JPH0578472A - Recovery of polyaryl ether - Google Patents
Recovery of polyaryl etherInfo
- Publication number
- JPH0578472A JPH0578472A JP31125291A JP31125291A JPH0578472A JP H0578472 A JPH0578472 A JP H0578472A JP 31125291 A JP31125291 A JP 31125291A JP 31125291 A JP31125291 A JP 31125291A JP H0578472 A JPH0578472 A JP H0578472A
- Authority
- JP
- Japan
- Prior art keywords
- polyaryl ether
- polymer
- solvent
- solution
- double
- 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.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、耐熱性および機械的強
度に優れたポリアリールエーテルを、重合反応溶液から
回収する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 recovering a polyaryl ether excellent in heat resistance and mechanical strength from a polymerization reaction solution.
【０００２】[0002]
【従来の技術及びその問題点】ポリアリールエーテル
は、二価フェノール、アルカリ金属化合物およびジハロ
ゲノジフェニル化合物を有機極性溶媒中で反応させて、
または、二価フェノールのアルカリ金属二塩をあらかじ
め合成しておいて、ジハロゲノジフェニル化合物と有機
極性溶媒中で重縮合反応させることによって、製造され
ることが知られている（特公昭４２−７７９９号、特公
昭４５−２１３１８号、特開昭４８−１９７００号）。2. Description of the Related Art Polyaryl ethers are obtained by reacting a dihydric phenol, an alkali metal compound and a dihalogenodiphenyl compound in an organic polar solvent.
Alternatively, it is known to be produced by preliminarily synthesizing an alkali metal disalt of a dihydric phenol and subjecting it to a polycondensation reaction with a dihalogenodiphenyl compound in an organic polar solvent (Japanese Patent Publication No. 42-7799). No. 45/21318, JP-A-48-19700).
【０００３】反応溶媒として極性の高い有機溶媒を用い
ることによって、高分子量の重合体を反応中に析出させ
ることなく製造することができる。さらに、前記の重合
体を含有する有機溶液から重合体を分離する方法として
は、溶液に重合体の貧溶媒を添加して重合体を沈澱析出
させた後、粒子状の重合体を水洗、乾燥する方法が提案
されている。例えば、添加溶媒として水（特開昭５２−
２７５００号）、低級アルコール（特公昭４６−１８１
４６号）、環状エーテル（特開昭６３−２２１１２９
号）、ジアルキルケトン（特開昭５９−１５５４３１
号）、非極性芳香族化合物（特開昭５９−７４１２５
号）、脂肪族炭化水素（特開昭５０−８９７１８号）、
あるいはアルコールとケトン混合溶液（特開平２−８８
６３９号）などが用いられている。しかしながら、これ
らの方法では、析出ポリアリールエーテルが大きな塊に
なりやいため、効率的に回収できず、また、重合体中か
ら溶媒が充分に除去できにくい。そのため、重合体の加
熱成形加工時に、残存溶媒の劣化、分解による重合体の
着色がおこる場合がある。By using a highly polar organic solvent as a reaction solvent, a high molecular weight polymer can be produced without precipitating during the reaction. Further, as a method of separating the polymer from the organic solution containing the polymer, a poor solvent for the polymer is added to the solution to precipitate the polymer, and then the particulate polymer is washed with water and dried. The method to do is proposed. For example, water is added as a solvent (Japanese Patent Laid-Open No. 52-
27500), lower alcohol (Japanese Patent Publication No. 46-181)
46), cyclic ethers (JP-A-63-221129)
No.), dialkyl ketone (JP-A-59-155431)
No.), non-polar aromatic compounds (JP-A-59-74125).
No.), aliphatic hydrocarbons (JP-A-50-89718),
Alternatively, a mixed solution of alcohol and ketone (JP-A-2-88
639) and the like are used. However, in these methods, the precipitated polyaryl ether is liable to form a large lump, so that it cannot be efficiently recovered, and it is difficult to sufficiently remove the solvent from the polymer. Therefore, when the polymer is heat-molded, the residual solvent may be deteriorated and the polymer may be colored due to decomposition.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、残存溶媒が
少ないポリアリールエーテルを、重合溶液から連続的に
効率よく回収する方法を提供する。DISCLOSURE OF THE INVENTION The present invention provides a method for continuously and efficiently recovering a polyaryl ether having a small residual solvent from a polymerization solution.
【０００５】[0005]
【課題を解決するための手段】本発明は、内管の吐出口
近くに攪拌機を備えた二重管式連続攪拌槽を用いて、二
重管の一方にアリールエーテルの有機溶媒溶液を、他方
に貧溶媒を連続的に流して混合すると同時に析出したポ
リアリールエーテルを攪拌機で粉砕することを特徴とす
るポリアリールエーテルの回収方法に関する。The present invention uses a double-tube type continuous stirring tank equipped with a stirrer near the discharge port of an inner tube, and uses an organic solvent solution of aryl ether in one of the double tubes and the other in the other. The present invention relates to a method for recovering polyaryl ether, characterized in that the poor solvent is continuously flowed and mixed, and the precipitated polyaryl ether is ground with a stirrer.
【０００６】ポリアリールエーテルは、二価フェノー
ル、アルカリ金属化合物およびジハロゲノジフェニル化
合物を有機溶媒中で反応させて、反応系で二価フェノー
ルのアルカリ金属二塩を合成して、又は、二価フェノー
ルのアルカリ金属二塩をあらかじめ合成しておいて、ジ
ハロゲノジフェニル化合物と有機極性溶媒中で重縮合反
応させることによって製造される。有機極性溶媒として
は、例えば、ジメチルスルホキシド、ジエチルスルホキ
シドなどのスルホキシド系溶媒、Ｎ，Ｎ−ジメチルホル
ムアミド、Ｎ，Ｎ−ジメチルアセトアミドなどのアミド
系溶媒、Ｎ−メチル−２−ピロリドン、Ｎ−ビニル−２
−ピロリドンなどのピロリドン系溶媒、Ｎ−メチル−２
−ピペリドンなどのピペリドン系溶媒、ヘキサメチレン
スルホキシド、γ−ブチロラクトン等、あるいは、１，
３−ジメチル−２−イミダゾリン、１，３−ジエチル−
２−イミダゾリン系溶媒、スルホランなどを挙げること
ができる。The polyaryl ether is obtained by reacting a dihydric phenol, an alkali metal compound and a dihalogenodiphenyl compound in an organic solvent to synthesize an alkali metal di-salt of the dihydric phenol in the reaction system, or a dihydric phenol. It is produced by previously synthesizing the alkali metal di-salt of and then subjecting the dihalogenodiphenyl compound to a polycondensation reaction in an organic polar solvent. Examples of the organic polar solvent include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide, N-methyl-2-pyrrolidone and N-vinyl-. Two
-Pyrrolidone-based solvents such as pyrrolidone, N-methyl-2
-Piperidone solvents such as piperidone, hexamethylene sulfoxide, γ-butyrolactone, etc., or 1,
3-dimethyl-2-imidazoline, 1,3-diethyl-
2-Imidazoline type solvent, sulfolane, etc. can be mentioned.
【０００７】ジハロゲノジフェニル化合物としては、一
般式The dihalogenodiphenyl compound has the general formula
【化１】 （式中、ＸおよびＸ’は同一あるいは異なったハロゲン
原子である。）で示されるものである。特に好ましいジ
ハロゲノジフェニル化合物としては、４，４’−ジクロ
ロジフェニルスルホン、４，４’−ジフルオロジフェニ
ルケトンなどを挙げることをできる。[Chemical 1] (In the formula, X and X ′ are the same or different halogen atoms.). Particularly preferred dihalogenodiphenyl compounds include 4,4′-dichlorodiphenyl sulfone and 4,4′-difluorodiphenyl ketone.
【０００８】二価フェノール化合物としては、ハイドロ
キノン、カテコール、レゾルシン、４，４’−ビフェノ
ール、ビス（ヒドロキシフェニル）アルカン類、ジヒド
ロキシジフェニルスルホン類、ジヒドロキシジフェニル
エーテル類、あるいはそれらのベンゼン環の水素の少な
くとも一つが、適当な置換基（例えば、メチル基、エチ
ル基、プロピル基などの低級アルキル基、メトキシ基、
エトキシ基などのアルコキシ基などの置換基）で置換さ
れたものを挙げられる。二価フェノール化合物として、
上記の化合物を二種類以上混合して用いることができ
る。二価フェノール化合物は実質上ジハロゲノジフェニ
ル化合物と等モル量で使用されることが好ましい。製造
するポリアリールエーテルの分子量を調節するために、
等モルから僅かに過剰量あるいは過少量で使用できる。
この目的のためには、少量のモノハロゲノジフェニル化
合物あるいは一価フェノール化合物を重合溶液中に添加
することができる。Examples of the dihydric phenol compound include hydroquinone, catechol, resorcin, 4,4'-biphenol, bis (hydroxyphenyl) alkanes, dihydroxydiphenylsulfones, dihydroxydiphenyl ethers, or at least one of hydrogens on their benzene rings. Is a suitable substituent (for example, a lower alkyl group such as a methyl group, an ethyl group and a propyl group, a methoxy group,
Those substituted with a substituent such as an alkoxy group such as an ethoxy group). As a dihydric phenol compound,
Two or more of the above compounds can be mixed and used. The dihydric phenol compound is preferably used in a substantially equimolar amount with the dihalogenodiphenyl compound. In order to control the molecular weight of the polyaryl ether produced,
It can be used in equimolar to slight excess or excess.
For this purpose, small amounts of monohalogenodiphenyl compounds or monohydric phenol compounds can be added to the polymerization solution.
【０００９】アルカリ金属化合物としては、アルカリ金
属炭酸塩、アルカリ金属水酸化物、アルカリ金属水素化
物、あるいはアルカリ金属アルコキシドなどが挙げられ
る。特に、炭酸ナトリウムおよび炭酸カリウムが好まし
い。該ポリアリールエーテルに対する貧溶媒としては、
例えば、メタノール、エタノール、イソプロパノール、
ブタノールなどのアルコール類、アセトニトリルなどの
ニトリル類、水などを挙げることができる。また、上記
の化合物を二種類以上混合して用いることができる。ま
た、上記の貧溶媒には、ポリマーが析出可能な範囲で、
前記の重合反応溶媒などのポリマーの良溶媒が含有され
ていてもよい。Examples of alkali metal compounds include alkali metal carbonates, alkali metal hydroxides, alkali metal hydrides, alkali metal alkoxides and the like. Particularly, sodium carbonate and potassium carbonate are preferable. As the poor solvent for the polyaryl ether,
For example, methanol, ethanol, isopropanol,
Examples thereof include alcohols such as butanol, nitriles such as acetonitrile, water and the like. Further, two or more kinds of the above compounds can be mixed and used. Further, in the above poor solvent, to the extent that the polymer can be precipitated,
A good solvent for the polymer such as the above-mentioned polymerization reaction solvent may be contained.
【００１０】ポリアリールエーテルを回収する方法とし
ては、ポリアリールエーテルの有機溶媒溶液を二重管式
で内管の吐出口近くに攪拌機を備えた連続攪拌槽を用い
て、重合終了後、無機物を濾過分離あるいは分離せず
に、ポリアリールエーテルの貧溶媒を二重管式供給管の
一方に連続的に供給しながら、ポリアリールエーテルの
有機溶媒溶液を他方に連続的に供給して、貧溶媒と混合
されて析出したポリアリールエーテルを攪拌機で粉砕す
る。粉砕された重合体を濾過あるいは遠心分離し、水洗
あるいは水洗せず乾燥して、ポリアリールエーテルを得
ることができる。As a method for recovering the polyaryl ether, a solution of the polyaryl ether in an organic solvent is double-tube type and a continuous stirring tank equipped with a stirrer near the discharge port of the inner tube is used. Without separating or separating by filtration, the poor solvent of the polyaryl ether is continuously supplied to one of the double-pipe type supply pipes, while the organic solvent solution of the polyaryl ether is continuously supplied to the other, to obtain the poor solvent. The polyaryl ether mixed with and precipitated is ground with a stirrer. The crushed polymer is filtered or centrifuged, and washed with water or dried without washing to obtain a polyaryl ether.
【００１１】攪拌機を備えた二重管式連続攪拌槽として
は、例えば特殊機化工業株式会社製パイプラインホモミ
キサー又はホモミックラインミルなどに、内管および外
管を有した二重管を接続したものを用いることができ
る。本発明において、ポリアリールエーテルを連続的に
回収する条件として、ポリアリールエーテルの有機溶媒
溶液の供給量、重合体濃度及び温度、貧溶媒の供給量及
び温度、攪拌機の攪拌翼形状及び回転数等の攪拌粉砕条
件などに特に制限はないが、以下の条件、即ち、ポリア
リールエーテルの有機溶媒溶液及び貧溶媒の供給温度は
有機溶媒の融点以上沸点以下、特に沸点が１５０℃を越
える場合は１５０℃以下が好ましく、重合体濃度は０．
１〜０．４ｋｇ／ｌが好ましく、ポリアリールエーテル
の有機溶媒溶液と貧溶媒の供給量の比は３／１〜１／１
０が好ましく、攪拌機の回転数は５００ｒｐｍ以上が好
ましく、特に１０００ｒｐｍ以上が好ましい。ポリアリ
ールエーテルの有機溶媒溶液および貧溶媒の連続攪拌槽
への供給方法として、ポリアリールエーテルの有機溶媒
溶液を内管及び貧溶媒を外管から、又は、ポリアリール
エーテルの有機溶媒溶液を外管及び貧溶媒を内管から供
給してもよい。As the double tube type continuous stirring tank equipped with a stirrer, for example, a pipe homomixer or a homomic line mill manufactured by Tokushu Kika Kogyo Co., Ltd. is connected with a double tube having an inner tube and an outer tube. What was done can be used. In the present invention, as conditions for continuously recovering the polyaryl ether, the supply amount of the organic solvent solution of the polyaryl ether, the polymer concentration and temperature, the supply amount and temperature of the poor solvent, the stirring blade shape and the rotation speed of the stirrer, etc. There is no particular limitation on the stirring and pulverizing conditions, but the following conditions, that is, the supply temperature of the solution of the polyaryl ether in the organic solvent and the poor solvent are not lower than the melting point of the organic solvent and not higher than the boiling point, and particularly 150 when the boiling point exceeds 150 ° C. C. or less is preferable, and the polymer concentration is 0.
1 to 0.4 kg / l is preferable, and the ratio of the supply amount of the organic solvent solution of polyaryl ether to the poor solvent is 3/1 to 1/1
0 is preferable, the rotation speed of the stirrer is preferably 500 rpm or more, and particularly preferably 1000 rpm or more. As a method for supplying the organic solvent solution of polyaryl ether and the poor solvent to the continuous stirring tank, the organic solvent solution of polyaryl ether is supplied from the inner tube and the poor solvent is supplied from the outer tube, or the organic solvent solution of polyaryl ether is supplied to the outer tube. Alternatively, the poor solvent may be supplied from the inner tube.
【００１２】[0012]
【発明の効果】本発明の方法によって、重合溶液から連
続的に効率よくポリアリールエーテルを回収することが
できる。また、従来法に比べて、重合体中の残存溶媒が
低減され、耐熱、耐酸化、耐薬品性に優れたポリアリー
ルエーテルを製造することができる。By the method of the present invention, the polyaryl ether can be continuously and efficiently recovered from the polymerization solution. Further, the residual solvent in the polymer is reduced as compared with the conventional method, and a polyaryl ether excellent in heat resistance, oxidation resistance and chemical resistance can be produced.
【００１３】[0013]
【実施例】以下に本発明の実施例を説明する。 参考例１ 有機溶媒として、Ｎ−メチル−２−ピロリドン６３Ｌ、
共沸脱水用トルエン４Ｌ、４，４’−ジクロロジフェニ
ルスルホン１７．６ｋｇ、ハイドロキノン３．３ｋｇ、
４，４’−ビフェノール５．６ｋｇ、及び炭酸カリウム
９．１ｋｇを使用して窒素雰囲気下、温度約１８０℃、
６時間攪拌し、重合溶液を得た。反応終了後、無機物を
重合溶液から分離するために窒素圧１．５ｋｇ／ｃｍ２
で濾過し、重合溶液（重合体濃度約２５重量％、溶液粘
度５０００ｃｐ（３０℃））を得た。EXAMPLES Examples of the present invention will be described below. Reference Example 1 As an organic solvent, N-methyl-2-pyrrolidone 63L,
Azeotropic dehydration toluene 4 L, 4,4′-dichlorodiphenyl sulfone 17.6 kg, hydroquinone 3.3 kg,
Using 4,4′-biphenol 5.6 kg and potassium carbonate 9.1 kg under nitrogen atmosphere, temperature about 180 ° C.,
The mixture was stirred for 6 hours to obtain a polymerization solution. After completion of the reaction, a nitrogen pressure of 1.5 kg / cm 2 was used to separate the inorganic matter from the polymerization solution.
To obtain a polymerization solution (polymer concentration: about 25% by weight, solution viscosity: 5000 cp (30 ° C.)).
【００１４】実施例１ 備えた二重管式連続攪拌槽（特殊機化工業株式会社製パ
イプラインホモミキサーに内管および外管を有した二重
管を接続）に、内管には参考例１で得た重合溶液を温度
１３０℃、供給量０．４ｋｇ／ｍｉｎを、及び外管には
貧溶媒として水を温度２５℃、供給量０．８ｋｇ／ｍｉ
ｎを各々連続的に供給し、析出した重合体を回転速度５
０００ｒｐｍの攪拌機で粉砕して粉体状にしながら、二
重管式連続攪拌槽の排出口より有機溶媒及び貧溶媒を含
むスラリー液を連続的に回収した。スラリー液から遠心
分離機で濾過、分離した重合体１ｋｇを２５℃の水６Ｌ
で洗浄後、９０℃で乾燥し、ポリアリールエーテルの粉
体を得た。得られたポリアリールエーテルの粉体中には
Ｎ−メチル−２−ピロリドンが０．９重量％含まれてい
た。Example 1 A double tube type continuous stirring tank (a pipe line homomixer manufactured by Tokushu Kika Kogyo Co., Ltd. was connected with a double tube having an inner tube and an outer tube), and a reference example was used for the inner tube. The temperature of the polymerization solution obtained in 1 was 130 ° C., the supply rate was 0.4 kg / min, and water was used as a poor solvent for the outer tube at a temperature of 25 ° C. and the supply rate was 0.8 kg / mi.
n was continuously supplied, and the precipitated polymer was rotated at a rotation speed of 5
A slurry liquid containing an organic solvent and a poor solvent was continuously recovered from the outlet of the double-tube type continuous stirring tank while pulverizing with a stirrer at 000 rpm to form a powder. 1 kg of the polymer separated and separated from the slurry liquid by a centrifuge was added with 6 L of water at 25 ° C.
After washing with and dried at 90 ° C., a powder of polyaryl ether was obtained. The obtained powder of polyaryl ether contained 0.9% by weight of N-methyl-2-pyrrolidone.
【００１５】実施例２ 実施例１と同じ二重管式連続攪拌槽に、内管には参考例
１で得た重合溶液を温度８０℃、供給量２．８ｋｇ／ｍ
ｉｎを、及び外管には貧溶媒として水を温度２５℃、供
給量０．８ｋｇ／ｍｉｎを各々連続的に供給し、析出し
た重合体を回転速度７０００ｒｐｍの攪拌機で粉砕して
粉体状にしながら、二重管式連続攪拌槽の排出口より有
機溶媒及び貧溶媒を含むスラリー液を連続的に回収し
た。スラリー液から遠心分離機で濾過、分離した重合体
１ｋｇを２５℃の水６Ｌで洗浄後、９０℃で乾燥し、ポ
リアリールエーテルの粉体を得た。得られたポリアリー
ルエーテルの粉体中にはＮ−メチル−２−ピロリドンが
０．８重量％含まれていた。Example 2 In the same double-tube type continuous stirring tank as in Example 1, the polymerization solution obtained in Reference Example 1 was supplied to the inner tube at a temperature of 80 ° C. and a supply rate of 2.8 kg / m 2.
in and water as a poor solvent in the outer tube at a temperature of 25 ° C. and a supply rate of 0.8 kg / min, respectively, were continuously supplied, and the precipitated polymer was pulverized with a stirrer at a rotation speed of 7,000 rpm to obtain a powder. Meanwhile, the slurry liquid containing the organic solvent and the poor solvent was continuously collected from the outlet of the double-tube continuous stirring tank. 1 kg of the polymer separated from the slurry liquid by filtration with a centrifuge was washed with 6 L of water at 25 ° C. and then dried at 90 ° C. to obtain a polyaryl ether powder. The obtained polyaryl ether powder contained 0.8% by weight of N-methyl-2-pyrrolidone.
【００１６】実施例３ 実施例１と同じ二重管式連続攪拌槽に、内管には参考例
１で得た重合溶液を温度８０℃、供給量０．４ｋｇ／ｍ
ｉｎを、及び外管には貧溶媒としてエタノールを温度５
℃、供給量１．６ｋｇ／ｍｉｎを各々連続的に供給し、
析出した重合体を回転速度１２００ｒｐｍの攪拌機で粉
砕して粉体状にしながら、二重管式連続攪拌槽の排出口
より有機溶媒及び貧溶媒を含むスラリー液を連続的に回
収した。スラリー液から遠心分離機で濾過、分離した重
合体１ｋｇを２５℃のエタノール６Ｌで洗浄後、９０℃
で乾燥し、ポリアリールエーテルの粉体を得た。得られ
たポリアリールエーテルの粉体中にはＮ−メチル−２−
ピロリドンが０．５重量％含まれていた。Example 3 In the same double-tube type continuous stirring tank as in Example 1, the inner tube was charged with the polymerization solution obtained in Reference Example 1 at a temperature of 80 ° C. and a supply rate of 0.4 kg / m 2.
in and ethanol in the outer tube as a poor solvent at a temperature of 5
At a temperature of 1.6 ° C and a supply rate of 1.6 kg / min.
The precipitated polymer was pulverized with a stirrer at a rotation speed of 1200 rpm to form a powder, and a slurry liquid containing an organic solvent and a poor solvent was continuously collected from an outlet of a double-tube type continuous stirring tank. 1 kg of the polymer separated and filtered from the slurry liquid by a centrifuge was washed with 6 L of ethanol at 25 ° C. and then at 90 ° C.
It was dried in a vacuum to obtain a powder of polyaryl ether. The obtained polyaryl ether powder contained N-methyl-2-
It contained 0.5% by weight of pyrrolidone.
【００１７】実施例４ 実施例１と同じ二重管式連続攪拌槽に、内管には参考例
１で得た重合溶液を温度８０℃、供給量０．４ｋｇ／ｍ
ｉｎを、及び外管には貧溶媒として３０重量％エタノー
ル水溶液を温度１０℃、供給量１．６ｋｇ／ｍｉｎを各
々連続的に供給し、析出した重合体を回転速度１２００
ｒｐｍの攪拌機で粉砕して粉体状にしながら、二重管式
連続攪拌槽の排出口より有機溶媒及び貧溶媒を含むスラ
リー液を連続的に回収した。スラリー液から遠心分離機
で濾過、分離した重合体１ｋｇを２５℃の水６Ｌで洗浄
後、９０℃で乾燥し、ポリアリールエーテルの粉体を得
た。得られたポリアリールエーテルの粉体中にはＮ−メ
チル−２−ピロリドンが０．７重量％含まれていた。Example 4 In the same double-tube type continuous stirring tank as in Example 1, the inner tube was charged with the polymerization solution obtained in Reference Example 1 at a temperature of 80 ° C. and a supply rate of 0.4 kg / m 2.
in, and a 30 wt% ethanol aqueous solution as a poor solvent to the outer tube at a temperature of 10 ° C. and a supply rate of 1.6 kg / min, respectively, were continuously supplied, and the precipitated polymer was rotated at a rotation speed of 1200.
A slurry liquid containing an organic solvent and a poor solvent was continuously collected from the outlet of the double-tube type continuous stirring tank while pulverizing with an rpm stirrer to form a powder. 1 kg of the polymer separated from the slurry liquid by filtration with a centrifuge was washed with 6 L of water at 25 ° C. and then dried at 90 ° C. to obtain a polyaryl ether powder. The obtained powder of polyaryl ether contained 0.7% by weight of N-methyl-2-pyrrolidone.
【００１８】比較例１ 参考例１で得た温度８０℃の重合溶液２ｋｇを、貧溶媒
の２５℃の水１４ｋｇに注ぎ、５０００ｒｐｍで攪拌し
ながら重合体を析出させ、遠心分離機で濾過、分離した
後、重合体を得た。この重合体０．１ｋｇを２５℃の水
０．６Ｌで洗浄後、９０℃で乾燥し、ポリアリールエー
テルの粉体を得た。得られたポリアリールエーテルの粉
体中にはＮ−メチル−２−ピロリドンが２．５重量％含
まれていた。Comparative Example 1 2 kg of the polymerization solution at a temperature of 80 ° C. obtained in Reference Example 1 was poured into 14 kg of water at 25 ° C. as a poor solvent to precipitate the polymer while stirring at 5000 rpm, which was then filtered and separated by a centrifuge. After that, a polymer was obtained. After washing 0.1 kg of this polymer with 0.6 L of water at 25 ° C., it was dried at 90 ° C. to obtain a polyaryl ether powder. The obtained powder of polyaryl ether contained 2.5% by weight of N-methyl-2-pyrrolidone.
【００１９】比較例２ 参考例１で得た温度８０℃の重合溶液２ｋｇを、貧溶媒
の１０℃のエタノール１４ｋｇに注ぎ、５０００ｒｐｍ
で攪拌しながら重合体を析出させ、遠心分離機で濾過、
分離した後、重合体を得た。この重合体０．１ｋｇを２
５℃のエタノール０．６Ｌで洗浄後、９０℃で乾燥し、
ポリアリールエーテルの粉体を得た。得られたポリアリ
ールエーテルの粉体中にはＮ−メチル−２−ピロリドン
が２．２重量％含まれていた。Comparative Example 2 2 kg of the polymerization solution having a temperature of 80 ° C. obtained in Reference Example 1 was poured into 14 kg of a poor solvent, 10 ° C. ethanol, and 5000 rpm.
Precipitate the polymer while stirring with, and filter with a centrifuge,
After separation, a polymer was obtained. 0.1 kg of this polymer is added to 2
After washing with 0.6 L of ethanol at 5 ° C, drying at 90 ° C,
A powder of polyaryl ether was obtained. The obtained powder of polyaryl ether contained 2.2% by weight of N-methyl-2-pyrrolidone.
【００２０】参考例２ 有機溶媒として、Ｎ−メチル−２−ピロリドン６８Ｌ、
共沸脱水用トルエン４Ｌ、４，４’−ジクロロジフェニ
ルスルホン１４．１ｋｇ、ハイドロキノン２．６ｋｇ、
４，４’−ビフェノール４．５ｋｇ、及び炭酸カリウム
７．３ｋｇを使用して窒素雰囲気下、温度約１８０℃、
１０時間攪拌し、重合溶液を得た。反応終了後、無機物
を重合溶液から分離するために窒素圧１．５ｋｇ／ｃｍ
２で濾過し、重合溶液（重合体濃度約２０重量％、溶液
粘度２５００ｃｐ（３０℃））を得た。Reference Example 2 N-methyl-2-pyrrolidone 68L as an organic solvent,
Azeotropic dehydration toluene 4 L, 4,4′-dichlorodiphenyl sulfone 14.1 kg, hydroquinone 2.6 kg,
Using 4,4'-biphenol (4.5 kg) and potassium carbonate (7.3 kg) in a nitrogen atmosphere at a temperature of about 180 ° C.
The mixture was stirred for 10 hours to obtain a polymerization solution. After completion of the reaction, nitrogen pressure of 1.5 kg / cm to separate inorganic substances from the polymerization solution.
The mixture was filtered through 2 to obtain a polymerization solution (polymer concentration: about 20% by weight, solution viscosity: 2500 cp (30 ° C.)).
【００２１】実施例５ 実施例１と同じ二重管式連続攪拌槽に、内管には参考例
２で得た重合溶液を温度８０℃、供給量０．４ｋｇ／ｍ
ｉｎを、及び外管には貧溶媒として水を温度３０℃、供
給量２．８ｋｇ／ｍｉｎを各々連続的に供給し、析出し
た重合体を回転速度７０００ｒｐｍの攪拌機で粉砕して
粉体状にしながら、二重管式連続攪拌槽の排出口より有
機溶媒及び貧溶媒を含むスラリー液を連続的に回収し
た。スラリー液から遠心分離機で濾過、分離した重合体
１ｋｇを２５℃の水 ６Ｌ で洗浄後、９０℃で乾燥
し、ポリアリールエーテルの粉体を得た。得られたポリ
アリールエーテルの粉体中にはＮ−メチル−２−ピロリ
ドンが０．６重量％含まれていた。Example 5 In the same double-tube type continuous stirring tank as in Example 1, the inner tube was charged with the polymerization solution obtained in Reference Example 2 at a temperature of 80 ° C. and a supply rate of 0.4 kg / m 2.
in and water to the outer tube as a poor solvent at a temperature of 30 ° C. and a supply rate of 2.8 kg / min, respectively, were continuously supplied, and the precipitated polymer was pulverized with a stirrer at a rotation speed of 7,000 rpm to obtain powder. Meanwhile, the slurry liquid containing the organic solvent and the poor solvent was continuously collected from the outlet of the double-tube continuous stirring tank. 1 kg of the polymer separated from the slurry liquid by filtration with a centrifuge was washed with 6 L of water at 25 ° C. and dried at 90 ° C. to obtain a polyaryl ether powder. The obtained powder of polyaryl ether contained 0.6% by weight of N-methyl-2-pyrrolidone.
【００２２】比較例３ 参考例２で得た温度８０℃の重合溶液２ｋｇを、貧溶媒
の５０℃の水１４ｋｇに注ぎ、５０００ｒｐｍで攪拌し
ながら重合体を析出させ、遠心分離機で濾過、分離した
後、重合体を得た。この重合体０．１ｋｇを２５℃の水
０．６Ｌで洗浄後、９０℃で乾燥し、ポリアリールエー
テルの粉体を得た。得られたポリアリールエーテルの粉
体中にはＮ−メチル−２−ピロリドンが２．２重量％含
まれていた。Comparative Example 3 2 kg of the polymerization solution at a temperature of 80 ° C. obtained in Reference Example 2 was poured into 14 kg of water of a poor solvent at 50 ° C. to precipitate a polymer while stirring at 5000 rpm, and the polymer was filtered and separated by a centrifuge. After that, a polymer was obtained. After washing 0.1 kg of this polymer with 0.6 L of water at 25 ° C., it was dried at 90 ° C. to obtain a polyaryl ether powder. The obtained powder of polyaryl ether contained 2.2% by weight of N-methyl-2-pyrrolidone.
【００２３】参考例３ 有機溶媒として、Ｎ−メチル−２−ピロリドン６５Ｌ、
共沸脱水用トルエン４Ｌ、４，４’−ジクロロジフェニ
ルスルホン１９．０ｋｇ、ビスフェノール−Ａ１４．８
ｋｇ、及び炭酸カリウム９．９ｋｇを使用して窒素雰囲
気下、温度約１８０℃、８時間攪拌し、重合溶液を得
た。反応終了後、無機物を重合溶液から分離するために
窒素圧１．５ｋｇ／ｃｍ２で濾過し、重合溶液（重合体
濃度約３０重量％、溶液粘度４０００ｃｐ（３０℃））
を得た。Reference Example 3 As an organic solvent, 65 L of N-methyl-2-pyrrolidone,
Azeotropic dehydration toluene 4 L, 4,4'-dichlorodiphenyl sulfone 19.0 kg, bisphenol-A 14.8
kg and 9.9 kg of potassium carbonate were stirred under a nitrogen atmosphere at a temperature of about 180 ° C. for 8 hours to obtain a polymerization solution. After the reaction was completed, the inorganic solution was filtered at a nitrogen pressure of 1.5 kg / cm 2 to separate it from the polymerization solution, and the polymerization solution (polymer concentration: about 30% by weight, solution viscosity: 4000 cp (30 ° C.))
Got
【００２４】実施例６ 実施例１と同じ二重管式連続攪拌槽に、内管には参考例
３で得た重合溶液を温度１００℃、供給量０．４ｋｇ／
ｍｉｎを、及び外管には貧溶媒として水を温度３０℃、
供給量１．６ｋｇ／ｍｉｎを各々連続的に供給し、析出
した重合体を回転速度３０００ｒｐｍの攪拌機で粉砕し
て粉体状にしながら、二重管式連続攪拌槽の排出口より
有機溶媒及び貧溶媒を含むスラリー液を連続的に回収し
た。スラリー液から遠心分離機で濾過、分離した重合体
１ｋｇを２５℃の水６Ｌで洗浄後、９０℃で乾燥し、ポ
リアリールエーテルの粉体を得た。得られたポリアリー
ルエーテルの粉体中にはＮ−メチル−２−ピロリドンが
０．９重量％含まれていた。Example 6 In the same double-tube type continuous stirring tank as in Example 1, the inner tube was charged with the polymerization solution obtained in Reference Example 3 at a temperature of 100 ° C. and a supply rate of 0.4 kg /
min, and water as a poor solvent in the outer tube at a temperature of 30 ° C.,
A supply rate of 1.6 kg / min was continuously supplied, and the precipitated polymer was pulverized with a stirrer at a rotation speed of 3000 rpm to form a powder, while the organic solvent and the poor solvent were discharged from the discharge port of the double-tube continuous stirring tank. The slurry liquid containing the solvent was continuously collected. 1 kg of the polymer separated from the slurry liquid by filtration with a centrifuge was washed with 6 L of water at 25 ° C. and then dried at 90 ° C. to obtain a polyaryl ether powder. The obtained powder of polyaryl ether contained 0.9% by weight of N-methyl-2-pyrrolidone.
【００２５】比較例４ 参考例３で得た温度１００℃の重合溶液２ｋｇを、貧溶
媒の２５℃の水１４ｋｇに注ぎ、５０００ｒｐｍで攪拌
しながら重合体を析出させ、遠心分離機で濾過、分離し
た後、重合体を得た。この重合体０．１ｋｇを２５℃の
水０．６Ｌで洗浄後、９０℃で乾燥し、ポリアリールエ
ーテルの粉体を得た。得られたポリアリールエーテルの
粉体中にはＮ−メチル−２−ピロリドンが２．４重量％
含まれていた。Comparative Example 4 2 kg of the polymerization solution at 100 ° C. obtained in Reference Example 3 was poured into 14 kg of water at 25 ° C. as a poor solvent to precipitate the polymer while stirring at 5000 rpm, and the mixture was filtered and separated with a centrifuge. After that, a polymer was obtained. After washing 0.1 kg of this polymer with 0.6 L of water at 25 ° C., it was dried at 90 ° C. to obtain a polyaryl ether powder. The obtained polyaryl ether powder contained 2.4% by weight of N-methyl-2-pyrrolidone.
Was included.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 木村 修 千葉県市原市五井南海岸８番の１ 宇部興 産株式会社千葉研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Osamu Kimura 8-1 Goi Minamikaigan, Ichihara City, Chiba Ube Industries Ltd. Chiba Research Institute
Claims (1)
式連続攪拌槽を用いて、二重管の一方にポリアリールエ
ーテルの有機溶媒溶液を、他方に貧溶媒を連続的に流し
て混合すると同時に析出したポリアリールエーテルを攪
拌機で粉砕することを特徴とするポリアリールエーテル
の回収方法。1. A double-tube type continuous stirring tank equipped with a stirrer near the discharge port of the inner tube is used to continuously supply an organic solvent solution of polyaryl ether to one of the double tubes and a poor solvent to the other. A method for recovering a polyaryl ether, which comprises pulverizing the precipitated polyaryl ether with a stirrer while flowing and mixing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31125291A JPH0578472A (en) | 1991-09-18 | 1991-09-18 | Recovery of polyaryl ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31125291A JPH0578472A (en) | 1991-09-18 | 1991-09-18 | Recovery of polyaryl ether |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0578472A true JPH0578472A (en) | 1993-03-30 |
Family
ID=18014918
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31125291A Pending JPH0578472A (en) | 1991-09-18 | 1991-09-18 | Recovery of polyaryl ether |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0578472A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0724736A (en) * | 1993-07-12 | 1995-01-27 | Nippon Steel Corp | Nozzle assembly for noise eliminated water jet |
| WO2001083586A1 (en) * | 2000-04-28 | 2001-11-08 | Mitsubishi Gas Chemical Company, Inc. | Method of precipitating polyphenylene ether |
| EP1471091A1 (en) * | 2002-02-01 | 2004-10-27 | Asahi Kasei Chemicals Corporation | Method for precipitation of polyphenylene ether |
| JP2008527124A (en) * | 2005-01-14 | 2008-07-24 | エボニック デグサ ゲーエムベーハー | Process for producing polyarylene ether ketone |
-
1991
- 1991-09-18 JP JP31125291A patent/JPH0578472A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0724736A (en) * | 1993-07-12 | 1995-01-27 | Nippon Steel Corp | Nozzle assembly for noise eliminated water jet |
| WO2001083586A1 (en) * | 2000-04-28 | 2001-11-08 | Mitsubishi Gas Chemical Company, Inc. | Method of precipitating polyphenylene ether |
| US6627727B1 (en) | 2000-04-28 | 2003-09-30 | Mitsubishi Gas Chemical Co | Method of precipitating polyphenylene ether |
| EP1471091A1 (en) * | 2002-02-01 | 2004-10-27 | Asahi Kasei Chemicals Corporation | Method for precipitation of polyphenylene ether |
| EP1471091A4 (en) * | 2002-02-01 | 2005-10-19 | Asahi Kasei Chemicals Corp | Method for precipitation of polyphenylene ether |
| JP2008527124A (en) * | 2005-01-14 | 2008-07-24 | エボニック デグサ ゲーエムベーハー | Process for producing polyarylene ether ketone |
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