JPH07330647A - Production of bisphenol compound - Google Patents
Production of bisphenol compoundInfo
- Publication number
- JPH07330647A JPH07330647A JP6125386A JP12538694A JPH07330647A JP H07330647 A JPH07330647 A JP H07330647A JP 6125386 A JP6125386 A JP 6125386A JP 12538694 A JP12538694 A JP 12538694A JP H07330647 A JPH07330647 A JP H07330647A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen atom
- general formula
- represent
- following general
- bisphenol compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、工業的に有用なビスフ
ェノール化合物の製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an industrially useful method for producing a bisphenol compound.
【０００２】[0002]
【従来の技術】ビスフェノール−Ｆ、ビスフェノール−
Ａ等のビスフェノール化合物は、エポキシ樹脂、ポリカ
ーボネート樹脂、等に工業的に広く使用されてきてい
る。これらのビスフェノール化合物は、フェノール類と
アルデヒド、ケトン等の縮合剤とを反応させることによ
り製造されるが、一般的にフェノールの多核体が副生し
やすく、ビスフェノール体の選択率を高くすることが困
難である。これらの問題を克服するため、工業的には、
縮合剤に対して、大過剰のフェノール類を反応させてい
る。2. Description of the Related Art Bisphenol-F, Bisphenol-
Bisphenol compounds such as A have been widely used industrially in epoxy resins, polycarbonate resins, and the like. These bisphenol compounds are produced by reacting a phenol with a condensing agent such as an aldehyde or a ketone. Generally, polynuclear bodies of phenol are easily produced as a byproduct, and it is possible to increase the selectivity of the bisphenol body. Have difficulty. To overcome these problems, industrially,
A large excess of phenols is reacted with the condensing agent.
【０００３】例えば、特公昭４８−３８６９４号公報に
示すビスフェノール−Ｆの選択的製造方法において、ホ
ルムアルデヒド１モルに対して６モルのフェノールを用
いている。さらに、ビスフェノール−Ｆの選択率を向上
させるための方法として、特開平１−２２６８４２号公
報には、ホルムアルデヒド１モルに対して２０モルのフ
ェノールを用い反応させた後、特定の有機溶剤でさらに
処理を行なう方法が開示されている。しかし、過剰量の
フェノール類を用いることは、反応器効率低下、および
反応後に過剰のフェノール類の除去を必要とし工業的に
好ましくない。For example, in the method for selectively producing bisphenol-F disclosed in JP-B-48-38694, 6 mol of phenol is used for 1 mol of formaldehyde. Further, as a method for improving the selectivity of bisphenol-F, in JP-A-1-226842, 20 mol of phenol is reacted with 1 mol of formaldehyde, followed by further treatment with a specific organic solvent. A method of doing is disclosed. However, it is industrially unfavorable to use an excessive amount of phenols because it requires a reduction in reactor efficiency and removal of excess phenols after the reaction.
【０００４】[0004]
【発明が解決しようとする課題】従って、本発明の目的
は、工業的に有利なビスフェノール化合物の製造方法を
提供することにある。Therefore, an object of the present invention is to provide an industrially advantageous method for producing a bisphenol compound.
【０００５】[0005]
【課題を解決するための手段】すなわち、本発明は、下
記一般式Means for Solving the Problems That is, the present invention provides the following general formula
【化７】 （但し、Ｒ1〜Ｒ4は水素原子または、炭素数１〜８の炭
化水素基を示し、かつＲ1〜Ｒ4のうち３個以上は同時に
水素原子ではない。また、Ａｒはベンゼン核を表わ
す。）で表わされるフェノール類２モルに対して、０．
８〜３．０モルの下記一般式、[Chemical 7] (However, R 1 to R 4 represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and three or more of R 1 to R 4 are not hydrogen atoms at the same time. Further, Ar represents a benzene nucleus. To 2 moles of the phenols represented by
8 to 3.0 mol of the following general formula,
【化８】 （但し、Ｒ5、Ｒ6は、水素原子または、炭素数１〜６の
炭化水素基を表わす。）または、下記一般式、[Chemical 8] (However, R 5 and R 6 represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.) Or the following general formula,
【化９】 （但し、Ｒ7〜Ｒ10は、水素原子または、メチル基を示
し、Ｒ11は、水素原子または、炭素数１〜４の炭化水素
基を示し、Ａｒはベンゼン核を示す。）で表わされる縮
合剤を用い、酸性触媒の存在下、生成する水、またはア
ルコールを反応系外に除きながら、かつ反応系内に目的
とするビスフェノール化合物の結晶を析出させつつ反応
させることを特徴とする下記一般式、[Chemical 9] (However, R 7 to R 10 represent a hydrogen atom or a methyl group, R 11 represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and Ar represents a benzene nucleus.). Using a condensing agent, in the presence of an acidic catalyst, while removing the produced water or alcohol out of the reaction system, and while reacting while precipitating crystals of the target bisphenol compound in the reaction system, the following general formula,
【化１０】 ｛但し、Ｒ1〜Ｒ4は水素原子または、炭素数１〜８の炭
化水素基を示し、かつＲ1〜Ｒ4のうち３個以上は同時に
水素原子ではない。また、Ａｒはベンゼン核を表わす。
さらに、Ｘは下記一般式、[Chemical 10] {However, R 1 to R 4 represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and three or more of R 1 to R 4 are not hydrogen atoms at the same time. Ar represents a benzene nucleus.
Further, X is the following general formula,
【化１１】 （但し、Ｒ5、Ｒ6は、水素原子または、炭素数１〜６の
炭化水素基を表わす。）または、下記一般式、[Chemical 11] (However, R 5 and R 6 represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.) Or the following general formula,
【化１２】 （但し、Ｒ7〜Ｒ10は水素原子またはメチル基を示し、
Ａｒはベンゼン核を表わす。）を表わす。｝で表わされ
るビスフェノール化合物の製造方法に関するものであ
る。[Chemical 12] (However, R 7 to R 10 represent a hydrogen atom or a methyl group,
Ar represents a benzene nucleus. ) Is represented. } It is related with the manufacturing method of the bisphenol compound represented by these.
【０００６】上記一般式化１で表わされるフェノール類
とは、Ｒ1〜Ｒ4が水素原子または、炭素数１〜８までの
炭化水素基であり、Ｒ1〜Ｒ4のうち３個以上が同時に水
素原子ではないフェノール類であり、ジ、トリ、または
テトラアルキルフェノール類を示している。たとえば、
２，４−キシレノール、２，６−キシレノール、２，４
−ジエチルフェノール、２，６−ジエチルフェノール、
２−ターシャリーブチル−５−メチルフェノール、２，
３，６−トリメチルフェノール、２，３，５，６−テト
ラメチルフェノール等が挙げられる。The phenols represented by the general formula 1 are hydrogen atoms of R 1 to R 4 or a hydrocarbon group having 1 to 8 carbon atoms, and three or more of R 1 to R 4 are At the same time, they are phenols that are not hydrogen atoms, and indicate di-, tri-, or tetraalkylphenols. For example,
2,4-xylenol, 2,6-xylenol, 2,4
-Diethylphenol, 2,6-diethylphenol,
2-tert-butyl-5-methylphenol, 2,
3,6-trimethylphenol, 2,3,5,6-tetramethylphenol and the like can be mentioned.
【０００７】上記一般式化２で表わされる縮合剤におい
て、Ｒ5，Ｒ6は水素原子または炭素数１〜６のアルキル
基を表わし、例えば、ホルマリン、パラホルムアルデヒ
ド、トリオキサン等のホルムアルデヒド、アセトアルデ
ヒド、ベンズアルデヒド等のアルデヒド類、またはアセ
トン、メチルエチルケトン、シクロヘキサノン等のケト
ン類が挙げられる。In the condensing agent represented by the general formula 2, R 5 and R 6 represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and for example, formaldehyde such as formalin, paraformaldehyde, trioxane, acetaldehyde and benzaldehyde. And the like, or ketones such as acetone, methyl ethyl ketone, and cyclohexanone.
【０００８】また、上記一般式化３で表わされる縮合剤
においてＲ7〜Ｒ10は、水素原子またはメチル基を示
し、例えば、ｐ−キシリレングリコール、ｍ−キシリレ
ングリコール、ｐ−キシリレングリコールジメチルエー
テル、ｐ−キシリレングリコールジエチルエーテル、
１，３−ビス（２−ヒドロキシ−２−プロピル）ベンゼ
ン、１，４−ビス（２−ヒドロキシ−２−プロピル）ベ
ンゼン等が挙げられる。In the condensing agent represented by the general formula 3, R 7 to R 10 each represent a hydrogen atom or a methyl group, for example, p-xylylene glycol, m-xylylene glycol, p-xylylene glycol. Dimethyl ether, p-xylylene glycol diethyl ether,
1,3-bis (2-hydroxy-2-propyl) benzene, 1,4-bis (2-hydroxy-2-propyl) benzene and the like can be mentioned.
【０００９】本発明における縮合剤の使用量はフェノー
ル類２モルに対して、０．８〜３．０モルの範囲であ
る。縮合剤の理論量は１．０モルであるが、縮合剤の使
用量を理論量以上とすることにより反応後の系内の残存
フェノール類の低減が可能であり、実用上、残存フェノ
ール類の影響を無視できる程度まで低減させることがで
きる。縮合剤の使用量がフェノール類２モルに対して
０．８より少ないと未反応フェノール類の量が多くな
り、釜効率を低下させるだけでなく、未反応フェノール
類の除去が困難になるとともに、生成したビスフェノー
ル化合物が過剰のフェノール類に溶解するため本発明の
特徴であるビスフェノール化合物の結晶を析出させなが
ら反応を行なうことが困難になる。結果として、溶解し
たビスフェノール化合物がさらに反応に関与することと
なり、ビスフェノール化合物の選択率が低下する。逆に
縮合剤の使用量が多くなると、過剰の縮合剤の除去が困
難になる。縮合剤のさらに好ましい使用量は、フェノー
ル類２モルに対して、０．９〜２．５モルの範囲であ
る。The amount of the condensing agent used in the present invention is in the range of 0.8 to 3.0 mol based on 2 mol of the phenols. Although the theoretical amount of the condensing agent is 1.0 mol, it is possible to reduce the residual phenols in the system after the reaction by adjusting the amount of the condensing agent to be more than the theoretical amount. The influence can be reduced to a negligible level. When the amount of the condensing agent used is less than 0.8 with respect to 2 mol of phenols, the amount of unreacted phenols increases, which not only lowers the pot efficiency but also makes it difficult to remove unreacted phenols. Since the produced bisphenol compound is dissolved in excess phenols, it becomes difficult to carry out the reaction while precipitating the crystals of the bisphenol compound, which is a feature of the present invention. As a result, the dissolved bisphenol compound is further involved in the reaction, and the selectivity of the bisphenol compound is lowered. On the contrary, when the amount of the condensing agent used is large, it becomes difficult to remove the excessive condensing agent. The more preferable amount of the condensing agent used is in the range of 0.9 to 2.5 mol based on 2 mol of the phenol.
【００１０】さらに、本発明は反応の過程で生成する
水、またはアルコールを系外に除きながら、かつ生成す
るビスフェノール化合物の結晶を析出させつつ反応を行
なう。生成したビスフェノール化合物を結晶として析出
させることにより、生成したビスフェノール化合物がさ
らに反応に関与することを抑えることが可能であり、結
果として多核フェノール化合物の生成を抑えることがで
き、目的とするビスフェノール化合物生成の選択率を大
幅に向上させることができる。Further, in the present invention, the reaction is carried out while removing water or alcohol produced in the course of the reaction out of the system and precipitating crystals of the produced bisphenol compound. By precipitating the generated bisphenol compound as crystals, it is possible to suppress the generated bisphenol compound from further participating in the reaction, and as a result, it is possible to suppress the production of the polynuclear phenol compound and to produce the desired bisphenol compound. The selectivity of can be greatly improved.
【００１１】本発明に用いる酸性触媒としては、一般に
知られる有機、無機系化合物の中から適宜選択され使用
される。例えば、シュウ酸、メタンスルホン酸、ｐ−ト
ルエンスルホン酸、トリフルオロ酢酸等の有機酸、又
は、塩酸、硫酸、りん酸、等の鉱酸、さらには活性白
土、ゼオライト、イオン交換樹脂等の固体酸等が挙げら
れる。装置の腐食、作業性の面からは有機酸を使用する
ことが好ましく、特に好ましくはシュウ酸が用いられ
る。その使用量は、通常、フェノール類に対して、０．
２〜５．０重量％の範囲である。The acidic catalyst used in the present invention is appropriately selected and used from generally known organic and inorganic compounds. For example, organic acids such as oxalic acid, methanesulfonic acid, p-toluenesulfonic acid and trifluoroacetic acid, or mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid, and solids such as activated clay, zeolite and ion exchange resins. Acid etc. are mentioned. From the viewpoint of corrosion and workability of the apparatus, it is preferable to use an organic acid, particularly preferably oxalic acid. The amount used is usually 0.
It is in the range of 2 to 5.0% by weight.
【００１２】反応は、通常、５０〜２００℃の範囲で行
なわれる。また、反応は無溶媒で行なうのが好ましい
が、場合により適量の溶媒を用いることができる。用い
る溶媒としては、水または、メタノール、エタノール、
イソプロパノール、ブタノール、エチレングリコール、
エチルセロソルブ等のアルコール類、ヘキサン、ヘプタ
ン、ベンゼン、トルエン、キシレン等の炭化水素類、ア
セトン、メチルエチルケトン等のケトン類、クロロエタ
ン、ジクロロエタン、クロロベンゼン等のハロゲン化溶
媒、エチルエーテル、テトラヒドロフラン等のエーテル
類、等が例示され、その使用量は用いるフェノール類に
対して通常、５〜１００％の範囲である。用いた溶媒は
ビスフェノール化合物の結晶を析出させた後、系外を除
いてもよいし、反応を行ないビスフェノール化合物の結
晶を析出させながら系外に除いてもよい。The reaction is usually carried out in the range of 50 to 200 ° C. The reaction is preferably carried out without solvent, but an appropriate amount of solvent can be used depending on the case. The solvent used is water or methanol, ethanol,
Isopropanol, butanol, ethylene glycol,
Alcohols such as ethyl cellosolve, hexane, heptane, benzene, toluene, hydrocarbons such as xylene, acetone, ketones such as methyl ethyl ketone, chloroethane, dichloroethane, halogenated solvents such as chlorobenzene, ethers such as ethyl ether and tetrahydrofuran, Etc. are exemplified, and the amount used is usually in the range of 5 to 100% with respect to the phenols used. The solvent used may be removed from the system after the crystals of the bisphenol compound are precipitated, or may be removed from the system while the reaction is performed to precipitate the crystals of the bisphenol compound.
【００１３】[0013]
【実施例】以下実施例により本発明をさらに具体的に説
明する。 （実施例１）３００mlフラスコに２，６−キシレノール
１２２ｇ（１．０モル）、９２％パラホルムアルデヒ
ド １７．１ｇ（０．５２５モル）およびシュウ酸
１．８３ｇを仕込み、撹拌しながら１２０℃に昇温し反
応させた。約３０分後、系内に結晶の析出が認められ
た。その間、生成する水は系外に除いた。さらに、縮合
水を系外に除きつつ、１３０℃まで昇温し２時間反応を
継続した。反応器内の生成物を液体クラマトグラフィー
で分析したところ、この時点で系内の未反応２，６−キ
シレノールは、０．９％となっていた。その後、減圧し
（３０mmHg）、さらに１５０℃まで昇温し１時間反応を
行なった後、淡黄色粉末状の３，３′，５，５′−テト
ラメチル−４，４′−ジヒドロキシジフェニルメタン
１２４．５ｇ（収率、９７．３ｇ）を得た。液体クラマ
トグラフィーで分析したところ、３，３′，５，５′−
テトラメチル−４，４′−ジヒドロキシジフェニルメタ
ンの純度は９９．１％であり、未反応２，６−キシレノ
ールは、０．１％以下であった。The present invention will be described in more detail with reference to the following examples. Example 1 A 300 ml flask was charged with 122 g (1.0 mol) of 2,6-xylenol, 17.1 g (0.525 mol) of 92% paraformaldehyde and oxalic acid.
1.83 g was charged and the temperature was raised to 120 ° C. with stirring to cause a reaction. After about 30 minutes, crystal precipitation was observed in the system. During that time, generated water was removed from the system. Further, while removing the condensed water to the outside of the system, the temperature was raised to 130 ° C. and the reaction was continued for 2 hours. When the product in the reactor was analyzed by liquid chromatography, unreacted 2,6-xylenol in the system at this point was 0.9%. Then, the pressure was reduced (30 mmHg), the temperature was further raised to 150 ° C., and the reaction was carried out for 1 hour.
124.5 g (yield, 97.3 g) was obtained. When analyzed by liquid chromatography, 3,3 ', 5,5'-
The purity of tetramethyl-4,4'-dihydroxydiphenylmethane was 99.1%, and the unreacted 2,6-xylenol was 0.1% or less.
【００１４】（実施例２）３００mlフラスコに２，６−
キシレノール １２２ｇ（１．０モル）、９２％パラホ
ルムアルデヒド ３５．９ｇ（１．１モル）およびシュ
ウ酸 ２．４４ｇを仕込み、撹拌しながら１１５℃に昇
温し反応させた。１０分後、系内に結晶の析出が認めら
れた。その間、生成する水は系外に除いた。さらに、縮
合水を系外に除きつつ、１時間反応を継続した。反応器
内の生成物を液体クラマトグラフィーで分析したとこ
ろ、この時点で系内の未反応２，６−キシレノールは、
０．１％以下であった。その後、減圧し（３０mmHg）、
さらに１５０℃まで昇温し１時間反応を行なった後、淡
黄色粉末状の３，３′，５，５′−テトラメチル−４，
４′−ジヒドロキシジフェニルメタン １２３．０ｇ
（収率、９６．１ｇ）を得た。液体クラマトグラフィー
で分析したところ、３，３′，５，５′−テトラメチル
−４，４′−ジヒドロキシジフェニルメタンの純度は９
８．６％であり、未反応２，６−キシレノールは、０．
１％以下であった。(Example 2) 2,6-
122 g (1.0 mol) of xylenol, 35.9 g (1.1 mol) of 92% paraformaldehyde and 2.44 g of oxalic acid were charged, and the temperature was raised to 115 ° C. with stirring to react. After 10 minutes, precipitation of crystals was observed in the system. During that time, generated water was removed from the system. Furthermore, the reaction was continued for 1 hour while removing the condensed water out of the system. When the product in the reactor was analyzed by liquid chromatography, unreacted 2,6-xylenol in the system at this point was
It was 0.1% or less. After that, depressurize (30 mmHg),
After further raising the temperature to 150 ° C. and reacting for 1 hour, 3,3 ′, 5,5′-tetramethyl-4, which is a pale yellow powder,
4'-dihydroxydiphenylmethane 123.0 g
(Yield, 96.1 g) was obtained. When analyzed by liquid chromatography, the purity of 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxydiphenylmethane was 9
8.6%, and unreacted 2,6-xylenol is less than 0.
It was 1% or less.
【００１５】（実施例３）３００mlフラスコに２，６−
キシレノール １２２ｇ（１．０モル）、９２％パラホ
ルムアルデヒド １５．５ｇ（０．４７５モル）および
シュウ酸 １．８３ｇを仕込み、撹拌しながら１２０℃
に昇温し反応させた。約３０分後、系内に結晶の析出が
認められた。その間、生成する水は系外に除いた。さら
に、縮合水を系外に除きつつ、１３０℃まで昇温し２時
間反応を継続した。反応器内の生成物を液体クラマトグ
ラフィーで分析したところ、この時点で系内の未反応
２，６−キシレノールは、３．６％であった。その後、
減圧下（３０mmHg）、１５０℃まで昇温し縮合水および
未反応２，６−キシレノールを留去後、淡黄色粉末状の
３，３′，５，５′−テトラメチル−４，４′−ジヒド
ロキシジフェニルメタン１１９．３ｇ（収率、９３．２
ｇ）を得た。液体クラマトグラフィーで分析したとこ
ろ、３，３′，５，５′−テトラメチル−４，４′−ジ
ヒドロキシジフェニルメタンの純度は９８．７％であ
り、未反応２，６−キシレノールは、０．１％以下であ
った。Example 3 In a 300 ml flask, 2,6-
122 g (1.0 mol) of xylenol, 15.5 g (0.475 mol) of 92% paraformaldehyde and 1.83 g of oxalic acid were charged, and the mixture was stirred at 120 ° C.
The temperature was raised to the reaction temperature. After about 30 minutes, crystal precipitation was observed in the system. During that time, generated water was removed from the system. Further, while removing the condensed water out of the system, the temperature was raised to 130 ° C. and the reaction was continued for 2 hours. When the product in the reactor was analyzed by liquid chromatography, unreacted 2,6-xylenol in the system at this point was 3.6%. afterwards,
Under reduced pressure (30 mmHg), the temperature was raised to 150 ° C., the condensed water and unreacted 2,6-xylenol were distilled off, and then pale yellow powdery 3,3 ′, 5,5′-tetramethyl-4,4′- 119.3 g of dihydroxydiphenylmethane (yield, 93.2
g) was obtained. When analyzed by liquid chromatography, the purity of 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxydiphenylmethane was 98.7%, and unreacted 2,6-xylenol was 0.1%. % Or less.
【００１６】（実施例４）３００mlフラスコに２，６−
キシレノール １２２ｇ（１．０モル）、１，４−ビス
（２−ヒドロキシ−２−プロピル）ベンゼン ９７ｇ
（０．５モル）、トルエン ３０mlおよびｐ−トルエン
スルホン酸 １．８ｇを仕込み、撹拌しながら１２０℃
に昇温し縮合水およびトルエンを系外に除きつつ反応さ
せた。約１時間後、系内に結晶の析出が認められた。そ
の後さらに、縮合水およびトルエンを系外に除きつつ、
１３０℃まで昇温し２時間反応を継続した。反応器内の
生成物を液体クラマトグラフィーで分析したところ、こ
の時点で系内の未反応２，６−キシレノールは、０．１
％以下となっていた。その後、減圧下（３０mmHg）、縮
合水および未反応の２，６−キシレノールを留去後、淡
黄色粉末状の１，４−ビス（３，５−ジメチル−４−ヒ
ドロキシクミル）ベンゼン ２００ｇ（収率、９９．５
％）を得た。液体クラマトグラフィーで分析したとこ
ろ、１，４−ビス（３，５−ジメチル−４−ヒドロキシ
クミル）ベンゼンの純度は９９．０％であり、未反応
２，６−キシレノールは、０．１％以下であった。Example 4 In a 300 ml flask, 2,6-
Xylenol 122 g (1.0 mol), 1,4-bis (2-hydroxy-2-propyl) benzene 97 g
(0.5 mol), toluene (30 ml) and p-toluenesulfonic acid (1.8 g) were charged, and the mixture was stirred at 120 ° C.
The temperature was raised to 0 and the reaction was performed while removing condensed water and toluene out of the system. After about 1 hour, precipitation of crystals was observed in the system. After that, while further removing condensed water and toluene from the system,
The temperature was raised to 130 ° C. and the reaction was continued for 2 hours. When the product in the reactor was analyzed by liquid chromatography, the amount of unreacted 2,6-xylenol in the system was 0.1
It was below%. Then, under reduced pressure (30 mmHg), water of condensation and unreacted 2,6-xylenol were distilled off, and then 200 g of 1,4-bis (3,5-dimethyl-4-hydroxycumyl) benzene in the form of a pale yellow powder ( Yield, 99.5
%) Was obtained. When analyzed by liquid chromatography, the purity of 1,4-bis (3,5-dimethyl-4-hydroxycumyl) benzene was 99.0%, and unreacted 2,6-xylenol was 0.1%. It was below.
【００１７】[0017]
【発明の効果】本発明により、エポキシ樹脂、ポリカー
ボネート等の用途に有用なビスフェノール化合物を高純
度で収率よく、工業的有利に製造することができる。INDUSTRIAL APPLICABILITY According to the present invention, a bisphenol compound useful for applications such as epoxy resins and polycarbonates can be produced with high purity in good yield and industrially advantageously.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｃ 39/15 9155−4Ｈ // Ｃ０７Ｂ 61/00 ３００ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Office reference number FI technical display location C07C 39/15 9155-4H // C07B 61/00 300
Claims (2)
化水素基を示し、かつＲ1〜Ｒ4のうち３個以上は同時に
水素原子ではない。また、Ａｒはベンゼン核を表わ
す。）で表わされるフェノール類２モルに対して、０．
８〜３．０モルの下記一般式、 【化２】 （但し、Ｒ5、Ｒ6は、水素原子または、炭素数１〜６の
炭化水素基を表わす。）または、下記一般式、 【化３】 （但し、Ｒ7〜Ｒ10は、水素原子または、メチル基を示
し、Ｒ11は、水素原子または、炭素数１〜４の炭化水素
基を示し、Ａｒはベンゼン核を示す。）で表わされる縮
合剤を用い、酸性触媒の存在下、生成する水、またはア
ルコールを反応系外に除きながら、かつ反応系内に目的
とするビスフェノール化合物の結晶を析出させつつ反応
させることを特徴とする下記一般式、 【化４】 ｛但し、Ｒ1〜Ｒ4は水素原子または、炭素数１〜８の炭
化水素基を示し、かつＲ1〜Ｒ4のうち３個以上は同時に
水素原子ではない。また、Ａｒはベンゼン核を表わす。
さらに、Ｘは下記一般式、 【化５】 （但し、Ｒ5、Ｒ6は、水素原子または、炭素数１〜６の
炭化水素基を表わす。）または、下記一般式、 【化６】 （但し、Ｒ7〜Ｒ10は水素原子またはメチル基を示し、
Ａｒはベンゼン核を表わす。）を表わす。｝で表わされ
るビスフェノール化合物の製造方法。1. The following general formula: (However, R 1 to R 4 represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and three or more of R 1 to R 4 are not hydrogen atoms at the same time. Further, Ar represents a benzene nucleus. To 2 moles of the phenols represented by
8-3.0 mol of the following general formula: (However, R 5 and R 6 represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.) Or, the following general formula: (However, R 7 to R 10 represent a hydrogen atom or a methyl group, R 11 represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and Ar represents a benzene nucleus.). Using a condensing agent, in the presence of an acidic catalyst, while removing the produced water or alcohol out of the reaction system, and while reacting while precipitating crystals of the target bisphenol compound in the reaction system, the following general Formula, {However, R 1 to R 4 represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and three or more of R 1 to R 4 are not hydrogen atoms at the same time. Ar represents a benzene nucleus.
Further, X is the following general formula: (Wherein R 5 and R 6 represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms), or a compound represented by the following general formula: (However, R 7 to R 10 represent a hydrogen atom or a methyl group,
Ar represents a benzene nucleus. ) Is represented. } The manufacturing method of the bisphenol compound represented by these.
ル、縮合剤としてホルムアルデヒドを用い、シュウ酸触
媒の存在下、反応させることを特徴とする請求項１に記
載のビスフェノール化合物の製造方法。2. The method for producing a bisphenol compound according to claim 1, wherein the reaction is carried out in the presence of an oxalic acid catalyst using 2,6-xylenol as the phenol and formaldehyde as the condensing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12538694A JP3638631B2 (en) | 1994-06-07 | 1994-06-07 | Method for producing bisphenol compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12538694A JP3638631B2 (en) | 1994-06-07 | 1994-06-07 | Method for producing bisphenol compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07330647A true JPH07330647A (en) | 1995-12-19 |
| JP3638631B2 JP3638631B2 (en) | 2005-04-13 |
Family
ID=14908858
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12538694A Expired - Fee Related JP3638631B2 (en) | 1994-06-07 | 1994-06-07 | Method for producing bisphenol compound |
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| Country | Link |
|---|---|
| JP (1) | JP3638631B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002187862A (en) * | 2000-12-19 | 2002-07-05 | Mitsubishi Chemicals Corp | Tetramethylbisphenol f, method for producing the same and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5291848A (en) * | 1976-01-24 | 1977-08-02 | Bayer Ag | Process for preparing 4*44dihydroxyy 3*3**5*5**tetraalkyldiphenylmethane |
| JPS55124730A (en) * | 1979-03-22 | 1980-09-26 | Ube Ind Ltd | Preparation of dihydroxydiphenylmethane |
| JPH037241A (en) * | 1989-03-22 | 1991-01-14 | Nippon Steel Chem Co Ltd | Novel dihydroxy compound and preparation thereof |
| JPH04211257A (en) * | 1988-07-07 | 1992-08-03 | Sumitomo Chem Co Ltd | Polyphenol compound |
| JPH04225012A (en) * | 1990-12-27 | 1992-08-14 | Nippon Kayaku Co Ltd | Tetra-nuclear phenolic novolak and its production |
-
1994
- 1994-06-07 JP JP12538694A patent/JP3638631B2/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5291848A (en) * | 1976-01-24 | 1977-08-02 | Bayer Ag | Process for preparing 4*44dihydroxyy 3*3**5*5**tetraalkyldiphenylmethane |
| JPS55124730A (en) * | 1979-03-22 | 1980-09-26 | Ube Ind Ltd | Preparation of dihydroxydiphenylmethane |
| JPH04211257A (en) * | 1988-07-07 | 1992-08-03 | Sumitomo Chem Co Ltd | Polyphenol compound |
| JPH037241A (en) * | 1989-03-22 | 1991-01-14 | Nippon Steel Chem Co Ltd | Novel dihydroxy compound and preparation thereof |
| JPH04225012A (en) * | 1990-12-27 | 1992-08-14 | Nippon Kayaku Co Ltd | Tetra-nuclear phenolic novolak and its production |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002187862A (en) * | 2000-12-19 | 2002-07-05 | Mitsubishi Chemicals Corp | Tetramethylbisphenol f, method for producing the same and application thereof |
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| Publication number | Publication date |
|---|---|
| JP3638631B2 (en) | 2005-04-13 |
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