JP2001233812A - Method for producing bisphenol a - Google Patents
Method for producing bisphenol aInfo
- Publication number
- JP2001233812A JP2001233812A JP2000046673A JP2000046673A JP2001233812A JP 2001233812 A JP2001233812 A JP 2001233812A JP 2000046673 A JP2000046673 A JP 2000046673A JP 2000046673 A JP2000046673 A JP 2000046673A JP 2001233812 A JP2001233812 A JP 2001233812A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- acetone
- reaction
- group
- hydrocarbon group
- 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
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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]
【発明の属する技術分野】本発明は、ビスフェノールＡ
の製造方法に関し、詳しくは、スルホン酸基含有炭化水
素基とメルカプト基含有炭化水素基を有する有機高分子
シロキサン触媒を用いて、アセトンとフェノールから高
活性でビスフェノールＡを製造する方法に関するもので
ある。TECHNICAL FIELD The present invention relates to a bisphenol A
More specifically, the present invention relates to a method for producing bisphenol A with high activity from acetone and phenol using an organic polymer siloxane catalyst having a sulfonic acid group-containing hydrocarbon group and a mercapto group-containing hydrocarbon group. .
【０００２】[0002]
【従来の技術】ビスフェノールＡは通常、固体触媒にア
セトンとモル比にして８〜１５倍過剰のフェノールを通
液する、所謂固定床流通反応の形態で連続的に製造され
ている。これらの固体触媒としては、陽イオン交換樹脂
もしくはメルカプトアルキルアミンを部分的に中和し、
メルカプト基を固定化したメルカプト変性陽イオン交換
樹脂などが用いられる。該触媒の触媒性能の低下を抑制
する方法として特開平８−３２５１８５号公報にメルカ
プト基含有化合物を反応系へ添加する方法が記載されて
いる。このように変性陽イオン交換樹脂触媒では長時間
運転における触媒活性の低下を防ぐことが重要な課題で
ある。2. Description of the Related Art Bisphenol A is usually produced continuously in the form of a so-called fixed bed flow reaction in which an 8 to 15-fold excess of phenol in molar ratio with acetone is passed through a solid catalyst. As these solid catalysts, a cation exchange resin or a mercaptoalkylamine is partially neutralized,
A mercapto-modified cation exchange resin having a mercapto group immobilized thereon is used. JP-A-8-325185 describes a method of adding a mercapto group-containing compound to a reaction system as a method for suppressing a decrease in catalytic performance of the catalyst. As described above, it is an important issue for the modified cation exchange resin catalyst to prevent a decrease in the catalytic activity in long-term operation.
【０００３】一方、イオン交換樹脂以外の触媒として、
特開平８−２０８５４５号、特開平９−１１０７６７
号、特開平９−１１０９８９号、特開平１０−２２５６
３８号公報にスルホン酸基含有炭化水素とメルカプト基
含有炭化水素基を有する有機高分子シロキサン触媒が記
載されている。On the other hand, as a catalyst other than an ion exchange resin,
JP-A-8-208545, JP-A-9-110767
JP-A-9-110889, JP-A-10-2256
No. 38 describes an organic polymer siloxane catalyst having a sulfonic acid group-containing hydrocarbon and a mercapto group-containing hydrocarbon group.
【０００４】有機高分子シロキサン触媒はイオン交換樹
脂触媒と比較して触媒活性及び選択性が非常に高い触媒
である事が知られている。これら、有機高分子シロキサ
ン触媒のビスフェノールＡを生成する能力は触媒調製時
の活性点の量に依存する。したがって、流通反応を行っ
ている際に触媒活性が不足している場合には、流通反応
を打ち切り活性の高い触媒と交換するか、運転条件をよ
り過酷にし選択率を犠牲にして活性を上げる方法が考え
られる。また、特願平１１−１０３３６９号公報では流
通反応の原料に水を添加し、経時的な活性低下を抑制す
る方法が記載されているが、この方法では、好ましくな
い初期活性の低下を招く。すなわち、これまでは簡便に
シロキサン触媒の活性を補充する方法がなかった。It is known that an organic high molecular siloxane catalyst is a catalyst having extremely high catalytic activity and selectivity as compared with an ion exchange resin catalyst. The ability of these organopolymeric siloxane catalysts to produce bisphenol A depends on the amount of active sites during catalyst preparation. Therefore, if the catalytic activity is insufficient during the flow reaction, the flow reaction is terminated and replaced with a catalyst having a higher activity, or the operating conditions are made more severe and the activity is increased at the expense of selectivity. Can be considered. Japanese Patent Application No. 11-103369 describes a method in which water is added to a raw material of a flow reaction to suppress a decrease in activity over time, but this method causes an undesirable decrease in initial activity. That is, there has been no simple method for replenishing the activity of the siloxane catalyst.
【０００５】[0005]
【発明が解決しようとする課題】本発明はスルホン酸基
含有炭化水素基とメルカプト基含有炭化水素基を有する
有機高分子シロキサンの存在下、アセトンとフェノール
を反応させてビスフェノールＡを得る反応の際に、触媒
の活性を向上させると同時に経時的な活性低下を防ぐ方
法を提供することを目的とするものである。DISCLOSURE OF THE INVENTION The present invention relates to a reaction for obtaining bisphenol A by reacting acetone and phenol in the presence of an organic high molecular siloxane having a sulfonic acid group-containing hydrocarbon group and a mercapto group-containing hydrocarbon group. Another object of the present invention is to provide a method for improving the activity of the catalyst and at the same time preventing the activity from decreasing over time.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、アセトン
とフェノールからビスフェノールＡを製造するに際し、
スルホン酸基含有炭化水素基とメルカプト基含有炭化水
素基を有する有機高分子シロキサン触媒の活性を向上さ
せると同時に経時的な活性低下を防ぐことを目的に鋭意
検討を行った結果、メルカプト基含有化合物を共存させ
ることにより、触媒の活性が向上する事を見出し、本発
明を完成するに至ったものである。Means for Solving the Problems In producing bisphenol A from acetone and phenol, the present inventors
As a result of diligent investigations aimed at improving the activity of the organic polymer siloxane catalyst having a sulfonic acid group-containing hydrocarbon group and a mercapto group-containing hydrocarbon group and at the same time preventing the activity from decreasing over time, a mercapto group-containing compound was obtained. Have been found to improve the activity of the catalyst by coexisting, and have completed the present invention.
【０００７】すなわち、本発明は、スルホン酸基含有炭
化水素基とメルカプト基含有炭化水素基を有する有機高
分子シロキサン触媒を用いて、アセトンとフェノールか
らビスフェノールＡを製造する方法において、メルカプ
ト基含有化合物の存在下にアセトンとフェノールを反応
させることを特徴とするビスフェノールＡの製造方法で
ある。That is, the present invention relates to a method for producing bisphenol A from acetone and phenol using an organic polymer siloxane catalyst having a sulfonic acid group-containing hydrocarbon group and a mercapto group-containing hydrocarbon group. A process for producing bisphenol A, comprising reacting acetone and phenol in the presence of phenol.
【０００８】[0008]
【発明の実施の形態】本発明で用いられるスルホン酸基
含有炭化水素基とメルカプト基含有炭化水素基を有する
有機高分子シロキサン触媒とは、特開平８−２０８５４
５号、特開平９−１１０９８９号、特開平１０−２２５
６３８号公報に記載されているシロキサン結合からなる
シリカマトリックス中に部分的にスルホン酸基を有する
炭化水素基とメルカプト基を有する炭化水素基が直接シ
リカマトリックス中のケイ素原子と炭素−ケイ素結合に
より結合した構造を有する有機高分子シロキサンであ
る。BEST MODE FOR CARRYING OUT THE INVENTION The organic polymer siloxane catalyst having a sulfonic acid group-containing hydrocarbon group and a mercapto group-containing hydrocarbon group used in the present invention is disclosed in JP-A-8-20854.
5, JP-A-9-110989, JP-A-10-225
No. 638, a hydrocarbon group having a sulfonic acid group and a hydrocarbon group having a mercapto group are directly bonded to a silicon atom in a silica matrix and a carbon-silicon bond in a silica matrix comprising a siloxane bond. Is an organic polymer siloxane having the following structure.
【０００９】このような有機高分子シロキサン触媒の調
製方法としては、例えば、(1)スルホン酸基含有炭化水
素基を有するアルコキシシランとメルカプト基含有炭化
水素基を有するアルコキシシランとテトラアルコキシシ
ランとを任意の割合で混合し、加水分解させて、重縮合
により合成する調製法、(2)水溶性のスルホン酸基含有
炭化水素基を有するアルコキシシランの加水分解物とメ
ルカプト基含有炭化水素基を有するアルコキシシランと
テトラアルコキシシランとを任意の割合で混合し、加水
分解させて重縮合により合成する調製法などの所謂アル
コキシシランのゾル−ゲル法による調製法と、(3)スル
ホン酸基含有炭化水素基を有する有機高分子シロキサン
に存在するシラノール基にメルカプト基含有炭化水素基
を有するアルコキシシランをシリル化し、メルカプト基
を固定化する、所謂シリル化による調製法が知られてい
る。As a method for preparing such an organic polymer siloxane catalyst, for example, (1) an alkoxysilane having a sulfonic acid group-containing hydrocarbon group, an alkoxysilane having a mercapto group-containing hydrocarbon group, and a tetraalkoxysilane are used. Mixing at an arbitrary ratio, hydrolyzing and preparing by polycondensation, (2) having a hydrolyzate of an alkoxysilane having a water-soluble sulfonic acid group-containing hydrocarbon group and a mercapto group-containing hydrocarbon group A method of mixing alkoxysilane and tetraalkoxysilane in an arbitrary ratio, a method of preparing a so-called alkoxysilane by a sol-gel method such as a method of synthesizing by hydrolysis and polycondensation, and (3) a sulfonic acid group-containing hydrocarbon Having a mercapto group-containing hydrocarbon group in the silanol group present in the organic polymer siloxane having a group The silylated, to immobilize the mercapto group is known preparing method by the so-called silylation.
【００１０】本発明はこれらの調整法によって得られた
スルホン酸基含有炭化水素基とメルカプト基含有炭化水
素基を有する有機高分子シロキサン触媒を用いてビスフ
ェノールＡ合成反応に使用する際に、メルカプト基を含
有する化合物を共存させて反応を実施するものである。The present invention relates to a method for preparing a bisphenol A synthesis reaction using an organic polymer siloxane catalyst having a sulfonic acid group-containing hydrocarbon group and a mercapto group-containing hydrocarbon group obtained by these preparation methods. The reaction is carried out in the presence of a compound containing
【００１１】このメルカプト基含有化合物とは、例えば
メチルメルカプタン、エチルメルカプタン、プロピルメ
ルカプタン、ブチルメルカプタンなどの低級アルキルメ
ルカプタン類、ベンジルメルカプタンなどの芳香族メル
カプタン類、2-メルカプト酢酸、3-メルカプトプロピオ
ン酸などのメルカプトカルボン酸類、2-メルカプトエタ
ノールなどのチオアルコール類などが挙げられるが、中
でも蒸気圧が高く臭気の少ない3-メルカプトプロピオン
酸の使用が好ましい。The mercapto group-containing compound includes, for example, lower alkyl mercaptans such as methyl mercaptan, ethyl mercaptan, propyl mercaptan and butyl mercaptan, aromatic mercaptans such as benzyl mercaptan, 2-mercaptoacetic acid, 3-mercaptopropionic acid and the like. And thioalcohols such as 2-mercaptoethanol. Among them, use of 3-mercaptopropionic acid having a high vapor pressure and a low odor is preferable.
【００１２】アセトンとフェノールの反応において、こ
れらメルカプト基含有化合物の存在下とは、原料と共存
していればよく、予め原料へ添加し反応器へ供給する方
法が好ましく用いられる。その量は原料混合物の０．０
０１重量％から１０重量％の範囲であり、好ましくは
０．０１重量％から８重量％、さらに好ましくは０．１
重量％から５重量％の範囲である。この範囲よりも少な
い場合には、触媒活性の向上効果が低く、またこれより
も高い範囲で使用しても添加見合いの向上効果が見られ
ず、むしろ経済的に不利となる。In the reaction of acetone and phenol, the presence of these mercapto group-containing compounds only needs to coexist with the raw materials, and a method in which the compounds are added to the raw materials in advance and supplied to the reactor is preferably used. The amount is 0.0% of the raw material mixture.
In the range of 0.01% to 10% by weight, preferably 0.01% to 8% by weight, more preferably 0.1% to 8% by weight.
% By weight to 5% by weight. When the amount is less than this range, the effect of improving the catalyst activity is low, and even when used in a range higher than this, the effect of improving the proportion of addition is not seen, and it is rather economically disadvantageous.
【００１３】また本発明は、原料のフェノールまたはア
セトンに水を含んでいてもよく、さらに含んでいること
が好ましい。水とメルカプト基含有化合物は、それぞれ
に触媒の活性低下を抑制する作用を有するが、これらが
共存していてもその作用を失うものではない。好ましい
水の含有量は、原料混合物に対して０．２重量％から５
重量％の範囲である。この範囲を超える水の含有は、初
期活性の低下を招くので好ましくない。In the present invention, the raw material phenol or acetone may contain water, and preferably further contains water. Water and the mercapto group-containing compound each have an action of suppressing a decrease in the activity of the catalyst. However, even when they coexist, the action is not lost. The preferred water content is between 0.2% by weight and 5% by weight of the raw material mixture.
% By weight. The content of water exceeding this range is not preferable because it causes a decrease in the initial activity.
【００１４】本反応は固定床流通反応、回分式反応、懸
濁式反応いずれの形態でも実施できるが、触媒分離の容
易さから固定床流通反応で行う事が好ましい。その場合
の滞留時間は特に限定されないが、通常は１分〜１５時
間程度、好ましくは１０分〜５時間の範囲である。また
原料のフェノールとアセトンの使用量比は特に限定され
ないが、通常アセトンに対してフェノールがモル比で２
〜５０倍の範囲であり、さらに好ましくは４〜２５倍の
範囲で実施することが推奨される。This reaction can be carried out in any of a fixed bed flow reaction, a batch reaction and a suspension reaction, but it is preferable to carry out the reaction in a fixed bed flow reaction because of the ease of separation of the catalyst. The residence time in that case is not particularly limited, but is usually in the range of about 1 minute to 15 hours, preferably 10 minutes to 5 hours. The ratio of the amounts of phenol and acetone used as raw materials is not particularly limited.
It is recommended to carry out in the range of 50 to 50 times, and more preferably in the range of 4 to 25 times.
【００１５】反応温度についても本発明では特に限定さ
れる事は無いが、４０〜２００℃の範囲で行われ、好ま
しくは５０〜１２０℃の範囲である。Although the reaction temperature is not particularly limited in the present invention, the reaction is carried out in the range of 40 to 200 ° C., preferably in the range of 50 to 120 ° C.
【００１６】本発明における反応で用いたメルカプト基
含有化合物は、一般的な分離方法、すなわち蒸留、抽
出、晶析などの方法によって分離され、繰り返し反応に
供する事ができる。The compound containing a mercapto group used in the reaction of the present invention is separated by a general separation method, that is, a method such as distillation, extraction, or crystallization, and can be repeatedly subjected to the reaction.
【００１７】[0017]
【実施例】以下、本発明を実施例により、具体的に説明
する。しかしながら、この実施例は単なる例示であっ
て、本発明はこれらに限定されるものではない。また、
実施例において、触媒の寿命を1００時間後の劣化率
（アセトン転化率において、反応後3時間目の値と1００
時間目の値との差を3時間目の値で除した値）で表わし
た。そこで、フェノールとアセトンのみを原料とした場
合の反応の劣化率（比較例１）を１００とした時、該反
応の劣化率の相対値（該反応の劣化率の値を、フェノー
ルとアセトンのみを原料とした場合の反応の劣化率の値
で除し１００を乗じた値）ついて、許容範囲が６０以内
を目安とした。The present invention will be specifically described below with reference to examples. However, this example is merely illustrative, and the present invention is not limited to these examples. Also,
In the examples, the life of the catalyst was degraded after 100 hours (in terms of acetone conversion, the value at the third hour after the reaction was 100 hours).
The difference from the value at the hour was divided by the value at the third hour). Therefore, when the degradation rate of the reaction when only phenol and acetone are used as raw materials (Comparative Example 1) is set to 100, the relative value of the degradation rate of the reaction (the value of the degradation rate of the reaction A value obtained by dividing by the value of the deterioration rate of the reaction in the case of using it as a raw material and multiplying by 100) was used as a guideline within an allowable range of 60 or less.
【００１８】（１）スルホン酸基含有アルコキシシラン
の合成 滴下ロートを取り付けた２口の５００ｍｌの丸底フラス
コに塩化メチレンを２００ｍｌ入れ、これにフェニルト
リクロロシラン１２４．０２ｇ（０．５８５ｍｏｌ）を
加え、氷冷した。これに無水硫酸４６．８０ｇ（０．５
８５ｍｏｌ）を塩化メチレン１００ｍｌに溶解させた溶
液を窒素気流下３０分かけて滴下した後、氷浴を取り外
し室温で１時間攪拌し、スルホン化を行った。滴下ロー
トを取り外し、窒素気流下、油浴を用いて１００℃に加
熱し、塩化メチレンを留去した。次いで、エタノール１
６１．５０ｇを窒素気流下、塩化水素を取り除きなが
ら、２時間かけて滴下し、エトキシ化反応を行った。得
られた不純物を含むフェニルスルホン酸基含有エトキシ
シランのエタノール溶液２３８．６０ｇを以下のスルホ
ン酸基含有炭化水素基とメルカプト基含有炭化水素基を
有する有機高分子シロキサン触媒のゾル−ゲル調製にお
けるスルホン酸成分の原料として用いた。(1) Synthesis of sulfonic acid group-containing alkoxysilane 200 ml of methylene chloride was put into a two-necked 500 ml round bottom flask equipped with a dropping funnel, and 124.02 g (0.585 mol) of phenyltrichlorosilane was added thereto. Ice cooled. 46.80 g of sulfuric anhydride (0.5
(85 mol) in 100 ml of methylene chloride was added dropwise over 30 minutes under a nitrogen stream, and then the ice bath was removed and the mixture was stirred at room temperature for 1 hour to perform sulfonation. The dropping funnel was removed, and the mixture was heated to 100 ° C. in an oil bath under a nitrogen stream to distill off methylene chloride. Then, ethanol 1
61.50 g was added dropwise over 2 hours in a nitrogen stream while removing hydrogen chloride to carry out an ethoxylation reaction. 238.60 g of an ethanol solution of ethoxysilane containing a phenylsulfonic acid group containing the obtained impurities was used to prepare a sol-gel for preparing a sol-gel of an organic polymer siloxane catalyst having a hydrocarbon group containing a sulfonic acid group and a hydrocarbon group containing a mercapto group. Used as a raw material for the acid component.
【００１９】（２）有機高分子ポリシロキサン触媒の調
製 触媒１ 攪拌棒を取り付けた２口の５００ｍｌの丸底フラスコに
上記したスルホン酸基含有エトキシシランのエタノール
溶液１７．５９ｇ（２１．３９ｍｍｏｌ）、テトラエト
キシシラン１５９．７４ｇ（７６６．７７ｍｍｏｌ）、
メルカプトメチルトリメトキシシラン３．６０ｇ（２
１．３９ｍｍｏｌ）、エタノール１５０ｍｌを入れて混
合し、さらに水２８．８ｇを３０分かけて滴下した。つ
いでこれを加熱し、６５℃で４時間攪拌した。放冷後、
２８％アンモニア水１０ｍｌと水６９．１ｍｌを混合し
た水溶液を滴下し、室温で４時間攪拌した。さらに６５
℃で３日間攪拌し、熟成させた。これをエバポレーター
で減圧留去し、白色の固体を得た。ついで２Ｎの塩酸３
００ｍｌを加え、室温で３０分間攪拌する操作を２回繰
り返し、プロトン型に戻した。濾別後、イオン交換水３
００ｍｌで洗浄する操作を２回繰り返して塩酸を取り除
いた。最後に減圧下、１００℃で６時間乾燥した。(2) Preparation of organic high molecular polysiloxane catalyst Catalyst 1 17.59 g (21.39 mmol) of the above sulfonic acid group-containing ethoxysilane ethanol solution was placed in a two-necked 500 ml round bottom flask equipped with a stir bar. 159.74 g (766.77 mmol) of tetraethoxysilane,
3.60 g of mercaptomethyltrimethoxysilane (2
1.39 mmol) and 150 ml of ethanol were added and mixed, and 28.8 g of water was further added dropwise over 30 minutes. It was then heated and stirred at 65 ° C. for 4 hours. After cooling down,
An aqueous solution obtained by mixing 10 ml of 28% aqueous ammonia and 69.1 ml of water was added dropwise, and the mixture was stirred at room temperature for 4 hours. Further 65
The mixture was stirred at a temperature of 3 ° C. for 3 days and aged. This was distilled off under reduced pressure using an evaporator to obtain a white solid. Then 2N hydrochloric acid 3
The operation of adding 00 ml and stirring at room temperature for 30 minutes was repeated twice to return to the proton type. After filtration, deionized water 3
The operation of washing with 00 ml was repeated twice to remove hydrochloric acid. Finally, it was dried at 100 ° C. under reduced pressure for 6 hours.
【００２０】以上の操作によりスルホン酸基含有炭化水
素基とメルカプト基含有炭化水素基を有する有機高分子
シロキサン５６．３ｇを得、触媒１とした。この触媒１
の固体酸量を測定したところ、０．３８ｍｅｑ／ｇであ
った。By the above operation, 56.3 g of an organic high molecular siloxane having a sulfonic acid group-containing hydrocarbon group and a mercapto group-containing hydrocarbon group was obtained, and was used as Catalyst 1. This catalyst 1
Was 0.38 meq / g.
【００２１】実施例１ 有機高分子シロキサン触媒１、２６．７ｇを円筒形反応
器（直径２．２ｃｍ、長さ４０ｃｍ）に充填した。この
反応器の下側から１重量％の3-メルカプトプロピオン酸
を含有するフェノール／アセトン混合物 (モル比 ５：
１、以下原料混合物と記す。)を２０ｇ／ｈｒの速度で
触媒中を通過させた。反応温度は１００℃とし、３時間
後に得られた反応生成物を液体クロマトグラフィーで分
析した結果、アセトンの転化率は９０％であり、ビスフ
ェノールＡ類（［２，２−ビス（４−ヒドロキシフェニ
ル）プロパン］、［２−（２’−ヒドロキシフェニ
ル）、２−（４’−ヒドロキシフェニル）プロパン］）
の選択率は９２％であった。Example 1 A cylindrical reactor (2.2 cm in diameter, 40 cm in length) was charged with 26.7 g of an organic high molecular siloxane catalyst. From the bottom of the reactor, a phenol / acetone mixture containing 1% by weight of 3-mercaptopropionic acid (molar ratio 5:
1, hereinafter referred to as a raw material mixture. ) Was passed through the catalyst at a rate of 20 g / hr. The reaction temperature was set to 100 ° C., and the reaction product obtained after 3 hours was analyzed by liquid chromatography. As a result, the conversion of acetone was 90%, and the bisphenol A ([2,2-bis (4-hydroxyphenyl) ) Propane], [2- (2′-hydroxyphenyl), 2- (4′-hydroxyphenyl) propane])
Was 92%.
【００２２】１００時間後に得られた反応生成物を同様
に、液体クロマトグラフィーで分析した結果、アセトン
の転化率は８６％であった。また、上述の方法により計
算した触媒寿命を１００時間後に評価したら、触媒の劣
化率は、で６．５％、後述の比較例１を１００とする劣
化率の相対値は４３であった。The reaction product obtained after 100 hours was similarly analyzed by liquid chromatography. As a result, the conversion of acetone was 86%. When the catalyst life calculated by the above method was evaluated after 100 hours, the deterioration rate of the catalyst was 6.5%, and the relative value of the deterioration rate with Comparative Example 1 described later as 100 was 43.
【００２３】実施例２ 原料混合物に対し１．５重量％の水を添加した他は実施
例１と同様に反応を行った。反応開始３時間後のアセト
ンの転化率は８５％、ビスフェノールＡ類の選択率は９
２％であり、１００時間後のアセトン転化率は８２％で
あった。また、上述の方法により計算した触媒寿命を１
００時間後に評価したら、触媒の劣化率は、で３．５
％、後述の比較例１を１００とする劣化率の相対値は２
３であった。Example 2 A reaction was carried out in the same manner as in Example 1 except that 1.5% by weight of water was added to the raw material mixture. After 3 hours from the start of the reaction, the conversion of acetone was 85%, and the selectivity of bisphenol A was 9%.
The acetone conversion after 100 hours was 82%. Further, the catalyst life calculated by the above method is set to 1
When evaluated after 00 hours, the catalyst degradation rate was 3.5
%, And the relative value of the deterioration rate is 100
It was 3.
【００２４】実施例３ 原料混合物に対し３重量％の3-メルカプトプロピオン酸
を添加した他は実施例２と同様に反応を行った。反応開
始３時間後のアセトンの転化率は９０％、ビスフェノー
ルＡ類の選択率は９２％であり、１００時間後のアセト
ン転化率は８７％であった。また、上述の方法により計
算した触媒寿命を１００時間後に評価したら、触媒の劣
化率は、で３．３％、後述の比較例１を１００とする劣
化率の相対値は２２であった。この反応をさらに３００
時間まで延長したところアセトンの転化率は８１％で、
３００時間後の劣化率は１０％であった。Example 3 A reaction was carried out in the same manner as in Example 2 except that 3% by weight of 3-mercaptopropionic acid was added to the raw material mixture. After 3 hours from the start of the reaction, the conversion of acetone was 90%, the selectivity of bisphenol A was 92%, and the conversion of acetone after 100 hours was 87%. When the catalyst life calculated by the above method was evaluated after 100 hours, the catalyst deterioration rate was 3.3%, and the relative value of the deterioration rate with Comparative Example 1 described later as 100 was 22. The reaction was further increased by 300
When extended to the time, the conversion of acetone was 81%,
The deterioration rate after 300 hours was 10%.
【００２５】実施例４ 3-メルカプトプロピオン酸に代え１重量％のベンジルチ
オールを添加した他は実施例１と同様に反応を行った。
反応開始３時間後のアセトンの転化率は８９％、ビスフ
ェノールＡ類の選択率は９２％であり、１００時間後の
アセトン転化率は８２％であった。また、上述の方法に
より計算した触媒寿命を１００時間後に評価したら、触
媒の劣化率は、で７．９％、後述の比較例１を１００と
する劣化率の相対値は５３であった。Example 4 A reaction was carried out in the same manner as in Example 1 except that 1% by weight of benzylthiol was added instead of 3-mercaptopropionic acid.
The conversion of acetone 3 hours after the start of the reaction was 89%, the selectivity of bisphenol A was 92%, and the conversion of acetone 100 hours later was 82%. When the catalyst life calculated by the above method was evaluated after 100 hours, the catalyst deterioration rate was 7.9%, and the relative value of the deterioration rate with Comparative Example 1 described later as 100 was 53.
【００２６】比較例１ 原料としてフェノール／アセトン混合物 (モル比 ５：
１)を用いた他は実施例１と同様に反応を行った。反応
開始3時間後のアセトンの転化率は８８％であり、１０
０時間後のアセトン転化率は７５％であった。また、上
述の方法により計算した触媒寿命を評価する触媒の劣化
率は、１００時間で１５％であった。Comparative Example 1 A phenol / acetone mixture (molar ratio: 5:
The reaction was carried out in the same manner as in Example 1 except that 1) was used. The conversion of acetone 3 hours after the start of the reaction was 88%,
The acetone conversion after 0 hour was 75%. The deterioration rate of the catalyst for evaluating the catalyst life calculated by the above method was 15% at 100 hours.
【００２７】[0027]
【発明の効果】本発明の方法により、有機高分子シロキ
サン触媒の活性を向上させると同時に経時的な活性低下
を防ぐことができ、工業上重要であるビスフェノールＡ
製造をプロセス上および経済上著しく優位に行うことが
できる。According to the method of the present invention, the activity of the organic polymer siloxane catalyst can be improved and at the same time, the activity can be prevented from decreasing over time.
Manufacturing can be carried out with significant process and economic advantages.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 高井 敏浩 大阪府高石市高砂１丁目６番地 三井化学 株式会社内 Ｆターム(参考） 4H006 AA02 AC25 BA53 BE60 4H039 CA19 CA41 CA60 CD10 CD40 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Toshihiro Takai 1-6-6 Takasago, Takaishi-shi, Osaka Mitsui Chemicals, Inc. F-term (reference) 4H006 AA02 AC25 BA53 BE60 4H039 CA19 CA41 CA60 CD10 CD40
Claims (3)
基含有炭化水素基を有する有機高分子シロキサン触媒を
用いて、アセトンとフェノールからビスフェノールＡを
製造する方法において、メルカプト基含有化合物の存在
下にアセトンとフェノールを反応させることを特徴とす
るビスフェノールＡの製造方法。1. A method for producing bisphenol A from acetone and phenol using an organic polymer siloxane catalyst having a sulfonic acid group-containing hydrocarbon group and a mercapto group-containing hydrocarbon group, the method comprising the steps of: A method for producing bisphenol A, comprising reacting acetone and phenol.
プロピオン酸である請求項1記載の方法。2. The method according to claim 1, wherein the mercapto group-containing compound is 3-mercaptopropionic acid.
ンとフェノールとの反応において、水を共存させること
を特徴とする請求項1記載の方法。3. The method according to claim 1, wherein water is allowed to coexist in the reaction between acetone and phenol in the presence of the mercapto group-containing compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000046673A JP2001233812A (en) | 2000-02-24 | 2000-02-24 | Method for producing bisphenol a |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000046673A JP2001233812A (en) | 2000-02-24 | 2000-02-24 | Method for producing bisphenol a |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001233812A true JP2001233812A (en) | 2001-08-28 |
Family
ID=18569045
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000046673A Pending JP2001233812A (en) | 2000-02-24 | 2000-02-24 | Method for producing bisphenol a |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001233812A (en) |
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|---|---|---|---|---|
| JP2004190021A (en) * | 2002-11-27 | 2004-07-08 | Mitsui Chemicals Inc | Organic polymeric siloxane and its application |
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2000
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|---|---|---|---|---|
| JP4571393B2 (en) * | 2002-11-27 | 2010-10-27 | 三井化学株式会社 | Organopolymer siloxane and its use |
| JP2004190021A (en) * | 2002-11-27 | 2004-07-08 | Mitsui Chemicals Inc | Organic polymeric siloxane and its application |
| US8735634B2 (en) | 2011-05-02 | 2014-05-27 | Sabic Innovative Plastics Ip B.V. | Promoter catalyst system with solvent purification |
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