JPH11179210A - Ion exchange resin and preparation of bisphenols using same as catalyst - Google Patents
Ion exchange resin and preparation of bisphenols using same as catalystInfo
- Publication number
- JPH11179210A JPH11179210A JP9349171A JP34917197A JPH11179210A JP H11179210 A JPH11179210 A JP H11179210A JP 9349171 A JP9349171 A JP 9349171A JP 34917197 A JP34917197 A JP 34917197A JP H11179210 A JPH11179210 A JP H11179210A
- Authority
- JP
- Japan
- Prior art keywords
- ion exchange
- exchange resin
- sulfonic acid
- acid type
- type ion
- 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
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、イオン交換樹脂及
びこれを触媒とするビスフェノール類の製造方法に関す
る。詳しくは、特定のメルカプトアミン化合物がイオン
結合してなる変性強酸性スルホン酸型イオン交換樹脂及
びこれを用いるビスフェノール類の製造方法に関する。
このイオン交換樹脂は、フェノールとアセトンの縮合反
応によりビスフェノールＡを製造する際の触媒として有
用である。ビスフェノールＡは、エポキシ樹脂やポリカ
ーボネート樹脂の原料となる有用な化合物である。TECHNICAL FIELD The present invention relates to an ion exchange resin and a method for producing bisphenols using the same as a catalyst. More specifically, the present invention relates to a modified strongly acidic sulfonic acid type ion exchange resin in which a specific mercaptoamine compound is ion-bonded and a method for producing bisphenols using the same.
This ion exchange resin is useful as a catalyst for producing bisphenol A by a condensation reaction between phenol and acetone. Bisphenol A is a useful compound that is a raw material for epoxy resins and polycarbonate resins.
【０００２】[0002]
【従来の技術】フェノールとアセトンの縮合反応により
ビスフェノールＡを製造する際の触媒として、強酸性ス
ルホン酸型イオン交換樹脂と共にメルカプト基を有する
化合物を併用する方法については、従来からいろいろ提
案がなされている。例えば、強酸性スルホン酸型イオン
交換樹脂と共に反応系内にメルカプト基を有する化合物
を共存させる方法（特公昭４５−１０３３７号公報、仏
国特許１３７３７９６号明細書等）、メルカプト基を有
する化合物を強酸性イオン交換樹脂に共有結合させる方
法（特公昭３７−１４７２１号、特開昭５６−２１６５
０号、特開昭５７−８７８４６号、特開昭５９−１０９
５０３号各公報等）、メルカプトアミン類を強酸性イオ
ン交換樹脂にイオン結合させる方法等が提案されてい
る。2. Description of the Related Art There have been proposed various methods of using a compound having a mercapto group together with a strongly acidic sulfonic acid type ion exchange resin as a catalyst for producing bisphenol A by a condensation reaction of phenol and acetone. I have. For example, a method of coexisting a compound having a mercapto group in a reaction system together with a strongly acidic sulfonic acid type ion exchange resin (Japanese Patent Publication No. 45-10337, French Patent 1373796, etc.), a method of converting a compound having a mercapto group into a strong acid (Japanese Patent Publication No. 37-14721, JP-A-56-2165)
0, JP-A-57-87846, JP-A-59-109
503), and a method of ion-bonding mercaptoamines to a strongly acidic ion exchange resin.
【０００３】これらの中で、メルカプトアミン類をイオ
ン結合させた変性強酸性イオン交換樹脂を使用する方法
は、１）メルカプトアミン類が生成物中に混入しない、
２）触媒調製が容易であるという点で、メルカプト基を
有する化合物を共有結合させる方法や、単に、反応系内
にメルカプト基を有する化合物を共存させる方法よりも
優れた方法である。[0003] Among them, the method of using a modified strong acidic ion exchange resin in which mercaptoamines are ion-bonded is as follows: 1) mercaptoamines are not mixed into a product;
2) This method is superior to a method of covalently bonding a compound having a mercapto group or a method of simply allowing a compound having a mercapto group to coexist in a reaction system in that catalyst preparation is easy.
【０００４】メルカプトアミン類をイオン結合させた変
性強酸性スルホン酸型イオン交換樹脂を使用する方法と
しては、２−メルカプトエチルアミン（特公昭４６−１
９９５３号、特開昭６２−２９８４５４号各公報）、Ｎ
−プロピルメルカプトアルキルアミン（特開昭６０−１
３７４４０号公報）をイオン結合させた変性強酸性スル
ホン酸型イオン交換樹脂を用いる方法が提案されてい
る。また、その第四級アンモニウム塩をイオン結合させ
た変性強酸性スルホン酸型イオン交換樹脂を使用する方
法としては、Ｎ，Ｎ，Ｎ−トリメチル−２−メルカプト
エチルアンモニウム、Ｎ−（２−ヒドロキシル−３−メ
ルカプトプロピル）ピリジニウム、Ｎ−メチル−Ｎ−
（２−ヒドロキシル−３−メルカプトプロピル）モルフ
ォリウム及びＮ−ベンジル−Ｎ，Ｎ−ジメチル−２−メ
ルカプトエチルアンモニウム（チェコスロバキア国特許
１８４９８８号明細書）をイオン結合させた変性強酸性
スルホン酸型イオン交換樹脂を用いる方法が提案されて
いる。[0004] As a method of using a modified strong acid sulfonic acid type ion exchange resin in which mercaptoamines are ion-bonded, 2-mercaptoethylamine (Japanese Patent Publication No. 46-1)
9953, JP-A-62-298454), N
-Propylmercaptoalkylamine (JP-A-60-1)
No. 37440) has been proposed in which a modified strongly acidic sulfonic acid type ion exchange resin having an ion-bonded ion-exchange resin is used. As a method of using a denatured strongly acidic sulfonic acid type ion exchange resin in which the quaternary ammonium salt is ion-bonded, N, N, N-trimethyl-2-mercaptoethylammonium, N- (2-hydroxyl- 3-mercaptopropyl) pyridinium, N-methyl-N-
Modified strong acid sulfonic acid ion in which (2-hydroxyl-3-mercaptopropyl) morpholium and N-benzyl-N, N-dimethyl-2-mercaptoethylammonium (Czechoslovak Patent 184988) are ion-bonded. A method using an exchange resin has been proposed.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、いずれ
の方法も、アセトン転化率は５０〜７５％程度しかない
という欠点があった。本発明は、フェノール類とケトン
類の反応によるビスフェノール類の製造に好適な触媒、
特に、アセトンの転化率が高く、且つ良好な選択性及び
安定性を有する、アセトンとフェノールの縮合反応によ
りビスフェノールＡを製造するための、強酸性スルホン
酸型イオン交換樹脂触媒を提供することを目的とする。However, both methods have a drawback that the acetone conversion is only about 50 to 75%. The present invention is a catalyst suitable for the production of bisphenols by the reaction of phenols and ketones,
In particular, an object of the present invention is to provide a strongly acidic sulfonic acid type ion exchange resin catalyst for producing bisphenol A by a condensation reaction of acetone and phenol, which has a high conversion rate of acetone and has good selectivity and stability. And
【０００６】[0006]
【課題を解決するための手段】本発明者らは、上記事情
に鑑み鋭意検討した結果、特定のメルカプトアミン化合
物により変性された強酸性スルホン酸型イオン交換樹脂
が、フェノールとアセトンとの縮合反応によるビスフェ
ノールＡの製造において、高いアセトン転化率、高い
４，４′−体選択率及び良好な安定性を示すことを見い
出し、本発明を完成するに至った。The present inventors have conducted intensive studies in view of the above circumstances, and as a result, have found that a strongly acidic sulfonic acid type ion exchange resin modified with a specific mercaptoamine compound is capable of undergoing a condensation reaction between phenol and acetone. In the production of bisphenol A, the present inventors have found that they show high acetone conversion, high 4,4'-isomer selectivity and good stability, and have completed the present invention.
【０００７】即ち、本発明の要旨は、 １．下記一般式（Ｉ）That is, the gist of the present invention is as follows. The following general formula (I)
【０００８】[0008]
【化２】 Embedded image
【０００９】（式中、Ｒ1 及びＲ2 は、それぞれ独立し
て、炭素数１又は２のアルキル基、炭素数５ないし１０
のシクロアルキル基又は炭素数６ないし１５のアリール
基を置換基として有していてもよい炭素数２ないし４の
アルキレン基を表す）で示されるメルカプトアミン化合
物が強酸性スルホン酸型イオン交換樹脂にイオン結合し
てなる変性強酸性スルホン酸型イオン交換樹脂、(Wherein R 1 and R 2 are each independently an alkyl group having 1 or 2 carbon atoms, 5 to 10 carbon atoms)
Represents a cycloalkyl group or an alkylene group having 2 to 4 carbon atoms which may have a substituent having 6 to 15 carbon atoms). Denatured strongly acidic sulfonic acid type ion exchange resin formed by ionic bonding,
【００１０】２．１項に記載の変性強酸性スルホン酸型
イオン交換樹脂の存在下、フェノール類とケトン類を縮
合させることを特徴とするビスフェノール類の製造方
法、にある。以下、本発明について詳細に説明する。A process for producing bisphenols, which comprises condensing a phenol and a ketone in the presence of the modified strongly acidic sulfonic acid type ion exchange resin described in section 2.1. Hereinafter, the present invention will be described in detail.
【００１１】[0011]
【発明の実施の形態】本発明の変性強酸性スルホン酸型
イオン交換樹脂に用いられるメルカプトアミン化合物
は、式（Ｉ）で示されるメルカプトアルキル基を二ケ有
するピリジン誘導体である。式（Ｉ）において、Ｒ1 及
びＲ2 は、それぞれ独立して、炭素数１又は２のアルキ
ル基、炭素数５ないし１０のシクロアルキル基又は炭素
数６ないし１５のアリール基を置換基として有していて
もよい炭素数２ないし４のアルキレン基であり、好まし
くは無置換の炭素数２又は３のアルキレン基である。Ｒ
1 又はＲ2 のアルキレン基の炭素数が５以上の場合は触
媒の寿命低下が予想されるため好ましくない。BEST MODE FOR CARRYING OUT THE INVENTION The mercaptoamine compound used in the modified strongly acidic sulfonic acid type ion exchange resin of the present invention is a pyridine derivative having two mercaptoalkyl groups represented by the formula (I). In the formula (I), R 1 and R 2 each independently have an alkyl group having 1 or 2 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms as a substituent. An alkylene group having 2 to 4 carbon atoms which may be substituted, and preferably an unsubstituted alkylene group having 2 or 3 carbon atoms. R
When the number of carbon atoms of the alkylene group of 1 or R 2 is 5 or more, it is not preferable because the life of the catalyst is expected to decrease.
【００１２】アルキル基の具体例は、メチル基及びエチ
ル基である。シクロアルキル基の具体例としては、例え
ばシクロペンチル基、シクロヘキシル基、シクロオクチ
ル基、メチルシクロペンチル基、メチルシクロヘキシル
基、エチルシクロヘキシル基、ジメチルシクロヘキシル
基等が挙げられる。また、アリール基の具体例として
は、例えばフェニル基、トリル基、キシリル基、ナフチ
ル基、メチルナフチル基等が挙げられる。Specific examples of the alkyl group are a methyl group and an ethyl group. Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a methylcyclopentyl group, a methylcyclohexyl group, an ethylcyclohexyl group, and a dimethylcyclohexyl group. Further, specific examples of the aryl group include, for example, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a methylnaphthyl group and the like.
【００１３】好ましいメルカプトアミン化合物の具体例
としては、３，５−ジ−（２−メルカプトエチル）ピリ
ジン（１）、２，５−ジ−（２−メルカプトエチル）ピ
リジン（２）、２，６−ジ−（２−メルカプトエチル）
ピリジン（３）、３，５−ジ−（２−メルカプトプロピ
ル）ピリジン（４）、２，５−ジ−（２−メルカプトプ
ロピル）ピリジン（５）、２，６−ジ−（２−メルカプ
トプロピル）ピリジン（６）、等が挙げられる。これら
の好ましい化合物の構造を表１に示す。Specific examples of preferred mercaptoamine compounds include 3,5-di- (2-mercaptoethyl) pyridine (1), 2,5-di- (2-mercaptoethyl) pyridine (2), 2,6 -Di- (2-mercaptoethyl)
Pyridine (3), 3,5-di- (2-mercaptopropyl) pyridine (4), 2,5-di- (2-mercaptopropyl) pyridine (5), 2,6-di- (2-mercaptopropyl ) Pyridine (6). Table 1 shows the structures of these preferred compounds.
【００１４】[0014]
【表１】 [Table 1]
【００１５】該メルカプトアミン化合物の合成方法とし
ては、例えば、３，５−ジ−（２−メルカプトエチル）
ピリジンは、３，５−ジブロモピリジンをパラジウムの
存在下でトリブチルビニル錫、ビニルマグネシウムブロ
ミド等のアリル基置換の典型金属とトランスメタル化反
応により３，５−ジビニルピリジンとした後に、チオ酢
酸と反応させ、チオアセチル化した後に還元することに
より得られ、３，５−ジ−（２−メルカプトプロピル）
ピリジンは、３，５−ジ−（２−ヒドロキシプロピル）
ピリジンをハロゲン化チオニル等でハロゲン化し、チオ
酢酸と反応させた後、還元する等の方法により合成する
ことができる。他のピリジンアルカンチオールも同様な
方法で製造することができる。As a method for synthesizing the mercaptoamine compound, for example, 3,5-di- (2-mercaptoethyl)
Pyridine is converted to 3,5-divinylpyridine by a transmetalation reaction of 3,5-dibromopyridine with an allyl-substituted typical metal such as tributylvinyltin or vinylmagnesium bromide in the presence of palladium, and then reacted with thioacetic acid. Thioacetylation, followed by reduction to give 3,5-di- (2-mercaptopropyl)
Pyridine is 3,5-di- (2-hydroxypropyl)
Pyridine can be synthesized by halogenation with thionyl halide or the like, reaction with thioacetic acid, and reduction. Other pyridine alkane thiols can be produced in a similar manner.
【００１６】メルカプトアミン化合物をイオン結合させ
るイオン交換樹脂としては、特に限定されないが、スチ
レン−ジビニルベンゼン共重合体からなる主な骨格とこ
れに結合したスルホン酸基を有する強酸性イオン交換樹
脂が好ましく、共重合体中のジビニルベンゼン単位の含
有量は、２〜４０％が好ましい。イオン交換樹脂の交換
容量は、含水状態で０．５〜２．５ｍｅｑ／ｍｌのもの
が、乾燥樹脂では３．０〜７．０ｍｅｑ／ｇのものが好
ましい。イオン交換樹脂の粒径分布は、２００〜１５０
０μｍのものが、９５％以上を占めるのが好ましい。The ion exchange resin for ion-bonding the mercaptoamine compound is not particularly limited, but is preferably a strongly acidic ion exchange resin having a main skeleton composed of a styrene-divinylbenzene copolymer and a sulfonic acid group bonded thereto. The content of divinylbenzene units in the copolymer is preferably 2 to 40%. The exchange capacity of the ion exchange resin is preferably 0.5 to 2.5 meq / ml in a hydrated state, and the exchange capacity of the dry resin is preferably 3.0 to 7.0 meq / g. The particle size distribution of the ion exchange resin is 200 to 150.
It is preferred that the thickness of 0 μm accounts for 95% or more.
【００１７】このようなイオン交換樹脂の具体例として
は、例えば、アンバーリスト１５、３１、３２（ローム
＆ハース社製商品名）、ダウエックス５０ｗ、８８（ダ
ウ・ケミカル社製商品名）、ダイヤイオンＳＫ１Ｂ、Ｓ
Ｋ１０２、ＳＫ１０４、ＰＫ２０８、ＰＫ２１２、ＲＣ
Ｐ１６０Ｈ、ＲＣＰ１７０Ｈ（三菱化学社製商品名）等
が挙げられる。これらのイオン交換樹脂は酸型で上記の
メルカプトアミン化合物との結合に供する。市販品は、
通常、ナトリウム型であるため、塩酸等の酸で処理した
酸型にして用いる。これらのイオン交換樹脂は水を含有
した状態で市販されているが、脱水等の特別な処理をす
ることなくそのまま使用することができる。Specific examples of such ion exchange resins include, for example, Amberlyst 15, 31, 32 (trade name, manufactured by Rohm & Haas), Dowex 50w, 88 (trade name, manufactured by Dow Chemical Company), diamond Ion SK1B, S
K102, SK104, PK208, PK212, RC
P160H, RCP170H (trade name, manufactured by Mitsubishi Chemical Corporation) and the like. These ion exchange resins are used in the acid form for binding to the above mercaptoamine compound. Commercial products are
Usually, since it is a sodium type, it is used in an acid type treated with an acid such as hydrochloric acid. These ion exchange resins are commercially available containing water, but can be used as they are without special treatment such as dehydration.
【００１８】強酸性スルホン酸型イオン交換樹脂のスル
ホン酸基にメルカプトアミン化合物を結合させるには、
先ず適当な溶媒、例えば、水、アルコール類、エーテル
類等に同アミン化合物を溶解させ、この溶液を予め同じ
溶媒に分散させた強酸性イオン交換樹脂に加え、適当な
時間、例えば０．１〜１０時間攪拌すればよい。例えば
水溶媒中で結合するには、同アミンをスルホン酸よりｐ
ｋａが大きい酸、例えば酢酸、トリフルオロ酢酸、モノ
クロロ酢酸等の水溶液に加えて溶解させ、この水溶液
を、予め水に分散させた強酸性スルホン酸型イオン交換
樹脂中に加え、０．１〜１０時間攪拌すればよい。In order to bond a mercaptoamine compound to a sulfonic acid group of a strongly acidic sulfonic acid type ion exchange resin,
First, the same amine compound is dissolved in a suitable solvent, for example, water, alcohols, ethers, etc., and this solution is added to a strongly acidic ion-exchange resin previously dispersed in the same solvent, for a suitable time, for example, What is necessary is just to stir for 10 hours. For example, in order to bind in an aqueous solvent, the amine is more p-type than sulfonic acid.
An acid having a large ka, for example, acetic acid, trifluoroacetic acid, monochloroacetic acid or the like is added to and dissolved in an aqueous solution, and this aqueous solution is added to a strongly acidic sulfonic acid type ion exchange resin previously dispersed in water, and 0.1 to 10%. Stir for hours.
【００１９】強酸性スルホン酸型イオン交換樹脂に対す
る、メルカプトアミン化合物の結合量は、通常、強酸性
スルホン酸型イオン交換樹脂の全スルホン酸基に対し、
２〜３０モル％、好ましくは５〜２０モル％である。イ
オン結合量が２モル％未満ではメルカプトアミン化合物
による触媒効果が十分発揮されず、また３０モル％を越
えると遊離のスルホン酸量の減少によって触媒活性が低
下するため好ましくない。本発明に係わるメルカプトア
ミン化合物がイオン結合した強酸性スルホン酸型イオン
交換樹脂は、フェノール類とケトン類の縮合反応によっ
て対応するビスフェノール類を生成させる方法に適用し
た場合、従来から知られているアミン化合物に比べ、非
常に高いアセトン転化率、及び４，４′−体の選択性を
示す。The amount of the mercaptoamine compound bound to the strongly acidic sulfonic acid type ion exchange resin is usually based on the total sulfonic acid groups of the strongly acidic sulfonic acid type ion exchange resin.
It is 2 to 30 mol%, preferably 5 to 20 mol%. If the amount of ionic bonds is less than 2 mol%, the catalytic effect of the mercaptoamine compound will not be sufficiently exhibited, and if it exceeds 30 mol%, the catalytic activity will decrease due to the decrease in the amount of free sulfonic acid, which is not preferable. The strongly acidic sulfonic acid type ion exchange resin to which the mercaptoamine compound according to the present invention is ion-bonded is a conventionally known amine when applied to a method for producing a corresponding bisphenol by a condensation reaction of phenols and ketones. It shows a very high conversion of acetone and a selectivity of the 4,4'-isomer compared to the compound.
【００２０】本発明方法において原料として使用される
フェノール類はヒドロキシル基に対してパラ位に置換基
を有しないことが必要であるが、オルト位又はメタ位に
はアルキル基、ハロゲン等の置換基を有していてもよ
い。具体的にはフェノール、ｏ−クレゾール、ｍ−クレ
ゾール、ｏ−クロロフェノール、ｍ−クロロフェノー
ル、ｏ−ｔ−ブチルフェノール、２，６−キシレノー
ル、２，６−ジ−ｔ−ブチルフェノール、ｏ−フェニル
フェノール等が例示される。ケトンとしては、アセト
ン、エチルメチルケトン、イソブチルメチルケトン、ア
セトフェノン、シクロヘキサノン、１，３−ジクロロア
セトン等が使用される。その中で最も好ましいものは、
フェノール類が非置換フェノールであり、ケトン類がア
セトンで、ビスフェノールＡを製造する方法である。以
下にこの方法について説明する。The phenol used as a raw material in the method of the present invention must have no substituent at the para-position with respect to the hydroxyl group, but a substituent such as an alkyl group or a halogen at the ortho- or meta-position. May be provided. Specifically, phenol, o-cresol, m-cresol, o-chlorophenol, m-chlorophenol, ot-butylphenol, 2,6-xylenol, 2,6-di-t-butylphenol, o-phenylphenol Etc. are exemplified. As the ketone, acetone, ethyl methyl ketone, isobutyl methyl ketone, acetophenone, cyclohexanone, 1,3-dichloroacetone and the like are used. The most preferred of them is
This is a method for producing bisphenol A, wherein phenols are unsubstituted phenols and ketones are acetone. Hereinafter, this method will be described.
【００２１】本発明に係わるメルカプトアミン化合物が
イオン結合した強酸性スルホン酸型イオン交換樹脂（以
下、変性樹脂と略記する）をアセトンとフェノールの縮
合反応に使用する場合には、前処理として変性樹脂を充
填した容器に変性樹脂の体積の５〜２００倍のイオン交
換水を２０〜８０℃の温度で、液時空間速度（ＬＨＳ
Ｖ）０．５〜５０ｈｒ-1で通液し、次いで変性樹脂の体
積の５〜２００倍のフェノールを４０〜１１０℃の温度
で、ＬＨＳＶ０．５〜５０ｈｒ-1で通液する。この処理
により変性樹脂に含まれている水をフェノールに置換し
てから、反応に供する。When a strongly acidic sulfonic acid type ion exchange resin (hereinafter abbreviated as “modified resin”) to which a mercaptoamine compound according to the present invention is ion-bonded is used for the condensation reaction of acetone and phenol, the modified resin is used as a pretreatment. At a temperature of 20-80 ° C. in a space filled with LHS at a temperature of 20-80 ° C.
V) The solution is passed at 0.5 to 50 hr -1 , and then phenol having a volume of 5 to 200 times the volume of the modified resin is passed at a temperature of 40 to 110 ° C. at an LHSV of 0.5 to 50 hr -1 . After the water contained in the modified resin is replaced with phenol by this treatment, it is subjected to the reaction.
【００２２】本反応は通常、上述の処理を経た変性樹脂
を充填した反応器に、フェノールとアセトンを含有する
原料混合物を連続的に供給して反応を行う固定床流通反
応方式で行われる。原料混合物の供給は、ＬＨＳＶ０．
１〜２０ｈｒ-1、好ましくは０．５〜１０ｈｒ-1の範囲
で行われる。反応温度は４０〜１２０℃、好ましくは６
０〜１００℃の範囲である。反応温度が４０℃未満では
反応速度が遅く、また１２０℃を越える温度では変性樹
脂の劣化が著しく副生物も増加するため好ましくない。This reaction is usually carried out by a fixed bed flow reaction system in which a raw material mixture containing phenol and acetone is continuously supplied to a reactor filled with the modified resin having undergone the above-mentioned treatment to carry out the reaction. The supply of the raw material mixture is LHSV0.
The reaction is performed in the range of 1 to 20 hr -1 , preferably 0.5 to 10 hr -1 . The reaction temperature is 40 to 120 ° C, preferably 6
It is in the range of 0-100 ° C. If the reaction temperature is lower than 40 ° C., the reaction rate is low, and if the reaction temperature is higher than 120 ° C., the denatured resin deteriorates remarkably and by-products increase, which is not preferable.
【００２３】反応に供するフェノールとアセトンのモル
比は、アセトン１モルに対してフェノールが３〜３０モ
ル、好ましくは５〜２０モルの範囲である。フェノール
の使用量が３モル未満では、副生成物が増加するため好
ましくなく、３０モルを越えて使用しても反応成績には
殆ど影響せず、むしろ反応混合物から回収再使用するフ
ェノールの量が増大するため経済的ではない。反応混合
物から目的物質であるビスフェノールＡを分離精製する
には、例えば、未反応フェノールを回収しビスフェノー
ルＡとフェノールの付加体を結晶として分離し、次いで
蒸留等の操作で付加体からフェノールを回収するという
公知の方法で行うことができる。The molar ratio of phenol to acetone used in the reaction is in the range of 3 to 30 moles, preferably 5 to 20 moles of phenol per mole of acetone. If the amount of phenol used is less than 3 moles, the amount of phenol recovered and reused from the reaction mixture is hardly affected even if it is used in an amount exceeding 30 moles. It is not economical because it increases. In order to separate and purify bisphenol A as a target substance from the reaction mixture, for example, unreacted phenol is recovered, an adduct of bisphenol A and phenol is separated as crystals, and then phenol is recovered from the adduct by an operation such as distillation. Can be performed by a known method.
【００２４】[0024]
【実施例】次に、実施例及び比較例により本発明を更に
具体的に説明するが、本発明は、その要旨を越えない限
り実施例に限定されるものではない。なお、実施例、比
較例中におけるアセトン転化率、４，４′−ビスフェノ
ールＡ（４，４′−ＢＰＡと略記する）選択率、変性率
及びスルホン酸残存率は次式により算出した（単位はい
ずれも％）。Next, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the examples unless it exceeds the gist thereof. The acetone conversion, 4,4'-bisphenol A (abbreviated as 4,4'-BPA) selectivity, modification rate, and sulfonic acid residual rate in Examples and Comparative Examples were calculated by the following formulas (unit: Both are%).
【００２５】[0025]
【数１】 (Equation 1)
【００２６】実施例１３，５−ジ−（メルカプトエチル）ピリジンイオン交換
樹脂 ５００ｍｌ三つ口フラスコに、３，５−ジブロモピリジ
ン（アルドリッチ社製）７．５ｇ（３２ｍｍｏｌ）とト
リブチルビニル錫３０ｇ（９５ｍｍｏｌ）、テトラキス
トリフェニルホスフィンパラジウム２．９ｇ（２．５ｍ
ｍｏｌ）、４−メチル−２，６−ｔ−ブチルフェノール
６０ｍｇを仕込んだ。窒素気流下に攪拌しながら、昇温
し２時間加熱還流した。反応液を水１Ｌに注ぎ、酢酸エ
チル３００ｍｌで数回抽出した。硫酸マグネシウムで乾
燥後、酢酸エチルを留去し、粗生成物４２ｇを得た。そ
れをシリカゲルカラムクロマトグラフィーで精製して
（溶出溶媒；酢酸エチル：ヘキサン＝１：３）、３，５
−ジビニルピリジン３．４ｇを得た。上記で得た３，５
−ジビニルピリジン３．４ｇ（２６ｍｍｏｌ）にチオ酢
酸７．９ｇを加え、８０℃で５時間反応した。反応液に
１Ｎ水酸化ナトリウム溶液１００ｍｌとジエチルエーテ
ル１００ｍｌを加え分液後、有機溶媒層を硫酸マグネシ
ウムで乾燥し、溶媒を留去後、粗生成物７．３ｇを得
た。それをシリカゲルクロマトグラフィーで精製して
（溶出溶媒；酢酸エチル：ヘキサン＝１：６）、３，５
−ジ−（２−アセチルチオエチル）ピリジン２．２ｇ
（ガスクロ純度８５％）を得た。１００ｍｌ三つ口フラ
スコに無水ジエチルエーテル５０ｍｌと水素化アルミニ
ウムリチウム０．７１ｇ（１８．７ｍｍｏｌ）を窒素気
流下で仕込み、室温攪拌下、上記の３，５−ジ−（２−
アセチルチオエチル）ピリジン２．２ｇ（ガスクロ純度
８５％）の無水ジエチルエーテル３０ｍｌ溶液を滴下し
た。２時間加熱還流した後、氷冷し、蒸留水０．３７
ｇ、酢酸１．２４ｇを加えた。無機物を濾別、酢酸エチ
ルで洗浄した有機層を無水硫酸マグネシウムで乾燥した
後、溶媒留去することにより粗生成物１．２８ｇが得ら
れた。シリカゲルクロマトグラフィーで精製して（溶出
溶媒；酢酸エチル：ヘキサン＝１：３）、３，５−ジ−
（２−メルカプトエチル）ピリジン１．１２ｇ得られ
た。（ガスクロマトグラフィーによる純度９８．８％） 水切りをしたダイヤイオンＳＫ１０４（Ｈ型）２０ｇ
（三菱化学社製、交換容量１．６３ｍｅｑ／ｇ）をイオ
ン交換水に懸濁させ、上記で得られた３，５−ジ−（２
−メルカプトエチル）ピリジン０．６５ｇと酢酸０．２
５ｇをイオン交換水２０ｍｌに溶解させた水溶液と混合
し、室温で１０時間攪拌した。イオン交換樹脂を濾過
し、イオン交換水で洗浄し、変性イオン交換樹脂を得
た。メルカプト基及びスルホン酸の残存量を分析したと
ころ、変性率は７．７％であり、スルホン酸残存率は９
１．９％であった。この変性イオン交換樹脂１４ｍｌを
内径７．６ｍｍ、全長３２０ｍｍのステンレスカラムに
充填し、イオン交換水２００ｍｌを２ｈｒ-1で流し、そ
の後７０℃でフェノールＬＨＳＶ−２ｈｒ-1で２４時間
流した。次に、フェノール／アセトン＝１０／１（モル
比）の混合液を７０℃、ＬＨＳＶ１．０ｈｒ-1で通液し
連続反応を行った。４０時間後のアセトンの転化率は９
４．７％、４，４′−ＢＰＡの選択率は９３．２％であ
り、３００時間後のアセトンの転化率は９４．９％、
４，４′−ＢＰＡの選択率は９４．２％であった。（表
２）Example 1 3,5-di- (mercaptoethyl) pyridine ion exchange
In a resin 500 ml three-necked flask, 7.5 g (32 mmol) of 3,5-dibromopyridine (manufactured by Aldrich), 30 g (95 mmol) of tributylvinyltin, and 2.9 g of tetrakistriphenylphosphine palladium (2.5 m
mol), and 60 mg of 4-methyl-2,6-t-butylphenol. The mixture was heated and refluxed for 2 hours while stirring under a nitrogen stream. The reaction solution was poured into 1 L of water and extracted several times with 300 ml of ethyl acetate. After drying over magnesium sulfate, ethyl acetate was distilled off to obtain 42 g of a crude product. It was purified by silica gel column chromatography (elution solvent; ethyl acetate: hexane = 1: 3) to give 3,5
3.4 g of divinylpyridine were obtained. 3,5 obtained above
7.9 g of thioacetic acid was added to 3.4 g (26 mmol) of divinylpyridine and reacted at 80 ° C. for 5 hours. 100 ml of 1N sodium hydroxide solution and 100 ml of diethyl ether were added to the reaction solution, and the mixture was separated. The organic solvent layer was dried over magnesium sulfate, and the solvent was distilled off. It was purified by silica gel chromatography (elution solvent; ethyl acetate: hexane = 1: 6) to give 3,5.
2.2 g of -di- (2-acetylthioethyl) pyridine
(Purity of gas chromatography: 85%). 50 ml of anhydrous diethyl ether and 0.71 g (18.7 mmol) of lithium aluminum hydride were charged into a 100 ml three-necked flask under a nitrogen stream, and the above 3,5-di- (2-
A solution of 2.2 g of (acetylthioethyl) pyridine (gas chromatography purity: 85%) in 30 ml of anhydrous diethyl ether was added dropwise. After heating and refluxing for 2 hours, the mixture was cooled on ice and distilled water 0.37
g and 1.24 g of acetic acid. The inorganic layer was separated by filtration, the organic layer washed with ethyl acetate was dried over anhydrous magnesium sulfate, and then the solvent was distilled off to obtain 1.28 g of a crude product. Purification by silica gel chromatography (elution solvent; ethyl acetate: hexane = 1: 3), 3,5-di-
1.12 g of (2-mercaptoethyl) pyridine was obtained. (Purity by gas chromatography: 98.8%) 20 g of drained Diaion SK104 (H type)
(Manufactured by Mitsubishi Chemical Corporation, exchange capacity 1.63 meq / g) was suspended in ion-exchanged water, and the 3,5-di- (2
-Mercaptoethyl) pyridine (0.65 g) and acetic acid (0.2)
5 g was mixed with an aqueous solution in which 20 ml of ion-exchanged water was dissolved, and the mixture was stirred at room temperature for 10 hours. The ion exchange resin was filtered and washed with ion exchange water to obtain a modified ion exchange resin. When the residual amounts of the mercapto group and the sulfonic acid were analyzed, the modification rate was 7.7%, and the sulfonic acid residual rate was 9%.
It was 1.9%. 14 ml of the denatured ion exchange resin was packed in a stainless steel column having an inner diameter of 7.6 mm and a total length of 320 mm, and 200 ml of ion exchanged water was flowed at 2 hr -1 and then flown at 70 ° C. with phenol LHSV-2 hr -1 for 24 hours. Next, a mixture of phenol / acetone = 10/1 (molar ratio) was passed at 70 ° C. and an LHSV of 1.0 hr −1 to carry out a continuous reaction. After 40 hours, the conversion of acetone was 9
4.7%, the selectivity of 4,4'-BPA is 93.2%, the conversion of acetone after 300 hours is 94.9%,
The selectivity for 4,4'-BPA was 94.2%. (Table 2)
【００２７】実施例２２，５−ジ−（２−メルカプトエチル）ピリジン交換樹
脂 実施例１において、３，５−ジブロモピリジンの代わり
に２，５−ジブロモピリジン（アルドリッチ社製）を３
２ミリモル用いた他は、実施例１と同様に反応を行い
２，５−ジビニルピリジンを３．５ｇ得た。このものに
ついて、実施例１と同様にして、チオ酢酸によるチオア
セチル化及び水素化リチウムアルミニウムによる還元を
行い、シリカゲルクロマトグラフィーによる精製により
２，５−ジ−（２−メルカプトエチル）ピリジン１．５
ｇを得た。ガスクロマトグラフィーによる分析の結果、
純度は９６．６％であった。水切りをしたダイヤイオン
ＳＫ１０４（Ｈ型）２０ｇ（三菱化学社製、交換容量
１．６３ｍｅｑ／ｇ）をイオン交換水に懸濁させ、上記
で得られた２，５−ジ−（２−メルカプトエチル）ピリ
ジン０．６５ｇと酢酸０．２５ｇをイオン交換水２０ｍ
ｌに溶解させた水溶液と混合し、室温で１０時間攪拌し
た。イオン交換樹脂を濾過し、イオン交換水で洗浄し、
変性イオン交換樹脂を得た。メルカプト基及びスルホン
酸の残存量を分析したところ、変性率は８．０％であ
り、スルホン酸残存率は９１．４％であった。この変性
樹脂を用い、実施例１と同一条件で反応評価を行った。
反応開始後４０時間と３００時間の反応結果を表２に示
した。Example 2 Exchanged 2,5-di- (2-mercaptoethyl) pyridine
In Example 1, 2,5-dibromopyridine (manufactured by Aldrich) was used instead of 3,5-dibromopyridine.
The reaction was carried out in the same manner as in Example 1 except that 2 mmol was used to obtain 3.5 g of 2,5-divinylpyridine. This was subjected to thioacetylation with thioacetic acid and reduction with lithium aluminum hydride in the same manner as in Example 1, and purified by silica gel chromatography to give 2,5-di- (2-mercaptoethyl) pyridine 1.5.
g was obtained. As a result of analysis by gas chromatography,
Purity was 96.6%. 20 g of drained Diaion SK104 (H type) (manufactured by Mitsubishi Chemical Corporation, exchange capacity 1.63 meq / g) was suspended in ion-exchanged water, and the 2,5-di- (2-mercaptoethyl) obtained above was suspended. ) 0.65 g of pyridine and 0.25 g of acetic acid were added to 20 m of ion-exchanged water.
and stirred at room temperature for 10 hours. Filter the ion exchange resin, wash with ion exchange water,
A modified ion exchange resin was obtained. When the residual amounts of the mercapto group and the sulfonic acid were analyzed, the modification ratio was 8.0% and the residual sulfonic acid ratio was 91.4%. Using this modified resin, the reaction was evaluated under the same conditions as in Example 1.
Table 2 shows the reaction results for 40 hours and 300 hours after the start of the reaction.
【００２８】比較例１２−アミノエタンチオール変性イオン交換樹脂 市販の２−アミノエタンチオール０．５８ｇと酢酸０．
４６ｇをイオン交換水２０ｍｌに溶解し、イオン交換水
３０ｍｌに懸濁させたダイヤイオンＳＫ１０４（Ｈ型）
３０．０ｇへ加え、室温で１時間攪拌した。イオン交換
樹脂を濾過し、イオン交換水で洗浄し、変性イオン交換
樹脂を得た。メルカプト基及びスルホン酸の残存量を分
析したところ、変性率は１５．２％であり、スルホン酸
残存率は８４．１％であった。この変性樹脂を用い、実
施例と同一条件で反応評価を行った。反応開始後４０時
間と３００時間の反応結果を表２に示した。Comparative Example 1 2-aminoethanethiol-modified ion exchange resin 0.58 g of commercially available 2-aminoethanethiol and 0.1 ml of acetic acid.
46 g of Diaion SK104 (H-type) dissolved in 20 ml of ion-exchanged water and suspended in 30 ml of ion-exchanged water
30.0 g, and stirred at room temperature for 1 hour. The ion exchange resin was filtered and washed with ion exchange water to obtain a modified ion exchange resin. When the residual amounts of the mercapto group and the sulfonic acid were analyzed, the modification ratio was 15.2%, and the residual ratio of the sulfonic acid was 84.1%. Using this modified resin, the reaction was evaluated under the same conditions as in the examples. Table 2 shows the reaction results for 40 hours and 300 hours after the start of the reaction.
【００２９】[0029]
【表２】 [Table 2]
【００３０】[0030]
【発明の効果】本発明のイオン交換樹脂を使用すれば、
フェノールとアセトンとの縮合反応により、高いアセト
ン転化率及び高い４，４′−ビスフェノールＡ選択率
で、且つその性能を長時間持続しながら、効率的にビス
フェノールＡを製造することができる。According to the present invention, if the ion exchange resin is used,
By the condensation reaction of phenol and acetone, bisphenol A can be efficiently produced with a high acetone conversion and a high 4,4'-bisphenol A selectivity and maintaining its performance for a long time.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ // Ｃ０７Ｂ 61/00 ３００ Ｃ０７Ｂ 61/00 ３００ (72)発明者 鯨 勝文 茨城県稲敷郡阿見町中央八丁目３番１号 三菱化学株式会社筑波研究所内 (72)発明者 岩根 寛 茨城県稲敷郡阿見町中央八丁目３番１号 三菱化学株式会社筑波研究所内────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification symbol FI // C07B 61/00 300 C07B 61/00 300 (72) Inventor Katsufumi Whale Katsumi 8-3-1 Chuo, Ami-cho, Inashiki-gun, Ibaraki Prefecture (72) Inventor Hiroshi Iwane 3-1-1, Chuo, Ami-cho, Inashiki-gun, Ibaraki Prefecture Within Tsukuba Research Laboratory, Mitsubishi Chemical Corporation
Claims (5)
又は２のアルキル基、炭素数５ないし１０のシクロアル
キル基又は炭素数６ないし１５のアリール基を置換基と
して有していてもよい炭素数２ないし４のアルキレン基
を表す）で示されるメルカプトアミン化合物が強酸性ス
ルホン酸型イオン交換樹脂にイオン結合してなる変性強
酸性スルホン酸型イオン交換樹脂。1. A compound represented by the following general formula (I) (Wherein, R 1 and R 2 each independently represent a carbon atom of 1
Or an alkylene group having 2 to 4 carbon atoms which may have a substituent having an alkyl group of 2 or a cycloalkyl group having 5 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms) A modified strongly acidic sulfonic acid type ion exchange resin in which a compound is ionically bonded to a strongly acidic sulfonic acid type ion exchange resin.
の量が、スルホン酸基の２〜３０モル％である請求項１
に記載のイオン交換樹脂。2. The method according to claim 1, wherein the amount of the mercaptoamine compound ion-bonded is 2 to 30 mol% of the sulfonic acid groups.
The ion exchange resin according to 1.
らなる骨格を有することを特徴とする請求項１又は２に
記載のイオン交換樹脂。3. The ion exchange resin according to claim 1, which has a skeleton composed of a styrene-divinylbenzene copolymer.
性強酸性スルホン酸型イオン交換樹脂の存在下、フェノ
ール類とケトン類を縮合させることを特徴とするビスフ
ェノール類の製造方法。4. A process for producing bisphenols, comprising condensing phenols and ketones in the presence of the modified strongly acidic sulfonic acid type ion exchange resin according to claim 1.
り、ケトン類がアセトンであることを特徴とする請求項
４に記載のビスフェノール類の製造方法。5. The method for producing bisphenols according to claim 4, wherein the phenol is an unsubstituted phenol and the ketone is acetone.
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| Application Number | Priority Date | Filing Date | Title |
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| JP34917197A JP3700361B2 (en) | 1997-12-18 | 1997-12-18 | Ion exchange resin and method for producing bisphenols using the same as a catalyst |
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| Application Number | Priority Date | Filing Date | Title |
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| JP34917197A JP3700361B2 (en) | 1997-12-18 | 1997-12-18 | Ion exchange resin and method for producing bisphenols using the same as a catalyst |
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| Publication Number | Publication Date |
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| JPH11179210A true JPH11179210A (en) | 1999-07-06 |
| JP3700361B2 JP3700361B2 (en) | 2005-09-28 |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US6534686B1 (en) | 2001-09-18 | 2003-03-18 | General Electric Company | Method for producing bisphenol catalysts and bisphenols |
| US6620939B2 (en) | 2001-09-18 | 2003-09-16 | General Electric Company | Method for producing bisphenol catalysts and bisphenols |
| JP2004516275A (en) * | 2000-12-19 | 2004-06-03 | ゼネラル・エレクトリック・カンパニイ | Amine-modified catalyst for bisphenol production |
| WO2004078345A1 (en) * | 2003-03-03 | 2004-09-16 | General Electric Company | Method for producing bisphenol catalysts and bisphenols |
| JP2007176840A (en) * | 2005-12-27 | 2007-07-12 | Mitsui Chemicals Inc | Thiol compound, modified ion exchange resin, and method for preparing bisphenol |
| JP5126771B2 (en) * | 2004-07-02 | 2013-01-23 | 三井化学株式会社 | Modified ion exchange resin and process for producing bisphenols |
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|---|---|---|---|---|
| JP2004516275A (en) * | 2000-12-19 | 2004-06-03 | ゼネラル・エレクトリック・カンパニイ | Amine-modified catalyst for bisphenol production |
| US6620939B2 (en) | 2001-09-18 | 2003-09-16 | General Electric Company | Method for producing bisphenol catalysts and bisphenols |
| US6884894B2 (en) | 2001-09-18 | 2005-04-26 | General Electric Company | Method for producing bisphenol catalysts and bisphenols |
| US6534686B1 (en) | 2001-09-18 | 2003-03-18 | General Electric Company | Method for producing bisphenol catalysts and bisphenols |
| WO2004078345A1 (en) * | 2003-03-03 | 2004-09-16 | General Electric Company | Method for producing bisphenol catalysts and bisphenols |
| JP2006513848A (en) * | 2003-03-03 | 2006-04-27 | ゼネラル・エレクトリック・カンパニイ | Bisphenol catalyst and method for producing bisphenol |
| JP5126771B2 (en) * | 2004-07-02 | 2013-01-23 | 三井化学株式会社 | Modified ion exchange resin and process for producing bisphenols |
| JP2007176840A (en) * | 2005-12-27 | 2007-07-12 | Mitsui Chemicals Inc | Thiol compound, modified ion exchange resin, and method for preparing bisphenol |
| 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 |
| US9290618B2 (en) | 2011-08-05 | 2016-03-22 | Sabic Global Technologies B.V. | Polycarbonate compositions having enhanced optical properties, methods of making and articles comprising the polycarbonate compositions |
| 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 |
| US9490405B2 (en) | 2012-02-03 | 2016-11-08 | Sabic Innovative Plastics Ip B.V. | Light emitting diode device and method for production thereof containing conversion material chemistry |
| 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 |
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| CN116273159A (en) * | 2022-12-05 | 2023-06-23 | 中国人民解放军军事科学院***工程研究院 | Sulfonated immobilized binary catalyst, preparation method and application thereof |
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