JPS63188635A - Production of 2-t-butyl-6-alkylphenol - Google Patents
Production of 2-t-butyl-6-alkylphenolInfo
- Publication number
- JPS63188635A JPS63188635A JP62020285A JP2028587A JPS63188635A JP S63188635 A JPS63188635 A JP S63188635A JP 62020285 A JP62020285 A JP 62020285A JP 2028587 A JP2028587 A JP 2028587A JP S63188635 A JPS63188635 A JP S63188635A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- alkylphenol
- isobutylene
- butyl
- reaction
- 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 abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 56
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- 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
- 238000004821 distillation Methods 0.000 abstract description 16
- 238000005260 corrosion Methods 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 239000010935 stainless steel Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 2
- 230000000996 additive effect Effects 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000012071 phase Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- BKZXZGWHTRCFPX-UHFFFAOYSA-N 2-tert-butyl-6-methylphenol Chemical compound CC1=CC=CC(C(C)(C)C)=C1O BKZXZGWHTRCFPX-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- -1 aluminum halide Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- SNKLPZOJLXDZCW-UHFFFAOYSA-N 4-tert-butyl-2-methylphenol Chemical compound CC1=CC(C(C)(C)C)=CC=C1O SNKLPZOJLXDZCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000725 suspension Substances 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
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は０−アルキルフェノールとイソブチレンとか
ら２−１−ブチル−６−アルキルフェノールを製造する
方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] This invention relates to a method for producing 2-1-butyl-6-alkylphenol from 0-alkylphenol and isobutylene.
（従来の技術〕
０−クレゾールとイソブチレンとから２−ｔ−ブチル−
６−メチルフェノールを製造する方法として、触媒に硫
酸を使用する方法（米国特許第２，８３６，６２７号）
、触媒にＴｘ（ＯＡｒ）ｎ・（Ａｒ’５Ｏ３）４−ｎ
（ただしＡｒ。(Prior art) From 0-cresol and isobutylene, 2-t-butyl-
A method for producing 6-methylphenol using sulfuric acid as a catalyst (US Pat. No. 2,836,627)
, Tx(OAr)n・(Ar'5O3)4-n on the catalyst
(However, Ar.
Ａｒ’はアリール基、ｎは３〜３．９）を使用する方法
（米国特許第３，２６７．１５２号）、触媒にチタン力
テコレートを使用する方法（米国特許第３，２６７．１
５５号）、触媒にアルミニウムハライドを使用する方法
（米国特許第２．９２３，７４５号）などが知られてい
る。Ar' is an aryl group and n is 3 to 3.9) (U.S. Pat. No. 3,267.152); a method using titanium tecolate as a catalyst (U.S. Pat. No. 3,267.1);
55) and a method using aluminum halide as a catalyst (US Pat. No. 2,923,745).
しかしながら、上記従来の方稙には次にような問題点が
ある。まず硫酸を触媒に使用する方法は。However, the above conventional method has the following problems. First, how to use sulfuric acid as a catalyst.
副生物として４−ｔ−ブチル−６−メチルフェノールが
多量（２５％）生成するために、目的物の収率は５０％
と極めて低い、またＴｉ（ＯＡｒ）、・（Ａｒ’５Ｏ２
）、−。Since a large amount (25%) of 4-t-butyl-6-methylphenol is produced as a by-product, the yield of the target product is 50%.
is extremely low, and Ti(OAr), ・(Ar'5O2
), -.
やチタン力テコレートを触媒に使用する方法は、Ｔｉ（
ｊｌ、をフェノールあるいはカテコールとを反応させて
触媒を調製する際に、塩化水素ガスが発生するので１反
応器の腐食の問題があるとともに、目的物の収率も４１
％とかなり低い。さらにアルミニウムハライドを触媒に
使用する方法もハロゲン化水素ガスの発生があり１反応
器の腐食の間層がある。The method of using titanium tecolate as a catalyst is as follows:
When preparing a catalyst by reacting Jl with phenol or catechol, hydrogen chloride gas is generated, which causes corrosion of the reactor and also reduces the yield of the target product.
% is quite low. Furthermore, the method using aluminum halide as a catalyst also generates hydrogen halide gas, and there is a layer of corrosion in one reactor.
本発明は上記問題点を解決するためのもので、腐食の心
配がなく、反応収率が高いとともに、触媒の除去が容易
な２−ｔ−ブチル−６−アルキルフェノールの製造方法
を提案することを目的としている。The present invention is intended to solve the above-mentioned problems, and aims to propose a method for producing 2-t-butyl-6-alkylphenol that is free from corrosion, has a high reaction yield, and allows easy removal of the catalyst. The purpose is
本発明は、０−アルキルフェノールとイソブチレンとを
アルミニウムｏ−アルキルフェノレート触媒の存在下に
反応させることを特徴とする２−ｔ−ブチル−６−アル
キルフェノールの製造方法である。The present invention is a method for producing 2-t-butyl-6-alkylphenol, which is characterized by reacting 0-alkylphenol and isobutylene in the presence of an aluminum o-alkylphenolate catalyst.
本発明において製造する２−ｔ−ブチル−６−アルキル
フェノールとしては特に制限はないが、６位に結合する
アルキル基としては例えば炭素数６以下の低級アルキル
基のものがある。The 2-t-butyl-6-alkylphenol produced in the present invention is not particularly limited, but examples of the alkyl group bonded to the 6-position include lower alkyl groups having 6 or less carbon atoms.
本発明において原料である０−アルキルフェノールとし
ては、特に制限はないが、０−クレゾール。The 0-alkylphenol used as a raw material in the present invention is not particularly limited, but may include 0-cresol.
０−エチルフェノール等の目的とする２−ｔ−ブチル−
６−アルキルフェノールに対応する０−アルキルフェノ
ールであって、その水分５４．１１０００ｐｐ以下のも
のが好ましい。Target 2-t-butyl- such as 0-ethylphenol
A 0-alkylphenol corresponding to 6-alkylphenol with a water content of 54.11000 pp or less is preferred.
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
ンを含有するブテンガスなどが使用できる。As the isobutylene, pure isobutylene or butene gas containing isobutylene can be used.
これらの反応に使用される触媒はアルミニウムｏ−アル
キルフェノレートであり、金属アルミニウムと０−アル
キルフェノールとの反応により得られる。この触媒は別
途調製したものを使用することもできるが、２−ｔ−ブ
チル−６−アルキルフェノールの製造に際して原料のＯ
−アルキルフェノールと金属アルミニウムを反応させて
触媒を調製することもできる。The catalysts used in these reactions are aluminum o-alkylphenolates, obtained by the reaction of metallic aluminum and o-alkylphenols. This catalyst can be used as one prepared separately, but when producing 2-t-butyl-6-alkylphenol,
- Catalysts can also be prepared by reacting alkylphenols with metal aluminum.
以下、図面の系統図に基づき、本発明の好ましい製造方
法を説明する。図面は好ましい実施態様を示し、１は触
媒調製槽、２は反応器、３は触媒除去槽、４は蒸留塔で
ある。この装置による製造工程は、触媒調製工程、反応
工程、触媒除去工程および蒸留精製工程の４つの工程か
ら成る６触媒調製工程は、窒素雰囲気上金属アルミニウ
ムと０−アルキルフェノールとを反応させてアルミニウ
ムＯ−フルキルフエル−ト触媒を調製する工程である。Hereinafter, a preferred manufacturing method of the present invention will be explained based on the system diagram in the drawings. The drawing shows a preferred embodiment, in which 1 is a catalyst preparation tank, 2 is a reactor, 3 is a catalyst removal tank, and 4 is a distillation column. The manufacturing process using this equipment consists of four steps: catalyst preparation step, reaction step, catalyst removal step, and distillation purification step.The catalyst preparation step consists of reacting aluminum metal and O-alkylphenol in a nitrogen atmosphere. This is a process for preparing a furkyl felt catalyst.
触媒調製槽１に金属アルミニウムおよびＯ−アルキルフ
ェノールを供給して触媒の調製が行われるが、触媒調製
槽１を省略し、反応器２において触媒の調製を行っても
よい。この触媒調製工程は金属アルミニウム１０−゛ア
ルキルフェノールを０．１〜１０重量％、好ましくは０
．３〜５重量％とじ。Although the catalyst is prepared by supplying metal aluminum and O-alkylphenol to the catalyst preparation tank 1, the catalyst preparation tank 1 may be omitted and the catalyst may be prepared in the reactor 2. This catalyst preparation step contains 0.1 to 10% by weight of metallic aluminum 10-alkylphenol, preferably 0.
．． 3-5% by weight binding.
反応温度１３０〜３００℃、好ましくは１６０〜２２０
℃、圧力常圧以上で０．１〜１０時間、好ましくは０．
１〜５時間、溶液または一部懸濁状態で反応を行う。Reaction temperature 130-300°C, preferably 160-220°C
℃, pressure above normal pressure for 0.1 to 10 hours, preferably 0.
The reaction is carried out in solution or in partial suspension for 1 to 5 hours.
反応工程は、窒素、水素またはそれらの混合ガス雰囲気
下に、アルミニウムｏ−アルキルフェノレート触媒の存
在下、０−アルキルフェノールとイソブチレンとを反応
させ２−ｔ−ブチル−６−アルキルフェノールを製造す
る工程である０反応器２にイソブチレンを供給するとと
もに、触媒調製槽１から触媒および過剰の０−アルキル
フェノールを供給して０−アルキルフェノールとイソブ
チレンの反応が行われる。反応器２において触媒を調製
した場合は、触媒調製後イソブチレンを供給して反応を
行う。The reaction step is a step of producing 2-t-butyl-6-alkylphenol by reacting 0-alkylphenol and isobutylene in the presence of an aluminum o-alkylphenolate catalyst in a nitrogen, hydrogen or mixed gas atmosphere. Isobutylene is supplied to a certain 0-reactor 2, and a catalyst and excess 0-alkylphenol are also supplied from the catalyst preparation tank 1 to cause a reaction between 0-alkylphenol and isobutylene. When a catalyst is prepared in the reactor 2, isobutylene is supplied after the catalyst preparation to carry out the reaction.
この反応工程はイソブチレン１０−アルキルフェノール
（モル比）を０．５〜３、好ましくは０．７〜１．５と
し、温度５ｏ−ｔａｏ℃、好ましくは７０−１３０℃、
圧力常圧以上で０．１〜２０時間、好ましくは０．１−
１０時間液相で反応させる。イソブチレン１０−アルキ
ルフェノール（モル比）が１．１、Ａｎｌｏ−アルキル
フェノールが０．０１５（モル比）１反応器度１００℃
、反応時間４時間の時、生成する２−ｔ−ブチル−６−
アルキルフェノール濃度は８８重量％、収率は９０モル
％程度となる。In this reaction step, the isobutylene 10-alkylphenol (molar ratio) is 0.5-3, preferably 0.7-1.5, the temperature is 5o-tao℃, preferably 70-130℃,
0.1 to 20 hours at normal pressure or higher, preferably 0.1-
React in liquid phase for 10 hours. Isobutylene 10-alkylphenol (mole ratio) is 1.1, Anlo-alkylphenol is 0.015 (mole ratio) 1 reactor temperature 100°C
, 2-t-butyl-6- produced when the reaction time was 4 hours.
The alkylphenol concentration is 88% by weight, and the yield is approximately 90% by mole.
未反応イソブチレンは反応終了後、あるいは次の触媒除
去工程でパージする６上記反応はバッチ式でも連続式で
も良い。連続式にするにはイソブチレン回収装置が必要
となるが、この装置はバッチ式の場合にも付けても良い
。Unreacted isobutylene is purged after the completion of the reaction or in the next catalyst removal step.6 The above reaction may be carried out batchwise or continuously. A continuous system requires an isobutylene recovery device, but this device may also be installed in a batch system.
触媒除去工程は触媒除去槽３において、５０〜９５℃、
好ましくは６０〜９０℃の温度で、硫酸水溶液等の酸水
溶液で１〜５回洗浄し、触媒を加水分解させて洗浄排水
とともに除去し、その後水酸化ナトリウム水溶液、炭酸
ナトリウム水溶液等のアルカリ水溶液で１〜５回洗浄す
る。アルカリ水溶液による洗浄は油相が９１１７以上に
なるまでくり返えす。The catalyst removal step is performed in the catalyst removal tank 3 at a temperature of 50 to 95°C.
The catalyst is washed 1 to 5 times with an acid aqueous solution such as a sulfuric acid aqueous solution at a temperature of preferably 60 to 90°C, and the catalyst is hydrolyzed and removed together with the washing waste water, and then an alkaline aqueous solution such as a sodium hydroxide aqueous solution or a sodium carbonate aqueous solution is used. Wash 1-5 times. Washing with the alkaline aqueous solution is repeated until the oil phase reaches 9117 or higher.
アルカリ水溶液による洗浄後、水洗を１〜５回行っても
よい。油相のＰＨ測定法は１分岐ロートに油相と同容量
のＰＨ７，０に調製した水を入れ、ＩＯ分間振とうして
１０分以上静置し、油水分離後、水相のｐＨを測定する
。After washing with an alkaline aqueous solution, washing with water may be performed 1 to 5 times. To measure the pH of the oil phase, pour the same volume of water adjusted to pH 7.0 as the oil phase into a single-branched funnel, shake for IO minutes, let stand for 10 minutes or more, and measure the pH of the water phase after separating the oil and water. do.
酸水溶液の濃度は１〜３０重量％、好ましくは３〜１５
重量％、アルカリ水溶液の濃度は１〜３０重量％、好ま
しくは３〜１５重量％である。洗浄に使用する第１回の
酸水溶液の量は、これに含まれる酸量が触媒のＡｆｌの
１７２〜１０当量、好ましくは１７２〜３当量になる量
であり、第２回以降は第１回の１／２０〜２倍、好まし
くは１ノ１０〜１倍量である。また第１回のアルカリ水
溶液の量は最終回の酸水溶液に含まれる酸量と当量基準
で０．０１〜５倍量、好ましくは０．１〜２倍量、第２
回以降は第１回の１７２０〜２倍量、好ましくは１／１
０〜１倍量である。洗浄の際の攪拌時間は０．０１〜５
時間、好ましくは０．１〜２時間、静置時間は０．１〜
５時間、好ましくは０．１〜２時間である。The concentration of the acid aqueous solution is 1 to 30% by weight, preferably 3 to 15% by weight.
The concentration of the alkaline aqueous solution is 1 to 30% by weight, preferably 3 to 15% by weight. The amount of the acid aqueous solution used in the first washing is such that the amount of acid contained therein is 172 to 10 equivalents, preferably 172 to 3 equivalents, of Afl of the catalyst, and from the second washing onwards, The amount is 1/20 to 2 times, preferably 1/10 to 1 times. In addition, the amount of the alkaline aqueous solution in the first step is 0.01 to 5 times, preferably 0.1 to 2 times the amount of acid contained in the acid aqueous solution in the final step, based on the equivalent amount, and the second
After the first time, 1720 to 2 times the amount of the first time, preferably 1/1
0 to 1 times the amount. Stirring time during cleaning is 0.01-5
time, preferably 0.1-2 hours, standing time 0.1-2 hours
5 hours, preferably 0.1 to 2 hours.
蒸留精製工程は生成した２−ｔ−ブチル−６−アルキル
フェノールを蒸留により精製し、製品として採取する工
程である。この工程は触媒除去槽３で触媒を除去した反
応液を蒸留塔４で蒸留精製する。The distillation purification step is a step in which the produced 2-t-butyl-6-alkylphenol is purified by distillation and collected as a product. In this step, the reaction liquid from which the catalyst has been removed in the catalyst removal tank 3 is purified by distillation in the distillation column 4.
蒸留塔４はトッピング塔４ａおよびテーリング塔４ｂか
らなり、トッピング塔４ａにおいて０−アルキルフェノ
ール、水等の低沸点留分を除去し、テーリング塔４ｂに
おいて製品である２−ｔ−ブチル−６−アルキルフェノ
ールを採取し、蒸留残査を排出する。The distillation column 4 consists of a topping column 4a and a tailing column 4b. The topping column 4a removes low-boiling fractions such as 0-alkylphenol and water, and the tailing column 4b removes the product 2-t-butyl-6-alkylphenol. sample and discharge the distillation residue.
触媒除去工程および蒸留精製工程では２−ｔ−ブチル−
６−アルキルフェノールは全く分解せず、蒸留回収率は
９９％以上となる。上記により製造される２−ｔ−ブチ
ル−６−アルキルフェノールは樹脂添加剤の原料等の用
途に利用される。In the catalyst removal step and distillation purification step, 2-t-butyl-
6-alkylphenol is not decomposed at all, and the distillation recovery rate is 99% or more. The 2-t-butyl-6-alkylphenol produced in the above manner is used as a raw material for resin additives.
本発明によれば、０−アルキルフェノールとイソブチレ
ンとをアルミニウム。−アルキルフェルレート触媒の存
在下に反応させるため、一般的な素材である耐食鋼製の
反応器であれば腐食の心配がなく、２−ｔ−ブチル−６
−アルキルフェノールの反応収率が良いとともに、蒸留
精製時に分離しにくい不純物が多量に生成せず、触媒の
除去も容易である。According to the invention, 0-alkylphenol and isobutylene are combined with aluminum. - Since the reaction is carried out in the presence of an alkyl ferrate catalyst, there is no fear of corrosion if the reactor is made of corrosion-resistant steel, which is a common material, and 2-t-butyl-6
- The reaction yield of alkylphenol is good, and a large amount of impurities that are difficult to separate during distillation purification are not produced, and the catalyst can be easily removed.
また触媒は金属アルミニウムと０−アルキルフェノール
により調製できるので、触媒コストが安い。Further, since the catalyst can be prepared from metallic aluminum and 0-alkylphenol, the cost of the catalyst is low.
さらにプロセスが簡素であるため設備費が安く、既存の
装置を転用しやすいとともに、ハンドリングが楽である
などの効果がある。Furthermore, since the process is simple, equipment costs are low, existing equipment can be easily reused, and handling is easy.
以下、本発明の実施例について説明する。各例中％は特
に言及しない限り重量％である。Examples of the present invention will be described below. The percentages in each example are by weight unless otherwise stated.
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容量の耐食ｍ （ＳＵＳ）製オートクレーブ
に、０−クレゾール２３０ｇと金属アルミニウム０．９
名を仕込んだ。Example 1 230 g of 0-cresol and 0.9 g of metal aluminum were placed in a corrosion-resistant (SUS) autoclave of IQ capacity equipped with an isobutylene supply pipe, a thermometer sheath, and a rotary stirrer.
I learned the name.
一方、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のヘッド部を一１０℃以下に冷
却し、その先にイソブチレンボンベを接続しておく。そ
してオートクレーブ内を窒素で置換し、加熱を開始した
。On the other hand, the head of the isobutylene supply pump connected to the isobutylene supply port of the autoclave is cooled to -10° C. or below, and an isobutylene cylinder is connected to the head. Then, the inside of the autoclave was replaced with nitrogen, and heating was started.
オートクレーブの内温か１９０℃に達した時点で、その
温度を維持しながら１時間３０分攪拌し、触媒（アルミ
ニウム０−クレゾレート）を調製した。その後、オート
クレーブの内温か１００℃になるまで冷却して脱圧し、
副生じた水素ガスを系外に放出して、さらにオートクレ
ーブ内を窒素で置換した。When the internal temperature of the autoclave reached 190°C, stirring was continued for 1 hour and 30 minutes while maintaining that temperature to prepare a catalyst (aluminum 0-cresolate). After that, the autoclave was cooled until the internal temperature reached 100°C and depressurized.
Hydrogen gas produced as a by-product was discharged to the outside of the system, and the inside of the autoclave was further purged with nitrogen.
次いでイソブチレン供給ポンプを作動して、イソブチレ
ン１３０．を１００℃の反応温度を維持しながら１時間
かけて供給し、さらに１００℃の反応湿度で３時間、後
反応を行い、２−ｔ−ブチル−６−メチルフェノールを
生成させた。反応終了後１．反応混合物の一部を取り出
し、少量の水を加え、触媒を加水分解した。この反応混
合物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、２−ｔ−ブチル−６−メチルフェノールの濃
度は８８％（収率は９０モル％）であった。The isobutylene feed pump is then activated to supply 130. was supplied over 1 hour while maintaining the reaction temperature at 100°C, and a post-reaction was further performed for 3 hours at 100°C and reaction humidity to produce 2-t-butyl-6-methylphenol. After the reaction 1. A portion of the reaction mixture was removed and a small amount of water was added to hydrolyze the catalyst. When this reaction mixture was analyzed using a gas chromatography analyzer, the concentration of 2-t-butyl-6-methylphenol was 88% (yield: 90 mol%).
実施例２
冷却管、温度計および回転式攪拌装置を付した保温ジャ
ケット付液抜きコック付フラスコに、実施例１で合成し
た反応液（加水分解前のもの）を３２０ｇ仕込み、ジャ
ケット内に温水を通して内温を７０℃まで昇温した。内
温が７０℃となった時点で、攪拌しながら１０％の硫酸
水溶液２００ｍｆｌを加え、１時間攪拌した。その後１
時間静置し、水相を抜き出した。再度攪拌しながら１０
％の硫酸水溶液５０ｍｆｉを加え、１時間攪拌および１
時間静置し、水相を抜き出した。次いで攪拌しながら１
０％の炭酸ナトリウム水溶液３０ｍ１２を加え、１時間
攪拌および１時間静置し、水相を抜き出した。さらに、
１０％の炭酸ナトリウム水溶液３０ｍｆｌを攪拌しなが
ら加え、１時間攪拌および１時間静置し、水相を抜き出
した。Example 2 320 g of the reaction solution synthesized in Example 1 (before hydrolysis) was charged into a flask with a drain cock and a heat insulation jacket equipped with a cooling tube, a thermometer, and a rotary stirrer, and hot water was poured into the jacket. The internal temperature was raised to 70°C. When the internal temperature reached 70°C, 200 mfl of a 10% aqueous sulfuric acid solution was added while stirring, and the mixture was stirred for 1 hour. then 1
The mixture was allowed to stand for an hour, and the aqueous phase was extracted. 10 while stirring again
% aqueous sulfuric acid solution was added, stirred for 1 hour, and
The mixture was allowed to stand for an hour, and the aqueous phase was extracted. Then, while stirring, 1
30 ml of 0% aqueous sodium carbonate solution was added, stirred for 1 hour and left to stand for 1 hour, and the aqueous phase was extracted. moreover,
30 mfl of 10% aqueous sodium carbonate solution was added with stirring, stirred for 1 hour and left to stand for 1 hour, and the aqueous phase was extracted.
その結果、洗浄浦和（触媒除去油相）３２１ｇを得た。As a result, 321 g of washed Urawa (catalyst-removed oil phase) was obtained.
この洗浄油相のｐＨは７．５であり、この洗浄油相の一
部をガスクロマトグラフィー分析装置により分析したと
ころ、２−ｔ−ブチル−６−メチルフェノールの濃度は
８８％であった。この値を実施例１の結果と比較すると
、触媒除去（洗浄）時に分解が起こっていないことを示
している。The pH of this washed oil phase was 7.5, and when a part of this washed oil phase was analyzed using a gas chromatography analyzer, the concentration of 2-t-butyl-6-methylphenol was 88%. Comparing this value with the results of Example 1 shows that no decomposition occurred during catalyst removal (cleaning).
次にこの洗浄油相３０３．９ｇを１５段オルダーショ蒸
留装置を用いて蒸留精製を行った結果、９９．１％の純
度の２−ｔ−ブチル−６−メチルフェノール留分（１３
２〜ｂ
蒸留回収率は９９．１％であり、蒸留時に分解は全く起
こっていない。Next, 303.9 g of this washed oil phase was purified by distillation using a 15-stage Oldersho distillation apparatus, resulting in a 2-t-butyl-6-methylphenol fraction (13
2-b The distillation recovery rate was 99.1%, and no decomposition occurred during distillation.
実施例３
実施例１と同様にして調製した触媒を用いて、実施例１
の反応温度を９５℃、イソブチレン量を１１５ｇ、後反
応時間を６時間に変更し、実験を行った。その結果、２
−ｔ−ブチル−６−メチルフェノールの収率は８３モル
％であった。Example 3 Using a catalyst prepared in the same manner as in Example 1, Example 1
The experiment was conducted by changing the reaction temperature to 95° C., changing the amount of isobutylene to 115 g, and changing the post-reaction time to 6 hours. As a result, 2
The yield of -t-butyl-6-methylphenol was 83 mol%.
実施例４
実施例１と同様にして調製した触媒を用いて、実施例１
の反応温度を１１０℃、イソブチレン量を１４２ｇ、後
反応時間を１時間に変更し、実験を行った。その結果、
２−ｔ−ブチル−６−メチルフェノールの収率は８２モ
ル％であった。Example 4 Example 1 was prepared using a catalyst prepared in the same manner as in Example 1.
The experiment was conducted by changing the reaction temperature to 110° C., changing the amount of isobutylene to 142 g, and changing the post-reaction time to 1 hour. the result,
The yield of 2-t-butyl-6-methylphenol was 82 mol%.
図面は実施態様を示す系統図である。
代理人 弁理士 柳 原 成
手続補正書
昭和６２年２月２６日
昭和６２年特 許 願第２０２８５号
２、発明の名称
２−ｔ−ブチル−６−アルキ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４３６−４７００６、補正の
対象 明細書の発明の詳細な説明の瀾７、補正の内容
６２、２．２７ ’＋The drawing is a system diagram showing an embodiment. Agent: Patent Attorney: Yanagi Hara Written Amendment: February 26, 1988 Patent Application No. 20285 2, Title of Invention: Method for producing 2-t-butyl-6-alkylphenol 3
, Relationship with the case of the person making the amendment Patent applicant representative Shogo Takebayashi 4, Agent 105 Telephone 436-47006, Subject of amendment Detailed explanation of the invention in the specification 7, Contents of amendment 62, 2.27 '＋
Claims (3)
ミニウムｏ−アルキルフェノレート触媒の存在下に反応
させることを特徴とする２−ｔ−ブチル−６−アルキル
フェノールの製造方法。(1) A method for producing 2-t-butyl-6-alkylphenol, which comprises reacting o-alkylphenol and isobutylene in the presence of an aluminum o-alkylphenolate catalyst.
ン含有ブテンガスである特許請求の範囲第１項記載の製
造方法。(2) The manufacturing method according to claim 1, wherein the isobutylene is pure isobutylene or isobutylene-containing butene gas.
属アルミニウムとｏ−アルキルフェノールとの反応によ
り得られるもの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) Claim 1 or 2, wherein the aluminum o-alkylphenolate catalyst is obtained by a reaction between metallic aluminum and o-alkylphenol.
Manufacturing method described in section.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62020285A JPH0774176B2 (en) | 1987-01-30 | 1987-01-30 | Process for producing 2-t-butyl-6-alkylphenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62020285A JPH0774176B2 (en) | 1987-01-30 | 1987-01-30 | Process for producing 2-t-butyl-6-alkylphenol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63188635A true JPS63188635A (en) | 1988-08-04 |
| JPH0774176B2 JPH0774176B2 (en) | 1995-08-09 |
Family
ID=12022897
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62020285A Expired - Fee Related JPH0774176B2 (en) | 1987-01-30 | 1987-01-30 | Process for producing 2-t-butyl-6-alkylphenol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0774176B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102161617A (en) * | 2010-02-23 | 2011-08-24 | 蓬莱红卫化工有限公司 | Synthesis method of 2-methyl-6-tert-butylphenol |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52136137A (en) * | 1976-03-22 | 1977-11-14 | Sterlitamaxky O Promyshlenny | Process for preparing 2*66dii terttbutyl phenol |
| JPS55133324A (en) * | 1979-04-03 | 1980-10-17 | Mitsui Petrochem Ind Ltd | Removal of aluminum component |
| JPS5795928A (en) * | 1980-12-05 | 1982-06-15 | Mitsui Petrochem Ind Ltd | Preparation of 2,6-di-t-butylphenol |
| JPS60252439A (en) * | 1984-05-29 | 1985-12-13 | Mitsubishi Yuka Fine Chem Co Ltd | Production of o-tert-alkylphenol |
| JPS6150934A (en) * | 1984-08-20 | 1986-03-13 | Maruzen Sekiyu Kagaku Kk | Production of ortho-tertiary alkylphenol |
| JPS62135442A (en) * | 1985-06-25 | 1987-06-18 | エシル コ−ポレ−シヨン | Alkylation of phenols |
-
1987
- 1987-01-30 JP JP62020285A patent/JPH0774176B2/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52136137A (en) * | 1976-03-22 | 1977-11-14 | Sterlitamaxky O Promyshlenny | Process for preparing 2*66dii terttbutyl phenol |
| JPS55133324A (en) * | 1979-04-03 | 1980-10-17 | Mitsui Petrochem Ind Ltd | Removal of aluminum component |
| JPS5795928A (en) * | 1980-12-05 | 1982-06-15 | Mitsui Petrochem Ind Ltd | Preparation of 2,6-di-t-butylphenol |
| JPS60252439A (en) * | 1984-05-29 | 1985-12-13 | Mitsubishi Yuka Fine Chem Co Ltd | Production of o-tert-alkylphenol |
| JPS6150934A (en) * | 1984-08-20 | 1986-03-13 | Maruzen Sekiyu Kagaku Kk | Production of ortho-tertiary alkylphenol |
| JPS62135442A (en) * | 1985-06-25 | 1987-06-18 | エシル コ−ポレ−シヨン | Alkylation of phenols |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102161617A (en) * | 2010-02-23 | 2011-08-24 | 蓬莱红卫化工有限公司 | Synthesis method of 2-methyl-6-tert-butylphenol |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0774176B2 (en) | 1995-08-09 |
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