JP2849464B2 - Purification method of 1,3-bis (3-aminophenoxy) benzene by thin film distillation - Google Patents
Purification method of 1,3-bis (3-aminophenoxy) benzene by thin film distillationInfo
- Publication number
- JP2849464B2 JP2849464B2 JP27928590A JP27928590A JP2849464B2 JP 2849464 B2 JP2849464 B2 JP 2849464B2 JP 27928590 A JP27928590 A JP 27928590A JP 27928590 A JP27928590 A JP 27928590A JP 2849464 B2 JP2849464 B2 JP 2849464B2
- Authority
- JP
- Japan
- Prior art keywords
- aminophenoxy
- benzene
- bis
- film distillation
- thin film
- 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.)
- Expired - Fee Related
Links
- DKKYOQYISDAQER-UHFFFAOYSA-N 3-[3-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(OC=3C=C(N)C=CC=3)C=CC=2)=C1 DKKYOQYISDAQER-UHFFFAOYSA-N 0.000 title claims description 28
- 238000004821 distillation Methods 0.000 title claims description 28
- 239000010409 thin film Substances 0.000 title claims description 22
- 238000000034 method Methods 0.000 title claims description 19
- 238000000746 purification Methods 0.000 title description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 14
- 229920001223 polyethylene glycol Polymers 0.000 claims description 14
- 229920001451 polypropylene glycol Polymers 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 description 20
- 238000009835 boiling Methods 0.000 description 12
- JHYZHLNKNMVBSP-UHFFFAOYSA-N 3-[3,5-bis(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(OC=3C=C(N)C=CC=3)C=C(OC=3C=C(N)C=CC=3)C=2)=C1 JHYZHLNKNMVBSP-UHFFFAOYSA-N 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- -1 3-aminophenoxy Chemical group 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000011403 purification operation Methods 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- BZXJAHGHOJFYRT-UHFFFAOYSA-N 3-[2-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C(=CC=CC=2)OC=2C=C(N)C=CC=2)=C1 BZXJAHGHOJFYRT-UHFFFAOYSA-N 0.000 description 1
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 1
- 229940018563 3-aminophenol Drugs 0.000 description 1
- NNKQLUVBPJEUOR-UHFFFAOYSA-N 3-ethynylaniline Chemical group NC1=CC=CC(C#C)=C1 NNKQLUVBPJEUOR-UHFFFAOYSA-N 0.000 description 1
- UCSYVYFGMFODMY-UHFFFAOYSA-N 3-phenoxyaniline Chemical compound NC1=CC=CC(OC=2C=CC=CC=2)=C1 UCSYVYFGMFODMY-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は1,3−ビス（３−アミノフェノキシ）ベンゼ
ンの精製方法に関する。さらに詳しくは、精製される1,
3−ビス（３−アミノフェノキシ）ベンゼンの純度が比
較的高く、その中に含有した高沸点不純物を薄膜蒸留装
置を用いて除去する精製方法に関する。The present invention relates to a method for purifying 1,3-bis (3-aminophenoxy) benzene. More specifically,
The present invention relates to a purification method in which 3-bis (3-aminophenoxy) benzene has a relatively high purity and high-boiling impurities contained therein are removed using a thin-film distillation apparatus.
1,3−ビス（３−アミノフェノキシ）ベンゼンは耐熱
性高分子単量体、とくにポリアミド、ポリイミドの原料
となる重要な物質である。例えば、1,3−ビス（３−ア
ミノフェノキシ）ベンゼン、3,3′,4,4′−ベンゾフェ
ノンテトラカルボン酸二無水物および３−アミノフェニ
ルアセチレンから製造されるアセチレン末端ポリイミド
は、ポリイミドの中で最も高い部類の耐熱性を有するポ
リマーであることが知られている（U.S.P.3,845,018、
U.S.P.3,879,349）。1,3-Bis (3-aminophenoxy) benzene is an important substance used as a raw material for heat-resistant high-molecular monomers, particularly polyamides and polyimides. For example, acetylene terminated polyimides made from 1,3-bis (3-aminophenoxy) benzene, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride and 3-aminophenylacetylene are among the polyimides Is known to be the highest class of heat resistant polymer (USP 3,845,018,
USP 3,879,349).
前述の1,3−ビス（３−アミノフェノキシ）ベンゼン
は、1,3,5トリハロゲノベンゼンと３−アミノフェノー
ルを脱ハロゲン化水素剤の存在下で反応させて得られる
1,3−ビス（３−アミノフェノキシ）−５−ハロゲノベ
ンゼンを、接触還元して脱ハロゲン化させて得られるこ
とが特開昭60−87247号公報によって既に公知である。The aforementioned 1,3-bis (3-aminophenoxy) benzene is obtained by reacting 1,3,5 trihalogenobenzene with 3-aminophenol in the presence of a dehydrohalogenating agent.
It is already known from JP-A-60-87247 that 1,3-bis (3-aminophenoxy) -5-halogenobenzene is obtained by catalytic reduction and dehalogenation.
該公報によると、1,3−ビス（３−アミノフェノキ
シ）ベンゼンは反応後、濾過して触媒等を除き、濃縮、
希釈等の方法で結晶として析出させるか、鉱酸の添加に
よって鉱酸塩として析出させ中和して得ることができ
る。According to the publication, 1,3-bis (3-aminophenoxy) benzene is reacted, filtered to remove a catalyst and the like, concentrated,
It can be obtained by precipitating it as crystals by a method such as dilution or by precipitating it as a mineral salt by adding a mineral acid and neutralizing it.
前述の方法に従えば、比較的容易に好収率で目的とす
る1,3−ビス（３−アミノフェノキシ）ベンゼンを得る
ことができるが、前記特許実施例に従って反応を行った
場合、副生物として1,3−ビス（３−アミノフェノキ
シ）ベンゼンよりも高沸点の1,3,5−トリ（３−アミノ
フェノキシ）ベンゼンが、全生成物の６ないし８％程度
の割合で副生することが判った。この他にも微量の副生
物の生成は認められるが、1,3,5−トリ（３−アミノフ
ェノキシ）ベンゼン以外の副生物は、反応に続く濃縮、
再結晶等の通常の精製操作により容易に目的物である1,
3−ビス（３−アミノフェノキシ）ベンゼンから除去し
得るのに対し、1,3,5−トリ（３−アミノフェノキシ）
ベンゼンはこれらの精製操作によっては除去し得ず、製
品の1,3−ビス（３−アミノフェノキシ）ベンゼン中に
不純物として混入する為、1,3−ビス（３−アミノフェ
ノキシ）ベンゼンの純度低下を引き起こす。According to the above-mentioned method, the desired 1,3-bis (3-aminophenoxy) benzene can be obtained relatively easily and in good yield. 1,3,5-tri (3-aminophenoxy) benzene having a higher boiling point than 1,3-bis (3-aminophenoxy) benzene is by-produced at a rate of about 6 to 8% of the total product. I understood. In addition, the generation of trace amounts of by-products is observed, but by-products other than 1,3,5-tri (3-aminophenoxy) benzene are concentrated following the reaction,
The target product is easily obtained by ordinary purification operations such as recrystallization.
1,3,5-tri (3-aminophenoxy) can be removed from 3-bis (3-aminophenoxy) benzene
Benzene cannot be removed by these purification operations and is mixed as an impurity into the product 1,3-bis (3-aminophenoxy) benzene, which lowers the purity of 1,3-bis (3-aminophenoxy) benzene. cause.
この不純物は該製品ジアミンを原料として得られるポ
リイミドの物性を低下させる原因となる。再結晶による
精製が困難であり、従って、1,3−ビス（３−アミノフ
ェノキシ）ベンゼンを蒸留により精製しようとする場合
は、1,3−ビス（３−アミノフェノキシ）ベンゼンは高
温下では熱分解を起こし、一般に塔蒸留は困難である。These impurities cause deterioration of the physical properties of the polyimide obtained from the product diamine as a raw material. It is difficult to purify by recrystallization, and therefore, when 1,3-bis (3-aminophenoxy) benzene is to be purified by distillation, 1,3-bis (3-aminophenoxy) benzene cannot be purified at high temperatures. Decomposition occurs and column distillation is generally difficult.
通常、化学工業などにおいては熱影響を受け易い物質
や、沸点の高い物質の蒸留精製の場合、高温にて瞬間的
に化合物を蒸発させる薄膜蒸留が行われている。Usually, in the chemical industry and the like, in the case of distillation and purification of a substance which is easily affected by heat or a substance having a high boiling point, thin-film distillation in which a compound is instantaneously evaporated at a high temperature is performed.
この方法は減圧下の蒸留装置内にコンデンサーを内蔵
し、塔壁加熱側面に濡壁状に挿入された処理液を、ワイ
パーなどを装置内に取りつけた円筒状の回転体を作動さ
せて壁面へ薄膜状に押し拡げて均一な処理液膜を形成さ
れ、これにより低沸点成分を短時間に蒸発させ、同時に
内蔵コンデンサーで凝集させて精流出液として取り出す
装置を用いたものや、あるいは遠心力により薄膜を形成
させる蒸留装置を用いた蒸留方法である。In this method, a condenser is built in the distillation apparatus under reduced pressure, and the processing liquid inserted in a wet wall shape on the heating side of the tower wall is moved to the wall by operating a cylindrical rotating body with a wiper etc. installed in the apparatus. It is spread out into a thin film to form a uniform processing liquid film, which evaporates low-boiling components in a short period of time, and at the same time uses a built-in condenser to aggregate and remove it as a pure effluent, or by centrifugal force This is a distillation method using a distillation apparatus for forming a thin film.
しかしながら、このような蒸発面を広くして短時間に
処理する薄膜蒸留法を行ったとしても、被処理液として
高沸点不純物を除去する目的で当初より純度の高い1,3
−ビス（３−アミノフェノキシ）ベンゼンを薄膜蒸留装
置に付した場合、目的精製物は瞬時に蒸発するものの、
被処理液の純度が高いため塔壁面上には液が流下され
ず、連続した薄膜を壁面につくらなくなる。そのため高
温状態下での滞留時間が長くなって残存処理液はポリマ
ー化され壁面へこびりつく。この状態は極めて危険であ
り放置するとポリマーが蓄積され、最終的にはワイパー
回転が不可能となり、装置の破損へもつながる。また、
たとえ処理装置が可能でも含有不純物の除去効率が悪く
なる。However, even if such a thin-film distillation method in which the evaporation surface is widened and the treatment is performed in a short time is performed, the purity of the 1,3,3
When -bis (3-aminophenoxy) benzene is applied to a thin-film distillation apparatus, the target purified product evaporates instantaneously,
Due to the high purity of the liquid to be treated, the liquid does not flow down on the tower wall, and a continuous thin film is not formed on the wall. For this reason, the residence time under a high temperature condition is prolonged, and the remaining treatment liquid is polymerized and sticks to the wall surface. This state is extremely dangerous, and if left untreated, the polymer will accumulate, and eventually the wiper will not be able to rotate, leading to damage to the device. Also,
Even if a processing apparatus is possible, the removal efficiency of the contained impurities deteriorates.
このような状況に鑑み、本発明者らは問題を解決すべ
く鋭意検討を行った結果、本発明方法を見い出したもの
である。In view of such a situation, the present inventors have made intensive studies to solve the problem, and as a result, have found the method of the present invention.
即ち、本発明は薄膜蒸留装置を用いて不純物を含有す
る1,3−ビス（３−アミノフェノキシ）ベンゼンを蒸留
精製するにあたり、ポリエチレングリコールおよび／ま
たはポリプロピレングリコールを1,3−ビス（３−アミ
ノフェノキシ）ベンゼンに混合溶解させて処理すること
を特徴とする1,3−ビス（３−アミノフェノキシ）ベン
ゼンの精製方法であり、このような処理方法により壁面
への処理液のこびりつきがなく、連続的に被処理液を流
下させて連続的な精製操作を可能ならしめた方法であ
る。That is, in the present invention, when a 1,3-bis (3-aminophenoxy) benzene containing impurities is distilled and purified using a thin-film distillation apparatus, polyethylene glycol and / or polypropylene glycol are converted to 1,3-bis (3-amino). A method for purifying 1,3-bis (3-aminophenoxy) benzene, characterized in that it is mixed and dissolved in phenoxy) benzene for treatment, and the treatment liquid does not stick to the wall surface by such a treatment method, and is continuous. This is a method in which the liquid to be treated is allowed to flow down to allow a continuous purification operation.
図−１は、スミス蒸留などと呼ばれる通常の薄膜蒸留
に用いられる実験室規模の蒸留装置の側面図であり、本
発明方法にも適応可能であり、これに基づき本発明方法
を説明する。FIG. 1 is a side view of a laboratory-scale distillation apparatus used for ordinary thin-film distillation called Smith distillation or the like, which is applicable to the method of the present invention, and the method of the present invention will be described based on this.
図−１中は、１は被処理液である1,3−ビス（３−ア
ミノフェノキシ）ベンゼンに高沸点化合物が混合溶解さ
れた溶液であり、加温状態に保たれている。蒸留塔２の
外壁はマントルヒーター３で加熱されており、塔内の中
心付近には冷却水又は冷却用熱媒を循環できる棒状体の
コンデンサー４が内蔵されてあり、その底部はコンデン
サーで凝縮された精留流出物の処理液を受ける受器５に
連通されている。また、棒状体コンデンサーの外側には
塔壁とわずかな空隙を有するように設置された円筒状枠
の回転体７が取り付けられてあり、蒸留中はモーター６
で駆動されている。また回転体の枠には数個の斜方に切
り込まれた溝のある棒状体のワイパー８がスプリングを
介してワイパー枠にはめ込まれている。In FIG. 1, reference numeral 1 denotes a solution in which a high-boiling compound is mixed and dissolved in 1,3-bis (3-aminophenoxy) benzene, which is a liquid to be treated, and is kept in a heated state. The outer wall of the distillation column 2 is heated by a mantle heater 3, and a rod-shaped condenser 4 capable of circulating cooling water or a cooling medium is built in the center of the column, and the bottom is condensed by the condenser. The rectification effluent is connected to a receiver 5 for receiving the processing liquid. A rotating body 7 of a cylindrical frame installed so as to have a slight gap with the tower wall is attached to the outside of the rod-shaped condenser.
It is driven by. A rod-shaped wiper 8 having several obliquely cut grooves is fitted into the wiper frame via a spring in the frame of the rotating body.
この装置を用いて薄膜蒸留を行う場合、被処理液の1,
3−ビス（３−アミノフェノキシ）ベンゼンと混合溶解
しているポリエチレングリコールおよび／またはポリプ
ロピレングリコールよりなる溶液１は、滴下速度をコッ
クにより任意に調節して導管10より装入される。塔壁を
濡壁状に伝わって流下する装入液は、回転体にはめ込ま
れたワイパー８により摺動されて均一に押し拡げられ、
薄膜状になって瞬時に蒸発が行われ、混合溶解したポリ
エチレングリコールおよび／またはポリプロピレングリ
コールより低沸点の1,3−ビス（３−アミノフェノキ
シ）ベンゼンは中心部に設置されているコンデンサー４
により凝縮され、精留分処理液として受器５に集められ
取り出される。また被処理液中に含有されている1,3−
ビス（３−アミノフェノキシ）ベンゼンよりさらに沸点
の高い副生物は、混合したポリエチレングリコールおよ
び／またはポリプロピレングリコールとともに塔壁を流
下して受器９へ集められる。When thin-film distillation is performed using this apparatus, 1, 1
The solution 1 composed of polyethylene glycol and / or polypropylene glycol mixed and dissolved with 3-bis (3-aminophenoxy) benzene is charged from the conduit 10 by adjusting the dropping speed arbitrarily with a cock. The charged liquid flowing down the tower wall in the form of a wet wall is slid by the wiper 8 fitted into the rotating body and uniformly spread.
Evaporation occurs instantaneously in the form of a thin film, and 1,3-bis (3-aminophenoxy) benzene having a boiling point lower than that of the mixed and dissolved polyethylene glycol and / or polypropylene glycol is supplied to the condenser 4 installed at the center.
And collected in the receiver 5 as a rectified fraction processing liquid and taken out. In addition, 1,3-
By-products having a higher boiling point than bis (3-aminophenoxy) benzene are collected in the receiver 9 along the mixed polyethylene glycol and / or polypropylene glycol down the column wall.
本発明方法では、被処理液に溶解するポリエチレング
リコールおよび／またはポリプロピレングリコールは、
被処理液に対し１〜80重量％、好ましくは５〜30重量％
用いる。ポリエチレングリコールおよび／またはポリプ
ロピレングリコール使用量が１重量％以下では効果に乏
しく、また、80重量％以上では無意味であり、経済的に
好ましくない。また、被処理液に対し相溶性の劣るもの
は、加熱された壁面において流下中の被処理液をはじ
き、残存処理液をこびりつかせる結果となるので好まし
くない。In the method of the present invention, the polyethylene glycol and / or polypropylene glycol dissolved in the liquid to be treated is
1 to 80% by weight, preferably 5 to 30% by weight based on the liquid to be treated
Used. When the amount of polyethylene glycol and / or polypropylene glycol is less than 1% by weight, the effect is poor. On the other hand, when the amount is more than 80% by weight, it is meaningless and economically undesirable. Further, those having poor compatibility with the liquid to be treated are not preferred because the liquid to be treated is repelled on the heated wall surface and the remaining treatment liquid is stuck.
被処理液に混合溶解されるポリエチレングリコールお
よび／またはポリプロピレングリコールは、被処理化合
物に対して相溶性があり、沸点が高く且つその沸点差が
大きく、薄膜蒸留に付した場合、1,3−ビス（３−アミ
ノフェノキシ）ベンゼンと容易に分離できる。ポリエチ
レングリコール、ポリプロピレングリコールのなかで
も、特に好ましい化合物は平均分子量2,000〜4,000を有
するポリエチレングリコールである。Polyethylene glycol and / or polypropylene glycol mixed and dissolved in the liquid to be treated are compatible with the compound to be treated, have a high boiling point and a large difference in the boiling point, and when subjected to thin-film distillation, 1,3-bis It can be easily separated from (3-aminophenoxy) benzene. Among polyethylene glycol and polypropylene glycol, a particularly preferred compound is polyethylene glycol having an average molecular weight of 2,000 to 4,000.
本発明の方法に従えば、反応で副生する1,3,5−トリ
（３−アミノフェノキシ）ベンゼンを薄膜蒸留により除
去できることから、極めて純度良く、工業的に極めて有
利に目的とする1,3−ビス（３−アミノフェノキシ）ベ
ンゼンを高回収率で得ることが可能であり、工業的に極
めて価値が高い。According to the method of the present invention, 1,3,5-tri (3-aminophenoxy) benzene, which is a by-product of the reaction, can be removed by thin-film distillation. 3-bis (3-aminophenoxy) benzene can be obtained at a high recovery rate, and is extremely valuable industrially.
以下、本発明を実施例及び比較例により、具体的に説
明する。Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.
実施例１ 1,3−ビス（３−アミノフェノキシ）ベンゼン反応溶
液から、溶媒及び低沸点副生物を留去濃縮して得た粗1,
3−ビス（３−アミノフェノキシ）ベンゼン（純度86.7
％、1,3,5−トリ（３−アミノフェノキシ）ベンゼン8.1
％含有）150gにポリエチレングリコール2,000（平均分
子量2,000）を15.0g（９％相当）を加え120℃に加熱混
合溶解させた。この溶液を図−１に示す装置を用いて装
入管10より1torrの減圧下、コンデンサーを115℃に保ち
壁温約290℃の塔内へ滴下して薄膜蒸留を行った。Example 1 From a 1,3-bis (3-aminophenoxy) benzene reaction solution, a solvent and low-boiling by-products were distilled off and concentrated to obtain a crude 1,1.
3-bis (3-aminophenoxy) benzene (purity 86.7
%, 1,3,5-tri (3-aminophenoxy) benzene 8.1
% Of 150 g), and 15.0 g (corresponding to 9%) of polyethylene glycol 2,000 (average molecular weight 2,000) was added thereto and dissolved by heating at 120 ° C. This solution was dropped into the tower having a wall temperature of about 290 ° C. while maintaining the condenser at 115 ° C. under a reduced pressure of 1 torr from the charging tube 10 using the apparatus shown in FIG.
処理時間は２時間を要し、精留分受器より油状の精1,
3−ビス（３−アミノフェノキシ）ベンゼン121.3gを得
た。純度97.6％、1,3,5−トリ（３−アミノフェノキ
シ）ベンゼン含有率1.8％であった。The processing time is 2 hours, and oily oils are collected from the rectification receiver.
121.3 g of 3-bis (3-aminophenoxy) benzene was obtained. The purity was 97.6% and the content of 1,3,5-tri (3-aminophenoxy) benzene was 1.8%.
これをさらに194gのイソプロパノールに加熱溶解後放
冷すると白色結晶が析出した。これを濾過し、乾燥する
ことにより目的物の1,3−ビス（３−アミノフェノキ
シ）ベンゼン116.6gを結晶として得た。粗1,3−ビス
（３−アミノフェノキシ）ベンゼンの回収率87.9％、純
度98.0％、1,3,5−トリ（３−アミノフェノキシ）ベン
ゼン含有率1.7％である。This was further dissolved in 194 g of isopropanol by heating and then allowed to cool, whereby white crystals precipitated. This was filtered and dried to obtain 116.6 g of 1,3-bis (3-aminophenoxy) benzene as a crystal as a target substance. The recovery of crude 1,3-bis (3-aminophenoxy) benzene is 87.9%, the purity is 98.0%, and the content of 1,3,5-tri (3-aminophenoxy) benzene is 1.7%.
また受器９より得られた蒸留されなかった高沸カット
分は43.7gであり、ポリエチレングリコール2,000約34
％、1,3−ビス（３−アミノフェノキシ）ベンゼン約27
％、1,3,5−トリ（３−アミノフェノキシ）ベンゼン約2
3％、その他の不純物約16％であった。処理後、装置壁
面には殆ど付着分はなく、同様な蒸留操作を10回以上繰
り返しても殆ど変化なく、ワイパーの回転は良好であっ
た。The amount of the high-boiling cut not distilled obtained from the receiver 9 was 43.7 g, and polyethylene glycol 2,000
%, 1,3-bis (3-aminophenoxy) benzene about 27
%, About 1,3,5-tri (3-aminophenoxy) benzene
3% and other impurities were about 16%. After the treatment, there was almost no adhesion on the wall surface of the apparatus, and even when the same distillation operation was repeated 10 times or more, there was almost no change, and the rotation of the wiper was good.
実施例２ 実施例１の薄膜蒸留で得られた油状の精1,3−ビス
（３−アミノフェノキシ）ベンゼン100g（純度97.6％、
1,3,5−トリ（３−アミノフェノキシ）ベンゼン含有率
1.8％）にポリエチレングリコール2,000（平均分子量2,
000）を10.0g（９％相当）を加え、実施例１と同様の条
件で再度薄膜蒸留を行った。Example 2 100 g of oily pure 1,3-bis (3-aminophenoxy) benzene obtained by the thin-film distillation of Example 1 (purity 97.6%,
1,3,5-tri (3-aminophenoxy) benzene content
1.8% polyethylene glycol 2,000 (average molecular weight 2,
000) was added thereto, and thin-film distillation was performed again under the same conditions as in Example 1.
処理時間は１時間20分を要し、精留分受器５より油状
の精1,3−ビス（３−アミノフェノキシ）ベンゼン88.8g
を得た。純度99.0％、1,3,5−トリ（３−アミノフェノ
キシ）ベンゼン含有率0.6％であった。The processing time required 1 hour and 20 minutes, and 88.8 g of oily pure 1,3-bis (3-aminophenoxy) benzene was obtained from the rectification receiver 5.
I got The purity was 99.0% and the content of 1,3,5-tri (3-aminophenoxy) benzene was 0.6%.
これをさらにイソプロパノール144gから再結晶、乾燥
して目的物の1,3−ビス（３−アミノフェノキシ）ベン
ゼン95.2gを結晶として得た。粗1,3−ビス（３−アミノ
フェノキシ）ベンゼンからの回収率79.9％、純度99.4
％、1,3,5−トリ（３−アミノフェノキシ）ベンゼン含
有率0.4％である。This was further recrystallized from 144 g of isopropanol and dried to obtain 95.2 g of the desired product, 1,3-bis (3-aminophenoxy) benzene, as crystals. 79.9% recovery from crude 1,3-bis (3-aminophenoxy) benzene, purity 99.4
%, 1,3,5-tri (3-aminophenoxy) benzene content 0.4%.
比較例１ 実施例１で使用した粗1,3−ビス（３−アミノフェノ
キシ）ベンゼン100gを薄膜蒸留による精製を行わず、16
0gのイソプロパノールより再結晶、乾燥を行った。得ら
れた1,3−ビス（３−アミノフェノキシ）ベンゼン91.3g
には1,3,5−トリ（３−アミノフェノキシ）ベンゼンが
8.5％含まれていた。（純度91.1％、粗1,3−ビス（３−
アミノフェノキシ）ベンゼンからの回収率96.0％）。Comparative Example 1 100 g of the crude 1,3-bis (3-aminophenoxy) benzene used in Example 1 was purified without thin-film distillation.
Recrystallization and drying were performed from 0 g of isopropanol. 91.3 g of the obtained 1,3-bis (3-aminophenoxy) benzene
Contains 1,3,5-tri (3-aminophenoxy) benzene
8.5% was included. (Purity 91.1%, crude 1,3-bis (3-
96.0% recovery from aminophenoxy) benzene.
比較例２ ポリエチレングリコール2,000（平均分子量2,000）を
用いないほかは実施例１と全く同様に薄膜蒸留を行った
が、処理液は液として流出することなく装置壁面にポリ
マーがこびりつき、ワイパー部回転不良となり中断せざ
るを得なかった。Comparative Example 2 Thin film distillation was performed in exactly the same manner as in Example 1 except that polyethylene glycol 2,000 (average molecular weight: 2,000) was not used. However, the treatment liquid did not flow out as a liquid, and the polymer adhered to the wall of the apparatus, and the wiper part did not rotate properly. It had to be interrupted.
図−１は本発明方法を実施する場合、使用できる薄膜蒸
留装置の側面図である。 １……被処理液 ２……薄膜蒸留塔 ３……マントルヒーター ４……コンデンサー ５……精留分受器 ６……モーター ７……回転体 ８……ワイパー ９……高沸点分受器FIG. 1 is a side view of a thin film distillation apparatus that can be used when the method of the present invention is carried out. DESCRIPTION OF SYMBOLS 1 ... Liquid to be processed 2 ... Thin film distillation column 3 ... Mantle heater 4 ... Condenser 5 ... Rectification receiver 6 ... Motor 7 ... Rotating body 8 ... Wiper 9 ... High boiling point receiver
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) C07C 217/90,213/10 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. 6 , DB name) C07C 217 / 90,213 / 10 CA (STN) REGISTRY (STN)
Claims (1)
3−ビス（３−アミノフェノキシ）ベンゼンを蒸留精製
するにあたり、ポリエチレングリコールおよび／またポ
リプロピレングリコールを、1,3−ビス（３−アミノフ
ェノキシ）ベンゼンに混合溶解させて処理することを特
徴とする、1,3−ビス（３−アミノフェノキシ）ベンゼ
ンの薄膜蒸留による精製方法。1. The method of claim 1, wherein the thin film distillation apparatus is used to contain impurities.
In distilling and purifying 3-bis (3-aminophenoxy) benzene, polyethylene glycol and / or polypropylene glycol are mixed and dissolved in 1,3-bis (3-aminophenoxy) benzene for treatment. A method for purifying 1,3-bis (3-aminophenoxy) benzene by thin-film distillation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27928590A JP2849464B2 (en) | 1990-10-19 | 1990-10-19 | Purification method of 1,3-bis (3-aminophenoxy) benzene by thin film distillation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27928590A JP2849464B2 (en) | 1990-10-19 | 1990-10-19 | Purification method of 1,3-bis (3-aminophenoxy) benzene by thin film distillation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04154746A JPH04154746A (en) | 1992-05-27 |
| JP2849464B2 true JP2849464B2 (en) | 1999-01-20 |
Family
ID=17609039
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27928590A Expired - Fee Related JP2849464B2 (en) | 1990-10-19 | 1990-10-19 | Purification method of 1,3-bis (3-aminophenoxy) benzene by thin film distillation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2849464B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014073843A1 (en) * | 2012-11-08 | 2014-05-15 | 주식회사 삼양제넥스 | Method for preparing high-purity anhydrosugar alcohol using sequential combination of thin film distillation and short path distillation |
| KR101475387B1 (en) * | 2012-11-08 | 2014-12-23 | 주식회사 삼양제넥스 | Method for producing highly pure anhydrosugar alcohols by thin film distillation using viscosity-controlling additive |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6008413A (en) * | 1999-01-14 | 1999-12-28 | National Starch And Chemical Investment Holding Corporation | Process for recrystallizing 1,3-bis(aminophenoxy benzene) |
-
1990
- 1990-10-19 JP JP27928590A patent/JP2849464B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014073843A1 (en) * | 2012-11-08 | 2014-05-15 | 주식회사 삼양제넥스 | Method for preparing high-purity anhydrosugar alcohol using sequential combination of thin film distillation and short path distillation |
| KR101435640B1 (en) * | 2012-11-08 | 2014-08-29 | 주식회사 삼양제넥스 | Method for producing highly pure anhydrosugar alcohols by using a sequential combination of wiped film distillation and short path distillation |
| KR101475387B1 (en) * | 2012-11-08 | 2014-12-23 | 주식회사 삼양제넥스 | Method for producing highly pure anhydrosugar alcohols by thin film distillation using viscosity-controlling additive |
| US9169263B1 (en) | 2012-11-08 | 2015-10-27 | Samyang Genex Corporation | Method for preparing high-purity anhydrosugar alcohol using sequential combination of thin film distillation and short path distillation |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04154746A (en) | 1992-05-27 |
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