity is low, so it is necessary to raise the addition temperature of the alkylene oxide, and other by-products are produced, resulting in the same drawbacks.

As a method to improve these drawbacks, there is a precedent example of improving the surface and gloss after plating by using a specific basic ion exchange resin as a catalyst and distilling and purifying the raw material 1,4-[10. It will be done. (British Patent No. 13481
No. 69) It is said that this method does not produce the above-mentioned by-products, but since the catalyst activity is low, the reaction temperature is lowered to suppress the production of by-products, so it is used.
- It is necessary to use a large amount of ion-exchange resin catalyst, such as 10 to 25 wt. The addition reaction of alkylene oxide tends to be non-uniform due to certain factors, and commercially available 1,
4-BD at a temperature of about 120-130℃, 2mmH
This prior method had drawbacks such as the complicated method of purifying the product by distillation under a reduced pressure of about 1.5 g.

"Problems to be Solved by the Invention" The present inventors have solved the above-mentioned undesirable by-products by a simple method without using a large amount of catalyst or by distillation-purified 1,4-[10. A method for producing a hydroxyalkyl ether of 1,4-BD that has the effect of improving the gloss of nickel plating without forming was investigated.

As a result of the above studies, we found that using an aqueous solution of 1.4-BD when reacting 1.4-BD with alkylene oxide causes the drawbacks mentioned above when performing nickel plating. The present invention was achieved by discovering that it is possible to produce a hydroxyalkyl etherified product of 1,4-BD that does not have the following properties. That is, the present invention involves the addition reaction of 1.0 to 3.0 moles of alkylene oxide to 1.4-BD in the presence of an alkali metal hydroxide at a reaction temperature of 40°C or higher and 60°C or lower. ．．
A method for producing a hydroxyalkyl etherified product of 1,4-BD characterized by using an aqueous solution of 30 to 60% by weight of 4-BD, and a nickel plating solution containing the etherified product produced by the above method. .

In carrying out the present invention, 1,4-loD is subjected to the etherification reaction as a 30-60% by weight aqueous solution. If the method of the present invention is carried out with less than 30% by weight, a large amount of alkylene glycol will be produced as a by-product, and the amount of liquid used for the reaction will increase, resulting in lower reaction efficiency, which is undesirable. By-products increase, and even if this product is used as a part of the nickel plating solution as described above, the effect of improving the surface gloss of the object to be plated is reduced, which is not preferable.

As mentioned above, the catalyst used in the method of the present invention is an alkali metal hydroxide, specifically sodium hydroxide, potassium hydroxide, and lithium hydroxide. The amount used is 0.05 to 2.0% by weight, preferably 0.1 to 1.0% by weight based on the raw material 1.4-BD.

The other raw materials, alkylene oxides, are specifically ethylene oxide and l or propylene oxide, each of which may be used alone or as a mixture. The amount used is 1.0 to 3.0 times the mole of 1.4-BD, and if it is more or less than this usage range, it can be used as a component of the nickel plating solution as described above. is not desirable.

As the addition reaction method of alkylene oxide to 1.4-BD, it is preferable to add a catalyst to the aqueous solution of 1,4-BD defined as above, and then sequentially add alkylene oxide. Considering that the reaction is exothermic, it is not preferable to add the entire amount at once.

The temperature of the above addition reaction must be 40°C or higher and 60°C or lower; if it is lower than 40°C, the reaction rate will be slow and impractical, and if it exceeds 60°C, the effect of improving plating gloss will be reduced. This is undesirable because products are formed.

The addition reaction pressure is preferably carried out at 6 to 5 atm, which is determined depending on the alkylene oxide addition rate, reaction temperature, etc., but is not particularly limited.

After the addition of alkylene oxide is completed, a ripening reaction is carried out until the pressure becomes constant, then the contents are taken out and neutralized with an organic acid such as acetic acid or salicylic acid or a mineral acid such as hydrochloric acid or sulfuric acid, and the neutralized salt is removed by adsorption filtration, etc. It can be removed almost completely without neutralization or by adsorption filtration using an adsorbent such as natural or synthetic activated clay.

Thus, the aqueous solution of the hydroxyalkyl etherate of 1,4-BD from which the catalyst has been removed consists of about 40 to 80 weight solids. Although the etherified product is used in the plating process described above by the method described below, it goes without saying that the etherified product can also be used in any other applications.

When used in a nickel plating solution, it is used as it is, or usually in a 40 to 70% by weight aqueous solution and added to the nickel plating bath.

"Example" The present invention will be described in more detail below with reference to Examples and Comparative Examples. In the following description, "1 part" indicates parts by weight unless otherwise specified.

Example 1 A commercially available aqueous solution 8 containing 1.4-80430 parts with a purity of 98% and mainly containing propargyl algol as an impurity.
27 parts (52% as 1,4-BD) were placed in an autoclave equipped with a stirring device, and 3.3 parts of powdered potassium hydroxide was added thereto.The autoclave was then sealed, and after being sufficiently purged with nitrogen gas, the mixture was stirred. 444 parts of ethylene oxide were added over a period of 1 hour at a temperature of 45-50°C.

At that time, the reaction pressure was maintained at 2.5 ate or less. After the addition was completed, stirring was continued for 5 hours at the same temperature, and no drop in pressure was observed, so the reaction was terminated and the autoclave was opened. Remove the contents and add 30 parts of artificial activated clay (Kyowado 600s Kyowa Kasei Co., Ltd. WI).
The mixture was stirred for several minutes to adsorb the catalyst, and then filtered. The catalyst was almost completely removed.

Nickel plating using this solution was performed in the following manner.

300g/u of nickel sulfate hydrate, 45g/11
0.6 g of the above adduct aqueous solution in an electrolyte aqueous solution IQ containing nickel chloride 6.hydrate and 41 g/It of boric acid,
4 g of 1,3-benzenedisulfonic acid and 2 g of lauryl alcohol were added together with the sodium salt of the monosulfate ester of 2 moles of ethylene oxide, and nickel and brass were placed therein as electrodes at a temperature of 60°C and a current density. 5
When plating was performed using A/d nf, a nickel plated body with brilliant luster was obtained.

Comparative Example 1 827 parts (52% as 1,4-80) of an aqueous solution containing 1.4-[10430 parts with a purity of 98% as in Example 1 was placed in the same autoclave as in Example 1, and then basic ions were added as a catalyst. Exchange resin Amberlite IRA400 (counter anion is used in the form of hydroxy ion) 10
0 parts was added, the mixture was sealed, and the atmosphere was replaced with nitrogen. After that, as in Example 1, ethylene oxide was added at 50°C for 1 hour, and the pressure was maintained at 2.5 atmospheres or less to cause an addition reaction, and the aging reaction was continued at 50°C for 20 hours, until the pressure drop stopped. Therefore, the reaction was terminated. The contents were taken out and the catalyst was removed by filtration.

A plated body plated with nickel in the same manner as in Example 1 using this reaction product had a rougher surface and poorer gloss than the plated body obtained in Example 1.

Comparative Example 2 1.4-80430 parts of the same 98% purity as in Example 1 were put into the same autoclave as in Example 1, and then 3.3 parts of powdered potassium hydroxide was added as a catalyst.
Next, this autoclave was sealed and after being sufficiently purged with nitrogen gas, 444 parts of ethylene oxide was heated at a temperature of 60°C with stirring.
It was added over a period of 1 hour. At that time, the reaction pressure was set to 2.6 a.
It was kept below te. After the addition was completed, stirring was continued for 5 hours at the same temperature, and no drop in pressure was observed, so the reaction was terminated and the autoclave was opened. The contents were taken out, 30 parts of artificial activated clay (Kyowado 600S, manufactured by Kyowa Kasei Co., Ltd.) was added, stirred for 30 minutes to adsorb the catalyst, and then filtered.

Most of the catalyst was removed.

A plated body plated with nickel in the same manner as in Example 1 using this reaction product had a rougher surface and poorer gloss than the plated body obtained in Example 1.

Example 2 550 parts of ethylene oxide, 4.0 parts of powdered sodium hydroxide as a catalyst, and artificial activated clay (Kirin-Wadlo 00)
5) 1, using the method described in Example 1 except that 45 parts were used.
An aqueous solution of hydroxyethyl ether of 4-BD was prepared. Furthermore, nickel plating was performed using this aqueous solution in the same manner as in Example 1, to obtain a plated body with a bright luster.

Example 3 250 parts of ethylene oxide and 29 parts of propylene oxide
Example 1 except that 4.1 parts of potassium hydroxide and artificial activated clay (Kyowado 6005) were used as catalysts.
The reaction was carried out in the same manner as above to produce a random adduct of 1.4-BD. Further, using this aqueous solution, nickel plating was performed in the same manner as in Example 1 to obtain a plated body with brilliant luster.

"Effects of the Invention" If the method of the present invention is used, commercially available 1.4-BD is used as a raw material without distillation purification, and hydroxyalkyl etherification is performed in an aqueous solution, it can be used as an additive to a nickel plating solution. An excellent product can be obtained, and as a result, the surface gloss of the plated object can be easily improved.

Claims (1)

[Scope of Claims] An addition reaction of 1.0 to 3.0 moles of alkylene oxide to 1,1,4-butynediol in the presence of an alkali metal hydroxide at a reaction temperature of 40°C to 60°C. 1. A method for producing a hydroxyalkyl ether of 1,4-butynediol, which comprises using a 30 to 60% by weight aqueous solution of 1,4-butynediol. 2. The method according to claim 1, wherein the alkylene oxide is ethylene oxide and/or propylene oxide. In carrying out an addition reaction of 1.0 to 3.0 moles of alkylene oxide to 3,1,4-butynediol in the presence of an alkali metal hydroxide at a reaction temperature of 40°C to 60°C, 1,4- A nickel plating solution containing a hydroxyalkyl ether of 1,4-butynediol, which is produced using a 30 to 60% by weight aqueous solution of butynediol. 4. The treatment liquid according to claim 3, wherein the alkylene oxide is ethylene oxide and/or propylene oxide.