JPH03215468A - Production of purified hydroperoxide - Google Patents

Abstract

PURPOSE:To purify the subject compound useful as a polymerization initiator, etc., in high efficiency, by reacting an olefin or an alcohol with a strong acid and hydrogen peroxide and washing the obtained crude hydroperoxide with a specific aqueous solution. CONSTITUTION:A crude hydroperoxide is produced by reacting an olefin or an alcohol with a strong acid and hydrogen peroxide. The obtained crude hydroperoxide is purified to obtain the objective compound by washing with an aqueous solution containing >=20wt.% in total of one or more compounds selected from sodium chloride, potassium chloride, sodium sulfate, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate (preferably further containing sodium hydroxide and/or potassium hydroxide at a total concentration of the sodium hydroxide and/or potassium hydroxide of <=3wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing purified hydroperoxide used as a polymerization initiator, and more specifically, the present invention relates to a method for producing purified hydroperoxide used as a polymerization initiator. The present invention relates to a method for producing purified hydroperoxides that have been removed from the environment.

[Conventional technology]

Hydroperoxides have conventionally been used as polymerization initiators and curing agents, and are also useful as raw materials for the synthesis of organic peroxides. Hydroperoxides are generally produced by reacting the corresponding olefin or alcohol with a strong acid such as sulfuric acid and hydrogen peroxide, followed by separation, neutralization, and dehydration steps.

Since the obtained crude hydroperoxide contains a small amount of hydrogen peroxide, when it is used as a raw material for synthesis, it may cause undesirable side reactions. Therefore, methods for removing hydrogen peroxide, which is an impurity, have been proposed.

For example, in West German Published Patent No. 1225645,
A method of contacting crude hydroperoxide with an alkaline earth oxide or hydroxide is disclosed. Further, US Pat. No. 2,573,947 discloses a method for obtaining highly pure hydroperoxides by using organic solvents such as chloroform and dichloromethane.

[Problem to be solved by the invention]

However, the method disclosed in the West German patent does not allow sufficient solid-liquid contact, and some hydrogen peroxide still remains after treatment.
Further, there was a problem in that a filtration operation for the post-contact treatment agent was required. Further, the method disclosed in the above-mentioned US patent requires separation and removal of the used organic solvent by a method such as distillation, and has the problem that it is not a practical method. Therefore, a method for efficiently removing hydrogen peroxide is required.

An object of the present invention is to provide a method for producing a purified hydroperoxide in which the hydroperoxide is obtained in high yield and hydrogen peroxide in the obtained hydroperoxide is highly removed.

[Means to solve the problem]

In general, hydroperoxides and hydrogen peroxide exhibit weak acidity and each react with an alkali compound to form a water-soluble alkali salt. Therefore, when a mixed solution of hydroperoxide and hydrogen peroxide is brought into contact with an alkaline aqueous solution,
Hydrogen peroxide alone or hydrogen peroxide and hydroperoxide are dissolved as alkali salts.

As a result of extensive research into methods for efficiently removing hydrogen peroxide from hydroperoxides, the present inventors discovered that only hydrogen peroxide can be removed by using a specific inorganic salt or a mixture of an inorganic salt and an alkali hydroxide compound. They have discovered that selective extraction is possible and have completed the present invention.

That is, in the first aspect of the present invention, a crude hydroperoxide is produced by reacting an olefin or alcohol with a strong acid and hydrogen peroxide, and then the crude hydroperoxide is reacted with sodium chloride, potassium chloride, sodium sulfate, sodium carbonate, or potassium carbonate. , sodium hydrogen carbonate, and potassium hydrogen carbonate (hereinafter collectively referred to as inorganic salts), and the total content of the above compounds is 20% by weight or more. This method is adopted.

Further, in the second invention, after producing a crude hydroperoxide by reacting an olefin or alcohol with a strong acid and hydrogen peroxide, the crude hydroperoxide is mixed with one or more of the above-mentioned inorganic salts and sodium hydroxide and/or potassium hydroxide. (hereinafter collectively referred to as alkali hydroxide compounds), the total concentration of the alkali hydroxide compounds is 3% by weight or less, and the total content of the above compounds is 20% by weight or more. This method is adopted.

Next, the above configuration of the present invention will be explained in detail.

The hydroperoxide which is the target compound of the present invention is represented by the following general formula.

C Hs RC-008 C H 3 In the formula, R represents an alkyl group having 1 to 5 carbon atoms.

Specific examples include t-butyl hydroperoxide, t-amyl hydroperoxide, t-hexyl hydroperoxide, and t-octyl hydroperoxide.

Next, the olefins that are the raw materials for this hydroperoxide include isobutylene, 2-methylbutene-1,2-
Methylpentene-1, diisobutylene, etc. can be used. In addition, examples of alcohol include t-butanol, t-amyl alcohol, t-hexyl alcohol,
, 4.4-1 trimethylpentanol-2, etc. can be used.

As the strong acid, sulfuric acid or the like can be used, and its concentration is about 70 to 85%. Also, hydrogen peroxide is usually 5
A concentration of about 0% is used.

The crude hydroperoxides are obtained by reaction of the corresponding olefins or alcohols mentioned above with strong acids and hydrogen peroxide. The reaction of this olefin or alcohol with a strong acid and hydrogen peroxide can be carried out, for example, by dropping the alcohol into a strong acid aqueous solution of a predetermined concentration, and then adding hydrogen peroxide dropwise and mixing.
This is done by heating for a predetermined period of time. Alternatively, hydrogen peroxide solution is dropped into a strong acid aqueous solution of a predetermined concentration, and then the olefin is added dropwise, mixed, and heated for a predetermined time. Crude hydroperoxide is thus obtained.

This crude hydroperoxide may contain, in addition to dialkyl peroxide and hydrogen peroxide, an acid such as sulfuric acid used in the reaction. Further, the water content may be 50% by weight or less. When the water content exceeds 50% by weight,
This is not preferable because a large amount of that water migrates into the aqueous solution of the inorganic salt, reducing the concentration of the inorganic salt. However, when using a highly concentrated or solid inorganic salt and mixing it with the crude hydroperoxide, if the concentration of the inorganic salt is 20% by weight or more, the water content in the crude hydroperoxide may exceed 50% by weight. .

Next, in the first invention, the above-mentioned specific inorganic salt is used as a compound that is mixed with the crude hydroperoxide to exhibit its cleaning action, and in the second invention, the above-mentioned specific inorganic salt and hydroxide are used. It is an alkaline compound. The total concentration of these aqueous solutions is 20% by weight or more. 20
Below % by weight, the solubility of the hydroperoxide in aqueous solution increases and the loss of the hydroperoxide increases. In addition, the concentration of the alkali hydroxide compound is 0.01 to
A preferred amount is 3% by weight. If it is less than 0.01% by weight, it is difficult to obtain the effect of adding the alkali hydroxide compound, and if it exceeds 3% by weight, the hydroperoxide will generate an alkali salt and dissolve, resulting in a large loss.

The amount of the inorganic salt or the aqueous solution of the inorganic salt and the alkali hydroxide compound to be used is usually 0.1 to 3 times the amount of crude hydroperoxide by weight.

Usage amount is 0. If it is less than 1 times the amount, the effect of removing hydrogen peroxide in the crude hydroperoxide is small, and even if more than 3 times the amount is used, the effect of increasing the amount is small and tends to be economically disadvantageous.

The crude hydroperoxide and the inorganic salt or the aqueous solution of the inorganic salt and the alkali hydroxide compound are mixed by stirring both with a conventional stirrer or with a mixing device such as a line mixer. This operation may be continuous or batchwise. Also, the temperature at that time is
Although there is no particular limitation, a temperature of lO to 30°C is generally suitable.

After mixing the two in this manner, the aqueous layer is separated to produce purified hydroperoxide.

[Examples 1 to 9 and Comparative Examples 1 to 3] Examples and comparative examples embodying the present invention will be described below. In each example, hydrogen peroxide and hydroperoxide were determined by measuring total active oxygen by the iodine method and by catalase (
It was determined by measuring active oxygen after decomposition of filtered hydrogen oxide (hydrogen peroxide decomposing enzyme).

(Example 1) (Production of t-butyl hydroperoxide) In a 5 L four-bottle flask equipped with a stirrer and a thermometer, 85
1,160 g of % sulfuric acid was added, and 1,720 g of t-butanol was added dropwise at 20° C. over 15 minutes. Add 1 part of 50% hydrogen peroxide to this
900g were mixed at 20°C and reacted at 50°C for 1 hour. After the resulting reaction solution was cooled and separated, calcium carbonate was added and stirred to neutralize the solution, followed by filtration to obtain 1780 g of crude t-butyl hydroperoxide. As a result of analyzing this,
Purity of t-butyl hydroperoxide 81%, hydrogen peroxide content 0.20%, di-t-butyl peroxide 6.
It was 5%.

Next, in a 300 ml four-necked flask equipped with a stirrer and a thermometer, 100 g of the crude t-butyl hydroperoxide, 24 g of sodium chloride, 1 g of sodium hydroxide, and 75 g of water were added.
100 g of an aqueous solution consisting of 100 g was added thereto, and the mixture was stirred at 20° C. for 30 minutes. Then, the aqueous layer was separated to produce purified t-butyl hydroperoxide 6. 5 g was obtained. The recovery rate of this t-butyl hydroperoxide was 98.5%, and analysis revealed that the hydrogen peroxide content was 0.5%. It was 0.04%.

As described above, according to the production method of this example, by using sodium chloride as an inorganic salt and sodium hydroxide as an alkali compound, the recovery rate of t-butyl hydroperoxide was as high as 98.5%. Moreover, the hydrogen peroxide content is extremely low at 0.004%.

(Example 2) (Production of t-butyl hydroperoxide) In the above Example 1, instead of using 100 g of an aqueous solution of sodium chloride and sodium hydroxide, 12 g of sodium chloride, 0.7 g of sodium carbonate, and 3 g of water were used. 3
The same operation as in Example 1 was performed except that 50 g of an aqueous solution consisting of As a result, purified t-butyl hydroperoxide was obtained. 2g was obtained. This t-
The recovery rate of butyl hydroperoxide was 99.0%, and analysis revealed that the hydrogen peroxide content was 0. 0 0 7%
Met.

As described above, according to the production method of this example, by using sodium chloride and sodium carbonate in combination, the recovery rate of t-butyl hydroperoxide is very high, and the hydrogen peroxide content is very low.

(Example 3) (Production of t-amyl hydroperoxide) In the same manner as in Example 1, except that 2050 g of t-amyl alcohol was used instead of 1720 g of t-butanol, crude t-amyl hydroperoxide was produced. 2010g was obtained. As a result of analyzing this, the purity of t-amyl hydroperoxide was 83%, and the content of hydrogen peroxide was 0.
．． 25%, di-t-amyl peroxide 3.6%.

Next, using the same reaction apparatus as in Example 1, 100 g of the crude t-amyl hydroperoxide and 23 g of sodium chloride were added.
100 g of an aqueous solution consisting of 2 g of sodium hydrogen carbonate and 75 g of water was added, and the mixture was stirred at 20°C for 30 minutes. Then purified t-amylhydride peroxy F 10 3. by separating the aqueous layer. 1 g was obtained. The recovery rate of this t-amyl hydroperoxide was 98.5%, and analysis revealed that the hydrogen peroxide content was O. O O 5
%Met.

Thus, according to the manufacturing method of this example, by using sodium chloride and sodium hydrogen carbonate together, t-
A high recovery rate of amyl hydroperoxide can be obtained and a very low hydrogen peroxide content can be achieved.

(Example 4) (Production of t-butyl hydroperoxide) In Example 1, instead of using 100 g of an aqueous solution of sodium chloride and sodium hydroxide, 6.9 g of potassium chloride and 0.0 g of potassium hydroxide were used. 15 g and 1 water
9. The same operation as in Example 1 was performed except that 30 g of an aqueous solution consisting of 95 g was used. The recovery rate of this t-butyl hydroperoxide was 99.2%, and analysis revealed that the hydrogen peroxide content was 0. It was 0.07%.

As described above, according to the production method of this example, by using potassium chloride and potassium hydroxide together, a high recovery rate of t-amyl hydroperoxide can be obtained, and
Hydrogen peroxide content can be lowered.

(Example 5) (Production of t-hexyl hydroperoxide) In a 11-liter four-necked flask equipped with a stirrer and a thermometer, 70 g.
Add 500g of 50% sulfuric acid and 240g of 50% hydrogen peroxide.
The mixture was added dropwise at ℃ for 1 hour. Then, 2-methylpentene-
87 g of 1 was added dropwise at 25°C over 2 hours. The reaction was then continued for 2 hours at 30°C. After further cooling and separation,
Add calcium carbonate, stir to neutralize, and filter to obtain crude T-
380 g of hexyl hydroperoxide were obtained. As a result of analyzing this, the purity of t-hexyl hydroperoxide was 8.
The hydrogen peroxide content was 0.13%.

Next, using the same reaction apparatus as in Example 1, the crude t-
100 g of an aqueous solution consisting of 100 g of hexyl hydroperoxide, 23 g of sodium sulfate, 1 g of sodium hydroxide, and 76 g of water was added, and the mixture was stirred at 20° C. for 30 minutes. Thereafter, the aqueous layer was separated to obtain 106.9 g of purified t-hexyl hydroperoxide. The recovery rate of this t-hexyl hydroperoxide was 99.1%, and analysis revealed that the hydrogen peroxide content was O. O O was 4%.

Thus, according to the production method of this example, by using sodium sulfate and sodium hydroxide together, a very high recovery rate of t-hexyl hydroperoxide can be obtained, and the hydrogen peroxide content can be greatly increased. can be reduced.

(Example 6) (Production of t-butyl hydroperoxide) Same as Example 1 except that 50 g of a 24% aqueous sodium chloride solution was used instead of 100 g of an aqueous solution of sodium chloride and sodium hydroxide. Purified t-butyl hydroperoxide 10
5. 0 g was obtained. The recovery rate of this t-butyl hydroperoxide was 99.0%, and analysis revealed that the hydrogen peroxide content was 0. It was 0.50%.

According to the production method of this example, by using sodium chloride as the inorganic salt, a very high recovery rate of t-butyl hydroperoxide can be obtained, and the hydrogen peroxide content can be reduced.

(Example 7) (Production of t-amyl hydroperoxide) Same as Example 3 except that 100 g of a 25% potassium chloride aqueous solution was used instead of 100 g of an aqueous solution of sodium chloride and sodium hydrogen carbonate. Purified t-amyl hydroperoxide 1
0 3. 5 g was obtained. The recovery rate of this t-amyl hydroperoxide was 99.3%, and the hydrogen peroxide content was 0.032% as a result of analysis.

According to the production method of this example, by using potassium chloride as the inorganic salt, a very high recovery rate of t-amyl hydroperoxide can be obtained, and the hydrogen peroxide content can be reduced.

(Comparative Example 1) (Production of t-butyl hydroperoxide) Same procedure as in Example 1 except that 100 g of 15% sodium sulfate was used instead of the long aqueous solution of sodium chloride and sodium hydroxide in Example 1. I did it. As a result, purified 1-butyl hydroperoxide 104. 2 g was obtained. The recovery rate of this t-butyl hydroperoxide was 90.5%. Also, as a result of the analysis, the hydrogen peroxide content was 0. It was 0.20%.

In this way, by using sodium sulfate instead of the combined use of sodium chloride and sodium hydroxide, the content of hydrogen peroxide as an impurity increased to 0.020%, and the recovery rate of t-butyl hydroperoxide also increased. decreased.

(Comparative Example 2) (Production of t-butyl hydroperoxide) Example 1 except that 10 g of a 1% aqueous sodium hydroxide solution was used instead of 100 g of an aqueous solution of sodium chloride and sodium hydroxide in Example 1. Purified t-butyl hydroperoxide 10 by performing the same operation as
0. 9 g was obtained. The recovery rate of this 1-butyl hydroperoxide was 93.2%, and as a result of analysis, the hydrogen peroxide content was 0.12%.

Thus, when only sodium hydroxide aqueous solution is used, the hydrogen peroxide content increases to 0.12%, and t-
The recovery of butyl hydroperoxide also decreases to 93.2%.

(Comparative Example 3) (Production of t-butyl hydroperoxide) Instead of using 100 g of an aqueous solution of sodium chloride and sodium hydroxide in Example 1, 100 g of an aqueous solution consisting of 19 g of sodium chloride, 5 g of sodium hydroxide, and 76 g of water was used. The same operation as in Example 1 was performed except for using the following. As a result, purified t-butyl hydroperoxide 10
0. 9 g was obtained.

The recovery rate of this t-butyl hydroperoxide was 95.7
%Met. Additionally, as a result of the analysis, the hydrogen peroxide content was 0.
．． It was 0.04%.

Thus, by increasing the concentration of sodium hydroxide, the recovery rate of t-butyl hydroperoxide decreased.

(Example 8) (Production of t-butyl hydroperoxide) Same as Example 1 except that 50 g of a 24% potassium hydrogen carbonate aqueous solution was used instead of 100 g of an aqueous solution of sodium chloride and sodium hydroxide in Example 1. Performed the same operation. As a result, purified t-butyl hydroperoxide was obtained. 3 g was obtained. The recovery rate of this t-butyl hydroperoxide was 99.3%. Also,
As a result of the analysis, the hydrogen peroxide content was 0. It was 0.05%.

Thus, according to this example, by using a 24% potassium bicarbonate aqueous solution, the recovery rate of t-butyl hydroperoxide is very high, and the content of hydrogen peroxide is very low.

(Example 9) (Production of t-butyl hydroperoxide) Instead of using 100 g of an aqueous solution of sodium chloride and sodium hydroxide in Example 1, an aqueous solution 5 consisting of 6 g of potassium chloride, 6 g of potassium carbonate, and 38 g of water was used.
The same operation as in Example 1 was performed except that 0 g was used. As a result, purified t-butyl hydroperoxide 10'7.0
I got g. The recovery rate of this t-butyl hydroperoxide was 99.1%. Additionally, as a result of the analysis, the hydrogen peroxide content was found to be O. O O was 4%.

Thus, according to this example, by using an aqueous solution of potassium chloride and potassium carbonate, the recovery rate of t-butyl hydroperoxide is very high, and the hydrogen peroxide content is very low.

〔Effect of the invention〕

According to the method for producing purified hydroperoxide in the first aspect of the present invention, not only the desired hydroperoxide can be obtained in high yield, but also hydrogen peroxide in the obtained hydroperoxide can be removed to a high degree. It has excellent effects.

Further, according to the method for producing purified hydroperoxide in the second invention, hydrogen peroxide in the hydroperoxide is removed to a higher degree, and the yield of the hydroperoxide is also high.

Claims (1)

[Claims] 1. After producing a crude hydroperoxide by reacting an olefin or alcohol with a strong acid and hydrogen peroxide, the crude hydroperoxide is converted into sodium chloride, potassium chloride, sodium sulfate, sodium carbonate, potassium carbonate, carbonic acid. A method for producing purified hydroperoxide, which comprises washing with an aqueous solution containing one or more compounds selected from the group consisting of sodium hydrogen carbonate and potassium hydrogen carbonate, the total content of which is 20% by weight or more. 2. After producing a crude hydroperoxide by reacting an olefin or alcohol with a strong acid and hydrogen peroxide, the crude hydroperoxide is converted into sodium chloride, potassium chloride, sodium sulfate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate. Contains one or more compounds selected from the group consisting of sodium hydroxide and/or potassium hydroxide, the total concentration of sodium hydroxide and/or potassium hydroxide is 3% by weight or less, and the total content of the above compounds A method for producing purified hydroperoxide, which comprises washing with an aqueous solution having an amount of 20% by weight or more.