JPH11246458A - Production of bisphenol - Google Patents
Production of bisphenolInfo
- Publication number
- JPH11246458A JPH11246458A JP10044834A JP4483498A JPH11246458A JP H11246458 A JPH11246458 A JP H11246458A JP 10044834 A JP10044834 A JP 10044834A JP 4483498 A JP4483498 A JP 4483498A JP H11246458 A JPH11246458 A JP H11246458A
- Authority
- JP
- Japan
- Prior art keywords
- group
- ketone
- bisphenol
- reaction
- mercaptoalkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はフェノール化合物と
ケトンとからビスフェノールを製造する方法に関するも
のである。特に本発明は新規な触媒を用いて高選択率で
４，４′一体のビスフェノールを製造する方法に関する
ものである。[0001] The present invention relates to a method for producing bisphenol from a phenol compound and a ketone. In particular, the present invention relates to a method for producing 4,4′-integrated bisphenol with high selectivity using a novel catalyst.
【０００２】[0002]
【従来の技術】フェノール化合物とケトンとを酸性触媒
の存在下に反応させてビスフェノールを製造することは
公知である。最も大規模に行われているのは、フェノー
ルとアセトンとを反応させてビスフェノールＡを製造す
ることである。この反応では種々の副生物が生成するの
で、目的とするビスフェノールＡの選択率を向上させる
ため、種々の提案がなされている。例えば米国特許第
４，４００，５５５号明細書には、複数の反応器を直列
に接続した反応装置を用い、アセトンを各反応器に分割
して供給することにより、副生物の生成を抑制して、高
選択率でビスフェノールＡを製造することができると記
載されている。2. Description of the Related Art It is known to produce bisphenol by reacting a phenol compound with a ketone in the presence of an acidic catalyst. The most widely practiced is the reaction of phenol with acetone to produce bisphenol A. Since various by-products are generated in this reaction, various proposals have been made to improve the selectivity of the target bisphenol A. For example, in US Pat. No. 4,400,555, the production of by-products is suppressed by using a reactor in which a plurality of reactors are connected in series and dividing and supplying acetone to each reactor. It is described that bisphenol A can be produced with high selectivity.
【０００３】[0003]
【発明が解決しようとする課題】しかし、本発明者らの
検討によれば、この米国特許で触媒として用いられてい
る、２−メルカプトエチルアミンで部分的に中和したス
ルホン酸型スチレン−ジビニルベンゼン系陽イオン交換
樹脂により得られるビスフェノールＡの選択率は、未だ
満足すべきものではない。従って本発明は、より高い選
択率で目的とする４，４′−体のビスフェノールを製造
することのできる方法を提供しようとするものである。However, according to the study of the present inventors, the sulfonic acid type styrene-divinylbenzene partially neutralized with 2-mercaptoethylamine used as a catalyst in this U.S. Pat. The selectivity of bisphenol A obtained by the system cation exchange resin is not yet satisfactory. Accordingly, an object of the present invention is to provide a method capable of producing a target 4,4'-bisphenol at a higher selectivity.
【０００４】[0004]
【課題を解決するための手段】本発明によれば、フェノ
ール化合物とケトンとを反応させてビスフェノールを製
造するに際し、触媒としてアルキル基の炭素数が１〜４
であるω−メルカプトアルキル基を有するω−メルカプ
トアルキルピリジン及びアルキル基の炭素数が３〜４で
あるω−メルカプトアルキル基を有し、かつ１個又は２
個のメチル基又はｔ−ブチル基で置換されていてもよい
ω−メルカプトアルキルアミンからなる群から選ばれた
ω−メルカプトアルキル基を有するアミン又はこれとケ
トンとの縮合物で部分的に中和された酸性陽イオン交換
樹脂を用い、かつケトンを少くとも２つの反応段階で供
給することにより、高選択率で４，４′−体のビスフェ
ノールを製造することができる。According to the present invention, when a phenol compound is reacted with a ketone to produce bisphenol, the alkyl group has 1 to 4 carbon atoms as a catalyst.
An ω-mercaptoalkylpyridine having an ω-mercaptoalkyl group and an ω-mercaptoalkyl group having an alkyl group having 3 to 4 carbon atoms, and one or two
Partially neutralized with an amine having an ω-mercaptoalkyl group selected from the group consisting of ω-mercaptoalkylamines which may be substituted with one or more methyl groups or t-butyl groups, or a condensate of this with a ketone By using the obtained acidic cation exchange resin and supplying the ketone in at least two reaction stages, it is possible to produce the 4,4'-form bisphenol with high selectivity.
【０００５】[0005]
【発明の実施の形態】本発明について詳細に説明する
に、本発明ではω−メルカプトアルキル基を有するアミ
ンで部分的に中和した酸性陽イオン交換樹脂を触媒とし
て用いる。酸性陽イオン交換樹脂としてはスルホン酸基
を官能基とするものが好ましい。通常はスチレンジビニ
ルベンゼン架橋共重合体をスルホン化して得られる、ス
チレン−ジビニルベンゼン系スルホン酸型陽イオン交換
樹脂を用いる。その架橋度は２〜２０％が好ましい。ま
た交換容量は含水状態で０．５〜２．５ｍｅｑ／ｍｌ、
乾燥状態で３．０〜７．０ｍｅｑ／ｍｌのものが好まし
い。市販品としては、アンバーリスト１５、３１、３２
（ローム アンド ハース社製品）、ダウエックス５０
Ｗ、８８（ダウ ケミカル社製品）、ダイヤイオンＳＫ
１Ｂ、ＳＫ１０２、ＳＫ１０４、ＰＫ２０８、ＰＫ２１
２、ＲＣＰ１６０Ｈ、ＲＣＰ１７０Ｈ（三菱化学社製
品）などが挙げられる。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, an acidic cation exchange resin partially neutralized with an amine having an ω-mercaptoalkyl group is used in the present invention as a catalyst. As the acidic cation exchange resin, those having a sulfonic acid group as a functional group are preferable. Usually, a styrene-divinylbenzene sulfonic acid type cation exchange resin obtained by sulfonating a crosslinked styrenedivinylbenzene copolymer is used. The degree of crosslinking is preferably 2 to 20%. The exchange capacity is 0.5 to 2.5 meq / ml in a hydrated state,
Those having a dry state of 3.0 to 7.0 meq / ml are preferred. As commercially available products, Amberlist 15, 31, 32
(Rohm and Haas products), Dowex 50
W, 88 (Dow Chemical Co., Ltd.), Diaion SK
1B, SK102, SK104, PK208, PK21
2, RCP160H, RCP170H (manufactured by Mitsubishi Chemical Corporation) and the like.
【０００６】酸性陽イオン交換樹脂を部分的に中和する
ω−メルカプトアルキル基を有するアミンとしては、２
−メルカプトメチルピリジン、３−メルカプトメチルピ
リジン、４−メルカプトメチルピリジン、２−（２−メ
ルカプトエチル）ピリジン、３−（２−メルカプトエチ
ル）ピリジン、４−（２−メルカプトエチル）ピリジ
ン、２−（３−メルカプトプロピル）ピリジン、３−
（３−メルカプトプロピル）ピリジン、４−（３−メル
カプトプロピル）ピリジン、２−（４−メルカプトブチ
ル）ピリジン、３−（４−メルカプトブチル）ピリジ
ン、４−（４−メルカプトブチル）ピリジンなどの炭素
数１〜４のω−メルカプトアルキル基を有するピリジン
や、Ｎ，Ｎ−ジメチル−Ｎ−（３−メルカプトプロピ
ル）アミン、Ｎ，Ｎ−ジメチル−Ｎ−（４−メルカプト
ブチル）アミン、Ｎ−メチル−Ｎ−（４−メルカプトブ
チル）アミン、３−メルカプトプロピルアミン、４−メ
ルカプトブチルアミン、Ｎ，Ｎ−ジ−ｔ−ブチル−Ｎ−
（４−メルカプトブチル）アミンなどの炭素数３〜４の
ω−メルカプトアルキル基を有し、かつ１個又は２個の
メチル基又はｔ−ブチル基で置換されていてもよいω−
メルカプトアルキルアミンを用いる。また、これらのア
ミンとケトンとの２：１縮合物を用いることもできる。As an amine having an ω-mercaptoalkyl group which partially neutralizes an acidic cation exchange resin, 2
-Mercaptomethylpyridine, 3-mercaptomethylpyridine, 4-mercaptomethylpyridine, 2- (2-mercaptoethyl) pyridine, 3- (2-mercaptoethyl) pyridine, 4- (2-mercaptoethyl) pyridine, 2- ( 3-mercaptopropyl) pyridine, 3-
Carbon such as (3-mercaptopropyl) pyridine, 4- (3-mercaptopropyl) pyridine, 2- (4-mercaptobutyl) pyridine, 3- (4-mercaptobutyl) pyridine and 4- (4-mercaptobutyl) pyridine Pyridine having an ω-mercaptoalkyl group of formulas 1 to 4, N, N-dimethyl-N- (3-mercaptopropyl) amine, N, N-dimethyl-N- (4-mercaptobutyl) amine, N-methyl -N- (4-mercaptobutyl) amine, 3-mercaptopropylamine, 4-mercaptobutylamine, N, N-di-t-butyl-N-
(4-mercaptobutyl) an ω-mercaptoalkyl group having 3 to 4 carbon atoms such as an amine, which may be substituted with one or two methyl groups or t-butyl groups.
A mercaptoalkylamine is used. Further, a 2: 1 condensate of these amine and ketone can also be used.
【０００７】酸性陽イオン交換樹脂をこれらのアミンで
部分的に中和するには、水、アルコール、ケトン、エー
テル、フェノールなどの適当な溶媒にこれらのアミンを
溶解し、予じめ同じ溶媒中に分散させた遊離型の酸性陽
イオン交換樹脂と混合して、撹拌すればよい。陽イオン
交換樹脂に対するアミンの使用量は、陽イオン交換樹脂
の官能基に対しアミノ基として２〜４０モル％、好まし
くは３〜２０モル％である。使用量が２モル％未満では
メルカプト基による触媒効果の発現が不十分であり、ま
た４０モル％を越えると遊離の官能基の減少により触媒
活性が低下するので、いずれも好ましくない。なお、こ
のようにして部分的に中和して調製した触媒は、反応に
用いるフェノール化合物で洗浄して溶媒を置換してか
ら、ビスフェノールの製造に供するのが好ましい。In order to partially neutralize the acidic cation exchange resin with these amines, these amines are dissolved in a suitable solvent such as water, alcohol, ketone, ether, phenol and the like, and are previously dissolved in the same solvent. What is necessary is just to mix it with the free acidic cation exchange resin dispersed in, and to stir it. The amount of the amine to be used in the cation exchange resin is 2 to 40% by mole, preferably 3 to 20% by mole as an amino group based on the functional groups of the cation exchange resin. If the amount is less than 2 mol%, the catalytic effect of the mercapto group is insufficient, and if it exceeds 40 mol%, the catalytic activity is lowered due to the decrease in free functional groups, and neither is preferred. The catalyst thus partially neutralized and prepared is preferably washed with a phenol compound to be used in the reaction to replace the solvent, and then supplied to the production of bisphenol.
【０００８】ビスフェノールの製造は、フェノール化合
物に対するケトンのモル比を５〜２５、好ましくは７〜
２０として行なう。反応温度は通常は５０〜１００℃、
好ましくは５０〜８０℃である。反応温度が低すぎると
反応速度が遅く、逆に高すぎると目的とするビスフェノ
ールの選択率が低下するばかりでなく、触媒の劣化が加
速される恐れがあるので好ましくない。反応圧力は通
常、常圧〜５ｋｇ／ｃｍ 2 Ｇである。[0008] The production of bisphenol is a phenol compound.
The molar ratio of ketone to product is 5 to 25, preferably 7 to
Perform as 20. The reaction temperature is usually 50-100 ° C,
Preferably it is 50-80 degreeC. If the reaction temperature is too low
If the reaction rate is slow, on the contrary
Not only the selectivity of the catalyst but also the deterioration of the catalyst
It is not preferable because it may be speeded up. Reaction pressure is
Normal, normal pressure-5 kg / cm TwoG.
【０００９】反応は固定床方式及び懸濁床方式のいずれ
でも行うことができる。好ましくは直列に接続された複
数、通常は２〜８、好ましくは２〜４個の固定床反応器
又は懸濁床反応器に、フェノール化合物及びケトンを連
続的に供給する流通式で反応が行なわれる。固定床方式
の場合には、液空間速度は通常は０．２〜５ｈｒ-1であ
る。反応装置へのフェノール化合物及びケトンの供給
は、通常はフェノール化合物の全量を第１の反応器に供
給し、ケトンは第１の反応器及びそれに続く少くとも一
つの反応器に分割して供給する。所望ならばフェノール
化合物も、第１の反応器及びそれに続く少くとも一つの
反応器に分割供給してもよいが、その場合には第１の反
応器に全フェノール化合物の８０％以上を供給するのが
好ましい。第２の反応器以降へのフェノール化合物の供
給比率が大き過ぎると、目的とするビスフェノールの選
択率が低下する恐れがあり好ましくない。なお、フェノ
ール化合物としては、ビスフェノールの製造プロセスか
ら回収される不純物を含む回収フェノールを用いること
もできる。各反応器へはケトン全量の１０〜７０％、好
ましくは２５〜６０％を分割供給する。通常は第１の反
応器に全ケトンの２５〜６０％を供給し、かつ後続する
各反応器に残りのケトンを分割供給するのが好ましい。
なお、第１の反応器を除き、後続する反応器にケトンを
供給するに際しては、ケトンが供給される反応液中のケ
トンの転化率が６０％以上、特に８５％以上であるのが
好ましい。ケトンの転化率が低い反応液中にケトンを供
給すると、目的とするビスフェノールの選択率が低下す
る傾向がある。なお、本発明方法によるビスフェノール
の製造は所望ならば回分方式で行うこともできる。この
場合にはフェノールの全量とケトンの一部を先ず反応器
に供給し、これに残りのケトンを連続的に供給するか又
は経時的に分割供給するのが好ましい。The reaction can be carried out in either a fixed bed system or a suspension bed system. The reaction is carried out in a flow system in which a phenol compound and a ketone are continuously supplied to a plurality of, usually 2 to 8, preferably 2 to 4 fixed bed reactors or suspension bed reactors preferably connected in series. It is. In the case of the fixed bed system, the liquid hourly space velocity is usually 0.2 to 5 hr -1 . The supply of the phenolic compound and the ketone to the reactor is usually performed by feeding the whole amount of the phenolic compound to the first reactor, and the ketone is dividedly supplied to the first reactor and at least one subsequent reactor. . If desired, the phenolic compound may also be fed split into the first reactor and at least one subsequent reactor, in which case the first reactor is fed with at least 80% of the total phenolic compound Is preferred. If the supply ratio of the phenol compound to the second and subsequent reactors is too large, the selectivity of the target bisphenol may decrease, which is not preferable. Note that, as the phenol compound, a recovered phenol containing impurities recovered from the bisphenol production process can also be used. 10 to 70%, preferably 25 to 60%, of the total amount of ketone is fed to each reactor in portions. It is usually preferred to feed 25-60% of the total ketone to the first reactor and to split feed the remaining ketone to each subsequent reactor.
When supplying ketone to the subsequent reactors except for the first reactor, the conversion of ketone in the reaction solution to which ketone is supplied is preferably 60% or more, particularly preferably 85% or more. When ketone is supplied into a reaction solution having a low conversion of ketone, the selectivity of a target bisphenol tends to decrease. The production of bisphenol according to the method of the present invention can be carried out batchwise if desired. In this case, it is preferred that the whole amount of the phenol and a part of the ketone are first supplied to the reactor, and the remaining ketone is continuously supplied to the reactor or divided over time.
【００１０】反応液からのビスフェノールの回収は常法
により行うことができる。例えば反応液から未反応フェ
ノールを回収し、目的物のビスフェノールをフェノール
との付加物として分離する。付加物からは常法によりフ
ェノールを回収してビスフェノールを取得する。[0010] Bisphenol can be recovered from the reaction solution by a conventional method. For example, unreacted phenol is recovered from the reaction solution, and the desired bisphenol is separated as an adduct with phenol. The phenol is recovered from the adduct by a conventional method to obtain bisphenol.
【００１１】[0011]
【実施例】以下に実施例により本発明をさらに具体的に
説明する。なお、アセトン転化率及びビスフェノールＡ
選択率は次式により算出した。The present invention will be described more specifically with reference to the following examples. The acetone conversion and bisphenol A
The selectivity was calculated by the following equation.
【００１２】[0012]
【数１】アセトン転化率（％）＝｛（供給アセトン量−
未反応アセトン量）／供給アセトン量｝×１００ ビスフェノールＡ（ＢＰＡ）選択率（％）＝｛生成ＢＰ
Ａ量／生成水を除く全生成物量｝×１００## EQU1 ## Acetone conversion (%) = ｛(amount of acetone supplied−
Unreacted acetone amount) / Acetone supply amount x 100 Bisphenol A (BPA) selectivity (%) = {BP formed
A amount / Total product amount excluding generated water｝ × 100
【００１３】反応液中の未反応アセトンはガスクロマト
グラフィーで定量し、ビスフェノールＡ及び副生物等は
高速液体クロマトグラフィーで定量した。Unreacted acetone in the reaction solution was determined by gas chromatography, and bisphenol A and by-products were determined by high performance liquid chromatography.
【００１４】実施例１ ３００ｍＬガラス製四つ口丸底フラスコに、ダイヤイオ
ンＳＫ１０４を４−（２−メルカプトエチル）ピリジン
で１６モル％中和した触媒を水膨潤状態で３０ｇ採取
し、７０℃のフェノールを用いて、洗浄液の含水率が
０．１重量％以下になるまで洗浄した。３００ｍＬの四
つ口丸底フラスコに５０℃のフェノール１８０ｇを採取
し、これにこの洗浄済の触媒を懸濁させ、アセトン２．
１４ｇを加えて反応を開始した。反応開始後、３０分、
６０分及び９０分の時点でそれぞれアセトン２．１４ｇ
を追加供給した。また反応開始後６０分の時点で６０℃
に昇温し、９０分の時点で更に７０℃に昇温し、以後は
この温度で反応を続行した。反応開始後２４０分の時点
で反応液を採取して分析した。結果を表−１に示す。Example 1 In a 300 mL glass four-necked round-bottomed flask, 30 g of a catalyst obtained by neutralizing Diaion SK104 with 16 mol% of 4- (2-mercaptoethyl) pyridine in a water-swelled state was collected, and the mixture was heated at 70 ° C. Washing was performed using phenol until the water content of the washing solution became 0.1% by weight or less. 180 g of phenol at 50 ° C. was collected in a 300 mL four-necked round-bottomed flask, and the washed catalyst was suspended therein.
The reaction was started by adding 14 g. 30 minutes after the start of the reaction,
2.14 g of acetone at 60 and 90 minutes respectively
Was additionally supplied. At 60 minutes after the start of the reaction,
The temperature was further increased to 70 ° C. at 90 minutes, and thereafter the reaction was continued at this temperature. At 240 minutes after the start of the reaction, the reaction solution was collected and analyzed. The results are shown in Table 1.
【００１５】実施例２ ３００ｍＬガラス製四つ口丸底フラスコに、アンバーリ
スト３１をＮ，Ｎ−ジメチル−Ｎ−（３−メルカプトプ
ロピル）アミンで１６モル％中和した触媒を水膨潤状態
で３０ｇ採取し、７０℃のフェノールを用いて、洗浄液
の含水率が０．１重量％以下になるまで洗浄した。３０
０ｍＬの四つ口丸底フラスコに７０℃のフェノール１５
３．７ｇを採取し、これにこの触媒を懸濁させ、アセト
ン４．７５ｇを加えて反応を開始した。反応開始後、６
０分の時点でアセトン４．７５ｇを追加供給した。反応
開始後１２０分の時点で反応液を採取して分析した。結
果を表−１に示す。Example 2 30 g of a catalyst obtained by neutralizing Amberlyst 31 with 16 mol% of N, N-dimethyl-N- (3-mercaptopropyl) amine in a 300 mL glass four-necked round-bottomed flask in a water-swelled state. The sample was collected and washed with phenol at 70 ° C. until the water content of the washing solution became 0.1% by weight or less. 30
Phenol 15 at 70 ° C in a 0 mL four-necked round bottom flask
3.7 g was collected, the catalyst was suspended in the suspension, and 4.75 g of acetone was added to start the reaction. After the reaction starts, 6
At time 0 minute, 4.75 g of acetone was additionally supplied. At 120 minutes after the start of the reaction, the reaction solution was collected and analyzed. The results are shown in Table 1.
【００１６】実施例３ 実施例２において、反応開始時に添加するアセトンを
２．３８ｇとし、かつ反応開始後３０分、６０分及び９
０分の時点でそれぞれアセトン２．３８ｇを追加供給し
た以外は、実施例１と同様にして反応を行った。反応開
始後２４０分の時点で反応液を採取して分析した。結果
を表−１に示す。Example 3 In Example 2, the amount of acetone added at the start of the reaction was 2.38 g, and 30 minutes, 60 minutes and 9 minutes after the start of the reaction.
The reaction was carried out in the same manner as in Example 1 except that 2.38 g of acetone was additionally supplied at the time point of 0 minute. At 240 minutes after the start of the reaction, the reaction solution was collected and analyzed. The results are shown in Table 1.
【００１７】実施例４ ５００ｍＬガラス製四つ口丸底フラスコに、ダイヤイオ
ンＳＫ１０４をＮ，Ｎ−（ジ−ｔ−ブチル）−４−メル
カプトブチルアミンで１６モル％中和した触媒を水膨潤
状態で３０ｇ採取し、７０℃のフェノールを用いて、洗
浄液中の含水率が０．１重量％になるまで洗浄した。５
００ｍＬガラス製四つ口丸底フラスコに７０℃のフェノ
ール３７０．７６ｇを採取し、これにこの触媒を懸濁さ
せ、アセトン１１．４４ｇを加えて反応を開始した。反
応開始後３０分の時点でアセトン１０．００ｇを追加供
給した。反応開始２４０分の時点で反応液を採取して分
析した。結果を表−１に示す。Example 4 A catalyst obtained by neutralizing Diaion SK104 with N, N- (di-t-butyl) -4-mercaptobutylamine at 16 mol% in a 500 mL glass four-necked round bottom flask in a water-swelled state. 30 g was collected and washed with phenol at 70 ° C. until the water content in the washing solution became 0.1% by weight. 5
370.76 g of phenol at 70 ° C. was collected in a 00 mL glass four-necked round-bottomed flask, the catalyst was suspended in this, and 11.44 g of acetone was added to start the reaction. 30 minutes after the start of the reaction, 10.00 g of acetone was additionally supplied. At 240 minutes after the start of the reaction, the reaction solution was collected and analyzed. The results are shown in Table 1.
【００１８】比較例１ ３００ｍＬガラス製四つ口丸底フラスコに、アンバーリ
ストを２−メルカプトエチルアミンで１６モル％中和し
た触媒を水膨潤状態で３０ｇ採取し、７０℃のフェノー
ルを用いて、洗浄液の含水率が０．１重量％以下になる
まで洗浄した。この触媒を用いた以外は実施例１と全く
同様にして反応を実施した。反応開始後２４０分の時点
で反応液を分析した。結果を表−１に示す。Comparative Example 1 In a 300 mL glass four-necked round-bottomed flask, 30 g of a catalyst obtained by neutralizing Amberlyst with 16 mol% of 2-mercaptoethylamine in a water-swelled state was collected, and the washing solution was washed with phenol at 70 ° C. Was washed until the water content became 0.1% by weight or less. The reaction was carried out in exactly the same manner as in Example 1 except that this catalyst was used. At 240 minutes after the start of the reaction, the reaction solution was analyzed. The results are shown in Table 1.
【００１９】比較例２ ３００ｍＬガラス製四つ口丸底フラスコに、７０℃のフ
ェノール１５３．７ｇを採取し、これに実施例２と同様
にして調製した触媒を懸濁させ、アセトン９．５ｇを加
えて反応を開始した。反応開始後６０分の時点で反応液
を分析した。結果を表−１に示す。Comparative Example 2 153.7 g of phenol at 70 ° C. was collected in a 300 mL glass four-necked round-bottom flask, and the catalyst prepared in the same manner as in Example 2 was suspended therein. In addition, the reaction was started. The reaction solution was analyzed 60 minutes after the start of the reaction. The results are shown in Table 1.
【００２０】[0020]
【表１】 [Table 1]
───────────────────────────────────────────────────── フロントページの続き (72)発明者 佐藤 詔雄 三重県四日市市東邦町１番地 三菱化学株 式会社四日市事業所内 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor, Setsuo Sato 1 Tohocho, Yokkaichi-shi, Mie Inside the Yokkaichi office of Mitsubishi Chemical Corporation
Claims (4)
てビスフェノールを製造する方法において、触媒とし
て、アルキル基の炭素数が１〜４であるω−メルカプト
アルキル基を有するω−メルカプトアルキルピリジン及
びアルキル基の炭素数が３〜４であるω−メルカプトア
ルキル基を有し、かつ１個又は２個のメチル基又はｔ−
ブチル基で置換されていてもよいω−メルカプトアルキ
ルアミンからなる群から選ばれたω−メルカプトアルキ
ル基を有するアミン又はこれとケトンとの縮合物で部分
的に中和された酸性陽イオン交換樹脂を用い、かつケト
ンを少くとも２つの反応段階で供給することを特徴とす
る方法。1. A method for producing a bisphenol by reacting a phenol compound with a ketone, wherein as a catalyst, an ω-mercaptoalkylpyridine having an ω-mercaptoalkyl group having 1 to 4 carbon atoms in the alkyl group and an alkyl group Has an ω-mercaptoalkyl group having 3 to 4 carbon atoms, and has 1 or 2 methyl groups or t-
An acidic cation exchange resin partially neutralized with an amine having an ω-mercaptoalkyl group selected from the group consisting of ω-mercaptoalkylamines which may be substituted with a butyl group, or a condensate thereof with a ketone And supplying the ketone in at least two reaction stages.
域を有する反応装置にフェノール化合物とケトンとを連
続的に供給してビスフェノールを製造する方法におい
て、触媒として、アルキル基の炭素数が１〜４であるω
−メルカプトアルキル基を有するω−メルカプトアルキ
ルピリジン及びアルキル基の炭素数が３〜４であるω−
メルカプトアルキル基を有し、かつ１個又は２個のメチ
ル基又はｔ−ブチル基で置換されていてもよいω−メル
カプトアルキルアミンからなる群から選ばれたω−メル
カプトアルキル基を有するアミン又はこれとケトンとの
縮合物で部分的に中和された酸性陽イオン交換樹脂を用
い、かつケトンを少くとも２つの反応帯域に分割して供
給することを特徴とする方法。2. A method for producing a bisphenol by continuously supplying a phenol compound and a ketone to a reactor having at least two reaction zones connected in series, wherein the alkyl group has 1 carbon atom as a catalyst. Ω which is ~ 4
-Ω-mercaptoalkylpyridine having a mercaptoalkyl group and ω- having 3 to 4 carbon atoms in the alkyl group
An amine having a ω-mercaptoalkyl group selected from the group consisting of ω-mercaptoalkylamines having a mercaptoalkyl group and optionally substituted with one or two methyl groups or t-butyl groups, or Using an acidic cation exchange resin partially neutralized with a condensate of a ketone and a ketone, and feeding the ketone divided into at least two reaction zones.
スルホン酸基を有するものであることを特徴とする請求
項１又は２記載の方法。3. The method according to claim 1, wherein the acidic cation exchange resin has a sulfonic acid group as a functional group.
０モル％がω−メルカプトアルキル基を有するアミン又
はこれとケトンとの縮合物で中和されていることを特徴
とする請求項１ないし３のいずれかに記載の方法。4. An acidic cation exchange resin having functional groups 2 to 4
The method according to any one of claims 1 to 3, wherein 0 mol% is neutralized with an amine having an ω-mercaptoalkyl group or a condensate thereof with a ketone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10044834A JPH11246458A (en) | 1998-02-26 | 1998-02-26 | Production of bisphenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10044834A JPH11246458A (en) | 1998-02-26 | 1998-02-26 | Production of bisphenol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11246458A true JPH11246458A (en) | 1999-09-14 |
Family
ID=12702506
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10044834A Pending JPH11246458A (en) | 1998-02-26 | 1998-02-26 | Production of bisphenol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11246458A (en) |
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