JP2004182910A - Production method for polyarylene sulfide - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for efficiently producing a linear high molecular weight PAS in a short period of time. <P>SOLUTION: The production method for the polyarylene sulfide involves at least the following processes 1 and 2. The process 1 is a process for preparing a sulfiding agent containing 0.05-0.6 mol of water per one mol of a sulfur component by dehydrating an alkali metal sulfide containing at least one mol of water per one mol of the sulfur component in the presence of an organic polar solvent of 0.05-0.6 mol per one mol of the sulfur component of the alkali metal sulfide. The process 2 is a process for polymerizing the sulfiding agent prepared by the process 1 with a dihalogenated aromatic compound by bringing them into contact with each other in the presence of at least one compound selected from an organic metal carboxylate, an alicyclic amine compound, an N-heteroaromatic compound and an organic sulfoxide compound, and water of 0.05-0.6 mol per one mol of the sulfur component of the sulfiding agent. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【００１６】
（Ｒ１，Ｒ２は水素、アルキル基、アルコキシ基、ハロゲン基から選ばれた置換基であり、Ｒ１とＲ２は同一でも異なっていてもよい）
この繰り返し単位を主要構成単位とする限り、下記の式（Ｌ）〜式（Ｎ）などで表される少量の分岐単位または架橋単位を含むことができる。これら分岐単位または架橋単位の共重合量は、−（Ａｒ−Ｓ）−の単位１モルに対して０〜１モル％の範囲であることが好ましい。
【００１７】
【化２】

【００１８】
また、本発明におけるＰＡＳは上記繰り返し単位を含むランダム共重合体、ブロック共重合体及びそれらの混合物のいずれかであってもよい。
【００１９】
更に、各種ＰＡＳはその分子量に特に制限はないが、通常、溶融粘度が５〜５，０００Ｐａ・ｓ（３００℃、剪断速度１０００／秒）の範囲が好ましい範囲として例示できる。
【００２０】
これらの代表的なものとして、ポリフェニレンスルフィド、ポリフェニレンスルフィドスルホン、ポリフェニレンスルフィドケトン、これらのランダム共重合体、ブロック共重合体及びそれらの混合物などが挙げられる。特に好ましいＰＡＳとしては、ポリマーの主要構成単位としてｐ−フェニレンスルフィド単位
【００２１】
【化３】

【００２２】
を８０モル％以上、特に９０モル％以上含有するポリフェニレンスルフィド（以下、ＰＰＳと略すこともある）の他、ポリフェニレンスルフィドスルホン、ポリフェニレンスルフィドケトンが挙げられる。
【００２３】
（２）重合溶媒
本発明では重合溶媒として有機極性溶媒を用いることが必要であり、好ましくは有機アミド溶媒を用いることが望ましい。具体例としては、Ｎ−メチル−２−ピロリドン、Ｎ−エチル−２−ピロリドンなどのＮ−アルキルピロリドン類、Ｎ−メチル−ε−カプロラクタムなどのカプロラクタム類、１，３−ジメチル−２−イミダゾリジノン、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミド、ヘキサメチルリン酸トリアミドなどに代表されるアプロチック有機溶媒、及びこれらの混合物などが、反応の安定性が高いために好ましく使用される。これらのなかでもＮ−メチル−２−ピロリドン（以下、ＮＭＰと略記することもある）が好ましく用いられる。
【００２４】
本発明において後述する工程１において用いる有機極性溶媒の使用量は、後述するアルカリ金属硫化物のイオウ成分１モルあたり０．０５〜０．６モルである必要があり、０．１〜０．５モルが好ましく、０．１５〜０．４５モルがより好ましい。少なすぎても、多すぎても後述する工程２以降での重合反応が進行しにくくなる傾向にある。
【００２５】
本発明において後述する工程２以降で重合溶媒として用いる有機極性溶媒の使用量に特に制限はないが、スルフィド化剤のイオウ成分１モル当たり０．２〜１５モルの範囲が例示できる。ただし、本発明の方法においては従来の技術で挙げたような方法と比べてより少ない重合溶媒の使用量でも射出成形及び押出成形などの樹脂の商業的利用の各種用途に適したＰＡＳを製造することが可能なため、重合溶媒として用いる有機極性溶媒の使用量は、好ましくはスルフィド化剤のイオウ成分１モル当たり１．０〜４．０モル、より好ましくは１．０〜３．５モル、更に好ましくは１．５〜２．５モルが好ましい範囲として例示できる。一般に重合溶媒の使用量が少ない方が単位体積当たりのポリマー量が多くなるので経済的に有利であるが、少なすぎると好ましくない反応が起こりやすくなり、多すぎると重合度が上がりにくくなる傾向にあり、また経済的にも不利となることがある。また、多すぎても少なすぎても反応に要する時間が長くなる傾向にあり、経済的に不利となる場合がある。ここで、反応系の有機極性溶媒量は、反応系内に導入した有機極性溶媒から、反応系外に除去された有機極性溶媒を差し引いた量である。
【００２６】
（３）ジハロゲン化芳香族化合物
本発明で使用されるジハロゲン化芳香族化合物としては、ｐ−ジクロロベンゼン、ｏ−ジクロロベンゼン、ｍ−ジクロロベンゼン、ｐ−ジブロモベンゼンなどのジハロゲン化ベンゼン、及び１−メトキシ−２，５−ジクロロベンゼン、３，５−ジクロロ安息香酸などのハロゲン以外の置換基をも含むジハロゲン化芳香族化合物などを挙げることができる。なかでも、ｐ−ジクロロベンゼンに代表されるｐ−ジハロゲン化ベンゼンを主成分にするジハロゲン化芳香族化合物が好ましい。特に好ましくは、ｐ−ジクロロベンゼンを８０〜１００モル％含むものであり、さらに好ましくは９０〜１００モル％含むものである。また、ＰＡＳ共重合体を製造するために異なる２種以上のジハロゲン化芳香族化合物を組み合わせて用いることも可能である。
【００２７】
ジハロゲン化芳香族化合物の使用量は、加工に適した粘度のポリアリーレンスルフィドを得る点から、スルフィド化剤のイオウ成分１モル当たり０．９〜２．０モルであることが好ましく、より好ましくは０．９５〜１．５モル、更に１．００５〜１．２モルの範囲が好ましい。
【００２８】
（４）スルフィド化剤・アルカリ金属硫化物
本発明ではスルフィド化剤としてイオウ成分１モル当たり１モル以上の水を含むアルカリ金属硫化物から水を除去することで得られる、イオウ成分１モル当たり０．０５〜０．６モルの水を含むスルフィド化剤を用いる。ここでスルフィド化剤の含む水の量はスルフィド化剤のイオウ成分１モル当たり０．１〜０．５モルが好ましく、０．１５〜０．４５モルがより好ましい。このようなイオウ成分１モル当たり１モル以上の水を含むアルカリ金属硫化物から前述の含水量のスルフィド化剤を調製する方法には、後述する脱水工程が採用される。
【００２９】
用いるアルカリ金属硫化物の具体例としては、例えば硫化リチウム、硫化ナトリウム、硫化カリウム、硫化ルビジウム、硫化セシウム及びこれら２種以上の混合物を好ましいものとして挙げることができ、なかでも硫化ナトリウムが好ましく用いられる。これらのアルカリ金属硫化物は、水和物または水性混合物として用いることができる。なお、水性混合物とは水溶液、もしくは水溶液と固体成分の混合物、もしくは水と固体成分の混合物のことをさす。ここで、アルカリ金属硫化物として水和物または水性混合物はイオウ成分１モル当たりの水の含有量が１モル以上であることが必要であり、好ましくは４モル以上、より好ましくは４モル以上３０モル以下のものを用いる。少なすぎると、アルカリ金属硫化物のハンドリング性が悪くなり、更には不純物を含みやすくなる傾向に有り、多すぎると脱水工程で除去すべき水の量が多量になり脱水に長時間が必要になる。
【００３０】
また、アルカリ金属水硫化物とアルカリ金属水酸化物及び／またはアルカリ金属水酸化物と硫化水素から調製されるアルカリ金属硫化物も前述のアルカリ金属硫化物と同じと見なして用いることができる。アルカリ金属水硫化物の具体例としては、例えば水硫化ナトリウム、水硫化カリウム、水硫化リチウム、水硫化ルビジウム、水硫化セシウム及びこれら２種以上の混合物を好ましいものとして挙げることができ、なかでも水硫化ナトリウムが好ましく用いられる。これらのアルカリ金属水硫化物は、水和物または水性混合物として、あるいは無水物の形で用いることができる。また、硫化水素は気体状、液体状、水溶液状のいずれの形態で用いても差し障り無い。
【００３１】
アルカリ金属水酸化物の具体例としては、例えば、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、水酸化ルビジウム、水酸化セシウム及びこれら２種以上の混合物を好ましいものとして挙げることができ、なかでも水酸化ナトリウムが好ましく用いられる。これらのアルカリ金属水酸化物は、水和物または水性混合物として、あるいは無水物の形で用いることができる。アルカリ金属水硫化物を用いる場合のアルカリ金属水酸化物の使用量はアルカリ金属水硫化物１モルに対し１．０〜１．２０モル、好ましくは１．００５〜１．１５モル、更に好ましくは１．０２〜１．１００モルの範囲が例示できる。硫化水素を用いる場合のアルカリ金属水酸化物の使用量は硫化水素１モルに対し２．０〜２．４０モル、好ましくは２．０１〜２．３０モル、更に好ましくは２．０４〜２．２０モルの範囲が例示できる。
【００３２】
本発明において、重合反応時の反応系内に存在するスルフィド化剤（以下、仕込みスルフィド化剤という場合もある）の量は、脱水操作などにより重合反応開始前にスルフィド化剤の一部損失が生じる場合には、実際の仕込み量から当該損失分を差し引いた残存量を意味するものとする。
【００３３】
（５）触媒化合物
本発明では少なくとも後述する工程２において有機カルボン酸金属塩、脂肪族環状アミン化合物、Ｎ−ヘテロ芳香族化合物、有機スルホキシド化合物から選ばれる少なくとも一種の化合物（以下、触媒化合物と称する場合もある）を、有機極性溶媒中でスルフィド化剤とジハロゲン化芳香族化合物が存在する反応系内に共存させることが必要である。このことは後述の工程２における反応速度を向上するため、また工程２の反応を極少量の重合溶媒の使用でも進行させるために重要である。ここで、反応速度の向上は重合反応に必要なプロセス時間を短時間化し、少量の重合溶媒使用は反応器の単位体積当たりのポリマー生産量を増大するため、経済的にポリマーを生産するために重要なことである。上記触媒化合物の中でも有機カルボン酸金属塩を用いることは、後述する重合助剤をかねることができる点で好ましい。
【００３４】
更に工程２では後述するようにスルフィド化剤のイオウ成分１モルあたり０．０５〜０．６モルの水の存在下で重合を行うことが必要であり、このことは触媒化合物の反応速度向上作用を発現させる上で重要である。
【００３５】
ここで触媒化合物が反応速度を向上させる理由は明瞭ではないが、触媒化合物が反応系内のスルフィド化剤と何らかの相互作用をすることにより、スルフィド化剤の反応系への溶解性を向上し、スルフィド化剤とジハロゲン化芳香族化合物との接触確率が向上することにより反応速度が向上すると推測している。
【００３６】
前記有機カルボン酸金属塩は、一般式Ｒ（ＣＯＯＭ）ｎ （式中、Ｒは、炭素数１〜２０を有するアルキル基、シクロアルキル基、アリール基、アルキルアリール基、アリールアルキル基、アミノアルキル基、炭素数２〜２０を有するＮ−アルキルアミノアルキル基及びＮ−フェニルアミノアルキル基であり、これらの中でもアルキル基、アリール基及びＮ−アルキルアミノアルキル基が好ましい。Ｍは、リチウム、ナトリウム、カリウム、ルビジウム及びセシウムから選ばれるアルカリ金属、もしくはマグネシウム、カルシウム、ストロンチウム及びバリウムから選ばれるアルカリ土類金属である。ｎは１〜３の整数である。）で表される化合物が好ましい例として挙げられる。有機カルボン酸金属塩の具体例としては、例えば、酢酸リチウム、酢酸ナトリウム、酢酸カリウム、酢酸マグネシウム、酢酸カルシウム、プロピオン酸リチウム、プロピオン酸ナトリウム、プロピオン酸カリウム、４−ヒドロキシ酪酸リチウム、４−ヒドロキシ酪酸ナトリウム、Ｎ−メチル−４−アミノ酪酸リチウム、Ｎ−メチル−４−アミノ酪酸ナトリウム、Ｎ−エチル−４−アミノ酪酸リチウム、Ｎ−エチル−４−アミノ酪酸ナトリウム、Ｎ−フェニル−４−アミノ酪酸リチウム、Ｎ−フェニル−４−アミノ酪酸ナトリウム、吉草酸リチウム、安息香酸ナトリウム、フェニル酢酸ナトリウム、ｐ−トルイル酸カリウムから選ばれる一種の化合物及びそれらの混合物などを挙げることができる。有機カルボン酸金属塩は有機酸と、水酸化アルカリ金属、炭酸アルカリ金属塩及び重炭酸アルカリ金属塩よりなる群から選ばれる一種以上の化合物とを、ほぼ等化学当量ずつ添加して反応させることにより形成させてもよい。上記有機カルボン酸金属塩の中で、リチウム塩は反応系への溶解性が高く助剤効果が大きいが高価であり、カリウム、ルビジウム、セシウム及びアルカリ土類金属塩は反応系への溶解性に劣ると推定しており、安価で、重合系への適度な溶解性を有するナトリウム塩が好ましく用いられる。
【００３７】
前記脂肪族環状アミン化合物の具体例としてはピペラジン、ピペリジン、ピロリジン、Ｎ，Ｎ’−ジメチルピペラジン、１，４−ジアザビシクロ［２，２，２］オクタン、１，５−ジアザビシクロ［４，３，０］−ノン−５−エン、１，８−ジアザビシクロ［５，４，０］−７−ウンデセン、１，５−ジアザビシクロ［４，４，０］−５−ノネン、ヘキサメチレンテトラミンから選ばれる一種の化合物及びそれらの混合物などを挙げることができる。
【００３８】
前記Ｎ−ヘテロ芳香族化合物の具体例としてはピリジン、ピリダジン、ピリミジン、ｓｙｍ−トリアジン、ｓｙｍ−テトラジン、キノリン、イソキノリン、キナゾリン、１，５−ナフチリジン、プテリジン、アクリジン、フェナジン、フェナントリジンから選ばれる一種の化合物及びそれらの混合物などを挙げることができる。
【００３９】
前記有機スルホキシド化合物の具体例としてはジメチルスルホキシド及び／またはテトラメチレンスルホキシドを挙げることができる。
【００４０】
以上の触媒化合物の中でも、酢酸ナトリウムは安価で入手も容易であり特に好ましい。
【００４１】
有機カルボン酸金属塩、脂肪族環状アミン化合物、Ｎ−ヘテロ芳香族化合物、有機スルホキシド化合物から選ばれる少なくとも一種の触媒化合物は、水和物または水溶液としても用いることができる。これら触媒化合物の使用量として、反応系内に存在するスルフィド化剤のイオウ成分１モル当たり０．００１〜１．０モル、好ましくは０．０１〜０．７モル、より好ましくは０．０２〜０．６モル、さらに好ましくは０．０５〜０．４５モルを反応系内に存在させると、特に大きな反応促進効果が得られる傾向にある。従って、短時間でＰＡＳを得るために触媒化合物使用量は前記範囲内にすることが望ましい。
【００４２】
（６）重合助剤
本発明法においては、高重合度のＰＡＳをより短時間で得るために重合助剤を用いることも可能である。ここで重合助剤とは得られるＰＡＳの粘度を増大させる作用を有する物質をさす。このような重合助剤の具体例としては、例えば、有機カルボン酸金属塩、水、アルカリ金属塩化物、有機スルホン酸金属塩、硫酸アルカリ金属塩、アルカリ土類金属酸化物、アルカリ金属リン酸塩、アルカリ土類金属リン酸塩などがあげられる。これらは単独で用いても、２種以上を同時に用いても差し障り無い。これらのなかでも有機カルボン酸金属塩および／または水が好ましく用いられる。
【００４３】
有機カルボン酸金属塩は、一般式Ｒ（ＣＯＯＭ）ｎ （式中、Ｒは、炭素数１〜２０を有するアルキル基、シクロアルキル基、アリール基、アルキルアリール基またはアリールアルキル基である。Ｍは、ナトリウム、カリウム、ルビジウム及びセシウムから選ばれるアルカリ金属である。ｎは１〜３の整数である。）で表される化合物である。有機カルボン酸金属塩は、水和物または水溶液としても用いることができる。有機カルボン酸塩の具体例としては、例えば、酢酸リチウム、酢酸ナトリウム、酢酸カリウム、プロピオン酸ナトリウム、安息香酸ナトリウム、フェニル酢酸ナトリウム、ｐ−トルイル酸カリウム、及びそれらの混合物などを挙げることができる。有機カルボン酸金属塩は、有機酸と、水酸化アルカリ金属、炭酸アルカリ金属塩及び重炭酸アルカリ金属塩よりなる群から選ばれる一種以上の化合物とを、ほぼ等化学当量ずつ添加して反応させることにより形成させてもよい。上記有機カルボン酸金属塩の中で、カリウム、ルビジウム及びセシウム塩は反応系への溶解性に劣ると推定しており、安価でかつ反応系への適度な溶解性を有する酢酸ナトリウムが好ましく用いられる。
【００４４】
なお、前述した触媒化合物として有機カルボン酸金属塩を用いた場合、これは触媒化合物としての効果と重合助剤としての効果の両方の効果を発現する場合もある。
【００４５】
これら有機カルボン酸金属塩の使用量は、仕込みスルフィド化剤のイオウ成分１モルに対し、０．０１〜０．７モルの範囲が好ましく、０．０２〜０．６モルの範囲がより好ましく、０．０５〜０．４５モルの範囲がよりいっそう好ましい。上記の範囲未満では、高重合度化効果が不十分になる傾向にあり、上記の範囲を越えて使用しても、それ以上の高重合度化効果は得にくくなる傾向にある。
【００４６】
重合助剤として水を用いる場合、重合系内の水分量が、仕込みスルフィド化剤のイオウ成分１モル当たり０．７〜５．０モルである工程を含むことが好ましい。水分量のより好ましい範囲は、仕込みのスルフィド化剤のイオウ成分１モル当たり０．８〜２．０モルであり、０．８５〜１．８モルが更に好ましい。この場合の水分量が上記の範囲未満であると、十分な高重合度化効果が得られない場合があり、一方上記の範囲を越えると、重合時間が逆に長くなるばかりか、反応器内圧の上昇が大きく、反応器により高い耐圧性能を有した反応器が必要となるため、経済的にも安全性の面でも好ましくない傾向にある。
【００４７】
また、重合助剤として水を用いる場合、有機カルボン酸金属塩を同時に用いることが好ましく、これにより重合助剤としての効果をより高めることができ、より少ない助剤の使用量でも短時間で高重合度ＰＡＳを得ることができる傾向にある。この場合の水分量の好ましい範囲は仕込みのスルフィド化剤のイオウ成分１モル当たり０．８〜２．０モルであり、０．８５〜１．８モルがより好ましい。また、有機カルボン酸金属塩の好ましい使用量の範囲は、仕込みのスルフィド化剤のイオウ成分１モル当たり０．０２〜０．６モルの範囲であり、０．０５〜０．４５モルの範囲がより好ましい。
【００４８】
（７）分子量調節剤・分岐・架橋剤
本発明においては、生成ＰＡＳの末端を形成させるか、あるいは重合反応や分子量を調節するなどのために、モノハロゲン化合物などの分子量調節剤（必ずしも芳香族化合物でなくともよい）を上記ジハロゲン化芳香族化合物と併用することができる。また、分岐または架橋重合体を形成させるために、トリハロゲン化以上のポリハロゲン化合物（必ずしも芳香族化合物でなくともよい）、活性水素含有ハロゲン化芳香族化合物及びハロゲン化芳香族ニトロ化合物などの分岐・架橋剤を併用することも可能である。ポリハロゲン化合物としては通常に用いられる化合物を用いることができるが、中でもポリハロゲン化芳香族化合物が好ましく、具体例としては、１，３，５−トリクロロベンゼン、１，２，４−トリクロロベンゼン、１，２，４，５−テトラクロロベンゼン、ヘキサクロロベンゼン、１，４，６−トリクロロナフタレン等を挙げることができ、中でも１，３，５−トリクロロベンゼン、１，２，４−トリクロロベンゼンが好ましい。前記、活性水素含有ハロゲン化芳香族化合物としては、例えばアミノ基、メルカプト基及びヒドロキシル基などの官能基を有するハロゲン化芳香族化合物を挙げることができる。具体例としては２，５−ジクロロアニリン、２，４−ジクロロアニリン、２，３−ジクロロアニリン、２，４，６−トリクロロアニリン、２，２’−ジアミノ−４，４’−ジクロロジフェニルエーテル、２，４’−ジアミノ−２’，４−ジクロロジフェニルエーテルなどを挙げることができる。前記、ハロゲン化芳香族ニトロ化合物としては、例えば２，４−ジニトロクロロベンゼン、２，５−ジクロロニトロベンゼン、２−ニトロ−４，４’−ジクロロジフェニルエーテル、３，３’−ジニトロ−４，４’−ジクロロジフェニルスルホン、２，５−ジクロロ−２−ニトロピリジン、２−クロロ−３，５−ジニトロピリジンなどを挙げることができる。
【００４９】
（８）重合安定剤
本発明においては、重合反応系を安定化し、副反応を防止するために、重合安定剤を用いることもできる。重合安定剤は、重合反応系の安定化に寄与し、望ましくない副反応を抑制する。副反応の一つの目安としては、チオフェノールの生成が挙げられ、重合安定剤の添加によりチオフェノールの生成を抑えることができる。重合安定剤の具体例としては、アルカリ金属水酸化物、アルカリ金属炭酸塩、アルカリ土類金属水酸化物、及びアルカリ土類金属炭酸塩などの化合物が挙げられる。そのなかでも、水酸化ナトリウム、水酸化カリウム、及び水酸化リチウムなどのアルカリ金属水酸化物が好ましい。前述した有機カルボン酸金属塩も重合安定剤として作用するので、本発明で使用する重合安定剤の一つに入る。
【００５０】
これら重合安定剤は、それぞれ単独で、あるいは２種以上を組み合わせて用いることができる。重合安定剤は、仕込みスルフィド化剤のイオウ成分１モルに対して、通常０．０１〜０．２モル、好ましくは０．０３〜０．１モルの割合で使用することが望ましい。この割合が少ないと安定化効果が不十分になる場合があり、逆に多すぎても経済的に不利益であったり、ポリマー収率が低下する傾向にある。なお、反応時にアルカリ金属硫化物の一部が分解して、硫化水素が発生する場合には、その結果生成したアルカリ金属水酸化物も重合安定剤となり得る。
【００５１】
（９）重合工程
本発明で製造するポリアリーレンスルフィドは、有機極性溶媒中でスルフィド化剤とジハロゲン化芳香族化合物を接触させて重合させる際に、少なくとも以下の工程１及び２を含むことを特徴として得られるものである。
工程１；イオウ成分１モル当たり１モル以上の水を含むアルカリ金属硫化物をアルカリ金属硫化物のイオウ成分１モル当たり０．０５〜０．６モルの有機極性溶媒存在下で脱水して、イオウ成分１モル当たり０．０５〜０．６モルの水を含むスルフィド化剤を調製する工程
工程２；工程１で調製したスルフィド化剤とジハロゲン化芳香族化合物を、有機カルボン酸金属塩、脂肪族環状アミン化合物、Ｎ−ヘテロ芳香族化合物、有機スルホキシド化合物から選ばれる少なくとも一種の化合物及びスルフィド化剤のイオウ成分１モル当たり０．０５〜０．６モルの水の存在下で接触させて重合させる工程。
【００５２】
また、工程１の後に工程２を行うことが好ましく、これら工程以外に前処理工程や後処理工程などの付加的な工程があってもよい。また工程１と工程２は同一の反応容器で行っても良いし、工程１を行った反応容器から反応混合物を異なる容器に移して工程２を行っても差し障り無い。
【００５３】
＜工程１＞本発明では、水を含むアルカリ金属硫化物を有機極性溶媒存在下で水を除去して、水を含むスルフィド化剤を調製する工程１を行う。
【００５４】
水を含むアルカリ金属硫化物は、アルカリ金属硫化物のイオウ成分１モル当たりの水の含有量が１モル以上のものを用いる。また、有機極性溶媒の使用量は前記水を含むアルカリ金属硫化物のイオウ成分１モル当たり０．０５〜０．６モルである。また、工程１で調製するスルフィド化剤の含む水の量はスルフィド化剤のイオウ成分１モル当たり０．０５〜０．６モルである。ここで調製されるスルフィド化剤の含む水の量が少なすぎると後述する工程２以降での重合反応が進行しにくくなり、多すぎると得られるスルフィド化剤に多量の水が残存してしまい、工程２における触媒化合物による反応促進効果が発現しにくくなる。
【００５５】
このようなイオウ成分１モル当たり１モル以上の水を含むアルカリ金属硫化物から前述の含水量のスルフィド化剤を調製する方法としては、特に制限はないが、例えば次のような脱水工程が採用される。すなわち望ましくは不活性ガス雰囲気下、常温〜１５０℃、好ましくは常温〜１００℃の温度範囲で、有機極性溶媒とアルカリ金属硫化物を混合し、常圧または減圧下、少なくとも１５０℃以上、好ましくは１７０〜２５０℃まで昇温し、水分を留去させる方法が挙げられる。この段階で前述の触媒化合物及び重合助剤を加えてもよい。また、水分の留去を促進するために、トルエンなどを加えて水の留去を行ってもよい。なお、有機極性溶媒や触媒化合物及び重合助剤等、アルカリ金属硫化物以外の化合物を水分を含む状態で仕込む場合も、脱水を行うことが好ましい。
【００５６】
また、ここで用いる有機極性溶媒は有機アミド溶媒であることが好ましく、これにより脱水工程においてスルフィド化剤に残留させる水分量のコントロールが容易となる場合が多い。
【００５７】
本発明によれば、脱水工程における有機極性溶媒量を特定の範囲にすることにより、容易に特定量の水を含むスルフィド化剤を調製することが可能である。
【００５８】
＜工程２＞本発明では、前記工程１で調製したスルフィド化剤とジハロゲン化芳香族化合物を、有機カルボン酸金属塩、脂肪族環状アミン化合物、Ｎ−ヘテロ芳香族化合物、有機スルホキシド化合物から選ばれる少なくとも一種の化合物及びスルフィド化剤のイオウ成分１モル当たり０．０５〜０．６モルの水の存在下で接触させて重合させる工程２を行う。
【００５９】
工程２における反応は、上記諸成分からなる反応混合物を通常１２０〜３００℃、好ましくは１８０〜２６０℃、更に好ましくは２００〜２５５℃の温度に加熱して、０．１〜４０時間、好ましくは０．５〜２０時間、更に好ましくは１〜１０時間加熱して重合反応を行なうことが好ましい。この反応温度が１２０℃未満では反応速度が遅く、また反応が著しく不均一になる可能性があり、一方、３００℃を超えると生成したポリマー成分の分解や、溶媒の劣化が起こりやすくなるだけでなく、反応器内圧の上昇が大きく、反応器により高い耐圧性能を有した反応器が必要となるため、経済的にも安全性の面でも好ましくない。また、重合は一定温度で行なう１段反応、段階的に温度を上げていく多段階反応、あるいは連続的に温度を変化させていく形式の反応のいずれでもかまわないが、重合初期の激しい反応を抑制するために１２０〜２４０℃である程度反応を行った後、更に２４０〜３００℃で重合を行う方法が好ましい。また、工程２の反応時間は使用した原料の種類や量、あるいは反応温度に依存するので一概に規定できないが、０．１時間未満では未反応成分の量が増大したり生成するポリマーが低分子量になる可能性が高く、また４０時間以上では本発明の目的である短時間でＰＡＳを得るということに反する。
【００６０】
本発明の工程２の反応においては、反応器に有機極性溶媒、ジハロゲン化芳香族化合物、前記工程１で調製したスルフィド化剤及び触媒化合物を仕込み、反応器中で充分に攪拌、混合し、それから昇温して重合温度で重合させる方法；反応器に有機極性溶媒、前記工程１で調製したスルフィド化剤及び触媒化合物を仕込み、反応器中で充分に攪拌、混合し、それから昇温して重合温度まで昇温した後、ジハロゲン化芳香族化合物を加え、重合させる方法；反応器中に有機極性溶媒、ジハロゲン化芳香族化合物及び触媒化合物を仕込み、反応器中で充分に攪拌した後、スルフィド化剤固体もしくはスラリー（水もしくは溶媒による）で加えて重合温度下で重合させる方法；工程１としてスルフィド化剤を調製した後、ここで用いた反応容器に有機極性溶媒、ジハロゲン化芳香族化合物及び触媒化合物を加え、十分に撹拌して重合温度下で重合させる方法；工程１で調製したスルフィド化剤を工程１とは異なる反応器に移送して有機極性溶媒、ジハロゲン化芳香族化合物及び触媒化合物などを加え十分に撹拌して重合温度下で重合させる方法；工程１とは異なる反応器に有機極性溶媒、ジハロゲン化芳香族化合物及び触媒化合物を仕込み、これに工程１で調製したスルフィド化剤を加え十分に撹拌して重合温度下で重合させる方法；工程１で触媒化合物存在下でスルフィド化剤を調製し、工程１と同じ反応容器に有機極性溶媒及びジハロゲン化芳香族化合物等を加え十分に撹拌して重合温度下で重合させる方法；工程１で触媒化合物存在下でスルフィド化剤を調製し、この触媒化合物を含むスルフィド化剤を工程１とは異なる反応器に移送した後、有機極性溶媒及びジハロゲン化芳香族化合物等を加え十分に撹拌して重合温度下で重合させる方法などを例示できる。
【００６１】
また、工程２における反応系内の水分量は反応開始時点、すなわち反応系に仕込んだジハロゲン化芳香族化合物（以下ＤＨＡと略することもある）の転化率が０の段階において、仕込みのスルフィド化剤のイオウ成分１モル当たり０．０５〜０．６モルである必要があり、０．１〜０．５モルが好ましく、０．１５〜０．４５モルがより好ましい。少なすぎると重合反応が進行しにくくなり、多すぎると本発明の特徴である触媒化合物による反応促進効果が発現しにくくなる。従って、工程１で調製されたスルフィド化剤以外の諸成分が水を含む場合、反応前に諸成分の脱水を行い、反応系内の水分量を調整する事が好ましい。また、反応系内の水分量が少ない場合、上記水分量の範囲内で水を添加しても差し障り無い。なお、ＤＨＡの転化率は、以下の式で算出した値である。ＤＨＡ残存量は、通常、ガスクロマトグラフ法によって求めることができる。
【００６２】
（ａ）ジハロゲン化芳香族化合物をスルフィド化剤に対しモル比で過剰に添加した場合
転化率＝［〔ＤＨＡ仕込み量（モル）−ＤＨＡ残存量（モル）〕／〔ＤＨＡ仕込み量（モル）−ＤＨＡ過剰量（モル）〕］×１００％
（ｂ）上記（ａ）以外の場合
転化率＝［〔ＤＨＡ仕込み量（モル）−ＤＨＡ残存量（モル）〕／〔ＤＨＡ仕込み量（モル）〕］×１００％
また、工程２で重合溶媒として用いる有機極性溶媒の使用量は、好ましくはスルフィド化剤のイオウ成分１モル当たり１．０〜４．０モル、より好ましくは１．０〜３．５モル、更に好ましくは１．５〜２．５モルが好ましい範囲として例示できる。一般に重合溶媒の使用量が少ない方が単位体積当たりのポリマー量が多くなるので経済的に有利であるが、少なすぎると好ましくない反応が起こりやすくなり、多すぎると重合度が上がりにくくなる傾向にあり、また経済的にも不利となることがある。また、多すぎても少なすぎても反応に要する時間が長くなる傾向にあり、経済的に不利となる場合がある。
【００６３】
さらに、本発明の該重合工程において、ジハロゲン化芳香族化合物の転化率が６０モル％以上、好ましくは７０％以上、より好ましくは８０％以上、更に好ましくは９０％以上になった段階で、下記の工程３を行うことが好ましい。
【００６４】
＜工程３＞工程３は、重合系内の水分量をスルフィド化剤のイオウ成分１モル当たり０．７以上５．０モル以下、好ましくは０．８〜２．０モル、より好ましくは０．８５〜１．８モルになるように調整し、更に重合を継続する工程である。
【００６５】
工程３は工程２に引き続き連続で行うことが好ましく、工程２と工程３は同一の反応器で行っても良いし、工程２における反応混合液を異なる反応器に移送して工程３を行っても良い。
【００６６】
工程２に続き工程３を行うことは、重合度の高いＰＡＳを短時間で得るために特に有効である。水の量が上記範囲以下では、高重合度化が不十分になる傾向にあり、一方、上記範囲以上では反応器内圧の上昇が大きく、反応器により高い耐圧性能を有した反応器が必要となる。重合系内の水分量を調整する際の方法に特に制限はないが、例えば不足分の水を反応系内に圧入する方法が例示できる。
【００６７】
工程３における反応は、上記諸成分からなる反応混合物を通常１２０〜３００℃、好ましくは２００〜３００℃、更に好ましくは２５５〜２８０℃の温度に加熱して、０．１〜４０時間、好ましくは０．２〜２０時間、更に好ましくは０．５〜１０時間加熱して重合反応を行なうことが好ましい。この反応温度が１２０℃未満では反応速度が遅く、また反応が不均一になる可能性があり、一方、３００℃を超えると生成したポリマー成分の分解や、溶媒の劣化が起こりやすくなるだけでなく、反応器内圧の上昇が大きく、反応器により高い耐圧性能を有した反応器が必要となるため、経済的にも安全性の面でも好ましくない。また、重合は一定温度で行なう１段反応、段階的に温度を上げていく多段階反応、あるいは連続的に温度を変化させていく形式の反応のいずれでもかまわない。また、工程３反応時間は使用した原料の種類や量、あるいは反応温度に依存するので一概に規定できないが、０．１時間未満では未反応成分の量が増大したり生成するポリマーが低分子量になる可能性が高く、また４０時間以上では本発明の目的である短時間でＰＡＳを得るということに反する。
【００６８】
また、工程３で重合溶媒として用いる有機極性溶媒の使用量は、好ましくはスルフィド化剤のイオウ成分１モル当たり１．０〜４．０モル、より好ましくは１．０〜３．５モル、更に好ましくは１．５〜２．５モルが好ましい範囲として例示できる。一般に重合溶媒の使用量が少ない方が単位体積当たりのポリマー量が多くなるので経済的に有利であるが、少なすぎると好ましくない反応が起こりやすくなり、多すぎると重合度が上がりにくくなる傾向にあり、また経済的にも不利となることがある。また、多すぎても少なすぎても反応に要する時間が長くなる傾向にあり、経済的に不利となる場合がある。
【００６９】
なお、本発明の重合には、バッチ方式、連続方式など公知の各重合方式を採用することができる。また、重合の際における雰囲気は非酸化性雰囲気下が望ましく、窒素、ヘリウム、アルゴン等の不活性ガス雰囲気下で行なうことが好ましく、特に、経済性及び取扱いの容易さの面からは窒素が好ましい。反応圧力については、使用した原料及び溶媒の種類や量、あるいは反応温度等に依存し一概に規定できないので、特に制限はない。
【００７０】
また、本発明では高重合度ＰＡＳをより短時間で得るために、全重合工程のうちの少なくとも一部を前述した重合助剤存在下で行うことが好ましい。重合助剤の添加時期に特に制限はなく、工程１の開始前、工程２開始時、工程２の途中、工程３の開始時、工程３の途中のいずれの時点で添加してもよく、また複数回に分けて添加してもよいが、少なくとも工程３を重合助剤存在下で行う様にすると短時間で高重合度ＰＡＳを得やすくなる。重合助剤は、無水物、水和物、水溶液または有機極性溶媒との混合物などいかなる形態で添加してもかまわないが、添加する重合助剤が水を含む場合で、かつ、ＤＨＡの転化率が９０％以下、好ましくは８０％以下、より好ましくは７０％以下、更に好ましくは６０％以下の時点で添加する場合は、重合助剤を添加し終えた段階における反応系内の水分量を仕込みのスルフィド化剤のイオウ成分イオウ成分１モル当たり０．０５〜０．６モルにすることが好ましい。
【００７１】
（１０）ポリマー回収
本発明のＰＡＳ樹脂の製造方法においては、重合工程終了後に、重合工程で得られた、ＰＡＳ樹脂成分及び溶剤などを含む固形物からＰＡＳを回収する。回収方法としては、例えばフラッシュ法、すなわち重合反応物を高温高圧（通常２５０℃以上、０．８ＭＰａ以上）の状態から常圧もしくは減圧の雰囲気中へフラッシュさせ溶媒回収と同時に重合体を粉粒状にして回収する方法、重合反応物を高温高圧の状態から徐々に冷却して回収する方法、重合反応物を高温高圧の状態から徐々に冷却して反応系内のＰＡＳ成分を析出させ、且つ１００℃以上状態で濾別することでＰＡＳ成分含む固体を回収する方法等が挙げられる。なおここで、ポリマー成分が析出した状態とは、生成したポリマー成分の少なくとも６０％以上が重合溶媒に溶融解しない状態になっている状態である。更に詳しくは、ある状態の反応系を１００℃以下まで急冷した際に得られる重合物中の固形成分を８０ｍｅｓｈふるいで回収した際に、仕込みのスルフィド化剤のすべてがＰＡＳに転化したと仮定した重量（理論量）を基準として、収率６０％以上で回収できる状態である。また、ここで仕込みのスルフィド化剤に含まれるイオウ成分のモル量が、ジハロゲン化芳香族化合物のモル量よりも多い場合は、すべてＰＡＳに転化することはあり得ない場合もあるが、この場合でも仕込みのスルフィド化剤の量を基準として考えることとする。
【００７２】
このようにして得られた固体のＰＡＳ樹脂を含む生成物は、有機溶媒及び／または水で洗浄する事が好ましい。
【００７３】
固体のＰＡＳ樹脂を含む生成物を有機溶媒で洗浄する場合の具体的方法としては、以下の方法を例示できる。すなわち、洗浄に用いる有機溶媒としては、ＰＡＳ樹脂を分解する作用などを有しないものであれば特に制限はないが、例えばＮ−メチル−２−ピロリドン、ジメチルホルムアミド、ジメチルアセトアミドなどの含窒素極性溶媒、ジメチルスルホキシド、ジメチルスルホンなどのスルホキシド・スルホン系溶媒、アセトン、メチルエチルケトン、ジエチルケトン、アセトフェノンなどのケトン系溶媒、ジメチルエーテル、ジプロピルエーテル、テトラヒドロフランなどのエーテル系溶媒、クロロホルム、塩化メチレン、トリクロロエチレン、２塩化エチレン、ジクロルエタン、テトラクロルエタン、クロルベンゼンなどのハロゲン系溶媒、メタノール、エタノール、プロパノール、ブタノール、ペンタノール、エチレングリコール、プロピレングリコール、フェノール、クレゾール、ポリエチレングリコールなどのアルコール・フェノール系溶媒、ベンゼン、トルエン、キシレンなどの芳香族炭化水素系溶媒などがあげられる。これらの有機溶媒のなかでＮ−メチル−２−ピロリドン、アセトン、ジメチルホルムアミド、クロロホルムなどの使用が好ましく、Ｎ−メチル−２−ピロリドンおよび／またはアセトンがより好ましい。また、これらの有機溶媒は１種類または２種類以上の混合で使用することができる。
【００７４】
有機溶媒による洗浄の方法としては、有機溶媒中にＰＡＳ樹脂を浸漬せしめるなどの方法があり、必要により適宜撹拌または加熱することも可能である。
【００７５】
有機溶媒でＰＡＳ樹脂を洗浄する際の洗浄温度については特に制限はなく、常温〜３００℃程度の任意の温度が選択できる。洗浄温度が高くなるほど洗浄効率が高くなる傾向があるが、通常は常温〜１５０℃の洗浄温度で十分効果が得られる。
【００７６】
ＰＡＳ樹脂と有機溶媒の割合は、有機溶媒の多いほうが好ましいが、通常、有機溶媒１リットルに対し、ＰＡＳ樹脂３００ｇ以下の浴比が選択される。
【００７７】
なお、回収方法として重合反応物を高温高圧の状態から徐々に冷却して回収する方法を用いて、粒状のＰＡＳ樹脂を含むスラリー状態で固体のＰＡＳ樹脂を含む生成物を得た場合は、有機溶媒による洗浄を行う前に、前記スラリーの濾別を行い、続いて有機溶媒による洗浄を行うことが好ましい。このような手順を踏むことで、同量の有機溶剤を用いた際により高い洗浄効果を得られることが多い。なお、濾別の方法に特に制限はないが篩い等による濾別、遠心分離による濾別、濾布を用いた濾別などを例示できる。
【００７８】
また固体のＰＡＳ樹脂を含む生成物から残留有機溶媒やイオン性不純物を除去するため、水で数回洗浄することが好ましい。
【００７９】
ＰＡＳ樹脂を水で洗浄する場合の方法としては、水にＰＡＳ樹脂を浸漬せしめるなどの方法があり、必要により適宜撹拌または加熱することも可能である。
【００８０】
水でＰＡＳ樹脂を洗浄する際の洗浄温度は２０℃〜２２０℃が好ましく、５０℃〜２００℃が更に好ましい。２０℃未満だと副生成物の除去が困難となり、２２０℃を越えると、高圧になり安全上好ましくない。
【００８１】
水洗浄で使用する水は蒸留水あるいは脱イオン水であることが好ましいが、必要に応じてギ酸、酢酸、プロピオン酸、酪酸、クロロ酢酸、ジクロロ酢酸、アクリル酸、クロトン酸、安息香酸、サリチル酸、シュウ酸、マロン酸、コハク酸、フタル酸、フマル酸などの有機酸性化合物びそのアルカリ金属、アルカリ土類金属塩、硫酸、リン酸、塩酸、炭酸、珪酸などの無機酸性化合物およびアンモニウムイオンなどを含む水溶液を用いてもよい。
【００８２】
１００℃以上の水で洗浄を行う熱水処理の操作は、通常、所定量の水に所定量のＰＡＳ樹脂を投入し、常圧であるいは圧力容器内で加熱、撹拌することにより行われる。ＰＡＳ樹脂と水との割合は、水の多いほうが好ましいが、通常、水１リットルに対し、ＰＡＳ樹脂２００ｇ以下の浴比が選択される。
【００８３】
（１１）その他の後処理
かくして得られたＰＡＳ樹脂は常圧下および／または減圧下に乾燥する。かかる乾燥温度としては、１２０〜２８０℃の範囲が好ましく、１４０〜２５０℃の範囲がより好ましい。乾燥雰囲気は、窒素、ヘリウム、減圧下などの不活性雰囲気でも、酸素、空気などの酸化性雰囲気、空気と窒素の混合雰囲気の何れでも良いが、減圧下で行うことが好ましく、特に常圧下で乾燥を行って水分等を除去した後、減圧下で再度乾燥することが好ましい。乾燥時間は、０．５〜５０時間が好ましく、１〜３０時間が好ましく、１〜２０時間がさらに好ましい。
【００８４】
本発明において得られたＰＡＳ樹脂を、揮発性成分を除去するために、或いは架橋高分子量化するために、１３０〜２６０℃の温度で処理することも可能である。
【００８５】
架橋高分子量化は抑制し、揮発分除去を目的として乾式熱処理を行う場合、その温度は１３０〜２５０℃が好ましく、１６０〜２５０℃の範囲がより好ましい。また酸素濃度５体積％未満、更には２体積％未満とすることが望ましい。減圧乾燥することも好ましい方法の一つである。処理時間は、０．５〜５０時間が好ましく、１〜２０時間がより好ましく、１〜１０時間が更に好ましい。
【００８６】
架橋高分子量化を目的として乾式熱処理する場合、その温度は１６０〜２６０℃が好ましく、１７０〜２５０℃の範囲がより好ましい。また酸素濃度５体積％以上、更には８体積％以上とすることが望ましい。処理時間は、１〜１００時間が好ましく、２〜５０時間がより好ましく、３〜２５時間が更に好ましい。
【００８７】
加熱処理の装置は通常の熱風乾燥機でもまた回転式あるいは撹拌翼付の加熱装置であってもよいが、効率よくしかもより均一に処理する場合は、回転式あるいは撹拌翼付の加熱装置を用いるのがより好ましい。
【００８８】
（１２）生成ＰＡＳ
本発明の方法により得られるＰＡＳは、耐熱性、耐薬品性、難燃性、電気的性質並びに機械的性質に優れ、射出成形、射出圧縮成形、ブロー成形用途のみならず、押出成形により、シート、フィルム、繊維及びパイプなどの押出成形品に成形することができる。
【００８９】
また、本発明で得られるＰＡＳは、単独で用いてもよいし、所望に応じて、ガラス繊維、炭素繊維、酸化チタン、炭酸カルシウムなどの無機充填剤、酸化防止剤、熱安定剤、紫外線吸収剤、着色剤などを添加することもでき、ポリアミド、ポリスルホン、ポリフェニレンエーテル、ポリカーボネート、ポリエーテルスルホン、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレン、ポリプロピレン、ポリテトラフルオロエチレン、エポキシ基、カルボキシル基、カルボン酸エステル基、酸無水物基などの官能基を有するオレフィン系コポリマー、ポリオレフィン系エラストマー、ポリエーテルエステルエラストマー、ポリエーテルアミドエラストマー、ポリアミドイミド、ポリアセタール、ポリイミドなどの樹脂を配合することもできる。
【００９０】
またその用途としては、例えばセンサー、ＬＥＤランプ、コネクター、ソケット、抵抗器、リレーケース、スイッチ、コイルボビン、コンデンサー、バリコンケース、光ピックアップ、発振子、各種端子板、変成器、プラグ、プリント基板、チューナー、スピーカー、マイクロフォン、ヘッドフォン、小型モーター、磁気ヘッドベース、パワーモジュール、半導体、液晶、ＦＤＤキャリッジ、ＦＤＤシャーシ、モーターブラッシュホルダー、パラボラアンテナ、コンピューター関連部品等に代表される電気・電子部品；ＶＴＲ部品、テレビ部品、アイロン、ヘアードライヤー、炊飯器部品、電子レンジ部品、音響部品、オーディオ・レーザーディスク・コンパクトディスク等の音声機器部品、照明部品、冷蔵庫部品、エアコン部品、タイプライター部品、ワードプロセッサー部品等に代表される家庭、事務電気製品部品；オフィスコンピューター関連部品、電話器関連部品、ファクシミリ関連部品、複写機関連部品、洗浄用治具、モーター部品、ライター、タイプライターなどに代表される機械関連部品：顕微鏡、双眼鏡、カメラ、時計等に代表される光学機器、精密機械関連部品；水道蛇口コマ、混合水栓、ポンプ部品、パイプジョイント、水量調節弁、逃がし弁、湯温センサー、水量センサー、水道メーターハウジングなどの水廻り部品；バルブオルタネーターターミナル、オルタネーターコネクター，ＩＣレギュレーター、ライトディヤー用ポテンシオメーターベース、排気ガスバルブ等の各種バルブ、燃料関係・排気系・吸気系各種パイプ、エアーインテークノズルスノーケル、インテークマニホールド、燃料ポンプ、エンジン冷却水ジョイント、キャブレターメインボディー、キャブレタースペーサー、排気ガスセンサー、冷却水センサー、油温センサー、スロットルポジションセンサー、クランクシャフトポジションセンサー、エアーフローメーター、ブレーキパッド摩耗センサー、エアコン用サーモスタットベース、暖房温風フローコントロールバルブ、ラジエーターモーター用ブラッシュホルダー、ウォーターポンプインペラー、タービンベイン、ワイパーモーター関係部品、デュストリビューター、スタータースイッチ、スターターリレー、トランスミッション用ワイヤーハーネス、ウィンドウォッシャーノズル、エアコンパネルスイッチ基板、燃料関係電磁気弁用コイル、ヒューズ用コネクター、ホーンターミナル、電装部品絶縁板、ステップモーターローター、ランプソケット、ランプリフレクター、ランプハウジング、ブレーキピストン、ソレノイドボビン、エンジンオイルフィルター、燃料タンク、点火装置ケース、車速センサー、ケーブルライナー等の自動車・車両関連部品、その他各種用途が例示できる。
【００９１】
本発明により得られたＰＡＳを用いたＰＡＳ樹脂フィルムの製造方法としては、公知の溶融製膜方法を採用することができ、例えば、単軸または２軸の押出機中でＰＡＳ樹脂を溶融後、フィルムダイより押出し冷却ドラム上で冷却してフィルムを作成する方法、あるいは、このようにして作成したフィルムをローラー式の縦延伸装置とテンターと呼ばれる横延伸装置にて縦横に延伸する二軸延伸法などにより製造することができるが、特にこれに限定されるものではない。
【００９２】
このようにして得られたＰＡＳ樹脂フィルムは、優れた機械特性、電気特性、耐熱性を有しており、フィルムコンデンサーやチップコンデンサーの誘電体フィルム用途、回路基板、絶縁基板用途、モーター絶縁フィルム用途、トランス絶縁フィルム用途、離型用フィルム用途など各種用途に好適に使用することができる。
【００９３】
本発明により得られるＰＡＳを用いたＰＡＳ樹脂繊維の製造方法としては、公知の溶融紡糸方法を適用することができ、例えば、原料であるＰＡＳ樹脂チップを単軸または２軸の押出機に供給しながら混練し、ついで押出機の先端部に設置したポリマー流線入替器、濾過層などを経て紡糸口金より押出し、冷却、延伸、熱セットを行う方法などを採用することができるが、特にこれに限定されるものではない。
【００９４】
このようにして得られたＰＡＳ樹脂のモノフィランメントあるいは短繊維は、抄紙ドライヤーキャンバス、ネットコンベヤー、バグフィルターなどの各種用途に好適に使用することができる。
【００９５】
【実施例】
以下、本発明の方法を実施例及び比較例により更に具体的に説明するが、本発明はこれら実施例のみに限定されるものではない。なお、物性の測定法は以下の通りである。
【００９６】
（１）ポリマー収率
ＰＡＳの収率は、重合開始前の反応器中のイオウを１当量含むスルフィド化剤が全てＰＡＳに転化したと仮定した重量（理論量）に対する、ＰＡＳの収量の割合とした。スルフィド化剤がジハロゲン化芳香族化合物よりも過剰に仕込まれた場合は、すべてＰＡＳに転化することはあり得ない場合もあるが、その場合でもスルフィド化剤の量を基準として考えることとする。
【００９７】
（２）ポリマーの溶融粘度
東洋精機社製キャピログラフＣ１（ダイス長１０ｍｍ、ダイス穴直径１ｍｍ）を用い、３００℃の条件で測定を行ない、せん断速度１０００／秒の溶融粘度を比較した。
【００９８】
［実施例１］
＜工程１＞
攪拌機付き１リットルオートクレーブに、濃度４７．５ｗｔ％の水硫化ナトリウム水溶液１１８ｇ（水硫化ナトリウム換算で１．０モル）、純度９６％水酸化ナトリウムを水１５０ｇに溶解した濃度２１．７ｗｔ％の水酸化ナトリウム水溶液１９４ｇ（水酸化ナトリウム換算で１．０５モル）、ＮＭＰ１０ｇ（０．１０モル）を室温で仕込んだ。仕込んだ水硫化ナトリウムが全て硫化ナトリウムに変換されると仮定した場合の、硫化ナトリウムのイオウ成分１モルに対する水の量は１２．８モル（２３０ｇ）、ＮＭＰの量は０．１０モルであった。
オートクレーブ上部に充填剤入りの精留塔を取り付け、常圧で窒素を通じて２４０ｒｐｍで撹拌しながら２３５℃まで約２時間かけて徐々に加熱して脱水を行い、留出液２３０ｇを得た。また、この留出液をガスクロマトグラフ法で分析したところ留出液の組成は水２２８ｇ、ＮＭＰが２ｇであり、反応系内に２ｇ（０．１１モル）の水が残存ししていることが判った。また、この脱水操作時に反応系から飛散した硫化水素は０．０００６モルであった。
工程１により、イオウ成分１モルあたり０．１１モルの水を含むスルフィド化剤を調製することができた。
＜工程２＞
次に、ｐ−ジクロロベンゼン（ｐ−ＤＣＢ）１５１ｇ（１．０３モル）、ＮＭＰ２８９ｇ（２．９モル）及び触媒化合物として無水酢酸ナトリウム４．１ｇ（０．０５モル）を加えた。反応系内の水の量は仕込みのスルフィド化剤のイオウ成分１モル当たり０．１１モル、ＮＭＰ量は３．０モルであった。
反応容器を窒素ガス下に密封し、４００ｒｐｍで撹拌しながら、２１０℃で２時間反応を行った後、室温近傍まで急冷した。
この反応によって得られた重合内容物中のｐ−ＤＣＢをガスクロマトグラフ法で測定してｐ−ＤＣＢの転化率を求めたところ、転化率は７２％であった。
【００９９】
［実施例２］
実施例１の工程２で加えた無水酢酸ナトリウムのかわりに安息香酸ナトリウム５．７ｇ（０．０５モル）を加えた以外は実施例１と同様に行った。得られた重合内容物中のｐ−ＤＣＢをガスクロマトグラフ法で測定してｐ−ＤＣＢの転化率を求めたところ、転化率は６８％であった。
【０１００】
［実施例３］
実施例１の工程２で加えた無水酢酸ナトリウムのかわりに４−ヒドロキシ酪酸ナトリウム６．３ｇ（０．０５モル）を加えた以外は実施例１と同様に行った。得られた重合内容物中のｐ−ＤＣＢをガスクロマトグラフ法で測定してｐ−ＤＣＢの転化率を求めたところ、転化率は７６％であった。
【０１０１】
［実施例４］
実施例１の工程２で加えた無水酢酸ナトリウムのかわりにピペリジン４．３ｇ（０．０５モル）を加えた以外は実施例１と同様に行った。得られた重合内容物中のｐ−ＤＣＢをガスクロマトグラフ法で測定してｐ−ＤＣＢの転化率を求めたところ、転化率は６６％であった。
【０１０２】
［実施例５］
実施例１の工程２で加えた無水酢酸ナトリウムのかわりに１，５−ジアザビシクロ［４，３，０］ノン−５−エン６．２ｇ（０．０５モル）を加えた以外は実施例１と同様に行った。得られた重合内容物中のｐ−ＤＣＢをガスクロマトグラフ法で測定してｐ−ＤＣＢの転化率を求めたところ、転化率は５１％であった。
【０１０３】
［実施例６］
実施例１の工程２で加えた無水酢酸ナトリウムのかわりにピリジン４．０ｇ（０．０５モル）を加えた以外は実施例１と同様に行った。得られた重合内容物中のｐ−ＤＣＢをガスクロマトグラフ法で測定してｐ−ＤＣＢの転化率を求めたところ、転化率は６２％であった。
【０１０４】
［実施例７］
実施例１の工程２で加えた無水酢酸ナトリウムのかわりにジメチルスルホキシド３．９ｇ（０．０５モル）を加えた以外は実施例１と同様に行った。得られた重合内容物中のｐ−ＤＣＢをガスクロマトグラフ法で測定してｐ−ＤＣＢの転化率を求めたところ、転化率は７５％であった。
【０１０５】
［実施例８］
実施例１の工程２で加えた無水酢酸ナトリウムの添加量を８．２ｇ（０．１モル）に変えた以外は実施例１と同様に行った。得られた重合内容物中のｐ−ＤＣＢをガスクロマトグラフ法で測定してｐ−ＤＣＢの転化率を求めたところ、転化率は７２％であった。
【０１０６】
［実施例９］
実施例１の工程２で加えた無水酢酸ナトリウムの添加量を２４．６ｇ（０．３モル）に変えた以外は実施例１と同様に行った。得られた重合内容物中のｐ−ＤＣＢをガスクロマトグラフ法で測定してｐ−ＤＣＢの転化率を求めたところ、転化率は６６％であった。
実施例１〜９の結果と以下の比較例１との対比から判るように、本発明で工程１としてイオウ成分１モル当たり１モル以上の水を含むアルカリ金属硫化物をアルカリ金属硫化物のイオウ成分１モル当たり０．０５〜０．６モルの有機極性溶媒存在下で脱水して、イオウ成分１モル当たり０．０５〜０．６モルの水を含むスルフィド化剤を調製した後、工程２で特定の触媒化合物存在下にスルフィド化剤とジハロゲン化芳香族化合物の反応を行うことで、重合反応を著しく促進できることがわかる。
【０１０７】
［比較例１］
実施例１の工程２で加えた無水酢酸ナトリウムを加えなかったこと以外は実施例１と同様に行った。
【０１０８】
得られた重合内容物中のｐ−ＤＣＢをガスクロマトグラフ法で測定してｐ−ＤＣＢの転化率を求めたところ、転化率は２９％であった。
工程２で触媒化合物を用いない場合、触媒化合物を用いた実施例１〜９と比べて重合反応が進行しにくいことが判る。
【０１０９】
［実施例１０］
＜工程１＞
攪拌機付き１リットルオートクレーブに、濃度４７．５ｗｔ％水硫化ナトリウム水溶液１１８ｇ（水硫化ナトリウム換算で１．０モル）、純度９６％水酸化ナトリウムを水１５０ｇに溶解した濃度２１．７ｗｔ％の水酸化ナトリウム水溶液１９４ｇ（水酸化ナトリウム換算で１．０５モル）、ＮＭＰ１７．５ｇ（０．１８モル）を室温で仕込んだ。仕込んだ水硫化ナトリウムが全て硫化ナトリウムに変換されると仮定した場合の、硫化ナトリウムのイオウ成分１モルに対する水の量は１２．８モル（２３０ｇ）、ＮＭＰの量は０．１８モルであった。
オートクレーブ上部に充填剤入りの精留塔を取り付け、常圧で窒素を通じて２４０ｒｐｍで撹拌しながら２３５℃まで約２時間かけて徐々に加熱して脱水を行い、留出液２２８ｇを得た。また、この留出液をガスクロマトグラフ法で分析したところ留出液の組成は水２２７ｇ、ＮＭＰが１ｇであり、反応系内に３ｇ（０．１７モル）の水が残存していることが判った。また、この脱水操作時に反応系から飛散した硫化水素は０．０００６モルであった。
工程１により、イオウ成分１モルあたり０．１７モルの水を含むスルフィド化剤を調製することができた。
＜工程２＞
次に、ｐ−ジクロロベンゼン（ｐ−ＤＣＢ）１５１ｇ（１．０３モル）、ＮＭＰ１５７ｇ（１．５９モル）及び触媒化合物として無水酢酸ナトリウム１４．４ｇ（０．１８モル）を加えた。反応系内の水の量は仕込みのスルフィド化剤のイオウ成分１モル当たり０．１７モル、ＮＭＰ量は１．７５モルであった。
反応容器を窒素ガス下に密封し、４００ｒｐｍで撹拌しながら、２３０℃で１時間反応を行った後、室温近傍まで急冷した。
この反応によって得られた重合内容物中のｐ−ＤＣＢをガスクロマトグラフ法で測定してｐ−ＤＣＢの転化率を求めたところ、転化率は６２％であった。
【０１１０】
［実施例１１］
実施例１０の工程１で仕込むＮＭＰを３０．７ｇ（０．３１モル）、工程２で仕込むＮＭＰを１４２．６ｇ（１．４４モル）にした以外は、実施例と同様に行った。工程１で得られた留出液は２２７ｇであり、この留出液をガスクロマトグラフ法で分析したところ留出液の組成は水２２５ｇ、ＮＭＰが２ｇであり、反応系内に５ｇ（０．２８モル）の水が残存していることがわかった。また工程２における反応系内の水の量は仕込みのスルフィド化剤のイオウ成分１モル当たり０．２８モル、ＮＭＰ量は１．７３モルであった。
この反応によって得られた重合内容物中のｐ−ＤＣＢをガスクロマトグラフ法で測定してｐ−ＤＣＢの転化率を求めたところ、転化率は５９％であった。
【０１１１】
［比較例２］
実施例１０の工程１で仕込むＮＭＰを４ｇ（０．０４モル）、工程２で仕込むＮＭＰを１６９．３ｇ（１．７１モル）にした以外は、実施例１０と同様に行った。工程１で得られた留出液は２３２ｇであり、この留出液をガスクロマトグラフ法で分析したところ留出液の組成は水２２９．５ｇ、ＮＭＰが２．５ｇであり、反応系内に０．５ｇ（０．０３モル）の水が残存していることがわかった。また工程２における反応系内の水の量は仕込みのスルフィド化剤のイオウ成分１モル当たり０．０３モル、ＮＭＰ量は１．７２モルであった。
反応後に回収した重合内容物は茶黒色であり、ガスクロマトグラフ法で分析した結果、著しく副反応が起こっていることがわかった。
【０１１２】
［比較例３］
実施例１０の工程１で仕込むＮＭＰを８１．２ｇ（０．８２モル）、工程２で仕込むＮＭＰを９２．１ｇ（０．９３モル）にした以外は、実施例１０と同様に行った。工程１で得られた留出液は２１７．５ｇであり、この留出液をガスクロマトグラフ法で分析したところ留出液の組成は水２１６ｇ、ＮＭＰが１．５ｇであり、反応系内に１４ｇ（０．７８モル）の水が残存していることがわかった。また工程２における反応系内の水の量は仕込みのスルフィド化剤のイオウ成分１モル当たり０．７８モル、ＮＭＰ量は１．７３モルであった。
この反応によって得られた重合内容物中のｐ−ＤＣＢをガスクロマトグラフ法で測定してｐ−ＤＣＢの転化率を求めたところ、転化率は２２％であった。
【０１１３】
［比較例４］
実施例１０の工程１で仕込むＮＭＰを１００ｇ（１．０１モル）、工程２で仕込むＮＭＰを７３．３ｇ（０．７４モル）にした以外は、実施例１０と同様に行った。工程１で得られた留出液は２１２ｇであり、この留出液をガスクロマトグラフ法で分析したところ留出液の組成は水２１０ｇ、ＮＭＰが２ｇであり、反応系内に２０ｇ（１．１１モル）の水が残存していることがわかった。なお、この脱水操作時に反応系から飛散した硫化水素は０．０１８モルであった。また工程２における反応系内の水の量は仕込みのスルフィド化剤のイオウ成分１モル当たり１．１１モル、ＮＭＰ量は１．７８モルであった。
この反応によって得られた重合内容物中のｐ−ＤＣＢをガスクロマトグラフ法で測定してｐ−ＤＣＢの転化率を求めたところ、転化率はほぼ０％でほとんど反応が進行していなかった。
【０１１４】
［実施例１２］
実施例１０の工程１で仕込むＮＭＰを２０．８ｇ（０．２１モル）、工程２で仕込むＮＭＰを１７７．５ｇ（１．７９モル）、無水酢酸ナトリウムを１６．４ｇ（０．２モル）にした以外は、実施例１０と同様に行った。工程１で得られた留出液は２２７ｇであり、この留出液をガスクロマトグラフ法で分析したところ留出液の組成は水２２６ｇ、ＮＭＰが１ｇであり、反応系内に４ｇ（０．２２モル）の水が残存していることがわかった。また工程２における反応系内の水の量は仕込みのスルフィド化剤のイオウ成分１モル当たり０．２２モル、ＮＭＰ量は１．９９モルであった。
【０１１５】
この反応によって得られた重合内容物中のｐ−ＤＣＢをガスクロマトグラフ法で測定してｐ−ＤＣＢの転化率を求めたところ、転化率は７０％であった。
【０１１６】
［比較例５］
実施例１２の工程１で仕込むＮＭＰを１００ｇ（１．０１モル）、工程２で仕込むＮＭＰを９８ｇ（０．９９モル）にした以外は、実施例１２と同様に行った。工程１で得られた留出液は２１２ｇであり、この留出液をガスクロマトグラフ法で分析したところ留出液の組成は水２１０ｇ、ＮＭＰが２ｇであり、反応系内に２０ｇ（１．１モル）の水が残存していることがわかった。なお、この脱水操作時に反応系から飛散した硫化水素は０．０１８モルであった。また工程２における反応系内の水の量は仕込みのスルフィド化剤のイオウ成分１モル当たり１．１モル、ＮＭＰ量は２．０２モルであった。
この反応によって得られた重合内容物中のｐ−ＤＣＢをガスクロマトグラフ法で測定してｐ−ＤＣＢの転化率を求めたところ、転化率はほぼ０％でほとんど反応が進行していなかった。
実施例１０、１１と比較例２〜４、及び実施例１２と比較例５との対比から判るように、本発明の方法によれば、触媒化合物による反応促進効果を著しく発現させることができるので、ごくわずかな重合溶媒使用量でも反応を進行させることができる。
【０１１７】
［実施例１３］
＜工程１＞
攪拌機付き１リットルオートクレーブに、濃度４７．５ｗｔ％水硫化ナトリウム水溶液１１８ｇ（水硫化ナトリウム換算で１．０モル）、純度９６％水酸化ナトリウムを水１５０ｇに溶解した濃度２１．７ｗｔ％の水酸化ナトリウム水溶液１９４ｇ（水酸化ナトリウム換算で１．０５モル）、ＮＭＰ１７．５ｇ（０．１８モル）及び無水酢酸ナトリウム１４．４ｇ（０．１８モル）を室温で仕込んだ。仕込んだ水硫化ナトリウムが全て硫化ナトリウムに変換されると仮定した場合の、硫化ナトリウムのイオウ成分１モルに対する水の量は１２．８モル（２３０ｇ）、ＮＭＰの量は０．１８モルであった。
オートクレーブ上部に充填剤入りの精留塔を取り付け、常圧で窒素を通じて２４０ｒｐｍで撹拌しながら２３５℃まで約２時間かけて徐々に加熱して脱水を行い、留出液２２８ｇを得た。また、この留出液をガスクロマトグラフ法で分析したところ留出液の組成は水２２７ｇ、ＮＭＰが１ｇであり、反応系内に３ｇ（０．１７モル）の水が残存ししていることが判った。また、この脱水操作時に反応系から飛散した硫化水素は０．０００６モルであった。
工程１により、イオウ成分１モルあたり０．１７モルの水を含むスルフィド化剤を調製することができた。
＜工程２＞
次に、ｐ−ジクロロベンゼン（ｐ−ＤＣＢ）１５１ｇ（１．０３モル）及びＮＭＰ１５５．８ｇ（１．５７モル）を加えた。反応系内の水の量は仕込みのスルフィド化剤のイオウ成分１モル当たり０．１７モル、ＮＭＰ量は１．７４モルであった。
反応容器を窒素ガス下に密封し、４００ｒｐｍで撹拌しながら、２００℃から２５０℃まで５０分かけて昇温した後、２５０分で９０分保持した。
＜工程３＞
反応系の温度を２５０℃に保持したまま、１０分かけて反応系内に水１８ｇ（１．０モル）を圧入した。これにより仕込みのスルフィド化剤のイオウ成分１モルに対する反応系内の水の量は１．１７モルとなった。
次に２５０℃から２７０℃まで２０分かけて昇温した後、２７０℃で９０分保持した。ついで２１０℃まで６０分かけて徐々に冷却した後、室温近傍まで急冷した。
＜ポリマー回収＞
内容物を取り出し、０．５リットルのＮＭＰで希釈しスラリーとして８５℃で３０分撹拌後、８０メッシュ金網で濾別して固形物を得た。得られた固形物を再度ＮＭＰ０．５リットルで洗浄濾別した。得られた固形物を再度１リットルの水（７０℃）で３回洗浄、濾別した。ついで、得られた固形物に酢酸０．５２ｇ及び水（７０℃）１リットルを加えて洗浄、濾別した。更に得られた固形物を再度１リットルの水（７０℃）で洗浄、濾別した。
＜後処理＞
このようにして得られた固形物を、１３０℃で熱風乾燥した。赤外分光測定により同定した結果、得られた固形物はＰＰＳであることがわかった。また、ポリマー収率は８５％、ポリマーの溶融粘度は１３６Ｐａ・ｓであり、本発明の方法によれば、ごくわずかな重合溶媒使用量でも高重合度ポリマーを高収率で得られることが判った。
また、工程３で水を添加する前まで上記と同様に操作を行った時点で重合系を急冷し、この重合内容物中のｐ−ＤＣＢをガスクロマトグラフ法で測定してｐ−ＤＣＢの転化率を求めたところ、転化率は９０％であった。
【０１１８】
［比較例６］
実施例１３の工程１で仕込むＮＭＰを４．０ｇ（０．０４モル）、工程２で仕込むＮＭＰを１６９．３ｇ（１．７１モル）にした以外は、実施例１３と同様に行った。工程１で得られた留出液は２３２ｇであり、この留出液をガスクロマトグラフ法で分析したところ留出液の組成は水２２９．５ｇ、ＮＭＰが２．５ｇであり、反応系内に０．５ｇ（０．０３モル）の水が残存していることがわかった。また工程２における反応系内の水の量は仕込みのスルフィド化剤のイオウ成分１モル当たり０．０３モル、ＮＭＰ量は１．７３モルであった。
反応後に得られた反応物は濃い茶色であり、ガスクロマトグラフ法で分析した結果、著しく副反応が進行していることが分かった。得られたポリマーの収率は５９％と低く、また、ポリマー溶融粘度は低く１０Ｐａ・ｓ以下であった。
また、工程３で水を添加する前まで上記と同様に操作を行った時点で重合系を急冷し、この重合内容物中のｐ−ＤＣＢをガスクロマトグラフ法で測定してｐ−ＤＣＢの転化率を求めたところ、転化率は８８％であった。
【０１１９】
［比較例７］
実施例１３の工程１で仕込むＮＭＰを８１．２ｇ（０．８２モル）、工程２で仕込むＮＭＰを９２．１ｇ（０．９３モル）にした以外は、実施例１３と同様に行った。工程１で得られた留出液は２１７．５ｇであり、この留出液をガスクロマトグラフ法で分析したところ留出液の組成は水２１６ｇ、ＮＭＰが１．５ｇであり、反応系内に１４ｇ（０．７８モル）の水が残存していることがわかった。また、工程２における反応系内の水の量は仕込みのスルフィド化剤のイオウ成分１モル当たり０．７８モル、ＮＭＰ量は１．７５モルであった。
反応後に得られた反応物は黒灰色であり、得られたポリマーの収率は５５％と低く、また、ポリマー溶融粘度は低く１０Ｐａ・ｓ以下であった。
また、工程３で水を添加する前まで上記と同様に操作を行った時点で重合系を急冷し、この重合内容物中のｐ−ＤＣＢをガスクロマトグラフ法で測定してｐ−ＤＣＢの転化率を求めたところ、転化率は４６％であった。
【０１２０】
［実施例１４］
実施例１３の工程２における反応条件を、２００℃から２３５℃まで３５分かけて昇温した後、２３５℃で１４０分保持するに変えた以外は実施例１３と同様に行った。
得られたポリマーの収率は８５％、ポリマーの溶融粘度は１０５Ｐａ・ｓであり、本発明の方法によれば、ごくわずかな重合溶媒使用量でも高重合度ポリマーを高収率で得られることが判った。
また、工程３で水を添加する前まで上記と同様に操作を行った時点で重合系を急冷し、この重合内容物中のｐ−ＤＣＢをガスクロマトグラフ法で測定してｐ−ＤＣＢの転化率を求めたところ、転化率は７２％であった。
【０１２１】
【発明の効果】
本発明によれば、線状の高分子量ＰＡＳを短時間に効率よく製造する方法を提供できる。したがって、本発明のＰＡＳの製造方法は、工業的規模でＰＡＳを安全かつ経済的に製造する方法として好適である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing polyarylene sulfide (hereinafter sometimes abbreviated as PAS), and more particularly, to a method for efficiently producing a linear PAS in a short time.
[0002]
[Prior art]
PAS is an engineering plastic with excellent heat resistance, chemical resistance, flame retardancy, mechanical strength, electrical properties, dimensional stability, etc., and is molded by various molding methods such as injection molding, extrusion molding and compression molding. Since it can be formed into articles, films, sheets, fibers and the like, it is widely used in a wide range of fields such as electric / electronic devices and automobile devices.
[0003]
As a method for producing PAS, a method has been proposed in which an alkali metal sulfide such as sodium sulfide and a polyhalo aromatic compound such as p-dichlorobenzene are reacted in an organic amide solvent such as N-methyl-2-pyrrolidone. However, only PAS having low molecular weight and low melt viscosity can be obtained. A commonly used method is to remove sodium sulfide containing a large amount of water of crystallization by heating it in an organic amide solvent of 1 mol or more per 1 mol of sulfur component of sodium sulfide to remove water contained in the sodium sulfide. Is a method for preparing a sulfide agent, and adding p-dichlorobenzene to the mixture to carry out heat polymerization. Not only does it take a long time to remove water from the hydrous sodium sulfide, but also the sulfide obtained by this method. Since 1.0 mol or more of water remains per 1 mol of the sulfur component of the sulfidizing agent, there is a problem that it takes a long time to obtain PAS (for example, see Patent Document 1). ).
[0004]
In order to improve the degree of polymerization of PAS, which is one of the problems of the above method, and to obtain a high molecular weight PAS at the time of polymerization, various production methods improved from the above method have been proposed. As a means for improving the polymerization method of PAS, a method of adding various polymerization auxiliaries when reacting an alkali metal sulfide with a dihalo aromatic compound in an organic amide solvent is typical. Using an alkali metal carboxylate (for example, see Patent Document 2), a method using an alkaline earth metal of an aromatic carboxylic acid (for example, see Patent Document 3), and also using an alkali metal halide (For example, see Patent Document 4), and a method of using a sodium salt of an aliphatic carboxylic acid (for example, see Patent Document 5). According to these methods, it is possible to obtain a linear and high molecular weight PAS by polymerization, but in order to obtain a higher molecular weight PAS, expensive polymer such as lithium acetate, lithium chloride and sodium benzoate is required. It is necessary to carry out the polymerization using an auxiliary agent, and even if an inexpensive polymerization auxiliary such as sodium acetate is simply applied, the polymerization time is prolonged, which is economically disadvantageous, and the amount of water in the reaction system is low. There is a problem that the reaction requires a long time because the polymerization aid does not exhibit a reaction promoting effect because the amount is too large.
[0005]
As a problem of the above method, that is, a method of controlling the amount of water in the reaction system, an alkali metal sulfide anhydride having a purity of 95% by weight or more and an alkali metal hydrosulfide contained as an impurity of 2% by weight or less is used. Water is present in the system in an amount of 0.1 to 0.8 mol per mol of alkali metal sulfide, and the molar concentration of the alkali metal sulfide is 2.5 to 5 mol / l. There is disclosed a method of reacting a product with a dihalo aromatic compound by heating (for example, see Patent Document 6). Since this method uses an anhydrous alkali metal sulfide, it can be expected that control of the water content in the system and the like is easy. However, in this method, it is essential to use an anhydrous alkali metal sulfide, and in order to obtain it, a large amount of energy is required, and a long time is required, which cannot be said to be sufficient for commercial production. Was. In addition, the degree of polymerization of PAS obtained by the method described in the publication was not sufficiently high. This is because anhydrous alkali metal sulfides are highly deliquescent and oxidizable and lack stability, so they often contain a large amount of impurities such as oxides. Such anhydrous alkali metal sulfides are used in the production of PAS. It is considered that when used, only a PAS having a low melt viscosity can be obtained as a result of inhibiting the degree of polymerization from increasing.
[0006]
Further, the reaction is carried out at a temperature of 235 to 280 ° C. in the presence of water of more than 0.5 mol and 5 mol or less per kg of aprotic solvent to obtain a dihalo aromatic compound conversion of 70 to 98 mol% and PAS After forming a prepolymer having a melt viscosity of 5 to 300 poise, water was added to the reaction system, and the temperature was raised to a temperature of 240 to 290 ° C. in the presence of 6 to 15 mol of water per 1 kg of the solvent. A method for continuing the reaction is disclosed (for example, see Patent Document 7). However, in this method, since the water-containing sulfur source is dehydrated by distilling the water-containing sulfur source in a large amount of an organic amide solvent, the amount of water in the reaction system is still large, and a catalyst such as an organic carboxylic acid metal salt is required during the reaction. Since no compound was used, a long time was required for the reaction, and the degree of polymerization of PAS obtained was not sufficient. Furthermore, it is essential to carry out the reaction using a reaction apparatus in which the liquid contact part of the reaction liquid is made of titanium, which is disadvantageous in cost.
[0007]
In addition, one or more metal sulfides selected from alkali metal sulfides and alkaline earth metal sulfides and having a water / sulfide molar ratio of 1.2 or less are converted into metal chlorides and metal carbonates. And at least one polymerization aid selected from the group consisting of metal carboxylate and a small amount of water, after pretreatment at a temperature of 45 to 230 ° C., and then pretreated metal sulfide and dihalogen aromatic compound (See, for example, Patent Document 8). In this method, a catalyst compound such as a metal salt of an organic carboxylic acid is used at the time of the reaction, so that it is expected that a sufficiently high degree of polymerization PAS is obtained. The reaction is not sufficiently developed, requires a long time for the reaction, and uses expensive sodium sulfide hemihydrate as a sulfidizing agent, which is disadvantageous in cost.
[0008]
Furthermore, there is disclosed a method for producing polyphenylene sulfide (hereinafter sometimes abbreviated as PPS) while keeping the water content of the reaction system in the range of 0.3 to 0.95 mol per sulfur source (see, for example, Japanese Patent Application Laid-Open Publication No. H11-157873). For example, see Patent Document 9.) In this method, inexpensive sodium sulfide nonahydrate is used after dehydration, and a catalyst compound such as a metal salt of an organic carboxylic acid is used at the time of the reaction, so that a sufficiently high degree of polymerization PAS can be expected. . However, in this method, since dehydration is performed by distilling sodium sulfide 9-hydrate in a large amount of an organic amide solvent, the amount of water in the reaction system during the polymerization reaction is still large, and the reaction promoting effect of the catalyst compound is not sufficient. It was not sufficiently expressed, and it took a long time to increase the molecular weight, which was not sufficient from the viewpoint of efficiently obtaining a PAS in a short time as the object of the present invention.
[0009]
As a method of reducing the water content in the reaction system by using inexpensive raw materials, an aqueous mixture composed of a sulfur source and a polar organic compound is dehydrated to form a dehydrated mixture. The molar ratio of the polar organic compound to the source should be in the range of 0.15 / 1 to about 0.9 / 1, and the dehydrated mixture and the polyhalo-substituted aromatic compound are optionally further treated. Disclosed are methods for producing a polymerization mixture by mixing in the presence of an additional polar organic compound, and subjecting the polymerization mixture to a polymerization reaction under conditions effective to effect a polymerization reaction (see, for example, patents). Reference 10). However, in this method, a catalyst compound such as a metal salt of an organic carboxylic acid was not used during the reaction, so that not only a long time was required for the reaction, but also only a low molecular weight PAS could be obtained.
[0010]
[Patent Document 1] Japanese Patent Publication No. 45-3368 (page 13)
[Patent Document 2] Japanese Patent Publication No. 52-12240 (pages 2 and 3)
[Patent Document 3] JP-A-59-219332 (pages 2 and 3)
[Patent Document 4] US Pat. No. 4,038,263 (pages 1, 2)
[Patent Document 5] JP-A-1-161022 (page 2) 4
[Patent Document 6] JP-A-4-145127 (pages 2 and 3)
[Patent Document 7] Japanese Patent Publication No. 7-121985 (pages 3 to 6)
[Patent Document 8] JP-A-64-9229 (pages 3 to 5)
[Patent Document 9] JP-A-59-98133 (page 2)
[Patent Document 10] JP-A-5-239210 (page 3)
[0011]
[Problems to be solved by the invention]
The present invention has been achieved as a result of studying solving the problems in the above-described conventional technology as a problem. Accordingly, an object of the present invention is to provide a method for efficiently producing a linear high molecular weight PAS in a short time.
[0012]
[Means for Solving the Problems]
The present invention employs the following means in order to solve such a problem. That is, a method for producing a polyarylene sulfide by bringing a sulfidizing agent and a dihalogenated aromatic compound into contact with each other in an organic polar solvent and polymerizing the same includes at least the following steps 1 and 2.
Step 1: an alkali metal sulfide containing 1 mol or more of water per 1 mol of a sulfur component is dehydrated in the presence of 0.05 to 0.6 mol of an organic polar solvent per 1 mol of a sulfur component of the alkali metal sulfide. Preparing a sulfidizing agent containing 0.05 to 0.6 moles of water per mole of the component,
Step 2: converting the sulfidizing agent and the dihalogenated aromatic compound prepared in Step 1 into at least one compound selected from a metal salt of an organic carboxylic acid, an aliphatic cyclic amine compound, an N-heteroaromatic compound, and an organic sulfoxide compound; A step of contacting and polymerizing in the presence of 0.05 to 0.6 mol of water per 1 mol of the sulfur component of the agent.
[0013]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, regarding the present invention, PAS, polymerization solvent, dihalogenated aromatic compound, sulfidizing agent, alkali metal sulfide, catalyst compound, polymerization aid, molecular weight regulator, branching / crosslinking agent, polymerization stabilizer, polymerization step, polymer The recovery, other post-processing, and the generated PAS will be described in detail in this order.
[0014]
(1) PAS
The PAS in the present invention is a homopolymer or copolymer having a repeating unit of the formula-(Ar-S)-as a main constituent unit, preferably containing at least 80 mol% of the repeating unit. Examples of Ar include units represented by the following formulas (A) to (K), and among them, formula (A) is particularly preferable.
[0015]
Embedded image

[0016]
(R1 and R2 are substituents selected from hydrogen, an alkyl group, an alkoxy group, and a halogen group, and R1 and R2 may be the same or different.)
As long as this repeating unit is the main constituent unit, it may contain a small amount of a branching unit or a crosslinking unit represented by the following formulas (L) to (N). The copolymerization amount of these branching units or crosslinking units is preferably in the range of 0 to 1 mol% based on 1 mol of-(Ar-S)-units.
[0017]
Embedded image

[0018]
Further, the PAS in the present invention may be any one of a random copolymer, a block copolymer and a mixture thereof containing the above repeating unit.
[0019]
Further, the molecular weight of various PASs is not particularly limited, but usually a preferred range is a melt viscosity of 5 to 5,000 Pa · s (300 ° C., shear rate 1000 / sec).
[0020]
Typical examples thereof include polyphenylene sulfide, polyphenylene sulfide sulfone, polyphenylene sulfide ketone, random copolymers, block copolymers thereof, and mixtures thereof. Particularly preferred PAS is a p-phenylene sulfide unit as a main structural unit of the polymer.
[0021]
Embedded image

[0022]
, In particular, polyphenylene sulfide (hereinafter sometimes abbreviated as PPS) containing 80 mol% or more, particularly 90 mol% or more, polyphenylene sulfide sulfone, and polyphenylene sulfide ketone.
[0023]
(2) Polymerization solvent
In the present invention, it is necessary to use an organic polar solvent as a polymerization solvent, and it is desirable to use an organic amide solvent. Specific examples include N-alkylpyrrolidones such as N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone, caprolactams such as N-methyl-ε-caprolactam, and 1,3-dimethyl-2-imidazolidy. Non-protic organic solvents such as N, N, N-dimethylacetamide, N, N-dimethylformamide, and hexamethylphosphoric triamide, and mixtures thereof are preferably used because of high reaction stability. Among them, N-methyl-2-pyrrolidone (hereinafter sometimes abbreviated as NMP) is preferably used.
[0024]
In the present invention, the amount of the organic polar solvent used in Step 1 described later must be 0.05 to 0.6 mol per 1 mol of the sulfur component of the alkali metal sulfide described later, and is 0.1 to 0.5 mol. Mole is preferred, and 0.15 to 0.45 mole is more preferred. If the amount is too small or too large, the polymerization reaction in step 2 or later described later tends to be difficult to proceed.
[0025]
In the present invention, the amount of the organic polar solvent used as the polymerization solvent in step 2 and subsequent steps, which will be described later, is not particularly limited. However, in the method of the present invention, a PAS suitable for various uses in the commercial use of resins such as injection molding and extrusion molding can be produced with a smaller amount of the polymerization solvent as compared with the methods described in the prior art. Therefore, the amount of the organic polar solvent used as the polymerization solvent is preferably 1.0 to 4.0 mol, more preferably 1.0 to 3.5 mol, per 1 mol of the sulfur component of the sulfidizing agent. More preferably, 1.5 to 2.5 mol can be exemplified as a preferable range. In general, a smaller amount of the polymerization solvent is economically advantageous because the amount of the polymer per unit volume increases, but an undesired reaction tends to occur when the amount is too small, and the degree of polymerization tends to hardly increase when the amount is too large. Yes, and can be economically disadvantageous. Also, if the amount is too large or too small, the time required for the reaction tends to be long, which may be economically disadvantageous. Here, the amount of the organic polar solvent in the reaction system is an amount obtained by subtracting the organic polar solvent removed outside the reaction system from the organic polar solvent introduced into the reaction system.
[0026]
(3) Dihalogenated aromatic compounds
Examples of the dihalogenated aromatic compound used in the present invention include dihalogenated benzenes such as p-dichlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dibromobenzene, and 1-methoxy-2,5-dichlorobenzene. And dihalogenated aromatic compounds which also contain a substituent other than halogen, such as 3,5-dichlorobenzoic acid. Above all, a dihalogenated aromatic compound mainly composed of p-dihalogenated benzene represented by p-dichlorobenzene is preferable. Particularly preferably, it contains 80 to 100 mol% of p-dichlorobenzene, and more preferably contains 90 to 100 mol%. It is also possible to use two or more different dihalogenated aromatic compounds in combination for producing a PAS copolymer.
[0027]
From the viewpoint of obtaining a polyarylene sulfide having a viscosity suitable for processing, the amount of the dihalogenated aromatic compound is preferably from 0.9 to 2.0 mol per mol of the sulfur component of the sulfidizing agent, more preferably The range is preferably from 0.95 to 1.5 mol, more preferably from 1.00 to 1.2 mol.
[0028]
(4) Sulfidizing agent / alkali metal sulfide
In the present invention, 0.05 to 0.6 mol of water is contained per 1 mol of a sulfur component obtained by removing water from an alkali metal sulfide containing 1 mol or more of water per 1 mol of a sulfur component as a sulfidizing agent. Use a sulfidizing agent. Here, the amount of water contained in the sulfidizing agent is preferably from 0.1 to 0.5 mol, more preferably from 0.15 to 0.45 mol, per mol of the sulfur component of the sulfidizing agent. In such a method for preparing a sulfidizing agent having the above-mentioned water content from an alkali metal sulfide containing 1 mol or more of water per 1 mol of a sulfur component, a dehydration step described later is employed.
[0029]
Specific examples of the alkali metal sulfide to be used include, for example, lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide and a mixture of two or more thereof. Among them, sodium sulfide is preferably used. . These alkali metal sulfides can be used as hydrates or aqueous mixtures. The aqueous mixture refers to an aqueous solution, a mixture of an aqueous solution and a solid component, or a mixture of water and a solid component. Here, the hydrate or the aqueous mixture as the alkali metal sulfide must have a water content of 1 mol or more per 1 mol of the sulfur component, preferably 4 mol or more, more preferably 4 mol or more. Use less than or equal to moles. If the amount is too small, the handleability of the alkali metal sulfide deteriorates, and furthermore, it tends to contain impurities.If the amount is too large, the amount of water to be removed in the dehydration step becomes large, and a long time is required for dehydration. .
[0030]
Further, an alkali metal sulfide and an alkali metal hydroxide and / or an alkali metal sulfide prepared from an alkali metal hydroxide and hydrogen sulfide can be used in the same manner as the alkali metal sulfide described above. Specific examples of the alkali metal hydrosulfide include, for example, sodium hydrogen sulfide, potassium hydrogen sulfide, lithium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide, and a mixture of two or more of these. Sodium sulfide is preferably used. These alkali metal hydrosulfides can be used as hydrates or aqueous mixtures or in anhydrous form. In addition, hydrogen sulfide can be used in any form of gas, liquid, and aqueous solution.
[0031]
Specific examples of the alkali metal hydroxide include, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, and a mixture of two or more thereof. In particular, sodium hydroxide is preferably used. These alkali metal hydroxides can be used as hydrates or aqueous mixtures or in anhydrous form. When the alkali metal hydrosulfide is used, the amount of the alkali metal hydroxide to be used is 1.0 to 1.20 mol, preferably 1.005 to 1.15 mol, more preferably 1 mol of the alkali metal hydrosulfide. A range of 1.02 to 1.100 mol can be exemplified. When hydrogen sulfide is used, the amount of the alkali metal hydroxide to be used is 2.0 to 2.40 mol, preferably 2.01 to 2.30 mol, more preferably 2.04 to 2.40 mol per mol of hydrogen sulfide. A range of 20 mol can be exemplified.
[0032]
In the present invention, the amount of the sulfidizing agent present in the reaction system at the time of the polymerization reaction (hereinafter, also referred to as the charged sulfidizing agent) may be partially lost by the dehydration operation or the like before the start of the polymerization reaction. When it occurs, it means the remaining amount obtained by subtracting the loss from the actual amount charged.
[0033]
(5) Catalyst compound
In the present invention, at least in step 2 described below, at least one compound selected from an organic carboxylic acid metal salt, an aliphatic cyclic amine compound, an N-heteroaromatic compound, and an organic sulfoxide compound (hereinafter, also referred to as a catalyst compound) may be used. It is necessary to coexist in a reaction system where a sulfidizing agent and a dihalogenated aromatic compound are present in an organic polar solvent. This is important in order to improve the reaction rate in Step 2 described below and to make the reaction in Step 2 proceed even with the use of a very small amount of a polymerization solvent. Here, the improvement of the reaction rate shortens the process time required for the polymerization reaction, and the use of a small amount of the polymerization solvent increases the amount of the polymer produced per unit volume of the reactor. It is important. The use of a metal salt of an organic carboxylic acid among the above-mentioned catalyst compounds is preferred in that it can also serve as a polymerization aid described later.
[0034]
Further, in the step 2, as described later, it is necessary to carry out the polymerization in the presence of 0.05 to 0.6 mol of water per 1 mol of the sulfur component of the sulfidizing agent. Is important in expressing
[0035]
Here, the reason why the catalyst compound improves the reaction rate is not clear, but the catalyst compound has some interaction with the sulfidizing agent in the reaction system, thereby improving the solubility of the sulfidizing agent in the reaction system, It is presumed that the reaction rate is improved by increasing the contact probability between the sulfidizing agent and the dihalogenated aromatic compound.
[0036]
The organic carboxylic acid metal salt may be a compound represented by the general formula R (COOM) n (where R is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group, an alkylaryl group, an arylalkyl group, an aminoalkyl group) , An N-alkylaminoalkyl group and an N-phenylaminoalkyl group having 2 to 20 carbon atoms, among which an alkyl group, an aryl group and an N-alkylaminoalkyl group are preferable. , An alkali metal selected from rubidium and cesium, or an alkaline earth metal selected from magnesium, calcium, strontium and barium. N is an integer of 1 to 3). . Specific examples of the organic carboxylic acid metal salt include, for example, lithium acetate, sodium acetate, potassium acetate, magnesium acetate, calcium acetate, lithium propionate, sodium propionate, potassium propionate, lithium 4-hydroxybutyrate, and 4-hydroxybutyric acid. Sodium, lithium N-methyl-4-aminobutyrate, sodium N-methyl-4-aminobutyrate, lithium N-ethyl-4-aminobutyrate, sodium N-ethyl-4-aminobutyrate, N-phenyl-4-aminobutyric acid One kind of compound selected from lithium, sodium N-phenyl-4-aminobutyrate, lithium valerate, sodium benzoate, sodium phenylacetate and potassium p-toluate, and a mixture thereof can be given. The organic carboxylic acid metal salt is obtained by adding an organic acid and one or more compounds selected from the group consisting of an alkali metal hydroxide, an alkali metal carbonate and an alkali metal bicarbonate, and reacting them by adding them in almost equal stoichiometric equivalents. It may be formed. Among the above metal salts of organic carboxylic acids, lithium salts have high solubility in the reaction system and have a large auxiliary effect, but are expensive, and potassium, rubidium, cesium and alkaline earth metal salts have a high solubility in the reaction system. It is presumed to be inferior, and a sodium salt which is inexpensive and has appropriate solubility in a polymerization system is preferably used.
[0037]
Specific examples of the aliphatic cyclic amine compound include piperazine, piperidine, pyrrolidine, N, N'-dimethylpiperazine, 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0 ] -Non-5-ene, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo [4,4,0] -5-nonene, hexamethylenetetramine Compounds and mixtures thereof can be mentioned.
[0038]
Specific examples of the N-heteroaromatic compound are selected from pyridine, pyridazine, pyrimidine, sym-triazine, sym-tetrazine, quinoline, isoquinoline, quinazoline, 1,5-naphthyridine, pteridine, acridine, phenazine, and phenanthridine. One kind of compounds and mixtures thereof can be mentioned.
[0039]
Specific examples of the organic sulfoxide compound include dimethyl sulfoxide and / or tetramethylene sulfoxide.
[0040]
Among the above catalyst compounds, sodium acetate is particularly preferable because it is inexpensive and easily available.
[0041]
At least one catalyst compound selected from an organic carboxylic acid metal salt, an aliphatic cyclic amine compound, an N-heteroaromatic compound, and an organic sulfoxide compound can be used as a hydrate or an aqueous solution. These catalyst compounds are used in an amount of 0.001 to 1.0 mol, preferably 0.01 to 0.7 mol, more preferably 0.02 to 1.0 mol per mol of the sulfur component of the sulfidizing agent present in the reaction system. When 0.6 mol, more preferably 0.05 to 0.45 mol is present in the reaction system, a particularly large reaction promoting effect tends to be obtained. Therefore, in order to obtain PAS in a short time, the amount of the catalyst compound used is desirably within the above range.
[0042]
(6) polymerization aid
In the method of the present invention, a polymerization aid can be used to obtain PAS having a high degree of polymerization in a shorter time. Here, the polymerization aid refers to a substance having an action of increasing the viscosity of the obtained PAS. Specific examples of such polymerization aids include, for example, organic carboxylic acid metal salts, water, alkali metal chlorides, organic sulfonic acid metal salts, alkali metal sulfates, alkaline earth metal oxides, alkali metal phosphates And alkaline earth metal phosphates. These may be used alone or in combination of two or more. Among these, metal salts of organic carboxylic acids and / or water are preferably used.
[0043]
The organic carboxylic acid metal salt has a general formula R (COOM) n (where R is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group, an alkylaryl group or an arylalkyl group. , Sodium, potassium, rubidium and cesium, and n is an integer of 1 to 3). The organic carboxylic acid metal salt can also be used as a hydrate or an aqueous solution. Specific examples of the organic carboxylate include lithium acetate, sodium acetate, potassium acetate, sodium propionate, sodium benzoate, sodium phenylacetate, potassium p-toluate, and mixtures thereof. The organic carboxylic acid metal salt is obtained by adding an organic acid and one or more compounds selected from the group consisting of an alkali metal hydroxide, an alkali metal carbonate and an alkali metal bicarbonate, and reacting them by adding approximately equal stoichiometric amounts. May be formed. Among the above metal salts of organic carboxylic acids, potassium, rubidium and cesium salts are presumed to have poor solubility in the reaction system, and sodium acetate which is inexpensive and has appropriate solubility in the reaction system is preferably used. .
[0044]
When an organic carboxylic acid metal salt is used as the above-mentioned catalyst compound, it may exhibit both effects as a catalyst compound and an effect as a polymerization aid in some cases.
[0045]
The use amount of these organic carboxylic acid metal salts is preferably in the range of 0.01 to 0.7 mol, more preferably 0.02 to 0.6 mol, per mol of the sulfur component of the charged sulfidizing agent, A range of 0.05 to 0.45 mol is even more preferred. If the amount is less than the above range, the effect of increasing the degree of polymerization tends to be insufficient, and even if the amount exceeds the above range, the effect of increasing the degree of polymerization further tends to be hardly obtained.
[0046]
When water is used as the polymerization aid, it is preferable to include a step in which the amount of water in the polymerization system is 0.7 to 5.0 mol per mol of the sulfur component of the charged sulfidizing agent. A more preferable range of the water content is 0.8 to 2.0 mol, more preferably 0.85 to 1.8 mol, per 1 mol of the sulfur component of the charged sulfidizing agent. If the amount of water in this case is less than the above range, a sufficient effect of increasing the degree of polymerization may not be obtained.On the other hand, if the amount of water exceeds the above range, not only the polymerization time becomes longer but also the internal pressure of the reactor. Therefore, there is a need for a reactor having higher pressure resistance performance, which is not preferable in terms of economy and safety.
[0047]
When water is used as the polymerization aid, it is preferable to use an organic carboxylic acid metal salt at the same time, whereby the effect as the polymerization aid can be further enhanced, and even when the amount of the auxiliary agent used is small, the effect can be increased in a short time. It tends to obtain a degree of polymerization PAS. In this case, the preferable range of the water content is 0.8 to 2.0 mol, more preferably 0.85 to 1.8 mol, per 1 mol of the sulfur component of the charged sulfidizing agent. The preferred range of the amount of the organic carboxylic acid metal salt is in the range of 0.02 to 0.6 mol per mol of the sulfur component of the charged sulfidizing agent, and preferably in the range of 0.05 to 0.45 mol. More preferred.
[0048]
(7) Molecular weight regulator / branching / crosslinking agent
In the present invention, a molecular weight regulator (not necessarily an aromatic compound) such as a monohalogen compound is used to form a terminal of the formed PAS or to control a polymerization reaction or a molecular weight. It can be used in combination with a group compound. In order to form a branched or crosslinked polymer, trihalogenated or higher polyhalogen compounds (not necessarily aromatic compounds), active hydrogen-containing halogenated aromatic compounds, halogenated aromatic nitro compounds, etc. -It is also possible to use a crosslinking agent together. As the polyhalogen compound, a commonly used compound can be used. Among them, a polyhalogenated aromatic compound is preferable, and specific examples thereof include 1,3,5-trichlorobenzene, 1,2,4-trichlorobenzene, Examples thereof include 1,2,4,5-tetrachlorobenzene, hexachlorobenzene, and 1,4,6-trichloronaphthalene. Among them, 1,3,5-trichlorobenzene and 1,2,4-trichlorobenzene are preferable. Examples of the active hydrogen-containing halogenated aromatic compound include a halogenated aromatic compound having a functional group such as an amino group, a mercapto group, and a hydroxyl group. Specific examples include 2,5-dichloroaniline, 2,4-dichloroaniline, 2,3-dichloroaniline, 2,4,6-trichloroaniline, 2,2′-diamino-4,4′-dichlorodiphenylether, , 4'-Diamino-2 ', 4-dichlorodiphenyl ether. Examples of the halogenated aromatic nitro compound include, for example, 2,4-dinitrochlorobenzene, 2,5-dichloronitrobenzene, 2-nitro-4,4′-dichlorodiphenyl ether, and 3,3′-dinitro-4,4′- Examples thereof include dichlorodiphenylsulfone, 2,5-dichloro-2-nitropyridine, and 2-chloro-3,5-dinitropyridine.
[0049]
(8) Polymerization stabilizer
In the present invention, a polymerization stabilizer can be used to stabilize the polymerization reaction system and prevent side reactions. The polymerization stabilizer contributes to stabilization of the polymerization reaction system and suppresses undesirable side reactions. One measure of the side reaction is the formation of thiophenol, and the addition of a polymerization stabilizer can suppress the formation of thiophenol. Specific examples of the polymerization stabilizer include compounds such as alkali metal hydroxides, alkali metal carbonates, alkaline earth metal hydroxides, and alkaline earth metal carbonates. Among them, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide are preferred. Since the above-mentioned metal salts of organic carboxylic acids also act as polymerization stabilizers, they are included in one of the polymerization stabilizers used in the present invention.
[0050]
These polymerization stabilizers can be used alone or in combination of two or more. The polymerization stabilizer is preferably used in a proportion of usually 0.01 to 0.2 mol, preferably 0.03 to 0.1 mol, per 1 mol of the sulfur component of the charged sulfidizing agent. If the proportion is small, the stabilizing effect may be insufficient. Conversely, if the proportion is too large, it is economically disadvantageous or the polymer yield tends to decrease. When a part of the alkali metal sulfide is decomposed during the reaction to generate hydrogen sulfide, the resulting alkali metal hydroxide can also be a polymerization stabilizer.
[0051]
(9) Polymerization step
The polyarylene sulfide produced by the present invention is obtained by including at least the following steps 1 and 2 when polymerizing a sulfidizing agent and a dihalogenated aromatic compound in contact with each other in an organic polar solvent. is there.
Step 1: an alkali metal sulfide containing 1 mol or more of water per 1 mol of a sulfur component is dehydrated in the presence of 0.05 to 0.6 mol of an organic polar solvent per 1 mol of a sulfur component of the alkali metal sulfide. Step of preparing a sulfidizing agent containing 0.05 to 0.6 mol of water per mol of the component
Step 2: converting the sulfidizing agent and the dihalogenated aromatic compound prepared in Step 1 into at least one compound selected from a metal salt of an organic carboxylic acid, an aliphatic cyclic amine compound, an N-heteroaromatic compound, and an organic sulfoxide compound; A step of contacting and polymerizing in the presence of 0.05 to 0.6 mol of water per 1 mol of the sulfur component of the agent.
[0052]
Further, it is preferable to perform the step 2 after the step 1, and there may be additional steps such as a pre-processing step and a post-processing step other than these steps. Further, Step 1 and Step 2 may be performed in the same reaction vessel, or Step 2 may be performed by transferring the reaction mixture from the reaction vessel in which Step 1 was performed to a different vessel.
[0053]
<Step 1> In the present invention, Step 1 of preparing a sulfidizing agent containing water is performed by removing water from an alkali metal sulfide containing water in the presence of an organic polar solvent.
[0054]
As the alkali metal sulfide containing water, an alkali metal sulfide having a water content of 1 mol or more per mol of the sulfur component is used. The amount of the organic polar solvent used is 0.05 to 0.6 mol per 1 mol of the sulfur component of the alkali metal sulfide containing water. The amount of water contained in the sulfidizing agent prepared in step 1 is 0.05 to 0.6 mol per 1 mol of the sulfur component of the sulfidizing agent. If the amount of water containing the sulfidizing agent prepared here is too small, the polymerization reaction in step 2 or later described below does not easily proceed, and if it is too large, a large amount of water remains in the obtained sulfidizing agent, The reaction promoting effect of the catalyst compound in step 2 is less likely to be exhibited.
[0055]
The method for preparing the above-mentioned water-containing sulfidizing agent from an alkali metal sulfide containing 1 mol or more of water per 1 mol of the sulfur component is not particularly limited. For example, the following dehydration step is employed. Is done. That is, the organic polar solvent and the alkali metal sulfide are mixed in a temperature range of room temperature to 150 ° C., preferably room temperature to 100 ° C., preferably under an inert gas atmosphere, and at normal pressure or reduced pressure, at least 150 ° C. or higher, preferably A method in which the temperature is raised to 170 to 250 ° C. to distill off water is mentioned. At this stage, the above-mentioned catalyst compound and polymerization aid may be added. Further, in order to promote the distillation of water, water may be distilled by adding toluene or the like. Dehydration is also preferably performed when compounds other than alkali metal sulfide, such as an organic polar solvent, a catalyst compound, and a polymerization aid, are charged in a state containing water.
[0056]
The organic polar solvent used here is preferably an organic amide solvent, which often makes it easy to control the amount of water remaining in the sulfidizing agent in the dehydration step.
[0057]
According to the present invention, by setting the amount of the organic polar solvent in the dehydration step to a specific range, it is possible to easily prepare a sulfidizing agent containing a specific amount of water.
[0058]
<Step 2> In the present invention, the sulfidizing agent and the dihalogenated aromatic compound prepared in the step 1 are selected from metal salts of organic carboxylic acids, aliphatic cyclic amine compounds, N-heteroaromatic compounds, and organic sulfoxide compounds. Step 2 of contacting and polymerizing at least one compound and the sulfur component of the sulfidizing agent in the presence of 0.05 to 0.6 mol of water per mol of the sulfur component is performed.
[0059]
In the reaction in step 2, the reaction mixture composed of the above-mentioned components is heated to a temperature of usually 120 to 300 ° C, preferably 180 to 260 ° C, more preferably 200 to 255 ° C, for 0.1 to 40 hours, preferably It is preferable to carry out the polymerization reaction by heating for 0.5 to 20 hours, more preferably 1 to 10 hours. If the reaction temperature is lower than 120 ° C., the reaction rate is low, and the reaction may be extremely uneven. On the other hand, if the reaction temperature is higher than 300 ° C., decomposition of the produced polymer component and deterioration of the solvent are easily caused. In addition, the internal pressure of the reactor increases greatly, and a reactor having a higher pressure resistance is required for the reactor, which is not preferable in terms of economy and safety. The polymerization may be a one-stage reaction performed at a constant temperature, a multi-stage reaction in which the temperature is gradually increased, or a reaction in which the temperature is continuously changed. In order to suppress the reaction, it is preferable to conduct a reaction at a temperature of 120 to 240 ° C. to a certain degree, and then carry out the polymerization at a temperature of 240 to 300 ° C. In addition, the reaction time in step 2 cannot be specified unconditionally because it depends on the type and amount of the raw materials used, or the reaction temperature. However, if the reaction time is less than 0.1 hour, the amount of unreacted components increases or the produced polymer has a low molecular weight. In the case of 40 hours or more, the PAS is obtained in a short time, which is the object of the present invention.
[0060]
In the reaction of Step 2 of the present invention, an organic polar solvent, a dihalogenated aromatic compound, a sulfidizing agent and a catalyst compound prepared in Step 1 are charged into a reactor, and the mixture is sufficiently stirred and mixed in the reactor. A method of raising the temperature and polymerizing at a polymerization temperature; charging an organic polar solvent, a sulfidizing agent and a catalyst compound prepared in the above step 1 into a reactor, sufficiently stirring and mixing in the reactor, and then raising the temperature to perform polymerization. After the temperature is raised to the temperature, a dihalogenated aromatic compound is added and polymerized; an organic polar solvent, a dihalogenated aromatic compound and a catalyst compound are charged into a reactor, and the mixture is sufficiently stirred in the reactor, and then sulfided. A method in which the agent is added as a solid or slurry (with water or a solvent) and polymerized at a polymerization temperature; in Step 1, a sulfidizing agent is prepared and then placed in the reaction vessel used here. A method in which a polar solvent, a dihalogenated aromatic compound and a catalyst compound are added, and the mixture is sufficiently stirred to polymerize at a polymerization temperature; the sulfidizing agent prepared in Step 1 is transferred to a reactor different from that in Step 1, and the organic polar solvent is added. A method in which a dihalogenated aromatic compound and a catalyst compound are added, and the mixture is sufficiently stirred and polymerized at a polymerization temperature; an organic polar solvent, a dihalogenated aromatic compound and a catalyst compound are charged into a reactor different from the step 1, and A method in which the sulfidizing agent prepared in Step 1 is added and the mixture is sufficiently stirred and polymerized at a polymerization temperature; a sulfidizing agent is prepared in the presence of a catalyst compound in Step 1, and the organic polar solvent and the dihalogen are placed in the same reaction vessel as in Step 1. A method of adding a fluorinated aromatic compound, etc., and sufficiently stirring and polymerizing at a polymerization temperature; preparing a sulfidizing agent in the presence of a catalyst compound in step 1; After transferring the non-sulfide agent in different reactors from steps 1, it can be exemplified a method of polymerizing a polymerization temperature under sufficiently agitated adding an organic polar solvent and the dihalogenated aromatic compound.
[0061]
In step 2, the amount of water in the reaction system is determined at the start of the reaction, that is, at the stage where the conversion of the dihalogenated aromatic compound (hereinafter may be abbreviated as DHA) charged into the reaction system is 0, and It must be 0.05 to 0.6 mol per mol of the sulfur component of the agent, preferably 0.1 to 0.5 mol, more preferably 0.15 to 0.45 mol. If the amount is too small, the polymerization reaction hardly proceeds. If the amount is too large, the effect of promoting the reaction by the catalyst compound, which is a feature of the present invention, is hardly exhibited. Therefore, when various components other than the sulfidizing agent prepared in Step 1 contain water, it is preferable to dehydrate the various components before the reaction to adjust the amount of water in the reaction system. In addition, when the amount of water in the reaction system is small, there is no problem even if water is added within the above range of the amount of water. The conversion rate of DHA is a value calculated by the following equation. The residual amount of DHA can usually be determined by gas chromatography.
[0062]
(A) When the dihalogenated aromatic compound is excessively added in a molar ratio to the sulfidizing agent
Conversion rate = [[DHA charge (mol) -DHA residual amount (mol)] / [DHA charge (mol) -DHA excess (mol)]] × 100%
(B) In cases other than (a) above
Conversion rate = [[DHA charge (mol) -DHA remaining amount (mol)] / [DHA charge (mol)]] × 100%
The amount of the organic polar solvent used as the polymerization solvent in Step 2 is preferably 1.0 to 4.0 mol, more preferably 1.0 to 3.5 mol, per 1 mol of the sulfur component of the sulfidizing agent. Preferably, 1.5 to 2.5 mol can be exemplified as a preferable range. In general, a smaller amount of the polymerization solvent is economically advantageous because the amount of the polymer per unit volume increases, but an undesired reaction tends to occur when the amount is too small, and the degree of polymerization tends to hardly increase when the amount is too large. Yes, and can be economically disadvantageous. Also, if the amount is too large or too small, the time required for the reaction tends to be long, which may be economically disadvantageous.
[0063]
Further, in the polymerization step of the present invention, at the stage when the conversion of the dihalogenated aromatic compound becomes 60 mol% or more, preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more, Step 3 is preferably performed.
[0064]
<Step 3> In step 3, the amount of water in the polymerization system is adjusted to 0.7 to 5.0 mol, preferably 0.8 to 2.0 mol, more preferably 0.1 to 2.0 mol per mol of the sulfur component of the sulfidizing agent. In this step, the concentration is adjusted to 85 to 1.8 mol, and the polymerization is further continued.
[0065]
Step 3 is preferably performed continuously after step 2, and steps 2 and 3 may be performed in the same reactor, or the reaction mixture in step 2 may be transferred to a different reactor to perform step 3. Is also good.
[0066]
Performing step 3 following step 2 is particularly effective for obtaining PAS having a high degree of polymerization in a short time. When the amount of water is less than the above range, the degree of polymerization tends to be insufficient.On the other hand, when the amount of water is more than the above range, a rise in the internal pressure of the reactor is large, and a reactor having a higher pressure resistance performance is required. Become. There is no particular limitation on the method for adjusting the amount of water in the polymerization system, but for example, a method of injecting insufficient water into the reaction system can be exemplified.
[0067]
In the reaction in step 3, the reaction mixture composed of the above components is heated to a temperature of usually 120 to 300 ° C, preferably 200 to 300 ° C, more preferably 255 to 280 ° C, for 0.1 to 40 hours, preferably The polymerization reaction is preferably performed by heating for 0.2 to 20 hours, more preferably 0.5 to 10 hours. If the reaction temperature is lower than 120 ° C., the reaction rate is slow, and the reaction may be non-uniform.On the other hand, if the reaction temperature is higher than 300 ° C., decomposition of the produced polymer component and deterioration of the solvent are not only likely to occur, but also Since the internal pressure of the reactor is greatly increased and a reactor having a higher pressure resistance is required for the reactor, it is not preferable in terms of economy and safety. The polymerization may be a one-stage reaction performed at a constant temperature, a multi-stage reaction in which the temperature is gradually increased, or a reaction in which the temperature is continuously changed. In addition, the reaction time in Step 3 cannot be specified unconditionally because it depends on the type and amount of the raw materials used, or the reaction temperature. However, if the reaction time is less than 0.1 hour, the amount of unreacted components increases or the produced polymer has a low molecular weight. In the case of 40 hours or more, it is contrary to the object of the present invention to obtain a PAS in a short time.
[0068]
The amount of the organic polar solvent used as the polymerization solvent in Step 3 is preferably 1.0 to 4.0 mol, more preferably 1.0 to 3.5 mol, per 1 mol of the sulfur component of the sulfidizing agent. Preferably, 1.5 to 2.5 mol can be exemplified as a preferable range. In general, a smaller amount of the polymerization solvent is economically advantageous because the amount of the polymer per unit volume increases, but an undesired reaction tends to occur when the amount is too small, and the degree of polymerization tends to hardly increase when the amount is too large. Yes, and can be economically disadvantageous. Also, if the amount is too large or too small, the time required for the reaction tends to be long, which may be economically disadvantageous.
[0069]
In the polymerization of the present invention, known polymerization systems such as a batch system and a continuous system can be employed. The atmosphere during the polymerization is preferably under a non-oxidizing atmosphere, preferably under an inert gas atmosphere such as nitrogen, helium, argon, etc., and particularly preferably nitrogen from the viewpoint of economy and ease of handling. . The reaction pressure is not particularly limited since it cannot be specified unconditionally depending on the types and amounts of the raw materials and the solvents used, the reaction temperature, and the like.
[0070]
In the present invention, in order to obtain a high polymerization degree PAS in a shorter time, it is preferable that at least a part of all the polymerization steps is performed in the presence of the above-mentioned polymerization aid. There is no particular limitation on the timing of addition of the polymerization aid, and it may be added at any time before the start of step 1, at the start of step 2, during the step 2, at the start of the step 3, or during the step 3, Although it may be added in plural times, if at least step 3 is performed in the presence of a polymerization aid, it becomes easy to obtain a high polymerization degree PAS in a short time. The polymerization aid may be added in any form such as an anhydride, a hydrate, an aqueous solution, or a mixture with an organic polar solvent. However, when the added polymerization aid contains water, and the DHA conversion rate is high. Is added at the time of 90% or less, preferably 80% or less, more preferably 70% or less, and still more preferably 60% or less, the amount of water in the reaction system at the stage when the addition of the polymerization aid has been completed is charged. The sulfur component of the sulfidizing agent is preferably 0.05 to 0.6 mol per mol of the sulfur component.
[0071]
(10) Polymer recovery
In the method for producing a PAS resin according to the present invention, after the polymerization step is completed, the PAS is recovered from a solid containing the PAS resin component, the solvent, and the like obtained in the polymerization step. As a recovery method, for example, a flash method, that is, a polymerization reaction product is flashed from a state of high temperature and high pressure (usually 250 ° C. or more, 0.8 MPa or more) to an atmosphere of normal pressure or reduced pressure, and the polymer is powdered simultaneously with solvent recovery. A method in which the polymerization reaction product is gradually cooled from a high-temperature and high-pressure state to recover the polymerization reaction product, and the polymerization reaction product is gradually cooled from a high-temperature and high-pressure state to precipitate the PAS component in the reaction system. A method of collecting a solid containing a PAS component by filtering under the above conditions may be used. Here, the state in which the polymer component is precipitated is a state in which at least 60% or more of the produced polymer component is in a state of not being melted and dissolved in the polymerization solvent. More specifically, it was assumed that when the solid component in the polymer obtained when the reaction system in a certain state was rapidly cooled to 100 ° C. or lower was recovered by an 80 mesh sieve, all of the charged sulfidizing agent was converted to PAS. It can be recovered in a yield of 60% or more based on the weight (theoretical amount). In addition, when the molar amount of the sulfur component contained in the sulfidizing agent charged here is larger than the molar amount of the dihalogenated aromatic compound, it may not be possible to convert all of them to PAS. However, it will be considered based on the amount of the sulfidizing agent charged.
[0072]
The product containing the solid PAS resin thus obtained is preferably washed with an organic solvent and / or water.
[0073]
The following method can be exemplified as a specific method for washing a product containing a solid PAS resin with an organic solvent. That is, the organic solvent used for washing is not particularly limited as long as it does not have a function of decomposing the PAS resin. For example, nitrogen-containing polar solvents such as N-methyl-2-pyrrolidone, dimethylformamide, and dimethylacetamide , Sulfoxide and sulfone solvents such as dimethyl sulfoxide and dimethyl sulfone; ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone and acetophenone; ether solvents such as dimethyl ether, dipropyl ether and tetrahydrofuran; chloroform, methylene chloride, trichloroethylene and dichloride Halogen solvents such as ethylene, dichloroethane, tetrachloroethane, chlorobenzene, methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene Glycol, phenol, cresol, alcohol phenol based solvents such as polyethylene glycol, benzene, toluene, and aromatic hydrocarbon solvents such as xylene. Among these organic solvents, use of N-methyl-2-pyrrolidone, acetone, dimethylformamide, chloroform or the like is preferable, and N-methyl-2-pyrrolidone and / or acetone is more preferable. These organic solvents can be used alone or in combination of two or more.
[0074]
As a method for washing with an organic solvent, there is a method such as immersing a PAS resin in an organic solvent, and if necessary, stirring or heating can also be performed.
[0075]
The washing temperature when washing the PAS resin with an organic solvent is not particularly limited, and an arbitrary temperature from normal temperature to about 300 ° C. can be selected. Although the cleaning efficiency tends to increase as the cleaning temperature increases, a sufficient effect is usually obtained at a cleaning temperature of room temperature to 150 ° C.
[0076]
The proportion of the PAS resin and the organic solvent is preferably as high as possible, but a bath ratio of 300 g or less of the PAS resin to 1 liter of the organic solvent is usually selected.
[0077]
When a product containing a solid PAS resin in a slurry state containing a granular PAS resin is obtained by using a method of gradually cooling and recovering a polymerization reaction product from a high-temperature and high-pressure state as a recovery method, an organic compound is used. It is preferable that the slurry is separated by filtration before washing with a solvent, and then washed with an organic solvent. By taking such a procedure, a higher cleaning effect can often be obtained when the same amount of organic solvent is used. The method of filtration is not particularly limited, and examples thereof include filtration by a sieve, filtration by centrifugation, and filtration using a filter cloth.
[0078]
In order to remove residual organic solvents and ionic impurities from the product containing the solid PAS resin, it is preferable to wash the product several times with water.
[0079]
As a method of washing the PAS resin with water, there is a method of immersing the PAS resin in water and the like, and it is also possible to agitate or heat as appropriate as needed.
[0080]
The washing temperature when washing the PAS resin with water is preferably from 20C to 220C, more preferably from 50C to 200C. If the temperature is lower than 20 ° C., it is difficult to remove by-products.
[0081]
The water used in the water washing is preferably distilled water or deionized water, but if necessary, formic acid, acetic acid, propionic acid, butyric acid, chloroacetic acid, dichloroacetic acid, acrylic acid, crotonic acid, benzoic acid, salicylic acid, Including organic acidic compounds such as oxalic acid, malonic acid, succinic acid, phthalic acid and fumaric acid, and their alkali metals, alkaline earth metal salts, inorganic acidic compounds such as sulfuric acid, phosphoric acid, hydrochloric acid, carbonic acid and silicic acid, and ammonium ions An aqueous solution may be used.
[0082]
The operation of the hot water treatment for washing with water at 100 ° C. or higher is usually performed by charging a predetermined amount of PAS resin into a predetermined amount of water, and heating and stirring at normal pressure or in a pressure vessel. The proportion of the PAS resin and water is preferably as high as possible. Usually, a bath ratio of 200 g or less of PAS resin to 1 liter of water is selected.
[0083]
(11) Other post-processing
The PAS resin thus obtained is dried under normal pressure and / or reduced pressure. The drying temperature is preferably in the range of 120 to 280C, more preferably in the range of 140 to 250C. The drying atmosphere may be nitrogen, helium, an inert atmosphere such as under reduced pressure, an oxidizing atmosphere such as oxygen or air, or a mixed atmosphere of air and nitrogen, but is preferably performed under reduced pressure, particularly under normal pressure. After drying to remove water and the like, it is preferable to dry again under reduced pressure. The drying time is preferably 0.5 to 50 hours, more preferably 1 to 30 hours, and even more preferably 1 to 20 hours.
[0084]
The PAS resin obtained in the present invention can be treated at a temperature of 130 to 260 ° C. in order to remove volatile components or to increase the molecular weight of the crosslinked polymer.
[0085]
When a dry heat treatment is performed for the purpose of suppressing cross-linking to increase the molecular weight and removing volatile components, the temperature is preferably from 130 to 250 ° C, and more preferably from 160 to 250 ° C. The oxygen concentration is preferably less than 5% by volume, more preferably less than 2% by volume. Drying under reduced pressure is also one of the preferable methods. The treatment time is preferably 0.5 to 50 hours, more preferably 1 to 20 hours, and still more preferably 1 to 10 hours.
[0086]
When performing dry heat treatment for the purpose of increasing the molecular weight of the crosslinked polymer, the temperature is preferably from 160 to 260 ° C, and more preferably from 170 to 250 ° C. It is desirable that the oxygen concentration be 5% by volume or more, and more preferably 8% by volume or more. The processing time is preferably 1 to 100 hours, more preferably 2 to 50 hours, and still more preferably 3 to 25 hours.
[0087]
The heating device may be an ordinary hot-air dryer or a rotary heating device or a heating device with a stirring blade. For efficient and more uniform treatment, a heating device with a rotary or stirring blade is used. Is more preferred.
[0088]
(12) Generated PAS
The PAS obtained by the method of the present invention is excellent in heat resistance, chemical resistance, flame retardancy, electrical properties and mechanical properties, and is not only used for injection molding, injection compression molding, blow molding, but also for extrusion. , Films, fibers and extruded articles such as pipes.
[0089]
The PAS obtained in the present invention may be used alone or, if desired, an inorganic filler such as glass fiber, carbon fiber, titanium oxide, and calcium carbonate, an antioxidant, a heat stabilizer, and an ultraviolet absorber. Agents, coloring agents, etc. can also be added, polyamide, polysulfone, polyphenylene ether, polycarbonate, polyether sulfone, polyethylene terephthalate, polybutylene terephthalate, polyethylene, polypropylene, polytetrafluoroethylene, epoxy group, carboxyl group, carboxylate Compounds such as olefin-based copolymers, polyolefin-based elastomers, polyetherester elastomers, polyetheramide elastomers, polyamideimides, polyacetals, and polyimides that have functional groups such as acid groups and acid anhydride groups Rukoto can also.
[0090]
Its applications include, for example, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable condenser cases, optical pickups, oscillators, various terminal boards, transformers, plugs, printed circuit boards, tuners , Speakers, microphones, headphones, small motors, magnetic head bases, power modules, semiconductors, liquid crystal, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, electrical and electronic parts such as computer-related parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave parts, audio parts, audio equipment parts such as audio, laser discs, compact discs, lighting parts, refrigerator parts, air conditioner parts, typera Home and office electrical products such as printer parts and word processor parts; office computer related parts, telephone related parts, facsimile related parts, copier related parts, cleaning jigs, motor parts, lighters, typewriters, etc. Representative machine-related parts: optical equipment such as microscopes, binoculars, cameras, clocks, etc., precision machinery-related parts; tap faucets, mixing faucets, pump parts, pipe joints, water flow control valves, relief valves, hot water temperature Plumbing parts such as sensors, water level sensors, and water meter housings; valve alternator terminals, alternator connectors, IC regulators, potentiometer bases for light drier, various valves such as exhaust gas valves, and various pipes related to fuel, exhaust, and intake systems , Air intake nozzle snow , Intake manifold, fuel pump, engine cooling water joint, carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake pad wear sensor, Thermostat base for air conditioner, heating hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, dust distributor, starter switch, starter relay, transmission wire harness, window washer nozzle, air conditioner Panel switch board, fuel-related electromagnetic valve coil, fuse connector, hose Automotive / vehicle-related parts such as terminals, electrical parts insulation plates, step motor rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters, fuel tanks, ignition devices cases, vehicle speed sensors, cable liners, etc. And various other uses.
[0091]
As a method for producing a PAS resin film using the PAS obtained according to the present invention, a known melt film-forming method can be employed. For example, after melting a PAS resin in a single-screw or twin-screw extruder, A method in which a film is extruded from a film die and cooled on a cooling drum to produce a film, or a biaxial stretching method in which the film thus produced is stretched longitudinally and transversely by a roller-type longitudinal stretching device and a transverse stretching device called a tenter. Etc., but is not particularly limited to this.
[0092]
The PAS resin film thus obtained has excellent mechanical properties, electrical properties, and heat resistance, and is used for dielectric films for film capacitors and chip capacitors, circuit boards, insulating boards, and motor insulating films. It can be suitably used for various applications such as a transformer insulating film application and a release film application.
[0093]
As a method for producing a PAS resin fiber using the PAS obtained by the present invention, a known melt spinning method can be applied. For example, a PAS resin chip as a raw material is supplied to a single-screw or twin-screw extruder. It is possible to adopt a method of extruding from a spinneret through a polymer streamline changer installed at the tip of an extruder, a filtration layer, etc., and then performing cooling, stretching, heat setting, and the like. It is not limited.
[0094]
The monofilament or short fiber of the PAS resin thus obtained can be suitably used for various uses such as a papermaking dryer canvas, a net conveyor, and a bag filter.
[0095]
【Example】
Hereinafter, the method of the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to only these Examples. In addition, the measuring method of physical properties is as follows.
[0096]
(1) Polymer yield
The yield of PAS was defined as a ratio of the yield of PAS to the weight (theoretical amount) assuming that the sulfidizing agent containing one equivalent of sulfur in the reactor before the polymerization was completely converted to PAS. If the sulfidizing agent is charged in excess of the dihalogenated aromatic compound, it may not be possible to convert all to PAS, but even in such a case, the amount of the sulfidizing agent is considered based on the amount.
[0097]
(2) Melt viscosity of polymer
The measurement was performed at 300 ° C. using a Capillograph C1 (a die length of 10 mm and a die hole diameter of 1 mm) manufactured by Toyo Seiki Co., Ltd., and the melt viscosities at a shear rate of 1000 / sec were compared.
[0098]
[Example 1]
<Step 1>
In a 1 liter autoclave equipped with a stirrer, 118 g of a 47.5 wt% aqueous sodium hydrogen sulfide solution (1.0 mol in terms of sodium hydrosulfide), and a 21.7 wt% aqueous solution prepared by dissolving 96% pure sodium hydroxide in 150 g of water. 194 g (1.05 mol in terms of sodium hydroxide) of an aqueous sodium solution and 10 g (0.10 mol) of NMP were charged at room temperature. Assuming that all the charged sodium bisulfide was converted to sodium sulfide, the amount of water was 12.8 mol (230 g) and the amount of NMP was 0.10 mol per mol of the sulfur component of sodium sulfide. .
A rectification column containing a filler was attached to the upper part of the autoclave, and dehydration was performed by gradually heating to 235 ° C. over about 2 hours while stirring at 240 rpm with nitrogen at normal pressure to obtain 230 g of a distillate. When the distillate was analyzed by gas chromatography, the composition of the distillate was 228 g of water and 2 g of NMP, and 2 g (0.11 mol) of water remained in the reaction system. understood. The amount of hydrogen sulfide scattered from the reaction system during this dehydration operation was 0.0006 mol.
By Step 1, a sulfidizing agent containing 0.11 mol of water per 1 mol of the sulfur component could be prepared.
<Step 2>
Next, 151 g (1.03 mol) of p-dichlorobenzene (p-DCB), 289 g (2.9 mol) of NMP, and 4.1 g (0.05 mol) of anhydrous sodium acetate as a catalyst compound were added. The amount of water in the reaction system was 0.11 mol per mol of the sulfur component of the charged sulfidizing agent, and the amount of NMP was 3.0 mol.
The reaction vessel was sealed under nitrogen gas, reacted at 210 ° C. for 2 hours while stirring at 400 rpm, and then rapidly cooled to around room temperature.
The p-DCB in the polymerization content obtained by this reaction was measured by gas chromatography to determine the conversion of p-DCB. The conversion was 72%.
[0099]
[Example 2]
The procedure was performed in the same manner as in Example 1 except that 5.7 g (0.05 mol) of sodium benzoate was added instead of the anhydrous sodium acetate added in Step 2 of Example 1. The p-DCB in the obtained polymerization content was measured by gas chromatography to determine the conversion of p-DCB. As a result, the conversion was 68%.
[0100]
[Example 3]
Example 1 was carried out in the same manner as in Example 1 except that 6.3 g (0.05 mol) of sodium 4-hydroxybutyrate was added instead of the anhydrous sodium acetate added in Step 2 of Example 1. The p-DCB in the obtained polymerization content was measured by gas chromatography to determine the conversion of p-DCB. As a result, the conversion was 76%.
[0101]
[Example 4]
Example 1 was carried out in the same manner as in Example 1 except that 4.3 g (0.05 mol) of piperidine was added instead of the anhydrous sodium acetate added in Step 2 of Example 1. The p-DCB in the obtained polymerization content was measured by gas chromatography to determine the conversion of p-DCB. As a result, the conversion was 66%.
[0102]
[Example 5]
Example 1 was repeated except that 6.2 g (0.05 mol) of 1,5-diazabicyclo [4,3,0] non-5-ene was added instead of the anhydrous sodium acetate added in Step 2 of Example 1. Performed similarly. The p-DCB in the obtained polymerization content was measured by gas chromatography to determine the conversion of p-DCB. As a result, the conversion was 51%.
[0103]
[Example 6]
Example 1 was carried out in the same manner as in Example 1 except that 4.0 g (0.05 mol) of pyridine was added instead of the anhydrous sodium acetate added in Step 2 of Example 1. The p-DCB in the obtained polymerization content was measured by gas chromatography to determine the conversion of p-DCB. The conversion was 62%.
[0104]
[Example 7]
Example 1 was carried out in the same manner as in Example 1 except that 3.9 g (0.05 mol) of dimethyl sulfoxide was added instead of the anhydrous sodium acetate added in Step 2 of Example 1. The p-DCB in the obtained polymerization content was measured by gas chromatography to determine the conversion of p-DCB. As a result, the conversion was 75%.
[0105]
Example 8
Example 1 was repeated except that the amount of anhydrous sodium acetate added in step 2 of Example 1 was changed to 8.2 g (0.1 mol). P-DCB in the obtained polymerization content was measured by gas chromatography to determine the conversion of p-DCB, and the conversion was 72%.
[0106]
[Example 9]
Example 1 was repeated except that the amount of anhydrous sodium acetate added in step 2 of Example 1 was changed to 24.6 g (0.3 mol). The p-DCB in the obtained polymerization content was measured by gas chromatography to determine the conversion of p-DCB. As a result, the conversion was 66%.
As can be seen from the comparison between the results of Examples 1 to 9 and Comparative Example 1, the alkali metal sulfide containing 1 mol or more of water per 1 mol of the sulfur component in the present invention was replaced with sulfur of the alkali metal sulfide. After dehydration in the presence of 0.05 to 0.6 mol of an organic polar solvent per 1 mol of the component to prepare a sulfidizing agent containing 0.05 to 0.6 mol of water per 1 mol of the sulfur component, Step 2 It can be seen that the reaction of the sulfidizing agent and the dihalogenated aromatic compound in the presence of the specific catalyst compound can significantly accelerate the polymerization reaction.
[0107]
[Comparative Example 1]
The procedure was performed in the same manner as in Example 1 except that the anhydrous sodium acetate added in Step 2 of Example 1 was not added.
[0108]
The p-DCB in the obtained polymerization content was measured by gas chromatography to determine the conversion of p-DCB. As a result, the conversion was 29%.
It can be seen that when no catalyst compound is used in step 2, the polymerization reaction is less likely to proceed than in Examples 1 to 9 using the catalyst compound.
[0109]
[Example 10]
<Step 1>
In a 1 liter autoclave equipped with a stirrer, 118 g of a 47.5 wt% aqueous sodium hydrosulfide solution (1.0 mol in terms of sodium hydrosulfide), and 21.7 wt% sodium hydroxide having a purity of 96% dissolved in 150 g of water. 194 g of an aqueous solution (1.05 mol in terms of sodium hydroxide) and 17.5 g (0.18 mol) of NMP were charged at room temperature. Assuming that all the charged sodium bisulfide was converted to sodium sulfide, the amount of water was 12.8 mol (230 g) and the amount of NMP was 0.18 mol per mol of the sulfur component of sodium sulfide. .
A rectification column containing a filler was attached to the upper part of the autoclave, and the mixture was gradually heated to 235 ° C. over about 2 hours while stirring at 240 rpm through nitrogen at normal pressure to perform dehydration, thereby obtaining 228 g of a distillate. The distillate was analyzed by gas chromatography to find that the composition of the distillate was 227 g of water and 1 g of NMP, and that 3 g (0.17 mol) of water remained in the reaction system. Was. The amount of hydrogen sulfide scattered from the reaction system during this dehydration operation was 0.0006 mol.
By Step 1, a sulfidizing agent containing 0.17 mol of water per 1 mol of the sulfur component could be prepared.
<Step 2>
Next, 151 g (1.03 mol) of p-dichlorobenzene (p-DCB), 157 g (1.59 mol) of NMP and 14.4 g (0.18 mol) of anhydrous sodium acetate as a catalyst compound were added. The amount of water in the reaction system was 0.17 mol per mol of the sulfur component of the charged sulfidizing agent, and the amount of NMP was 1.75 mol.
The reaction vessel was sealed under nitrogen gas, reacted at 230 ° C. for 1 hour while stirring at 400 rpm, and then rapidly cooled to around room temperature.
The p-DCB in the polymerization content obtained by this reaction was measured by gas chromatography to determine the conversion of p-DCB. The conversion was 62%.
[0110]
[Example 11]
Example 10 was carried out in the same manner as in Example 10 except that the amount of NMP charged in Step 1 was 30.7 g (0.31 mol) and the amount of NMP charged in Step 2 was 142.6 g (1.44 mol). The distillate obtained in the step 1 was 227 g, and the distillate was analyzed by gas chromatography to find that the composition of the distillate was 225 g of water, 2 g of NMP, and 5 g (0.28 g) in the reaction system. Mol) of water remained. The amount of water in the reaction system in Step 2 was 0.28 mol per mol of the sulfur component of the charged sulfidizing agent, and the amount of NMP was 1.73 mol.
The p-DCB in the polymerization content obtained by this reaction was measured by gas chromatography to determine the conversion of p-DCB. As a result, the conversion was 59%.
[0111]
[Comparative Example 2]
Example 10 was carried out in the same manner as in Example 10, except that the amount of NMP charged in Step 1 was 4 g (0.04 mol) and the amount of NMP charged in Step 2 was 169.3 g (1.71 mol). The distillate obtained in the step 1 was 232 g, and the distillate was analyzed by gas chromatography to find that the composition of the distillate was 229.5 g of water, 2.5 g of NMP, and 0 g in the reaction system. It was found that 0.5 g (0.03 mol) of water remained. The amount of water in the reaction system in step 2 was 0.03 mol per mol of the sulfur component of the charged sulfidizing agent, and the amount of NMP was 1.72 mol.
The polymerization content recovered after the reaction was brown-black, and as analyzed by gas chromatography, it was found that significant side reactions had occurred.
[0112]
[Comparative Example 3]
Example 10 was carried out in the same manner as in Example 10, except that NMP charged in Step 1 was 81.2 g (0.82 mol) and NMP charged in Step 2 was 92.1 g (0.93 mol). The distillate obtained in the step 1 was 217.5 g, and the distillate was analyzed by gas chromatography to find that the composition of the distillate was 216 g of water, 1.5 g of NMP, and 14 g in the reaction system. (0.78 mol) of water remained. The amount of water in the reaction system in step 2 was 0.78 mol per mol of the sulfur component of the charged sulfidizing agent, and the amount of NMP was 1.73 mol.
The p-DCB in the polymerization content obtained by this reaction was measured by gas chromatography to determine the conversion of p-DCB. The conversion was 22%.
[0113]
[Comparative Example 4]
Example 10 was carried out in the same manner as in Example 10, except that the amount of NMP charged in Step 1 was 100 g (1.01 mol) and the amount of NMP charged in Step 2 was 73.3 g (0.74 mol). The distillate obtained in the step 1 was 212 g, and the distillate was analyzed by gas chromatography. The composition of the distillate was 210 g water, 2 g NMP, and 20 g (1.11 g) in the reaction system. Mol) of water remained. The amount of hydrogen sulfide scattered from the reaction system during this dehydration operation was 0.018 mol. The amount of water in the reaction system in step 2 was 1.11 mol per mol of the sulfur component of the charged sulfidizing agent, and the amount of NMP was 1.78 mol.
The p-DCB in the polymerization content obtained by this reaction was measured by gas chromatography to determine the conversion of p-DCB. The conversion was almost 0%, and the reaction hardly proceeded.
[0114]
[Example 12]
20.8 g (0.21 mol) of NMP charged in Step 1 of Example 10, 177.5 g (1.79 mol) of NMP charged in Step 2, and 16.4 g (0.2 mol) of anhydrous sodium acetate Except having performed, it carried out similarly to Example 10. The distillate obtained in the step 1 was 227 g, and the distillate was analyzed by gas chromatography to find that the composition of the distillate was 226 g of water, 1 g of NMP, and 4 g (0.22 g) in the reaction system. Mol) of water remained. The amount of water in the reaction system in Step 2 was 0.22 mol per mol of the sulfur component of the charged sulfidizing agent, and the amount of NMP was 1.99 mol.
[0115]
P-DCB in the polymerization content obtained by this reaction was measured by gas chromatography to determine the conversion of p-DCB. The conversion was 70%.
[0116]
[Comparative Example 5]
Example 12 was carried out in the same manner as in Example 12, except that the amount of NMP charged in Step 1 was 100 g (1.01 mol) and the amount of NMP charged in Step 2 was 98 g (0.99 mol). The distillate obtained in the step 1 was 212 g, and the distillate was analyzed by gas chromatography to find that the composition of the distillate was 210 g water, 2 g NMP, and 20 g (1.1 g) in the reaction system. Mol) of water remained. The amount of hydrogen sulfide scattered from the reaction system during this dehydration operation was 0.018 mol. The amount of water in the reaction system in step 2 was 1.1 mol per mol of the sulfur component of the charged sulfidizing agent, and the amount of NMP was 2.02 mol.
The p-DCB in the polymerization content obtained by this reaction was measured by gas chromatography to determine the conversion of p-DCB. The conversion was almost 0%, and the reaction hardly proceeded.
As can be seen from the comparison between Examples 10 and 11 and Comparative Examples 2 to 4 and Example 12 and Comparative Example 5, according to the method of the present invention, the reaction promoting effect of the catalyst compound can be significantly exhibited. The reaction can proceed even with a very small amount of the polymerization solvent.
[0117]
Example 13
<Step 1>
In a 1 liter autoclave equipped with a stirrer, 118 g of a 47.5 wt% aqueous sodium hydrosulfide solution (1.0 mol in terms of sodium hydrosulfide), and 21.7 wt% sodium hydroxide having a purity of 96% dissolved in 150 g of water. 194 g of an aqueous solution (1.05 mol in terms of sodium hydroxide), 17.5 g (0.18 mol) of NMP and 14.4 g (0.18 mol) of anhydrous sodium acetate were charged at room temperature. Assuming that all the charged sodium bisulfide was converted to sodium sulfide, the amount of water was 12.8 mol (230 g) and the amount of NMP was 0.18 mol per mol of the sulfur component of sodium sulfide. .
A rectification column containing a filler was attached to the upper part of the autoclave, and the mixture was gradually heated to 235 ° C. over about 2 hours while stirring at 240 rpm through nitrogen at normal pressure to perform dehydration, thereby obtaining 228 g of a distillate. When the distillate was analyzed by gas chromatography, the composition of the distillate was 227 g of water, 1 g of NMP, and 3 g (0.17 mol) of water remained in the reaction system. understood. The amount of hydrogen sulfide scattered from the reaction system during this dehydration operation was 0.0006 mol.
By Step 1, a sulfidizing agent containing 0.17 mol of water per 1 mol of the sulfur component could be prepared.
<Step 2>
Next, 151 g (1.03 mol) of p-dichlorobenzene (p-DCB) and 155.8 g (1.57 mol) of NMP were added. The amount of water in the reaction system was 0.17 mol per mol of the sulfur component of the charged sulfidizing agent, and the amount of NMP was 1.74 mol.
The reaction vessel was sealed under nitrogen gas, and the temperature was raised from 200 ° C. to 250 ° C. over 50 minutes while stirring at 400 rpm, and then held at 250 minutes for 90 minutes.
<Step 3>
While maintaining the temperature of the reaction system at 250 ° C., 18 g (1.0 mol) of water was injected into the reaction system over 10 minutes. As a result, the amount of water in the reaction system with respect to 1 mol of the sulfur component of the charged sulfidizing agent was 1.17 mol.
Next, the temperature was raised from 250 ° C. to 270 ° C. over 20 minutes, and then kept at 270 ° C. for 90 minutes. Next, the mixture was gradually cooled to 210 ° C. over 60 minutes, and then rapidly cooled to around room temperature.
<Polymer recovery>
The contents were taken out, diluted with 0.5 liter of NMP, stirred as a slurry at 85 ° C. for 30 minutes, and filtered through an 80 mesh wire net to obtain a solid. The obtained solid was washed and filtered again with 0.5 L of NMP. The obtained solid was washed again three times with 1 liter of water (70 ° C.) and filtered. Subsequently, 0.52 g of acetic acid and 1 liter of water (70 ° C.) were added to the obtained solid, which was washed and filtered. Further, the obtained solid was washed again with 1 liter of water (70 ° C.) and filtered.
<Post-processing>
The solid thus obtained was dried with hot air at 130 ° C. As a result of identification by infrared spectroscopy, the obtained solid was found to be PPS. Further, the polymer yield was 85%, and the melt viscosity of the polymer was 136 Pa · s. According to the method of the present invention, it was found that a high polymerization degree polymer could be obtained in a high yield even with a very small amount of polymerization solvent used. Was.
Further, at the point when the same operation as above was performed until water was added in step 3, the polymerization system was quenched, and p-DCB in the polymerization content was measured by gas chromatography to determine the conversion of p-DCB. The conversion was 90%.
[0118]
[Comparative Example 6]
Example 13 was carried out in the same manner as in Example 13 except that the amount of NMP charged in Step 1 was 4.0 g (0.04 mol) and the amount of NMP charged in Step 2 was 169.3 g (1.71 mol). The distillate obtained in the step 1 was 232 g, and the distillate was analyzed by gas chromatography to find that the composition of the distillate was 229.5 g of water, 2.5 g of NMP, and 0 g in the reaction system. It was found that 0.5 g (0.03 mol) of water remained. The amount of water in the reaction system in step 2 was 0.03 mol per mol of the sulfur component of the charged sulfidizing agent, and the amount of NMP was 1.73 mol.
The reaction product obtained after the reaction was dark brown and was analyzed by gas chromatography, and as a result, it was found that side reactions had progressed remarkably. The yield of the obtained polymer was as low as 59%, and the polymer melt viscosity was as low as 10 Pa · s or less.
Further, at the point when the same operation as above was performed until water was added in step 3, the polymerization system was quenched, and p-DCB in the polymerization content was measured by gas chromatography to determine the conversion of p-DCB. The conversion was 88%.
[0119]
[Comparative Example 7]
Example 13 was carried out in the same manner as in Example 13 except that the amount of NMP charged in Step 1 was 81.2 g (0.82 mol) and the amount of NMP charged in Step 2 was 92.1 g (0.93 mol). The distillate obtained in the step 1 was 217.5 g, and the distillate was analyzed by gas chromatography to find that the composition of the distillate was 216 g of water, 1.5 g of NMP, and 14 g in the reaction system. (0.78 mol) of water remained. The amount of water in the reaction system in step 2 was 0.78 mol per mol of the sulfur component of the charged sulfidizing agent, and the amount of NMP was 1.75 mol.
The reaction product obtained after the reaction was black-grey, the yield of the obtained polymer was as low as 55%, and the polymer melt viscosity was as low as 10 Pa · s or less.
Further, at the point when the same operation as above was performed until water was added in step 3, the polymerization system was quenched, and p-DCB in the polymerization content was measured by gas chromatography to determine the conversion of p-DCB. The conversion was 46%.
[0120]
[Example 14]
Example 13 was carried out in the same manner as in Example 13 except that the reaction condition in Step 2 was changed from 200 ° C to 235 ° C over 35 minutes and then kept at 235 ° C for 140 minutes.
The yield of the obtained polymer is 85%, and the melt viscosity of the polymer is 105 Pa · s. According to the method of the present invention, a high polymerization degree polymer can be obtained in a high yield even with a very small amount of a polymerization solvent. I understood.
Further, at the point when the same operation as above was performed until water was added in step 3, the polymerization system was quenched, and p-DCB in the polymerization content was measured by gas chromatography to determine the conversion of p-DCB. The conversion was 72%.
[0121]
【The invention's effect】
According to the present invention, a method for efficiently producing a linear high molecular weight PAS in a short time can be provided. Therefore, the method for producing PAS of the present invention is suitable as a method for producing PAS safely and economically on an industrial scale.

Claims (8)

A method for producing polyarylene sulfide by contacting and polymerizing a sulfidizing agent and a dihalogenated aromatic compound in an organic polar solvent, the method comprising producing at least the following steps 1 and 2 .
Step 1: an alkali metal sulfide containing 1 mol or more of water per 1 mol of a sulfur component is dehydrated in the presence of 0.05 to 0.6 mol of an organic polar solvent per 1 mol of a sulfur component of the alkali metal sulfide. Preparing a sulfidizing agent containing 0.05 to 0.6 moles of water per mole of the component,
Step 2: converting the sulfidizing agent and the dihalogenated aromatic compound prepared in Step 1 into at least one compound selected from a metal salt of an organic carboxylic acid, an aliphatic cyclic amine compound, an N-heteroaromatic compound, and an organic sulfoxide compound; A step of contacting and polymerizing in the presence of 0.05 to 0.6 mol of water per 1 mol of the sulfur component of the agent. The method for producing a polyarylene sulfide according to claim 1, wherein the organic polar solvent is an organic amide solvent. The polycarboxylic acid according to claim 1, wherein the compound selected from the group consisting of a metal salt of an organic carboxylic acid, an aliphatic cyclic amine compound, an N-heteroaromatic compound, and an organic sulfoxide compound in the step 2 is a metal salt of an organic carboxylic acid. Manufacturing method of arylene sulfide. 4. The process for producing a polyarylene sulfide according to claim 1, wherein in the step 2, when the conversion of the dihalogenated aromatic compound becomes 60 mol% or more, the following step 3 is performed. Method.
Step 3: a step of reducing the amount of water in the polymerization system to 0.7 to 5.0 mol per mol of the sulfur component of the sulfidizing agent, and further continuing the polymerization. The method for producing polyarylene sulfide according to any one of claims 1 to 4, wherein step 2 is performed in a temperature range of 180 to 260 ° C. The method for producing polyarylene sulfide according to claim 4 or 5, wherein step 3 is performed in a temperature range of 200 to 300 ° C. The method for producing a polyarylene sulfide according to any one of claims 1 to 6, wherein the step 2 is performed in the presence of 1.0 to 4.0 mol of an organic polar solvent per 1 mol of a sulfur component of the sulfidizing agent. . The process for producing a polyarylene sulfide according to any one of claims 4 to 7, wherein step 3 is performed in the presence of 1.0 to 4.0 mol of an organic polar solvent per 1 mol of a sulfur component of the sulfidizing agent. .