JPS59219249A - Preparation of nucleus-dihydroxylated benzophenone - Google Patents

Preparation of nucleus-dihydroxylated benzophenone

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Publication number
JPS59219249A
JPS59219249A JP9417283A JP9417283A JPS59219249A JP S59219249 A JPS59219249 A JP S59219249A JP 9417283 A JP9417283 A JP 9417283A JP 9417283 A JP9417283 A JP 9417283A JP S59219249 A JPS59219249 A JP S59219249A
Authority
JP
Japan
Prior art keywords
benzophenone
aqueous solution
formula
crystals
dihydroxylated
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
Application number
JP9417283A
Other languages
Japanese (ja)
Inventor
Katsuhisa Isogai
勝久 磯貝
Koichi Iwabuchi
岩「淵」 耕一
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
K I KASEI KK
Original Assignee
K I KASEI KK
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by K I KASEI KK filed Critical K I KASEI KK
Priority to JP9417283A priority Critical patent/JPS59219249A/en
Publication of JPS59219249A publication Critical patent/JPS59219249A/en
Pending legal-status Critical Current

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

PURPOSE:To obtain the titled crystal having excellent workability such as stirrability, filterability, etc., by hydrolyzing a halogenated benzophenone, and adding a mineral acid to the aqueous solution of the obtained compound to precipitate the objective compound, wherein the precipitation process is carried out in a specific temperature range. CONSTITUTION:The halogenated benzophenone of formula I (X1 and X2 are halogen) is hydrolyzed with an aqueous solution of an alkali hydroxide to obtain an aqueous solution of the compound of formula II (M is alkali metal). The aqueous solution is added with a mineral acid (preferably hydrochloric acid or suluric acid) to precipitate the crystal of the nucleus-hydroxylated benzophenone of formula III. The objective compound having large particle size can be obtained by carrying out the precipitation at 70-100 deg.C, preferably 80-90 deg.C. EFFECT:The stirring during the precipitation of the crystal can be carried out easily without necessitating the addition of water, and the obtained crystal can be filtered and handled easily. USE:Raw material for engineering plastics.

Description

【発明の詳細な説明】 本発明は、例えば4.4′−ジヒドロキシベンゾフェノ
ンのような核ジヒドロキジル化ベンゾフェノンの製造方
法に関するものであり、さらに詳しく言えば攪拌性、ろ
過性などの作業性に優れた高純度の核ジヒドロキジル化
ベンゾフェノンの結晶を製造する方法に関する。
DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a nuclear dihydroxylated benzophenone such as 4,4'-dihydroxybenzophenone. The present invention relates to a method for producing crystals of highly pure nuclear dihydroxylated benzophenone.

核ジヒドロキジル化ベンゾフェノン、例えば4゜4′−
ジヒドロキシベンゾフェノン(以下4.4’−DHBP
と表わす)は近年になりエンジニアリングプラスチック
の原料として重要性を増してきているが、その製造法と
しては4−ヒドロキシ安息香酸トフェノールよシ、ある
いは4−メトキシベンジイルクロリドとアニソールより
、いずれも多量の触媒の存在下、フリーデルクラフッ反
応により得る方法、4.4’−ジクロロベンゾフェノン
を触媒存在下に水酸化アルカリ水溶液で加水分解したの
ち、生成した水溶液を次式のように鉱酸で処理し結晶化
させる方法などが知られている。
Nuclear dihydroxylated benzophenones, e.g. 4°4'-
Dihydroxybenzophenone (hereinafter referred to as 4.4'-DHBP)
) has become increasingly important as a raw material for engineering plastics in recent years, but its production methods include 4-hydroxybenzoic acid tophenol, or 4-methoxybenziyl chloride and anisole, both of which require large quantities. In the presence of a catalyst, 4.4'-dichlorobenzophenone is hydrolyzed with an aqueous alkali hydroxide solution in the presence of a catalyst, and the resulting aqueous solution is treated with a mineral acid as shown in the following formula. Methods of crystallization are known.

コ(7)4.4’−ジクロロベンゾフェノンの旬日水分
解による方法は、通常、反応速度を早めたり、副生物の
生成を抑えるため、水酸化アルカリを化学量論量よシ過
剰に使用し、結晶化処理は、強アルカリ性の反応液に対
するグラスライニング製反応容器の耐性並びに生成結晶
の水溶液中の溶解変分のロスの低減などを考慮して20
〜40℃のような比較的低温に維持して行われてきた。
(7) In the method of hydrolyzing 4.4'-dichlorobenzophenone on a daily basis, alkali hydroxide is usually used in excess of the stoichiometric amount in order to speed up the reaction rate and suppress the production of by-products. The crystallization treatment was carried out at a temperature of 20% in consideration of the resistance of the glass-lined reaction vessel to strongly alkaline reaction liquids and the reduction of loss of dissolution variation of the formed crystals in the aqueous solution.
It has been carried out by maintaining relatively low temperatures such as ~40°C.

また、結晶化の反応容器は、実際上、鉱酸にも耐えられ
る必要からグラスライニング製にほぼ限定されていた。
In addition, crystallization reaction vessels are practically limited to glass-lined vessels because they must be able to withstand mineral acids.

しかしながら、この方法の場合、析出した4、4′−D
HBPの結晶が、粒径が極めて微細なため結晶化の途中
でスラリーの粘度が急激に上昇し、攪拌が困難となり、
多量の水を追加して粘度を低下させる必要が生じる、ま
た、結晶のろ過性も悪いなどの欠点があった。まだエン
ジニアプラスチック原料とする場合特に灰分の少ない4
 、4’−DHBPが必要とされるが、この方法による
と灰分数が多くなり、そのため、さらに有機溶剤による
抽出精製を行わなければならず、操作性や作業性の面に
おいても問題があった。
However, in the case of this method, the precipitated 4,4'-D
Because the HBP crystals have extremely fine particle sizes, the viscosity of the slurry increases rapidly during crystallization, making stirring difficult.
There were drawbacks such as the need to add a large amount of water to reduce the viscosity, and the filterability of the crystals was poor. 4 with low ash content, especially when used as raw material for engineered plastics
, 4'-DHBP is required, but this method results in a high ash content, which necessitates further extraction and purification using an organic solvent, which poses problems in terms of operability and workability. .

本発明者らはこの4.4’−DHBPの製造法の欠点を
克服するため種々研究を重ねだ結果、4.4’−ジクロ
ロベンゾフェノンを加水分解したのち、生成した水溶液
金鉱酸で処理して、4.4’−DHBPの結晶を析出さ
せるに当シ、この反応を特定の温度で行わせることによ
り、攪拌性、ろ過性の良好な粒径の大きい、かつ灰分の
少ない4.4’−DHBPの結晶が析出することを見い
出した。不発明はこの知見に基づきなされるに至ったも
のである。
The present inventors have conducted various studies to overcome the drawbacks of this method for producing 4.4'-DHBP, and found that after hydrolyzing 4.4'-dichlorobenzophenone, it was treated with the aqueous gold mineral acid produced. , 4.4'-DHBP crystals are precipitated by carrying out this reaction at a specific temperature. It was found that DHBP crystals were precipitated. The non-invention was made based on this knowledge.

すなわち本発明は、一般式 (式中X1及びX2はハロゲン原子を示し、互いに同じ
でも異なっていてもよい。) で表わされるハロゲン化ベンゾフェノンを水酸化アルカ
リ水溶液で加水分解して得た一般式(式中Mはアルカリ
金属を示す。) で表わされる化合物の水溶液に鉱酸を加えて、式で表わ
される核ジヒドロキジル化ペンツフェノンの結晶を析出
させるに当り、この結晶の析出を70〜100℃の温度
で行うことを特徴とする核ジヒドロキジル化ベンゾフェ
ノンの製造方法を提供するものである。
That is, the present invention provides compounds of the general formula (wherein X1 and X2 represent halogen atoms, which may be the same or different) obtained by hydrolyzing a halogenated benzophenone with an aqueous alkali hydroxide solution. (In the formula, M represents an alkali metal.) When adding a mineral acid to an aqueous solution of the compound represented by the formula to precipitate the crystals of the nuclear dihydroxylated pentuphenone represented by the formula, the precipitation of the crystals was carried out at 70 to 100°C. The present invention provides a method for producing nuclear dihydroxylated benzophenone, which is characterized in that the process is carried out at high temperatures.

以下、本発明の詳細な説明する。The present invention will be explained in detail below.

本発明において、前記一般式〔I〕のノ・ロゲン化ベン
ゾフェノンを、例えばオートクレーブ中、触媒の存在下
で水酸化アルカリ水溶液で加水分解し、前記一般式[I
I]の化合物とMX()・ロゲン化アルカリ)と水を生
成させる。この際に使用する水酸化アルカリの量は、通
常一般式〔I]で表わされるベンゾフェノンに対して4
.5〜10モル倍、好ましくは5〜7モル倍であシ、水
の使用計は同様に30〜300モル倍、好ましくは45
〜100モル倍である。壕だ、触媒としては、CuSO
4CuOlCuCL%CuCL、、などの無機銅塩を0
.01〜5モル倍、好ましくは0.1〜1モル倍添加す
る。反応温度は180〜250℃、好ましくは210〜
240℃であり、この温度がりまシ低いと反応が完全に
進まず中間生成物で停止してしまい、逆に、あ″!!、
シ高いと脱ハロゲン化物が生ずる。反応圧力は15〜2
5に9/cJ aが好ましく、反応時間は通常3〜8時
間程度である。
In the present invention, the no-rogenated benzophenone of the general formula [I] is hydrolyzed with an aqueous alkali hydroxide solution in the presence of a catalyst, for example in an autoclave, and the
I] compound, MX ()・alkali rogenide), and water are generated. The amount of alkali hydroxide used at this time is usually 4
.. 5 to 10 times by mole, preferably 5 to 7 times by mole, and the total amount of water used is similarly 30 to 300 times by mole, preferably 45 times by mole.
~100 times the mole. Well, as a catalyst, CuSO
0 inorganic copper salts such as 4CuOlCuCL%CuCL, .
.. It is added in an amount of 0.1 to 5 moles, preferably 0.1 to 1 mole. The reaction temperature is 180-250°C, preferably 210-250°C.
The temperature is 240℃, and if this temperature is too low, the reaction will not proceed completely and will stop at the intermediate product.
If the temperature is high, dehalogenation products will occur. The reaction pressure is 15-2
5 to 9/cJ a is preferable, and the reaction time is usually about 3 to 8 hours.

この反応後、反応液を100℃以下に冷却したのち、加
えた上記触媒を固液分離によシ除く。
After this reaction, the reaction solution is cooled to 100° C. or lower, and then the added catalyst is removed by solid-liquid separation.

次いで、上記一般式[II]の化合物を含む分離母液に
所定量の鉱酸を添加し、前記式[II[)で表わされる
核ジヒドロキジル化ベンゾフェノンの結晶を析出させる
が、本発明ではこの析出時の液温を70〜100℃の範
囲、好ましくは80〜90℃とする。このような温度範
囲に設定することにより、適度な粒径で攪拌性、ろ過性
にすぐれ、かつ灰分含有量の少ない結晶の析出がみられ
る。しかし、反応温度が70℃未満では粒径が微細とな
シろ過性が悪いだけでなく灰分が残存しやすくなる。一
方、100℃を越えると製品の着色原因となるとともに
作業性が悪くなる。なお、母液には、過剰の水酸化アル
カリが残存しているので、結晶の析出に先立って、過剰
分の水酸化アルカリを中和する際は、容器の保護のため
に20〜40℃の低温が好ましい。
Next, a predetermined amount of mineral acid is added to the separated mother liquor containing the compound of the above general formula [II] to precipitate crystals of the nuclear dihydroxylated benzophenone represented by the above formula [II]. The liquid temperature at this time is in the range of 70 to 100°C, preferably 80 to 90°C. By setting the temperature within such a range, crystals with a suitable particle size, excellent stirrability and filterability, and low ash content can be precipitated. However, if the reaction temperature is less than 70° C., the particle size will be fine and the filterability will be poor, and ash will likely remain. On the other hand, if the temperature exceeds 100°C, it may cause discoloration of the product and workability may deteriorate. In addition, since excess alkali hydroxide remains in the mother liquor, when neutralizing the excess alkali hydroxide prior to precipitation of crystals, the temperature should be kept at a low temperature of 20 to 40°C to protect the container. is preferred.

上記鉱酸としては、塩酸及び硫酸が好ましく用いられる
。使用する塩酸の濃度は通常25〜36重量%程度であ
り、硫酸の濃度は通常40〜98重量俤程度である。ま
だ鉱酸の使用量は混合物のpHが2.0以下となるまで
の址が必要である。
As the mineral acid, hydrochloric acid and sulfuric acid are preferably used. The concentration of hydrochloric acid used is usually about 25 to 36% by weight, and the concentration of sulfuric acid is usually about 40 to 98% by weight. It is still necessary to use the amount of mineral acid until the pH of the mixture becomes 2.0 or less.

以上のようにして核ジヒドロキジル化ベンゾフェノンの
結晶を析出させると、沈降性の良好な結晶を含む混合液
が得られるので、混合液を冷却したのち、核ジヒドロキ
ジル化ベンゾフェノンの結晶をろ過、デカンテーション
などにより分離する。
When crystals of nuclear dihydroxylated benzophenone are precipitated as described above, a mixed solution containing crystals with good sedimentation properties is obtained. After cooling the mixed solution, the crystals of nuclear dihydroxylated benzophenone are filtered and decanted. Separate by cation, etc.

分離した核ジヒドロキシベンゾフェノンは常法によシ、
水洗、乾燥される。このように本発明方法によれば、前
記式[III)で表わされる4、4’−DHBP % 
 2.4’ −DHBP、3.4’−DHBPなどの核
ジヒドロキジル化ベンゾフェノンが得られる。
The separated nuclear dihydroxybenzophenone is prepared by a conventional method.
Washed with water and dried. As described above, according to the method of the present invention, 4,4'-DHBP% represented by the above formula [III]
Nuclear dihydroxylated benzophenones such as 2.4'-DHBP and 3.4'-DHBP are obtained.

本発明によれば、粒径の大きい核ジヒドロキジル化ベン
ゾフェノンの結晶が得られるため結晶の析出時における
攪拌が良好となシ、水を追加して粘度を下ける必要もな
く、またろ過性が優れるので、該結晶の分離、水洗、乾
燥などにおいて取扱いが容易であシ、工業的に好ましい
。その上、このようにして得られた結晶は灰分の含有量
が非常に少なく品質の優れているものである。
According to the present invention, since crystals of dihydroxylated benzophenone with a large nucleus can be obtained, stirring during precipitation of the crystals is good, there is no need to lower the viscosity by adding water, and filterability is improved. It is industrially preferable because it is easy to handle in separation, washing with water, drying, etc. of the crystals. Moreover, the crystals thus obtained have a very low ash content and are of excellent quality.

次に本発明を実施例に基づきさらに詳細に説明する。Next, the present invention will be explained in more detail based on examples.

実施例 攪拌機及び温度調節器を有する301容ステンレス製オ
ートクレーフニ、4,4′−ジクロロベンゾフェノン5
. Q 2 Ices水酸化ナトリウム4.4ky。
Example 301 capacity stainless steel autoclave with stirrer and temperature controller, 4,4'-dichlorobenzophenone 5
.. Q 2 Ices sodium hydroxide 4.4ky.

水20に、及びCuS04240 ?を仕込み、密閉し
た。
water 20, and CuS04240? was prepared and sealed.

220℃に昇温し、同温度で5時間反応を行った。The temperature was raised to 220°C, and the reaction was carried out at the same temperature for 5 hours.

反応中、圧力は20 ’f/、、11 Gに昇圧してい
た。反応後、混合液を冷却し、ろ過にょシ、−沈殿した
触媒を分離し、アルカリ性の水溶液29.5 kgを得
た。
During the reaction, the pressure was increased to 20'f/, 11 G. After the reaction, the mixture was cooled and filtered to separate the precipitated catalyst, yielding 29.5 kg of an alkaline aqueous solution.

攪拌器及びジャケットを有する5Ot容のグラスライニ
ング製容器に上記の方法で得た水溶液29、5 kpを
仕込み、36重量%濃度の塩酸を加えた。はじめは過剰
分の水酸化ナトリウム約1.2kgを中和するために、
36重量%塩酸約3 kgを20〜40℃で添加してp
H9〜1oとなし、続いて、4.4’−DHBPの結晶
を析出させるために80℃又は90℃に加熱し、同温度
で36重量%塩酸をpHが1.5になるまで添加したと
ころ、攪拌下に、粘度かはとんど上昇せず反応が進行し
結晶が析出した。
29.5 kp of the aqueous solution obtained by the above method was charged into a 5 Ot capacity glass-lined container equipped with a stirrer and a jacket, and 36% by weight hydrochloric acid was added thereto. Initially, in order to neutralize about 1.2 kg of excess sodium hydroxide,
Approximately 3 kg of 36% hydrochloric acid was added at 20 to 40°C to
H9-1o, then heated to 80°C or 90°C to precipitate crystals of 4.4'-DHBP, and at the same temperature 36% by weight hydrochloric acid was added until the pH reached 1.5. Under stirring, the reaction proceeded and crystals precipitated without increasing the viscosity.

次いで、反応液を35℃に冷却し、同温度で結晶をろ過
したが、目づまシなどは起らず、水1tで洗浄し冬のち
乾燥して4.4’−DHBPの結晶4、1 kpを得た
Next, the reaction solution was cooled to 35°C, and the crystals were filtered at the same temperature, but no blockage occurred, and the crystals were washed with 1 t of water and dried after winter to obtain 4.4'-DHBP crystals 4,1. I got kp.

なお比較のために、結晶析出時の温度を40℃又は50
℃とした以外は上記と同様にして4.4′−DHBPの
結晶を製造したところ、結晶析出時スラリーは粘性が高
く充分な攪拌ができない状態であ)、ろ過は結晶の粒径
が小さいだめ時間ががかシ振シ切シが悪い状態であった
For comparison, the temperature during crystal precipitation was set at 40°C or 50°C.
When crystals of 4.4'-DHBP were produced in the same manner as above except that the temperature was set at It took a long time and the condition was poor.

上記で得られた4、4’−DHBPの結晶につき、平均
粒径及び灰分量を測定した結果を次表に示した。
The results of measuring the average particle size and ash content of the 4,4'-DHBP crystals obtained above are shown in the following table.

Claims (1)

【特許請求の範囲】 一般式 (式中X□及びX2はハロゲン原子を示し、互いに同じ
でも異なっていてもよい。) で表わされるハロゲン化ベンゾフェノンを水酸化アルカ
リ水溶液で加水分解して得た一般式(式中Mはアルカリ
金属を示す。) で表わされる化合物の水溶液に鉱酸を加えて、式で表わ
される核ジヒドロキジル化ベンゾフェノンの結晶を析出
させるにラシ、この結晶の析出を70〜100℃の温度
で行うことを特徴とする核ジヒドロキジル化ベンゾフェ
ノンの製造方法。
[Claims] A general compound obtained by hydrolyzing a halogenated benzophenone represented by the general formula (wherein X□ and X2 represent a halogen atom and may be the same or different) with an aqueous alkali hydroxide solution. A mineral acid is added to an aqueous solution of a compound represented by the formula (wherein M represents an alkali metal) to precipitate crystals of the nuclear dihydroxylated benzophenone represented by the formula. A method for producing nuclear dihydroxylated benzophenone, characterized in that the process is carried out at a temperature of °C.
JP9417283A 1983-05-30 1983-05-30 Preparation of nucleus-dihydroxylated benzophenone Pending JPS59219249A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP9417283A JPS59219249A (en) 1983-05-30 1983-05-30 Preparation of nucleus-dihydroxylated benzophenone

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP9417283A JPS59219249A (en) 1983-05-30 1983-05-30 Preparation of nucleus-dihydroxylated benzophenone

Publications (1)

Publication Number Publication Date
JPS59219249A true JPS59219249A (en) 1984-12-10

Family

ID=14102921

Family Applications (1)

Application Number Title Priority Date Filing Date
JP9417283A Pending JPS59219249A (en) 1983-05-30 1983-05-30 Preparation of nucleus-dihydroxylated benzophenone

Country Status (1)

Country Link
JP (1) JPS59219249A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5015778A (en) * 1989-12-18 1991-05-14 The Dow Chemical Company Catalytic method to produce hydroxy substituted arylophenones
US5250738A (en) * 1989-06-30 1993-10-05 Hoechst Aktiengesellschaft Process for the preparation of 1,4-bis(4-hydroxybenzoyl)-benzene
CN105884602A (en) * 2016-06-08 2016-08-24 连云港德洋化工有限公司 Synthetic method of 4-hydroxybenzophenone

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5250738A (en) * 1989-06-30 1993-10-05 Hoechst Aktiengesellschaft Process for the preparation of 1,4-bis(4-hydroxybenzoyl)-benzene
US5015778A (en) * 1989-12-18 1991-05-14 The Dow Chemical Company Catalytic method to produce hydroxy substituted arylophenones
CN105884602A (en) * 2016-06-08 2016-08-24 连云港德洋化工有限公司 Synthetic method of 4-hydroxybenzophenone

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