JP4840750B2 - Method for producing high purity 4,4'-dihydroxydiphenylsulfone - Google Patents
Method for producing high purity 4,4'-dihydroxydiphenylsulfone Download PDFInfo
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Description
【0001】
【発明の属する技術分野】
本発明は、4,4′−ジヒドロキシジフェニルスルホン(以下、4,4′−体ともいう)、2,4′−ジヒドロキシジフェニルスルホン(以下、2,4′−体ともいう)、トリヒドロキシトリフェニルジスルホン(以下、トリ体ともいう)等を含有するジヒドロキシジフェニルスルホン類の異性体混合物から4,4′−体を選択的に回収する高純度4,4′−ジヒドロキシジフェニルスルホンの製造方法に関する。
【0002】
【従来の技術と発明が解決しようとする課題】
4,4′−体および2,4′−体等を含む異性体混合物から4,4′−体を回収する方法としては、例えば、特公昭43−6453号公報に、粗ジヒドロキシジフェニルスルホンを、高めた温度で、塩基性物質を溶解含有する水に溶解させ、冷却、晶析させて母液から分離する方法が記載されている。しかしながら、ここでいう「高めた温度」とは、通常の水の沸騰温度、つまり約100℃までの温度である。また、塩基性物質の使用量が比較的多いこと等から、例えば収率において満足できるものではない。
【0003】
また、特公平4−82142号公報には、4,4′−体および2,4′−体等を含む異性体混合物を溶解するのに充分高いpHをもつ塩基性水溶液に、該異性体混合物を溶解して異性体混合物溶液を形成し、次いで酸を添加して、該異性体混合物溶液のpHを7より大きいがより低いpH(例えば、約9)に下げて、4,4′−体の結晶を選択的に沈殿させることを特徴とする、異性体混合物から4,4′−体を回収する方法が記載されている。しかしながら、この方法では、塩基と酸を併用するため、経済的、工業的に不利である。しかも、高純度の目的物を高収率で得ることができない。
【0004】
本発明は、4,4′−体、2,4′−体、トリ体等を含有するジヒドロキシジフェニルスルホン類の異性体混合物から、4,4′−体を選択的に回収し、高純度の4,4′−体を高収率で工業的に有利に製造する方法を提供することを目的とする。
【0005】
【課題を解決するための手段】
本発明者らは、上記課題を解決すべく鋭意検討した結果、ジヒドロキシジフェニルスルホン類の異性体混合物を、必要に応じて塩基性物質を添加した水系溶媒に、温度102〜140℃で溶解させ、次いで冷却することにより、4,4′−体を選択的に回収し得ることを見出し、本発明を完成するに至った。
【0006】
すなわち、本発明は、下記に示すとおりの高純度4,4′−ジヒドロキシジフェニルスルホンの製造方法を提供するものである。
項1. 4,4′−ジヒドロキシジフェニルスルホンを75重量%以上、ならびに2,4′−ジヒドロキシジフェニルスルホンおよびトリヒドロキシトリフェニルジスルホンを合計で25重量%以下含有する異性体混合物を、必要に応じて塩基性物質を添加した水系溶媒に、温度102〜140℃で溶解させ、次いで冷却して4,4′−ジヒドロキシジフェニルスルホンを析出させて分離することを特徴とする高純度4,4′−ジヒドロキシジフェニルスルホンの製造方法。
項2. 異性体混合物における2,4′−ジヒドロキシジフェニルスルホンおよびトリヒドロキシトリフェニルジスルホンの合計含有量が0.1〜25重量%であり、2,4′−ジヒドロキシジフェニルスルホンおよびトリヒドロキシトリフェニルジスルホンの合計量に対して、塩基性物質を0.1〜20倍モル添加することを特徴とする項1に記載の高純度4,4′−ジヒドロキシジフェニルスルホンの製造方法。
項3. 水系溶媒の量が、異性体混合物に対して10重量倍以下であることを特徴とする項2に記載の高純度4,4′−ジヒドロキシジフェニルスルホンの製造方法。
項4. 異性体混合物における2,4′−ジヒドロキシジフェニルスルホンおよびトリヒドロキシトリフェニルジスルホンの合計含有量が1重量%以下であり、水系溶媒に塩基性物質を添加しないことを特徴とする項1に記載の高純度4,4′−ジヒドロキシジフェニルスルホンの製造方法。
項5. 水系溶媒の量が、異性体混合物に対して20重量倍以下であることを特徴とする項4に記載の高純度4,4′−ジヒドロキシジフェニルスルホンの製造方法。
【0007】
【発明の実施の形態】
本発明に用いられるジヒドロキシジフェニルスルホン類の異性体混合物とは、主成分として4,4′−体を含み、その他に副生成物または不純物として2,4′−体およびトリ体等を含む異性体混合物であり、4,4′−体を75重量%以上、ならびに2,4′−体およびトリ体を合計で25重量%以下含有する異性体混合物である。好ましくは、4,4′−体を90重量%以上、ならびに2,4′−体およびトリ体を合計で10重量%以下含有する異性体混合物である。
【0008】
このような異性体混合物は、例えば、フェノールと硫酸とを反応させて得られるジヒドロキシジフェニルスルホン類の粗製品であってもよいが、これに限定されるものではない。
【0009】
なお、このような粗製品として、上記異性体混合物にスルホン酸等の酸分が付着していたり、反応溶媒が共存している可能性もあるが、そのような場合にも、本発明の方法を適用することができる。例えば、酸分が付着している場合には、その酸分を中和し得る相当量の塩基性物質を加えて中和処理することにより、精製工程に影響を与えることは無くなる。また、反応溶媒については、本発明の処理前もしくは処理後に蒸留して除去するか、または、溶解処理の途中で分液等により除去することができる。
【0010】
本発明に用いられる塩基性物質としては、アルカリ金属の水酸化物、炭酸塩、炭酸水素塩、アルカリ土類金属の水酸化物、炭酸塩、炭酸水素塩、および、アンモニア、アミン等が挙げられる。これらの塩基性物質は、単独でまたは2種以上を組み合わせて用いられる。中でも、解離性の良い水酸化ナトリウム、水酸化カリウム等のアルカリ金属の水酸化物、炭酸ナトリウム、炭酸カリウム等のアルカリ金属の炭酸塩等が好ましい。
【0011】
本発明においては、必要に応じて塩基性物質を水系溶媒に添加して溶解させる。
【0012】
添加する塩基性物質の量は、上記異性体混合物に含まれる2,4′−体およびトリ体の合計量に基づいて決定される。
【0013】
すなわち、上記異性体混合物が2,4′−体およびトリ体を合計で0.1〜25重量%含有する場合においては、塩基性物質の添加量は、2,4′−体およびトリ体の合計量に対して、0.1〜20倍モルであるのが好ましく、0.5〜10倍モルであるのがより好ましく、0.5〜5倍モルであるのが特に好ましい。20倍モルを超えると、収率の点から好ましくない。ただし、塩基性物質の添加量は、上記異性体混合物の総量に対して、20モル%以下であるのが好ましく、15モル%以下であるのがより好ましい。20モル%を超えると、収率等の理由から好ましくない。
【0014】
また、上記異性体混合物が2,4′−体およびトリ体を合計で0.1〜10重量%含有する場合においても、塩基性物質の添加量は上記と同様である。
【0015】
一方、上記異性体混合物が2,4′−体およびトリ体を合計で1重量%以下含有する場合においては、水系溶媒に塩基性物質を添加しなくても本発明の目的を達成することができる。
【0016】
本発明に用いられる水系溶媒としては、水、または、メタノール、エタノール、イソプロピルアルコール等の低級アルコールやアセトン等の水溶性有機溶媒と水との混合溶媒等が用いられる。
【0017】
水系溶媒の使用量は、上記異性体混合物に含まれる2,4′−体およびトリ体の合計量に基づいて決定される。
【0018】
すなわち、上記異性体混合物が2,4′−体およびトリ体を合計で0.1〜25重量%含有し、水系溶媒に塩基性物質を添加する場合には、水系溶媒の使用量は、異性体混合物に対して、好ましくは10重量倍以下であり、より好ましくは0.3〜5重量倍であり、特に好ましくは1〜3重量倍である。また、上記異性体混合物が2,4′−体およびトリ体を合計で0.1〜10重量%含有し、水系溶媒に塩基性物質を添加する場合においても、水系溶媒の使用量は上記と同様である。
【0019】
一方、上記異性体混合物が2,4′−体およびトリ体を合計で1重量%以下含有し、水系溶媒に塩基性物質を添加しない場合には、水系溶媒の使用量は、異性体混合物に対して、好ましくは20重量倍以下であり、より好ましくは0.5〜15重量倍であり、特に好ましくは1〜10重量倍である。
【0020】
本発明において、上記異性体混合物を水系溶媒に溶解させる温度は、102〜140℃であり、好ましくは110〜130℃である。温度が102℃未満では異性体混合物が完全に溶解しないため、2,4′−体および/またはトリ体の除去が不十分となる。また、140℃を超える温度は必要ではない。
【0021】
本発明において、上記温度範囲を保持するために、通常はオートクレーブ等の密閉容器を用いて加熱し、好ましくは加熱撹拌する。
【0022】
次に、上記異性体混合物を溶解させた水系溶液を冷却すると、所定温度で4,4′−体の結晶が析出し始める。冷却は通常の方法が適用され、好ましくは撹拌しながら温度を徐々に下げていく。最終的には、水冷等によって70℃〜常温付近まで冷却し、濾過、水洗し、白色の精製結晶を得る。必要に応じて、これを乾燥して、乾燥精製結晶を得ることができる。
【0023】
なお、必要に応じて、活性炭処理、還元剤添加処理および/またはキレート化剤添加処理等を、適宜の段階で実施しても良い。また、必要に応じて、前回の濾液の一部または全部を、水系溶媒として再使用することもできる。より高純度の製品を得たい場合には、これらの処理を繰り返すことにより、容易に達成することができる。
【0024】
さらに、上記異性体混合物が、合計で1重量%を超える2,4′−体およびトリ体を含有する場合に、塩基性物質を使用して本発明の方法を実施し、2,4′−体およびトリ体を合計で1重量%以下含有する異性体混合物を得た後に、この得られた異性体混合物について、塩基性物質を使用せずに再び本発明の方法を実施することにより、より高純度の4,4′−体を得ることができる。
【0025】
【発明の効果】
本発明の方法によれば、ジヒドロキシジフェニルスルホン類の異性体混合物から、高純度の4,4′−ジヒドロキシジフェニルスルホンを、高収率で工業的に有利に製造することができ、その工業的利用価値は極めて大きい。
【0026】
【実施例】
以下、実施例により、本発明の方法をさらに具体的、詳細に説明する。
【0027】
実施例1
4,4′−体/2,4′−体/トリ体=95/3/2(重量比)のジヒドロキシジフェニルスルホン類の異性体混合物100g(0.4モル)に対し、水150gおよび水酸化ナトリウム1.6g(0.04モル)を加えて、オートクレーブ中で加熱撹拌した。内温120℃で内容物が完全に溶解した。この状態から撹拌しながら冷却、晶析して内温40℃になった時点で濾過、水洗し、白色の含水精製結晶100gを得た。これを乾燥して、乾燥精製結晶90gを得た。HPLC(高速液体クロマトグラフィー)分析の結果、4,4′−体/2,4′−体/トリ体=99.7/0.3/0.0(重量比)の組成であった。収率は、原料異性体混合物に対して90%、原料異性体混合物中の4,4′−体に対して95%であった。
【0028】
実施例2
4,4′−体/2,4′−体/トリ体=95/3/2(重量比)のジヒドロキシジフェニルスルホン類の異性体混合物100g(0.4モル)に対し、水300gおよび水酸化ナトリウム1.6g(0.04モル)を加えて、オートクレーブ中で加熱撹拌した。内温120℃で内容物が完全に溶解した。この状態から撹拌しながら冷却、晶析して内温40℃になった時点で濾過、水洗し、白色の含水精製結晶100gを得た。これを乾燥して、乾燥精製結晶90gを得た。HPLC分析の結果、4,4′−体/2,4′−体/トリ体=99.7/0.3/0.0(重量比)の組成であった。収率は、原料異性体混合物に対して90%、原料異性体混合物中の4,4′−体に対して95%であった。
【0029】
実施例3
4,4′−体/2,4′−体/トリ体=90/5/5(重量比)のジヒドロキシジフェニルスルホン類の異性体混合物100g(0.4モル)に対し、水150gおよび水酸化ナトリウム2.0g(0.05モル)を加えて、オートクレーブ中で加熱撹拌した。内温120℃で内容物が完全に溶解した。この状態から撹拌しながら冷却、晶析して内温40℃になった時点で濾過、水洗し、白色の含水精製結晶95gを得た。これを乾燥して、乾燥精製結晶86gを得た。HPLC分析の結果、4,4′−体/2,4′−体/トリ体=99.4/0.5/0.1(重量比)の組成であった。収率は、原料異性体混合物に対して86%、原料異性体混合物中の4,4′−体に対して95%であった。
【0030】
実施例4
実施例1で得た精製結晶90g(0.36モル)に対し、水270gを加えて、オートクレーブ中で加熱撹拌した。内温121℃で内容物が完全に溶解した。この状態から撹拌しながら冷却、晶析して内温40℃になった時点で濾過、水洗し、白色の含水二次精製結晶99gを得た。これを乾燥して、乾燥二次精製結晶89gを得た。HPLC分析の結果、4,4′−体/2,4′−体/トリ体=99.92/0.08/0.00(重量比)の組成であった。収率は、原料精製結晶に対して99%、原料精製結晶中の4,4′−体に対して99%であった。
【0031】
比較例1
4,4′−体/2,4′−体/トリ体=95/3/2(重量比)のジヒドロキシジフェニルスルホン類の異性体混合物100g(0.4モル)に対し、水150gおよび水酸化ナトリウム1.6g(0.04モル)を加えて、フラスコ中で加熱撹拌した。内温98℃で30分間、内容物が溶解しないまま保温した後、水冷して内温40℃になった時点で濾過、水洗し、淡赤褐色の含水精製結晶100gを得た。これを乾燥して、淡赤褐色の乾燥精製結晶90gを得た。HPLC分析の結果、4,4′−体/2,4′−体/トリ体=98.5/1.4/0.1(重量比)の組成であった。収率は、原料異性体混合物に対して90%、原料異性体混合物中の4,4′−体に対して93%であった。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to 4,4'-dihydroxydiphenylsulfone (hereinafter also referred to as 4,4'-form), 2,4'-dihydroxydiphenylsulfone (hereinafter also referred to as 2,4'-form), trihydroxytriphenyl. The present invention relates to a process for producing high-purity 4,4′-dihydroxydiphenylsulfone, wherein 4,4′-isomer is selectively recovered from an isomer mixture of dihydroxydiphenylsulfones containing disulfone (hereinafter also referred to as tri-isomer) and the like.
[0002]
[Prior art and problems to be solved by the invention]
As a method for recovering the 4,4′-isomer from the isomer mixture including the 4,4′-isomer and the 2,4′-isomer, etc., for example, Japanese Patent Publication No. 43-6453 discloses crude dihydroxydiphenyl sulfone. A method is described in which a basic substance is dissolved in water containing it at an elevated temperature, cooled and crystallized to be separated from the mother liquor. However, the “increased temperature” referred to here is a normal boiling temperature of water, that is, a temperature up to about 100 ° C. Further, since the amount of the basic substance used is relatively large, for example, the yield is not satisfactory.
[0003]
Japanese Examined Patent Publication No. 4-82142 discloses a mixture of isomers in a basic aqueous solution having a pH high enough to dissolve isomer mixtures including 4,4'-isomers and 2,4'-isomers. Is dissolved to form an isomer mixture solution, and then acid is added to lower the pH of the isomer mixture solution to a pH greater than 7 but lower (eg, about 9) to give 4,4'-isomer A method for recovering the 4,4'-isomer from a mixture of isomers is described, characterized in that the crystals are selectively precipitated. However, this method is economically and industrially disadvantageous because a base and an acid are used in combination. In addition, a high-purity target product cannot be obtained in high yield.
[0004]
The present invention selectively recovers a 4,4′-isomer from a mixture of isomers of dihydroxydiphenylsulfones containing 4,4′-isomer, 2,4′-isomer, tri-isomer, etc. It is an object of the present invention to provide a method for producing a 4,4'-isomer in a high yield and industrially advantageously.
[0005]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the inventors of the present invention dissolved an isomer mixture of dihydroxydiphenyl sulfones in an aqueous solvent to which a basic substance was added as necessary at a temperature of 102 to 140 ° C. Subsequently, it was found that the 4,4′-form can be selectively recovered by cooling, and the present invention has been completed.
[0006]
That is, the present invention provides a method for producing high-purity 4,4′-dihydroxydiphenylsulfone as described below.
Item 1. An isomer mixture containing at least 75% by weight of 4,4′-dihydroxydiphenylsulfone and a total of not more than 25% by weight of 2,4′-dihydroxydiphenylsulfone and trihydroxytriphenyldisulfone is optionally added as a basic substance. Of high-purity 4,4'-dihydroxydiphenylsulfone, which is dissolved in an aqueous solvent to which is added at a temperature of 102 to 140 ° C and then cooled to precipitate 4,4'-dihydroxydiphenylsulfone. Production method.
Item 2. The total content of 2,4′-dihydroxydiphenylsulfone and trihydroxytriphenyldisulfone in the isomer mixture is 0.1 to 25% by weight, and the total amount of 2,4′-dihydroxydiphenylsulfone and trihydroxytriphenyldisulfone Item 2. The method for producing high-purity 4,4'-dihydroxydiphenylsulfone according to Item 1, wherein the basic substance is added in an amount of 0.1 to 20 moles.
Item 3. Item 3. The method for producing high-purity 4,4'-dihydroxydiphenylsulfone according to Item 2, wherein the amount of the aqueous solvent is 10 times by weight or less with respect to the isomer mixture.
Item 4. Item 2. The high content according to Item 1, wherein the total content of 2,4'-dihydroxydiphenylsulfone and trihydroxytriphenyldisulfone in the isomer mixture is 1% by weight or less, and no basic substance is added to the aqueous solvent. A method for producing 4,4'-dihydroxydiphenyl sulfone having a purity of 4.
Item 5. Item 5. The method for producing high-purity 4,4'-dihydroxydiphenylsulfone according to Item 4, wherein the amount of the aqueous solvent is 20 times by weight or less with respect to the isomer mixture.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The isomer mixture of dihydroxydiphenyl sulfones used in the present invention includes 4,4'-isomer as a main component and other isomers including 2,4'-isomer and triisomer as by-products or impurities. The mixture is an isomer mixture containing 75% by weight or more of the 4,4′-isomer and 25% by weight or less of the 2,4′-isomer and the tri-isomer in total. Preferred is an isomer mixture containing 90% by weight or more of the 4,4′-isomer and 10% by weight or less of the 2,4′-isomer and the tri-isomer in total.
[0008]
Such an isomer mixture may be, for example, a crude product of dihydroxydiphenyl sulfones obtained by reacting phenol with sulfuric acid, but is not limited thereto.
[0009]
As such a crude product, there is a possibility that an acid component such as sulfonic acid is attached to the above isomer mixture or a reaction solvent coexists. In such a case, the method of the present invention is also possible. Can be applied. For example, in the case where an acid content is attached, the purification process is not affected by adding a substantial amount of a basic substance capable of neutralizing the acid content to neutralize the acid content. The reaction solvent can be removed by distillation before or after the treatment of the present invention, or can be removed by liquid separation or the like during the dissolution treatment.
[0010]
Examples of the basic substance used in the present invention include alkali metal hydroxides, carbonates, hydrogen carbonates, alkaline earth metal hydroxides, carbonates, hydrogen carbonates, ammonia, amines, and the like. . These basic substances are used alone or in combination of two or more. Of these, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide having good dissociation properties, and alkali metal carbonates such as sodium carbonate and potassium carbonate are preferable.
[0011]
In the present invention, a basic substance is added to an aqueous solvent and dissolved as necessary.
[0012]
The amount of the basic substance to be added is determined based on the total amount of 2,4′-isomer and triisomer contained in the isomer mixture.
[0013]
That is, when the isomer mixture contains a total of 0.1 to 25% by weight of the 2,4′-isomer and the triisomer, the amount of the basic substance added is that of the 2,4′-isomer and the triisomer. The total amount is preferably from 0.1 to 20 times mol, more preferably from 0.5 to 10 times mol, particularly preferably from 0.5 to 5 times mol. If it exceeds 20 times mol, it is not preferable from the viewpoint of yield. However, the addition amount of the basic substance is preferably 20 mol% or less, and more preferably 15 mol% or less, based on the total amount of the isomer mixture. If it exceeds 20 mol%, it is not preferred for reasons such as yield.
[0014]
Further, when the isomer mixture contains a total of 0.1 to 10% by weight of the 2,4′-isomer and the tri-isomer, the basic substance is added in the same amount as described above.
[0015]
On the other hand, when the above isomer mixture contains a total of 1% by weight or less of the 2,4′-isomer and the tri-isomer, the object of the present invention can be achieved without adding a basic substance to the aqueous solvent. it can.
[0016]
As the aqueous solvent used in the present invention, water, a lower alcohol such as methanol, ethanol or isopropyl alcohol, a mixed solvent of water and a water-soluble organic solvent such as acetone, or the like is used.
[0017]
The amount of the aqueous solvent used is determined based on the total amount of 2,4′-isomer and triisomer contained in the isomer mixture.
[0018]
That is, when the above isomer mixture contains a total of 0.1 to 25% by weight of the 2,4′-isomer and the tri-isomer and a basic substance is added to the aqueous solvent, the amount of aqueous solvent used is Preferably it is 10 weight times or less with respect to a body mixture, More preferably, it is 0.3-5 weight times, Most preferably, it is 1-3 weight times. Even when the isomer mixture contains a total of 0.1 to 10% by weight of the 2,4′-isomer and the tri-isomer, and a basic substance is added to the aqueous solvent, the amount of the aqueous solvent used is as described above. It is the same.
[0019]
On the other hand, when the isomer mixture contains a total of 1% by weight or less of the 2,4′-isomer and the tri-isomer and no basic substance is added to the aqueous solvent, the amount of aqueous solvent used is the same as that of the isomer mixture. On the other hand, it is preferably 20 times by weight or less, more preferably 0.5 to 15 times by weight, and particularly preferably 1 to 10 times by weight.
[0020]
In the present invention, the temperature at which the isomer mixture is dissolved in the aqueous solvent is 102 to 140 ° C, preferably 110 to 130 ° C. If the temperature is lower than 102 ° C., the isomer mixture is not completely dissolved, so that removal of the 2,4′-isomer and / or the tri-isomer is insufficient. Also, a temperature exceeding 140 ° C. is not necessary.
[0021]
In the present invention, in order to maintain the above-mentioned temperature range, heating is usually performed using a closed container such as an autoclave, preferably heating and stirring.
[0022]
Next, when the aqueous solution in which the isomer mixture is dissolved is cooled, 4,4′-form crystals begin to precipitate at a predetermined temperature. A normal method is applied for cooling, and the temperature is preferably gradually lowered while stirring. Finally, it is cooled to 70 ° C. to near room temperature by water cooling or the like, filtered and washed with water to obtain white purified crystals. If necessary, this can be dried to obtain dried purified crystals.
[0023]
If necessary, activated carbon treatment, reducing agent addition treatment, and / or chelating agent addition treatment may be performed at an appropriate stage. If necessary, a part or all of the previous filtrate can be reused as an aqueous solvent. If it is desired to obtain a product with higher purity, it can be easily achieved by repeating these processes.
[0024]
Further, when the above isomer mixture contains a total of more than 1% by weight of 2,4′-isomer and triisomer, the method of the present invention is carried out using a basic substance, and 2,4′- After obtaining an isomer mixture containing a total of 1% by weight or less of the isomer and the tri isomer, the obtained isomer mixture is subjected to the method of the present invention again without using a basic substance. A highly pure 4,4′-isomer can be obtained.
[0025]
【The invention's effect】
According to the method of the present invention, high-purity 4,4'-dihydroxydiphenylsulfone can be produced industrially advantageously in high yield from an isomer mixture of dihydroxydiphenylsulfones. The value is extremely great.
[0026]
【Example】
Hereinafter, the method of the present invention will be described more specifically and in detail by way of examples.
[0027]
Example 1
For 100 g (0.4 mol) of an isomer mixture of 4,4′-isomer / 2,4′-isomer / tri-isomer = 95/3/2 (weight ratio) dihydroxydiphenyl sulfones, 1.6 g (0.04 mol) of sodium was added, and the mixture was heated and stirred in an autoclave. The contents were completely dissolved at an internal temperature of 120 ° C. From this state, the mixture was cooled and crystallized with stirring, and when the internal temperature reached 40 ° C., it was filtered and washed with water to obtain 100 g of white water-containing purified crystals. This was dried to obtain 90 g of dried and purified crystals. As a result of HPLC (high performance liquid chromatography) analysis, the composition was 4,4′-isomer / 2,4′-isomer / tri-isomer = 99.7 / 0.3 / 0.0 (weight ratio). The yield was 90% with respect to the raw material isomer mixture and 95% with respect to the 4,4′-isomer in the raw material isomer mixture.
[0028]
Example 2
For 100 g (0.4 mol) of an isomer mixture of 4,4′-isomer / 2,4′-isomer / tri-isomer = 95/3/2 (weight ratio) dihydroxydiphenyl sulfones, 1.6 g (0.04 mol) of sodium was added, and the mixture was heated and stirred in an autoclave. The contents were completely dissolved at an internal temperature of 120 ° C. From this state, the mixture was cooled and crystallized with stirring, and when the internal temperature reached 40 ° C., it was filtered and washed with water to obtain 100 g of white water-containing purified crystals. This was dried to obtain 90 g of dried and purified crystals. As a result of HPLC analysis, the composition was 4,4′-isomer / 2,4′-isomer / tri-isomer = 99.7 / 0.3 / 0.0 (weight ratio). The yield was 90% with respect to the raw material isomer mixture and 95% with respect to the 4,4′-isomer in the raw material isomer mixture.
[0029]
Example 3
For 100 g (0.4 mol) of an isomer mixture of 4,4′-isomer / 2,4′-isomer / tri-isomer = 90/5/5 (weight ratio) dihydroxydiphenyl sulfones, Sodium (2.0 g, 0.05 mol) was added, and the mixture was heated and stirred in an autoclave. The contents were completely dissolved at an internal temperature of 120 ° C. From this state, the mixture was cooled and crystallized with stirring, and filtered and washed with water when the internal temperature reached 40 ° C. to obtain 95 g of white water-containing purified crystals. This was dried to obtain 86 g of dried and purified crystals. As a result of HPLC analysis, the composition was 4,4′-isomer / 2,4′-isomer / tri-isomer = 99.4 / 0.5 / 0.1 (weight ratio). The yield was 86% with respect to the raw material isomer mixture and 95% with respect to the 4,4′-isomer in the raw material isomer mixture.
[0030]
Example 4
270 g of water was added to 90 g (0.36 mol) of the purified crystal obtained in Example 1, and the mixture was heated and stirred in an autoclave. The contents were completely dissolved at an internal temperature of 121 ° C. From this state, the mixture was cooled and crystallized with stirring, and when the internal temperature reached 40 ° C., it was filtered and washed with water to obtain 99 g of white water-containing secondary purified crystals. This was dried to obtain 89 g of dried secondary purified crystals. As a result of HPLC analysis, the composition was 4,4′-isomer / 2,4′-isomer / tri-isomer = 99.92 / 0.08 / 0.00 (weight ratio). The yield was 99% with respect to the raw material purified crystal and 99% with respect to the 4,4′-form in the raw material purified crystal.
[0031]
Comparative Example 1
For 100 g (0.4 mol) of an isomer mixture of 4,4′-isomer / 2,4′-isomer / tri-isomer = 95/3/2 (weight ratio) dihydroxydiphenyl sulfones, 1.6 g (0.04 mol) of sodium was added, and the mixture was heated and stirred in the flask. After keeping the contents undissolved for 30 minutes at an internal temperature of 98 ° C., it was cooled with water and filtered and washed with water when the internal temperature reached 40 ° C. to obtain 100 g of light reddish brown water-containing purified crystals. This was dried to obtain 90 g of light reddish brown dried purified crystals. As a result of HPLC analysis, the composition was 4,4′-isomer / 2,4′-isomer / tri-isomer = 98.5 / 1.4 / 0.1 (weight ratio). The yield was 90% with respect to the raw material isomer mixture, and 93% with respect to the 4,4′-isomer in the raw material isomer mixture.
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JPS6150958A (en) * | 1984-08-16 | 1986-03-13 | Konishi Kagaku Kogyo Kk | Method of purifying 4,4'-dihydroxydiphenylsulfone |
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