JPH0910597A - Alkylation catalyst for aromatic compound, preparation thereof, and preparation of tertiary alkyl phenol - Google Patents
Alkylation catalyst for aromatic compound, preparation thereof, and preparation of tertiary alkyl phenolInfo
- Publication number
- JPH0910597A JPH0910597A JP7162145A JP16214595A JPH0910597A JP H0910597 A JPH0910597 A JP H0910597A JP 7162145 A JP7162145 A JP 7162145A JP 16214595 A JP16214595 A JP 16214595A JP H0910597 A JPH0910597 A JP H0910597A
- Authority
- JP
- Japan
- Prior art keywords
- phenol
- catalyst
- reaction
- phenols
- weight
- 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.)
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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
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、芳香族化合物用アルキ
ル化触媒、その製造方法、及びこのアルキル化触媒を用
いた第3級アルキルフェノール類の製造方法に関する。TECHNICAL FIELD The present invention relates to an alkylation catalyst for aromatic compounds, a method for producing the same, and a method for producing tertiary alkylphenols using this alkylation catalyst.
【0002】[0002]
【従来の技術】アルキル化フェノール類は、各種の化学
原料として用いられ、その中でも第3級アルキルフェノ
ール類は、ホルマリンと縮合して、各種の粘着付与剤と
して、ゴム用接着剤の原料として広く使用され、またロ
ジンと反応させインキ用の樹脂としても使用されてい
る。またポリカーボネート樹脂の分子量調節剤等にも用
いられている。2. Description of the Related Art Alkylated phenols are used as various chemical raw materials, and among them, tertiary alkylphenols are condensed with formalin to be widely used as various tackifiers and raw materials for rubber adhesives. It is also used as a resin for ink by reacting with rosin. It is also used as a molecular weight regulator for polycarbonate resins.
【0003】従来、フェノール類の第3級アルキル化に
よる第3級アルキルフェノール類の製造方法に関して、
触媒として、硫酸、アルキル置換又は無置換フェニルス
ルホン酸、フェノールスルホン酸、トルエンスルホン酸
等を多量に使用することは、公知の事実であり、例え
ば、インダストリアル・エンジニアリング・ケミスト
リ(Ind.Eng.Chem.)誌35巻(1943
年)266頁には、濃硫酸を触媒としてクレゾール10
0重量部に対して5重量部と多量に使用して反応を行っ
た後、水酸化ナトリウム水溶液を用いて高温下で中和
し、次いで中和塩を含有する水相を分離し、多量の温水
で油相を洗浄し、水相を分離することで、触媒として用
いた濃硫酸を除去する例が挙げられており、また、特
開昭52−91830号公報には、触媒として濃硫酸
を、フェノール100重量部に対して2重量部用いて反
応を行い、反応後、触媒を中和し、反応液を水洗し、反
応生成物を含有する油相と水相を分離することで中和塩
を水相に抽出分離し、更に油相中の残存酸触媒をアルカ
リ水溶液で中和洗浄後、油相とアルカリ性水相を分離す
ることで、触媒除去を行った後、反応生成物を含有する
該油相を蒸留精製工程に移送する例が開示されている。
また更に、特開昭51−113833号公報には、ト
ルエンスルホン酸水溶液を触媒として、クレゾール10
0重量部に対して5〜15重量部と、多量に使用して反
応を行った後、該反応生成物100重量部に対し10重
量部の水酸化ナトリウムのメタノール溶液で中和後、多
量の温水で洗浄して、中和塩を水相に抽出し、水相を分
離することで、触媒として用いたトルエンスルホン酸を
除去する例が記載されている。Conventionally, regarding a method for producing tertiary alkylphenols by tertiary alkylation of phenols,
It is a known fact that a large amount of sulfuric acid, alkyl-substituted or unsubstituted phenylsulfonic acid, phenolsulfonic acid, toluenesulfonic acid and the like is used as a catalyst, for example, Industrial Engineering Chemistry (Ind. Eng. Chem. ) Magazine 35 (1943
Year) 266, cresol 10 with concentrated sulfuric acid as catalyst
After the reaction was carried out by using a large amount of 5 parts by weight with respect to 0 parts by weight, the mixture was neutralized with an aqueous solution of sodium hydroxide at high temperature, and then the aqueous phase containing the neutralized salt was separated, There is an example in which the concentrated sulfuric acid used as a catalyst is removed by washing the oil phase with warm water and separating the aqueous phase. Further, JP-A-52-91830 discloses that concentrated sulfuric acid is used as a catalyst. , 2 parts by weight with respect to 100 parts by weight of phenol, after the reaction, the catalyst is neutralized, the reaction solution is washed with water, and the oil phase containing the reaction product and the aqueous phase are separated to neutralize. The salt is extracted and separated into an aqueous phase, and the residual acid catalyst in the oil phase is neutralized and washed with an alkaline aqueous solution, and then the oil phase and the alkaline aqueous phase are separated to remove the catalyst, and then the reaction product is contained. An example of transferring the oil phase to a distillation purification step is disclosed.
Further, in Japanese Patent Laid-Open No. 51-113833, cresol 10 is prepared by using an aqueous solution of toluenesulfonic acid as a catalyst.
The reaction was carried out by using a large amount of 5 to 15 parts by weight with respect to 0 parts by weight, and then neutralized with 10 parts by weight of a methanol solution of sodium hydroxide based on 100 parts by weight of the reaction product. An example is described in which toluene sulfonic acid used as a catalyst is removed by washing with warm water, extracting a neutralized salt into an aqueous phase, and separating the aqueous phase.
【0004】[0004]
【発明が解決しようとする課題】しかし、、又は
等の方法では、反応生成物であるアルキル化フェノール
類の蒸留精製時の脱アルキル化を防止するため、反応終
了後アルキル化フェノール類の蒸留精製前に、触媒を中
和して系から除去することが必要であり、該触媒の中和
塩を除去せずに、あるいはその一部を除去せずに、反応
生成物であるアルキル化フェノール類の蒸留精製を行っ
た場合には、反応液が濃縮されて中和塩が析出し、流動
性が低下して攪拌効率が低くなり、蒸発潜熱を確保でき
ず蒸気の留出量が少なくなってしまうため、目的生成物
の回収率が低下するという欠点がある。また、中和塩を
含有する釜残液を、温度、蒸気圧を低下させた後に排出
させる際、該中和塩が析出し配管の閉鎖が起きてしまう
という問題も生ずる。However, in the method of or, etc., in order to prevent dealkylation of the alkylated phenols, which is a reaction product, during distillation and purification, the distillation and purification of the alkylated phenols after the reaction is completed. Before, it is necessary to neutralize the catalyst and remove it from the system. Without removing the neutralization salt of the catalyst, or without removing a part thereof, the alkylated phenols which are the reaction products. In the case of the distillation purification, the reaction solution was concentrated and neutralized salts were precipitated, the fluidity was lowered, the stirring efficiency was lowered, the latent heat of vaporization could not be secured, and the amount of vapor distilled was reduced. Therefore, there is a drawback that the recovery rate of the target product decreases. Further, when the residual liquid containing the neutralizing salt is discharged after the temperature and the vapor pressure are lowered, the neutralizing salt is deposited and the pipe is closed.
【0005】そのため、反応に用いた触媒を、中和後、
中和塩を含む反応液が蒸留の際、常に流動性を維持でき
る程度にまで中和塩を除去する工程として、触媒の中和
を含む反応液の水洗、分離を繰り返す等、煩雑な後処理
工程が必要となる。Therefore, after neutralizing the catalyst used in the reaction,
When the reaction solution containing the neutralization salt is distilled, as a step of removing the neutralization salt to such an extent that the fluidity can always be maintained, the reaction solution containing the neutralization of the catalyst is repeatedly washed with water and separated, and the complicated post-treatment is performed. A process is required.
【0006】また、該反応に用いている触媒量が多量で
あるため、該触媒の処理工程も一層複雑なものとなって
いるという問題点がある。しかし一方で該触媒の分離除
去を容易にするため、触媒量を減らして該反応を行う
と、反応速度が遅くなり、生産性を著しく損ねるという
欠点が生じる。Further, since the amount of the catalyst used in the reaction is large, there is a problem that the treatment process of the catalyst becomes more complicated. On the other hand, however, if the amount of the catalyst is reduced to carry out the reaction in order to facilitate the separation and removal of the catalyst, the reaction rate becomes slow and the productivity is significantly impaired.
【0007】本発明の課題は、生産性を落とさずに用い
る触媒量を低減し、また反応後の後処理工程を簡便にで
きる芳香族化合物用アルキル化触媒を開発し、該アルキ
ル化触媒の製造方法、また更に、この触媒を用いたアル
キルフェノール類の製造方法を確立することである。An object of the present invention is to develop an alkylation catalyst for aromatic compounds which can reduce the amount of the catalyst used without lowering the productivity and can simplify the post-treatment step after the reaction, and to produce the alkylation catalyst. A method, and further, to establish a method for producing alkylphenols using this catalyst.
【0008】[0008]
【課題を解決するための手段】本発明者らは、上記課題
を解決するため鋭意検討した結果、スルホン酸基を芳香
核上に有しており、かつ、フェノール性水酸基がスルホ
ン酸エステルを形成しているフェノール誘導体は、フェ
ノール類、トルエン、キシレン等の芳香族化合物用のア
ルキル化触媒として用いると高活性作用を示すこと、こ
のアルキル化触媒は、硫酸とフェノール類とを反応させ
る方法で、容易に製造できること、アルキル化フェノー
ル類の製造方法に該触媒を用いると、触媒活性が高いた
めに、使用する触媒量を大幅に減少することができ、か
つ、これに伴い反応後の触媒を中和して生成する中和塩
も大幅に減少でき、更に該中和塩自体が微細に反応液中
に分散してスラリー状態を保持し、流動性を維持できる
性質を有するため、反応後触媒に用いた該フェノール誘
導体の中和塩を除去せず、中和塩の存在下で反応生成物
の蒸留分離を行っても、反応液が流動性を保持し易く、
蒸留操作が可能となることを見いだし、本発明を完成す
るに至った。Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that they have a sulfonic acid group on an aromatic nucleus and a phenolic hydroxyl group forms a sulfonic acid ester. The phenol derivative has a high activity when used as an alkylation catalyst for aromatic compounds such as phenols, toluene and xylene. This alkylation catalyst is a method of reacting sulfuric acid and phenols. It can be easily produced, and when the catalyst is used in the method for producing an alkylated phenol, the amount of the catalyst used can be greatly reduced because the catalyst activity is high, and the catalyst after the reaction can be reduced accordingly. The neutralization salt produced by the addition can be greatly reduced, and the neutralization salt itself has a property that it can be finely dispersed in the reaction liquid to maintain a slurry state and maintain fluidity. Without removing the neutralized salt of the phenol derivative used in the catalyst after the reaction, even when the distillation separation of the reaction product in the presence of a neutral salt, easier reaction solution retains fluidity,
The inventors have found that a distillation operation is possible and have completed the present invention.
【0009】即ち、本発明は、スルホン酸基を芳香核上
に有しており、かつ、フェノール性水酸基がスルホン酸
エステルを形成しているフェノール誘導体からなること
を特徴とする芳香族化合物用アルキル化触媒、硫酸とフ
ェノール類とを反応させることを特徴とする芳香族化合
物用アルキル化触媒の製造方法、及び第3級オレフィン
とフェノール類とを、酸触媒の存在下に反応させる第3
級アルキルフェノール類の製造方法であって、該酸触媒
として、スルホン酸基を芳香核上に有しており、かつ、
フェノール性水酸基がスルホン酸エステルを形成してい
るフェノール誘導体を用いることを特徴とする第3級ア
ルキルフェノール類の製造方法を提供するものである。That is, the present invention is characterized by comprising a phenol derivative having a sulfonic acid group on the aromatic nucleus and having a phenolic hydroxyl group forming a sulfonic acid ester. -Catalyst, method for producing alkylation catalyst for aromatic compound characterized by reacting sulfuric acid and phenol, and third reaction of tertiary olefin and phenol in the presence of acid catalyst
A method for producing a primary alkylphenol, wherein the acid catalyst has a sulfonic acid group on an aromatic nucleus, and
It is intended to provide a method for producing a tertiary alkylphenol, which comprises using a phenol derivative in which a phenolic hydroxyl group forms a sulfonate ester.
【0010】本発明の芳香族化合物用アルキル化触媒と
しては、スルホン酸基を芳香核上に有しており、かつ、
フェノール性水酸基がスルホン酸エステルを形成してい
るフェノール誘導体であれば良く、例えばモノスルホン
化フェノール、ジスルホン化フェノール又はトリスルホ
ン化フェノールのジ硫酸エステル;モノスルホン化フェ
ノール、ジスルホン化フェノール又はトリスルホン化フ
ェノールのモノ硫酸エステル;モノスルホン化クレゾー
ル、ジスルホン化クレゾール又はトリスルホン化クレゾ
ールのジ硫酸エステル;モノスルホン化クレゾール、ジ
スルホン化クレゾール、又はトリスルホン化クレゾール
のモノ硫酸エステル;モノスルホン化キシレノール、ジ
スルホン化キシレノール又はトリスルホン化キシレノー
ルのジ硫酸エステル;モノスルホン化キシレノール、ジ
スルホン化キシレノール又はトリスルホン化キシレノー
ルのモノ硫酸エステル等のフェノール誘導体が挙げら
れ、これらはそれぞれ単独で、あるいは2種以上を混合
して用いることができる。The alkylation catalyst for aromatic compounds of the present invention has a sulfonic acid group on the aromatic nucleus, and
Any phenol derivative in which the phenolic hydroxyl group forms a sulfonic acid ester may be used, and examples thereof include monosulfonated phenol, disulfonated phenol or disulphonic acid ester of trisulfonated phenol; monosulfonated phenol, disulfonated phenol or trisulfonated. Phenol monosulfate; monosulfonated cresol, disulfonated cresol or trisulfonated cresol disulfate; monosulfonated cresol, disulfonated cresol, or trisulfonated cresol monosulfate; monosulfonated xylenol, disulfonated Xylenol or trisulfonated xylenol disulfate; monosulfonated xylenol, disulfonated xylenol or trisulfonated xylenol monosulfate They include phenol derivatives such as Le, these may be used alone or in combination of two or more.
【0011】これらのアルキル化触媒の中では、例えば
トリスルホン化フェノールジ硫酸エステル、ジスルホン
化フェノールジ硫酸エステル、トリスルホン化フェノー
ルモノ硫酸エステル等の、スルホン酸基を1個の芳香核
上に2又は3個有するものが、触媒活性が高いため特に
好ましく、更にその中でも、例えばトリスルホン化フェ
ノールジ硫酸エステル、ジスルホン化フェノールジ硫酸
エステル等の、ジ硫酸エステル類が更に好ましい。Among these alkylation catalysts, sulfonic acid groups such as trisulfonated phenol disulfate, disulfonated phenol disulfate, trisulfonated phenol monosulfate, etc. Or, those having three units are particularly preferable because of high catalytic activity, and among these, disulfuric acid esters such as trisulfonated phenol disulfuric acid ester and disulfonated phenol disulfuric acid ester are more preferable.
【0012】該フェノール誘導体は、フェノール類や、
トルエン、ベンゼン、キシレン等の芳香族化合物を、第
3級オレフィンを用い、反応温度50〜140℃でアル
キル化する反応等の触媒として用いることができる。The phenol derivative includes phenols and
An aromatic compound such as toluene, benzene or xylene can be used as a catalyst for a reaction such as alkylation at a reaction temperature of 50 to 140 ° C. using a tertiary olefin.
【0013】これら本発明の芳香族化合物用アルキル化
触媒の製造方法は、特に限定されないが、例えば、本発
明の製造方法、すなわち、硫酸とフェノール類とを反応
させることを特徴とする方法で製造することができる。The method for producing the alkylation catalyst for aromatic compounds of the present invention is not particularly limited, but for example, it is produced by the method of the present invention, that is, a method characterized by reacting sulfuric acid and phenols. can do.
【0014】上記芳香族化合物用アルキル化触媒の製造
方法において用いられるフェノール類としては、例え
ば、フェノール、クレゾール、キシレノール等の低級ア
ルキル基置換もしくは非置換のフェノールや、スルホン
化フェノール、スルホン化クレゾール、スルホン化キシ
レノール等、スルホン酸基で置換されているフェノール
類等を用いることができるが、その中でもフェノール、
又は1〜3個のスルホン酸基で置換されているフェノー
ルである、モノスルホン化フェノール、ジスルホン化フ
ェノール、トリスルホン化フェノールを用いるのが好ま
しく、更にその中でも、フェノールを用いるのが工業的
に容易に入手できるので好ましい。Examples of the phenols used in the method for producing an alkylation catalyst for aromatic compounds include phenols substituted or unsubstituted with a lower alkyl group such as phenol, cresol and xylenol, sulfonated phenols and sulfonated cresols. Sulfonated xylenol and the like, phenols substituted with a sulfonic acid group and the like can be used. Among them, phenol,
Or, it is preferable to use monosulfonated phenol, disulfonated phenol, or trisulfonated phenol, which is a phenol substituted with 1 to 3 sulfonic acid groups, and among them, it is industrially easy to use phenol. It is preferable because it can be obtained.
【0015】また、上記芳香族化合物用アルキル化触媒
の製造方法において用いられる硫酸は、工業的に入手で
きる汎用品の規格を満足していればよいが、中でも例え
ば、濃硫酸や発煙硫酸が好ましく用いられるが、その中
でも通常は、98重量%以上の硫酸を使用するのが好ま
しい。Further, the sulfuric acid used in the method for producing the alkylation catalyst for aromatic compounds may satisfy the standard of industrially available general-purpose products, among which concentrated sulfuric acid and fuming sulfuric acid are preferable. Although it is used, it is usually preferable to use 98% by weight or more of sulfuric acid.
【0016】該反応に於ける、硫酸とフェノール類との
モル比は2:1〜4:1で行うのが好ましく、その中で
もモル比が2.5:1〜3.5:1の割合で行うのが特
に好ましい。In the reaction, the molar ratio of sulfuric acid to phenols is preferably 2: 1 to 4: 1. Among them, the molar ratio is 2.5: 1 to 3.5: 1. It is particularly preferable to carry out.
【0017】また、該反応に於ける硫酸とフェノール類
との反応温度としては、50〜100℃で行うことが好
ましく、その中でも特に80〜100℃の範囲で行うこ
とが好ましい。The reaction temperature of sulfuric acid and phenols in the reaction is preferably 50 to 100 ° C, and particularly preferably 80 to 100 ° C.
【0018】本発明の芳香族化合物用アルキル化触媒の
製造方法において、通常、硫酸とフェノール類との反応
は、まずフェノール類の芳香核が順次スルホン化され、
次に、フェノール性水酸基がスルホン酸エステルとな
り、赤外線吸収スペクトル分析により3640〜360
0cm-1のOH吸収の消失で、反応終点を確認して終了
しているが、生成される混合物中、モノスルホン化フェ
ノール類のスルホン酸エステルの混合比率は低く、トリ
スルホン化フェノールジ硫酸エステル、ジスルホン化フ
ェノールジ硫酸エステル、トリスルホン化フェノールジ
硫酸エステル等の、ジスルホン化フェノール類のスルホ
ン酸エステル、又はトリスルホン化フェノール類のスル
ホン酸エステルが高い混合比率で生成されるが、生成
後、精製して用いても良いが、精製せず、混合物をその
まま触媒として使用することもできる。In the method for producing an alkylation catalyst for aromatic compounds of the present invention, in the reaction between sulfuric acid and phenols, first, the aromatic nucleus of phenols is sequentially sulfonated,
Next, the phenolic hydroxyl group becomes a sulfonic acid ester, which is 3640 to 360 by infrared absorption spectrum analysis.
The reaction was completed by confirming the end point of the reaction by the disappearance of OH absorption at 0 cm -1 , but the mixture ratio of the sulfonate ester of monosulfonated phenols was low in the resulting mixture, and trisulfonated phenol disulfate ester was obtained. , Disulfonated phenol disulfate, trisulfonate phenol disulfate, etc., sulfonates of disulfonated phenols, or sulfonates of trisulfonated phenols are produced at a high mixing ratio. Although it may be used after being purified, the mixture can be directly used as a catalyst without being purified.
【0019】本発明の第3級アルキル化フェノール類の
製造方法において用いるフェノール類としては、触媒と
して使用するフェノール誘導体の製造に用いることので
きるフェノール類の中から任意に選択することができる
が、その中でも、フェノール、メタクレゾール、パラク
レゾール、混合メタ・パラクレゾール、2,4−キシレ
ノール等の、低級アルキル基置換もしくは非置換のフェ
ノールが好ましい。更にその中でも、フェノールが特に
好ましい。The phenols used in the method for producing the tertiary alkylated phenols of the present invention can be arbitrarily selected from the phenols that can be used for producing the phenol derivative used as the catalyst, Among these, lower alkyl group-substituted or unsubstituted phenols such as phenol, meta-cresol, para-cresol, mixed meta-para-cresol, and 2,4-xylenol are preferable. Among them, phenol is particularly preferable.
【0020】また、本発明で用いる第3級オレフィンと
しては、イソブチレン、2−メチル−1−ブテン、2−
メチル−2−ブテン、ジイソブチレン、α−メチルスチ
レン等が挙げられるが、中でもイソブチレン、ジイソブ
チレンを用いるのが特に好ましい。As the tertiary olefin used in the present invention, isobutylene, 2-methyl-1-butene, 2-
Methyl-2-butene, diisobutylene, α-methylstyrene and the like can be mentioned, but among them, isobutylene and diisobutylene are particularly preferable.
【0021】本発明の目的生成物である、第3級アルキ
ルフェノール類としては、例えば、パラターシャリーブ
チルフェノール、パラターシャリーオクチルフェノー
ル、パラクミルフェノール等のモノ第3級アルキルフェ
ノール類;2,4−ジターシャリーブチルフェノール等
のジ第3級アルキルフェノール類等があげられるが、そ
れぞれの製造方法において、第3級オレフィンの使用量
としては、モノ第3級アルキルフェノール類を製造する
場合には、フェノール類1モルに対して、0.2〜0.
8モルの範囲が、転化率、及び選択率が共に良く、高純
度品が収率良く得られるため好ましく、なかでも0.3
〜0.6モルが特に好ましい。また、ジ第3級アルキル
フェノール類を製造する場合には、フェノール類1モル
に対して、1.2〜2.0モルの範囲が好ましく、なか
でも1.5〜1.7モルが特に好ましい。The tertiary alkylphenols, which are the target products of the present invention, include, for example, monotertiary alkylphenols such as paratertiary butylphenol, paratertiary octylphenol and paracumylphenol; 2,4-ditertiary. Examples include ditertiary alkylphenols such as butylphenol. In each production method, the amount of the tertiary olefin used is 1 mole of the phenol when producing monotertiary alkylphenols. 0.2 to 0.
The range of 8 mol is preferable because both the conversion rate and the selectivity are good and a high-purity product can be obtained with a high yield.
~ 0.6 mol is particularly preferred. Further, in the case of producing ditertiary alkylphenols, the range of 1.2 to 2.0 mol is preferable with respect to 1 mol of phenols, and the range of 1.5 to 1.7 mol is particularly preferable.
【0022】本発明において酸触媒として用いるフェノ
ール誘導体は、フェノール類100重量部に対して、
0.05〜1重量部の範囲内で用いるのが好ましく、そ
の中でもフェノール類100重量部に対して、0.05
〜0.5重量部の範囲内で用いるのが特に好ましい。The phenol derivative used as the acid catalyst in the present invention is based on 100 parts by weight of phenols.
It is preferably used within the range of 0.05 to 1 part by weight, and among them, 0.05 parts by weight based on 100 parts by weight of phenols.
It is particularly preferable to use it within a range of from 0.5 to 0.5 parts by weight.
【0023】本発明の、第3級オレフィンとフェノール
類との反応工程としては、まずアルキル基の付加反応
が、その後続いて不均化反応が行われるが、該付加反応
は、通常60〜110℃で、その中でも70〜100℃
で行うのが好ましく、また、該不均化反応は、通常90
〜160℃で、その中でも100〜150℃で行うのが
好ましい。In the reaction step of the tertiary olefin and phenols of the present invention, an addition reaction of an alkyl group and then a disproportionation reaction are carried out. The addition reaction is usually 60 to 110. ℃, among them 70-100 ℃
The disproportionation reaction is usually performed at 90 ° C.
It is preferably carried out at ˜160 ° C., and especially at 100˜150 ° C.
【0024】また、本発明における反応時間は、付加反
応時間として2〜6時間で行うのが好ましく、不均化反
応時間として、5〜10時間で行うのが好ましい。本発
明の、第3級オレフィンとフェノール類との反応におけ
るフェノール類、第3級オレフィン、触媒として用いる
フェノール誘導体の供給順序は、通常はフェノール類に
触媒として用いるフェノール誘導体を添加後、第3級オ
レフィンを供給するのが好ましい。また用いる第3級オ
レフィンは液状で供給しても、又は気化器等を用いて蒸
気にして反応に供給しても良い。The reaction time in the present invention is preferably 2 to 6 hours as the addition reaction time, and preferably 5 to 10 hours as the disproportionation reaction time. The order of supplying the phenols, the tertiary olefins, and the phenol derivative used as the catalyst in the reaction of the tertiary olefin with the phenols of the present invention is usually the addition of the phenol derivative used as the catalyst to the phenol and then the tertiary Preference is given to supplying olefins. The tertiary olefin to be used may be supplied in liquid form, or may be vaporized using a vaporizer or the like and supplied to the reaction.
【0025】反応は常圧、減圧、加圧のいずれの場合で
も実施できるが、通常は、経済的に優位である常圧下で
行うのが好ましい。本発明における反応様式は、例え
ば、回分式、連続式等が挙げられるが、工業的には、例
えば、常圧下、連続的に供給されてくるフェノール類に
触媒として用いるフェノール誘導体を加え、ついでこの
中に液状又は気化した第3級オレフィンを連続的に供給
して付加反応させる、等の連続方法が好ましい。The reaction can be carried out under any of normal pressure, reduced pressure and increased pressure, but it is usually preferable to carry out under normal pressure which is economically advantageous. The reaction mode in the present invention includes, for example, a batch system and a continuous system, but industrially, for example, under normal pressure, a phenol derivative continuously used is added to a phenol compound continuously supplied, and then a phenol derivative used as a catalyst is added. A continuous method such as continuously supplying a liquid or vaporized tertiary olefin therein to carry out an addition reaction is preferable.
【0026】本発明の反応後の後処理工程としては、通
常、触媒として用いたフェノール誘導体を中和後、生成
した中和塩を該中和塩量の10〜20倍量の水で30〜
100℃で洗浄して、中和塩を水槽に抽出して、水相を
分離した後、反応液を蒸留処理する方法や、また、酸触
媒を中和後、中和塩を含有したまま反応液を直接蒸留処
理する方法が挙げられるが、通常、中和塩を含有したま
ま反応液を直接蒸留処理する方法が、行程が簡便なため
好ましい。In the post-treatment step after the reaction of the present invention, usually, after neutralizing the phenol derivative used as a catalyst, the produced neutralization salt is treated with 30 to 30 times the amount of the neutralization salt in water.
Washing at 100 ° C., extracting the neutralized salt into a water tank, separating the aqueous phase, and distilling the reaction solution. Alternatively, after neutralizing the acid catalyst, the reaction is carried out with the neutralized salt still contained. A method of directly distilling the liquid can be mentioned. Usually, a method of directly distilling the reaction liquid while containing the neutralized salt is preferable because the process is simple.
【0027】中和塩を含有したまま反応液を直接蒸留処
理する場合、通常140〜200℃で、3〜7時間かけ
て行うのが好ましい。工業的には、反応液中の触媒を中
和後、中和塩を含有しまま、単蒸留釜で蒸留して、有効
成分を塔頂留分として回収し、塔底成分として非揮発性
の中和塩とタール(高沸点物)の混合物であるスラリー
を取り出す方法が好ましい。When the reaction solution is directly subjected to the distillation treatment while containing the neutralized salt, it is usually carried out at 140 to 200 ° C. for 3 to 7 hours. Industrially, after neutralizing the catalyst in the reaction solution, while still containing the neutralized salt, it is distilled in a simple distillation pot to recover the active ingredient as a top fraction, and a non-volatile component as a bottom component. A method of taking out a slurry which is a mixture of neutralized salt and tar (high boiling point material) is preferable.
【0028】[0028]
【実施例】以下、参考例、実施例及び比較例により本発
明を更に詳述するが、本発明は実施例により何等制限さ
れるものではない。尚、例中の%は重量%を表す。EXAMPLES The present invention will be described in more detail with reference to Reference Examples, Examples and Comparative Examples, but the present invention is not limited to the Examples. In addition,% in an example represents weight%.
【0029】実施例1 温度計、還流冷却器、滴下ロート及び攪拌器の付いた2
00ml4つ口フラスコにジスルホン化フェノール40
gを入れ、70℃で攪拌した。そこに濃硫酸16gを3
0分で滴下した。滴下終了後95℃に昇温し、1時間反
応させ、反応後室温まで冷却し、スルホン酸基を1個の
芳香核上に2個有するものと、又は3個有するものと
の、フェノール性水酸基がスルホン酸エステルを形成し
ている、フェノール誘導体の混合物56gを得た(以
下、アルキル化触媒1とする。)。得られたアルキル化
触媒1のIR吸収を調べたが、フェノール性水酸基の吸
収である3640〜3600cm-1の吸収ピークは認め
られなかった。Example 1 2 with thermometer, reflux condenser, dropping funnel and stirrer
Disulfonated phenol 40 in a 00 ml 4-neck flask
g, and stirred at 70 ° C. 3 g of concentrated sulfuric acid 16g
It was added dropwise in 0 minutes. After completion of the dropping, the temperature is raised to 95 ° C., the reaction is carried out for 1 hour, the reaction is cooled to room temperature, and the phenolic hydroxyl group having two or three sulfonic acid groups on one aromatic nucleus. As a result, 56 g of a mixture of phenol derivatives in which sulfonic acid ester was formed (hereinafter referred to as alkylation catalyst 1) was obtained. When the IR absorption of the obtained alkylation catalyst 1 was examined, the absorption peak of 3640 to 3600 cm −1 , which is the absorption of the phenolic hydroxyl group, was not recognized.
【0030】実施例2 温度計、還流冷却器、滴下ロート及び攪拌器の付いた2
00ml4つ口フラスコにフェノール40gを入れ、7
0℃で攪拌した。そこに濃硫酸120gを60分で滴下
した。滴下終了後100℃に昇温し、3時間反応させ、
反応後室温まで冷却し、スルホン酸基を1個の芳香核上
に2個有するものと、又は3個有するものとの、フェノ
ール性水酸基がスルホン酸エステルを形成している、フ
ェノール誘導体の混合物160gを得た(以下、アルキ
ル化触媒2とする。)。アルキル化触媒2のIR吸収を
調べたが、フェノール性水酸基の吸収である3640〜
3600cm-1の吸収ピークは認められなかった。Example 2 2 with thermometer, reflux condenser, dropping funnel and stirrer
Put 40 g of phenol in a 00 ml four-necked flask, and
Stirred at 0 ° C. 120 g of concentrated sulfuric acid was added dropwise thereto in 60 minutes. After the dropping, the temperature is raised to 100 ° C. and the reaction is performed for 3 hours.
After the reaction, the mixture is cooled to room temperature, and 160 g of a mixture of a phenol derivative having two sulfonic acid groups on one aromatic nucleus or one having three sulfonic acid groups, in which a phenolic hydroxyl group forms a sulfonate ester. Was obtained (hereinafter referred to as alkylation catalyst 2). The IR absorption of the alkylation catalyst 2 was examined, and it was found that the absorption of the phenolic hydroxyl group was 3640-
No absorption peak at 3600 cm -1 was observed.
【0031】実施例3 温度計、還流冷却器、滴下ロート及び攪拌器の付いた5
00ml4つ口フラスコにフェノール300gとアルキ
ル化触媒1を0.7g(フェノール100重量部に対し
0.2重量部)入れ、攪拌しながら95℃に昇温した。
そこにイソブチレン72gを3時間で供給し付加反応を
行い、イソブチレン供給終了後、続けて130℃で7時
間攪拌して不均化反応を行い、反応生成物372.7g
を得た。Example 3 5 equipped with a thermometer, reflux condenser, dropping funnel and stirrer
300 g of phenol and 0.7 g of alkylation catalyst 1 (0.2 part by weight relative to 100 parts by weight of phenol) were placed in a 00 ml four-necked flask, and the temperature was raised to 95 ° C. with stirring.
72 g of isobutylene was added thereto for 3 hours to carry out an addition reaction, and after the completion of the supply of isobutylene, stirring was continued at 130 ° C. for 7 hours to carry out a disproportionation reaction, and 372.7 g of a reaction product.
I got
【0032】該反応生成物に、20%水酸化ナトリウム
水溶液1.6gを添加して触媒を中和した後、該中和塩
を除去せず含有したまま精製工程に移送して、150℃
において6時間減圧蒸留を行った。蒸留により低沸成分
とパラターシャリーブチルフェノールを含む高沸成分と
を蒸留分離した。釜残から、蒸留により、更に高沸点で
ある2,4−ジターシャリーブチルフェノールを分離し
て、純度99.8%のパラターシャリーブチルフェノー
ル173gを得た。After adding 1.6 g of 20% aqueous sodium hydroxide solution to the reaction product to neutralize the catalyst, the catalyst was transferred to the refining step while containing the neutralized salt without removal, and the temperature was changed to 150 ° C.
Was vacuum distilled for 6 hours. A low boiling component and a high boiling component containing para-tertiary butylphenol were separated by distillation. Higher boiling point 2,4-ditertiary butylphenol was separated from the bottom of the kettle by distillation to obtain 173 g of para-tertiary butylphenol having a purity of 99.8%.
【0033】この時中和塩を含んだ釜残量は2.5g
(反応生成物100重量部に対し0.7重量部)で、該
釜残液は、50℃に降温させるまで、スラリー状で、流
動性を保持するものであったため、蒸留釜より配管を通
して蒸留系外に流出させることができた。At this time, the remaining amount of the pot containing the neutralized salt is 2.5 g.
(0.7 parts by weight relative to 100 parts by weight of the reaction product), the residual liquid in the kettle was in a slurry state and maintained fluidity until the temperature was lowered to 50 ° C. It was possible to let it out of the system.
【0034】実施例4 温度計、還流冷却器、滴下ロート及び攪拌器の付いた5
00ml4つ口フラスコにフェノール300gとアルキ
ル化触媒2を0.9g(フェノール100重量部に対し
0.3重量部)用い、攪拌しながら75℃に昇温した。
そこにイソブチレン72gを5時間で供給して付加反応
を行い、イソブチレン供給後、続けて120℃で8時間
攪拌して不均化反応を行い、反応生成物372.9を得
た。Example 4 5 equipped with a thermometer, reflux condenser, dropping funnel and stirrer
300 g of phenol and 0.9 g of alkylation catalyst 2 (0.3 parts by weight per 100 parts by weight of phenol) were placed in a 00 ml four-necked flask, and the temperature was raised to 75 ° C. with stirring.
72 g of isobutylene was added thereto for 5 hours to carry out an addition reaction, and after the supply of isobutylene, stirring was continued at 120 ° C. for 8 hours to carry out a disproportionation reaction to obtain a reaction product 372.9.
【0035】該反応生成物に、20%水酸化ナトリウム
水溶液2.1gを添加して触媒を中和した。該中和塩を
除去せず含有したまま、実施例3と同様にして150℃
において6時間蒸留を行い、純度99.0%のパラタシ
ャリーブチルフェノール170gを得た。To the reaction product, 2.1 g of 20% aqueous sodium hydroxide solution was added to neutralize the catalyst. 150 ° C. in the same manner as in Example 3 while containing the neutralized salt without removing it.
Was distilled for 6 hours to obtain 170 g of para-tertiary butylphenol having a purity of 99.0%.
【0036】このとき中和塩を含んだ釜残量は、蒸留終
了後4.4g(反応生成物100重量部に対し1.2重
量部)であり、該釜残液は、50℃に降温させるまで流
動性を保持するものであったため、蒸留釜より配管を通
して蒸留系外に流出させることができた。At this time, the remaining amount of the kettle containing the neutralized salt was 4.4 g (1.2 parts by weight relative to 100 parts by weight of the reaction product) after the completion of the distillation, and the remaining liquid in the kettle was cooled to 50 ° C. Since the fluidity was maintained until it was allowed to flow, it could be flowed out of the distillation system from the distillation pot through the pipe.
【0037】実施例5 温度計、還流冷却器、滴下ロート及び攪拌器の付いた5
00ml4つ口フラスコにフェノール300gとアルキ
ル化触媒1を0.3g(フェノール100重量部に対し
0.1重量部)入れ、攪拌しながら80℃に昇温した。
そこにイソブチレン286gを5時間で供給して付加反
応を行い、イソブチレン供給後、続けて110℃で9時
間攪拌をして不均化反応を行い、反応生成物586.3
gを得た。Example 5 5 equipped with a thermometer, reflux condenser, dropping funnel and stirrer
300 g of phenol and 0.3 g of alkylation catalyst 1 (0.1 part by weight relative to 100 parts by weight of phenol) were placed in a 00 ml four-necked flask, and the temperature was raised to 80 ° C. with stirring.
Then, 286 g of isobutylene was fed thereto for 5 hours to carry out an addition reaction, and after feeding isobutylene, the mixture was stirred at 110 ° C. for 9 hours to carry out a disproportionation reaction to obtain a reaction product 586.3.
g was obtained.
【0038】該反応生成物に、20%水酸化ナトリウム
水溶液0.7gを添加し触媒を中和した。該中和塩を除
去せず含有したまま精製工程に移送して、180℃にお
いて4時間減圧蒸留を行った。蒸留により、目的生成物
である2,4−ジターシャリーブチルフェノールより低
沸点をパラターシャリーブチルフェノールを含む低沸成
分を分離し、また更に釜残から、蒸留により、2,4−
ジターシャリーブチルフェノールに比べ、高沸点である
2,4,6トリターシャリーブチルフェノールを含む高
沸成分を分離回収し、純度98.9%の2,4ジターシ
ャリーブチルフェノール400gを得た。The catalyst was neutralized by adding 0.7 g of a 20% aqueous sodium hydroxide solution to the reaction product. The neutralized salt was transferred to the purification step without being removed, and distilled under reduced pressure at 180 ° C. for 4 hours. By distillation, a low boiling point component having a lower boiling point than paratertiary butylphenol, which is lower than that of the target product 2,4-ditert-butylphenol, is separated.
Compared with ditert-butylphenol, high-boiling components including high boiling point 2,4,6-tritert-butylphenol were separated and collected to obtain 400 g of 2,4-ditert-butylphenol having a purity of 98.9%.
【0039】この時中和塩を含んだ釜残量は3.9g
(反応生成物100重量部に対し0.7重量部)であ
り、該釜残液は、50℃に降温させるまで、スラリー状
で、流動性を保持するものであったため、蒸留釜より配
管を通して蒸留系外に流出させることができた。At this time, the remaining amount of the pot containing the neutralized salt was 3.9 g.
(0.7 parts by weight with respect to 100 parts by weight of the reaction product), and the residual liquid in the kettle was in a slurry form and maintained fluidity until the temperature was lowered to 50 ° C. It was possible to make it flow out of the distillation system.
【0040】実施例6 温度計、還流冷却器、滴下ロート及び攪拌器の付いた5
00ml4つ口フラスコにフェノール300g及びアル
キル化触媒1を0.3g(フェノール100重量部に対
し0.1重量部)入れ、攪拌しながら80℃に昇温し
た。そこにジイソブチレン179gを5時間で供給して
付加反応を行い、その後続けて110℃で9時間攪拌し
て不均化反応を行い、反応生成物479.3gを得た。Example 6 5 equipped with a thermometer, reflux condenser, dropping funnel and stirrer
300 g of phenol and 0.3 g of alkylation catalyst 1 (0.1 part by weight relative to 100 parts by weight of phenol) were placed in a 00 ml four-necked flask, and the temperature was raised to 80 ° C. with stirring. Diisobutylene (179 g) was supplied thereto for 5 hours to carry out an addition reaction, followed by stirring at 110 ° C. for 9 hours to carry out a disproportionation reaction to obtain 479.3 g of a reaction product.
【0041】該反応生成物に、0.7gの20%水酸化
ナトリウム水溶液を添加し触媒を中和した。該中和塩を
除去せず含有したまま精製工程に移送して、180℃に
おいて4時間減圧蒸留を行った。蒸留により、目的生成
物であるパラターシャリーオクチルフェノールより、低
沸成分を分離し、また該目的生成物を含む釜残から、蒸
留により、更に高沸成分を分離回収して除去し、純度9
8.5%のパラターシャリーオクチルフェノール290
gを得た。To the reaction product, 0.7 g of 20% aqueous sodium hydroxide solution was added to neutralize the catalyst. The neutralized salt was transferred to the purification step without being removed, and distilled under reduced pressure at 180 ° C. for 4 hours. By distillation, a low boiling component was separated from the target product paratertiary octylphenol, and a higher boiling component was separated and recovered from the kettle residue containing the target product by distillation to obtain a purity of 9%.
8.5% paratertiary octylphenol 290
g was obtained.
【0042】釜残の高沸点物を蒸留回収後の中和塩を含
んだ釜残量は、3.1g(反応生成物100重量部に対
し0.7重量部)であり、該釜残液は、50℃に降温さ
せるまで、スラリー状で、流動性を保持するものであっ
たため、蒸留釜より配管を通して蒸留系外に流出させる
ことができた。The residual amount of the kettle containing the neutralized salt after the distillation of the high boiling substance in the kettle residue was 3.1 g (0.7 parts by weight based on 100 parts by weight of the reaction product). It was a slurry and kept fluidity until the temperature was lowered to 50 ° C., so that it could be flowed out of the distillation system from the distillation pot through the pipe.
【0043】比較例1 アルキル化触媒1に代えて濃硫酸6.0g(フェノール
100重量部に対し2.0重量部)を用いた以外は、実
施例3と同様にして、反応生成物378gを得た。Comparative Example 1 378 g of a reaction product was obtained in the same manner as in Example 3 except that 6.0 g of concentrated sulfuric acid (2.0 parts by weight based on 100 parts by weight of phenol) was used in place of the alkylation catalyst 1. Obtained.
【0044】該反応生成物に、20%水酸化ナトリウム
水溶液9.0gを添加して、酸触媒の中和を行った。該
中和塩を除去せず、含有したまま実施例3と同様にし
て、150℃で蒸留を行ったが、蒸留後半に攪拌効率が
低くなり、反応液の流動性が低下し、熱伝導が困難とな
り、蒸気の留出量が少なくなってしまったため、蒸留操
作は、その時点で終了させ、純度99.8%のパラター
シャリーブチルフェノール145gを得た。To the reaction product, 9.0 g of a 20% aqueous sodium hydroxide solution was added to neutralize the acid catalyst. Distillation was carried out at 150 ° C in the same manner as in Example 3 without removing the neutralized salt, but the stirring efficiency was lowered in the latter half of the distillation, the fluidity of the reaction liquid was lowered, and the thermal conductivity was reduced. Since it became difficult and the amount of vapor distilled out became small, the distillation operation was terminated at that point, and 145 g of paratertiarybutylphenol having a purity of 99.8% was obtained.
【0045】このとき中和塩を含んだ釜残量は20.0
g(反応生成物100重量部に対し5.4重量部)であ
った。蒸留工程が、途中で閉塞されてしまったため、次
に同様にして得た、中和後の反応生成物を、以下のよう
に長い工程を用いて精製を行った。At this time, the remaining amount of the pot containing the neutralized salt is 20.0.
g (5.4 parts by weight per 100 parts by weight of reaction product). Since the distillation step was blocked during the process, the reaction product after neutralization obtained in the same manner was purified using a long step as follows.
【0046】該反応生成物を80℃に冷却して、50g
の水を添加して攪拌後、30分静置し、上層と下層に分
離した。pH11の下層の水溶液77gを分離除去し
た。水洗後分液した水溶液中には、フェノール15gと
硫酸ナトリウム、フェノールスルホン酸ナトリウムが含
有されていた。The reaction product was cooled to 80 ° C. and 50 g
After adding water and stirring, the mixture was allowed to stand for 30 minutes and separated into an upper layer and a lower layer. 77 g of an aqueous solution of the lower layer of pH 11 was separated and removed. The aqueous solution separated after washing with water contained 15 g of phenol, sodium sulfate and sodium phenolsulfonate.
【0047】再度水を30g添加し、水洗後静置し、p
H7の下層の水溶液35gを分離した。水洗後分液した
水溶液中に5gのフェノールが溶解していた。これらの
下層の水溶液中よりフェノールを回収するため、回収装
置(溶剤抽出設備)に送り処理し、フェノールを20g
回収した。回収したフェノールを上層に加えた。30 g of water was added again, washed with water and allowed to stand, and p
35 g of a lower aqueous solution of H7 was separated. 5 g of phenol was dissolved in the aqueous solution separated after washing with water. In order to recover phenol from these lower aqueous solutions, it is sent to a recovery device (solvent extraction equipment) and treated to 20 g of phenol.
Collected. The recovered phenol was added to the upper layer.
【0048】上層を精製工程に送り、150℃において
6時間蒸留し、純度99.8%のパラターシャリーブチ
ルフェノール173gを得た。蒸留を終了した時点で、
釜残量は1.5g(反応生成物100重量部に対し0.
4重量部)であった。The upper layer was sent to the refining step and distilled at 150 ° C. for 6 hours to obtain 173 g of para-tert-butylphenol having a purity of 99.8%. At the end of distillation,
The remaining amount of the kettle is 1.5 g (0.
4 parts by weight).
【0049】比較例2 アルキル化触媒1に代えてパラトルエンスルホン酸を1
5.0g(フェノール100重量部に対し5.0重量
部)用いた以外は、実施例3と同様にして、反応生成物
387gを得た。Comparative Example 2 In place of the alkylation catalyst 1, 1 part of paratoluenesulfonic acid was used.
387 g of a reaction product was obtained in the same manner as in Example 3 except that 5.0 g (5.0 parts by weight based on 100 parts by weight of phenol) was used.
【0050】該反応生成物に、20%水酸化ナトリウム
水溶液9.0gを添加して、酸触媒の中和を行った。該
中和塩を除去せず、含有したまま実施例3と同様にし
て、150℃で蒸留を行ったが、蒸留後半に攪拌効率が
低くなり、反応液の流動性が低下し、熱伝導が困難とな
り、蒸気の留出量が少なくなってしまったため、蒸留操
作は、その時点で終了させ、純度99.8%のパラター
シャリーブチルフェノール140gを得た。To the reaction product, 9.0 g of a 20% aqueous sodium hydroxide solution was added to neutralize the acid catalyst. Distillation was carried out at 150 ° C in the same manner as in Example 3 without removing the neutralized salt, but the stirring efficiency was lowered in the latter half of the distillation, the fluidity of the reaction liquid was lowered, and the thermal conductivity was reduced. Since it became difficult and the amount of vapor distilled out became small, the distillation operation was terminated at that point, and 140 g of paratertiarybutylphenol having a purity of 99.8% was obtained.
【0051】このとき中和塩を含んだ釜残量は25.0
g(反応生成物100重量部に対し6.5重量部)。 比較例3 アルキル化触媒1に代えて濃硫酸1.0g(フェノール
100重量部に対し0.3重量部)を用い、イソブチレ
ン供給後130℃で不均化反応を終了させるのに20時
間を要した以外は、実施例3と同様に反応を行い、目的
生成物であるパラターシャリーブチルフェノール(PT
BP)の含有量は少なく、またその他の副生成物の含有
量が多い反応生成物373gを得た。該反応生成物にお
ける組成比を、実施例3に比較し表1に示す。At this time, the remaining amount of the pot containing the neutralized salt is 25.0.
g (6.5 parts by weight based on 100 parts by weight of reaction product). Comparative Example 3 Instead of the alkylation catalyst 1, 1.0 g of concentrated sulfuric acid (0.3 parts by weight relative to 100 parts by weight of phenol) was used, and 20 hours were required to complete the disproportionation reaction at 130 ° C. after the supply of isobutylene. Other than the above, the reaction was performed in the same manner as in Example 3 to obtain the desired product, paratertiary butylphenol (PT
373 g of a reaction product containing a small amount of BP) and a large amount of other by-products was obtained. The composition ratio of the reaction product is shown in Table 1 in comparison with Example 3.
【0052】[0052]
【表1】 *1 パラターシャリーブチルフェノール *2 オルソターシャリーブチルフェノール *3 2,6−ジターシャリーブチルフェノール *4 2,4−ジターシャリーブチルフェノール[Table 1] * 1 Paratertiary butylphenol * 2 Orthotertiary butylphenol * 3 2,6-Ditertiary butylphenol * 4 2,4-Ditertiary butylphenol
【0053】該反応生成物に、20%水酸化ナトリウム
水溶液3.0gを添加し、酸触媒の中和を行った。該中
和塩を除去せず、含有させたまま、実施例3と同様にし
て150℃で蒸留を行った。To the reaction product, 3.0 g of a 20% aqueous sodium hydroxide solution was added to neutralize the acid catalyst. Distillation was carried out at 150 ° C. in the same manner as in Example 3 without removing the neutralized salt, while keeping it contained.
【0054】反応液の仕込に対する蒸留の回収率90%
(釜残10%)時点より、釜に硫酸ナトリウムの結晶が
付着し始め、攪拌効率が低下し、蒸気量が減少し始め
た。更に蒸留を継続し、10時間かけて蒸留して、純度
98.0%のパラターシャリーブチルフェノール150
gを得た。Distillation recovery rate 90% with respect to reaction liquid charge
From the time of (10% remaining in the kettle), crystals of sodium sulfate began to adhere to the kettle, the stirring efficiency decreased, and the amount of steam started to decrease. Distillation is continued for 10 hours to obtain 98.0% pure para-tertiarybutylphenol 150.
g was obtained.
【0055】この時中和塩を含んだ釜残量は、6.4g
(反応生成物100重量部に対し1.5重量部)であっ
た。At this time, the remaining amount of the pot containing the neutralized salt was 6.4 g.
(1.5 parts by weight based on 100 parts by weight of reaction product).
【0056】[0056]
【発明の効果】本発明によれば、触媒活性が高いため
に、使用する触媒量を大幅に減少することが可能とな
り、これに伴い反応後の触媒を中和して生成する中和塩
を大幅に減少でき、かつ該中和塩自体が微細に反応液中
に分散しスラリー状態を保持し、流動性を維持できる性
質を有するため、該中和塩を反応液中に含有したまま蒸
留を行っても、蒸留中常に流動性を維持できるため、蒸
発に必要な熱量(蒸発潜熱)の伝熱に支障がなく、蒸気
の留出量を保って蒸留を連続的に行うことができ、また
中和塩を含有した釜残液を除去する際も、流動性を保ち
配管の閉鎖を起こすことなく排出できるため、反応後の
後処理工程が簡便となる、芳香族化合物用アルキル化触
媒、その製造方法及びこのアルキル化触媒を用いた第3
級アルキルフェノール類の製造法を提供できる。EFFECTS OF THE INVENTION According to the present invention, since the catalytic activity is high, it is possible to greatly reduce the amount of the catalyst used, and accordingly, the neutralized salt produced by neutralizing the catalyst after the reaction is formed. Since the neutralization salt itself can be significantly reduced, and the neutralization salt itself can be finely dispersed in the reaction solution to maintain a slurry state and maintain fluidity, distillation can be performed with the neutralization salt contained in the reaction solution. Even if it goes, the fluidity can always be maintained during the distillation, so there is no obstacle to the heat transfer of the amount of heat required for evaporation (latent heat of vaporization), and the distillation can be carried out continuously with the amount of vapor distilled kept, Even when removing the residual liquid containing the neutralized salt, since it can be discharged without retaining the fluidity and causing the pipe to be closed, the post-treatment step after the reaction is simplified, and an alkylation catalyst for an aromatic compound, Production method and third method using this alkylation catalyst
A method for producing a primary alkylphenol can be provided.
Claims (13)
かつ、フェノール性水酸基がスルホン酸エステルを形成
しているフェノール誘導体からなることを特徴とする芳
香族化合物用アルキル化触媒。1. Having a sulfonic acid group on an aromatic nucleus,
Also, an alkylation catalyst for aromatic compounds, which comprises a phenol derivative in which a phenolic hydroxyl group forms a sulfonate ester.
個の芳香核上に2又は3個有するものである請求項1記
載のアルキル化触媒。2. A phenol derivative having a sulfonic acid group of 1
The alkylation catalyst according to claim 1, which has 2 or 3 on each aromatic nucleus.
を特徴とする芳香族化合物用アルキル化触媒の製造方
法。3. A method for producing an alkylation catalyst for aromatic compounds, which comprises reacting sulfuric acid with phenols.
1のモル比で反応させる請求項3記載の製造方法。4. Sulfuric acid and phenols are used in a ratio of 2: 1 to 4:
The method according to claim 3, wherein the reaction is carried out at a molar ratio of 1.
の温度条件下に反応させる請求項4記載の製造方法。5. Sulfuric acid and phenols at 50 to 100 ° C.
The method according to claim 4, wherein the reaction is carried out under the temperature condition of.
3〜5のいずれか1つに記載の製造方法。6. The production method according to claim 3, wherein the phenol is phenol.
酸触媒の存在下に反応させる第3級アルキルフェノール
類の製造方法であって、該酸触媒として、スルホン酸基
を芳香核上に有しており、かつ、フェノール性水酸基が
スルホン酸エステルを形成しているフェノール誘導体を
用いることを特徴とする第3級アルキルフェノール類の
製造方法。7. A tertiary olefin and a phenolic compound,
A method for producing a tertiary alkylphenol which is reacted in the presence of an acid catalyst, wherein the acid catalyst has a sulfonic acid group on an aromatic nucleus and the phenolic hydroxyl group forms a sulfonic acid ester. The method for producing tertiary alkylphenols is characterized by using the phenol derivative described above.
が、スルホン酸基を1個の芳香核上に2又は3個有する
ものである請求項7記載の製造方法。8. The method according to claim 7, wherein the phenol derivative used as the acid catalyst has two or three sulfonic acid groups on one aromatic nucleus.
使用量が、フェノール類100重量部に対して0.05
〜1重量部である請求項7又は8記載の製造方法。9. The amount of the phenol derivative used as the acid catalyst is 0.05 based on 100 parts by weight of the phenols.
The manufacturing method of Claim 7 or 8 which is -1 part by weight.
求項9記載の製造方法。10. The production method according to claim 9, wherein the reaction temperature is 50 to 140 ° C.
項7〜10のいずれか1つに記載の製造方法。11. The method according to claim 7, wherein the phenol is phenol.
はジイソブチレンである請求項7〜11のいずれか1つ
に記載の製造方法。12. The production method according to claim 7, wherein the tertiary olefin is isobutylene or diisobutylene.
た後、中和塩の存在下に蒸留する請求項7〜12のいず
れか1つに記載の製造方法。13. The production method according to claim 7, wherein the reaction product is neutralized with an aqueous alkaline solution and then distilled in the presence of a neutralized salt.
Priority Applications (1)
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Applications Claiming Priority (1)
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Family
ID=15748899
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112194766A (en) * | 2020-09-29 | 2021-01-08 | 天津大学 | Method for treating phenol-based rectifying still residues |
-
1995
- 1995-06-28 JP JP7162145A patent/JPH0910597A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112194766A (en) * | 2020-09-29 | 2021-01-08 | 天津大学 | Method for treating phenol-based rectifying still residues |
CN112194766B (en) * | 2020-09-29 | 2023-05-26 | 天津大学 | Treatment method of phenol-based rectifying still residue |
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