【０００１】[0001]
【産業上の利用分野】本発明は、分岐オレフィンから高
品質の第３級ヒドロペルオキシドを高収率で得る製造方
法に関する。FIELD OF THE INVENTION The present invention relates to a process for producing a high quality tertiary hydroperoxide in high yield from a branched olefin.
【０００２】[0002]
【従来の技術】一般に、分岐オレフィンからの第３級ヒ
ドロペルオキシドの製造方法としては、分岐オレフィン
と硫酸との反応物を作り、その反応物に過酸化水素を滴
下し反応させる方法、又は硫酸と過酸化水素より過硫酸
を作り、それに分岐オレフィンを滴下する方法によって
いた。2. Description of the Related Art Generally, as a method for producing a tertiary hydroperoxide from a branched olefin, a reaction product of a branched olefin and sulfuric acid is prepared, and hydrogen peroxide is added dropwise to the reaction product, or a reaction is performed with sulfuric acid. The method was to make persulfuric acid from hydrogen peroxide and add a branched olefin to it.
【０００３】[0003]
【発明が解決しようとする問題点】しかしながら、過酸
化水素を滴下する従来の方法では目的とする第３級ヒド
ロペルオキシドに加え、副生成物としてジアルキルペル
オキシドが多く生成し、目的とする高品質の第３級ヒド
ロペルオキシドを高収率で得ることができなかった。However, in the conventional method of dropping hydrogen peroxide, in addition to the desired tertiary hydroperoxide, a large amount of dialkyl peroxide is produced as a by-product, and the desired high quality is obtained. The tertiary hydroperoxide could not be obtained in high yield.
【０００４】[0004]
【問題点を解決するための手段】かかる観点から、本発
明者らは種々研究を重ねた結果、分岐オレフィンと硫酸
を加え、それに過酸化水素を加えるのではなく、分岐オ
レフィンと硫酸との反応物を作り、その反応物を特定の
温度条件で過酸化水素に加えることによって高品質の第
３級ヒドロペルオキシドを高収率で得られることを見い
出し、本発明を完成した。From these viewpoints, the inventors of the present invention have conducted various studies and as a result, as a result of adding a branched olefin and sulfuric acid, and not adding hydrogen peroxide to the reaction, a reaction between the branched olefin and sulfuric acid. It was found that a high quality tertiary hydroperoxide can be obtained in a high yield by preparing a product and adding the reaction product to hydrogen peroxide under specific temperature conditions, and thus the present invention has been completed.
【０００５】すなわち、本発明は分岐オレフィン、硫酸
及び過酸化水素から第３級ヒドロペルオキシドを製造す
る際、分岐オレフィンと硫酸との反応物を作り、その反
応物を３０℃以下の温度で過酸化水素中に滴下する事を
特徴とする第３級ヒドロペルオキシドの製造方法であ
る。なお、ここで反応物としているのは、分岐オレフィ
ンと硫酸を混ぜ合わせた際、発熱を伴うので、両者が反
応を起こしていると考えられるからである。That is, according to the present invention, when a tertiary hydroperoxide is produced from a branched olefin, sulfuric acid and hydrogen peroxide, a reaction product of the branched olefin and sulfuric acid is prepared and the reaction product is peroxidized at a temperature of 30 ° C. or lower. It is a method for producing a tertiary hydroperoxide, characterized in that it is added dropwise to hydrogen. The reaction product is used here because when the branched olefin and sulfuric acid are mixed with each other, heat is generated, and it is considered that the two react with each other.
【０００６】本発明は３０℃以下の温度で反応を行い、
好ましくは０〜２０℃である。反応温度が３０℃を越え
ると副生成物が多い。又、本発明によって使用される硫
酸と過酸化水素の濃度は硫酸５０〜８０％、過酸化水素
４０〜６０％が好ましい。使用量は、通常分岐オレフィ
ン１モルに対して硫酸０．５〜２．０モル、好ましくは
１．０〜１．５モル。過酸化水素１〜５モル、好ましく
は２〜４モルである。In the present invention, the reaction is carried out at a temperature of 30 ° C. or lower,
It is preferably 0 to 20 ° C. If the reaction temperature exceeds 30 ° C, there are many by-products. The concentrations of sulfuric acid and hydrogen peroxide used according to the present invention are preferably 50-80% sulfuric acid and 40-60% hydrogen peroxide. The amount used is usually 0.5 to 2.0 mol of sulfuric acid, preferably 1.0 to 1.5 mol, per mol of the branched olefin. Hydrogen peroxide is 1 to 5 mol, preferably 2 to 4 mol.
【０００７】本発明で使用できる分岐オレフィンとして
は、２−メチルペンテン−１、２−メチルペンテン−
２、２，３−ジメチルブテン−１、２，３−ジメチルブ
テン−２、２−メチルヘキセン−１、２−メチルヘキセ
ン−２、２，３−ジメチルヘキセン−１、２，３−ジメ
チルヘキセン−２、２−メチルヘプテン−１、２−メチ
ルヘプテン−２、２，３−ジメチルヘプテン−１、２，
３−ジメチルヘプテン−２、２−メチルオクテン−１、
２−メチルオクテン−２、２，３−ジメチルオクテン−
１、２，３−ジメチルオクテン−２、等がある。The branched olefins usable in the present invention include 2-methylpentene-1,2-methylpentene-
2,2,3-dimethylbutene-1,2,3-dimethylbutene-2,2-methylhexene-1,2-methylhexene-2,2,3-dimethylhexene-1,2,3-dimethylhexene- 2,2-methylheptene-1,2-methylheptene-2,2,3-dimethylheptene-1,2
3-dimethylheptene-2,2-methyloctene-1,
2-methyloctene-2,2,3-dimethyloctene-
1,2,3-dimethyloctene-2, etc.
【０００８】[0008]
【発明の効果】以上述べた本発明の第３級ヒドロペルオ
キシド製造において、分岐オレフィンと硫酸の反応物を
過酸化水素に滴下し反応させる製造法の特徴は、従来の
分岐オレフィンに硫酸を加えた後、過酸化水素を加えて
反応させる製造法に比べ、副生成物であるジアルキルペ
ルオキシドの生成が少なく、目的物である第３級ヒドロ
ペルオキシドを高品質で収率良く得られる製造法であ
る。In the production of the tertiary hydroperoxide of the present invention described above, the characteristic feature of the production method in which a reaction product of a branched olefin and sulfuric acid is added dropwise to hydrogen peroxide for reaction is to add sulfuric acid to a conventional branched olefin. After that, compared to the production method in which hydrogen peroxide is added and reacted, the production of the by-product dialkyl peroxide is less and the objective tertiary hydroperoxide can be obtained in high quality and in good yield.
【０００９】[0009]
【実施例】以下に実施例により本発明の方法をさらに詳
細に説明する。但し、本発明は実施例に限定されるもの
ではない。The method of the present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to the examples.
【００１０】[0010]
【実施例１】温度計、滴下ロート及び攪拌機を備えた内
容３００ｍｌの反応器に、２−メチルペンテン−１、５
５ｇ（０．６５モル）を仕込み、外部から冷却して内温
を１０℃に保ちながら、そこへ６５％硫酸９８．５ｇ
（０．６５モル）を滴下し、オレフィンと硫酸との反応
物を作った。次に６０％過酸化水素６６．７ｇ（１．３
モル）を同様の反応器に仕込み、内温を１０℃に保ちな
がらオレフィンと硫酸との反応物を滴下し、その温度で
５時間反応を行った。反応終了後、水層を分離し有機層
を水洗、乾燥し目的とする第３級ヒドロペルオキシドを
得た。Example 1 A reactor having a content of 300 ml equipped with a thermometer, a dropping funnel and a stirrer was charged with 2-methylpentene-1,5.
While charging 5 g (0.65 mol) and cooling from the outside to maintain the internal temperature at 10 ° C., 98.5 g of 65% sulfuric acid was added thereto.
(0.65 mol) was added dropwise to form a reaction product of olefin and sulfuric acid. Next, 66.7 g of 60% hydrogen peroxide (1.3%
(Mol) was charged in the same reactor, the reaction product of olefin and sulfuric acid was added dropwise while maintaining the internal temperature at 10 ° C., and the reaction was carried out at that temperature for 5 hours. After the reaction was completed, the aqueous layer was separated and the organic layer was washed with water and dried to obtain the desired tertiary hydroperoxide.
【００１１】[0011]
【実施例２】出発原料として、２−メチルペンテン−２
を用いた以外は実施例１に準じて反応を行った。そして
実施例１と同様に精製し、純度・収率を求めた。Example 2 As a starting material, 2-methylpentene-2
The reaction was carried out according to Example 1 except that was used. Then, the product was purified in the same manner as in Example 1 to determine the purity and yield.
【００１２】[0012]
【実施例３】出発原料として、２，３−ジメチルブテン
−１を用いた以外は実施例１に準じて反応を行った。そ
して実施例１と同様に精製し、純度・収率を求めた。Example 3 The reaction was carried out in the same manner as in Example 1 except that 2,3-dimethylbutene-1 was used as the starting material. Then, the product was purified in the same manner as in Example 1 to determine the purity and yield.
【００１３】[0013]
【比較例１】温度計、滴下ロート及び攪拌機を備えた内
容３００ｍｌの反応器に、２−メチルペンテン−１、５
５ｇ（０．６５モル）を仕込み、外部から冷却して内温
を１０℃に保ちながら、そこへ６５％硫酸９８．５ｇ
（０．６５モル）を滴下し、オレフィンと硫酸との反応
物を作った。次にこの反応物を１０℃に保ち、６０％過
酸化水素６６．７ｇ（１．３モル）を滴下し、その温度
で５時間反応を行った。反応終了後、水層を分離し有機
層を水洗、乾燥し目的とする第３級ヒドロペルオキシド
を得た。[Comparative Example 1] 2-Methylpentene-1, 5 was added to a reactor having a content of 300 ml equipped with a thermometer, a dropping funnel and a stirrer.
While charging 5 g (0.65 mol) and cooling from the outside to maintain the internal temperature at 10 ° C., 98.5 g of 65% sulfuric acid was added thereto.
(0.65 mol) was added dropwise to form a reaction product of olefin and sulfuric acid. Next, this reaction product was kept at 10 ° C., 66.7 g (1.3 mol) of 60% hydrogen peroxide was added dropwise, and the reaction was carried out at that temperature for 5 hours. After the reaction was completed, the aqueous layer was separated and the organic layer was washed with water and dried to obtain the desired tertiary hydroperoxide.
【００１４】[0014]
【比較例２】オレフィンと硫酸との反応物を過酸化水素
に滴下する際の温度を４０℃とする以外は、実施例１に
準じて反応を行った。そして実施例１と同様に精製し、
純度、収率を求めた。Comparative Example 2 A reaction was carried out in the same manner as in Example 1 except that the temperature at which the reaction product of olefin and sulfuric acid was dropped into hydrogen peroxide was 40 ° C. Then, purify in the same manner as in Example 1,
Purity and yield were determined.
【００１５】実施例１〜３、比較例１〜２の結果を表１
に示す。The results of Examples 1 to 3 and Comparative Examples 1 and 2 are shown in Table 1.
Shown in.
【００１６】これらの結果より明らかなように、オレフ
ィンと硫酸との反応物に過酸化水素を滴下する方法で
は、過酸化水素にオレフィンと硫酸との反応物を滴下す
る方法に比べてジアルキルペルオキシドが多く生成して
いるため純度が低く、収率も悪い。又、反応温度が３０
℃を越えた場合も同様に純度、収率が悪い。As is clear from these results, in the method in which hydrogen peroxide is added dropwise to the reaction product of olefin and sulfuric acid, the amount of dialkyl peroxide is higher than that in the method in which reaction product of olefin and sulfuric acid is added to hydrogen peroxide. Since much is produced, the purity is low and the yield is poor. Also, the reaction temperature is 30
When the temperature exceeds ℃, the purity and yield are also poor.
【表１】[Table 1]
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26820792AJP3214923B2 (en) | 1992-09-09 | 1992-09-09 | Method for producing tertiary hydroperoxide |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26820792AJP3214923B2 (en) | 1992-09-09 | 1992-09-09 | Method for producing tertiary hydroperoxide |
| Publication Number | Publication Date |
|---|---|
| JPH0770055Atrue JPH0770055A (en) | 1995-03-14 |
| JP3214923B2 JP3214923B2 (en) | 2001-10-02 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26820792AExpired - Fee RelatedJP3214923B2 (en) | 1992-09-09 | 1992-09-09 | Method for producing tertiary hydroperoxide |
| Country | Link |
|---|---|
| JP (1) | JP3214923B2 (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN120554269A (en)* | 2025-07-30 | 2025-08-29 | 淄博正华助剂股份有限公司 | Synthesis process of 1,1,3,3-tetramethylbutyl hydroperoxide |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN120554269A (en)* | 2025-07-30 | 2025-08-29 | 淄博正华助剂股份有限公司 | Synthesis process of 1,1,3,3-tetramethylbutyl hydroperoxide |
| Publication number | Publication date |
|---|---|
| JP3214923B2 (en) | 2001-10-02 |
| Publication | Publication Date | Title |
|---|---|---|
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| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees | Free format text:JAPANESE INTERMEDIATE CODE: R250 | |
| LAPS | Cancellation because of no payment of annual fees |