JP3521021B2 - Method for producing polybenzazole and method for recovering polyphosphoric acid used in the production - Google Patents
Method for producing polybenzazole and method for recovering polyphosphoric acid used in the productionInfo
- Publication number
- JP3521021B2 JP3521021B2 JP13582895A JP13582895A JP3521021B2 JP 3521021 B2 JP3521021 B2 JP 3521021B2 JP 13582895 A JP13582895 A JP 13582895A JP 13582895 A JP13582895 A JP 13582895A JP 3521021 B2 JP3521021 B2 JP 3521021B2
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- JP
- Japan
- Prior art keywords
- phosphoric acid
- concentrated
- waste liquid
- polyphosphoric acid
- treatment
- 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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- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
【発明の詳細な説明】Detailed Description of the Invention
【０００１】[0001]
【産業上の利用分野】本発明はポリリン酸を重合溶媒と
して用いるポリベンズアゾールの製造方法に関するもの
であり、特にポリベンズアゾールの製造に際して生成す
るリン酸廃液の回収、再利用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 producing polybenzazole using polyphosphoric acid as a polymerization solvent, and more particularly to the recovery and reuse of a phosphoric acid waste solution produced during the production of polybenzazole.
【０００２】[0002]
【従来の技術】ポリパラフェニレンベンゾビスオキサゾ
ール、ポリパラフェニレンベンゾビスチアゾール、ポリ
パラフェニレンベンゾビスイミダゾール等に代表される
ポリベンズアゾール類ポリマーの重合では、一般にポリ
リン酸が重合溶媒兼縮合剤として用いられる。ポリリン
酸は解重合して最終的には希釈されたリン酸廃液として
得られるため、廃液量は多くなり、その処理方法が問題
となる。この廃液処理に関する従来の技術としては、リ
ン酸廃液を水酸化マグネシウム、水酸化カルシウム等の
アルカリ土類金属水酸化物で処理して、リン酸のアルカ
リ土類金属塩として回収し、埋没処理する方法が挙げら
れる。しかしながら、この方法では大量の廃液処理が困
難であり、またリン酸を使い捨てすることになるため、
経済的にまた環境的にも問題がある。2. Description of the Related Art Polyphosphoric acid is generally used as a polymerization solvent and a condensing agent in the polymerization of polybenzazole polymers represented by polyparaphenylene benzobisoxazole, polyparaphenylene benzobisthiazole, polyparaphenylene benzobisimidazole and the like. To be Since polyphosphoric acid is depolymerized and finally obtained as a diluted phosphoric acid waste liquid, the amount of the waste liquid increases and the treatment method thereof becomes a problem. As a conventional technique regarding this waste liquid treatment, the phosphoric acid waste liquid is treated with an alkaline earth metal hydroxide such as magnesium hydroxide or calcium hydroxide to recover as an alkaline earth metal salt of phosphoric acid, and then buried. There is a method. However, this method is difficult to process a large amount of waste liquid, and since phosphoric acid is to be thrown away,
There are economic and environmental problems.
【０００３】一方、リン酸の回収、再利用を目的とした
一般的処理方法としては、湿式リン酸の精製／濃縮法が
提案されており、具体的には有機溶媒で抽出する方法、
活性炭で脱色する方法、塩素酸塩及び塩化水素で処理す
る方法（特公昭５５−１６０９３）、硫化水素で処理す
る方法（特開昭５０−１８３８８）、高温に加熱処理す
る方法（特公昭５７−３１５２４）、過酸化水素で酸化
処理する方法（特開昭５８−９９１０８）等が挙げられ
る。On the other hand, as a general treatment method for the purpose of recovering and reusing phosphoric acid, a method for refining / concentrating wet phosphoric acid has been proposed, specifically, a method of extracting with an organic solvent,
A method of decolorizing with activated carbon, a method of treating with chlorate and hydrogen chloride (JP-B-55-16093), a method of treating with hydrogen sulfide (JP-A-50-18388), and a method of heat treatment at high temperature (JP-B-57-57). 31524), a method of oxidizing treatment with hydrogen peroxide (JP-A-58-99108) and the like.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、これら
の処理法はポリベンズアゾールの製造に再利用可能なポ
リリン酸の再生には適用できないことが判明した。例え
ば、有機溶媒で抽出する方法や活性炭で処理する方法で
は有機物の除去が不十分であった。また塩素酸塩及び塩
酸を併用する方法では有機物の分解は可能であるが、一
般的な反応装置では塩酸による腐食が問題となった。さ
らに単に高温で加熱する方法では有機物の分解が不十分
であった。かくして、いずれの処理方法によっても、ポ
リベンズアゾールの製造に再利用可能なポリリン酸の再
生はできないことが判明した。本発明はかかる従来技術
の現状に鑑み創案されたものであり、その目的とすると
ころはポリベンズアゾールの製造に際して生成するリン
酸廃液を回収してポリベンズアゾールの製造に再利用可
能なポリリン酸を再生する方法およびその再生ポリリン
酸を用いたポリベンズアゾールの製造方法を提供するも
のである。However, it has been found that these treatment methods cannot be applied to the regeneration of polyphosphoric acid, which can be reused in the production of polybenzazole. For example, the removal of organic substances was insufficient by the method of extracting with an organic solvent or the method of treating with activated carbon. Moreover, although the organic substances can be decomposed by the method of using chlorate and hydrochloric acid together, the corrosion by hydrochloric acid becomes a problem in a general reaction apparatus. Further, the decomposition of organic substances was insufficient by the method of simply heating at a high temperature. Thus, it was revealed that polyphosphoric acid, which can be reused in the production of polybenzazole, cannot be regenerated by any of the treatment methods. The present invention was devised in view of the current state of the art, and an object thereof is to recover polyphosphoric acid waste liquid generated during the production of polybenzazole and to reuse polyphosphoric acid in the production of polybenzazole. And a method for producing polybenzazole using the regenerated polyphosphoric acid.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、かかる目
的を達成するために鋭意検討した結果、リン酸廃液を一
旦５０％以上に濃縮した後、次いでこの濃縮廃液に対し
て１０重量％以下の酸化剤で加熱下、酸化処理し、更に
処理液を高減圧下に１００％以上に高濃縮することによ
り、ポリベンズアゾールの製造に再利用可能なポリリン
酸を再生できることを見出し、本発明を完成するに至っ
た。Means for Solving the Problems The inventors of the present invention have made earnest studies to achieve such an object. As a result, the phosphoric acid waste liquid was once concentrated to 50% or more, and then 10% by weight based on the concentrated waste liquid. It was found that polyphosphoric acid that can be reused in the production of polybenzazole can be regenerated by performing an oxidation treatment with the following oxidizing agent under heating and further highly concentrating the treatment liquid to 100% or more under high reduced pressure, and the present invention. Has been completed.
【０００６】即ち、本発明は重合溶媒としてポリリン酸
を用いるポリベンズアゾールの製造方法において、廃液
として得られるポリリン酸およびリン酸廃液を５０％以
上に濃縮した後、この濃縮廃液に対して１０重量％以下
の酸化剤で加熱下、酸化処理し、さらに減圧下で１００
％以上に濃縮したポリリン酸を重合溶媒として用いるこ
とを特徴とするポリベンズアゾールの製造方法である。That is, according to the present invention, in a method for producing polybenzazole using polyphosphoric acid as a polymerization solvent, polyphosphoric acid and phosphoric acid waste liquid obtained as waste liquid are concentrated to 50% or more, and then 10 wt% of the concentrated waste liquid is concentrated. % Oxidation agent under heating, and further 100% under reduced pressure
% Of polyphosphoric acid is used as a polymerization solvent, which is a method for producing polybenzazole.
【０００７】また、本発明はポリベンズアゾールの製造
で得られるポリリン酸およびリン酸廃液を回収する方法
において、前記廃液を５０％以上に濃縮した後、この濃
縮廃液に対して１０重量％以下の酸化剤で加熱下、酸化
処理し、さらに減圧下で１００％以上に濃縮することを
特徴とするポリリン酸の回収方法である。Further, the present invention is a method for recovering polyphosphoric acid and a phosphoric acid waste liquid obtained in the production of polybenzazole, wherein the waste liquid is concentrated to 50% or more and then 10% by weight or less based on the concentrated waste liquid. It is a method for recovering polyphosphoric acid, which is characterized in that the polyphosphoric acid is subjected to oxidation treatment under heating with an oxidizing agent and further concentrated under reduced pressure to 100% or more.
【０００８】本発明においてポリベンズアゾールとは、
下記一般式１〜３で表される構造を主たる構成単位とす
る複素環含有ホモポリマー及びコポリマーの総称であ
る：In the present invention, polybenzazole means
It is a general term for heterocycle-containing homopolymers and copolymers having the structures represented by the following general formulas 1 to 3 as main constituent units:
【化１】 [Chemical 1]
【化２】 [Chemical 2]
【化３】
（但し、ＺはＯ，Ｓ又はＮＨから選ばれるものを表す）
ポリベンズアゾールの具体例としては、シス−又はトラ
ンスポリパラフェニレンベンゾビスオキサゾール、シス
−又はトランスポリパラフェニレンベンゾビスチアゾー
ル、シス−又はトランスポリパラフェニレンベンゾビス
イミダゾール、ポリ（２，５−ベンゾオキサゾール）、
ポリ（２，６−ベンゾチアゾール）等が挙げられる。[Chemical 3] (However, Z represents one selected from O, S or NH.) Specific examples of polybenzazole include cis- or trans polyparaphenylene benzobisoxazole, cis- or trans polyparaphenylene benzobisthiazole, cis- Or trans polyparaphenylene benzobisimidazole, poly (2,5-benzoxazole),
Examples thereof include poly (2,6-benzothiazole).
【０００９】また本発明においてリン酸廃液とは、主に
ポリベンズアゾールの重合に際して使用されたポリリン
酸がポリマー凝固浴で抽出されて得られる希薄リン酸溶
液であるが、ポリマー製造過程で発生するその他のリン
酸廃液等も含まれる。リン酸廃液の濃度は、通常５〜５
０％程度であり、本発明においてはこのリン酸廃液を一
旦５０％以上に濃縮するが、６０〜９０％に濃縮するこ
とが好ましい。ここで濃縮操作を最初に行う理由は、酸
性度を高めることにより次の酸化反応を容易にすること
であり、より少ない酸化剤量で処理が行えるためであ
る。また処理量を小さくすることで、取扱いを容易にす
るためである。濃縮方法は加熱による蒸留濃縮であり、
常圧、減圧のいずれでも行える。In the present invention, the phosphoric acid waste liquor is a dilute phosphoric acid solution obtained by extracting polyphosphoric acid mainly used in the polymerization of polybenzazole in a polymer coagulation bath. Other phosphoric acid waste liquids are also included. The concentration of phosphoric acid waste liquid is usually 5 to 5
It is about 0%, and in the present invention, this phosphoric acid waste liquid is once concentrated to 50% or more, but it is preferable to concentrate it to 60 to 90%. The reason why the concentration operation is performed first here is that the subsequent oxidation reaction is facilitated by increasing the acidity, and the treatment can be performed with a smaller amount of oxidizing agent. This is also because the amount of treatment is reduced to facilitate handling. The concentration method is distillation concentration by heating,
It can be performed at either normal pressure or reduced pressure.
【００１０】次いで本発明では、不純物として含まれる
有機物を分解するために、上記濃縮リン酸廃液の酸化処
理を行う。酸化剤としては、一般の酸化剤すべてが用い
られるが、特に過塩酸、過臭素酸及びこれらの塩、若し
くは過酸化水素が好ましい。酸化剤の使用量はリン酸廃
液中の有機物の種類及び量によって変わるが、通常は濃
縮リン酸廃液に対して０．００１〜１０重量％使用す
る。酸化処理は酸化剤の共存下、濃縮リン酸廃液を加熱
攪拌して行うが、通常は５０〜１５０℃で加熱を行う。
酸化処理によりリン酸廃液中の有機物が分解しているこ
とは、液の着色が減少し、無色透明になることからも確
認できる。Next, in the present invention, in order to decompose the organic matter contained as impurities, the concentrated phosphoric acid waste liquid is oxidized. As the oxidizing agent, all common oxidizing agents are used, but perchloric acid, perbromic acid and salts thereof, or hydrogen peroxide is particularly preferable. Although the amount of the oxidizing agent used varies depending on the type and amount of organic substances in the phosphoric acid waste liquid, it is usually used in an amount of 0.001 to 10% by weight based on the concentrated phosphoric acid waste liquid. The oxidation treatment is carried out by heating and stirring the concentrated phosphoric acid waste liquid in the coexistence of an oxidant, and it is usually carried out at 50 to 150 ° C.
The fact that the organic substances in the phosphoric acid waste liquid are decomposed by the oxidation treatment can be confirmed from the fact that the coloring of the liquid is reduced and the liquid becomes colorless and transparent.
【００１１】本発明では上記の酸化処理されたリン酸廃
液をさらに高濃度に濃縮する。この際、強制攪拌式の薄
膜蒸留装置を使用するが、これは高濃度のリン酸では粘
度が上昇するために、強制的に攪拌して薄膜化する必要
があるからである。高濃度のリン酸濃縮は高温で行われ
るため、使用する薄膜蒸留装置の材質は耐腐食性である
必要がある。具体的には、パイレックスガラス、ハステ
ロイＣ、ハステロイＢ等が挙げられる。濃縮は通常、２
００〜３００℃、高減圧下に行われるが、好ましくは２
５０〜２８０℃、０．１ｍｍＨｇ以下で行う。濃縮後の
リン酸は縮合したポリリン酸であり、リン酸濃度で１０
０〜１２０％であるが、再利用の点からは１１０〜１２
０％であることが好ましい。ポリリン酸は吸湿性である
ため、濃縮後は水分をさけて保存する。In the present invention, the phosphoric acid waste liquid subjected to the above-mentioned oxidation treatment is concentrated to a higher concentration. At this time, a forced agitation type thin film distillation apparatus is used, because it is necessary to forcibly stir to form a thin film because the viscosity increases with high concentration phosphoric acid. Since the concentrated phosphoric acid is concentrated at a high temperature, the material of the thin film distillation apparatus used must be corrosion resistant. Specific examples include Pyrex glass, Hastelloy C, Hastelloy B, and the like. Concentration is usually 2
It is carried out under high vacuum at 00 to 300 ° C., preferably 2
It is performed at 50 to 280 ° C. and 0.1 mmHg or less. The phosphoric acid after concentration is condensed polyphosphoric acid, and the phosphoric acid concentration is 10
0 to 120%, but from the point of reuse 110 to 12
It is preferably 0%. Since polyphosphoric acid is hygroscopic, it should be stored in a water-free state after being concentrated.
【００１２】本発明の方法では、使用する酸化剤の種類
及び量によっては、濃縮廃液の酸化処理後にさらに還元
処理を行うことで、ポリベンズアゾールの重合をより良
好に行うことができる。In the method of the present invention, depending on the type and amount of the oxidizing agent used, the reduction treatment is further performed after the oxidation treatment of the concentrated waste liquid, whereby the polymerization of polybenzazole can be more favorably performed.
【００１３】本発明の方法により、ポリベンズアゾール
の製造に際して生成するリン酸廃液からポリベンズアゾ
ールの製造に再利用可能なポリリン酸を再生することが
可能になった。本発明は回収リン酸の再利用という点か
ら経済的に有用であり、また環境的にも優れた方法であ
る。The method of the present invention has made it possible to regenerate polyphosphoric acid that can be reused in the production of polybenzazole from the phosphoric acid waste liquid produced in the production of polybenzazole. The present invention is economically useful from the viewpoint of reusing recovered phosphoric acid, and is also an environmentally superior method.
【００１４】[0014]
【実施例】本発明を以下の実施例によりさらに詳細に説
明するが、本実施例は本発明の範囲を限定するものでは
ない。尚、実施例中、ハーゼンＮｏはＪＩＳ−Ｋ−６９
０１−１９６８によるものである。また極限粘度は、メ
タンスルホン酸を溶媒として２５℃で測定したものであ
る。EXAMPLES The present invention will be explained in more detail by the following examples, but these examples do not limit the scope of the present invention. In the examples, Hazen No. is JIS-K-69.
01-1968. The intrinsic viscosity is measured at 25 ° C. using methanesulfonic acid as a solvent.
【００１５】実施例 １
シス−ポリパラフェニレンベンゾビスオキサゾールの製
造に際して生成したリン酸廃水溶液（リン酸濃度：１８
％）を薄膜蒸留装置により、８０℃、１０ｍｍＨｇの条
件で濃縮し、８０％のリン酸濃縮液を得た。得られた濃
縮リン酸の着色度は、ハーゼンＮｏで１０００以上であ
った。次に８０％リン酸濃縮液１０００ｇに対して、１
０ｇの過塩素酸ナトリウムを加え、８０℃で２時間加熱
処理を行った。処理開始１５分後から脱色が始まり、処
理後のハーゼンＮｏは５００であった。得られた処理液
に塩化スズ（II) ５ｇを加え、５０℃で１時間加熱処理
した。次いで同液を強制攪拌機を備えたパイレックスガ
ラス製の薄膜蒸留装置に移し、２００℃、１ｍｍＨｇで
１１０％まで濃縮した。さらに同装置にて２６０℃、
０．１ｍｍＨｇの条件で濃縮し、リン酸濃度で１１６
％、ハーゼンＮｏで５０のポリリン酸を得た。Example 1 Waste phosphoric acid aqueous solution (phosphoric acid concentration: 18) produced in the production of cis-polyparaphenylenebenzobisoxazole
%) Was concentrated by a thin film distillation apparatus under the conditions of 80 ° C. and 10 mmHg to obtain an 80% concentrated phosphoric acid solution. The coloring degree of the obtained concentrated phosphoric acid was 1,000 or more in Hazen No. Next, for every 1000 g of 80% phosphoric acid concentrate, 1
0 g of sodium perchlorate was added, and heat treatment was performed at 80 ° C. for 2 hours. Decolorization started 15 minutes after the start of treatment, and Hazen No. after treatment was 500. 5 g of tin (II) chloride was added to the obtained treatment liquid, and the mixture was heated at 50 ° C. for 1 hour. Then, the liquid was transferred to a thin film distillation apparatus made of Pyrex glass equipped with a forced stirrer and concentrated to 110% at 200 ° C. and 1 mmHg. In addition, the same equipment at 260 ℃,
Concentrated under the condition of 0.1mmHg, phosphoric acid concentration 116
%, Hazen No. 50 polyphosphoric acid was obtained.
【００１６】かくして得られたポリリン酸４３．８６ｇ
に窒素気流下、五酸化二リン１４．４９ｇを加えた後、
４，６−ジアミノレゾルシノール二塩酸塩９．１０ｇ及
びテレフタル酸７．１０ｇを加え、７０℃で攪拌混合し
た後、１２０℃で１９時間、さらに２００℃で２時間攪
拌して重合させ、シス−ポリパラフェニレンベンゾビス
オキサゾールとした。得られたポリマーの極限粘度は、
６１（ｄｌ／ｇ）であり、ポリマードープの色は黄色で
あり、新しいポリリン酸から重合したポリマーと差は無
かった。43.86 g of polyphosphoric acid thus obtained
After adding 14.49 g of diphosphorus pentoxide under nitrogen stream,
After adding 9.10 g of 4,6-diaminoresorcinol dihydrochloride and 7.10 g of terephthalic acid and stirring and mixing at 70 ° C., polymerization was performed by stirring at 120 ° C. for 19 hours and further at 200 ° C. for 2 hours to polymerize. It was paraphenylene benzobisoxazole. The intrinsic viscosity of the obtained polymer is
It was 61 (dl / g) and the color of the polymer dope was yellow, which was not different from the polymer polymerized from fresh polyphosphoric acid.
【００１７】実施例 ２〜４
実施例１における過塩素酸ナトリウムの代わりに、表１
に示す酸化剤を使用して酸化処理を行い、以下同様に濃
縮処理して１１６〜１１８％のリン酸を得た。表１に示
す通り、得られたリン酸の着色は少なく、またこれを実
施例１同様にシス−ポリパラフェニレンベンゾビスオキ
サゾールの重合で再利用した場合でも、極限粘度で５０
〜５９（ｄｌ／ｇ）の黄色ポリマーが得られた。Examples 2-4 Instead of sodium perchlorate in Example 1, Table 1
Oxidizing treatment was carried out using the oxidizing agent shown in (1), and thereafter concentration treatment was carried out in the same manner to obtain 116 to 118% phosphoric acid. As shown in Table 1, the phosphoric acid obtained was less colored, and when it was reused in the polymerization of cis-polyparaphenylenebenzobisoxazole as in Example 1, the intrinsic viscosity was 50%.
A yellow polymer of ˜59 (dl / g) was obtained.
【００１８】比較例 １
実施例１における酸化処理に際して、酸化剤を使用せず
に加熱処理のみを行い、以下実施例１と同様に濃縮処理
を行って１１７％のリン酸を得た。表１に示す通り、ハ
ーゼンＮｏで１０００以上と着色は著しく、またこれを
実施例１同様にシス−ポリパラフェニレンベンゾビスオ
キサゾールの重合で再利用した場合、極限粘度で１０
（ｄｌ／ｇ）の黒色ポリマーが得られた。Comparative Example 1 In the oxidation treatment in Example 1, only a heat treatment was carried out without using an oxidizing agent, and a concentration treatment was carried out in the same manner as in Example 1 to obtain 117% phosphoric acid. As shown in Table 1, the Hazen No. was 1000 or more, and the coloring was remarkable, and when this was reused in the polymerization of cis-polyparaphenylenebenzobisoxazole as in Example 1, the intrinsic viscosity was 10
A black polymer (dl / g) was obtained.
【００１９】[0019]
【表１】 [Table 1]
【００２０】実施例 ５
トランス−ポリパラフェニレンベンゾビスチアゾールの
製造に際して生成したリン酸廃水溶液（リン酸濃度：２
１％）を薄膜蒸留装置により、８０℃、１０ｍｍＨｇの
条件で濃縮し、８１％のリン酸濃縮液を得た。得られた
濃縮リン酸の着色度は、ハーゼンＮｏで１０００以上で
あった。次に８１％リン酸濃縮液１０００ｇに対して、
１０ｇの過塩素酸ナトリウムを加え、８０℃で２時間加
熱処理を行った。処理開始１０分後から脱色が始まり、
処理後のハーゼンＮｏは５５０であった。得られた処理
液に塩化スズ（II) ５ｇを加え、５０℃で１時間加熱処
理した。次いで同液を強制攪拌機を備えたパイレックス
ガラス製の薄膜蒸留装置に移し、２００℃、１ｍｍＨｇ
で１１１％まで濃縮した。さらに同装置にて２６０℃、
０．１ｍｍＨｇの条件で濃縮し、リン酸濃度で１１６
％、ハーゼンＮｏで６０のポリリン酸を得た。Example 5 Waste aqueous solution of phosphoric acid produced during the production of trans-polyparaphenylene benzobisthiazole (phosphoric acid concentration: 2
1%) was concentrated by a thin film distillation apparatus under the conditions of 80 ° C. and 10 mmHg to obtain an 81% phosphoric acid concentrate. The coloring degree of the obtained concentrated phosphoric acid was 1,000 or more in Hazen No. Next, for 1000 g of 81% phosphoric acid concentrate,
10 g of sodium perchlorate was added, and heat treatment was performed at 80 ° C. for 2 hours. Decolorization begins 10 minutes after the start of treatment,
Hazen No. after the treatment was 550. 5 g of tin (II) chloride was added to the obtained treatment liquid, and the mixture was heated at 50 ° C. for 1 hour. Next, the solution was transferred to a Pyrex glass thin-film distillation apparatus equipped with a forced stirrer, 200 ° C., 1 mmHg
Was concentrated to 111%. In addition, the same equipment at 260 ℃,
Concentrated under the condition of 0.1mmHg, phosphoric acid concentration 116
%, Hazen No. 60 polyphosphoric acid was obtained.
【００２１】かくして得られたポリリン酸４３．８６ｇ
に窒素気流下、五酸化二リン１４．４９ｇを加えた後、
２，５−ジアミノ−１，４−ベンゼンジチオール二塩酸
塩９．１０ｇ及びテレフタル酸６．１７ｇを加え、７０
℃で攪拌混合した後、１２０℃で１９時間、さらに２０
０℃で２時間攪拌して重合させ、シス−ポリパラフェニ
レンベンゾビスチアゾールとした。得られたポリマーの
極限粘度は、５９（ｄｌ／ｇ）であり、ポリマードープ
の色は濃黄緑色であり、新しいポリリン酸から重合した
ポリマーと差は無かった。43.86 g of polyphosphoric acid thus obtained
After adding 14.49 g of diphosphorus pentoxide under nitrogen stream,
2,5-Diamino-1,4-benzenedithiol dihydrochloride 9.10 g and terephthalic acid 6.17 g were added to give 70
After stirring and mixing at ℃, for 19 hours at 120 ℃, 20 more
The mixture was stirred at 0 ° C. for 2 hours and polymerized to obtain cis-polyparaphenylene benzobisthiazole. The intrinsic viscosity of the obtained polymer was 59 (dl / g), the color of the polymer dope was dark yellow green, and there was no difference from the polymer polymerized from fresh polyphosphoric acid.
【００２２】実施例 ６〜８
実施例５における過塩素酸ナトリウムの代わりに、表２
に示す酸化剤を使用して酸化処理を行い、以下同様に濃
縮処理して１１６〜１１８％のリン酸を得た。表２に示
す通り、得られたリン酸の着色は少なく、またこれを実
施例５同様にトランス−ポリパラフェニレンベンゾビス
チアゾールの重合で再利用した場合でも、極限粘度で５
５〜６０（ｄｌ／ｇ）のポリマーが得られた。Examples 6-8 Instead of sodium perchlorate in Example 5, Table 2
Oxidizing treatment was carried out using the oxidizing agent shown in (1), and thereafter concentration treatment was carried out in the same manner to obtain 116 to 118% phosphoric acid. As shown in Table 2, the obtained phosphoric acid showed little coloring, and even when it was reused in the polymerization of trans-polyparaphenylene benzobisthiazole as in Example 5, the intrinsic viscosity was 5
Polymers of 5-60 (dl / g) were obtained.
【００２３】比較例 ２
実施例５における酸化処理に際して、酸化剤を使用せず
に加熱処理のみを行い、以下実施例５と同様に濃縮処理
を行って１１６％のリン酸を得た。表２に示す通り、ハ
ーゼンＮｏで１０００以上と着色は著しく、またこれを
実施例５同様にトランス−ポリパラフェニレンベンゾビ
スチアゾールの重合で再利用した場合、極限粘度で１２
（ｄｌ／ｇ）の黒色ポリマーが得られた。Comparative Example 2 At the time of the oxidation treatment in Example 5, only a heat treatment was performed without using an oxidizing agent, and a concentration treatment was performed in the same manner as in Example 5 to obtain 116% phosphoric acid. As shown in Table 2, the Hazen No. was 1000 or more, and the coloring was remarkable, and when this was reused in the polymerization of trans-polyparaphenylene benzobisthiazole as in Example 5, the intrinsic viscosity was 12
A black polymer (dl / g) was obtained.
【００２４】[0024]
【表２】 [Table 2]
【００２５】実施例 ９
ポリパラフェニレンベンゾビスイミダゾールの製造に際
して生成したリン酸廃水溶液（リン酸濃度：２０％）を
薄膜蒸留装置により、８０℃、１０ｍｍＨｇの条件で濃
縮し、８０％のリン酸濃縮液を得た。得られた濃縮リン
酸の着色度は、ハーゼンＮｏで１０００以上であった。
次に８０％リン酸濃縮液１０００ｇに対して、１０ｇの
過塩素酸ナトリウムを加え、８０℃で２時間加熱処理を
行った。処理開始２０分後から脱色が始まり、処理後の
ハーゼンＮｏは６００であった。得られた処理液に塩化
スズ（II) ５ｇを加え、５０℃で１時間加熱処理した。
次いで同液を強制攪拌機を備えたパイレックスガラス製
の薄膜蒸留装置に移し、２００℃、１ｍｍＨｇで１１０
％まで濃縮した。さらに同装置にて２６０℃、０．１ｍ
ｍＨｇの条件で濃縮し、リン酸濃度で１１６％、ハーゼ
ンＮｏで７０のポリリン酸を得た。Example 9 A phosphoric acid waste aqueous solution (phosphoric acid concentration: 20%) produced in the production of polyparaphenylenebenzobisimidazole was concentrated by a thin film distillation apparatus at 80 ° C. and 10 mmHg to obtain 80% phosphoric acid. A concentrated liquid was obtained. The coloring degree of the obtained concentrated phosphoric acid was 1,000 or more in Hazen No.
Next, 10 g of sodium perchlorate was added to 1000 g of 80% phosphoric acid concentrated liquid, and heat treatment was performed at 80 ° C. for 2 hours. Decolorization started 20 minutes after the start of treatment, and Hazen No. after treatment was 600. 5 g of tin (II) chloride was added to the obtained treatment liquid, and the mixture was heated at 50 ° C. for 1 hour.
Then, the solution was transferred to a Pyrex glass thin-film distillation apparatus equipped with a forced stirrer and heated at 200 ° C. and 1 mmHg for 110 hours.
Concentrated to%. Furthermore, with the same equipment, 260 ℃, 0.1m
Concentration was performed under the condition of mHg to obtain polyphosphoric acid having a phosphoric acid concentration of 116% and Hazen No. 70.
【００２６】かくして得られたポリリン酸４３．８６ｇ
に窒素気流下、五酸化二リン１４．４９ｇを加えた後、
１，２，４，５−テトラアミノベンゼン四塩酸塩９．１
０ｇ及びテレフタル酸５．３２ｇを加え、７０℃で攪拌
混合した後、１２０℃で１９時間、さらに２００℃で２
時間攪拌して重合させ、ポリパラフェニレンベンゾビス
イミダゾールとした。得られたポリマーの極限粘度は、
５０（ｄｌ／ｇ）であり、ポリマードープの色は濃青色
であり、新しいポリリン酸から重合したポリマーと差は
無かった。43.86 g of polyphosphoric acid thus obtained
After adding 14.49 g of diphosphorus pentoxide under nitrogen stream,
1,2,4,5-Tetraaminobenzene tetrahydrochloride 9.1
0 g and 5.32 g of terephthalic acid were added and mixed with stirring at 70 ° C., then at 120 ° C. for 19 hours, and at 200 ° C. for 2 hours.
Polymerization was carried out by stirring for a time to obtain polyparaphenylene benzobisimidazole. The intrinsic viscosity of the obtained polymer is
It was 50 (dl / g) and the color of the polymer dope was dark blue, which was not different from the polymer polymerized from fresh polyphosphoric acid.
【００２７】実施例 １０〜１２
実施例９における過塩素酸ナトリウムの代わりに、表３
に示す酸化剤を使用して酸化処理を行い、以下同様に濃
縮処理して１１５〜１１６％のリン酸を得た。表３に示
す通り、得られたリン酸の着色は少なく、またこれを実
施例９同様にポリパラフェニレンベンゾビスイミダゾー
ルの重合で再利用した場合でも、極限粘度で４５〜５３
（ｄｌ／ｇ）のポリマーが得られた。Examples 10-12 Instead of sodium perchlorate in Example 9, Table 3
Oxidizing treatment was carried out using the oxidizing agent shown in (1), and thereafter concentration treatment was carried out in the same manner to obtain 115 to 116% phosphoric acid. As shown in Table 3, the obtained phosphoric acid showed little coloring, and when it was reused in the polymerization of polyparaphenylenebenzobisimidazole as in Example 9, the intrinsic viscosity was 45 to 53.
A polymer of (dl / g) was obtained.
【００２８】比較例 ３
実施例９における酸化処理に際して、酸化剤を使用せず
に加熱処理のみを行い、以下実施例９と同様に濃縮処理
を行って１１６％のリン酸を得た。表３に示す通り、ハ
ーゼンＮｏで１０００以上と着色は著しく、またこれを
実施例９同様にポリパラフェニレンベンゾビスイミダゾ
ールの重合で再利用した場合、極限粘度で１０（ｄｌ／
ｇ）の黒色ポリマーが得られた。Comparative Example 3 In the oxidation treatment in Example 9, only heat treatment was carried out without using an oxidizing agent, and the same concentration treatment was carried out as in Example 9 to obtain 116% phosphoric acid. As shown in Table 3, the Hazen No. was 1000 or more, and the coloring was remarkable, and when this was reused in the polymerization of polyparaphenylenebenzobisimidazole as in Example 9, the intrinsic viscosity was 10 (dl / dl /
A black polymer of g) was obtained.
【００２９】[0029]
【表３】 [Table 3]
【００３０】[0030]
【発明の効果】本発明の方法により、ポリベンズアゾー
ルの製造に際して生成するリン酸廃液からポリベンズア
ゾールの製造に再利用可能なポリリン酸を再生すること
が可能になった。本発明は回収リン酸の再利用という点
から経済的に有用であり、また環境的にも優れた方法で
ある。Industrial Applicability According to the method of the present invention, it becomes possible to regenerate polyphosphoric acid that can be reused in the production of polybenzazole from the phosphoric acid waste liquid produced in the production of polybenzazole. The present invention is economically useful from the viewpoint of reusing recovered phosphoric acid, and is also an environmentally superior method.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭55−3386（ＪＰ，Ａ) 特開 昭55−100206（ＪＰ，Ａ) 特開 昭60−166208（ＪＰ，Ａ) 特開 昭61−17408（ＪＰ，Ａ) 特開 昭63−222009（ＪＰ，Ａ) 特開 平２−84510（ＪＰ，Ａ) 特表 昭60−501899（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08G 73/00 - 73/26 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP 55-3386 (JP, A) JP 55-100206 (JP, A) JP 60-166208 (JP, A) JP 61- 17408 (JP, A) JP-A-63-222009 (JP, A) JP-A-2-84510 (JP, A) Special table Sho-60-501899 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) C08G 73/00-73/26
Claims (2)
ベンズアゾールの製造方法において、廃液として得られ
るポリリン酸およびリン酸廃液を５０％以上に濃縮した
後、この濃縮廃液に対して１０重量％以下の酸化剤で加
熱下、酸化処理し、さらに減圧下で１００％以上に濃縮
したポリリン酸を重合溶媒として用いることを特徴とす
るポリベンズアゾールの製造方法。1. A method for producing polybenzazole using polyphosphoric acid as a polymerization solvent, wherein polyphosphoric acid and phosphoric acid waste liquid obtained as waste liquid are concentrated to 50% or more, and then 10% by weight or less based on the concentrated waste liquid. A method for producing polybenzazole, comprising using polyphosphoric acid, which has been subjected to an oxidation treatment under heating with an oxidizing agent and further concentrated under reduced pressure to 100% or more, as a polymerization solvent.
リリン酸およびリン酸廃液を回収する方法において、前
記廃液を５０％以上に濃縮した後、この濃縮廃液に対し
て１０重量％以下の酸化剤で加熱下、酸化処理し、さら
に減圧下で１００％以上に濃縮することを特徴とするポ
リリン酸の回収方法。2. A method for recovering polyphosphoric acid and a phosphoric acid waste liquid obtained in the production of polybenzazole, wherein the waste liquid is concentrated to 50% or more, and then 10% by weight or less of an oxidizing agent is added to the concentrated waste liquid. A method for recovering polyphosphoric acid, which comprises subjecting to oxidation treatment under heating and further concentrating to 100% or more under reduced pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13582895A JP3521021B2 (en) | 1995-05-08 | 1995-05-08 | Method for producing polybenzazole and method for recovering polyphosphoric acid used in the production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13582895A JP3521021B2 (en) | 1995-05-08 | 1995-05-08 | Method for producing polybenzazole and method for recovering polyphosphoric acid used in the production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08302017A JPH08302017A (en) | 1996-11-19 |
| JP3521021B2 true JP3521021B2 (en) | 2004-04-19 |
Family
ID=15160746
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13582895A Expired - Lifetime JP3521021B2 (en) | 1995-05-08 | 1995-05-08 | Method for producing polybenzazole and method for recovering polyphosphoric acid used in the production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3521021B2 (en) |
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1995
- 1995-05-08 JP JP13582895A patent/JP3521021B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08302017A (en) | 1996-11-19 |
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