JPH10328573A - Ion exchange resin and utilization thereof - Google Patents
Ion exchange resin and utilization thereofInfo
- Publication number
- JPH10328573A JPH10328573A JP9139798A JP13979897A JPH10328573A JP H10328573 A JPH10328573 A JP H10328573A JP 9139798 A JP9139798 A JP 9139798A JP 13979897 A JP13979897 A JP 13979897A JP H10328573 A JPH10328573 A JP H10328573A
- Authority
- JP
- Japan
- Prior art keywords
- ion exchange
- exchange resin
- pyridine
- sulfonic acid
- phenol
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は変性強酸性スルホン
酸型イオン交換樹脂に関する。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ってビスフェノー
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。[0001] The present invention relates to a modified strongly acidic sulfonic acid type ion exchange resin. This ion exchange resin
It is useful as a catalyst when producing bisphenol A by a condensation reaction of 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っ
てビスフェノール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は公知であり、具体的には、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、フランス国特許１３
７３７９６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、特開昭５６−２１６５０、特開昭５
７−８７８４６号、特開昭５９−１０９５０３号公報
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知られている。2. Description of the Related Art As a catalyst for producing bisphenol A by a condensation reaction of phenol and acetone, a method of using a compound having a mercapto group together with a strongly acidic sulfonic acid type ion exchange resin is known. Method for coexisting a compound having a mercapto group in a reaction system (Japanese Patent Publication No. 45-10337, French Patent 13
No. 73796, etc.), a method of covalently bonding a compound having a mercapto group to a strongly acidic ion exchange resin (JP-B-37-14721, JP-A-56-21650, JP-A-56-21650,
Nos. 7-87846, JP-A-59-109503, etc.) and a method of ion-bonding mercaptoamines to a strongly acidic ion exchange resin are known.
【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 these, a method using a strongly acidic ion exchange resin in which mercaptoamines are ion-bonded is described as follows.
1) Mercaptoamines are not mixed in the 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強
酸性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４６−１９９５３、特開昭
６２−２９８４５４号公報）、Ｎ−プロピルメルカプト
アルキルアミン（特開昭６０−１３７４４０号公報）を
イオン結合させた強酸性イオン交換樹脂を用いる方法が
知られている。また、四級アンモニウム塩をイオン結合
させた強酸性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）モルフォリウムおよび
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
号公報）をイオン結合させた強酸性イオン交換樹脂を用
いる方法が知られている。しかしながらいずれの方法で
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。[0004] As a method of using a strongly acidic ion exchange resin to which mercaptoamines are ion-bonded, 2-mercaptoethylamine (JP-B-46-19553, JP-A-62-298454), N-propylmercaptoalkylamine (Japanese Patent Application Laid-Open No. 60-137440) is known which uses a strongly acidic ion-exchange resin in which ionic bonds are formed. Also, as a method of using a strongly acidic ion exchange resin ion-bonded with a quaternary ammonium salt,
N, N, N-trimethyl-2-mercaptoethylammonium, N- (2-hydroxyl-3-mercaptopropyl) pyridinium, N-methyl-N- (2-hydroxyl-3-mercaptopropyl) morpholium and N-benzyl -N, N-dimethyl-2-mercaptoethylammonium (Czechoslovak Patent 184988)
A method using a strongly acidic ion-exchange resin ion-bonded to the above-mentioned method is known. However, both methods have a drawback that the conversion of acetone is only about 50 to 75%.
【０００５】[0005]
【発明が解決しようとする課題】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の製造に好適
な触媒を提供することを目的とする。特に、アセトンの
転化率が高く、かつ良好な選択性および安定性を有す
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
換樹脂を提供することを目的とする。SUMMARY OF THE INVENTION An object of the present invention is to provide a catalyst suitable for producing bisphenol by reacting phenols and ketones. In particular, it is an object of the present invention to provide a strongly acidic sulfonic acid type ion exchange resin 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. I do.
【０００６】[0006]
【課題を解決するための手段】上記目的のため、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、ケトン
類の転化率が高く、かつ良好な選択性を有するビスフェ
ノールの製造触媒であることを見い出し、本発明に到達
した。すなわち、本発明は、下記式（１）For the above purpose, as a result of intensive studies, it has been found that a strongly acidic sulfonic acid type ion exchange resin modified with a specific mercaptoamine compound has a high conversion of ketones and a good conversion. The present inventors have found that this is a bisphenol production catalyst having selectivity, and arrived at the present invention. That is, the present invention provides the following formula (1)
【０００７】[0007]
【化２】 Embedded image
【０００８】（式中、ｎは１〜４の整数であり、Ｘおよ
びＹはそれぞれ独立に水素、炭素数１〜６のアルキル
基、炭素数６〜１２のアリール基、または炭素数５〜１
０のシクロアルキル基を表す）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
ン結合している変性強酸性スルホン酸型イオン交換樹脂
に存する。以下本発明につき詳細に説明する。前記式
（１）で示されるメルカプトアミン化合物において、ｎ
は１から４の整数であり、好ましくは１から３であり、
より好ましくは１または２であり、特に好ましいのはｎ
が１のときである。ｎが５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。また、本発明では、フェニ
ル基に置換しているアミン部分がピリジン環であるた
め、良好な活性、寿命を示す。アミン部分がアルキルア
ミン、アニリン骨格の場合には、活性は高いが、寿命低
下がみられるため好ましくない。ピリジン環の置換位置
は２〜６位のいずれでも好ましく、フェニル基上のメル
カプトアルキル基とピリジン環の置換の位置関係は特に
限定しないが、パラ位が特に好ましい。フェニル基には
置換基はない方が好ましい。その他の置換基ＸおよびＹ
はそれぞれ独立に水素、炭素数１〜６のアルキル基、炭
素数６〜１２のアリール基、または炭素数５〜１０のシ
クロアルキル基であり、好ましくは水素または炭素数１
〜２のアルキル基であり、特に好ましくは水素である。Wherein n is an integer of 1 to 4, and X and Y are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or 5 to 1 carbon atoms.
(Representing a cycloalkyl group of 0) in a modified strongly acidic sulfonic acid type ion exchange resin in which a mercaptoamine compound represented by the following formula: Hereinafter, the present invention will be described in detail. In the mercaptoamine compound represented by the formula (1), n
Is an integer from 1 to 4, preferably from 1 to 3,
It is more preferably 1 or 2, and particularly preferably n
Is 1. When n is 5, the life of the catalyst is expected to decrease, which is not preferable. Further, in the present invention, since the amine moiety substituted on the phenyl group is a pyridine ring, good activity and good life are exhibited. When the amine moiety is an alkylamine or aniline skeleton, the activity is high, but the life is shortened, which is not preferable. The substitution position of the pyridine ring is preferably any of positions 2 to 6, and the positional relationship between the mercaptoalkyl group on the phenyl group and the substitution of the pyridine ring is not particularly limited, but the para position is particularly preferred. It is preferable that the phenyl group has no substituent. Other substituents X and Y
Is each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a cycloalkyl group having 5 to 10 carbon atoms, preferably hydrogen or 1 carbon atom.
And 2 alkyl groups, particularly preferably hydrogen.
【０００９】好ましいメルカプトアミン化合物の具体例
としては２−（４−メルカプトメチルフェニル）ピリジ
ン、３−（４−メルカプトメチルフェニル）ピリジン、
４−（４−メルカプトメチルフェニル）ピリジン、２−
〔４−（２−メルカプトエチル）フェニル〕ピリジン、
３−〔４−（２−メルカプトエチル）フェニル〕ピリジ
ン、４−〔４−（２−メルカプトエチル）フェニル〕ピ
リジン、２−（３−メルカプトメチルフェニル）ピリジ
ン、３−（３−メルカプトメチルフェニル）ピリジン、
４−（３−メルカプトメチルフェニル）ピリジン、２−
〔３−（２−メルカプトエチル）フェニル〕ピリジン、
３−〔３−（２−メルカプトエチル）フェニル〕ピリジ
ン、４−〔３−（２−メルカプトエチル）フェニル〕ピ
リジン、２−（２−メルカプトメチルフェニル）ピリジ
ン、３−（２−メルカプトメチルフェニル）ピリジン、
４−（２−メルカプトメチルフェニル）ピリジン、２−
〔２−（２−メルカプトエチル）フェニル〕ピリジン、
３−〔２−（２−メルカプトエチル）フェニル〕ピリジ
ン、４−〔２−（２−メルカプトエチル）フェニル〕ピ
リジン等が挙げられる。Specific examples of preferred mercaptoamine compounds include 2- (4-mercaptomethylphenyl) pyridine, 3- (4-mercaptomethylphenyl) pyridine,
4- (4-mercaptomethylphenyl) pyridine, 2-
[4- (2-mercaptoethyl) phenyl] pyridine,
3- [4- (2-mercaptoethyl) phenyl] pyridine, 4- [4- (2-mercaptoethyl) phenyl] pyridine, 2- (3-mercaptomethylphenyl) pyridine, 3- (3-mercaptomethylphenyl) Pyridine,
4- (3-mercaptomethylphenyl) pyridine, 2-
[3- (2-mercaptoethyl) phenyl] pyridine,
3- [3- (2-mercaptoethyl) phenyl] pyridine, 4- [3- (2-mercaptoethyl) phenyl] pyridine, 2- (2-mercaptomethylphenyl) pyridine, 3- (2-mercaptomethylphenyl) Pyridine,
4- (2-mercaptomethylphenyl) pyridine, 2-
[2- (2-mercaptoethyl) phenyl] pyridine,
3- [2- (2-mercaptoethyl) phenyl] pyridine, 4- [2- (2-mercaptoethyl) phenyl] pyridine and the like.
【００１０】該メルカプトアミン化合物の合成方法とし
ては、例えば、ビニルフェニル基で置換されたピリジン
体を、置換シリルチオールと反応させてシリルチオール
エーテルとした後、シリル基を脱離させる事等により合
成することができる。強酸性スルホン酸型イオン交換樹
脂としては、特に限定されるものではないが、スルホン
化されたスチレン−ジビニルベンゼン共重合体からなる
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、水含有状態で０．５〜２．
５ｍｅｑ／ｍｌのものが、乾燥樹脂では３．０〜７．０
ｍｅｑ／ｇのものが好ましい。イオン交換樹脂の粒径分
布は、２００〜１５００μｍの粒径の樹脂が９５％以上
含まれるようなものが好ましい。具体的には、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、ＳＫ１０２、Ｓ
Ｋ１０４、ＰＫ２０８、ＰＫ２１２、ＲＣＰ１６０Ｈ、
ＲＣＰ１７０Ｈ（三菱化学社製商品名）なとが例示でき
る。これらのイオン交換樹脂は酸型で使用する。ナトリ
ウム型の場合は、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。The mercaptoamine compound is synthesized, for example, by reacting a pyridine compound substituted with a vinylphenyl group with a substituted silylthiol to form a silylthiol ether, and then removing the silyl group. can do. The strongly acidic sulfonic acid type ion exchange resin is not particularly limited, but a strongly acidic ion exchange resin composed of a sulfonated styrene-divinylbenzene copolymer is preferable, and a divinylbenzene unit in the copolymer is preferably used. The content is preferably 2 to 40%. The exchange capacity of the ion exchange resin is 0.5-2.
5 meq / ml is 3.0 to 7.0 for dry resin.
Meq / g is preferred. The particle size distribution of the ion exchange resin is preferably such that the resin having a particle size of 200 to 1500 μm is contained in 95% or more. Specifically, for example,
Amberlist 15, 31, 32 (trade name, manufactured by Rohm & Haas), Dowex 50w, 88 (trade name, manufactured by Dow Chemical Company), Diaion SK1B, SK102, S
K104, PK208, PK212, RCP160H,
RCP170H (trade name, manufactured by Mitsubishi Chemical Corporation) can be exemplified. These ion exchange resins are used in the acid form. In the case of the sodium type, the acid type treated with an acid such as hydrochloric acid is used. These ion exchange resins are commercially available containing water, but can be used as they are without special treatment such as dehydration.
【００１１】強酸性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、まず同アミン
化合物を溶解する溶媒、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、あらかじめ同
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時間撹拌することによりな
される。例えば水溶媒中で結合する方法としては、同ア
ミンをスルホン酸よりｐｋａ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、
それぞれの塩とした水溶液を、予め水に分散させた強酸
性イオン交換樹脂中に加え、０．１〜１０時間撹拌する
方法等が可能である。In order to bond a mercaptoamine compound to a sulfonic acid group of a strongly acidic ion exchange resin, first, the amine compound is dissolved in a solvent in which the amine compound is dissolved, for example, water, alcohols, ethers, etc. This is performed by adding to the strongly acidic ion exchange resin dispersed in the same solvent and stirring for an appropriate time, for example, 0.1 to 10 hours. For example, as a method of binding in an aqueous solvent, an acid having a higher pka than the sulfonic acid, such as acetic acid, is used.
In addition to aqueous solutions such as trifluoroacetic acid and monochloroacetic acid,
For example, a method of adding the aqueous solution of each salt to a strongly acidic ion exchange resin dispersed in water in advance and stirring for 0.1 to 10 hours is possible.
【００１２】強酸性イオン交換樹脂に対する、メルカプ
トアミン化合物の使用量は、通常、強酸性イオン交換樹
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％以
下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％以上ではスルホン酸量の減少によ
って触媒活性が低下するおそれがあるため好ましくな
い。本発明のメルカプトアミン化合物がイオン結合した
強酸性イオン交換樹脂は、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、ならびに選択性を
示す。The amount of the mercaptoamine compound to be used for the strongly acidic ion exchange resin is usually 2 to 30 mol%, preferably 5 to 20 mol%, based on all the sulfonic acid groups of the strongly acidic ion exchange resin. If the amount of ionic bonds is 2 mol% or less, the catalytic effect of the mercaptoamine compound is not sufficiently exhibited, and if it is 30% or more, the catalytic activity may be reduced due to the decrease in the amount of sulfonic acid, which is not preferable. The strongly acidic ion-exchange resin to which the mercaptoamine compound of the present invention is ion-bonded, when applied to a method of forming the corresponding bisphenol by a condensation reaction of phenols and ketones, is much more expensive than a conventionally known amine compound. Shows high acetone conversion and selectivity.
【００１３】本発明のメルカプトアミン化合物がイオン
結合した強酸性イオン交換樹脂（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
（ＬＨＳＶ）０．５〜５０ｈｒ-1で通液し、さらに変性
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は水からフェノールへ溶媒交換
され、反応に使用できるようになる。When a strongly acidic ion exchange resin (hereinafter, abbreviated as a modified resin) to which a mercaptoamine compound of the present invention is ion-bonded is used for the condensation reaction of acetone and phenol, a pretreatment of 5 times the volume of the modified resin is performed. ~ 200-fold ion-exchanged water is passed through at a temperature of 20-80 ° C at a liquid hourly space velocity (LHSV) of 0.5-50 hr -1 , and phenol having a volume of 5-200 times the volume of the modified resin is passed through 40- 110
The solution is passed at a temperature of ° C and an LHSV of 0.5 to 50 hr -1 .
By this treatment, the modified resin is solvent-exchanged from water to phenol, and can be used for the reaction.
【００１４】本反応は通常、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６０〜１００℃の範囲で
ある。反応温度が４０℃以下では反応速度が遅く、また
１２０℃以上の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 a modified resin to carry out the reaction.
The supply of the raw material mixture is performed at an LHSV of 0.1 to 20 hr -1 , preferably 0.5 to 10 hr -1 . The reaction temperature ranges from 40 to 120C, preferably from 60 to 100C. When the reaction temperature is 40 ° C. or lower, the reaction rate is low, and when the reaction temperature is 120 ° C. or higher, the denaturation of the denatured resin is remarkably deteriorated and the by-products are increased, which is not preferable.
【００１５】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
モル以下だと、副生成物が増加するため好ましくなく、
３０モル以上使用してもその効果にほとんど影響はな
く、むしろ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とフェノールのアダク
トを結晶として分離、蒸留等の操作でアダクトからフェ
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 is in the range of 3 to 30 moles, preferably 5 to 20 moles of phenol per mole of acetone. 3 phenols used
If it is less than mol, by-products increase, which is not preferable,
Even if it is used in an amount of 30 mol or more, the effect is hardly affected, and it is not economical because the amount of phenol to be recovered and reused increases. In order to separate and purify bisphenol A as a target substance from the reaction mixture, for example, a known method of collecting unreacted phenol, separating an adduct of bisphenol A and phenol as crystals, and collecting phenol from the adduct by an operation such as distillation. Can be done with
【００１６】[0016]
【実施例】次に、実施例および比較例により本発明をさ
らに具体的に説明する。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）選択率、変性率およびスルホン酸
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. The conversion of acetone in Examples and Comparative Examples was 4,4'-bisphenol A (4,4).
The selectivity, denaturation rate and residual sulfonic acid ratio were calculated by the following formulas (all units are%).
【００１７】[0017]
【数１】 (Equation 1)
【００１８】実施例１２−（４−メルカプトメチルフェニル）ピリジンイオン
交換樹脂 ５００ｍｌ三つ口フラスコに２−（ｐ−トリル）ピリジ
ン（東京化成社製）１１．２ｇ、Ｎ−ブロモこはく酸イ
ミド１２．３ｇ、クロロホルム２００ｍｌを仕込み、赤
外ランプで３時間加熱還流した。クロロホルムを留去
し、粗生成物をシリカゲルクロマトグラフィーで分離精
製し、２−（４−ブロモメチルフェニル）ピリジン６．
４８ｇを得た。この臭化物５．４８ｇを、５００ｍｌナ
ス型フラスコ中でＴＨＦ３５０ｍｌに溶解し、チオ酢酸
カリウム２．７９ｇを加え、４０℃で２時間撹拌した。
氷冷下で１Ｎ水酸化ナトリウム溶液３５０ｍｌを加え酢
酸エチル３００ｍｌで抽出した。酢酸エチル層を硫酸マ
グネシウムで乾燥した後、溶媒留去し、残留物をシリカ
ゲルクロマトグラフィー（展開溶媒 酢酸エチル：ヘキ
サン＝１：１０）により分離し２−（４−アセチルチオ
メチルフェニル）ピリジン３．４ｇを得た。Example 1 2- (4-mercaptomethylphenyl) pyridine ion
To a 500 ml exchange resin three-necked flask were charged 11.2 g of 2- (p-tolyl) pyridine (manufactured by Tokyo Chemical Industry Co., Ltd.), 12.3 g of N-bromosuccinimide, and 200 ml of chloroform, and the mixture was heated and refluxed with an infrared lamp for 3 hours. . Chloroform was distilled off, and the crude product was separated and purified by silica gel chromatography, and 2- (4-bromomethylphenyl) pyridine was added.
48 g were obtained. 5.48 g of this bromide was dissolved in 350 ml of THF in a 500 ml eggplant type flask, 2.79 g of potassium thioacetate was added, and the mixture was stirred at 40 ° C. for 2 hours.
Under ice cooling, 350 ml of a 1N sodium hydroxide solution was added, and the mixture was extracted with 300 ml of ethyl acetate. After the ethyl acetate layer was dried over magnesium sulfate, the solvent was distilled off, and the residue was separated by silica gel chromatography (developing solvent: ethyl acetate: hexane = 1: 10) to give 2- (4-acetylthiomethylphenyl) pyridine. 4 g were obtained.
【００１９】１００ｍｌ三つ口フラスコに無水ジエチル
エーテル３０ｍｌと水素化アルミニウムリチウム０．３
１ｇを窒素気流下で仕込み、室温撹拌下、上記のチオア
セテート１．６５ｇの無水ジエチルエーテル２０ｍｌ溶
液を滴下した。１時間加熱還流した後、氷冷し、蒸留水
０．１６ｇ、酢酸０．５５ｇ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、溶媒留去する事により２−（４−メルカプ
トメチルフェニル）ピリジン１．２１ｇが得られた。
（ガスクロマトグラフィーによる純度９９．２％）In a 100 ml three-necked flask, 30 ml of anhydrous diethyl ether and 0.3 ml of lithium aluminum hydride were placed.
1 g was charged under a nitrogen stream, and a solution of 1.65 g of the above thioacetate in 20 ml of anhydrous diethyl ether was added dropwise with stirring at room temperature. After heating under reflux for 1 hour, the mixture was ice-cooled, and 0.16 g of distilled water and 0.55 g of acetic acid were added. Filter inorganic matter,
The organic layer washed with ethyl acetate was dried over anhydrous magnesium sulfate, and the solvent was distilled off, thereby obtaining 1.21 g of 2- (4-mercaptomethylphenyl) pyridine.
(Purity by gas chromatography: 99.2%)
【００２０】２−（４−メルカプトメチルフェニル）ピ
リジン１．２１ｇをメタノール３０ｍｌに溶解し、メタ
ノール３０ｍｌに懸濁させたダイヤイオンＫ１０４（Ｈ
型）２０．０ｇ（商品名：三菱化学社製、交換容量１．
６３ｍｅｑ／ｇ）へ加え、室温で１０時間撹拌した。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。メルカプト基およびスルホン酸の
残存量を分析したところ、変性率は１４．８％であり、
スルホン酸残存率は８６．８％であった。1.21 g of 2- (4-mercaptomethylphenyl) pyridine was dissolved in 30 ml of methanol, and Diaion K104 (H2) suspended in 30 ml of methanol was dissolved.
(Type) 20.0 g (trade name: manufactured by Mitsubishi Chemical Corporation, exchange capacity 1.
63meq / g) and 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 mercapto groups and sulfonic acids were analyzed, the modification rate was 14.8%,
The residual ratio of sulfonic acid was 86.8%.
【００２１】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ＬＨＳＶ２ｈｒ-1で流
し、その後７０℃でフェノールをＬＨＳＶ２ｈｒ-1で２
４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９４．９％、４，４′−ＢＰＡの選択率は９４．８
％であり、３００時間後のアセトンの転化率は９４．５
％、４，４′−ＢＰＡの選択率は９４．４％であった。[0021] The modified ion exchange resin 14ml inner diameter 7.6 mm, was packed into a stainless column of full length 320 mm, the ion-exchanged water 200ml flushed with LHSV2hr -1, thereafter LHSV2hr -1 phenol at 70 ° C. 2
Run for 4 hours. Next, phenol / acetone = 10/1
The mixture (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 94.9%, and the selectivity of 4,4'-BPA was 94.8.
%, And the conversion of acetone after 300 hours was 94.5.
%, Selectivity for 4,4'-BPA was 94.4%.
【００２２】実施例２４−（４−メルカプトメチルフェニル）ピリジンイオン
交換樹脂 実施例１で使用した２−（ｐ−トリル）ピリジンの代わ
りに、４−（ｐ−トリル）ピリジンを次に示す方法で合
成した。２００ｍｌ三つ口フラスコに、マグネシウム
２．６７ｇ、エーテル８０ｍｌを仕込み、４−メチルブ
ロモベンゼン１７．１ｇのエーテル２０ｍｌ溶液を滴下
した。発熱し、４−メチルマグネシウムブロマイドが生
成した。上澄み液を１００ｍｌ滴下管に移した。３００
ｍｌの三つ口フラスコに塩化亜鉛１３．６ｇとＴＨＦ５
０ｍｌを仕込み、２００℃で２時間加熱し、乾燥させパ
ウダー状としたものに、窒素気流下、上記の４−メチル
マグネシウムブロマイドのＴＨＦ溶液を室温で滴下し、
４−メチルチンクロライドとした。Example 2 4- (4-mercaptomethylphenyl) pyridine ion
Exchange resin In place of 2- (p-tolyl) pyridine used in Example 1, 4- (p-tolyl) pyridine was synthesized by the following method. 2.67 g of magnesium and 80 ml of ether were charged into a 200 ml three-necked flask, and a solution of 17.1 g of 4-methylbromobenzene in 20 ml of ether was added dropwise. An exotherm occurred, producing 4-methylmagnesium bromide. The supernatant was transferred to a 100 ml dropping tube. 300
13.6 g of zinc chloride and THF5
0 ml, heated at 200 ° C. for 2 hours, dried and powdered, the above-mentioned THF solution of 4-methylmagnesium bromide was dropped at room temperature under a nitrogen stream,
This was 4-methyltin chloride.
【００２３】５００ｍｌ三つ口フラスコに窒素気流下、
４−ブロモピリジン７．９ｇとＴＨＦ５０ｍ、テトラト
リフェニルホスフィンパラジウム１．１６ｇを仕込み、
上記で調整した４−メチルチンクロライドを滴下し、５
時間室温で撹拌した。反応後ＴＨＦを留去し、蒸留水１
５０ｍｌと、塩化ナトリウム３５ｇを加えクロロホルム
３００ｍｌで抽出した。有機層を無水硫酸マグネシウム
で乾燥し、クロロホルムを留去した後、残留物をシリカ
ゲルカラムクロマトグラフィー（展開溶媒クロロホル
ム：ヘキサン＝９：１）で分離精製し、４−（ｐ−トリ
ル）ピリジン５．７ｇを得た。この４−（ｐ−トリル）
ピリジン用い、実施例１と同様に反応を行い、４−（４
−ブロモメチルフェニル）ピリジンを得た。同じくチオ
酢酸カリウムによるチオアセチル化、水素化リチウムア
ルミニウムによる還元を行い、４−（４−メルカプトメ
チルフェニル）ピリジンを得た。Under a nitrogen stream in a 500 ml three-necked flask,
7.9 g of 4-bromopyridine, 50 m of THF and 1.16 g of tetratriphenylphosphine palladium were charged,
4-methyltin chloride prepared above was added dropwise, and 5
Stirred at room temperature for hours. After the reaction, THF was distilled off, and distilled water 1
50 ml and 35 g of sodium chloride were added, and extracted with 300 ml of chloroform. The organic layer was dried over anhydrous magnesium sulfate, chloroform was distilled off, and the residue was separated and purified by silica gel column chromatography (developing solvent: chloroform: hexane = 9: 1) to give 4- (p-tolyl) pyridine. 7 g were obtained. This 4- (p-tolyl)
Using pyridine, the reaction was carried out in the same manner as in Example 1, and 4- (4
-Bromomethylphenyl) pyridine was obtained. Similarly, thioacetylation with potassium thioacetate and reduction with lithium aluminum hydride were performed to obtain 4- (4-mercaptomethylphenyl) pyridine.
【００２４】４−（４−メルカプトメチルフェニル）ピ
リジン１．２１ｇをメタノール３０ｍｌに溶解し、メタ
ノール３０ｍｌに懸濁させたダイヤイオンＫ１０４（Ｈ
型）２０．０ｇ（商品名：三菱化学社製、交換容量１．
６３ｍｅｑ／ｇ）へ加え、室温で１０時間撹拌した。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。メルカプト基およびスルホン酸の
残存量を分析したところ、変性率は１４．４％であり、
スルホン酸残存率は８６．７％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−１、２に示
す。1.21 g of 4- (4-mercaptomethylphenyl) pyridine was dissolved in 30 ml of methanol, and Diaion K104 (H
(Type) 20.0 g (trade name: manufactured by Mitsubishi Chemical Corporation, exchange capacity 1.
63meq / g) and 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 mercapto groups and sulfonic acids were analyzed, the modification rate was 14.4%,
The residual ratio of sulfonic acid was 86.7%. Using this modified resin, the reaction was evaluated under the same conditions as in the examples. Tables 1 and 2 show the reaction results for 40 hours and 300 hours after the start of the reaction.
【００２５】実施例３４−〔４−（２−メルカプトエチル）フェニル〕ピリジ
ンイオン交換樹脂 １００ｍｌ三つ口フラスコに、マグネシウム１．６０
ｇ、ＴＨＦ５０ｍｌを仕込み、４−ビニルブロモベンゼ
ン１０．９８ｇのＴＨＦ５０ｍｌ溶液を滴下した。発熱
し、４−ビニルマグネシウムブロマイドが生成した。上
澄み液を１００ｍｌ滴下管に移した。３００ｍｌの三つ
口フラスコに塩化亜鉛８．７２ｇとＴＨＦ５０ｍｌを仕
込み、２００℃で２時間加熱し、乾燥させパウダー状と
したものに、窒素気流下、上記の４−ビニルマグネシウ
ムブロマイドのＴＨＦ溶液を室温で滴下し、４−ビニル
チンクロライドとした。Example 3 4- [4- (2-Mercaptoethyl) phenyl] pyridi
To N'ion exchange resin 100ml three-necked flask, magnesium 1.60
g of THF and 50 ml of THF were added, and a solution of 10.98 g of 4-vinylbromobenzene in 50 ml of THF was added dropwise. An exotherm occurred, producing 4-vinylmagnesium bromide. The supernatant was transferred to a 100 ml dropping tube. 8.72 g of zinc chloride and 50 ml of THF were charged into a 300 ml three-necked flask, heated at 200 ° C. for 2 hours, dried and powdered, and the above-mentioned THF solution of 4-vinylmagnesium bromide was cooled to room temperature under a nitrogen stream. To give 4-vinyltin chloride.
【００２６】５００ｍｌ三つ口フラスコに窒素気流下、
４−ブロモピリジン６．３２ｇとＴＨＦ５０ｍ、テトラ
トリフェニルホスフィンパラジウム０．９２ｇを仕込
み、上記で調整した４−ビニルチンクロライドを滴下
し、１０時間室温で撹拌した。反応後ＴＨＦを留去し、
蒸留水１５０ｍｌと、塩化ナトリウム２５ｇを加えクロ
ロホルム３００ｍｌで抽出した。有機層を無水硫酸マグ
ネシウムで乾燥し、クロロホルムを留去した後、残留物
をシリカゲルカラムクロマトグラフィー（展開溶媒クロ
ロホルム：酢酸エチル＝４：１）で分離精製し、４−
（４−ビニルフェニル）ピリジン４．７ｇを得た。In a 500 ml three-necked flask, under a nitrogen stream,
6.32 g of 4-bromopyridine, 50 m of THF and 0.92 g of tetratriphenylphosphine palladium were charged, and the above-prepared 4-vinyltin chloride was added dropwise, followed by stirring at room temperature for 10 hours. After the reaction, THF was distilled off.
150 ml of distilled water and 25 g of sodium chloride were added, and extracted with 300 ml of chloroform. The organic layer was dried over anhydrous magnesium sulfate, chloroform was distilled off, and the residue was separated and purified by silica gel column chromatography (developing solvent: chloroform: ethyl acetate = 4: 1).
4.7 g of (4-vinylphenyl) pyridine were obtained.
【００２７】４−〔４−（２−ビニル）フェニル〕ピリ
ジン２．５ｇ、トリフェニルシリルチオール４．８４
ｇ、ベンゼン７０ｍｌを仕込み、２，２′−アゾビス
（イソブチルニトリル）０．６８ｇを添加し、窒素気流
下、３時間加熱還流した。溶媒を留去した後、シリカゲ
ルクロマトグラフィーで分離し、（展開溶媒酢酸エチ
ル：ヘキサン＝１：４）４−〔４−（２−トリフェニル
シリルチオエチル）フェニル〕ピリジン３．４ｇ（ガス
クロマトグラフィー純度９９％）を得た。2.5 g of 4- [4- (2-vinyl) phenyl] pyridine, 4.84 of triphenylsilylthiol
g, 70 ml of benzene, and 0.68 g of 2,2'-azobis (isobutylnitrile) were added, and the mixture was heated and refluxed for 3 hours in a nitrogen stream. After evaporating the solvent, the residue was separated by silica gel chromatography, and 3.4 g of (developing solvent: ethyl acetate: hexane = 1: 4) 4- [4- (2-triphenylsilylthioethyl) phenyl] pyridine (gas chromatography) was used. Purity 99%).
【００２８】５００ｍｌナスフラスコに４−〔４−（２
−トリフェニルシリルチオエチル）フェニル〕ピリジン
３．４ｇとクロロホルム２００ｍｌ、メタノール１００
ｍｌを加え、４０℃で２時間加熱撹拌した。クロロホル
ムとメタノールを留去した後、残留物をシリカゲルクロ
マトグラフィー（展開溶媒 酢酸エチル：クロロホルム
＝１：１０）により分離精製して、４−〔４−（２−メ
ルカプトエチル）フェニル〕ピリジン１．４９ｇを得
た。In a 500 ml eggplant flask, 4- [4- (2
-Triphenylsilylthioethyl) phenyl] pyridine 3.4 g, chloroform 200 ml, methanol 100
Then, the mixture was heated and stirred at 40 ° C. for 2 hours. After distilling off chloroform and methanol, the residue was separated and purified by silica gel chromatography (developing solvent: ethyl acetate: chloroform = 1: 10) to give 1.49 g of 4- [4- (2-mercaptoethyl) phenyl] pyridine. I got
【００２９】４−〔４−（２−メルカプトエチル）フェ
ニル〕ピリジン１．４９ｇをメタノール３０ｍｌに溶解
し、メタノール３０ｍｌに懸濁させたダイヤイオンＫ１
０４（Ｈ型）２３．０ｇ（商品名：三菱化学社製、交換
容量１．６３ｍｅｑ／ｇ）へ加え、室温で１０時間撹拌
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。メルカプト基およびス
ルホン酸の残存量を分析したところ、変性率は１３．３
％であり、スルホン酸残存率は８３．９％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−
１、２に示す。1.49 g of 4- [4- (2-mercaptoethyl) phenyl] pyridine was dissolved in 30 ml of methanol, and Diaion K1 was suspended in 30 ml of methanol.
04 (H type) 23.0 g (trade name: manufactured by Mitsubishi Chemical Corporation, exchange capacity 1.63 meq / g), 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 mercapto groups and sulfonic acids were analyzed, the modification rate was 13.3.
%, And the sulfonic acid residual ratio was 83.9%. Using this modified resin, the reaction was evaluated under the same conditions as in the examples. The reaction results at 40 hours and 300 hours after the start of the reaction are shown in the table.
1 and 2.
【００３０】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）
（商品名）３０．０ｇへ加え、室温で１時間撹拌した。
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。メルカプト基およびスルホン酸
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−１、２
に示す。Comparative Example 1 2-aminoethanethiol-modified ion-exchange resin 0.58 g of commercially available 2-aminoethanethiol and 0.1% 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
(Trade name) was added to 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. Tables 1 and 2 show the reaction results at 40 hours and 300 hours after the start of the reaction.
Shown in
【００３１】比較例２４−〔４−（２−メルカプトエチル）フェニル〕−Ｎ，
Ｎ−ジメチルアニリン交換樹脂 １００ｍｌ三つ口フラスコに、マグネシウム１．６０
ｇ、ＴＨＦ５０ｍｌを仕込み、４−ビニルブロモベンゼ
ン１０．９８ｇのＴＨＦ５０ｍｌ溶液を滴下した。発熱
し、４−ビニルマグネシウムブロマイドが生成した。上
澄み液を１００ｍｌ滴下管に移した。３００ｍｌの三つ
口フラスコに塩化亜鉛８．７２ｇとＴＨＦ５０ｍｌを仕
込み、２００℃で２時間加熱し、乾燥させパウダー状と
したものに、窒素気流下、上記の４−ビニルマグネシウ
ムブロマイドのＴＨＦ溶液を室温で滴下し、４−ビニル
チンクロライドとした。Comparative Example 2 4- [4- (2-mercaptoethyl) phenyl] -N,
In a 100 ml N-dimethylaniline exchange resin 100 ml three-necked flask, magnesium 1.60 was added.
g of THF and 50 ml of THF were added, and a solution of 10.98 g of 4-vinylbromobenzene in 50 ml of THF was added dropwise. An exotherm occurred, producing 4-vinylmagnesium bromide. The supernatant was transferred to a 100 ml dropping tube. 8.72 g of zinc chloride and 50 ml of THF were charged into a 300 ml three-necked flask, heated at 200 ° C. for 2 hours, dried and powdered, and the above-mentioned THF solution of 4-vinylmagnesium bromide was cooled to room temperature under a nitrogen stream. To give 4-vinyltin chloride.
【００３２】５００ｍｌ三つ口フラスコに窒素気流下、
４−ブロモピリジン６．３２ｇとＴＨＦ５０ｍ、テトラ
トリフェニルホスフィンパラジウム０．９２ｇを仕込
み、上記で調整した４−ビニルチンクロライドを滴下
し、１０時間室温で撹拌した。反応後ＴＨＦを留去し、
残留水１００ｍｌと、塩化ナトリウム２５ｇを加えクロ
ロホルム３００ｍｌで抽出した。有機層を無水硫酸マグ
ネシウムで乾燥し、クロロホルムを留去した後、残留物
をシリカゲルカラムクロマトグラフィー（展開溶媒ヘキ
サン：クロロホルム＝７：３）で分離精製し、４−（４
−ビニルフェニル）−Ｎ，Ｎ−ジメチルアニリン５．７
ｇを得た。In a 500 ml three-necked flask, under a nitrogen stream,
6.32 g of 4-bromopyridine, 50 m of THF and 0.92 g of tetratriphenylphosphine palladium were charged, and the above-prepared 4-vinyltin chloride was added dropwise, followed by stirring at room temperature for 10 hours. After the reaction, THF was distilled off.
100 ml of residual water and 25 g of sodium chloride were added, and the mixture was extracted with 300 ml of chloroform. The organic layer was dried over anhydrous magnesium sulfate, chloroform was distilled off, and the residue was separated and purified by silica gel column chromatography (developing solvent: hexane: chloroform = 7: 3) to give 4- (4
-Vinylphenyl) -N, N-dimethylaniline 5.7
g was obtained.
【００３３】１００ｍｌ三つ口フラスコに４−（４−ビ
ニルフェニル）−Ｎ，Ｎ−ジメチルアニリン３．９１
ｇ、トリフェニルシランチオール２０．１ｇ、ベンゼン
３５ｍｌを仕込み、２，２′−アゾビス（イソブチルニ
トリル）０．８６ｇを添加し、窒素気流下、２時間加熱
還流した。溶媒を留去した後、残留物をシリカゲルクロ
マトグラフィー（展開溶媒 クロロホルム：ヘキサン＝
４：１）で分離精製し、４−〔４−（２−トリフェニル
シリルチオエチル）フェニル〕−Ｎ，Ｎ−ジメチルアニ
リン３．３ｇ（ガスクロマトグラフィー純度９９％）を
得た。In a 100 ml three-necked flask, 4- (4-vinylphenyl) -N, N-dimethylaniline 3.91
g, 20.1 g of triphenylsilanethiol and 35 ml of benzene, 0.86 g of 2,2'-azobis (isobutylnitrile) was added, and the mixture was heated and refluxed for 2 hours under a nitrogen stream. After the solvent was distilled off, the residue was subjected to silica gel chromatography (developing solvent: chloroform: hexane =
4: 1) to give 3.3 g of 4- [4- (2-triphenylsilylthioethyl) phenyl] -N, N-dimethylaniline (purity: 99% by gas chromatography).
【００３４】１００ｍｌ三つ口フラスコに４−〔４−
（２−トリフェニルシリルチオエチル）フェニル〕−
Ｎ，Ｎ−ジメチルアニリン３．３ｇをクロロホルム７０
ｍｌに溶解し、トリフルオロ酢酸８．６ｇを加えて室温
で３時間撹拌した。反応溶液に１Ｎ水酸化ナトリウム溶
液１２０ｍｌを加え、分液した。有機層を硫酸マグネシ
ウムで乾燥し、クロロホルムを留去した後、残留物をシ
リカゲルクロマトグラフィー（展開溶媒 クロロホル
ム）により分離精製して、４−〔４−（２−メルカプト
エチル）フェニル〕−Ｎ，Ｎ−ジメチルアニリン１．６
１ｇを得た。In a 100 ml three-necked flask, 4- [4-
(2-triphenylsilylthioethyl) phenyl]-
3.3 g of N, N-dimethylaniline in chloroform 70
Then, 8.6 g of trifluoroacetic acid was added, and the mixture was stirred at room temperature for 3 hours. 120 ml of a 1N sodium hydroxide solution was added to the reaction solution, and the mixture was separated. The organic layer was dried over magnesium sulfate, chloroform was distilled off, and the residue was separated and purified by silica gel chromatography (developing solvent: chloroform) to give 4- [4- (2-mercaptoethyl) phenyl] -N, N -Dimethylaniline 1.6
1 g was obtained.
【００３５】４−〔４−（２−メルカプトエチル）フェ
ニル〕−Ｎ，Ｎ−ジメチルアニリン１．５１ｇをメタノ
ール３０ｍｌに溶解し、メタノール３０ｍｌに懸濁させ
たダイヤイオンＫ１０４（Ｈ型）２１．０ｇ（商品名：
三菱化学社製、交換容量１．６３ｍｅｑ／ｇ）へ加え、
室温で１０時間撹拌した。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
カプト基およびスルホン酸の残存量を分析したところ、
変性率は１１．４％であり、スルホン酸残存率は８８．
６％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−１、２に示す。1.51 g of 4- [4- (2-mercaptoethyl) phenyl] -N, N-dimethylaniline was dissolved in 30 ml of methanol, and 21.0 g of Diaion K104 (H type) suspended in 30 ml of methanol. (Product name:
In addition to the exchange capacity 1.63 meq / g manufactured by Mitsubishi Chemical Corporation,
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 mercapto groups and sulfonic acids were analyzed,
The modification ratio was 11.4%, and the residual ratio of sulfonic acid was 88.
6%. Using this modified resin, the reaction was evaluated under the same conditions as in the examples. Tables 1 and 2 show the reaction results for 40 hours and 300 hours after the start of the reaction.
【００３６】[0036]
【表１】 [Table 1]
【００３７】[0037]
【表２】 [Table 2]
【００３８】[0038]
【発明の効果】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
の反応結果を表に示した。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および高い４，４′−ビスフェノー
ルＡ選択率で、か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。Using this modified resin, the reaction was evaluated under the same conditions as in the examples. The results of the reaction for 40 hours and 300 hours after the start of the reaction are shown in the table. If the ion exchange resin of the present invention 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 (72)発明者 鯨 勝文 茨城県稲敷郡阿見町中央８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８丁目３番１号 三菱化学株式会社筑波研究所内 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Katsufumi Whale 8-3-1 Chuo, Ami-cho, Inashiki-gun, Ibaraki Prefecture Inside Tsukuba Research Laboratory, Mitsubishi Chemical Corporation (72) Inventor Hiroshi Iwane 8-Chome, Ami-cho, Inashiki-gun, Ibaraki Prefecture No.3-1 Inside the Tsukuba Research Laboratory, Mitsubishi Chemical Corporation
Claims (5)
れ独立に水素、炭素数１〜６のアルキル基、炭素数６〜
１２のアリール基、または炭素数５〜１０のシクロアル
キル基を表す）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いる
変性強酸性スルホン酸型イオン交換樹脂。[Claim 1] The following general formula: (In the formula, n is an integer of 1 to 4, X and Y are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms,
A modified strong acid sulfonic acid type ion exchange resin in which a mercaptoamine compound represented by the following formula: represents an aryl group having 12 or a cycloalkyl group having 5 to 10 carbon atoms).
の量が、スルホン酸基の２〜３０モル％である請求項１
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 as described.
ベンゼン共重合体からなる骨格を有することを特徴とす
る請求項１または２に記載のイオン交換樹脂。3. The ion exchange resin according to claim 1, wherein the ion exchange resin has a skeleton composed of a styrene-divinylbenzene copolymer.
酸型イオン交換樹脂の存在下、フェノール類とケトン類
を縮合することを特徴とするビスフェノールの製造方
法。4. A method for producing bisphenol, comprising condensing a phenol and a ketone 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記載のビスフェノールの製造方法。5. The method according to claim 4, wherein the phenol is an unsubstituted phenol and the ketone is acetone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13979897A JP3826489B2 (en) | 1997-05-29 | 1997-05-29 | Ion exchange resin and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13979897A JP3826489B2 (en) | 1997-05-29 | 1997-05-29 | Ion exchange resin and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10328573A true JPH10328573A (en) | 1998-12-15 |
| JP3826489B2 JP3826489B2 (en) | 2006-09-27 |
Family
ID=15253686
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13979897A Expired - Lifetime JP3826489B2 (en) | 1997-05-29 | 1997-05-29 | Ion exchange resin and use thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3826489B2 (en) |
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