JPH0597742A - Production of high-grade bisphenol compound - Google Patents
Production of high-grade bisphenol compoundInfo
- Publication number
- JPH0597742A JPH0597742A JP3292210A JP29221091A JPH0597742A JP H0597742 A JPH0597742 A JP H0597742A JP 3292210 A JP3292210 A JP 3292210A JP 29221091 A JP29221091 A JP 29221091A JP H0597742 A JPH0597742 A JP H0597742A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- dissolved oxygen
- reaction
- bisphenol
- mixed solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、色相にすぐれたビスフ
ェノ−ル化合物の製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a bisphenol compound having an excellent hue.
【０００２】[0002]
【従来技術及びその問題点】ビスフェノ−ル化合物を製
造するために、過剰の一価フェノ−ル化合物に、アルデ
ヒド化合物及びケトン化合物の中から選ばれるカルボニ
ル化合物を混合し、酸触媒の存在下で反応させる方法は
知られている。また、この反応生成物から高純度ビスフ
ェノ−ル化合物を分離回収するために、反応生成物を晶
析処理してビスフェノ−ル化合物と一価フェノ−ル化合
物との結晶アダクト（以下、単に結晶アダクトとも言
う）を析出させ、得られた結晶アダクトから一価フェノ
−ル化合物を除去することも知られている。このような
ビスフェノ−ル化合物の製造方法においては、その製品
の品質は、結晶アダクトの品質に大きく依存することか
ら、高品質の結晶アダクトを製造する方法に多くの研究
がなされている。一方、高品質の結晶アダクトを得る観
点からは、その原料液である一価フェノ−ル化合物とカ
ルボニル化合物との反応生成物中の不純物濃度が低いこ
と、特に、結晶アダクトから分離困難な着色不純物濃度
が低いこと、換言すれば、その反応における着色不純物
の副生量を抑制することが重要である。2. Description of the Related Art In order to produce a bisphenol compound, an excess monovalent phenol compound is mixed with a carbonyl compound selected from an aldehyde compound and a ketone compound in the presence of an acid catalyst. Methods of reacting are known. In order to separate and collect a high-purity bisphenol compound from this reaction product, the reaction product is subjected to a crystallization treatment to form a crystal adduct of the bisphenol compound and the monovalent phenol compound (hereinafter, simply referred to as a crystal adduct. It is also known to remove the monovalent phenol compound from the obtained crystal adduct. In such a method for producing a bisphenol compound, since the quality of the product largely depends on the quality of the crystal adduct, much research has been conducted on a method for producing a high quality crystal adduct. On the other hand, from the viewpoint of obtaining a high-quality crystal adduct, the impurity concentration in the reaction product of the monovalent phenol compound and the carbonyl compound, which is the raw material liquid, is low, and in particular, colored impurities that are difficult to separate from the crystal adduct. The concentration is low, in other words, it is important to suppress the amount of colored impurities by-produced in the reaction.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、一価フェノ
−ル化合物とカルボニル化合物を酸触媒の存在下で反応
させてビスフェノ−ル化合物を製造するに際し、着色不
純物の副生量を抑制し、色相の良好な反応生成物を得た
めの方法を提供することをその課題とする。DISCLOSURE OF THE INVENTION The present invention suppresses the amount of color impurities by-produced when a monovalent phenol compound and a carbonyl compound are reacted in the presence of an acid catalyst to produce a bisphenol compound. It is an object of the present invention to provide a method for obtaining a reaction product having a good hue.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、前記課題
を解決すべく鋭意研究した結果、本発明を完成するに至
った。即ち、本発明によれば、実質的に溶存酸素を含有
しないカルボニル化合物と一価フェノ−ル化合物との混
合液を、酸性触媒の存在下で反応させることを特徴とす
るビスフェノ−ル化合物の製造方法が提供される。The present inventors have completed the present invention as a result of intensive research to solve the above problems. That is, according to the present invention, a mixed solution of a carbonyl compound containing substantially no dissolved oxygen and a monovalent phenol compound is reacted in the presence of an acidic catalyst to produce a bisphenol compound. A method is provided.
【０００５】本発明における一価フェノ−ル化合物とカ
ルボニル化合物との反応によりビスフェノ−ル化合物を
生成させる反応は、従来公知の反応で、塩酸や強酸型イ
オン交換樹脂等の酸触媒の存在下で実施される。一価フ
ェノ−ル化合物としては、フェノ−ルがその代表例であ
るが、他の一価フェノ−ルも使用でき、カルボニル化合
物としては、アルデヒド及びケトンが包含され、アセト
ンがその代表例であるが、他のケトン及びアルデヒドも
使用できる。本発明においては、反応に際し、実質的に
溶存酸素を含有しないカルボニル化合物と一価フェノ−
ル化合物との混合液を調製する。このような混合液は、
実質的に溶存酸素を含有しないカルボニル化合物と、実
質的に溶存酸素を含有しない一価フェノール化合物とを
混合する方法、カルボニル化合物と一価フェノール化合
物とを混合液から、それに含まれる溶存酸素を除去する
方法がある。カルボニル化合物、一価フェノール化合物
及びそれらの混合液からの溶存酸素の除去方法として
は、従来公知の方法が適用できる。このような方法とし
ては蒸留する方法、窒素ガスやアルゴンガス等の不活性
ガスを吹込む方法、ヒドラジンなどの分解性還元剤を添
加し、貴金属触媒と接触させ、その際に発生した水素を
溶存酸素と反応させて除去する方法、酸素分離膜を用い
て溶存酸素を透過除去する方法等がある。なお、本明細
書における実質的に溶存酸素を含有しない一価フェノ−
ル化合物、カルボニル化合物及びそれらの混合物とは、
その溶存酸素量が０．５ｗｔｐｐｍ以下であることを意
味する。本発明における反応において、その反応温度は
一価フェノ−ル化合物の融点以上の温度であり、通常、
４０〜１００℃、好ましくは５０〜８０℃の温度であ
る。反応圧力は、１．０〜１．５気圧、好ましくは常圧
ないし微加圧である。反応時間は、１５〜２００分、好
ましくは５０〜１００分である。また、反応に際して
は、従来公知の反応促進剤、例えば、メルカプタン化合
物を添加することもできる。この場合、メルカプタン化
合物は公知の方法により触媒樹脂に固定化して用いても
よい。The reaction for producing a bisphenol compound by the reaction of a monovalent phenol compound and a carbonyl compound in the present invention is a conventionally known reaction in the presence of an acid catalyst such as hydrochloric acid or a strong acid ion exchange resin. Be implemented. A typical example of the monovalent phenol compound is phenol, but other monovalent phenols can also be used, and examples of the carbonyl compound include aldehydes and ketones, and acetone is a typical example. However, other ketones and aldehydes can be used. In the present invention, during the reaction, a carbonyl compound and a monovalent phenol which do not substantially contain dissolved oxygen are used.
A mixed solution with a compound is prepared. Such a mixture is
A method of mixing a carbonyl compound containing substantially no dissolved oxygen and a monohydric phenol compound containing substantially no dissolved oxygen, and removing the dissolved oxygen contained in the mixture of the carbonyl compound and the monohydric phenol compound There is a way to do it. As a method for removing the dissolved oxygen from the carbonyl compound, the monohydric phenol compound and a mixed solution thereof, a conventionally known method can be applied. As such a method, a method of distilling, a method of blowing an inert gas such as nitrogen gas or argon gas, adding a decomposable reducing agent such as hydrazine, contacting with a noble metal catalyst, and dissolving the hydrogen generated at that time There are a method of removing oxygen by reacting with oxygen, a method of permeating and removing dissolved oxygen using an oxygen separation membrane, and the like. In the present specification, a monovalent phenol containing substantially no dissolved oxygen is used.
And carbonyl compounds and mixtures thereof,
It means that the amount of dissolved oxygen is 0.5 wtppm or less. In the reaction of the present invention, the reaction temperature is a temperature equal to or higher than the melting point of the monovalent phenol compound,
The temperature is 40 to 100 ° C, preferably 50 to 80 ° C. The reaction pressure is 1.0 to 1.5 atm, preferably normal pressure to slightly increased pressure. The reaction time is 15 to 200 minutes, preferably 50 to 100 minutes. Further, in the reaction, a conventionally known reaction accelerator, for example, a mercaptan compound can be added. In this case, the mercaptan compound may be used after being immobilized on the catalyst resin by a known method.
【０００６】[0006]
【発明の効果】本発明により得られる反応生成物は、着
色不純物の副生量の非常に少ないもので良好な色相を示
す。また、この反応生成物を、それからフェノ−ル化合
物の一部を留去した後、晶析処理し、精製フェノ−ルで
洗浄して得られる結晶アダクトの溶融色ＡＰＨＡは、通
常、２０以下である。The reaction product obtained by the present invention has a very small amount of coloring impurities as a by-product and exhibits a good hue. The melt color APHA of the crystal adduct obtained by distilling a part of the phenol compound from this reaction product, crystallization treatment and washing with purified phenol is usually 20 or less. is there.
【０００７】[0007]
【実施例】次に本発明を実施例によりさらに詳細に説明
する。 参考例１ 市販アセトン（溶存酸素量：８０ｍｇ／１）中に窒素ガ
スを１０分間バブリングした後、その溶存酸素量を溶存
酸素メ−タで測定したところ、酸素は検知されず、実質
的に溶存酸素を含有しないことが確認された。 参考例２ 市販アセトン中にヒドラジンを０．００５ｗｔ％添加
し、パラジウムを担持したイオン交換樹脂と接触させた
後、その溶存酸素量を測定したところ、酸素は検知され
なかった。 参考例３ 市販のアセトンを酸素分離膜と接触させた後、その溶存
酸素量を測定したところ、酸素は検知されなかった。 参考例４ 溶融色ＡＰＨＡが１０以下の精製フェノ−ル（溶存酸素
量：３００ｍｇ／１）に窒素ガスを１０分間バブリング
した後、その溶存酸素量を測定したところ、酸素は検知
されなかった。EXAMPLES Next, the present invention will be described in more detail by way of examples. Reference Example 1 Commercially available acetone (dissolved oxygen amount: 80 mg / 1) was bubbled with nitrogen gas for 10 minutes, and then the dissolved oxygen amount was measured by a dissolved oxygen meter. As a result, oxygen was not detected and it was substantially dissolved. It was confirmed that it did not contain oxygen. Reference Example 2 0.005 wt% of hydrazine was added to commercially available acetone, and after contacting with an ion exchange resin supporting palladium, the dissolved oxygen amount was measured, and oxygen was not detected. Reference Example 3 When commercially available acetone was brought into contact with an oxygen separation membrane and the amount of dissolved oxygen was measured, oxygen was not detected. Reference Example 4 Purified phenol (melted oxygen amount: 300 mg / 1) having a melt color APHA of 10 or less was bubbled with nitrogen gas for 10 minutes, and the dissolved oxygen amount was measured. As a result, oxygen was not detected.
【０００８】実施例１ ロ−ムアンドハ−ス社製強酸型イオン交換樹脂「アンバ
−ライトＩＲ−１１８Ｈ+をステンレス反応管に充填し
た。次に、この反応管に、前記溶存酸素除去処理を施し
たフェノ−ルとアセトンの混合液（混合モル比：１２／
１）に反応促進剤としてエチルメルカプタン０．１５ｗ
ｔ％を添加し、反応温度７０℃、接触時間７５分の条件
で流通反応させて、ビスフェノ−ルＡを１５．１ｗｔ％
含む反応生成物を得た。このものの溶融色ＡＰＨＡは１
２であった。 実施例２ 酸性点の２０％をジメチルチアゾリジンで中和した「ア
ンバーライトＩＲ−１１８Ｈ+」をステンレス反応管に
充填した。次にこの反応管に前記溶存酸素除去処理を施
したフェノールとアセトンの混合液（混合モル比：１２
／１）を反応温度７０℃、接触時間７５分の条件で流通
反応させて、ビスフェノールＡ１４．１ｗｔ％を含む反
応生成物を得た。このものの溶融色ＡＰＨＡは１４であ
った。 比較例１ 実施例１において、アセトン及びフェノ−ルとして、溶
存酸素除去処理を施していないものを用いた以外は同様
にして実験を行い、ビスフェノ−ルＡを１５．４ｗｔ％
含む反応生成物を得た。このものの溶融色ＡＰＨＡは６
０であった。Example 1 A stainless acid reaction tube was filled with a strong acid type ion exchange resin "Amberlite IR-118H +" manufactured by Rohm and Haas Company. Then, the reaction tube was subjected to the above-mentioned dissolved oxygen removal treatment. Mixed solution of phenol and acetone (mixing molar ratio: 12 /
Ethyl mercaptan 0.15w as a reaction accelerator in 1)
t% was added and the reaction was allowed to flow under the conditions of a reaction temperature of 70 ° C. and a contact time of 75 minutes, and 15.1 wt% of bisphenol A was added.
A containing reaction product was obtained. The melting color APHA of this product is 1
It was 2. Example 2 "Amberlite IR-118H +" obtained by neutralizing 20% of acid points with dimethylthiazolidine was charged into a stainless reaction tube. Next, this reaction tube was subjected to the above-mentioned dissolved oxygen removal treatment, and a mixed solution of phenol and acetone (mixing molar ratio: 12
/) Was flow-reacted under the conditions of a reaction temperature of 70 ° C and a contact time of 75 minutes to obtain a reaction product containing 14.1 wt% of bisphenol A. The melt color APHA of this product was 14. Comparative Example 1 An experiment was conducted in the same manner as in Example 1 except that acetone and phenol which were not subjected to the dissolved oxygen removal treatment were used, and 15.4 wt% of bisphenol A was added.
A containing reaction product was obtained. The melting color APHA of this product is 6
It was 0.
Claims (1)
ル化合物と一価フェノール化合物との混合液を、酸性触
媒の存在下で反応させることを特徴とするビスフェノ−
ル化合物の製造方法。1. A bisphenol-compound characterized by reacting a mixed solution of a carbonyl compound containing substantially no dissolved oxygen and a monohydric phenol compound in the presence of an acidic catalyst.
A method for producing a compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3292210A JPH0597742A (en) | 1991-10-11 | 1991-10-11 | Production of high-grade bisphenol compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3292210A JPH0597742A (en) | 1991-10-11 | 1991-10-11 | Production of high-grade bisphenol compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0597742A true JPH0597742A (en) | 1993-04-20 |
Family
ID=17778948
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3292210A Pending JPH0597742A (en) | 1991-10-11 | 1991-10-11 | Production of high-grade bisphenol compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0597742A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06340564A (en) * | 1993-06-01 | 1994-12-13 | Chiyoda Corp | Production of bisphenol a |
| US5833848A (en) * | 1995-02-21 | 1998-11-10 | General Electric Company | Filter for high-viscosity fluids |
| EP1123912B1 (en) * | 2000-02-10 | 2003-08-20 | Bayer Ag | Process for eliminating dissolved oxygen from phenol |
| JP2007532591A (en) | 2004-04-14 | 2007-11-15 | デグサ ゲーエムベーハー | Catalytic removal of dissolved oxygen from organic liquids. |
| JP2018115154A (en) * | 2017-01-16 | 2018-07-26 | 三菱ケミカル株式会社 | Method of manufacturing bisphenol compound |
-
1991
- 1991-10-11 JP JP3292210A patent/JPH0597742A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06340564A (en) * | 1993-06-01 | 1994-12-13 | Chiyoda Corp | Production of bisphenol a |
| US5833848A (en) * | 1995-02-21 | 1998-11-10 | General Electric Company | Filter for high-viscosity fluids |
| EP1123912B1 (en) * | 2000-02-10 | 2003-08-20 | Bayer Ag | Process for eliminating dissolved oxygen from phenol |
| JP2007532591A (en) | 2004-04-14 | 2007-11-15 | デグサ ゲーエムベーハー | Catalytic removal of dissolved oxygen from organic liquids. |
| JP2018115154A (en) * | 2017-01-16 | 2018-07-26 | 三菱ケミカル株式会社 | Method of manufacturing bisphenol compound |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0597742A (en) | Production of high-grade bisphenol compound | |
| AU749982B2 (en) | Method for preparing methyl carbazate | |
| JPH06277516A (en) | Method for stabilizing rhodium compound | |
| US4945075A (en) | Oxidative secondary rhodium recovery process | |
| JPS6363629A (en) | Production of 2,2-bis(4'-hydroxyphenyl)propane | |
| EP2860172B1 (en) | Method for preparing acetamidophenyl | |
| JP2790601B2 (en) | Method for producing chloroformate compound | |
| JP4631129B2 (en) | Method for continuous crystallization of tetrabromobisphenol A | |
| US5502188A (en) | Production of almost colorless solutions of n-methylmorpholine oxide | |
| JPH0360826B2 (en) | ||
| JP3008552B2 (en) | Method for producing high quality tetrabromobisphenol A | |
| US3655781A (en) | Crystallization of 2-nitro-2-methyl-1-propanol | |
| JP3173733B2 (en) | Method for producing high-grade bisphenol A | |
| US4967004A (en) | Process for producing N,N-diethylaminophenols | |
| JPS6114227A (en) | Production of polycarbonate resin | |
| JP2887300B2 (en) | Method for producing high-grade bisphenol A | |
| JP3661198B2 (en) | Method for producing hydroxyphenylpropionic acid ester | |
| US3155688A (en) | Purification of phthalic anhydride | |
| JPH0551338A (en) | Production of high-purity bisphenol a | |
| JP3041547B2 (en) | Method for separating high purity bisphenol A | |
| JP2874276B2 (en) | Method for producing high quality tetrabromobisphenol A | |
| JPS5896034A (en) | Preparation of phloroglucin | |
| JPH05117224A (en) | Production of 4-benzyloxy-4'-hydroxydiphenylsulfone | |
| US5399783A (en) | Preparation of 6,6'-dihydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindane | |
| JP2532010B2 (en) | Method for producing purified phenol and method for cleaning crystal adduct of bisphenol A and phenol |