JPH05294875A - Production of bisphenol compounds - Google Patents
Production of bisphenol compoundsInfo
- Publication number
- JPH05294875A JPH05294875A JP4126775A JP12677592A JPH05294875A JP H05294875 A JPH05294875 A JP H05294875A JP 4126775 A JP4126775 A JP 4126775A JP 12677592 A JP12677592 A JP 12677592A JP H05294875 A JPH05294875 A JP H05294875A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- cation exchange
- exchange resin
- acidic cation
- 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
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
- 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】本発明はビスフェノ−ルＡ等のビ
スフェノ−ル類製造方法に関する。詳しくは、ビスフェ
ノ−ル類製造に使用される触媒を改質して、ビスフェノ
−ル類を製造する方法に関する。FIELD OF THE INVENTION The present invention relates to a method for producing bisphenols such as bisphenol A. More specifically, it relates to a method for producing bisphenols by modifying a catalyst used for producing bisphenols.
【０００２】[0002]
【従来の技術】ビスフェノ−ル類、例えばビスフェノ−
ルＡ、すなわち２，２−ビス（４−ヒドロキシフェニ
ル）プロパンは、アセトンと過剰量のフェノ−ルを酸性
触媒の存在下に反応させることにより得られる。酸性触
媒としては、塩酸等の強酸の他、酸性陽イオン交換樹脂
のような固体状の酸触媒が使用されており、特に酸性陽
イオン交換樹脂は、装置の腐食等の問題がないだけでな
く、反応収率も優れるので、多用されている。酸性陽イ
オン交換樹脂を触媒として使用するとき、反応速度、選
択率等を向上させるため、促進剤を使用することが普通
であり、通常メルカプタン類が原料に混合されて使用さ
れる。しかしながら、メルカプタン類は臭い等の問題が
あるので、これを加える代わりに、メルカプトアミン等
の酸性陽イオン交換樹脂と結合性の基とメルカプト基を
有する含窒素硫黄化合物で修飾する方法が知られている
（特開昭５６−４６８３１号、特開昭５２−１９１８９
号、特開昭５７−３５５３３号、特開昭５３−１４６８
０号等）。BACKGROUND OF THE INVENTION Bisphenols such as bisphenol
Leu A, that is, 2,2-bis (4-hydroxyphenyl) propane, is obtained by reacting acetone with an excess amount of phenol in the presence of an acidic catalyst. As acidic catalysts, in addition to strong acids such as hydrochloric acid, solid acid catalysts such as acidic cation exchange resins are used.In particular, acidic cation exchange resins have not only problems such as equipment corrosion but also Since the reaction yield is excellent, it is widely used. When an acidic cation exchange resin is used as a catalyst, it is common to use a promoter in order to improve the reaction rate, selectivity, etc. Usually, mercaptans are used as a raw material in a mixture. However, since mercaptans have problems such as odor, a method of modifying with a nitrogen-containing sulfur compound having a mercapto group-bonding group with an acidic cation exchange resin such as mercaptoamine is known instead of adding it. (JP-A-56-46831, JP-A-52-19189)
JP-A-57-35533, JP-A-53-1468
No. 0).
【０００３】このような酸性陽イオン交換樹脂の修飾
は、反応器に充填する前に行うことが通常であるが、場
合によっては反応開始後に行う必要があることがある。
酸性陽イオン交換樹脂の修飾は、酸性陽イオン交換樹脂
の酸基の一部についてのみ行う必要があるが、充填され
た酸性陽イオン交換樹脂については、攪拌ができないた
め、含窒素硫黄化合物の溶液が流れる上流側の層のみ修
飾され、下流側は修飾されないという問題がある。しか
も、修飾された上流側の層は、修飾率が高すぎるという
問題がある。Such modification of the acidic cation exchange resin is usually carried out before filling the reactor, but in some cases it may be necessary to be carried out after the start of the reaction.
It is necessary to modify the acidic cation exchange resin only for a part of the acid groups of the acidic cation exchange resin. However, since the filled acidic cation exchange resin cannot be stirred, the solution of the nitrogen-containing sulfur compound cannot be stirred. There is a problem that only the layer on the upstream side of the flowing stream is modified and the downstream side is not modified. Moreover, the modified upstream layer has a problem that the modification rate is too high.
【０００４】反応器に充填された酸性陽イオン交換樹脂
を、均一に修飾する方法として、特開昭５３−１４６８
０号公報では、予め不均一に修飾したのち、酸性の水溶
液を十分な時間流して、均一化をはかることを提案して
いる。しかしながら、この方法は時間がかかるだけでな
く、かなり速い流速を必要とし、更に酸を使用すること
による装置の腐食等のいくつかの問題がある。As a method for uniformly modifying the acidic cation exchange resin packed in the reactor, Japanese Patent Laid-Open No. 53-1468.
Japanese Patent Laid-Open No. 0 proposes to make a uniform modification in advance and then homogenize it by flowing an acidic aqueous solution for a sufficient time. However, this method is not only time consuming, it requires a fairly high flow rate and there are some problems such as equipment corrosion due to the use of acid.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、反応器に充
填され、反応に使用された酸性陽イオン交換樹脂を、充
填層全体にわたって均一な修飾率となるように含窒素硫
黄化合物で修飾し、ビスフェノ−ル類の収率、反応速
度、選択率等を向上させるものである。SUMMARY OF THE INVENTION In the present invention, the acidic cation exchange resin packed in a reactor and used in the reaction is modified with a nitrogen-containing sulfur compound so as to have a uniform modification rate throughout the packed bed. , The yield of bisphenols, the reaction rate, the selectivity, etc. are improved.
【０００６】[0006]
【課題を解決するための手段】本発明は、カルボニル化
合物とフェノ−ル類を含む原料を、酸性陽イオン交換樹
脂が充填された反応器に装入し、反応させてビスフェノ
−ル類を製造する方法において、一旦反応を中断し、フ
ェノ−ル類及び／又はカルボニル化合物と比誘電率が
１．８〜５．０の有機化合物との混合溶媒に含窒素硫黄
化合物を溶解させた溶液を該反応器に装入して酸性陽イ
オン交換樹脂を該含窒素硫黄化合物で修飾し、その後反
応を再開することを特徴とするビスフェノ−ル類の製造
方法である。According to the present invention, a raw material containing a carbonyl compound and a phenol compound is charged into a reactor filled with an acidic cation exchange resin and reacted to produce a bisphenol compound. In the method described above, the reaction is once suspended, and a solution obtained by dissolving a nitrogen-containing sulfur compound in a mixed solvent of a phenol compound and / or a carbonyl compound and an organic compound having a relative dielectric constant of 1.8 to 5.0 is prepared. A method for producing bisphenols, which comprises charging an acidic cation exchange resin with a nitrogen-containing sulfur compound in a reactor and then restarting the reaction.
【０００７】ビスフェノ−ル類としては、ビスフェノ−
ルＡ、ビスフェノ−ルＦ等があり、カルボニル化合物と
しては、アルデヒド又はケトンであり、フェノ−ル類と
しては水酸基に対してパラ位に置換基を有しないフェノ
−ル、クレゾ−ル、キシレノ−ル等がある。好適には、
本発明は、アセトンとフェノ−ルを原料とするビスフェ
ノ−ルＡの製造に適用できる。Bisphenols include bisphenols.
Examples of the carbonyl compound include aldehydes and ketones, and examples of the phenols include phenol, cresol, and xylen which do not have a substituent at the para position with respect to the hydroxyl group. There are such as Le. Preferably,
The present invention can be applied to the production of bisphenol A using acetone and phenol as raw materials.
【０００８】触媒として使用する酸性陽イオン交換樹脂
は、スルホン酸系のものが好ましく、母体となる樹脂と
しては、スチレン−ジビニルベンゼン共重合体系、パ−
フルオルエチレン共重合体系、フェノ−ル−ホルムアル
デヒド重合体系等があるが、スチレン−ジビニルベンゼ
ン共重合体系が一般的である。本発明で使用する酸性陽
イオン交換樹脂はこれに限るものではなく、強酸性陽イ
オン交換樹脂であれば、任意ものが使用可能である。そ
して、これは含窒素硫黄化合物で酸基の一部が修飾され
てもよい。この酸性陽イオン交換樹脂は、反応器に充填
され固定床を形成する。The acidic cation exchange resin used as a catalyst is preferably a sulfonic acid type resin, and as a base resin, a styrene-divinylbenzene copolymer system, a perfluorocarbon type resin is used.
There are fluorethylene copolymer system, phenol-formaldehyde polymer system, etc., but styrene-divinylbenzene copolymer system is common. The acidic cation exchange resin used in the present invention is not limited to this, and any strongly acidic cation exchange resin can be used. And, in this, a part of the acid group may be modified with a nitrogen-containing sulfur compound. The acidic cation exchange resin is loaded into the reactor to form a fixed bed.
【０００９】この反応器へは、前記のような原料を流
し、反応を連続的に行う。この反応の際、メルカプタン
類を原料中に混入させてもよい。このような反応を行
い、含窒素硫黄化合物の修飾が必要になったとき、本発
明の修飾を行う。なお、修飾を必要とするときとは、充
填前に修飾したが、それが外れて修飾率が低下したと
き、当初は修飾しなかったが、修飾することが望ましい
と判断されたときなどである。このようなとき、反応を
一旦中断し、以下のような方法で修飾を行う。The above raw materials are flowed into this reactor to continuously carry out the reaction. During this reaction, mercaptans may be mixed in the raw material. When the nitrogen-containing sulfur compound needs to be modified by carrying out such a reaction, the modification of the present invention is carried out. In addition, when the modification is required, the modification is performed before the filling, but the modification rate is lowered due to the modification, the modification is not performed initially, but it is determined that the modification is desirable. . In such a case, the reaction is temporarily stopped and the modification is carried out by the following method.
【００１０】修飾に使用する含窒素硫黄化合物は、前記
のとおりメルカプトアミン又はこの前駆体のような、酸
性陽イオン交換樹脂と結合性の基とメルカプト基を有す
る化合物である。具体てきには、チオエタノ−ルアミ
ン、プロピルメルカプトアミン等のアルキルメルカプト
アミン類、アミノチオカルボン酸類又はシステイン等の
そのエステル類、アミノチオフェノ−ル等の環状メルカ
プトアミン類、ピリジンアルカンチオ−ル類などが挙げ
られる。また、前駆体としてはメルカプトアミン類を生
成するチアゾリジン化合物がある。この含窒素硫黄化合
物は酸性陽イオン交換樹脂と接触すると、迅速にイオン
交換反応して、結合する。本発明でいう修飾はこれを意
味し、また修飾率は、イオン交換率で表され、通常、ス
ルホン酸基等の酸基の１０〜４０％がイオン交換される
のがよいとされている。The nitrogen-containing sulfur compound used for modification is a compound having a group capable of binding to an acidic cation exchange resin and a mercapto group, such as mercaptoamine or its precursor as described above. Specifically, alkyl mercaptoamines such as thioethanolamine and propylmercaptoamine, aminothiocarboxylic acids or esters thereof such as cysteine, cyclic mercaptoamines such as aminothiophenol, pyridine alkanethiols, etc. Can be mentioned. As the precursor, there is a thiazolidine compound that produces mercaptoamines. When this nitrogen-containing sulfur compound comes into contact with an acidic cation exchange resin, it rapidly undergoes an ion exchange reaction and bonds. The modification in the present invention means this, and the modification rate is represented by an ion exchange rate, and it is generally said that 10 to 40% of acid groups such as sulfonic acid groups should be ion-exchanged.
【００１１】上記の含窒素硫黄化合物を水溶液等の溶液
とし、これを酸性陽イオン交換樹脂の充填層に流すと上
流側から修飾が進行し、上流側が１００％進行しても、
下流側反応殆ど０％ということが多い。本発明では、こ
れを均一化するため、含窒素硫黄化合物を特定の溶媒に
溶解した溶液として、充填層に流す。溶媒としては上記
原料となるアセトン等のカルボニル化合物とフェノ−ル
類のいずれか又は両方に比誘電率が１．８〜５．０の有
機化合物を混合したものである。比誘電率が１．８〜
５．０の有機化合物としては、ベンゼン、トルエン、キ
シレン、エチルベンゼン等の芳香族炭化水素、ヘキサ
ン、ヘプタン、オクタン、シクロヘキサン、メチルシク
ロヘキサン等の脂肪族炭化水素が挙げられる。この有機
化合物は、単独でも混合物でもよいが、含窒素硫黄化合
物及びカルボニル化合物又はフェノ−ル類と相溶性のあ
るものが好ましい。また、溶媒中への配合量は５〜３０
％が適当である。溶液中の含窒素硫黄化合物の濃度は、
１〜１５ｗｔ％程度が適当である。溶液の使用量は、酸
性陽イオン交換樹脂を所定の修飾率とするに足る計算量
の含窒素硫黄化合物量となる量がよい。When the above-mentioned nitrogen-containing sulfur compound is made into a solution such as an aqueous solution, and this solution is flowed through a packed bed of acidic cation exchange resin, modification proceeds from the upstream side, and even if the upstream side proceeds 100%,
The downstream reaction is often almost 0%. In the present invention, in order to make this uniform, a solution containing a nitrogen-containing sulfur compound dissolved in a specific solvent is passed through the packed bed. As the solvent, one or both of a carbonyl compound such as acetone as the above-mentioned raw material and phenols are mixed with an organic compound having a relative dielectric constant of 1.8 to 5.0. Relative permittivity is 1.8-
Examples of the organic compound of 5.0 include aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, and aliphatic hydrocarbons such as hexane, heptane, octane, cyclohexane and methylcyclohexane. These organic compounds may be used alone or as a mixture, but those which are compatible with the nitrogen-containing sulfur compound and the carbonyl compound or the phenols are preferable. Further, the compounding amount in the solvent is 5 to 30.
% Is appropriate. The concentration of the nitrogen-containing sulfur compound in the solution is
About 1 to 15 wt% is suitable. The amount of the solution used is preferably such that the amount of the nitrogen-containing sulfur compound is a calculated amount sufficient to bring the acidic cation exchange resin to a predetermined modification rate.
【００１２】酸性陽イオン交換樹脂の修飾は、これが充
填された反応器へ、上記含窒素硫黄化合物の溶液を、全
体が浸たるように流し込むことにより行うことができ
る。この場合、溶液を循環させながら流してもよいし、
反応器出口のバルブを閉めて溶液を溜めて行ってもい。
温度は常温〜１００℃、接触時間は１〜５０ｈｒ程度で
ある。修飾終了後、洗浄等をしたのち、反応を再開す
る。The acid cation exchange resin can be modified by pouring the solution of the nitrogen-containing sulfur compound into a reactor filled with the resin so that the whole solution is immersed. In this case, the solution may be circulated while flowing,
The valve at the reactor outlet may be closed to collect the solution.
The temperature is room temperature to 100 ° C., and the contact time is about 1 to 50 hours. After the modification is completed, the reaction is restarted after washing and the like.
【００１３】[0013]
【作用】溶液中に比誘電率が比較的低い有機化合物が存
在することにより、イオン交換速度が遅くなり、均一に
修飾が行われると考えられる。It is considered that the presence of an organic compound having a relatively low relative dielectric constant in the solution slows down the ion exchange rate and allows uniform modification.
【００１４】[0014]
実施例１ 内径２０ｍｍ、長さ３００ｍｍの金属カラムに、フェノ
−ルで洗浄したスルホン酸型酸性陽イオン交換樹脂９０
ｍｌを充填した。カラム内を６０℃に保ちながら、カラ
ム上部より２−メルカプトエチルアミン濃度６．８ｗｔ
％のフェノ−ル／トルエン＝９０／１０（ｗｔ比）溶液
を、ＬＨＳＶ＝１で流し込み、カラム内がこの溶液で満
たされたことを確認したのち、カラム下部のバルブを閉
じ、３０時間放置した。その後、カラム内をフェノ−ル
で洗浄した。カラム上部から１０ｍｌ、下部から１０ｍ
ｌの酸性陽イオン交換樹脂を抜き出し、２−メルカプト
エチルアミンによる修飾率を測定したところ、上部では
スルホン酸基の２１％が、下部ではスルホン酸基の１８
％がイオン交換されており、ほぼ均一に修飾されてい
た。これに対し、溶媒としてフェノ−ルのみを用いた溶
液を用いた場合、上部ではスルホン酸基の９５％が、下
部ではスルホン酸基の０．５％がイオン交換されてお
り、不均一に修飾されていた。Example 1 A sulfonic acid type acidic cation exchange resin 90 washed with phenol on a metal column having an inner diameter of 20 mm and a length of 300 mm.
ml was filled. While maintaining the inside of the column at 60 ° C., the concentration of 2-mercaptoethylamine from the upper part of the column is 6.8 wt.
% Phenol / toluene = 90/10 (wt ratio) solution was poured at LHSV = 1, and after confirming that the inside of the column was filled with this solution, the valve at the bottom of the column was closed and left for 30 hours. . Then, the inside of the column was washed with phenol. 10 ml from the top of the column, 10 m from the bottom
The acid cation exchange resin (1) was taken out and the modification ratio with 2-mercaptoethylamine was measured. As a result, 21% of the sulfonic acid groups in the upper part and 18% of the sulfonic acid groups in the lower part were measured.
% Was ion-exchanged and was almost uniformly modified. On the other hand, when a solution using only phenol as a solvent was used, 95% of the sulfonic acid groups were ion-exchanged in the upper part and 0.5% of the sulfonic acid groups were ion-exchanged in the lower part, resulting in non-uniform modification. It had been.
【００１５】[0015]
【発明の効果】本発明の製造方法によれば、酸性陽イオ
ン交換樹脂の性能を容易に改良することができ、ビスフ
ェノ−ル類の収率、選択率等を向上させることができ
る。また、原料中に添加するメルカプタン類を減少又は
無くすことができる。According to the production method of the present invention, the performance of the acidic cation exchange resin can be easily improved, and the yield and selectivity of bisphenols can be improved. Further, the mercaptans added to the raw material can be reduced or eliminated.
Claims (1)
料を、酸性陽イオン交換樹脂が充填された反応器に装入
し、反応させてビスフェノ−ル類を製造する方法におい
て、一旦反応を中断し、フェノ−ル類及び／又はカルボ
ニル化合物と比誘電率が１．８〜５．０の有機化合物と
の混合溶媒に含窒素硫黄化合物を溶解させた溶液を該反
応器に装入して酸性陽イオン交換樹脂を該含窒素硫黄化
合物で修飾し、その後反応を再開することを特徴とする
ビスフェノ−ル類の製造方法。1. A method for producing a bisphenol by charging a raw material containing a carbonyl compound and a phenol into a reactor filled with an acidic cation exchange resin, and reacting the raw material, to suspend the reaction. Then, a solution prepared by dissolving a nitrogen-containing sulfur compound in a mixed solvent of a phenol compound and / or a carbonyl compound and an organic compound having a relative dielectric constant of 1.8 to 5.0 is charged into the reactor and acidified. A method for producing bisphenols, which comprises modifying a cation exchange resin with the nitrogen-containing sulfur compound and then restarting the reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12677592A JP3172576B2 (en) | 1992-04-20 | 1992-04-20 | Method for producing bisphenols |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12677592A JP3172576B2 (en) | 1992-04-20 | 1992-04-20 | Method for producing bisphenols |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05294875A true JPH05294875A (en) | 1993-11-09 |
| JP3172576B2 JP3172576B2 (en) | 2001-06-04 |
Family
ID=14943628
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12677592A Expired - Fee Related JP3172576B2 (en) | 1992-04-20 | 1992-04-20 | Method for producing bisphenols |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3172576B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08323210A (en) * | 1995-06-01 | 1996-12-10 | Chiyoda Corp | Regeneration of catalyst for producing bisphenol a |
| US8735634B2 (en) | 2011-05-02 | 2014-05-27 | Sabic Innovative Plastics Ip B.V. | Promoter catalyst system with solvent purification |
| US9711695B2 (en) | 2012-02-03 | 2017-07-18 | Sabic Global Technologies B.V. | Light emitting diode device and method for production thereof containing conversion material chemistry |
| US9772086B2 (en) | 2013-05-29 | 2017-09-26 | Sabic Innovative Plastics Ip B.V. | Illuminating devices with color stable thermoplastic light transmitting articles |
| US9771452B2 (en) | 2012-02-29 | 2017-09-26 | Sabic Global Technologies B.V. | Plastic composition comprising a polycarbonate made from low sulfur bisphenol A, and articles made therefrom |
| US9821523B2 (en) | 2012-10-25 | 2017-11-21 | Sabic Global Technologies B.V. | Light emitting diode devices, method of manufacture, uses thereof |
| US9957351B2 (en) | 2011-08-05 | 2018-05-01 | Sabic Global Technologies B.V. | Polycarbonate compositions having enhanced optical properties, methods of making and articles comprising the polycarbonate compositions |
-
1992
- 1992-04-20 JP JP12677592A patent/JP3172576B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08323210A (en) * | 1995-06-01 | 1996-12-10 | Chiyoda Corp | Regeneration of catalyst for producing bisphenol a |
| US8735634B2 (en) | 2011-05-02 | 2014-05-27 | Sabic Innovative Plastics Ip B.V. | Promoter catalyst system with solvent purification |
| US9056821B2 (en) | 2011-05-02 | 2015-06-16 | Sabic Global Technologies B.V. | Promoter catalyst system with solvent purification |
| US9957351B2 (en) | 2011-08-05 | 2018-05-01 | Sabic Global Technologies B.V. | Polycarbonate compositions having enhanced optical properties, methods of making and articles comprising the polycarbonate compositions |
| US9711695B2 (en) | 2012-02-03 | 2017-07-18 | Sabic Global Technologies B.V. | Light emitting diode device and method for production thereof containing conversion material chemistry |
| US9771452B2 (en) | 2012-02-29 | 2017-09-26 | Sabic Global Technologies B.V. | Plastic composition comprising a polycarbonate made from low sulfur bisphenol A, and articles made therefrom |
| US9821523B2 (en) | 2012-10-25 | 2017-11-21 | Sabic Global Technologies B.V. | Light emitting diode devices, method of manufacture, uses thereof |
| US9772086B2 (en) | 2013-05-29 | 2017-09-26 | Sabic Innovative Plastics Ip B.V. | Illuminating devices with color stable thermoplastic light transmitting articles |
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|---|---|
| JP3172576B2 (en) | 2001-06-04 |
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