JPH10211433A - Ion exchange resin and manufacture of bisphenol using this resin - Google Patents
Ion exchange resin and manufacture of bisphenol using this resinInfo
- Publication number
- JPH10211433A JPH10211433A JP9015212A JP1521297A JPH10211433A JP H10211433 A JPH10211433 A JP H10211433A JP 9015212 A JP9015212 A JP 9015212A JP 1521297 A JP1521297 A JP 1521297A JP H10211433 A JPH10211433 A JP H10211433A
- Authority
- JP
- Japan
- Prior art keywords
- sulfonic acid
- exchange resin
- ion exchange
- strongly acidic
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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、
ビスフェノール、例えばフェノールとアセトンとの縮合
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 for producing bisphenol A by a condensation reaction of bisphenol, for example, 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との縮合反応によ
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メルカプト基を有する
化合物を併用する方法が種々提案されている。例えば強
酸性スルホン酸型イオン交換樹脂を触媒とし、さらに反
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、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
を強酸性スルホン酸型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５６−２１６
５０号、特開昭５７−８７８４６号、特開昭５９−１０
９５０３号公報等）、メルカプト基を有するアミンを強
酸性スルホン酸型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。これらの中で、メルカプト基を有
するアミン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は、触媒調製が容易であ
り、かつメルカプト基を有するアミンは生成物中に混入
しないので、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。2. Description of the Related Art Various methods have been proposed in which a strongly acidic sulfonic acid type ion exchange resin and a compound having a mercapto group are used in combination as a catalyst for producing bisphenol A by a condensation reaction of phenol and acetone. For example, a method using a strongly acidic sulfonic acid type ion exchange resin as a catalyst and coexisting a compound having a mercapto group in the 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 sulfonic acid type ion exchange resin (JP-B-37-14721, JP-A-56-216).
No. 50, JP-A-57-87846, JP-A-59-10
No. 9503) and a method of ion-bonding an amine having a mercapto group to a strongly acidic sulfonic acid type ion exchange resin. Among them, the method using a modified strong acidic sulfonic acid type ion exchange resin in which an amine having a mercapto group is ion-bonded is easy in catalyst preparation, and an amine having a mercapto group is not mixed into a product. Therefore, the 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.
【０００３】メルカプト基を有するアミンをイオン結合
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
４６−１９９５３号、特許２５２８４６９号公報）、Ｎ
−プロピルメルカプトアルキルアミン（特公平３−３６
５７６号公報）、Ｎ，Ｎ−ジアルキルメルカプトアルキ
ルアミン等（チェコスロバキア国特許２１９４３２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
用いる方法が知られている。しかしながら、いずれの方
法も、アセトン転化率は５０〜７５％程度という低い反
応成績しか与えないという欠点があった。As a method of using a modified strong acidic sulfonic acid type ion exchange resin in which an amine having a mercapto group is ion-bonded, 2-mercaptoethylamine (Japanese Patent Publication No. 46-19553, Japanese Patent No. 2528469), N
-Propylmercaptoalkylamine (JP-B-3-36)
No. 576), and a method using a modified strongly acidic sulfonic acid type ion exchange resin in which N, N-dialkylmercaptoalkylamine or the like (Czechoslovak Patent 219432) is ion-bonded. As a method of using a denatured strongly acidic sulfonic acid type ion exchange resin in which a quaternary ammonium salt is ion-bonded, N, N, N-
Trimethyl-2-mercaptoethylammonium, N-
(2-hydroxyl-3-mercaptopropyl) pyridinium, N-methyl-N- (2-hydroxyl-3-mercaptopropyl) morpholium and N-benzyl-
There is known a method of using a modified strongly acidic sulfonic acid type ion exchange resin to which N, N-dimethyl-2-mercaptoethylammonium (Czechoslovak Patent 184988) is ion-bonded. However, both methods have a drawback that the conversion of acetone gives only a low reaction result of about 50 to 75%.
【０００４】[0004]
【発明が解決しようとする課題】本発明はフェノール類
とケトン類とからのビスフェノールの製造に好適な触媒
として有用な、特に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を製造するに際し、高いアセトン
転化率と良好な選択性を示し、かつ長期安定性を有す
る、変性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 The present invention is useful as a catalyst suitable for the production of bisphenol from phenols and ketones. Particularly, when producing bisphenol A by the condensation reaction of acetone and phenol, a high conversion of acetone is obtained. It is an object of the present invention to provide a modified strongly acidic sulfonic acid type ion exchange resin having excellent selectivity and long-term stability.
【０００５】[0005]
【課題を解決するための手段】本発明に係る変性強酸性
スルホン酸型イオン交換樹脂は、強酸性スルホン酸型イ
オン交換樹脂のスルホン酸基の一部に、下記の一般式
（１）で示される１，４−ジメルカプトアルキルピペリ
ジンがイオン結合したものである。The modified strongly acidic sulfonic acid type ion exchange resin according to the present invention is represented by the following general formula (1) in a part of the sulfonic acid groups of the strongly acidic sulfonic acid type ion exchange resin. 1,4-dimercaptoalkylpiperidine is ionic-bonded.
【化２】 Embedded image
【０００６】（式中、Ｘ及びＹは、それぞれ独立して、
水素原子、メチル基またはエチル基を表わし、ａ及びｂ
は、それぞれ独立して、１〜４の整数を表わす。但し、
ａ及び／又はｂが２〜４の場合には、複数のａ及び／又
はｂのそれぞれは別のものを表わしてもよい）Wherein X and Y are each independently:
A represents a hydrogen atom, a methyl group or an ethyl group;
Each independently represents an integer of 1 to 4. However,
When a and / or b are 2 to 4, each of the plurality of a and / or b may represent another one)
【０００７】[0007]
【発明の実施の形態】本発明について詳細に説明する
と、本発明に係る変性強酸性スルホン酸型イオン交換樹
脂の調製に使用される１，４−ジメルカプトアルキルピ
ペリジンは、例えば４−ピペリジンアルカノールにクロ
ロアルカノールを反応させ、得られたジオールをハロゲ
ン化し、チオ酢酸と反応させたのち還元する等の方法に
より合成することができる。（１）式で表わされる化合
物のいくつかを例示すると、１，４−ビス（２−メルカ
プトエチル）ピペリジン、１−（３−メルカプトプロピ
ル）−４−（２−メルカプトエチル）ピペリジン、１−
（４−メルカプトブチル）−４−（２−メルカプトエチ
ル）ピペリジン、１−（５−メルカプトペンチル）−４
−（２−メルカプトエチル）ピペリジン、１−（１−メ
チル−２−メルカプトエチル）−４−（２−メルカプト
エチル）ピペリジン、１−（１−エチル−２−メルカプ
トエチル）−４−（２−メルカプトエチル）ピペリジ
ン、１−（２−メルカプトエチル）−４−（４−メルカ
プトブチル）ピペリジン、１−（１−メチル−２−メル
カプトエチル）−４−（４−メルカプトブチル）ピペリ
ジンなどが挙げられる。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail. The 1,4-dimercaptoalkylpiperidine used in the preparation of the modified strongly acidic sulfonic acid type ion exchange resin according to the present invention is, for example, 4-piperidinealkanol. It can be synthesized by a method of reacting chloroalkanol, halogenating the obtained diol, reacting with thioacetic acid, and then reducing. Some examples of the compound represented by the formula (1) include 1,4-bis (2-mercaptoethyl) piperidine, 1- (3-mercaptopropyl) -4- (2-mercaptoethyl) piperidine,
(4-mercaptobutyl) -4- (2-mercaptoethyl) piperidine, 1- (5-mercaptopentyl) -4
-(2-mercaptoethyl) piperidine, 1- (1-methyl-2-mercaptoethyl) -4- (2-mercaptoethyl) piperidine, 1- (1-ethyl-2-mercaptoethyl) -4- (2- Mercaptoethyl) piperidine, 1- (2-mercaptoethyl) -4- (4-mercaptobutyl) piperidine, 1- (1-methyl-2-mercaptoethyl) -4- (4-mercaptobutyl) piperidine and the like. .
【０００８】１，４−ジメルカプトアルキルピペリジン
をイオン結合させるイオン交換樹脂としては、スチレン
−ジビニルベンゼン共重合体からなる骨格とこれに結合
したスルホン酸基を有する強酸性スルホン酸型イオン交
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。またイオン交換樹脂
の交換容量は、含水状態で０．５〜２．５ｍｅｑ／ｍｌ
のものが好ましい。イオン交換樹脂の粒径分布は、２０
０〜１５００μｍの粒径のものが９５％以上を占めるの
が好ましい。市販品としては例えば、ダイヤイオンＳＫ
１Ｂ、ＳＫ１０２、ＳＫ１０４、ＰＫ２０８、ＰＫ２１
２、ＲＣＰ１６０Ｈ、ＲＣＰ１７０Ｈ（三菱化学社製
品、ダイヤイオンは三菱化学社の登録商標）、アンバー
リスト１５、３１（ローム＆ハース社製品）、ダウエッ
クス５０ｗ、８８（ダウケミカル社製品）などがある。[0008] As the ion exchange resin for ion-bonding 1,4-dimercaptoalkylpiperidine, a strongly acidic sulfonic acid type ion exchange resin having a skeleton composed of a styrene-divinylbenzene copolymer and a sulfonic acid group bonded thereto is used. Preferably, the content of divinylbenzene units in the copolymer is preferably from 2 to 40%. The exchange capacity of the ion exchange resin is 0.5 to 2.5 meq / ml in a hydrated state.
Are preferred. The particle size distribution of the ion exchange resin is 20
Preferably, particles having a particle size of 0 to 1500 μm account for 95% or more. As a commercially available product, for example, Diaion SK
1B, SK102, SK104, PK208, PK21
2, RCP160H, RCP170H (Mitsubishi Chemical Co., Ltd., Diaion is a registered trademark of Mitsubishi Chemical Co., Ltd.), Amberlyst 15, 31 (Rohm & Haas Co., Ltd.), Dowex 50w, 88 (Dow Chemical Co., Ltd.) and the like.
【０００９】これらのイオン交換樹脂は酸型で上述の
１，４−ジアルキルメルカプトピペリジンとの結合に供
する。市販品は通常はナトリウム型なので、塩酸等の酸
で処理し酸型にして用いる。これらのイオン交換樹脂は
含水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。強酸性スル
ホン酸型イオン交換樹脂のスルホン酸基に１，４−ジメ
ルカプトアルキルピペリジンを結合するには、適当な溶
媒、例えば、水、アルコール類、ケトン類、エーテル類
等にこのメルカプトピペリジンを溶解させ、この溶液を
同じ溶媒に分散させた強酸性スルホン酸型イオン交換樹
脂に加え、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、このメルカプトピペリジンをス
ルホン酸よりｐｋa が大きい酸、例えば酢酸の水溶液に
加え、酢酸塩として用いることも可能である。These ion exchange resins are used in the acid form for binding to the above-mentioned 1,4-dialkylmercaptopiperidine. Since commercially available products are usually of the sodium type, they are treated with an acid such as hydrochloric acid and used in the acid form. These ion exchange resins are commercially available in a water-containing state, but can be used as they are without special treatment such as dehydration. In order to bond 1,4-dimercaptoalkylpiperidine to the sulfonic acid group of the strongly acidic sulfonic acid type ion exchange resin, the mercaptopiperidine is dissolved in an appropriate solvent, for example, water, alcohols, ketones, ethers and the like. This solution is added to a strongly acidic sulfonic acid type ion exchange resin dispersed in the same solvent, and the mixture may be stirred for 0.1 to 10 hours. For example, to bind water solvent is, pk a greater acid than the mercapto piperidine sulfonic acids, for example, added to an aqueous solution of acetic acid, it can also be used as the acetate.
【００１０】強酸性スルホン酸型イオン交換樹脂に対す
る、１，４−ジメルカプトアルキルピペリジンの結合量
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３〜２０
モル％である。結合量が２モル％未満では１，４−ジメ
ルカプトアルキルピペリジンによる触媒効果が十分発揮
されず、また３０モル％を超えると遊離のスルホン酸基
の減少によって触媒活性が低下するためいずれも好まし
くない。本発明に係る１，４−ジメルカプトアルキルピ
ペリジンがイオン結合した変性強酸性スルホン酸型イオ
ン交換樹脂は、他のものに比べ非常に高いアセトン転化
率、及び４，４’−ビスフェノールＡ選択性を示す。The amount of 1,4-dimercaptoalkylpiperidine bound to the strongly acidic sulfonic acid type ion exchange resin is usually 2 to 30 mol% based on all sulfonic acid groups of the strongly acidic sulfonic acid type ion exchange resin. Preferably 3 to 20
Mol%. If the amount is less than 2 mol%, the catalytic effect of 1,4-dimercaptoalkylpiperidine will not be sufficiently exhibited, and if it exceeds 30 mol%, the catalytic activity will be reduced due to the decrease in free sulfonic acid groups, and neither is preferred. . The modified strongly acidic sulfonic acid type ion exchange resin in which 1,4-dimercaptoalkylpiperidine is ion-bonded according to the present invention has a very high acetone conversion and 4,4′-bisphenol A selectivity as compared with other resins. Show.
【００１１】上記のようにして得られた１，４−ジメル
カプトアルキルピペリジンがイオン結合した変性強酸性
スルホン酸型イオン交換樹脂は、調製の際の溶媒を含ん
でいるので、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、まず樹脂の体積の５〜２０
０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で樹脂に通液し、引
続いて樹脂の体積の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強酸性スルホン酸型イオン交
換樹脂の溶媒はフェノールに置換され、反応に使用する
ことができるようになる。アセトンとフェノールの縮合
反応は、通常、上述の処理を経た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
的に供給する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
℃以上の温度では樹脂の劣化が著しく副生物も増加する
ので、いずれも好ましくない。The 1,4-dimer obtained as described above
Denatured strong acid with captoalkylpiperidine ionically bound
Sulfonic acid type ion exchange resin contains solvent during preparation
Used for the condensation reaction of acetone and phenol.
When the pretreatment is performed, first, the volume of the resin is 5 to 20%.
0x ion exchanged water at a temperature of 20-80 ° C and liquid hourly space velocity
Degree (LHSV) 0.5-50hr-1Through the resin and pull
Then, phenol of 5 to 200 times the volume of the resin
At a temperature of 110 ° C., LHSV 0.5 to 50 hours -1With liquid
I do. By this treatment, denatured strongly acidic sulfonic acid type ion exchange
The solvent of the exchange resin is replaced by phenol and used for the reaction
Will be able to do it. Condensation of acetone and phenol
The reaction is usually carried out in a reactor filled with the resin that has undergone the above treatment.
Raw material mixture containing phenol and acetone
The reaction is carried out by a fixed bed flow reaction system which is supplied in a continuous manner. Raw material mixing
Supply of goods is LHSV0.1-20hr-1,Preferably
0.5-10hr-1It is performed in the range. Reaction temperature is 40
To 120 ° C, preferably 60 to 100 ° C.
When the reaction temperature is 40 ° C. or less, the reaction rate is slow, and
At temperatures above ℃, resin degradation is remarkable and by-products increase
Therefore, neither is preferable.
【００１２】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５〜２０モ
ル、好ましくは７〜１５モルの範囲である。フェノール
の使用量が５モル倍未満では、副生成物の増加が顕著で
ある。また、２０モル倍を超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のフェノールの
回収量がいたずらに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、反応混合物から未反応フェノールを
回収してビスフェノール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 for the reaction is in the range of 5 to 20 moles, preferably 7 to 15 moles of phenol per mole of acetone. If the amount of phenol used is less than 5 moles, the amount of by-products is remarkable. Further, even if it is used in an amount of more than 20 moles, the reaction result is hardly affected, and it is not economical because the amount of phenol recovered from the reaction mixture is unnecessarily increased. In order to separate and purify the target substance bisphenol A from the reaction mixture, for example, unreacted phenol is recovered from the reaction mixture, the adduct of bisphenol A and phenol is separated as crystals, and then the adduct is removed from the adduct by an operation such as distillation. It can be carried out by a known method of recovering phenol.
【００１３】[0013]
【実施例】次に、実施例及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、変性率及びスルホン酸基残存率は次式に
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 acetone conversion, 4,4'-bisphenol A (abbreviated as 4,4'-BPA) selectivity, modification rate and sulfonic acid group remaining rate in the examples were calculated by the following formulas (all units are%).
【００１４】アセトン転化率＝〔（供給したアセトン量
−未反応アセトン量）／（供給したアセトン量）〕×１
００ ４，４’−ＢＰＡ選択率＝〔（生成した４，４’−ＢＰ
Ａのモル数）／（反応で消費されたアセトンのモル
数）〕×１００ 変性率＝〔（イオン交換樹脂と結合したメルカプト化合
物のモル数）／（メルカプト化合物との反応に供したイ
オン交換樹脂のスルホン酸基のモル数）〕×１００ スルホン酸基残存率＝〔（反応後のイオン交換樹脂の遊
離のスルホン酸基のモル数）／（メルカプト化合物との
反応に供したイオン交換樹脂のスルホン酸基のモル
数）〕×１００Acetone conversion = [(amount of supplied acetone−amount of unreacted acetone) / (amount of supplied acetone)] × 1
00 4,4′-BPA selectivity = [(4,4′-BP generated
A) / (moles of acetone consumed in the reaction)] × 100 Modification rate = [(moles of mercapto compound bound to ion exchange resin) / (ion exchange resin subjected to reaction with mercapto compound) Mole number of sulfonic acid groups)] × 100 Residual rate of sulfonic acid groups = [(molar number of free sulfonic acid groups of ion-exchange resin after reaction) / (sulfone of ion-exchange resin subjected to reaction with mercapto compound) Number of moles of acid group)] × 100
【００１５】実施例１ １−（５−メルカプトペンチル）−４−（２−メルカプ
トエチル）ピペリジンがイオン結合した強酸性スルホン
酸型イオン交換樹脂を触媒とするビスフェノールＡの製
造 １−（５−メルカプトペンチル）−４−（２−メルカプ
トエチル）ピペリジンの合成；５００ｍｌナス型フラス
コに、４−（２−ヒドロキシエチル）ピペリジン（広栄
化学社製）２０ｇ（１５５ミリモル）と２−プロパノー
ル１００ｍｌを仕込んだ。８０℃、窒素気流下に攪拌し
ながら、これに１５ｍｌの２−プロパノールに溶解させ
た５−クロロペンタノール（Ｌａｎｃａｓｔｅｒ社製）
８．６ｇ（７０ミリモル）を滴下した。８０℃で２時間
反応させたのち、２−プロパノールを留去し、得られた
残液に２５％水酸化ナトリウム水溶液１１．３ｇ（７０
ミリモル）を加え、酢酸エチルで数回抽出した。酢酸エ
チルを留去し、さらに減圧蒸留して１−（５−ヒドロキ
シペンチル）−４−（２−ヒドロキシエチル）ピペリジ
ン（ｂ．ｐ．１６７〜１７５℃／０．７ｍｍＨｇ）７．
０ｇを得た。Example 1 Production of bisphenol A using 1- (5-mercaptopentyl) -4- (2-mercaptoethyl) piperidine ion-bonded with a strongly acidic sulfonic acid type ion exchange resin as a catalyst Synthesis of Pentyl) -4- (2-mercaptoethyl) piperidine; A 500-ml eggplant-shaped flask was charged with 20 g (155 mmol) of 4- (2-hydroxyethyl) piperidine (manufactured by Koei Chemical Co., Ltd.) and 100 ml of 2-propanol. While stirring at 80 ° C. under a nitrogen stream, 5-chloropentanol (manufactured by Lancaster) dissolved in 15 ml of 2-propanol was added thereto.
8.6 g (70 mmol) were added dropwise. After reacting at 80 ° C. for 2 hours, 2-propanol was distilled off, and 11.3 g (70%) of a 25% aqueous sodium hydroxide solution was added to the obtained residue.
Mmol) and extracted several times with ethyl acetate. Ethyl acetate was distilled off, and the residue was further distilled under reduced pressure to give 1- (5-hydroxypentyl) -4- (2-hydroxyethyl) piperidine (bp 167 to 175 ° C / 0.7 mmHg).
0 g was obtained.
【００１６】クロロホルムに上記で得た１−（５−ヒド
ロキシペンチル）−４−（２−ヒドロキシエチル）ピペ
リジン３．２ｇ（１５ミリモル）と、４．８ｇ（４１ミ
リモル）の塩化チオニル（和光純薬社製）を添加し、室
温で一昼夜反応させた。クロロホルムを留去し、粗１−
（５−クロロペンチル）−４−（２−クロロエチル）ピ
ペリジン５．３ｇを得た。この粗クロロ化物５．１ｇを
水６５ｍｌに溶解し、チオ酢酸カリウム（和光純薬社
製）４．６ｇ（４０ミリモル）を加え、加熱還流下で１
時間反応させた。反応液を氷冷し、酢酸エチルで数回抽
出した。次いで酢酸エチルを留去して、１−（５−アセ
チルチオペンチル）−４−（２−アセチルチオエチル）
ピペリジン４．９ｇを得た。In chloroform, 3.2 g (15 mmol) of 1- (5-hydroxypentyl) -4- (2-hydroxyethyl) piperidine obtained above and 4.8 g (41 mmol) of thionyl chloride (Wako Pure Chemical Industries, Ltd.) Was added and the reaction was carried out at room temperature overnight. Chloroform was distilled off and crude 1-
5.3 g of (5-chloropentyl) -4- (2-chloroethyl) piperidine were obtained. 5.1 g of the crude chlorinated product was dissolved in 65 ml of water, and 4.6 g (40 mmol) of potassium thioacetate (manufactured by Wako Pure Chemical Industries, Ltd.) was added.
Allowed to react for hours. The reaction solution was cooled on ice and extracted several times with ethyl acetate. Then, ethyl acetate was distilled off, and 1- (5-acetylthiopentyl) -4- (2-acetylthioethyl)
4.9 g of piperidine were obtained.
【００１７】水素化リチウムアルミニウム（和光純薬社
製）１．３ｇ（３６ミリモル）と乾燥エチルエーテルを
乾燥した２００ｍｌ３口フラスコに窒素気流下で仕込
み、室温で攪拌しながら、これに上記で得たチオアセチ
ル体４．９ｇをエチルエーテル１５ｍｌに溶解した溶液
を滴下した。加熱還流下で１時間反応させたのち、水
０．７ｇ（３９ミリモル）と酢酸２．４ｇ（３９ミリモ
ル）を加え、過剰の水素化リチウムアルミニウムを分解
したのち、濾過した。得られたエーテル溶液を脱水後、
エーテルを留去し、続いて減圧蒸留して、１−（５−メ
ルカプトペンチル）−４−（２−メルカプトエチル）ピ
ペリジン（ｂ．ｐ．１４４℃／０．５ｍｍＨｇ）１．０
ｇ（ガスクロマトグラフィー純度９６％）を得た。1.3 g (36 mmol) of lithium aluminum hydride (manufactured by Wako Pure Chemical Industries) and dry ethyl ether were charged into a dry 200 ml three-necked flask under a nitrogen stream and stirred at room temperature to obtain the above. A solution of 4.9 g of the thioacetyl compound dissolved in 15 ml of ethyl ether was added dropwise. After reacting under heating and refluxing for 1 hour, 0.7 g (39 mmol) of water and 2.4 g (39 mmol) of acetic acid were added to decompose excess lithium aluminum hydride, followed by filtration. After dehydrating the obtained ether solution,
The ether was distilled off, followed by distillation under reduced pressure to give 1- (5-mercaptopentyl) -4- (2-mercaptoethyl) piperidine (bp 144 ° C./0.5 mmHg) 1.0.
g (gas chromatography purity 96%).
【００１８】変性強酸性スルホン酸型イオン交換樹脂の
調製；水切りをしたダイヤイオンＳＫ１０４（Ｈ型）１
４．６ｇをイオン交換水２０ｍｌに懸濁させ、上記で得
られた１−（５−メルカプトペンチル）−４−（２−メ
ルカプトエチル）ピペリジン９５０ｍｇ（３．８ミリモ
ル）と酢酸０．２５ｇ（４．２ミリモル）をイオン交換
水１０ｍｌに溶解させた水溶液と混合し、室温で１０時
間攪拌した。濾過してイオン交換樹脂を分離し、イオン
交換水で洗浄して、１−（５−メルカプトペンチル）−
４−（２−メルカプトエチル）ピペリジンが結合した変
性強酸性スルホン酸型イオン交換樹脂を得た。メルカプ
ト基及びスルホン酸基の残存量の分析をしたところ、変
性率は１６．７％、スルホン酸基残存率は８４．２％で
あった。Preparation of modified strongly acidic sulfonic acid type ion exchange resin; Drained SK104 (H type) 1
4.6 g was suspended in 20 ml of ion-exchanged water, and 950 mg (3.8 mmol) of 1- (5-mercaptopentyl) -4- (2-mercaptoethyl) piperidine obtained above and 0.25 g of acetic acid (4 mg) were obtained. .2 mmol) was mixed with an aqueous solution of 10 ml of ion-exchanged water and stirred at room temperature for 10 hours. The ion-exchange resin is separated by filtration, washed with ion-exchanged water, and 1- (5-mercaptopentyl)-
A modified strongly acidic sulfonic acid type ion exchange resin to which 4- (2-mercaptoethyl) piperidine was bound was obtained. When the residual amounts of mercapto groups and sulfonic acid groups were analyzed, the modification rate was 16.7% and the residual rate of sulfonic acid groups was 84.2%.
【００１９】ビスフェノールＡの製造上記で得た変性強
酸性スルホン酸型イオン交換樹脂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、引
続いて７０℃でフェノールをＬＨＳＶ２ｈｒ-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℃、ＬＨＳＶ１ｈｒ-1で通液し反応
を行った。４０時間後のアセトン転化率は９８．３％、
４，４’−ＢＰＡ選択率は９５．５％であり、１５０時
間後のアセトン転化率は９８．３％、４，４’−ＢＰＡ
選択率は９５．０％であった。Production of bisphenol A 14 ml of the modified strongly acidic sulfonic acid type ion exchange resin obtained above was used with an inner diameter of 7.
6 mm, packed in a 320 mm long stainless steel column,
Flowing deionized water 200ml with LHSV2hr -1, phenol was run at LHSV2hr -1 24 hours at 70 ° C. and subsequently. Next, a mixture of phenol / acetone = 10/1 (molar ratio) was passed at 70 ° C. at an LHSV of 1 hr −1 to carry out a reaction. Acetone conversion after 40 hours is 98.3%,
The 4,4'-BPA selectivity is 95.5%, the acetone conversion after 150 hours is 98.3%, and the 4,4'-BPA is
The selectivity was 95.0%.
【００２０】実施例２ １−（３−メルカプトプロピル）−４−（２−メルカプ
トエチル）ピペリジンがイオン結合した強酸性スルホン
酸型イオン交換樹脂を触媒とするビスフェノールＡの製
造 １−（３−メルカプトプロピル）−４−（２−メルカプ
トエチル）ピペリジンの合成；実施例１において、５−
クロロペンタノールの代わりに３−クロロプロパノール
（Ａｌｄｒｉｃｈ社製）を７０ミリモル用いた他は、実
施例１と同様に反応を行い１−（３−ヒドロキシプロピ
ル）−４−（２−ヒドロキシエチル）ピペリジン（ｂ
ｐ．１４５〜１５０℃／１ｍｍＨｇ）を６．１ｇ得た。
このものについて、実施例１と同様にして塩化チオニル
によるクロル化、チオ酢酸カリウム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、
減圧蒸留により１−（３−メルカプトプロピル）−４−
（２−メルカプトエチル）ピペリジン１．２ｇ（ｂｐ．
１２９〜１３５℃／１ｍｍＨｇ）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９６．５％であっ
た。Example 2 Production of bisphenol A using a strongly acidic sulfonic acid type ion-exchange resin ion-bonded with 1- (3-mercaptopropyl) -4- (2-mercaptoethyl) piperidine 1- (3-mercaptopropyl) Synthesis of propyl) -4- (2-mercaptoethyl) piperidine;
1- (3-hydroxypropyl) -4- (2-hydroxyethyl) piperidine was reacted in the same manner as in Example 1 except that 70 mmol of 3-chloropropanol (manufactured by Aldrich) was used instead of chloropentanol. (B
p. 145-150 ° C / 1 mmHg).
This was subjected to chlorination with thionyl chloride, thioacetylation with potassium thioacetate and reduction with lithium aluminum hydride in the same manner as in Example 1,
By distillation under reduced pressure, 1- (3-mercaptopropyl) -4-
1.2 g of (2-mercaptoethyl) piperidine (bp.
129-135 ° C / 1 mmHg). As a result of analysis by gas chromatography, the purity was 96.5%.
【００２１】変性強酸性スルホン酸型イオン交換樹脂の
調製；水切りをしたダイヤイオンＳＫ１０４（Ｈ型）１
４．６ｇをイオン交換水に懸濁させ、上記で得られた１
−（３−メルカプトプロピル）−４−（２−メルカプト
エチル）ピペリジン８４０ｍｇ（３．８ミリモル）と酢
酸０．２５ｇ（４．２ミリモル）をイオン交換水１０ｍ
ｌに溶解させた水溶液と混合し、室温で１０時間攪拌し
た。濾過してイオン交換樹脂を分離し、イオン交換水で
洗浄して、１−（３−メルカプトプロピル）−４−（２
−メルカプトエチル）ピペリジンが結合した変性強酸性
スルホン酸型イオン交換樹脂を得た。メルカプト基及び
スルホン酸基の残存量の分析をしたところ、変性率は１
５．９％、スルホン酸基残存率は８３．９％であった。Preparation of modified strongly acidic sulfonic acid type ion exchange resin; Drained SK104 (H type) 1
4.6 g was suspended in ion-exchanged water, and the 1
840 mg (3.8 mmol) of-(3-mercaptopropyl) -4- (2-mercaptoethyl) piperidine and 0.25 g (4.2 mmol) of acetic acid were ion-exchanged with 10 m of water.
and stirred at room temperature for 10 hours. The ion-exchange resin was separated by filtration, washed with ion-exchanged water, and washed with 1- (3-mercaptopropyl) -4- (2
(-Mercaptoethyl) piperidine was bound to obtain a modified strongly acidic sulfonic acid type ion exchange resin. When the residual amounts of mercapto groups and sulfonic acid groups were analyzed, the modification rate was 1
5.9% and the residual ratio of sulfonic acid groups were 83.9%.
【００２２】ビスフェノールＡの製造；上記で得た変性
強酸性スルホン酸型イオン交換樹脂１４ｍｌを用いた以
外は、実施例１と同様にして溶媒置換及びフェノールと
アセトンの縮合反応を行った。その結果、４０時間後の
アセトン転化率は９７．０％、４，４’−ＢＰＡ選択率
は９５．２％であり、１５０時間後のアセトン転化率は
９７．１％、４，４’−ＢＰＡ選択率は９５．２％であ
った。Production of bisphenol A: The solvent substitution and the condensation reaction of phenol and acetone were carried out in the same manner as in Example 1 except that 14 ml of the modified strongly acidic sulfonic acid type ion exchange resin obtained above was used. As a result, the conversion of acetone after 40 hours was 97.0% and the selectivity of 4,4'-BPA was 95.2%, and the conversion of acetone after 150 hours was 97.1% and 4,4'-BPA. The BPA selectivity was 95.2%.
【００２３】比較例１ １−エチル−４−（２−メルカプトエチル）ピペリジン
がイオン結合した強酸性スルホン酸型イオン交換樹脂を
触媒とするビスフェノールＡの製造 １−エチル−４−（２−メルカプトエチル）ピペリジン
の合成；３００ｍｌ４口フラスコに、塩化チオニル１
３．４ｇ（１１３ミリモル）とクロロホルム５０ｍｌを
仕込んだ。室温で攪拌しながら、これに４−（２−ヒド
ロキシエチル）ピペリジン１０ｇ（７７ミリモル）をク
ロロホルム４０ｍｌに溶解させた溶液を滴下した。滴下
終了後室温でさらに２．５時間反応させた。減圧にして
過剰の塩化チオニル及びクロロホルムを留去し、粗４−
（２−クロロエチル）ピペリジン塩酸塩１３．７ｇを得
た。COMPARATIVE EXAMPLE 1 Production of bisphenol A catalyzed by a strongly acidic sulfonic acid type ion exchange resin having 1-ethyl-4- (2-mercaptoethyl) piperidine ionically bonded thereto 1-ethyl-4- (2-mercaptoethyl) ) Synthesis of piperidine; thionyl chloride 1 in a 300 ml 4-neck flask
3.4 g (113 mmol) and 50 ml of chloroform were charged. While stirring at room temperature, a solution prepared by dissolving 10 g (77 mmol) of 4- (2-hydroxyethyl) piperidine in 40 ml of chloroform was added dropwise thereto. After the completion of the dropwise addition, the reaction was further performed at room temperature for 2.5 hours. Excessive thionyl chloride and chloroform were distilled off under reduced pressure to give crude 4-
13.7 g of (2-chloroethyl) piperidine hydrochloride were obtained.
【００２４】３００ｍｌナス型フラスコに、水酸化カリ
ウム４．０ｇ（７１ミリモル）と水４８ｍｌを仕込ん
だ。攪拌しながら、これにチオ酢酸４．６ｇ（６０ミリ
モル）を加え、さらに１０分間室温で攪拌した。この溶
液に上記で得られたクロル化物１０ｇを水３０ｍｌに溶
解させた水溶液を約３０分間で滴下した。滴下終了後加
熱還流下で１時間反応させた。反応液を１００ｍｌのエ
ーテルで抽出することを３回繰り返した。脱水後エーテ
ルを留去し、１−アセチル−４−（２−アセチルチオエ
チル）ピペリジン７．８ｇを得た。３００ｍｌ４口フラ
スコに、水素化リチウムアルミニウム３．７ｇ（９６ミ
リモル）及び乾燥エーテル１００ｍｌを仕込み、室温で
攪拌しながら、これに窒素気流下、上記のチオアセチル
体６．０ｇ（３２ミリモル）をエーテル２０ｍｌに溶解
させた溶液を滴下した。滴下終了後、加熱還流下で１時
間反応させた。反応終了後氷冷し、水１．７ｇ（９６ミ
リモル）及び酢酸６．３ｇ（１０５ミリモル）を加え、
過剰の水素化リチウムアルミニウムを分解したのち濾過
した。得られたエーテル溶液からエーテルを留去し、１
−エチル−４−（２−メルカプトエチル）ピペリジン
１．１ｇを得た。A 300 ml eggplant-shaped flask was charged with 4.0 g (71 mmol) of potassium hydroxide and 48 ml of water. While stirring, 4.6 g (60 mmol) of thioacetic acid was added thereto, and the mixture was further stirred at room temperature for 10 minutes. To this solution, an aqueous solution in which 10 g of the chlorinated product obtained above was dissolved in 30 ml of water was dropped over about 30 minutes. After the completion of the dropwise addition, the mixture was reacted for 1 hour under reflux with heating. Extraction of the reaction solution with 100 ml of ether was repeated three times. After dehydration, ether was distilled off to obtain 7.8 g of 1-acetyl-4- (2-acetylthioethyl) piperidine. In a 300 ml four-necked flask, 3.7 g (96 mmol) of lithium aluminum hydride and 100 ml of dry ether were charged, and while stirring at room temperature, 6.0 g (32 mmol) of the above thioacetyl compound was added to 20 ml of ether under a nitrogen stream. The dissolved solution was added dropwise. After the completion of the dropwise addition, the mixture was reacted for 1 hour under heating and reflux. After completion of the reaction, the mixture was ice-cooled, and 1.7 g (96 mmol) of water and 6.3 g (105 mmol) of acetic acid were added.
Excess lithium aluminum hydride was decomposed and filtered. The ether was distilled off from the obtained ether solution, and 1
1.1 g of -ethyl-4- (2-mercaptoethyl) piperidine were obtained.
【００２５】変性強酸性スルホン酸型イオン交換樹脂の
調製；水切りをしたダイヤイオンＳＫ１０４（Ｈ型）１
４ｇをイオン交換水２０ｍｌに懸濁させ、上記で得られ
た１−エチル−４−（２−メルカプトエチル）ピペリジ
ン６５４ｍｇ（３．８ミリモル）及び酢酸０．２７ｇ
（４．５ミリモル）を、水２０ｍｌとメタノール５ｍｌ
の混合液に溶解させた溶液を加え、室温で２時間攪拌し
た。濾過してイオン交換樹脂を分離し、イオン交換水で
洗浄して、１−エチル−４−（２−メルカプトエチル）
ピペリジンが結合した変性強酸性スルホン酸型イオン交
換樹脂を得た。メルカプト基及びスルホン酸基の残存量
の分析をしたところ、変性率は１５．０％、スルホン酸
基残存率は８６．８％であった。Preparation of modified strongly acidic sulfonic acid type ion exchange resin; Drained SK104 (H type) 1
4 g were suspended in 20 ml of ion-exchanged water, 654 mg (3.8 mmol) of 1-ethyl-4- (2-mercaptoethyl) piperidine obtained above and 0.27 g of acetic acid were obtained.
(4.5 mmol) in 20 ml of water and 5 ml of methanol
Was added to the above mixture, and the mixture was stirred at room temperature for 2 hours. The ion-exchange resin is separated by filtration, washed with ion-exchanged water, and 1-ethyl-4- (2-mercaptoethyl)
A modified strongly acidic sulfonic acid type ion exchange resin to which piperidine was bound was obtained. When the residual amounts of mercapto groups and sulfonic acid groups were analyzed, the modification rate was 15.0% and the residual rate of sulfonic acid groups was 86.8%.
【００２６】ビスフェノールＡの製造；上記で得た変性
強酸性スルホン酸型イオン交換樹脂１４ｍｌを用いた以
外は、実施例１と同様にして溶媒置換及びフェノールと
アセトンの縮合反応を行った。４０時間後及び１５０時
間後の反応結果を表１に示した。Production of bisphenol A: The solvent substitution and the condensation reaction of phenol and acetone were carried out in the same manner as in Example 1 except that 14 ml of the modified strongly acidic sulfonic acid type ion exchange resin obtained above was used. The reaction results after 40 hours and 150 hours are shown in Table 1.
【００２７】比較例２ メルカプト化合物として２−メルカプトエチルアミンを
用いた以外は、実施例１と同様にして変性強酸性スルホ
ン酸型イオン交換樹脂を調製した。変性率は１５．２％
であった。この変性強酸性スルホン酸型イオン交換樹脂
を用いた以外は、実施例１と同様にしてビスフェノール
Ａの製造を行い、結果を表１に示した。Comparative Example 2 A modified strongly acidic sulfonic acid type ion exchange resin was prepared in the same manner as in Example 1 except that 2-mercaptoethylamine was used as the mercapto compound. Denaturation rate is 15.2%
Met. Bisphenol A was produced in the same manner as in Example 1 except that this modified strongly acidic sulfonic acid type ion exchange resin was used. The results are shown in Table 1.
【００２８】比較例３ メルカプト化合物としてＮ−エチルビス（２−メルカプ
トエチル）アミンを用いた以外は、実施例１と同様にし
て変性強酸性スルホン酸型イオン交換樹脂を調製した。
変性率は９．１％であった。この変性強酸性スルホン酸
型イオン交換樹脂を用いた以外は、実施例１と同様にし
てビスフェノールＡの製造を行い、結果を表１に示し
た。Comparative Example 3 A modified strongly acidic sulfonic acid type ion exchange resin was prepared in the same manner as in Example 1 except that N-ethylbis (2-mercaptoethyl) amine was used as the mercapto compound.
The modification rate was 9.1%. Bisphenol A was produced in the same manner as in Example 1 except that this modified strongly acidic sulfonic acid type ion exchange resin was used. The results are shown in Table 1.
【００２９】[0029]
【発明の効果】本発明に係る１，４−ジメルカプトアル
キルピペリジンが結合した変性強酸性スルホン酸型イオ
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。According to the present invention, when the modified strongly acidic sulfonic acid type ion exchange resin to which 1,4-dimercaptoalkylpiperidine is bonded is used, a high conversion rate of acetone and a high conversion rate of 4 are achieved by the condensation reaction between phenol and acetone. , 4 '
Bisphenol A can be efficiently produced at a bisphenol A selectivity and while maintaining its performance for a long time.
【００３０】[0030]
【表１】 [Table 1]
───────────────────────────────────────────────────── 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 住谷 直子 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────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. 6 Identification symbol FI // C07B 61/00 300 C07B 61/00 300 (72) Inventor Naoko Sumiya 8-3-1 Chuo, Ami-cho, Inashiki-gun, Ibaraki Prefecture (72) Inventor Hiroshi Iwane 8-3-1 Chuo, Ami-cho, Inashiki-gun, Ibaraki Prefecture Within Tsukuba Research Laboratory, Mitsubishi Chemical Corporation
Claims (6)
ジメルカプトアルキルピペリジンが、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。 【化１】 （式中、Ｘ及びＹは、それぞれ独立して、水素原子、メ
チル基又はエチル基を表わし、ａ及びｂは、それぞれ独
立して、１〜４の整数を表わす。但し、ａ及び／又はｂ
が２〜４の場合には、複数のａ及び／又はｂのそれぞれ
は別のものを表わしてもよい）1. A 1,4-formula represented by the following general formula (1):
A modified strongly acidic sulfonic acid type ion exchange resin in which dimercaptoalkylpiperidine is ionically bonded to a strongly acidic sulfonic acid type ion exchange resin. Embedded image (Wherein X and Y each independently represent a hydrogen atom, a methyl group or an ethyl group, a and b each independently represent an integer of 1 to 4, provided that a and / or b
Is 2 to 4, each of the plurality of a and / or b may represent another one)
−ジメルカプトアルキルピペリジンが結合していること
を特徴とする請求項１記載の変性強酸性スルホン酸型イ
オン交換樹脂。2. The method according to claim 1, wherein 2 to 30 mol% of the sulfonic acid groups have 1,4
2. The modified strongly acidic sulfonic acid type ion exchange resin according to claim 1, wherein a dimercaptoalkylpiperidine is bonded.
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
記載の変性強酸性スルホン酸型イオン交換樹脂。3. The modified strongly acidic sulfonic acid type 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に、フェ
ノール類とケトン類とを反応させ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 reacting a phenol with a ketone in the presence of the modified strongly acidic sulfonic acid type ion exchange resin according to claim 1.
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 for producing bisphenol according to claim 4, wherein the phenol is phenol and the ketone is acetone.
モル比が、アセトン１モルに対しフェノール５〜２０モ
ルであることを特徴とする請求項５記載のビスフェノー
ルの製造方法。6. The process for producing bisphenol according to claim 5, wherein the molar ratio of acetone and phenol used for the reaction is from 5 to 20 mol of phenol to 1 mol of acetone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01521297A JP3757516B2 (en) | 1997-01-29 | 1997-01-29 | Ion exchange resin and method for producing bisphenol using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01521297A JP3757516B2 (en) | 1997-01-29 | 1997-01-29 | Ion exchange resin and method for producing bisphenol using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10211433A true JPH10211433A (en) | 1998-08-11 |
| JP3757516B2 JP3757516B2 (en) | 2006-03-22 |
Family
ID=11882578
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP01521297A Expired - Fee Related JP3757516B2 (en) | 1997-01-29 | 1997-01-29 | Ion exchange resin and method for producing bisphenol using the same |
Country Status (1)
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|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007176840A (en) * | 2005-12-27 | 2007-07-12 | Mitsui Chemicals Inc | Thiol compound, modified ion exchange resin, and method for preparing bisphenol |
| US20100324341A1 (en) * | 2003-09-30 | 2010-12-23 | Takashi Terajima | Modified acidic ion-exchange resin and method for preparing bisphenol |
| US7968612B2 (en) | 2004-07-02 | 2011-06-28 | Mitsui Chemicals, Inc. | Modified ion exchange resin and process for producing bisphenols |
| US9162221B1 (en) * | 2012-09-19 | 2015-10-20 | John Henry Walker | Heterogeneous liquid phase catalytic process for the dehydration of monoethanolamine to ethylenimine |
-
1997
- 1997-01-29 JP JP01521297A patent/JP3757516B2/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100324341A1 (en) * | 2003-09-30 | 2010-12-23 | Takashi Terajima | Modified acidic ion-exchange resin and method for preparing bisphenol |
| US8436055B2 (en) * | 2003-09-30 | 2013-05-07 | Mitsui Chemicals, Inc. | Modified acidic ion-exchange resin and method for preparing bisphenol |
| US7968612B2 (en) | 2004-07-02 | 2011-06-28 | Mitsui Chemicals, Inc. | Modified ion exchange resin and process for producing bisphenols |
| US20110224315A1 (en) * | 2004-07-02 | 2011-09-15 | Takashi Terajima | Modified ion exchange resin and process for producing bisphenols |
| US20110224461A1 (en) * | 2004-07-02 | 2011-09-15 | Takashi Terajima | Modified ion exchange resin and process for producing bisphenols |
| 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 |
| US8426479B2 (en) | 2004-07-02 | 2013-04-23 | Mitsui Chemicals, Inc. | 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 |
| US9162221B1 (en) * | 2012-09-19 | 2015-10-20 | John Henry Walker | Heterogeneous liquid phase catalytic process for the dehydration of monoethanolamine to ethylenimine |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3757516B2 (en) | 2006-03-22 |
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