JPS6281341A - Production of 2,5-di-tert-butylhydroquinone - Google Patents
Production of 2,5-di-tert-butylhydroquinoneInfo
- Publication number
- JPS6281341A JPS6281341A JP22019985A JP22019985A JPS6281341A JP S6281341 A JPS6281341 A JP S6281341A JP 22019985 A JP22019985 A JP 22019985A JP 22019985 A JP22019985 A JP 22019985A JP S6281341 A JPS6281341 A JP S6281341A
- Authority
- JP
- Japan
- Prior art keywords
- toluene
- butylhydroquinone
- tert
- dtbhq
- extraction residue
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000012452 mother liquor Substances 0.000 claims abstract description 6
- 239000011541 reaction mixture Substances 0.000 claims abstract description 5
- 230000029936 alkylation Effects 0.000 claims 1
- 238000005804 alkylation reaction Methods 0.000 claims 1
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 abstract description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 7
- 239000004250 tert-Butylhydroquinone Substances 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 6
- 238000000605 extraction Methods 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 5
- 238000001953 recrystallisation Methods 0.000 abstract description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 4
- 235000019281 tert-butylhydroquinone Nutrition 0.000 abstract description 4
- 230000002152 alkylating effect Effects 0.000 abstract description 3
- 239000003963 antioxidant agent Substances 0.000 abstract description 2
- 230000003078 antioxidant effect Effects 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 229920001971 elastomer Polymers 0.000 abstract description 2
- 239000010687 lubricating oil Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000004033 plastic Substances 0.000 abstract description 2
- 229920003023 plastic Polymers 0.000 abstract description 2
- 239000005060 rubber Substances 0.000 abstract description 2
- 238000010186 staining Methods 0.000 abstract description 2
- 229940044119 2-tert-butylhydroquinone Drugs 0.000 abstract 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 abstract 2
- 239000006227 byproduct Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000035558 fertility Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は２ ＋ ５− ｔｅｒｔ−ブチルヒドロキノン
の製造方法に関するもの１ある。２，５−ジ−ｔｅｒ
ｔ−ブチルヒドロキノンはプラスチック、ゴム、＠滑油
等の非汚染性酸化防止剤として広く用いられている有用
な化合物である。更に、近年ではその化学的構造を利用
した有機反応の原料としても使用されており、その高純
度化が要望されている。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing 2 + 5-tert-butylhydroquinone. 2,5-ter
T-Butylhydroquinone is a useful compound widely used as a non-staining antioxidant for plastics, rubber, lubricating oils, etc. Furthermore, in recent years, it has been used as a raw material for organic reactions that utilize its chemical structure, and there is a demand for its high purity.
２．５−ジ−ｔｅｒｔ−ブチルヒドロキノンはヒドロキ
ノｙをｔ−ｆチルアルコールまたはイソゾテンファルキ
ル化することによって合成されるが、この合成反応には
触媒として塩化亜鉛（米国特許第２５１１１９３号）ま
たは５０〜８０％硫酸（米国特許第２８３２８０８号）
が使用されているが、生成物からの触媒の分離等の後処
理の簡便さから硫酸触媒を使用する方法が一般に行われ
ている。丁なわち、硫酸水浴液に分離させたヒドロキノ
ンにガス状のイソブチンを導入して反応させ、浮上する
反応生成物をｆ過によって硫酸水溶液と分離し、次いで
多葉の水または温水！洗浄して未反応の原料、副生物、
付着した硫酸を除き、乾燥して目的物の２．５−ノーｔ
ｅｒｔ−ゾチルヒドロキノンを得ている。2.5-Di-tert-butylhydroquinone is synthesized by t-f tyl alcohol or isozotenphalkylation of hydroquinone, and this synthesis reaction uses zinc chloride (US Pat. No. 2,511,193) as a catalyst. or 50-80% sulfuric acid (U.S. Patent No. 2,832,808)
However, a method using a sulfuric acid catalyst is generally used because of the ease of post-treatment such as separation of the catalyst from the product. In other words, gaseous isobutyne is introduced into hydroquinone separated in a sulfuric acid water bath solution, and the reaction product is separated from the sulfuric acid aqueous solution by filtration. Washed and unreacted raw materials, by-products,
Remove the attached sulfuric acid and dry to remove the target 2.5-note.
ert-zotylhydroquinone is obtained.
しかしながら上記のような従来の製法費は、水または温
水で反応生成物を繰返し洗浄する精製工程があるだけで
あって、このような精製工程だげでは２，５−ジ−ｔｅ
ｒ ｔ−ブチルヒドロキノンの結晶内に取り込まれた不
純物や温水に難溶性の副生物などを充分に除去すること
ができず、これらの物質は製品着色の原因ともなり、高
純度の２，５−ジ−ｔｅｒｔ−ブチルヒドロキノンを得
ることが困難−ＩＪ）つた。因みに従来法によって得ら
れた２、５−ジ−ｔｅｒ ｔ−ブチルヒドロキノンのＭ
ｌｌは略９９．０％であり、Ｍ点は２１０〜２１２℃マ
ある。また、触媒として使用する硫酸が製品中に残留し
ていると２．５−シーｔｅｒｔ−ブチルヒドロキノンが
使用時に分解する恐れがあった。However, the cost of the conventional manufacturing method as mentioned above is only that there is a purification step in which the reaction product is repeatedly washed with water or hot water, and such a purification step alone cannot produce 2,5-di-te.
r It is not possible to sufficiently remove impurities incorporated into the crystals of t-butylhydroquinone and by-products that are poorly soluble in hot water, and these substances may cause coloring of the product. Difficult to obtain di-tert-butylhydroquinone - IJ). Incidentally, M of 2,5-di-tert-butylhydroquinone obtained by the conventional method
ll is approximately 99.0%, and the M point is 210 to 212°C. Furthermore, if sulfuric acid used as a catalyst remained in the product, there was a risk that 2,5-tert-butylhydroquinone would decompose during use.
〔問題点を解決するための手段及び作用〕本発明方法に
よれば、’１−ｔｅｒｔ−ブチルヒドロキノン（以下Ｔ
ＢＨＱと記す）製造の際に副生ずる抽残物の主要成分〒
ある２、５−ジ−ｔｅｒｔ−ブチルヒドロキノン（以下
ＤＴＢＨＱと記す）をトルエンを使用して再結晶法によ
り単離することにより高純度のＤＴＢ）ＩＱが得られる
。[Means and effects for solving the problems] According to the method of the present invention, '1-tert-butylhydroquinone (hereinafter referred to as T
Main components of raffinate produced by-product during production (denoted as BHQ)
High purity DTB) IQ can be obtained by isolating a certain 2,5-di-tert-butylhydroquinone (hereinafter referred to as DTBHQ) by a recrystallization method using toluene.
ＴＢＩＩＱは、例えばヒドロキノンをリン酸触媒の存在
下でイソブチン〒アルキル化することによって製造され
るが、最も選択性がよい場合でも１０数モル％のＤＴＢ
ＨＱが副生する。 この反応混合物を水マスラリ−にし
、温水′ｔ％ＴＢＨＱを抽出するとＤＴＢＨＱを主成分
とする抽残物が得られる。TBIIQ is produced, for example, by alkylating hydroquinone with isobutyne in the presence of a phosphoric acid catalyst, but even with the best selectivity, only a few mol% of DTB is produced.
HQ is a byproduct. This reaction mixture is made into a water slurry, and when t% TBHQ is extracted with hot water, a raffinate containing DTBHQ as a main component is obtained.
この抽残物に対して６〜５倍量のトルエンを加え、１０
０〜１５０°Ｃに加熱し、次に冷却し、晶析した結晶を
適当な方法を母液と分離する。この晶析母液は〒きるだ
けよく脱液した方が高純度のＤＴＢＨＱが得られる。分
離した結晶に付着しているトルエンは水と共沸して除去
する。こうして得られたスラリーを冷却、脱水、乾燥す
ると高純度のＤ Ｔ Ｂ ＨＱが得られる。結晶から分
離した晶析母液から水との共沸によりトルエンを回収し
、再結晶用溶媒として使用する。ここｆｆ１）ルエン留
去後に母液を室温まマ冷却すると共沸残置は固化し、全
体がスラリー状になる。このスラリーは適当な方法で脱
水し、得られた固形分は焼却処分する。Add 6 to 5 times the amount of toluene to this raffinate, and
It is heated to 0-150°C, then cooled and the crystallized crystals are separated from the mother liquor by a suitable method. DTBHQ of higher purity can be obtained by removing the liquid from this crystallization mother liquor as thoroughly as possible. Toluene adhering to the separated crystals is azeotropically removed with water. When the slurry thus obtained is cooled, dehydrated, and dried, highly pure D T B HQ is obtained. Toluene is recovered from the crystallization mother liquor separated from the crystals by azeotropy with water and used as a recrystallization solvent. Here ff1) When the mother liquor is cooled to room temperature after toluene distillation, the azeotropic residue solidifies and the whole becomes slurry-like. This slurry is dehydrated by an appropriate method, and the resulting solids are incinerated.
以下の実施例によって本発明を史に具体的に説明する。The present invention will be illustrated by the following examples.
実施例
容ｔ３ｍ’の反応器にヒドロキノンａｓｏｘｐ、 ６０
％リン酸１４９ＫＰおよびトルエン１５００１を入れ、
１２０℃に加熱する。これにインブテン２４４ＫＰを５
時間かかって添加する。イソブチンの添加終了後、反応
混合物を１００°Ｃに冷却し、３０分間静置後トルエン
層をデカンテーションして別の攪拌槽に移し、リン酸お
よび未反応のヒドロキノンを水洗して除去し、次に水フ
共沸してトルエンを除去する。こうして得られた生成物
を７０〜８０℃に冷却して水スラリーとし、温水により
ＴＢＨＱを抽出する。Example: In a reactor with a volume of t3 m', hydroquinone asoxp, 60
% phosphoric acid 149KP and toluene 15001,
Heat to 120°C. Add 244 KP of Inbuten to this.
Add it over time. After the addition of isobutyne was completed, the reaction mixture was cooled to 100 °C, left to stand for 30 minutes, the toluene layer was decanted and transferred to another stirring tank, phosphoric acid and unreacted hydroquinone were removed by washing with water, and then Toluene is removed by azeotroping with water. The product thus obtained is cooled to 70-80°C to form a water slurry, and TBHQ is extracted with hot water.
抽出後に得られる抽残物はＤＴＢＨＱに富んでおり、Ｄ
ＴＢＨＱ６９．４東盾％、ＴＢＨＱ６．９重量％、水１
０．０重１％、その他の有＋！１物１３．７重寸％から
成る。The raffinate obtained after extraction is rich in DTBHQ and D
TBHQ69.4 Toshiki%, TBHQ6.9% by weight, water 1
0.0 weight 1%, other +! Each item consists of 13.7% by weight.
この抽残物４５５ Ｋ９にトルエン２．０１を加え、１
４０℃に加熱し、溶解−する。温度が１４０℃に達し溶
解した後直ちに常温まで冷却すると結晶が析出する。Add 2.01 l of toluene to this raffinate 455 K9,
Heat to 40°C to dissolve. Immediately after the temperature reaches 140°C and melts, it is cooled to room temperature to precipitate crystals.
トルエン１．９ ｍ”を１過して除去した後、得られた
ケーキに水を加え、加熱して水と共沸してトルエンを除
去する。温度が水の沸点に達したときに、混合物を常温
に冷却し、脱水し、乾燥する。純度９９．８％、融点２
１４〜２１８℃のＤＴＢＨＱ ３００ Ｋｙが得られる
。抽残物中のＤＴＢＨＱの回収率は９５％フある。ｅ過
したトルエンは水と共沸してトルエン１．８５ ｍ”を
回収し、共沸残漬９６に２が得られる。After removing 1.9 m" of toluene by filtration, water is added to the resulting cake and heated to remove the toluene azeotropically with the water. When the temperature reaches the boiling point of water, the mixture Cool to room temperature, dehydrate, and dry. Purity 99.8%, melting point 2.
DTBHQ 300 Ky of 14-218°C is obtained. The recovery rate of DTBHQ in the raffinate is 95%. The filtered toluene is azeotroped with water to recover 1.85 m'' of toluene, yielding 2 as an azeotropic residue 96.
本発明方法によれば、（１）より付加価値の島い２−ｔ
ｅｒｔ−ブチルヒドロキノンが副生され、原料のヒドロ
キノンやイソブチンを有効に使用〒きる； （２＋ ２
。According to the method of the present invention, (1) 2-t with higher added value
Ert-butylhydroquinone is produced as a by-product, and the raw materials hydroquinone and isobutyne can be used effectively; (2+2
.
５−ジ−ｔｅｒｔ−ブチルヒドロキノンのみの製造工程
より々る従来法と比較して生殖性が高い；（３）熱水に
よる抽出によって水溶性不純物が除去され、トルエンに
よる再結晶によって油溶性不純物が除去されるのｔ＠酸
等を含まない高純度の２，５−ノーｔｅｒｔ−ブチルヒ
ドロキノンが得られる；（４）熱水抽出は２− ｔｅｒ
ｔ−ブチルヒドロキノンの設備を使用でき、実際にはト
ルエンによる再結晶の設備だけを増設すればよく、生産
設備が簡単に構築される；（５）除去した不純物は焼却
等により容易に処理される。It has higher fertility compared to the conventional method, which involves the production of only 5-di-tert-butylhydroquinone; (3) Extraction with hot water removes water-soluble impurities, and recrystallization with toluene removes oil-soluble impurities. Highly purified 2,5-tert-butylhydroquinone containing no acid is obtained; (4) Hot water extraction is performed using 2-tert
Equipment for t-butylhydroquinone can be used, and production equipment can be easily constructed by simply adding equipment for recrystallization with toluene; (5) Removed impurities can be easily disposed of by incineration, etc. .
Claims (1)
を温水で抽出し、２，５−ジ−ｔｅｒｔ−ブチルヒドロ
キノンよりなる抽残物をトルエンで再結晶し、母液と分
離することを特徴とする２，５−ジ−ｔｅｒｔ−ブチル
ヒドロキノンの製造方法。2, characterized in that the reaction mixture obtained by alkylation of hydroquinone is extracted with hot water, the raffinate consisting of 2,5-di-tert-butylhydroquinone is recrystallized with toluene, and separated from the mother liquor; Method for producing 5-di-tert-butylhydroquinone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22019985A JPS6281341A (en) | 1985-10-04 | 1985-10-04 | Production of 2,5-di-tert-butylhydroquinone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22019985A JPS6281341A (en) | 1985-10-04 | 1985-10-04 | Production of 2,5-di-tert-butylhydroquinone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6281341A true JPS6281341A (en) | 1987-04-14 |
Family
ID=16747439
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22019985A Pending JPS6281341A (en) | 1985-10-04 | 1985-10-04 | Production of 2,5-di-tert-butylhydroquinone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6281341A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104072340A (en) * | 2014-06-23 | 2014-10-01 | 华南理工大学 | Recrystallization purification method of 2,5-di-tert-butylhydroquinone |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2722556A (en) * | 1952-03-19 | 1955-11-01 | Eastman Kodak Co | Preparation of tertiary butyl hydroquinone |
-
1985
- 1985-10-04 JP JP22019985A patent/JPS6281341A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2722556A (en) * | 1952-03-19 | 1955-11-01 | Eastman Kodak Co | Preparation of tertiary butyl hydroquinone |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104072340A (en) * | 2014-06-23 | 2014-10-01 | 华南理工大学 | Recrystallization purification method of 2,5-di-tert-butylhydroquinone |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS6118537B2 (en) | ||
| EP0293037A1 (en) | Preparation of 4,4'-dihydroxydiphenyl sulfone | |
| JPH0446253B2 (en) | ||
| JPH029576B2 (en) | ||
| GB2103214A (en) | Process for the purification of nitro-phenoxybenzoic acid derivatives | |
| JP3291987B2 (en) | Purification method of O, S-dimethyl-N-acetylphosphoramidothioate | |
| US4686301A (en) | Process for the preparation of 2,4-dinitrophenol alkoxyalkyl ethers | |
| JP3570760B2 (en) | Method for producing 2-t-butylhydroquinone | |
| JP2697054B2 (en) | Method for producing p-hydroxybenzaldehyde | |
| JP2697056B2 (en) | Method for producing p-hydroxybenzaldehyde | |
| JP3570759B2 (en) | Method for simultaneously producing high-purity 2-t-butylhydroquinone and 2,5-di-t-butylhydroquinone | |
| JPH04360879A (en) | Purification of aromatic triazoles | |
| KR830000275B1 (en) | Preparation of Tricycleazole | |
| US2878281A (en) | Preparation of amino benzoic acids | |
| JPH05221963A (en) | Urea fusion process for synthesis of 3-phenoxy- 1-azetidinecarboxyamide | |
| US2447419A (en) | Preparation of diphenylacetonitrile | |
| JP2697055B2 (en) | Method for producing p-hydroxybenzaldehyde | |
| JPH07206763A (en) | Process for producing purified 3,3 ', 4,4'-biphenyltetracarboxylic acid or acid dianhydride thereof | |
| US3155673A (en) | Process for preparing vitamin b | |
| JP3184638B2 (en) | Method for producing tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate | |
| US1930753A (en) | Chlorination of cresidine | |
| US3221052A (en) | Salicylanilide process | |
| US3231611A (en) | Purification of salicylanilide | |
| JP5079416B2 (en) | Process for producing 5- (3-benzyloxycyclobutane) hydantoin | |
| GB2110680A (en) | Method for purifying phloroglucin |