JPH0769976A - Method for purifying 4,4'-biphenyldicarboxylic acid - Google Patents
Method for purifying 4,4'-biphenyldicarboxylic acidInfo
- Publication number
- JPH0769976A JPH0769976A JP23734693A JP23734693A JPH0769976A JP H0769976 A JPH0769976 A JP H0769976A JP 23734693 A JP23734693 A JP 23734693A JP 23734693 A JP23734693 A JP 23734693A JP H0769976 A JPH0769976 A JP H0769976A
- Authority
- JP
- Japan
- Prior art keywords
- biphenyldicarboxylic acid
- solvent
- acid
- crude
- parts
- 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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は液晶樹脂原料等として有
用な４，４’−ビフェニルジカルボン酸の精製方法に関
するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for purifying 4,4'-biphenyldicarboxylic acid useful as a raw material for liquid crystal resins.
【０００２】[0002]
【従来の技術】４，４’−ビフェニルジカルボン酸の製
造方法としては、４，４’−ジアルキルビフェニルをコ
バルト、マンガン等の金属塩を触媒に用いて液相酸化す
る方法と、安息香酸又はその誘導体をパラジウム、ニッ
ケル等の金属触媒を用いてカップリングする方法に大別
されるが、いずれの方法も反応終了後の生成物中に反応
原料、中間体、副生成物、触媒等が混在するため、その
ままでは樹脂原料として使用できず、精製操作が必要で
ある。そして、この様な不純物を含む粗４，４’−ビフ
ェニルジカルボン酸の精製法として従来知られている方
法には、 ４，４’−ビフェニルジカルボン酸をアルカリ塩と
し、水に溶解させた後、精製する方法（特開昭58-8584
1、特開平2-76837 、特開平4-202158） ジメチルスルフォキサイド（特開昭57-149244 ）、
Ｎ，Ｎ−ジメチルホルムアミド（特開平2-235843）を用
いて４，４’−ビフェニルジカルボン酸を再結晶する方
法 等が知られている。しかしながら、の精製方法では、
アルカリ塩をカルボン酸に戻す段階で酸析操作が入るた
め生成する４，４’−ビフェニルジカルボン酸が微粒子
となり、４，４’−ビフェニルジカルボン酸の固液分離
工程、４，４’−ビフェニルジカルボン酸を用いた樹脂
製造工程での取扱いが困難であった。また、の精製方
法は再結晶であるため精製後の粒子径の観点からは好ま
しいが、Ｎ，Ｎ−ジメチルホルムアミドを溶媒に用いた
場合、Ｎ，Ｎ−ジメチルホルムアミドへの４，４’−ビ
フェニルジカルボン酸の溶解度が１２０℃でも約１ｇ／
溶媒１００ｇと低く、工業的に容易でなかった。ジメチ
ルスルフォキサイドを溶媒に用いた場合、ジメチルスル
フォキサイドの高温での分解、低温での固化による使用
温度の制約があり、改善が望まれていた。2. Description of the Related Art As a method for producing 4,4'-biphenyldicarboxylic acid, a method of liquid phase oxidation of 4,4'-dialkylbiphenyl using a metal salt of cobalt, manganese or the like as a catalyst, and benzoic acid or its derivative It is roughly classified into a method of coupling a derivative with a metal catalyst such as palladium or nickel, but in any method, a reaction raw material, an intermediate, a by-product, a catalyst and the like are mixed in the product after the reaction is completed. Therefore, it cannot be used as a resin raw material as it is, and a purification operation is required. Then, in a method conventionally known as a method for purifying crude 4,4′-biphenyldicarboxylic acid containing such impurities, 4,4′-biphenyldicarboxylic acid is converted to an alkali salt and dissolved in water. Purification method (JP-A-58-8584)
1, JP-A-2-76837, JP-A-4-202158) dimethyl sulfoxide (JP-A-57-149244),
A method of recrystallizing 4,4′-biphenyldicarboxylic acid using N, N-dimethylformamide (JP-A-2-235843) is known. However, in the purification method of
4,4'-biphenyldicarboxylic acid produced due to the acid precipitation operation at the stage of returning the alkali salt to carboxylic acid becomes fine particles, and the solid-liquid separation step of 4,4'-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid It was difficult to handle in the resin manufacturing process using an acid. Further, the purification method of is recrystallization, which is preferable from the viewpoint of particle size after purification, but when N, N-dimethylformamide is used as a solvent, 4,4′-biphenyl to N, N-dimethylformamide is used. The solubility of dicarboxylic acid is about 1g / 120 ° C
The solvent was as low as 100 g, which was not industrially easy. When dimethyl sulfoxide is used as a solvent, there is a restriction on the use temperature due to decomposition of dimethyl sulfoxide at high temperature and solidification at low temperature, and improvement has been desired.
【０００３】[0003]
【発明が解決しようとする課題】従って本発明の目的
は、４，４’−ビフェニルジカルボン酸の精製方法とし
て望ましい再結晶法において、溶解度が高く、使用温度
等の制約が少ない溶媒を見出し、工業的に実施し易く経
済的な４，４’−ビフェニルジカルボン酸の精製方法を
提供することにある。Therefore, an object of the present invention is to find a solvent having high solubility and less restriction on use temperature in a recrystallization method which is desirable as a method for purifying 4,4'-biphenyldicarboxylic acid. To provide a method for purifying 4,4′-biphenyldicarboxylic acid that is easy to carry out and economical.
【０００４】[0004]
【課題を解決するための手段】そこで本発明者らは上記
方法を確立するため、鋭意研究を行った結果、下記一般
式（１） Ｒ1 （Ｒ3 ）Ｎ−ＣＯ−Ｎ（Ｒ4 ）Ｒ2 ────（１） 又は下記一般式（２） Ｒ1 （Ｒ3 ）Ｎ−ＣＯ−Ｒ2 ────（２） で表される構造を有する溶媒を用いて４，４’−ビフェ
ニルジカルボン酸を再結晶すれば、４，４’−ビフェニ
ルジカルボン酸のこれらの溶媒への溶解度が比較的高い
ために、工業的に実施し易く経済的な４，４’−ビフェ
ニルジカルボン酸の精製方法となることを見出し、本発
明を完成した。即ち、本発明は、粗４，４’−ビフェニ
ルジカルボン酸を精製するにあたり、下記一般式（１） Ｒ1 （Ｒ3 ）Ｎ−ＣＯ−Ｎ（Ｒ4 ）Ｒ2 ────（１） 又は下記一般式（２） Ｒ1 （Ｒ3 ）Ｎ−ＣＯ−Ｒ2 ────（２） （但し、一般式（１）及び（２）において、Ｒ1 、
Ｒ2 、Ｒ3 及びＲ4 はアルキル基を示す。また、Ｒ1 と
Ｒ2 が結合し、環化したものでもよい。）で表される１
種又は２種以上の溶媒を用いて再結晶することを特徴と
する４，４’−ビフェニルジカルボン酸の精製方法であ
る。The inventors of the present invention have conducted extensive studies to establish the above method, and as a result, the following general formula (1) R 1 (R 3 ) N—CO—N (R 4 ) R 2 ───────────────────────────────────── ((2) R 1 (R 3 ) N—CO—R 2 -If biphenyldicarboxylic acid is recrystallized, the solubility of 4,4'-biphenyldicarboxylic acid in these solvents is relatively high, and therefore it is easy to carry out industrially and economically, 4,4'-biphenyldicarboxylic acid. The inventors have found that the method is a purification method and completed the present invention. That is, in the present invention, when purifying crude 4,4′-biphenyldicarboxylic acid, the following general formula (1) R 1 (R 3 ) N—CO—N (R 4 ) R 2 ────────── (1) Or the following general formula (2) R 1 (R 3 ) N—CO—R 2 ───── (2) (wherein in the general formulas (1) and (2), R 1 ,
R 2 , R 3 and R 4 represent an alkyl group. Further, R 1 and R 2 may be bonded and cyclized. ) Represented by 1
A method for purifying 4,4′-biphenyldicarboxylic acid, which comprises recrystallizing using one kind or two or more kinds of solvents.
【０００５】以下、本発明の精製方法について、詳細に
説明する。本発明は溶媒を用いた再結晶による精製法で
あるため、４，４’−ビフェニルジカルボン酸の溶媒へ
の溶解、冷却、固液分離、リンス及び乾燥等の工程より
構成されている。The purification method of the present invention will be described in detail below. Since the present invention is a purification method by recrystallization using a solvent, it comprises steps of dissolving 4,4′-biphenyldicarboxylic acid in a solvent, cooling, solid-liquid separation, rinsing and drying.
【０００６】本発明において使用する粗４，４’−ビフ
ェニルジカルボン酸は、安息香酸またはその誘導体をパ
ラジウム、ニッケル等の金属触媒を用いてカップリング
して得られたものでもよいし、以下の様な４，４’−ビ
フェニルジ置換体、すなわち、４，４’−ジメチルビフ
ェニル、４，４’−ジエチルビフェニル、４，４’−ジ
イソプロピルビフェニル、４−アルキル−４’−ホルミ
ルビフェニル、４−アルキル−４’−アシルビフェニル
等をコバルト、マンガン等の金属塩を触媒に用いて液相
酸化し得られたものでもよい。精製原料として用いる粗
４，４’−ビフェニルジカルボン酸の純度には格別の制
限はないが、好ましくは８０〜９９％、より好ましくは
９０〜９８％である。The crude 4,4'-biphenyldicarboxylic acid used in the present invention may be one obtained by coupling benzoic acid or its derivative with a metal catalyst such as palladium or nickel. 4,4'-biphenyl di-substituted product, that is, 4,4'-dimethylbiphenyl, 4,4'-diethylbiphenyl, 4,4'-diisopropylbiphenyl, 4-alkyl-4'-formylbiphenyl, 4-alkyl It may be obtained by liquid-phase oxidation of -4'-acyl biphenyl or the like using a metal salt of cobalt, manganese or the like as a catalyst. The purity of the crude 4,4′-biphenyldicarboxylic acid used as a purification raw material is not particularly limited, but it is preferably 80 to 99%, more preferably 90 to 98%.
【０００７】本発明で使用する溶媒は、下記一般式
（１） Ｒ1 （Ｒ3 ）Ｎ−ＣＯ−Ｎ（Ｒ4 ）Ｒ2 ────（１） 又は下記一般式（２） Ｒ1 （Ｒ3 ）Ｎ−ＣＯ−Ｒ2 ────（２） で表される構造を有する溶媒である。ここでＲ1 、
Ｒ2 、Ｒ3 及びＲ4 はアルキル基を示す。また、Ｒ1 と
Ｒ2 が結合し、環化したものでもよい。この様な構造を
有する溶媒であり市販されているものとしては、１，３
−ジメチルプロピレンウレア（別名：１，３−ジメチル
−３，４，５，６−テトラヒドロ−２（１Ｈ）−ピリミ
ジノン、沸点：２３０℃）、１，３−ジメチル−２−イ
ミダゾリジノン（融点：８．２℃、沸点：２２５℃）、
１−メチル−２−ピロリジノン（別名：Ｎ−メチル−２
−ピロリドン、融点：−２４℃、沸点：２０４℃）、
１，１，３，３−テトラメチルウレア（融点：−１℃、
沸点：１７７℃）、Ｎ，Ｎ−ジメチルアセトアミド（融
点：−２０℃、沸点：１６５℃）、Ｎ，Ｎ−ジエチルア
セトアミド（沸点：１８６℃）等を挙げる事ができる。
特に１，３−ジメチルプロピレンウレア、１，３−ジメ
チル−２−イミダゾリジノン、１−メチル−２−ピロリ
ジノン、１，１，３，３−テトラメチルウレア、Ｎ，Ｎ
−ジメチルアセトアミドは４，４’−ビフェニルジカル
ボン酸の溶解度が高いという点及び工業的な入手が可能
であるという点から、本発明の溶媒として好ましい。[0007] The solvent used in the present invention is represented by the following general formula (1) R 1 (R 3 ) N-CO-N (R 4) R 2 ──── (1) or the following general formula (2) R 1 (R 3 ) N-CO-R 2 ─────────────────── (2) Where R 1 ,
R 2 , R 3 and R 4 represent an alkyl group. Further, R 1 and R 2 may be bonded and cyclized. Commercially available solvents having such a structure include 1,3
-Dimethylpropyleneurea (alias: 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone, boiling point: 230 ° C), 1,3-dimethyl-2-imidazolidinone (melting point: 8.2 ° C, boiling point: 225 ° C),
1-methyl-2-pyrrolidinone (also known as N-methyl-2)
-Pyrrolidone, melting point: -24 ° C, boiling point: 204 ° C),
1,1,3,3-tetramethylurea (melting point: -1 ° C,
Boiling point: 177 ° C.), N, N-dimethylacetamide (melting point: −20 ° C., boiling point: 165 ° C.), N, N-diethylacetamide (boiling point: 186 ° C.) and the like.
Particularly 1,3-dimethylpropyleneurea, 1,3-dimethyl-2-imidazolidinone, 1-methyl-2-pyrrolidinone, 1,1,3,3-tetramethylurea, N, N
-Dimethylacetamide is preferred as the solvent of the present invention because of its high solubility of 4,4'-biphenyldicarboxylic acid and its industrial availability.
【０００８】本発明での溶媒の最適使用量は、溶媒の種
類、溶解温度によって異なるが、通常、粗４，４’−ビ
フェニルジカルボン酸１重量部に対して５〜５０重量
部、好ましくは１０〜３０重量部である。溶媒の使用量
が５重量部以下であれば、４，４’−ビフェニルジカル
ボン酸が完全には溶解しない場合が多い。また、５０重
量部以上であれば、溶解後の冷却、結晶析出に続く固液
分離の際、溶媒に溶解する４，４’−ビフェニルジカル
ボン酸の絶対量が多くなり、４，４’−ビフェニルジカ
ルボン酸の回収率が低下する。The optimum amount of the solvent used in the present invention varies depending on the kind of the solvent and the melting temperature, but is usually 5 to 50 parts by weight, preferably 10 parts by weight to 1 part by weight of crude 4,4'-biphenyldicarboxylic acid. ~ 30 parts by weight. If the amount of the solvent used is 5 parts by weight or less, the 4,4′-biphenyldicarboxylic acid is often not completely dissolved. Further, when the amount is 50 parts by weight or more, the absolute amount of 4,4′-biphenyldicarboxylic acid dissolved in the solvent becomes large at the time of cooling after dissolution, solid-liquid separation subsequent to crystal precipitation, and 4,4′-biphenyl. The recovery rate of dicarboxylic acid decreases.
【０００９】粗４，４’−ビフェニルジカルボン酸の溶
媒への溶解温度は、１００〜３００℃、好ましくは１３
０〜２８０℃である。溶解温度が溶媒の沸点を越える場
合は、加圧し溶媒が液体になる様に保つ。この際、溶解
しない金属等の不純物があれば熱濾過して取り除くこと
が好ましい。また、脱色、特定微量不純物の除去を目的
として、粗４，４’−ビフェニルジカルボン酸が溶解し
た溶液に活性炭等の吸着剤を加え、着色成分、特定微量
不純物を吸着させた後、吸着剤を固液分離する操作を加
えてもよい。The dissolution temperature of the crude 4,4'-biphenyldicarboxylic acid in the solvent is 100 to 300 ° C, preferably 13
It is 0-280 degreeC. If the dissolution temperature exceeds the boiling point of the solvent, pressurize to keep the solvent liquid. At this time, it is preferable to remove any impurities such as insoluble metals by hot filtration. In addition, for the purpose of decolorization and removal of specific trace impurities, an adsorbent such as activated carbon is added to a solution in which crude 4,4′-biphenyldicarboxylic acid is dissolved, and after adsorbing coloring components and specific trace impurities, the adsorbent is added. An operation for solid-liquid separation may be added.
【００１０】粗４，４’−ビフェニルジカルボン酸が溶
解した溶液の冷却温度は、溶媒の融点によって異なる
が、通常、−２０〜３０℃、好ましくは−２０〜１５℃
である。冷却温度が−２０℃以下であれば、溶媒が固化
する場合が多く、また、３０℃以上であれば、４，４’
−ビフェニルジカルボン酸の溶媒への溶解が無視できな
くなり、４，４’−ビフェニルジカルボン酸の回収率が
低下する。また、４，４’−ビフェニルジカルボン酸の
回収率を高めるために、水、メタノ−ル、エタノ−ル、
イソプロパノ−ルの様な低級アルコール、ヘキサン、ヘ
プタン等のパラフィン、アセトン、エチルメチルケトン
等のケトン又はベンゼン、トルエン等の芳香族炭化水素
を貧溶媒として冷却後に添加し、４，４’−ビフェニル
ジカルボン酸を強制的に沈殿させて高純度の４，４’−
ビフェニルジカルボン酸を分離することもできる。この
様な再結晶法によれば、４，４’−ビフェニルジカルボ
ン酸の粒子径が比較的大きいので、固液分離等の各工程
での操作性が容易となる。The cooling temperature of the solution in which the crude 4,4'-biphenyldicarboxylic acid is dissolved depends on the melting point of the solvent, but is usually -20 to 30 ° C, preferably -20 to 15 ° C.
Is. If the cooling temperature is -20 ° C or lower, the solvent often solidifies, and if it is 30 ° C or higher, 4,4 '.
-Dissolution of biphenyldicarboxylic acid in a solvent cannot be ignored, and the recovery rate of 4,4'-biphenyldicarboxylic acid decreases. Further, in order to improve the recovery rate of 4,4′-biphenyldicarboxylic acid, water, methanol, ethanol,
Lower alcohols such as isopropanol, paraffins such as hexane and heptane, ketones such as acetone and ethyl methyl ketone, or aromatic hydrocarbons such as benzene and toluene are added as a poor solvent after cooling, and 4,4′-biphenyldicarboxylic acid is added. Highly pure 4,4'-forcibly precipitated acid
It is also possible to separate the biphenyldicarboxylic acid. According to such a recrystallization method, since the particle diameter of 4,4′-biphenyldicarboxylic acid is relatively large, the operability in each step such as solid-liquid separation becomes easy.
【００１１】固液分離後の母液が付着した結晶は、再結
晶に用いたものと同種の溶媒によってリンスし、付着母
液を取り除くことが望ましい。リンスに用いる溶媒の使
用量は、固液分離後の結晶１重量部に対して０．５〜５
重量部、好ましくは０．５〜３重量部である。また、リ
ンスに用いる溶媒の温度は、固液分離時の母液の温度と
同一温度が好ましい。The crystals to which the mother liquor after solid-liquid separation adheres are preferably rinsed with the same solvent as that used for recrystallization to remove the adhered mother liquor. The amount of the solvent used for rinsing is 0.5 to 5 with respect to 1 part by weight of the crystal after solid-liquid separation.
Parts by weight, preferably 0.5 to 3 parts by weight. The temperature of the solvent used for rinsing is preferably the same as the temperature of the mother liquor during solid-liquid separation.
【００１２】結晶の乾燥を行うにあたり、溶媒の沸点が
高く乾燥工程で溶媒が除去しにくい場合には、再結晶に
用いたと同種の溶媒によるリンス後、低沸点の有機溶媒
で再リンスし、結晶に付着する溶媒を低沸点の有機溶媒
に置換して乾燥を容易にさせることができる。固液分離
後の再結晶母液が付着した結晶を直接、低沸点の有機溶
媒でリンスしても良い。この様な低沸点の有機溶媒とし
ては、メタノ−ル、エタノ−ル、イソプロパノ−ルの様
な低級アルコール、ヘキサン、ヘプタン等のパラフィン
又はアセトン、エチルメチルケトン等のケトンのうち、
常圧での沸点が１００℃以下のものが好ましい。When the crystals are dried, if the solvent has a high boiling point and is difficult to remove in the drying step, after rinsing with the same solvent as that used for recrystallization, re-rinsing with an organic solvent having a low boiling point The solvent attached to the can be replaced with an organic solvent having a low boiling point to facilitate drying. The crystals to which the recrystallization mother liquor after solid-liquid separation adheres may be directly rinsed with an organic solvent having a low boiling point. Examples of such a low boiling point organic solvent include lower alcohols such as methanol, ethanol and isopropanol, paraffins such as hexane and heptane, or ketones such as ethyl methyl ketone.
It preferably has a boiling point of 100 ° C. or less at normal pressure.
【００１３】再結晶母液及びリンスに用いた後の溶媒の
一部又は全量を、再度、再結晶溶媒として用いてもよ
い。特にリンスに用いた溶媒が再結晶に用いたと同種の
溶媒であるときは、そのリンス後の溶媒は不純物含有量
が少なく、全量をそのまま再結晶溶媒として再利用する
のが好ましい。Part or all of the solvent used after the recrystallization mother liquor and the rinse may be used again as the recrystallization solvent. In particular, when the solvent used for rinsing is the same solvent as used for recrystallization, the solvent after rinsing has a low impurity content, and it is preferable to reuse the entire amount as it is as a recrystallization solvent.
【００１４】溶媒の付着した結晶の乾燥操作での乾燥温
度は室温〜２００℃、好ましくは室温〜１００℃であ
る。必要に応じて減圧を行う。The drying temperature in the drying operation of the crystals to which the solvent is attached is room temperature to 200 ° C, preferably room temperature to 100 ° C. Reduce pressure if necessary.
【００１５】[0015]
【実施例】以下、実施例に基づいて、本発明を具体的に
説明するが、本発明はこれらの実施例によって限定され
るものではない。なお、実施例における部及び％はそれ
ぞれ重量部及び重量％を示す。EXAMPLES The present invention will be specifically described below based on examples, but the present invention is not limited to these examples. In addition, the part and% in an Example show a weight part and weight%, respectively.
【００１６】実施例１ 電磁攪拌器付きチタン製オ−トクレ−ブに、コバルト濃
度０．２％、マンガン濃度０．２％、臭素濃度０．６％
の触媒酢酸溶液２０００部を予め装入し、反応温度２０
０℃、反応圧２５ｋｇ／ｃｍ2 ・Ｇに保持しながら、
４，４’−ジエチルビフェニル及び圧縮空気を連続的に
反応器に供給し、酸化反応を行った。コバルトは酢酸コ
バルトとして、マンガンは酢酸マンガンとして、臭素は
臭化ナトリウムとしてそれぞれ添加した。４，４’−ジ
エチルビフェニルは毎時３００部の割合で１時間供給
し、４，４’−ジエチルビフェニル供給終了後も、反応
器の温度と圧力を保持したまま圧縮空気を１５分間供給
した。反応終了後、反応液を８０℃まで冷却し、固液分
離した。得られた結晶を酢酸洗浄、水洗後乾燥し、純度
９６％の粗４，４’−ビフェニルジカルボン酸を２８５
部得た。この様にして得られた純度９６％の粗４，４’
−ビフェニルジカルボン酸を２０部、１，３−ジメチル
プロピレンウレアを２５０部、それぞれ攪拌器付きガラ
ス製フラスコに加え、２００℃にて４，４’−ビフェニ
ルジカルボン酸を完全に溶解させた。溶液に活性炭５部
を加え、緩やかに攪拌した。活性炭を濾過した後、１０
℃まで冷却し、析出した結晶を固液分離した。母液の付
着した結晶を１０℃の１，３−ジメチルプロピレンウレ
ア３０部でリンスした。引き続き２０部のエチルメチル
ケトンでリンスし、結晶から１，３−ジメチルプロピレ
ンウレアを除去した。結晶を５０℃で減圧乾燥し、純度
９９．９％の精製４，４’−ビフェニルジカルボン酸を
１４部得た。Example 1 A titanium autoclave equipped with an electromagnetic stirrer was used, and a cobalt concentration of 0.2%, a manganese concentration of 0.2%, and a bromine concentration of 0.6%.
2000 parts of catalyst acetic acid solution was charged in advance and the reaction temperature was 20
While maintaining at 0 ° C and reaction pressure of 25 kg / cm 2 · G,
4,4'-Diethylbiphenyl and compressed air were continuously supplied to the reactor to carry out the oxidation reaction. Cobalt was added as cobalt acetate, manganese was added as manganese acetate, and bromine was added as sodium bromide. 4,4'-diethylbiphenyl was supplied at a rate of 300 parts per hour for 1 hour, and after the completion of the 4,4'-diethylbiphenyl supply, compressed air was supplied for 15 minutes while maintaining the temperature and pressure of the reactor. After completion of the reaction, the reaction solution was cooled to 80 ° C. and solid-liquid separated. The obtained crystals were washed with acetic acid, washed with water, and dried to give 285 crude 4,4′-biphenyldicarboxylic acid having a purity of 96%.
I got a copy. 96% pure crude 4,4 'thus obtained
20 parts of biphenyldicarboxylic acid and 250 parts of 1,3-dimethylpropyleneurea were added to a glass flask equipped with a stirrer, and 4,4′-biphenyldicarboxylic acid was completely dissolved at 200 ° C. 5 parts of activated carbon was added to the solution and gently stirred. After filtering the activated carbon, 10
After cooling to ℃, the precipitated crystals were separated into solid and liquid. The crystals to which the mother liquor was attached were rinsed with 30 parts of 1,3-dimethylpropyleneurea at 10 ° C. Subsequently, the crystals were rinsed with 20 parts of ethyl methyl ketone to remove 1,3-dimethylpropyleneurea from the crystals. The crystals were dried under reduced pressure at 50 ° C. to obtain 14 parts of purified 4,4′-biphenyldicarboxylic acid having a purity of 99.9%.
【００１７】実施例２ 実施例１と同じ純度９６％の粗４，４’−ビフェニルジ
カルボン酸を２０部、１−メチル−２−ピロリジノンを
２００部、それぞれ攪拌器付きオ−トクレ−ブに加え、
２５０℃にて４，４’−ビフェニルジカルボン酸を溶解
させた。次いで０℃まで冷却し、析出した結晶を固液分
離した。母液の付着した結晶を４０部のイソプロパノ−
ルでリンスし、結晶から１−メチル−２−ピロリジノン
を除去した。結晶を３０℃で減圧乾燥し、純度９９．８
％の精製４，４’−ビフェニルジカルボン酸を１６部得
た。Example 2 20 parts of crude 4,4'-biphenyldicarboxylic acid having the same purity as 96% of Example 1 and 200 parts of 1-methyl-2-pyrrolidinone were added to an autoclave equipped with a stirrer. ,
4,4'-biphenyldicarboxylic acid was dissolved at 250 ° C. Then, it was cooled to 0 ° C., and the precipitated crystal was separated into solid and liquid. 40 parts of isopropanol containing crystals with mother liquor attached
1-Methyl-2-pyrrolidinone was removed from the crystals by rinsing with a filter. The crystals are dried under reduced pressure at 30 ° C. to obtain a purity of 99.8.
% Of purified 4,4′-biphenyldicarboxylic acid was obtained.
【００１８】実施例３ 実施例１と同じ純度９６％の粗４，４’−ビフェニルジ
カルボン酸を２０部、Ｎ，Ｎ−ジメチルアセトアミドを
５２０部、それぞれ攪拌器付きガラス製フラスコに加
え、１７０℃にて完全に４，４’−ビフェニルジカルボ
ン酸を溶解させた。溶液に活性炭４部を加え、緩やかに
攪拌した。活性炭を濾過した後、−１０℃まで冷却し、
析出した結晶を固液分離した。母液の付着した結晶を−
１０℃のＮ，Ｎ−ジメチルアセトアミド３０部でリンス
した。引き続き２０部のアセトンでリンスし、結晶から
Ｎ，Ｎ−ジメチルアセトアミドを除去した。結晶を室温
で減圧乾燥し、純度９９．９％の精製４，４’−ビフェ
ニルジカルボン酸を１５部得た。Example 3 20 parts of crude 4,4'-biphenyldicarboxylic acid of the same 96% purity as in Example 1 and 520 parts of N, N-dimethylacetamide were added to a glass flask equipped with a stirrer at 170 ° C. At 4,4'-biphenyldicarboxylic acid was completely dissolved. 4 parts of activated carbon was added to the solution and gently stirred. After filtering the activated carbon, cooling to -10 ° C,
The precipitated crystals were solid-liquid separated. Crystals with mother liquor attached-
Rinse with 30 parts of N, N-dimethylacetamide at 10 ° C. Subsequently, the crystal was rinsed with 20 parts of acetone to remove N, N-dimethylacetamide from the crystal. The crystals were dried at room temperature under reduced pressure to obtain 15 parts of purified 4,4′-biphenyldicarboxylic acid having a purity of 99.9%.
【００１９】[0019]
【発明の効果】本発明によれば、入手が容易で４，４’
−ビフェニルジカルボン酸の溶解度が高く、使用温度等
の制約が少ない溶媒を用いて粗４，４’−ビフェニルジ
カルボン酸を再結晶することにより、高純度で比較的粒
子径の大きな４，４’−ビフェニルジカルボン酸を回収
することができる。これにより、工業的に実施し易く経
済的な４，４’−ビフェニルジカルボン酸の精製方法が
確立でき、有意義である。According to the present invention, it is easy to obtain 4,4 '
-By recrystallizing crude 4,4'-biphenyldicarboxylic acid with a solvent in which the solubility of biphenyldicarboxylic acid is high and there are few restrictions such as use temperature, 4,4'- with high purity and a relatively large particle size Biphenyldicarboxylic acid can be recovered. As a result, a method for purifying 4,4′-biphenyldicarboxylic acid that is industrially easy to implement and economical can be established, which is significant.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 川村 正行 福岡県北九州市戸畑区小芝２−10−９ ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masayuki Kawamura 2-10-9 Koshiba, Tobata-ku, Kitakyushu, Fukuoka
Claims (2)
精製するにあたり、下記一般式（１） Ｒ1 （Ｒ3 ）Ｎ−ＣＯ−Ｎ（Ｒ4 ）Ｒ2 ────（１） 又は下記一般式（２） Ｒ1 （Ｒ3 ）Ｎ−ＣＯ−Ｒ2 ────（２） （但し、一般式（１）及び（２）において、Ｒ1 、
Ｒ2 、Ｒ3 及びＲ4 はアルキル基を示す。また、Ｒ1 と
Ｒ2 が結合し、環化したものでもよい。）で表される１
種又は２種以上の溶媒を用いて再結晶することを特徴と
する４，４’−ビフェニルジカルボン酸の精製方法。Upon purifying 1. A crude 4,4'-biphenyl dicarboxylic acid, the following general formula (1) R 1 (R 3 ) N-CO-N (R 4) R 2 ──── (1) or The following general formula (2) R 1 (R 3 ) N-CO-R 2 ──── (2) (wherein in the general formulas (1) and (2), R 1 ,
R 2 , R 3 and R 4 represent an alkyl group. Further, R 1 and R 2 may be bonded and cyclized. ) Represented by 1
A method for purifying 4,4′-biphenyldicarboxylic acid, which comprises recrystallizing using one kind or two or more kinds of solvents.
レア、１，３−ジメチル−２−イミダゾリジノン、１−
メチル−２−ピロリジノン、１，１，３，３−テトラメ
チルウレア、Ｎ，Ｎ−ジメチルアセトアミドから選ばれ
る１種又は２種以上の溶媒である請求項１記載の４，
４’−ビフェニルジカルボン酸の精製方法。2. The solvent is 1,3-dimethylpropyleneurea, 1,3-dimethyl-2-imidazolidinone, 1-
The solvent according to claim 1, which is one or more solvents selected from methyl-2-pyrrolidinone, 1,1,3,3-tetramethylurea and N, N-dimethylacetamide.
A method for purifying 4'-biphenyldicarboxylic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23734693A JP3223362B2 (en) | 1993-08-30 | 1993-08-30 | Method for purifying 4,4'-biphenyldicarboxylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23734693A JP3223362B2 (en) | 1993-08-30 | 1993-08-30 | Method for purifying 4,4'-biphenyldicarboxylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0769976A true JPH0769976A (en) | 1995-03-14 |
| JP3223362B2 JP3223362B2 (en) | 2001-10-29 |
Family
ID=17014032
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23734693A Expired - Fee Related JP3223362B2 (en) | 1993-08-30 | 1993-08-30 | Method for purifying 4,4'-biphenyldicarboxylic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3223362B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002128729A (en) * | 2000-10-23 | 2002-05-09 | Nippon Steel Chem Co Ltd | Method for producing high-purity 4,4'- biphenyldicarboxylic acid |
| JP2009120541A (en) * | 2007-11-15 | 2009-06-04 | Ueno Fine Chem Ind Ltd | Method for purifying 6,6'-(ethylenedioxy)bis-2-naththoic acid |
| WO2024122345A1 (en) * | 2022-12-05 | 2024-06-13 | 国立大学法人北海道大学 | Method for producing homo-coupling reaction product |
-
1993
- 1993-08-30 JP JP23734693A patent/JP3223362B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002128729A (en) * | 2000-10-23 | 2002-05-09 | Nippon Steel Chem Co Ltd | Method for producing high-purity 4,4'- biphenyldicarboxylic acid |
| JP2009120541A (en) * | 2007-11-15 | 2009-06-04 | Ueno Fine Chem Ind Ltd | Method for purifying 6,6'-(ethylenedioxy)bis-2-naththoic acid |
| WO2024122345A1 (en) * | 2022-12-05 | 2024-06-13 | 国立大学法人北海道大学 | Method for producing homo-coupling reaction product |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3223362B2 (en) | 2001-10-29 |
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