JPS63159334A - Production of 2,4-di-tertiary butylphenol - Google Patents
Production of 2,4-di-tertiary butylphenolInfo
- Publication number
- JPS63159334A JPS63159334A JP61307549A JP30754986A JPS63159334A JP S63159334 A JPS63159334 A JP S63159334A JP 61307549 A JP61307549 A JP 61307549A JP 30754986 A JP30754986 A JP 30754986A JP S63159334 A JPS63159334 A JP S63159334A
- Authority
- JP
- Japan
- Prior art keywords
- isobutylene
- phenol
- catalyst
- solid acid
- mentioned
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 title description 15
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000011973 solid acid Substances 0.000 claims abstract description 23
- 239000004927 clay Substances 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 10
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 claims abstract description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims abstract description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 238000006386 neutralization reaction Methods 0.000 abstract description 4
- 238000005406 washing Methods 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- -1 recovery phenol etc. Chemical compound 0.000 abstract description 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 2
- 238000006384 oligomerization reaction Methods 0.000 abstract 2
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 238000004821 distillation Methods 0.000 description 13
- 239000012969 di-tertiary-butyl peroxide Substances 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- PFEFOYRSMXVNEL-UHFFFAOYSA-N 2,4,6-tritert-butylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 PFEFOYRSMXVNEL-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は２，４−ジ−ｔ−ブチルフェノール（以下、２
゜４−ＤＴＢＰと記す）の製造方法、特にフェノールと
イソブチレンとを固体酸触媒の存在下に反応させて２．
４−ＤＴＢＰを製造する方法に関するものである。Detailed Description of the Invention [Industrial Field of Application] The present invention relates to 2,4-di-t-butylphenol (hereinafter referred to as 2-t-butylphenol).
4-DTBP), in particular, by reacting phenol and isobutylene in the presence of a solid acid catalyst.
The present invention relates to a method for producing 4-DTBP.
２．４−ＤＴＢＰの製造方法としてアルキル化反応触媒
の存在下にフェノールとイソブチレンを反応させる方法
がある。従来の製造方法では触媒として、硫酸およびリ
ン酸（スペイン特許第８３５，７９４号）、フッ素化ア
ルミナ（米国特許第４，２７５．２１１９号）、ならび
にリチウム化アルミナ（米国特許第４，２６０，８３３
号）などが使用されている。As a method for producing 2.4-DTBP, there is a method in which phenol and isobutylene are reacted in the presence of an alkylation reaction catalyst. Conventional production methods use sulfuric and phosphoric acids (Spanish Patent No. 835,794), fluorinated alumina (U.S. Pat. No. 4,275.2119), and lithiated alumina (U.S. Pat. No. 4,260,833) as catalysts.
No.) etc. are used.
しかしながら、上記の製造方法において、触媒として硫
酸またはリン酸を用いると、イソブチレンがオリゴマー
化して有効利用率を低下させるとともに、触媒の中和、
水洗工程を必要とし、フェノールを含む廃水が大量に発
生して、公害の問題を伴う。また触媒としてフッ素化ア
ルミナまたはリチウム化アルミナを用いると、イソブチ
レンオリゴマーの生成は抑制されるが、触媒のコストが
高くなるなどの問題点があった。However, in the above production method, when sulfuric acid or phosphoric acid is used as a catalyst, isobutylene is oligomerized and the effective utilization rate is reduced, and the catalyst is neutralized.
It requires a water washing process and generates a large amount of wastewater containing phenol, resulting in pollution problems. Furthermore, when fluorinated alumina or lithiated alumina is used as a catalyst, the production of isobutylene oligomers is suppressed, but there are problems such as an increase in the cost of the catalyst.
本発明は上記問題点を解決するためのもので。The present invention is intended to solve the above problems.
安価な触媒を用い、イソブチレンオリゴマーの生成を抑
制して２．４−ＤＴＢＰを高収率で製造でき、かつ中和
、水洗等の操作を必要としない２．４−ＤＴＩ３Ｐの製
造方法を捉案することを目的としている。A method for producing 2.4-DTI3P that can produce 2.4-DTBP in high yield by suppressing the production of isobutylene oligomers using an inexpensive catalyst and does not require operations such as neutralization and water washing has been proposed. It is intended to.
本発明は、遊離酸価２畦にＯＨ／ｇ以下、固体酸量ｐＫ
ａ＝−３，０のものが２０ｍｅｑ／ １００ｇ以上含ま
れる固体酸触媒の存在下に、フェノールにイソブチレン
を供給しながら反応させ、イソブチレンの供給終了後直
ちに反応液から固体酸触媒を除去することを特徴とする
２、４−ジ−ｔ−ブチルフェノールの製造方法である。The present invention has a free acid value of 2 OH/g or less, a solid acid amount pK
In the presence of a solid acid catalyst containing 20 meq/100 g or more of a = -3,0, phenol is reacted while supplying isobutylene, and the solid acid catalyst is removed from the reaction solution immediately after the supply of isobutylene is finished. This is a characteristic method for producing 2,4-di-t-butylphenol.
本発明において原料であるフェノールとしては、純フェ
ノール、２−または４−ｔ−ブチルフェノール（以下、
２−または４−ＴＢＰと記す）等のブチルフェノールを
含む回収フェノール、あるいはこれらの混合物などが使
用できる。イソブチレンとしては純イソブチレンまたは
イソブチレン含有ブテンガスなどが使用できる。In the present invention, the raw material phenol is pure phenol, 2- or 4-t-butylphenol (hereinafter referred to as
Recovered phenol containing butylphenol such as 2- or 4-TBP), or a mixture thereof can be used. As the isobutylene, pure isobutylene or butene gas containing isobutylene can be used.
本発明において使用する触媒は遊離酸価２ｍｇＫＯＨ／
ｇ以下、固体酸量ｐＫａ＝−３，０のものが２０ｍｅｑ
／１００ｇ以上含まれる固体酸触媒である。上記固体酸
量のｍｅｑ／１００ｇは試料１００ｇに含まれる酸量（
ミリ当量）であり、０．ＩＮブチルアミン滴定数ｘ力価
×１０７試料ｇで計算できる。上記の固体酸触媒として
は例えば粒状または粉状の活性白土、酸性白土などがあ
げられるが、他の固体酸触媒でもよい。市販品としては
例えば日本活性白土■製の５Ａ−２５４、Ｋ−５００、
０−３６（いずれも商標）などがあり、いずれも遊離酸
価２ ｍｇＫＯＨ／ｇ以下、固体酸Ｑ ｐＫａ ニー
３ 、０のものが２５＋ｍａｑ／ １００ｇ以上含まれ
る。The catalyst used in the present invention has a free acid value of 2 mgKOH/
20 meq of solid acid with pKa = -3.0
/100g or more of solid acid catalyst. The amount of solid acid meq/100g is the amount of acid contained in 100g of sample (
milliequivalent) and 0. It can be calculated as IN butylamine titration number x titer x 107 sample g. Examples of the above-mentioned solid acid catalyst include granular or powdered activated clay, acid clay, etc., but other solid acid catalysts may also be used. Commercially available products include, for example, 5A-254, K-500, manufactured by Nippon Kakushirado ■.
0-36 (all trademarks), all of which have a free acid value of 2 mgKOH/g or less, solid acid Q pKa
Contains 25+maq/100g or more of 3.0.
固体酸触媒が上記範囲に限定される理由は、遊離酸価が
上記範囲を越えると、反応中にイソブチレンオリゴマー
が生成するとともに、反応生成物の中和および水洗が必
要となり、また固体酸量が上記範囲未満ではフェノール
とイソブチレンとの反応が進行しないためである。The reason why the solid acid catalyst is limited to the above range is that if the free acid value exceeds the above range, isobutylene oligomers will be produced during the reaction, and the reaction product will need to be neutralized and washed with water, and the amount of solid acid will decrease. This is because the reaction between phenol and isobutylene does not proceed below the above range.
２．４−ＤＴ［３Ｐの製造は上記の触媒の存在下にフェ
ノールにイソブチレンを供給しながら反応させる。2.4-DT[3P is produced by reacting phenol with isobutylene in the presence of the above catalyst.
このとき粒状または粉状の触媒を、仕込みフェノールに
対し０．１〜１０重量％、好ましくは０．１〜５重量％
となるようにフェノールに懸濁し、温度６０〜１８０℃
、好ましくは８０〜１２０℃、圧力常圧〜３０ｋｇ／ｃ
ｄＧ、好ましくは常圧〜１０ｋＥ／ａｌＴＧで、上記憑
濁液にイソブチレンをイソブチレン／フェノール（モル
比）１．２〜３、好ましくは１．６〜２．３となるよう
に１０分〜２０時間、好ましくは３０分〜６時間かけて
供給し、液相で反応させると２．４−ＤＴｎＰが生成す
る。イソブチレンの供給終了後直ちに固液分離により固
体酸触媒を反応液から分離除去し、反応を停止させる。At this time, the granular or powdered catalyst is added in an amount of 0.1 to 10% by weight, preferably 0.1 to 5% by weight, based on the charged phenol.
Suspend in phenol so that
, preferably 80 to 120°C, normal pressure to 30 kg/c
dG, preferably normal pressure to 10 kE/alTG, isobutylene is added to the above suspension for 10 minutes to 20 hours so that the molar ratio of isobutylene/phenol is 1.2 to 3, preferably 1.6 to 2.3. , preferably over 30 minutes to 6 hours, and react in a liquid phase to produce 2.4-DTnP. Immediately after the supply of isobutylene is finished, the solid acid catalyst is separated and removed from the reaction solution by solid-liquid separation to stop the reaction.
このように触媒を分離する手段としては、濾過、遠心分
離など、機械的な固液分離手段を採用すると、余分な化
学物質を介在させることなく、容易に短時間で触媒を分
離できるから好ましい。As a means for separating the catalyst in this manner, it is preferable to employ a mechanical solid-liquid separation means such as filtration or centrifugation because the catalyst can be easily separated in a short time without intervening extra chemical substances.
触媒の除去はイソブチレンの供給終了後２時間以内、好
ましくは１時間以内に終了するのが望ましい。触媒の除
去後蒸留等により目的化合物である２、４−ＤＴＢＰを
取得する。It is desirable that the removal of the catalyst be completed within 2 hours, preferably within 1 hour after the end of the supply of isobutylene. After removing the catalyst, the target compound 2,4-DTBP is obtained by distillation or the like.
このように触媒として上記固体酸触媒を使用し、イソブ
チレンの供給後直ちに触媒を除去することにより、イソ
ブチレンオリゴマーの生成が抑制される結果、２．４−
ＤＴＢＰの収率が高くなる。そして中和操作を行わなく
てもブチルフェノール類は分解しない。By using the above-mentioned solid acid catalyst as a catalyst and removing the catalyst immediately after isobutylene is supplied, the production of isobutylene oligomers is suppressed, resulting in 2.4-
The yield of DTBP becomes higher. And butylphenols do not decompose even without performing a neutralization operation.
イソブチレン／フェノール（モル比）２．０、触媒量１
．０重斌％で、反応時間（イソブチレンの供給時間）４
時間の場合、イソブチレンオリゴマーの生成率は３重量
％以下で、２，４−ＤＴＢＰの収率は８１モル％、蒸留
回収率は９９重量％以上となる。Isobutylene/phenol (mole ratio) 2.0, catalyst amount 1
．． At 0 weight%, reaction time (isobutylene supply time) 4
In the case of time, the production rate of isobutylene oligomer is 3% by weight or less, the yield of 2,4-DTBP is 81 mol%, and the distillation recovery rate is 99% by weight or more.
こうして製造された２、４−ＤＴＢＰは樹脂等の酸化防
止剤の原料などに使用される。また副生する２−または
４−ＴＢＰを含む低沸点留分はリサイクルし、原料とし
て使用される。The 2,4-DTBP produced in this way is used as a raw material for antioxidants such as resins. Furthermore, the low-boiling fraction containing 2- or 4-TBP produced as a by-product is recycled and used as a raw material.
本発明によれば、特定の固体酸触媒を使用し、イソブチ
レンの供給終了後直ちに触媒を除去するようにしたので
、安価な触媒を使用しながらも、イソブチレンオリゴマ
ーの生成を抑制して２．４−ＤＴＢＰを高収率で製造で
き、中和、水洗等の操作を省略することができる。According to the present invention, since a specific solid acid catalyst is used and the catalyst is removed immediately after the supply of isobutylene is finished, the production of isobutylene oligomers can be suppressed while using an inexpensive catalyst. -DTBP can be produced in high yield, and operations such as neutralization and water washing can be omitted.
以下、本発明の実施例について説明する。実施例中、１
％」は特に言及しない限り重量％である。Examples of the present invention will be described below. In the examples, 1
%" is by weight unless otherwise specified.
実施例１
イソブチレン供給管、温度計鞘および回転式攪拌装置を
備えたＩＱ容量のＳＵＳ製オートクレーブに、フェノー
ル２００ｇと活性白土（日本活性白土■製５Ａ−２５４
） ２．０ｇとを仕込んだ、オートクレーブのイソブチ
レン供給口に接続したイソブチレン供給ポンプには、イ
ソブチレンボンベを接続し、ポンプヘッドをドライアイ
スで冷却しておく、そしてオートクレーブ内を窒素で置
換した後、加熱を開始した。Example 1 In an IQ capacity SUS autoclave equipped with an isobutylene supply pipe, a thermometer sheath, and a rotary stirrer, 200 g of phenol and activated clay (5A-254 manufactured by Nippon Shakuto) were placed.
) An isobutylene cylinder was connected to the isobutylene supply pump connected to the isobutylene supply port of the autoclave, which was charged with 2.0 g, and the pump head was cooled with dry ice.After purging the inside of the autoclave with nitrogen, Heating started.
オートクレーブの内温か８５℃になった時にイソブチレ
ン供給バルブを開き、イソブチレン供給ポンプを作動さ
せて、イソブチレン２４０ｇを９０℃の反応温度を維持
させながら、４時間で一定量づつ供給した。When the internal temperature of the autoclave reached 85° C., the isobutylene supply valve was opened, the isobutylene supply pump was activated, and 240 g of isobutylene was supplied in fixed amounts over 4 hours while maintaining the reaction temperature at 90°C.
イソブチレン供給終了後、直ちにブフナロートと耐圧ビ
ンを用いて減圧濾過を行い、活性白土を除去した。得ら
れた反応生成物４２８ｇをガスクロマトグラフィー分析
装置を用いて分析したところ。Immediately after the supply of isobutylene was completed, vacuum filtration was performed using a Buchna funnel and a pressure bottle to remove activated clay. 428 g of the obtained reaction product was analyzed using a gas chromatography analyzer.
イソブチレンのオリゴマー生成率は供給したイソブチレ
ンの２％であり、２．４−ＤＴＢＰの濃度は８１％（収
率８１モル％）であった。The oligomer production rate of isobutylene was 2% of the supplied isobutylene, and the concentration of 2.4-DTBP was 81% (yield: 81 mol%).
この反応生成物３４６ｇを１５段オルダーショウ蒸留装
置を用いて蒸留４１製を行った結果、 ９９．０％の純
度の２．４−ＤＴＢＰ留分（ｂ、ｐ、１８５℃７８０ｍ
ｍＨｇ）が２５２ｇ得られた。このとき４−ＴＢＰと２
．４−ＤＴＢＰとの混合留分（低沸点留分）が４４ｇ、
２，４．６− トリーｔ−ブチルフェノールを主成分と
する蒸留残渣が５８ｇ得られた。蒸留回収率は９９．４
％であり、蒸留時の分解は全く起こっていなかった。346 g of this reaction product was distilled using a 15-stage Oldershaw distillation apparatus, resulting in a 99.0% pure 2.4-DTBP fraction (b, p, 185°C, 780 m
mHg) was obtained. At this time, 4-TBP and 2
．． 44g of mixed fraction (low boiling point fraction) with 4-DTBP,
58 g of a distillation residue containing 2,4.6-tri-t-butylphenol as a main component was obtained. Distillation recovery rate is 99.4
%, and no decomposition occurred during distillation.
実施例２
実施例１の活性白土を日本活性白土■製の５Ａ−２５４
から同に−５００に、イソブチレン供給量を２４０ｇか
ら２１７ｇに、反応温度を９０℃から１００℃に、イソ
ブチレン供給時間を４時間から２時間に変更して実験を
行った。その結果、２．４−ＤＴＢＰの濃度は７４％（
収率７４モル％）、イソブチレンオリゴマー生成率は供
給イソブチレンの０．５％であった。この生成物３３０
ｇを実施例１と同様の減圧蒸留装置を用いて蒸留精製し
たところ、 ９８．５％の純度の２．４−ＤＴＢＰ留分
が２０３ｇ得られた。蒸留回収率は９９．４％であり。Example 2 The activated clay of Example 1 was used as 5A-254 manufactured by Nippon Activated White Clay.
The experiment was conducted by changing the isobutylene supply amount from 240 g to 217 g, the reaction temperature from 90° C. to 100° C., and the isobutylene feeding time from 4 hours to 2 hours. As a result, the concentration of 2.4-DTBP was 74% (
The yield was 74 mol%), and the isobutylene oligomer production rate was 0.5% of the supplied isobutylene. This product 330
When purified by distillation using the same vacuum distillation apparatus as in Example 1, 203 g of 2.4-DTBP fraction with a purity of 98.5% was obtained. The distillation recovery rate was 99.4%.
蒸留により２，４−ＤＴＢＰの分解は起こらなかった。No decomposition of 2,4-DTBP occurred upon distillation.
実施例３
実施例１の原料として、フェノール２００ｇの他に４−
ｔ−ＴＢＰ２０ ｇを仕込み、活性白土（日本活性白土
■製５Ａ−２５４）を２．０ｇからｌＯ，Ｏｇに、イソ
ブチレン供給量を２４０ｇから２６２ｇに変更し、他は
実施例１と同様にして実験を行った。Example 3 In addition to 200 g of phenol, 4-
The experiment was carried out in the same manner as in Example 1, except that 20 g of t-TBP was charged, activated clay (5A-254 manufactured by Nippon Shakuto) was changed from 2.0 g to 1O, Og, and the amount of isobutylene supplied was changed from 240 g to 262 g. I did it.
その結果、生成物中の２．４−ＤＴＢＰｆｉ度は７８％
（収率７８モル％）、イソブチレンオリゴマー生成率は
供給イソブチレンの３％であった。この生成物３５０ｇ
を実施例１と同様に蒸留精製したところ、９９．０％の
純度の２．４−ＤＴＢＰ留分が２４０ｇ得られ、蒸留回
収率は９９．２％であり、蒸留時の分解は認められなか
った。As a result, the 2.4-DTBPfi degree in the product was 78%.
(yield: 78 mol%), and the isobutylene oligomer production rate was 3% of the supplied isobutylene. 350g of this product
When purified by distillation in the same manner as in Example 1, 240 g of 2.4-DTBP fraction with a purity of 99.0% was obtained, the distillation recovery rate was 99.2%, and no decomposition was observed during distillation. Ta.
以上の結果より１本発明の製造方法によれば、イソブチ
レンオリゴマーの生成率は低く、２，４−ＤＴＢＰの収
率が高いことがわかる。From the above results, it can be seen that according to the production method of the present invention, the production rate of isobutylene oligomer is low and the yield of 2,4-DTBP is high.
代理人 弁理士 柳 原 成
手続補正書
昭和６２年３月２３日
１、事件の表示
昭和６１年特許願第３０７５４９号
２、発明の名称
２．４−ジ−ｔ−ブチルフェノールの製造方法３、補正
をする者
事件との関係 特許出願人
代表者 竹林省吾
４、代理人 〒１０５電話４３６−４７００７、補正の
内容
（１）明細書第６頁第１６行［、蒸留・・・・・・以上
」を削除する。Agent Patent Attorney Yanagi Hara Written Procedural Amendment March 23, 1985 1. Case Description 1985 Patent Application No. 307549 2. Title of Invention 2. Process for Producing 4-Di-t-Butylphenol 3. Amendment Relation to the case of a person who does the following: Patent applicant representative: Shogo Takebayashi 4, agent: 105 Telephone: 436-47007 Contents of amendment (1) Specification, page 6, line 16 [, Distillation, etc.] Delete.
（２）同第９頁第１５行「ｔ−」を削除する。(2) Delete "t-" on page 9, line 15.
Claims (5)
＝−３．０のものが２０ｍｅｑ／１００ｇ以上含まれる
固体酸触媒の存在下に、フェノールにイソブチレンを供
給しながら反応させ、イソブチレンの供給終了後直ちに
反応液から固体酸触媒を除去することを特徴とする２，
４−ジ−を−ブチルフェノールの製造方法。(1) Free acid value 2 mgKOH/g or less, solid acid amount pKa
In the presence of a solid acid catalyst containing 20 meq/100 g or more of -3.0, phenol is reacted while supplying isobutylene, and the solid acid catalyst is removed from the reaction solution immediately after the supply of isobutylene is finished. 2,
A method for producing 4-di-butylphenol.
請求の範囲第１項記載の製造方法。(2) The manufacturing method according to claim 1, wherein the solid acid catalyst is activated clay or acid clay.
含む回収フェノール、またはこれらの混合物である特許
請求の範囲第１項または第２項記載の製造方法。(3) The manufacturing method according to claim 1 or 2, wherein the phenol is pure phenol, recovered phenol containing butylphenol, or a mixture thereof.
ン含有ブテンガスである特許請求の範囲第１項ないし第
３項のいずれかに記載の製造方法。(4) The manufacturing method according to any one of claims 1 to 3, wherein the isobutylene is pure isobutylene or isobutylene-containing butene gas.
求の範囲第１項ないし第４項のいずれかに記載の製造方
法。(5) The manufacturing method according to any one of claims 1 to 4, wherein the solid acid catalyst is removed by filtration.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61307549A JPH0725713B2 (en) | 1986-12-23 | 1986-12-23 | Method for producing 2,4-di-t-butylphenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61307549A JPH0725713B2 (en) | 1986-12-23 | 1986-12-23 | Method for producing 2,4-di-t-butylphenol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63159334A true JPS63159334A (en) | 1988-07-02 |
| JPH0725713B2 JPH0725713B2 (en) | 1995-03-22 |
Family
ID=17970428
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61307549A Expired - Fee Related JPH0725713B2 (en) | 1986-12-23 | 1986-12-23 | Method for producing 2,4-di-t-butylphenol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0725713B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR19980075740A (en) * | 1997-04-01 | 1998-11-16 | 유현식 | Apparatus for producing 2,4-di (tertiary-butyl) phenol |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4275249A (en) * | 1979-11-30 | 1981-06-23 | Uop Inc. | Preparation of 2,4-Di-t-alkylphenol |
| JPS60255742A (en) * | 1984-06-01 | 1985-12-17 | Mitsui Petrochem Ind Ltd | Production of 2,4-di-tert-butylphenol |
| JPS61200934A (en) * | 1985-03-02 | 1986-09-05 | Maruzen Sekiyu Kagaku Kk | Production of tert-butylphenol compound |
-
1986
- 1986-12-23 JP JP61307549A patent/JPH0725713B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4275249A (en) * | 1979-11-30 | 1981-06-23 | Uop Inc. | Preparation of 2,4-Di-t-alkylphenol |
| JPS60255742A (en) * | 1984-06-01 | 1985-12-17 | Mitsui Petrochem Ind Ltd | Production of 2,4-di-tert-butylphenol |
| JPS61200934A (en) * | 1985-03-02 | 1986-09-05 | Maruzen Sekiyu Kagaku Kk | Production of tert-butylphenol compound |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR19980075740A (en) * | 1997-04-01 | 1998-11-16 | 유현식 | Apparatus for producing 2,4-di (tertiary-butyl) phenol |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0725713B2 (en) | 1995-03-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4314090A (en) | Linear alpha olefin production | |
| KR940019666A (en) | Process for preparing α-olefin oligomer and α-olefin oligomer composition | |
| JPH03212405A (en) | Removal of bf3 from olefinoligomer by bf3 catalyst | |
| EP0116319B1 (en) | Process for producing high purity metallic compound | |
| US8492604B2 (en) | Method for preparing linear alpha-olefins with removal of aromatic by-products and reactor system therefor | |
| WO2000002835A1 (en) | Alkylation process | |
| JPS63159334A (en) | Production of 2,4-di-tertiary butylphenol | |
| US6476271B2 (en) | Process for the preparation of ether-free salts of tetrakis(pentafluorophenyl) borate | |
| JPS61200934A (en) | Production of tert-butylphenol compound | |
| EP0366211B1 (en) | Process for producing alpha olefins | |
| US3895071A (en) | Separation of nitroketone from a crude nitrooxidation reaction product | |
| US3651165A (en) | Method for recovery and purification of isobutylene | |
| EP0729931B1 (en) | Process for the preparation of 1,5-hexadiene | |
| US4176086A (en) | Catalyst preparation | |
| EP0861221B1 (en) | Coproduction of vinylidene alcohols and vinylidene hydrocarbons | |
| US4864072A (en) | Solvent recovery from solutions of organic aluminum compound | |
| JPS63303937A (en) | Manufacture of propynol | |
| JPS61251633A (en) | Production of highly pure p-tert-butylphenol | |
| JPH0158194B2 (en) | ||
| JPS63159333A (en) | Production of 2,4-di-tertiary butylphenol | |
| US3691238A (en) | Process for the treating crude alkylated phenols | |
| US5208383A (en) | Process for producing aromatic acylation product | |
| JPH01203340A (en) | Production of acetylene alcohol | |
| EP0659717B1 (en) | Method of alkylating the side chain of alkyl-substituted aromatic hydrocarbons | |
| JPH10316603A (en) | Eparation and purification of 1-butylmethylphenol isomer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |