JP3043571B2 - Purification method of diaminodiphenyl ether - Google Patents
Purification method of diaminodiphenyl etherInfo
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- JP3043571B2 JP3043571B2 JP6157260A JP15726094A JP3043571B2 JP 3043571 B2 JP3043571 B2 JP 3043571B2 JP 6157260 A JP6157260 A JP 6157260A JP 15726094 A JP15726094 A JP 15726094A JP 3043571 B2 JP3043571 B2 JP 3043571B2
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- JP
- Japan
- Prior art keywords
- diaminodiphenyl ether
- distillation
- solvent
- mmhg
- reduction reaction
- 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.)
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Description
【０００１】[0001]
【産業上の利用分野】本発明は３，４′―ジアミノジフ
ェニルエーテルで代表されるジアミノジフェニルエーテ
ル類の製造方法に関し、更に詳しくはアラミド繊維の原
料に供し得る高純度ジアミノジフェニルエーテルの精製
方法に係わる。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing diaminodiphenyl ethers represented by 3,4'-diaminodiphenyl ether, and more particularly to a method for purifying high-purity diaminodiphenyl ether which can be used as a raw material for aramid fiber.
【０００２】[0002]
【従来の技術】ジアミノジフェニルエーテル類の製造技
術は、ジニトロジフェニルエーテル類またはニトロフェ
ニルアミノフェニルエーテル類を水素により還元する方
法等によって公知であると共に商業化技術として確立さ
れている。また、アラミド原料には高純度のジアミノジ
フェニルエーテルが要求されることも知られている。そ
して、純粋なジアミノジフェニルエーテルを得るために
種々な提案がなされている。その代表的なものは、高純
度の目的物（ジアミノジフェニルエーテル）を得るため
に、あらかじめ出発原料として純度の高いものを使用す
る方法である。特開平１―２５８６５１号公報にはジニ
トロジフェニルエーテルやニトロフェニルアミノフェニ
ルエーテル原料中のハロニトロベンゼン類の含量を１．
５ｗｔ％以下とすべきことが提示されている。また、特
定の目的物、例えば３，４′―ジアミノジフェニルエー
テルを得る場合には、原料の異性体の混入を避けること
が有効であり、特開昭６１―２２５１５５号公報には、
原料４―クロロニトロベンゼンに占める異性体２―クロ
ロニトロベンゼンの含有量が０．１ｗｔ％以下である純
度の高いものを用いて縮合乃至水素還元すべきことが開
示されている。高い純度の原料を使用すれば純粋な目的
物が精製されることは自明と云えるかもしれない。高純
度のジアミノジフェニルエーテルを如何に低コストで得
るかという点に創意が求められているのであって、原
料、反応溶媒、生成物（目的物）のうちのいずれを対象
とすれば低コストで高純度のものが得られるかが技術の
上の課題である。2. Description of the Related Art The production technology of diaminodiphenyl ethers is known by a method of reducing dinitrodiphenyl ethers or nitrophenylaminophenyl ethers with hydrogen, and has been established as a commercialization technology. It is also known that high purity diaminodiphenyl ether is required for aramid raw materials. Various proposals have been made to obtain pure diaminodiphenyl ether. A typical example is a method of using a high-purity starting material in advance to obtain a high-purity target product (diaminodiphenyl ether). Japanese Patent Application Laid-Open No. 1-258651 discloses that the content of halonitrobenzenes in the raw material of dinitrodiphenyl ether or nitrophenylaminophenyl ether is 1.
It is proposed that the content should be 5 wt% or less. Further, when obtaining a specific target product, for example, 3,4'-diaminodiphenyl ether, it is effective to avoid mixing of isomers of the raw materials, and JP-A-61-225155 discloses that
It is disclosed that condensation or hydrogen reduction should be carried out using a high-purity material in which the content of the isomer 2-chloronitrobenzene in the raw material 4-chloronitrobenzene is 0.1 wt% or less. It may be self-evident that a pure target can be purified by using a high-purity raw material. There is a need for creativity on how to obtain high-purity diaminodiphenyl ether at low cost. If any of raw materials, reaction solvents, and products (objectives) is targeted, low cost and high cost are required. It is a technical challenge to obtain a product of purity.
【０００３】[0003]
【発明が解決しようとする課題】特開平１―２７２５５
８号公報には、ジアミノジフェニルエーテルの精製法が
提案されている。この技術は二段蒸留法であって、粗蒸
留と精密蒸留とを組合せたものである。ジアミノジフェ
ニルエーテルの反応において副生された重質化物（３，
４′―ジアミノジフェニルエーテルより沸点の高いも
の）を除去する粗蒸留を済ませた後に精密蒸留を行うも
のであって、粗蒸留によって数パーセントを占める重質
化物が除かれることとなる。Problems to be Solved by the Invention
No. 8 proposes a method for purifying diaminodiphenyl ether. This technique is a two-stage distillation method in which crude distillation and precision distillation are combined. Heavy products by-produced in the reaction of diaminodiphenyl ether (3,
This is a method in which crude distillation is performed after crude distillation for removing 4'-diaminodiphenyl ether (which has a boiling point higher than that of 4'-diaminodiphenyl ether), and heavy substances that account for several percent are removed by the crude distillation.
【０００４】ところで、高純度の原料を使用すれば純度
の高い生成物が得られることは事実であるが、副反応に
よって副生成を回避できない場合がある。副生成量は少
ないものの、例えばジアミノジフェニルエーテルは、還
元反応時の溶媒であるジメチルホルムアミドやＮ―メチ
ルピロリドンと副反応によってアミジン類が形成されて
いると推測され、Ｎ―フェニル―ホルムアミドやＮ，
Ｎ′―ジフェニル―ホルムアミドが重質化物として存在
している。従って、重質化物の除去は不可欠であると共
に、目的となる生成物と溶媒との副反応を如何に抑制す
るかが課題である。更に重質化物は蒸留の過程で分解
し、精製しようとする主成分中に混入してくる問題があ
る。従って分解を抑制して重質化物のままで蒸留塔の塔
底部に残溜せしめることが望ましい。Although it is true that a high-purity raw material can be obtained by using a high-purity raw material, it is sometimes impossible to avoid by-products due to side reactions. Although the amount of by-products is small, for example, diaminodiphenyl ether is presumed to form amidines by a side reaction with dimethylformamide or N-methylpyrrolidone as a solvent during the reduction reaction, and N-phenyl-formamide, N,
N'-diphenyl-formamide is present as a heavier. Therefore, the removal of heavy materials is indispensable, and the problem is how to suppress the side reaction between the target product and the solvent. Furthermore, there is a problem that the heavy material is decomposed in the course of distillation and is mixed into the main component to be purified. Therefore, it is desirable to suppress the decomposition and leave the heavy material as it is at the bottom of the distillation column.
【０００５】これらの問題点を解決すべく、本発明者ら
は鋭意検討を試みた結果、ジアミノジフェニルエーテル
と特定溶媒であるジメチルホルムアミドやＮ―メチルピ
ロリドンとが重合物を形成しない条件で混合物中より特
定溶媒の一部を除去する方法を講ずる（溶媒を系外に蒸
留除去し、ジアミノジフェニルエーテルを濃縮する）プ
ロセス及び濃縮された混合物からジアミノジフェニルエ
ーテルを蒸留し精製するプロセスを組合わせることによ
って、高純度のジアミノジフェニルエーテルが得られる
ことを見い出し、本発明に到達できたものである。The inventors of the present invention have made intensive studies to solve these problems. As a result, diaminodiphenyl ether and dimethylformamide or N-methylpyrrolidone, which is a specific solvent, are not dissolved in a mixture under the condition that a polymer is not formed. By combining the process of removing a part of the specific solvent (distilling off the solvent out of the system and concentrating diaminodiphenyl ether) and the process of distilling and refining diaminodiphenyl ether from the concentrated mixture, high purity is achieved. It was found that diaminodiphenyl ether of the formula (1) was obtained, and the present invention was achieved.
【０００６】[0006]
【発明の構成】本発明は、ジアミノジフェニルエーテル
と還元反応に用いた溶媒との混合物から反応に供した触
媒を濾別して除去し、次いで該混合物を蒸留塔に導き、
塔底温度６０〜１５０℃、塔頂圧力１〜２００ｍｍＨｇ
の条件下で長くとも８時間以内に減圧蒸留し、前記溶媒
の一部を留去して濃縮し、しかる後塔頂圧力５０ｍｍＨ
ｇ以下の条件でジアミノジフェニルエーテルを蒸留する
ことからなるジアミノジフェニルエーテルの精製法であ
る。本発明は還元反応に用いた溶媒がジメチルフォルム
アミド又はＮ―メチルピロリドンの場合に有効であり、
溶媒を混合物から留去する濃縮工程とジアミノジフェニ
ルエーテルを蒸留により精製する工程とからなるもので
あり、還元反応において副生されるアミジン類を極力抑
制する精製技術である。According to the present invention, the catalyst used for the reaction is removed by filtration from a mixture of diaminodiphenyl ether and the solvent used for the reduction reaction, and then the mixture is guided to a distillation column.
Column bottom temperature 60-150 ° C, column top pressure 1-200mmHg
The solvent was distilled under reduced pressure within 8 hours at most, and a part of the solvent was distilled off and concentrated.
This is a method for purifying diaminodiphenyl ether, which comprises distilling diaminodiphenyl ether under conditions of not more than g. The present invention is effective when the solvent used for the reduction reaction is dimethylformamide or N-methylpyrrolidone,
It comprises a concentration step of distilling off the solvent from the mixture and a step of purifying diaminodiphenyl ether by distillation, and is a purification technique for minimizing amidines by-produced in the reduction reaction.
【０００７】本発明を説明する。The present invention will be described.
【０００８】本発明の精製法の特徴は、 （１）減圧蒸留によって溶媒（例えばＮ―メチルピロリ
ドン）の一部を留去するものである。この際ジアミノジ
フェニルエーテルと溶媒とが重合物を実質的に形成しな
いように、約１００℃以下、３時間を越えない条件下
で、溶媒を系外に留去し、目的生成物のジアミノジフェ
ニルエーテルを濃縮するものである。The features of the purification method of the present invention are as follows: (1) Part of a solvent (eg, N-methylpyrrolidone) is distilled off under reduced pressure. At this time, the solvent is distilled out of the system under a condition of not more than about 100 ° C. and not more than 3 hours so that the diaminodiphenyl ether and the solvent do not substantially form a polymer, and the desired product diaminodiphenyl ether is concentrated. Is what you do.
【０００９】（２）従来技術では、ジアミノジフェニル
エーテル主成分中に不純物（例えばアミジン誘導体が形
成される）が含まれると、この重質化物が分解し、精製
しようとする主成分中に混入することとなる結果、高純
度化は極めて困難であった。これに対し、本発明方法で
は重質化物が分解しない条件で溶媒の一部を除き、更に
重質化物を残したままで、主たる留分のＤＡＰＥを減圧
蒸留し、不純物の混入を回避して、ＤＡＰＥを精製せし
めることが可能となったものである。(2) In the prior art, if an impurity (for example, an amidine derivative is formed) is contained in the main component of diaminodiphenyl ether, the heavy material is decomposed and mixed into the main component to be purified. As a result, high purification was extremely difficult. On the other hand, in the method of the present invention, a part of the solvent is removed under the condition that the heavy material is not decomposed, and DAPE of the main fraction is distilled under reduced pressure while leaving the heavy material further, to avoid contamination with impurities, This makes it possible to purify DAPE.
【００１０】本発明では、先ず還元反応で得られた粗ジ
アミノジフェニルエーテルと還元反応触媒（通常白金、
パラジウム等の白金族金属が用いられる）との混合物か
ら、前記還元反応触媒を濾別することにより除去し、こ
の触媒を回収する。In the present invention, first, the crude diaminodiphenyl ether obtained by the reduction reaction and a reduction reaction catalyst (usually platinum,
(A platinum group metal such as palladium is used), and the reduction reaction catalyst is removed by filtration, and the catalyst is recovered.
【００１１】次に、前記反応生成物（粗ジアミノジフェ
ニルエーテル）を減圧蒸留し、還元反応の際使用してい
た溶媒の一部を留去し、反応生成物を濃縮する。この
際、反応釜の塔底温度を６０〜１５０℃とし、塔頂圧力
を１〜２００ｍｍＨｇの状態に保つ。塔底温度が１５０
℃を超えると、ＤＡＰＥと溶媒、殊にＮ―メチルピロリ
ドンやジメチルホルムアミド（ＤＭＦ）の場合、との間
でアミジン誘導体が副生され易い。従って蒸留は低目の
塔底温度が好ましい。また蒸留時間が長くなると徐々に
アミジン誘導体が形成されるため、蒸留時間は８時間以
内が望ましい。勿論蒸留時間は短い程よいが、蒸留の終
結まで３〜４時間を要する条件を選択するとよい。この
ような蒸留時間の経過に伴う高沸点の重質分の副生量は
例えば図１から知り得る。塔底温度約６０〜１００℃の
条件で、重質分は約３時間経過後増加してくる。Next, the reaction product (crude diaminodiphenyl ether) is distilled under reduced pressure, a part of the solvent used in the reduction reaction is distilled off, and the reaction product is concentrated. At this time, the temperature at the bottom of the reactor is set at 60 to 150 ° C., and the pressure at the top is maintained at 1 to 200 mmHg. The bottom temperature is 150
When the temperature exceeds ℃, an amidine derivative is easily produced as a by-product between DAPE and a solvent, particularly in the case of N-methylpyrrolidone or dimethylformamide (DMF). Therefore, a lower column temperature is preferred for distillation. In addition, since the amidine derivative is gradually formed as the distillation time becomes longer, the distillation time is desirably 8 hours or less. Of course, the shorter the distillation time, the better, but it is preferable to select a condition that requires 3 to 4 hours to complete the distillation. The amount of by-products of high-boiling heavy components with the lapse of the distillation time can be known from, for example, FIG. Under the condition of the bottom temperature of about 60 to 100 ° C., the heavy fraction increases after about 3 hours.
【００１２】これらの知見に基づけば、蒸留時の条件と
して塔頂圧力は前記した約１〜２００ｍｍＨｇ程度であ
り、好ましくは約１〜１００ｍｍＨｇ、更に好ましくは
１〜６０ｍｍＨｇ程度である。また塔底温度は６０〜１
５０℃、好ましくは６０〜１２０℃、更に好ましくは６
０〜１００℃である。[0012] Based on these findings, the distillation column pressure is about 1 to 200 mmHg, preferably about 1 to 100 mmHg, and more preferably about 1 to 60 mmHg. The bottom temperature is 60-1.
50 ° C, preferably 60 to 120 ° C, more preferably 6 ° C
0-100 ° C.
【００１３】第一段階の溶媒の蒸留による濃縮の工程で
はジアミノジフェニルエーテルは全く蒸留されていな
い。濃縮工程に続けて第二段階においてジアミノジフェ
ニルエーテルを蒸留することとなる。この蒸留の条件
は、塔頂圧力を５０ｍｍＨｇ以下とし、理論段として少
くとも１０段の充填塔を備えた蒸留装置を用いるもので
ある。塔頂圧力は好ましくは３０ｍｍＨｇ以下とし、回
分蒸留により、初期留分を除いた後に、主たる留分であ
るジアミノジフェニルエーテルを得ることができる。In the first step of concentration by distillation of the solvent, diaminodiphenyl ether is not distilled at all. Following the concentration step, diaminodiphenyl ether will be distilled in the second stage. The distillation conditions are such that the pressure at the top of the column is 50 mmHg or less, and a distillation apparatus equipped with at least 10 packed columns as theoretical plates is used. The pressure at the top of the column is preferably 30 mmHg or less, and diaminodiphenyl ether, which is the main fraction, can be obtained by removing the initial fraction by batch distillation.
【００１４】本発明の精製法に較べて、従来技術の一つ
である特開平１―２７２５５８号は、粗蒸留と精密蒸留
の２段階とも目的生成物ジアミノジフェニルエーテルを
蒸留させていることから、エネルギーコストが高くなら
ざるを得ない。また、製品のジアミノジフェニルエーテ
ルの回収率を高めるには粗蒸留の段階でかなり炊上げる
必要があり（この場合は釜残となったジアミノジフェニ
ルエーテルはロスとなることから、収率を高めるために
も釜残が少なくなるように長時間蒸留を続ける）、更に
エネルギーコストを要することとなる。また、本発明者
らの知見では従来技術における粗蒸留中の塔底温度は２
００〜３３０℃程度であり、この温度では別な重質物が
生成する原因を有し、収率の低減を招くものである。Compared to the purification method of the present invention, Japanese Patent Application Laid-Open No. 1-272558, which is one of the prior arts, discloses that the target product diaminodiphenyl ether is distilled in both of the crude distillation and the precision distillation. The cost must be high. In addition, in order to increase the recovery of diaminodiphenyl ether from the product, it is necessary to cook considerably in the stage of crude distillation (in this case, diaminodiphenyl ether remaining in the pot is lost, so the pot is also used to increase the yield. The distillation is continued for a long time so as to reduce the residue), which further requires energy costs. According to the knowledge of the present inventors, the column bottom temperature during crude distillation in the prior art was 2 ° C.
The temperature is about 00 to 330 ° C., and at this temperature, there is a cause that another heavy material is generated, and the yield is reduced.
【００１５】このような理由から、６０〜１５０℃、好
ましくは６０〜１００℃の塔底温度を採用する本発明は
精製コストが少く有利となる。[0015] For this reason, the present invention employing a bottom temperature of 60 to 150 ° C, preferably 60 to 100 ° C, is advantageous because the purification cost is low.
【００１６】[0016]
【実施例１】 ［Ｉ. ３，４′―ジアミノジフェニルエーテルの合成］
メタアミノフェノール４５８ｇとパラクロルニトロベン
ゼン６８４ｇとを炭酸カリウム３１８ｇの存在下、１５
８０ｇのジメチルホルムアミド（ＤＭＦ）溶媒中におい
て１５０℃、９時間反応せしめた。その結果、生成した
塩（塩化カリ）を濾別し、３―アミノフェニル―４′―
ニトロフェニルエーテル混合液を得た。Example 1 [I. Synthesis of 3,4'-diaminodiphenyl ether]
458 g of metaaminophenol and 684 g of parachloronitrobenzene were added to 15 g of potassium carbonate in the presence of 318 g of potassium carbonate.
The reaction was carried out in 150 g of dimethylformamide (DMF) solvent at 150 ° C. for 9 hours. As a result, the generated salt (potassium chloride) was filtered off, and 3-aminophenyl-4'-
A nitrophenyl ether mixture was obtained.
【００１７】この混合液２１７０ｇにパラジウム―カー
ボン触媒１６ｇの存在下において、水素圧７ｋｇ／ｃｍ
2 Ｇ、１００℃の条件で６時間還元反応を行った。しか
る後還元触媒を濾別し、ガスクロマトグラフィにより反
応生成物を分析したところ、アラミド原料である３，
４′―ジアミノジフェニルエーテル（３，４′―ＤＡＰ
Ｅと略記する）７９５ｇを含む混合溶液２０９０ｇが得
られた。A hydrogen pressure of 7 kg / cm was added to 2170 g of this mixture in the presence of 16 g of a palladium-carbon catalyst.
The reduction reaction was performed at 2 G and 100 ° C. for 6 hours. Thereafter, the reduction catalyst was filtered off, and the reaction product was analyzed by gas chromatography.
4'-diaminodiphenyl ether (3,4'-DAP
2090 g of a mixed solution containing 795 g (abbreviated as E) were obtained.
【００１８】［II. 濃縮］前記Ｉの合成工程で得られた
３，４′―ＤＡＰＥ混合液を塔頂圧力３０〜６０ｍｍＨ
ｇ、塔底温度１００〜１１０℃、還流比０の条件におい
て３時間単蒸留したところ１１８５ｇの濃縮液が得られ
た。この濃縮液をガスクロマトグラフィーにより分析し
たところ、下記式で定義される３，４′―ＤＡＰＥより
も沸点の高い有機不純物（ＨＥ：ヘビーエンド）の割合
は２．５％であった。[II. Concentration] The 3,4'-DAPE mixed solution obtained in the synthesis step I was subjected to a top pressure of 30 to 60 mmH.
g, a simple distillation for 3 hours under the conditions of a bottom temperature of 100 to 110 ° C. and a reflux ratio of 0 gave 1185 g of a concentrated liquid. When this concentrated liquid was analyzed by gas chromatography, the ratio of organic impurities (HE: heavy end) having a higher boiling point than 3,4'-DAPE defined by the following formula was 2.5%.
【００１９】[0019]
【数１】 (Equation 1)
【００２０】［III.蒸留］前記IIで得られた濃縮液を理
論段１５段の充填塔を備えた蒸留装置に仕込み、塔頂圧
力１５ｍｍＨｇ、塔底温度２５５〜２７０℃、還流比３
の条件で回分蒸留を行った。塔頂温度１５０〜２４４℃
の留分６０４ｇを初留として除いた後、塔頂温度２４４
〜２４８℃の主留分３６１ｇを得た。この主留分をガス
クロマトグラフィにより分析し他ところ、純度９９．９
２％の３，４′―ＤＡＰＥであった。[III. Distillation] The concentrated liquid obtained in the above II was charged into a distillation apparatus equipped with a packed column having 15 theoretical stages, and a top pressure of 15 mmHg, a bottom temperature of 255 to 270 ° C., and a reflux ratio of 3
Batch distillation was performed under the following conditions. Tower temperature 150-244 ° C
After removing 604 g of a fraction as the initial fraction, the top temperature was 244 g.
361 g of a main fraction at ２248 ° C. were obtained. The main fraction was analyzed by gas chromatography and found to have a purity of 99.9.
It was 2% 3,4'-DAPE.
【００２１】[0021]
【比較例１】実施例１と同様にして得られた３，４′―
ジアミノジフェニル混合液２２６５ｇの濃縮を常圧下、
塔底温度１５０〜１８０℃、還流比０．５〜１．０の条
件で２０時間蒸留したところ、１２１７ｇの濃縮液が得
られた。この濃縮液をガスクロマトグラフィーで分析
し、前記、定義式の３，４′―ジアミノジフェニルエー
テルよりも沸点の高い有機不純物の割合を計算したとこ
ろ４３％であった。これは濃縮蒸留中に３，４′―ジア
ミノジフェニルエーテルが重質分に変化したためであ
り、その後の精密蒸留は沸点が高くなり過ぎて、精密蒸
留をすることができなかった。Comparative Example 1 3,4′- obtained in the same manner as in Example 1.
The concentration of 2265 g of the diaminodiphenyl mixture was concentrated under normal pressure.
Distillation was performed at a tower bottom temperature of 150 to 180 ° C. and a reflux ratio of 0.5 to 1.0 for 20 hours to obtain 1217 g of a concentrated liquid. This concentrated solution was analyzed by gas chromatography, and the ratio of organic impurities having a boiling point higher than that of 3,4'-diaminodiphenyl ether of the above defined formula was calculated to be 43%. This is because 3,4'-diaminodiphenyl ether was changed into heavy components during the concentration distillation, and the precision distillation thereafter could not be carried out because the boiling point was too high.
【００２２】[0022]
【実施例２〜１４】実施例１と同様な濃縮操作の実験を
行った。この結果を表１に実施例２〜１４として示す。
また、そのとき３，４′―ジアミノジフェニルエーテル
よりも沸点の高い有機不純物の生成される割合を図１に
グラフとして示した。Examples 2 to 14 The same concentration experiment as in Example 1 was performed. The results are shown in Table 1 as Examples 2 to 14.
FIG. 1 is a graph showing the proportion of organic impurities having a higher boiling point than 3,4'-diaminodiphenyl ether.
【００２３】[0023]
【表１】 [Table 1]
【００２４】[0024]
【発明の効果】本発明の精製法によれば、蒸留精製に伴
って副生される不純物の量が殆どないことから、高純度
製品を得ることができる。従来技術では粗蒸留の際の塔
底温度が２００〜３３０℃であるのに対し、本発明では
６０〜１００℃でよく、高純度製品を得る点に加えてエ
ネルギーコストも低くなる利点がある。According to the purification method of the present invention, a high-purity product can be obtained because there is almost no amount of impurities produced as a result of distillation purification. In the prior art, the tower bottom temperature during crude distillation is 200 to 330 ° C., whereas in the present invention, the temperature may be 60 to 100 ° C., which is advantageous in that a high-purity product is obtained and the energy cost is low.
【図１】本発明における実施例であって、蒸留操作時間
（横軸）の経過と共に副生される重質分の割合（縦軸）
を示すグラフである。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an embodiment of the present invention, in which the proportion of heavy components by-produced as the distillation operation time (horizontal axis) elapses (vertical axis).
FIG.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 隅谷 浩二 愛媛県松山市北吉田町77番地 帝人株式 会社 松山事業所内 (56)参考文献 特開 平１−272558（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C07C 217/90 C07C 213/02 C07C 213/10 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Koji Sumiya, Inventor Koji Sumida 77, Kitayoshida-cho, Matsuyama-shi, Ehime Teijin Co., Ltd. Matsuyama Office (56) References JP-A-1-272558 (JP, A) (58) Field (Int.Cl. 7 , DB name) C07C 217/90 C07C 213/02 C07C 213/10
Claims (2)
に用いた溶媒との混合物から還元反応触媒を濾別して除
去し、次いで該混合物を塔底温度６０〜１５０℃、塔頂
圧力１〜２００ｍｍＨｇの条件下で８時間以下減圧蒸留
し前記溶媒の一部を留去して濃縮し、しかる後塔頂圧力
５０ｍｍＨｇ以下の条件でジアミノジフェニルエーテル
を蒸留することからなるジアミノジフェニルエーテルの
精製法。1. A reduction reaction catalyst is removed by filtration from a mixture of diaminodiphenyl ether and a solvent used for the reduction reaction, and then the mixture is treated at a column bottom temperature of 60 to 150 ° C. and a column top pressure of 1 to 200 mmHg under a condition of 8 mmHg. A method for purifying diaminodiphenyl ether, comprising distilling off a part of the solvent by distillation under reduced pressure for a period of not more than time and concentrating the solvent, and then distilling diaminodiphenyl ether under a condition of a top pressure of 50 mmHg or less.
ムアミド又はＮ―メチルピロリドンである請求項１に記
載のジアミノジフェニルエーテルの精製法。2. The method for purifying diaminodiphenyl ether according to claim 1, wherein the solvent used for the reduction reaction is dimethylformamide or N-methylpyrrolidone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6157260A JP3043571B2 (en) | 1994-07-08 | 1994-07-08 | Purification method of diaminodiphenyl ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6157260A JP3043571B2 (en) | 1994-07-08 | 1994-07-08 | Purification method of diaminodiphenyl ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0827077A JPH0827077A (en) | 1996-01-30 |
| JP3043571B2 true JP3043571B2 (en) | 2000-05-22 |
Family
ID=15645769
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6157260A Expired - Fee Related JP3043571B2 (en) | 1994-07-08 | 1994-07-08 | Purification method of diaminodiphenyl ether |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3043571B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5027572B2 (en) * | 2007-06-28 | 2012-09-19 | 帝人株式会社 | Method for producing 3,4'-diaminodiphenyl ether |
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1994
- 1994-07-08 JP JP6157260A patent/JP3043571B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0827077A (en) | 1996-01-30 |
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