JP2004107567A - Method for manufacturing polyarylene sulfide - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a high molecular-weight polyarylene sulfide efficiently, without cumbersome work of water control. <P>SOLUTION: A dihaloaromatic compound and a sulfidation agent are reacted in an organic polar solvent to form a polyarylene sulfide, wherein (1) the sulfidation agent is a mixture of an alkali metal sulfide and an alkali metal hydrosulfide, (2) the molar ratio of water in the reaction system at the end of the polymerization to the total amount of the sulfidation agent used for the polymerization (water/sulfidation agent) is controlled to be less than 1, and (3) the molar ratio of the dihaloaromatic compound to the sulfidation agent remaining at the end of the polymerization (dihaloaromatic compound/sulfidation agent) is controlled to be less than 1. <P>COPYRIGHT: (C)2004,JPO

Description

【００１４】
前記一般式（１）〜（４）中、Ｘはハロゲン原子を、またＹは水素原子、水酸基、炭素数１〜１８のアルキル基、炭素数３〜１８のシクロアルキル基、炭素数６〜１８のアリール基、カルボキシル基、炭素数１〜１８のアルコキシカルボニル基、ナトリウムカルボキシレート基、シアノ基、アミノ基若しくはニトロ基を表す。また、前記Ｘは塩素または臭素が好ましい。
【００１５】
また、一般式（４）中のＶは、下記構造式（５）〜（１０）で表わされる２価の連結基を表す。
【化２】

（式中、Ｒ’及びＲ”は、それぞれ独立に、水素原子、炭素数１〜１８のアルキル基、炭素数３〜１８のシクロアルキル基、炭素数６〜１８のアリール基を表す。）
【００１６】
一般式（１）中のｍは２を、ｎは、０〜４の整数を表す。また、一般式（２）中のａは２を、ｂは０〜６の整数を表す。一般式（３）中でｃは０〜２、ｄは０〜２、ｅは０〜３、ｆは０〜２の整数をそれぞれ表わし、且つｃとｄはｃ＋ｄ＝２を満足する。また、一般式（４）中でｇは０〜２、ｈは０〜２で且つｉ及びｊは、０≦ｉ、及びｊ≦２を満足する整数を表す。
【００１７】
前記、一般式（１）〜（４）のジハロ芳香族化合物の具体例としては、ｐ−ジハロベンゼン、ｍ−ジハロベンゼン、ｏ−ジハロベンゼン、２，５−ジハロトルエン、１，４−ジハロナフタリン、１−メトキシ−２，５−ジハロベンゼン、４，４’−ジハロビフェニル、３，５−ジハロ安息香酸、２，４−ジハロ安息香酸、２，５−ジハロニトロベンゼン、２，４−ジハロニトロベンゼン、２，４−ジハロアニソール、２，５−ジハロアニリン、３，５−ジハロアニリン、ｐ，ｐ’−ジハロジフェニルエーテル、４，４’−ジハロベンゾフェノン、４，４’−ジハロジフェニルスルホン、４，４’−ジハロジフェニルスルホキシド、４，４’−ジハロジフェニルスルフィド等であり、なかでも、ｐ−ジハロベンゼン、ｍ−ジハロベンゼン、４，４’−ジハロベンゾフェノンおよび４，４’−ジハロジフェニルスルホンが好ましく、その中でもｐ−ジクロロベンゼン、ｍ−ジクロロベンゼン、４，４’−ジクロロベンゾフェノンおよび４，４’−ジクロロジフェニルスルホンは特に好適に使用される。
【００１８】
ジハロ芳香族化合物の適当な選択組み合わせによって２種以上の異なる反応単位を含む共重合体を得ることもでき、その組み合わせには特に制限はない。ｐ−ジクロロベンゼンと４，４’−ジクロロベンゾフェノンもしくは４，４’−ジクロロフェニルスルホンとを組み合わせて使用すれば、種々の物性に優れたＰＡＳを得ることができるので、好ましい。また、ｐ−ジハロベンゼンをジハロ芳香族化合物中７０モル％以上、好ましくは９０モル％以上、更に好ましくは９５モル％以上用いて重合すると種々の物性に優れたＰＡＳが得られるのでとくに好ましい。また、ジハロベンゼンのみの重合体であるＰＰＳは種々の物性に優れており、中でもジクロロベンゼンの使用は生産性等の点でより好ましい。
【００１９】
なお、本発明によるＰＡＳは上記ジハロ芳香族化合物の重合体であるが、生成重合体の末端を形成させるため、あるいは重合反応ないし分子量を調節するためにモノハロ化合物を併用することも、分岐または架橋重合体を形成させるためにトリハロ以上のポリハロ化合物を併用することも可能である。これらのモノハロまたはポリハロ化合物を併用する場合は、例えばジハロベンゼンに若干量のトリクロロベンゼンを組み合わせて使用すれば、分岐を持ったフェニレンスルフィド重合体を得ることができ、トリクロロベンゼン等の３個以上のハロゲン原子を置換基として有するポリハロ化合物の使用は得られるポリマーの高粘度化の点で有用である。また、モノハロ化合物または３個以上のハロゲン原子を置換基として有するポリハロ化合物の使用量は目的あるいは反応条件によっても異なるので一概に規定できないが、ジハロ芳香族化合物１モルに対して好ましくは０．１モル％以下、更に好ましくは０．０６モル％以下である。トリクロロベンゼンに代表される３個以上のハロゲン原子を置換基として有するポリハロ化合物の使用量が上記範囲の場合には、得られるポリマーのリニアリティーをほとんど損なうことなく、高粘度化できるので好ましい。なお、モノハロ化合物及び３個以上のハロゲン原子を置換基として有するポリハロ化合物は共に必ずしも芳香族化合物でなくとも良い。
【００２０】
本発明の重合反応に使用する有機極性溶媒は、活性水素を有しない有機極性溶媒、すなわちアプロチックタイプの有機極性溶媒である。
【００２１】
前記有機極性溶媒は、前記重合反応を阻害せず、原料であるジハロ芳香族化合物及びＳ^２−を与えるスルフィド化剤を反応に必要な濃度に溶解することができる程度の溶解能を持つものであれば、とくに限定されない。これらの中でも、この溶媒は、窒素原子、酸素原子、硫黄原子を有する極性溶媒であることが普通である。更に、この溶媒は原料ジハロ芳香族化合物と同様な脱ハロゲン化／硫化反応に関与しうるものでないことが望ましい。従って例えばハロ芳香族炭化水素ではないことが望ましい。
【００２２】
前記有機極性溶媒は、制御された少量の水を重合反応に提供するためのものであるから、溶質としてのこの水が溶媒和しうるものであることが望ましい。
【００２３】
また、本発明の製造方法から明らかなように、前記有機極性溶媒の沸点は水の沸点より高いことが望ましい。前述の条件を満足するものとしては、例えば、（１）アミド類、例えば、ヘキサメチルリン酸トリアミド（ＨＭＰＡ）、Ｎ−メチルピロリドン（ＮＭＰ）、Ｎ−シクロヘキシルピロリドン（ＮＣＰ）、Ｎ−メチルカプロラクタム、テトラメチル尿素（ＴＭＵ）、ジメチルホルムアミド（ＤＭＦ）、ジメチルアセトアミド（ＤＭＡ）等、（２）エーテル化ポリエチレングリコール類、例えばポリエチレングリコールジアルキルエーテル（重合度は２０００程度まで、アルキル基はＣ_１〜Ｃ_２０程度）等、（３）スルホキシド類、例えば、テトラメチレンスルホキシド、ジメチルスルホキシド（ＤＭＳＯ）等が挙げられる。前記溶媒の中でも、Ｎ−メチルカプロラクタムおよびＮＭＰは、化学的安定性が高いので、特に好ましい。
【００２４】
前記有機極性溶媒の使用量は、使用する溶媒の種類及び系内の溶媒に対する水分量によっても異なるが均一な重合反応が可能な反応系の粘度を保持すること、また、ある程度の生産性を維持するためには、重合に用いるスルフィド化剤中の硫黄原子１モル当り１．０〜８．０モルの範囲が好ましい。また、生産性を更に考慮すると、重合に用いるスルフィド化剤中の硫黄原子１モル当り１．０〜６．０モルの範囲が好ましく、また、更に好ましい使用溶媒量は重合に用いるスルフィド化剤中の硫黄原子１モル当り１．２〜５．０モルである。
【００２５】
重合系内の水分量、あるいは含水スルフィド化剤の水分量を調整するための水は、反応を阻害するものが含まれなければ良く、そのため蒸留水、イオン交換水等、反応を阻害するアニオンやカチオン等を除いた水が好ましい。
【００２６】
本発明の重合反応に存在させる水分は、加水分解反応などの併発を回避させるために、なるべく少ない方が良い。他方、重合反応が全く無水の状態である場合は、反応速度が著しく遅くなるといった問題がある。従って、本発明の重合反応において反応系内に存在すべき水分量は、重合に使用した該スルフィド化剤１モルに対して、重合反応終了時１モル未満でなければならない。また、反応が円滑に進行する点からは、重合に使用した該スルフィド化剤１モルに対して、０．０２モル以上存在させることが好ましい。これらの中でも重合に使用した該スルフィド化剤１モルに対して０．０３〜０．６０の範囲が好ましく、０．０５〜０．４０の範囲が特に好ましい。上記範囲を満たす場合には、反応速度の制御の制御性、及び高分子量化の両立がより容易に行える。
【００２７】
本発明においては、有機極性溶媒中で、ジハロ芳香族化合物とスルフィド化剤とを反応させるポリアリーレンスルフィドの製造において、スルフィド化剤がアルカリ金属硫化物とアルカリ金属水硫化物の混合物であり、重合反応終了時の反応系内の水と重合に使用した全該スルフィド化剤とのモル比（水／スルフィド化剤）が１未満で、重合反応終了時の残存するジハロ芳香族化合物とスルフィド化剤とのモル比（ジハロ芳香族化合物／スルフィド化剤）が１より小さいことを特徴とするが、上記特徴を満たす限り、重合方法に特に制限はない。すなわち、ジハロ芳香族化合物、スルフィド化剤、有機極性溶媒、水等の原料の仕込み順序仕込み方法には特に制限は無い。
【００２８】
前記スルフィド化剤が、含水スルフィド化剤の場合は、本発明の製造方法の特徴を満たすためには脱水が必要となるが、本発明としては脱水と重合を同時に行っても良いし、あるいは脱水と重合を別々に行っても良いし、あるいは重合を行いながら適宜脱水を行っても良い。
【００２９】
脱水と重合を同時に行う方法としては、例えば重合反応が実質的に進行し得る温度、２００〜３００℃、好ましくは２１０〜２８０℃、更に好ましくは２１５〜２６０℃の温度に有機極性溶媒（有機極性溶媒に対して０．５モル以下の水を含んでいて良い）及びジハロ芳香族化合物の混合物を加熱して、反応系内の水分量が上記範囲内にコントロールされ得る速度で含水スルフィド化剤を混合物に導入して余分の水を系外に除去し、反応系内の水分量を上記範囲内にコントロールした後、さらに２００〜３００℃、好ましくは２１０〜２８０℃の温度に加熱して４０時間以下、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う方法でも良い。
【００３０】
また、脱水と重合を別々に行う方法としては、例えば重合反応が、ほとんど進行しない温度、即ち１２０〜２００℃、好ましくは１５０〜１９０℃に有機極性溶媒（有機極性溶媒に対して０．５モル以下の水を含んでいて良い）及びジハロ芳香族化合物の混合物を保ち、反応系内の水分量をスルフィド化剤１モルに対して１モル未満にコントロールされ得る速度でスルフィド化剤を混合物に導入して余分の水を系外に除去し、反応系内の水分量をスルフィド化剤１モルに対して１モル未満にコントロールした後、調製した有機極性溶媒、ジハロ芳香族化合物及び含水スルフィド化剤の混合物を重合反応が実質的に進行する温度、即ち、２００〜３００℃、好ましくは２１０〜２８０℃の温度に加熱して４０時間以下、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う方法でも良い。
【００３１】
また、重合を行いながら適宜脱水を行う方法としては、例えば、下記の方法が挙げられる。▲１▼好ましくは不活性ガス雰囲気下、有機極性溶媒中にスルフィド化剤を加え、常圧あるいは減圧下、あるいは加圧下、１５０℃以上、好ましくは１８０〜２５０℃まで昇温し、水分をスルフィド化剤１モル当たり、１〜１．５モルに調整し、更にジハロ芳香族化合物を加え、重合反応が進行する温度、即ち、２００〜３００℃、好ましくは２１０〜２８０℃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い、重合反応を行っている間に、連続的にあるいは一時的にあるいは断続的に系内の水分を除去し、反応系内の水分量を反応系内のスルフィド化剤１モルに対して１モル未満にコントロールする方法。
【００３２】
▲２▼重合反応がほとんど進行しない温度、即ち１２０〜２００℃、好ましくは１５０〜１９０℃に有機極性溶媒（有機極性溶媒に対して０．５モル以下の水を含んでいて良い）及びジハロ芳香族化合物の混合物を保ち、反応系内の水分量がコントロールできる速度でスルフィド化剤を混合物に導入して余分の水を系外に除去し、反応系内の水分量を反応系内のスルフィド化剤１モルに対して１モル未満にコントロールした後、調製した有機極性溶媒、ジハロ芳香族化合物及び含水スルフィド化剤の混合物を重合反応が実質的に進行する温度、即ち、２００〜３００℃、好ましくは２１０〜２８０℃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い、重合反応を行っている間に、必要に応じて更に連続的にあるいは一時的にあるいは断続的に系内の水分を除去して更に水分量を低減する重合方法。
【００３３】
▲３▼重合反応が進行し得る温度、２００〜３００℃、好ましくは２１０〜２８０℃、更に好ましくは２１５〜２６０℃の温度に有機極性溶媒（有機極性溶媒に対して０．５モル以下の水を含んでいて良い）及びジハロ芳香族化合物の混合物を加熱して、反応系内の水分量がコントロールされ得る速度で含水スルフィド化剤を混合物に導入して余分の水を系外に除去し、反応系内の水分量を反応系内のスルフィド化剤１モルに対して１モル未満になるようにコントロールした後、さらに２００〜３００℃、好ましくは２１０〜２８０℃の温度に加熱して４０時間以下、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い、重合反応を行っている間に、連続的にあるいは一時的にあるいは断続的に系内の水分を除去して更に水分量を低減する重合方法。
【００３４】
上記重合方法の中でも、生産性等の点から、重合を行いながら適宜脱水をする方法が好ましい。これらの中でも重合反応が実質的に進行し得る温度に有機極性溶媒及びジハロ芳香族化合物の混合物を加熱して、反応系内の水分量がコントロールされ得る速度で含水スルフィド化剤を混合物に導入して余分の水を系外に除去し、反応系内の水分量をコントロールした後、さらに重合反応を行い、重合反応を行っている間に、必要に応じて連続的にあるいは一時的にあるいは断続的に系内の水分を除去して更に水分量を低減する重合方法が好ましく、特に重合工程全般を通じて反応系内の水分量が、反応系内のスルフィド化剤１モルに対して１モル未満になっている重合方法（前記▲３▼）が最も好ましい。
【００３５】
上記の含水スルフィド化剤を導入する速度は反応系内の水分量を該有機極性溶媒１モルに対して目的の範囲にコントロールできるように余分の水を系外に除去できる速度であれば特に制限はない。導入時間はコントロールする水分量、導入する際の温度、含水スルフィド化剤の含水率等によっても異なるので一概には規定できないが、含水スルフィド化剤を０．１〜２０時間、好ましくは０．５〜１０時間かけて導入することが好ましい。この時間内であると、反応系の水分量あるいは温度等を制御しやすく、また生産性も良い。
【００３６】
また、含水スルフィド化剤を導入する温度もコントロールする水分量、導入する際の速度、含水スルフィド化剤の含水率あるいは反応の形式によっても異なるので一概には規定できないが、脱水と重合を別々に行うのであれば、１２０〜２００℃、好ましくは１５０〜１９０℃で導入すると良い。また、脱水と重合を同時に行うのであれば、２００〜３００℃、好ましくは２１０〜２８０℃、更に好ましくは２１５〜２６０℃の温度で導入すれば良い。
【００３７】
重合反応は、２００〜３００℃、好ましくは２１０〜２８０℃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時間加熱して行うことが好ましい。この範囲内であると反応の進行がスムーズである。
【００３８】
なお、重合時の水の除去方法としては、反応系の温度・圧力をコントロールすることによって容易に行える。即ち、水、溶媒、ジハロ芳香族化合物の各蒸気圧曲線によりコントロールすべき温度・圧力が容易に推定でき、その温度・圧力でコントロールすれば所望の系内水分量にすることができる。
【００３９】
本発明の製造方法において使用するジハロ芳香族化合物及びスルフィド化剤の使用量には、重合反応終了時の残存するジハロ芳香族化合物と残存するスルフィド化剤とのモル比（ジハロ芳香族化合物／スルフィド化剤）が１未満であれば、特に制限はない。例えば、ジハロ芳香族化合物とスルフィド化剤とを添加する方法としては、下記の（ａ）、（ｂ）の方法が挙げられる
（ａ）予め、重合反応終了時の残存するジハロ芳香族化合物と残存するスルフィド化剤とのモル比（ジハロ芳香族化合物／スルフィド化剤）が１未満となるように、ジハロ芳香族化合物とスルフィド化剤とを仕込んで、反応してもよい。また、（ｂ）重合反応終了時の残存するジハロ芳香族化合物と残存するスルフィド化剤とのモル比（ジハロ芳香族化合物／スルフィド化剤）が１以上になるように、ジハロ芳香族化合物とスルフィド化剤とを仕込んだ後、重合途中でジハロ芳香族化合物を系外に除去して、重合反応終了時の残存するジハロ芳香族化合物と残存するスルフィド化剤とのモル比（ジハロ芳香族化合物／スルフィド化剤）が１未満となるように調整してもよい。これらの中でも、前記（ａ）が好ましい。
【００４０】
前記（ａ）または（ｂ）の方法の何れの場合でも、重合反応終了時の残存するジハロ芳香族化合物と残存するスルフィド化剤とのモル比（ジハロ芳香族化合物／スルフィド化剤）が１未満であることが必須であり、１以上の場合には本発明の目的であるポリマーの高分子量化が達成できず、好ましくない。但し、あまり小さすぎるとポリマーの分解反応により、分子量低下が起こりえるため、０．０５以上であることが好ましい。これらの中でも、重合反応終了時の残存するジハロ芳香族化合物と残存するスルフィド化剤とのモル比（ジハロ芳香族化合物／スルフィド化剤）が０．１〜０．５の範囲が特に好ましい。この範囲を満たす場合には分解反応を併発することなく、より高分子量化を達成し得る。
【００４１】
従って前記（ａ）または（ｂ）の方法の何れの場合でも、〔（全使用ジハロ芳香族化合物（モル））−（系外に除去したジハロ芳香族化合物（モル））〕と〔（全使用スルフィド化剤（モル））−（系外に除去した硫黄分（モル））〕との比が０．９０より大きく１より小さい範囲が物性の優れたポリマー、即ちより高分子量のポリマーを得るのに好ましい。上記範囲を満たす場合には、前記の残存するモノマー比の好ましい範囲を満足しやすいので好ましい。また、上記範囲が０．９２〜０．９９の場合には高分子量化の点で更に好ましい。
【００４２】
なおジハロ芳香族化合物の残存量については通常ガスクロマトグラフ法によって求められる。また、アルカリ金属硫化物及びアルカリ金属水硫化物等のスルフィド化剤の残存量は、例えば硝酸銀滴定法によって求めることができる。
【００４３】
本発明の重合反応においては、接液部がチタンあるいはクロムあるいはジルコニウム等でできた重合缶を用い、通常、窒素、ヘリウム、アルゴン等の不活性ガス雰囲気下で行うことが好ましく、特に、経済性及び取扱いの容易さの面から窒素が好ましい。
【００４４】
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するので一概に規定できないので、特に制限はない。また、反応液の調整及び重合体の生成反応は一定温度で行う１段反応でも良いし、段階的に温度を上げていく多段階反応でも良いし、あるいは連続的に温度を変化させていく形式の反応でもかまわない。
【００４５】
本発明では、有機極性溶媒中で、ジハロ芳香族化合物とスルフィド化剤とを反応させるポリアリーレンスルフィドポリマーの製造において、スルフィド化剤がアルカリ金属硫化物とアルカリ金属水硫化物の混合物であり、重合反応終了時の反応系内の水と重合に使用した全該スルフィド化剤とのモル比（水／スルフィド化剤）が１未満で、重合反応終了時の残存するジハロ芳香族化合物とスルフィド化剤とのモル比（ジハロ芳香族化合物／スルフィド化剤）が１より小さいことを特徴とするが、前処理工程あるいは後処理工程などの付加的な工程があっても良い。
【００４６】
本発明においては、重合反応終了後の後処理を、常法によって行うことができる。例えば、重合反応終了後、反応混合物をそのまま、あるいは水で、あるいは反応溶媒等の有機溶媒で希釈して、必要に応じて酸あるいは塩基を加えた後、濾別し、更に必要に応じて中和を行い、水洗、濾別および乾燥をすることによって行うことができる。また、別法としては、反応混合物をそのまま、あるいは酸または塩基を加えた後、減圧下または常圧下で加熱して溶媒だけを留去し、ついで缶残固形物に必要に応じて酸あるいは塩基を加え、水あるいはアセトン等のケトン類あるいはメタノール等のアルコール類あるいは反応溶媒等の有機溶媒で１回または２回以上洗浄し、それから必要に応じて中和し、水洗、濾別および乾燥をすることによって行うことができる。なお、上記の洗浄及び濾別操作を行う温度には特に制限はない。また、酸、塩基の代わりに、塩化アンモニウム等の塩などで処理してももちろんかまわない。
【００４７】
単離した重合体は実質的に水等の溶媒が蒸発する温度に加熱して乾燥を行う。乾燥は真空下で行っても良いし、空気中あるいは窒素のような不活性ガス雰囲気下で行っても良い。
【００４８】
本発明により得られる重合体は従来のＰＡＳに比べて高分子量であるので、そのまま各種成形材料等に利用できるが、空気あるいは酸素富化空気中あるいは減圧下で熱処理することにより増粘することが可能であり、必要に応じてこのような増粘操作を行った後、各種成形材料等に利用しても良い。この熱処理温度は処理時間によっても異なるし処理する雰囲気によっても異なるので一概に規定できないが、通常は１８０℃以上で行うことが好ましい。熱処理温度が１８０℃未満では増粘速度が非常に遅く生産性が悪く好ましくない。熱処理は押出機等を用いて重合体の融点以上で、溶融状態で行っても良い。但し、重合体の劣化の可能性あるいは作業性等から、融点プラス１００℃以下で行うことが好ましい。
【００４９】
本発明により得られた重合体は、従来のＰＡＳ同様そのまま射出成形、押出成形、圧縮成形、ブロー成形のごとき各種溶融加工法により、耐熱性、成形加工性、寸法安定性等に優れた成形物にすることができる。しかしながら強度、耐熱性、寸法安定性等の性能をさらに改善するために、本発明の目的を損なわない範囲で各種充填材と組み合わせて使用することも可能である。充填材としては、繊維状充填材、無機充填材等が挙げられる。
【００５０】
また、成形加工の際に添加剤として本発明の目的を逸脱しない範囲で少量の、離型剤、着色剤、耐熱安定剤、紫外線安定剤、発泡剤、防錆剤、難燃剤、滑剤、カップリング剤を含有せしめることができる。更に、同様に下記のごとき合成樹脂及びエラストマーを混合して使用できる。これら合成樹脂としては、ポリエステル、ポリアミド、ポリイミド、ポリエーテルイミド、ポリカーボネート、ポリフェニレンエーテル、ポリスルフォン、ポリエーテルスルフォン、ポリエーテルエーテルケトン、ポリエーテルケトン、ポリアリーレン、ポリエチレン、ポリプロピレン、ポリ四弗化エチレン、ポリ二弗化エチレン、ポリスチレン、ＡＢＳ樹脂、エポキシ樹脂、シリコーン樹脂、フェノール樹脂、ウレタン樹脂、液晶ポリマー等が挙げられ、エラストマーとしては、ポリオレフィン系ゴム、弗素ゴム、シリコーンゴム、等が挙げられる。
【００５１】
本発明の重合体及びその組成物は、従来の方法で得られるＰＰＳ同様耐熱性、寸法安定性等が優れるので、例えば、コネクタ・プリント基板・封止成形品などの電気・電子部品、ランプリフレクター・各種電装部品などの自動車部品、各種建築物や航空機・自動車などの内装用材料、あるいはＯＡ機器部品・カメラ部品・時計部品などの精密部品等の射出成形・圧縮成形品、あるいは繊維・フィルム・シート・パイプなどの押出成形・引抜成形品等として幅広く利用可能である。
【００５２】
【実施例】
以下に本発明を実施例により具体的に説明するが、本発明はこれら実施例にのみ限定されるものではない。
【００５３】
使用原料
１．スルフィド化剤
含水フレーク状硫化ナトリウム（以下、Ｎａ_２Ｓ・ｘＨ_２Ｏと略称する。純度−Ｎａ_２Ｓ：５８．９重量％、ＮａＳＨ：１．３重量％）はナガオ（株）製品を使用した。また、含水フレーク状水硫化ナトリウム（以下、ＮａＳＨ・ｙＨ_２Ｏと略称する。純度−ＮａＳＨ：７１．２重量％、Ｎａ_２Ｓ：２．７重量％）はナガオ（株）製品を使用した。
【００５４】
２．溶媒
Ｎ−メチルピロリドン（以下、ＮＭＰと略称する）はＢＡＳＦジャパン（株）製品を使用した。
【００５５】
３．ジハロ芳香族化合物
ｐ−ジクロロベンゼン（以下、ｐ−ＤＣＢと略称する）は保土谷化学（株）製品を使用した。
【００５６】
４．水
水道水を蒸留した後イオン交換を施したものを使用した。
【００５７】
５．水酸化ナトリウム（以下、ＮａＯＨと略称する）
和光純薬工業（株）試薬を使用した。
【００５８】
６．１，３，５−トリクロロベンゼン（以下、ＴＣＢと略称する）
東京化成（株）試薬を使用した。
【００５９】
物性評価
得られた重合体の溶融粘度（η）は、東洋精機（株）製キャピログラフ１Ｂを用いて測定した（３００℃、剪断速度１００／秒、ノズル孔径１ｍｍ、長さ１０ｍｍ）。
【００６０】
分子量は、（株）センシュー科学製高温ゲルパーミエーションクロマトグラフ（高温ＧＰＣ）ＳＳＣ−７０００を用いて測定した（溶媒：１−クロロナフタレン、温度：２１０℃、検出器：ＵＶ検出器（３６０ｎｍ）、サンプル注入量：２００μｌ（濃度：０．２重量％）。流速１ｍｌ／分）。なお、分子量はポリスチレン換算で算出し、分子量分布のピークトップの値Ｍｐで比較を行った。
【００６１】
実施例１
温度センサー、冷却塔、滴下槽、滴下ポンプ、留出物分離槽を連結した攪拌翼付ステンレス製（チタンライニング）４リットルオートクレーブにｐ−ＤＣＢ　７３５．０ｇ（５．０モル）、ＮＭＰ　１９８３ｇ（２０モル）、水　３６．０ｇ（２．０モル）を室温で仕込み、攪拌しながら窒素雰囲気下で１００℃まで２０分かけて昇温し、系を閉じ、更に２２０℃まで４０分かけて昇温し、その温度で内圧を０．２２ＭＰａにコントロールして、Ｎａ_２Ｓ・ｘＨ_２Ｏ　６００ｇ、ＮａＳＨ・ｙＨ_２Ｏ　９０ｇ、水１７０ｇの混合液（Ｎａ_２Ｓ：４．５６モル、ＮａＳＨ：１．２８モル、水分５０．３ｗｔ％）を３時間かけて滴下した。滴下中は同時に脱水操作を行い、水は系外に除去し、水と共に留出するｐ−ＤＣＢは連続的にオートクレーブに戻した。なお、脱水操作とｐ−ＤＣＢを戻す操作は２４０℃昇温完了まで行い、昇温完了時に系を密閉した。
【００６２】
その後、そのままの温度圧力で１時間保持した後、１時間かけて、内圧を０．１７ＭＰａに下げながら、内温を２４０℃まで昇温し、その温度で１時間保持して反応を終了し、室温まで冷却した。留出液の分析結果は、水が４５０ｇ、ＮＭＰ１８ｇであった。結果的に、反応終了時の反応系内の水分量は全使用スルフィド化剤に対して０．１８（モル／モル）であった。なお、ｐ−ＤＣＢについては、留出した全量をオートクレーブ内に戻したので、系外に除去したｐ−ＤＣＢは実質的に０であった。また系外に飛散した硫化水素量は１９ｇであった。従って反応の実質的なモル比〔（仕込みｐ−ＤＣＢ（モル））−（系外に除去したｐ−ＤＣＢ（モル））〕／〔（全使用スルフィド化剤（モル））−（系外に除去したＨ_２Ｓ（モル））〕は０．９５であった。得られた反応スラリーを一部サンプリングし、ガスクロマトグラフにより残存ＤＣＢ量を測定し、自動滴定装置を用いた硝酸銀滴定により残存スルフィド化剤量を測定した。その結果は、仕込みのＤＣＢ１モルに対して残存ＤＣＢ：１．５モル％、残存Ｎａ_２Ｓ：３．５モル％、残存ＮａＳＨ：４．４モル％であった。得られた反応スラリー２００ｇを１リットルの水に注いで８０℃で１時間攪拌した後、濾過した。このケーキを再び５００ミリリットルの湯で１時間攪拌、洗浄した後、濾過した。この操作を４回繰り返し、濾過後、熱風乾燥機で１２０℃−１０時間乾燥して白色粉末状のポリマーを得た。得られたポリマーの溶融粘度は１９００ポイズであり、分子量（Ｍｐ）は４２４００であった（精製法−１）。また、また、得られた反応スラリー２００ｇを減圧下（−０．０８ＭＰａ）、１２０℃に加熱することにより反応溶媒を留去し、残査に１リットルの水を注いで８０℃で１時間攪拌した後、濾過した。このケーキを再び５００ミリリットルの湯で１時間攪拌、洗浄した後、濾過した。この操作を３回繰り返し、更に５００ミリリットルの水を加え、２００℃で１時間攪拌後、濾過し、熱風乾燥機で１２０℃−１０時間乾燥して白色粉末状のポリマーを得た。得られたポリマーの溶融粘度は１９４０ポイズであった（精製法−２）。得られた反応スラリー２００ｇにＮＭＰを１００ｇ加え、８０℃で１時間攪拌した後、濾過した。このケーキを再び５００ミリリットルの湯で１時間攪拌、洗浄した後、濾過した。この操作を４回繰り返し、濾過後、熱風乾燥機で１２０℃−１０時間乾燥して白色粉末状のポリマーを得た。得られたポリマーの溶融粘度は２３６０ポイズであった（精製法−３）。結果を表１に示す。
【００６３】
実施例２、３
表１に示すような条件で、実施例１と同様に実施した。結果は表１に示すとおりである。
【００６４】
実施例４
滴下時間を５時間にする以外は実施例１と同様に実施した。結果を表２に示す。
【００６５】
実施例５
昇温前にＴＣＢ０．４５ｇ（０．００２５モル）を追加で仕込む以外は実施例１と同様に実施した。結果を表２に示す。
【００６６】
実施例６
ｐ−ＤＣＢの仕込量を７５０ｇ（５．１モル）として実施例１と同様に反応を行った。ただし、滴下中は留出したｐ−ＤＣＢを連続的に全量オートクレーブに戻し、昇温工程では留出したｐ−ＤＣＢのオートクレーブに戻す量を制御して、オートクレーブ内より１５ｇ系外に抜き出した。結果を表２に示す
【００６７】
比較例１
Ｎａ_２Ｓ・ｘＨ_２Ｏの使用量を６６８ｇ、ＮａＳＨ・ｙＨ_２Ｏを使用せずその代わりにＮａＯＨを１０ｇ使用し、水を１４０ｇ使用して実施例１と同様に実施した。滴下した混合液の組成はＮａ_２Ｓ：５．２０モル、ＮａＯＨ：０．１０モル、水分５０．３ｗｔ％であった。得られたポリマーは精製法−１で２１０ポイズと実施例に比較して低粘度であった。
【００６８】
比較例２
２２０℃滴下時のコントロールする圧力を０．５５ＭＰａ、２４０℃昇温時のコントロールする圧力を０．９０ＭＰａとする以外は実施例４と同様に実施した。反応終了時の水の量は全使用スルフィド化剤に対して１．１３（モル／モル）であった。得られたポリマーは精製法−１で１２０ポイズと実施例に比較して低粘度であった。
【００６９】
比較例３
使用するＤＣＢの量を７９３．８ｇ（５．４モル）とする以外は実施例１と同様に実施した。残存したモノマーは、仕込みのＤＣＢ１モルに対して残存ＤＣＢ：８．９モル％、残存Ｎａ_２Ｓ：３．２モル％、残存ＮａＳＨ：３．９モル％であった。得られたポリマーは精製法−１で１５０ポイズと実施例に比較して低粘度であった。
【００７０】
【表１】

【００７１】
【表２】

【００７２】
なお、表１及び２中の「反応実質モル比」とは、次式で算出される値を表す。反応実質モル比＝〔（仕込みｐ−ＤＣＢ（モル））−（系外に除去したｐ−ＤＣＢ（モル））〕／〔（全使用スルフィド化剤（モル））−（系外に除去したＨ_２Ｓ（モル））〕
【００７３】
【発明の効果】
本発明の製造方法によれば、有機極性溶媒中で、ジハロ芳香族化合物とスルフィド化剤とを反応させるポリアリーレンスルフィドポリマーの製造において、スルフィド化剤としてアルカリ金属硫化物とアルカリ金属水硫化物の混合物を用い、かつ水分量及びモノマー比を特定範囲にコントロールすることにより、ＰＡＳの高分子量化が達成できる。従って靱性等の力学的強度が向上した製品を、高い生産性で提供できる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing a polyarylene sulfide represented by a polyphenylene sulfide by reacting a sulfidizing agent with a dihalo aromatic compound. (Hereinafter, polyarylene sulfide is referred to as PAS, and polyphenylene sulfide is referred to as PPS.) More specifically, the present invention relates to a method for efficiently producing PAS having a high molecular weight and excellent stability.
[0002]
[Prior art]
As a method for producing PAS such as PPS, for example, an alkali metal sulfide, particularly sodium sulfide having crystal water (hereinafter abbreviated as hydrous sodium sulfide) is heated in a polar solvent to contain the hydrous sodium sulfide. There is a method in which water is removed, dichlorobenzene is added thereto, and heat polymerization is performed. However, this method physically removes the water contained in one of the raw materials, hydrous sodium sulfide (including the reaction product of hydrous sodium hydrosulfide and sodium hydroxide), by physically heating and distilling it in a polymerization solvent. However, there is a problem that sufficient dehydration is difficult, that is, 1 mol or more of water per mole of sodium sulfide remains in the system, and it is difficult to increase the molecular weight.
[0003]
As a technique for solving the above problems, for example, `` in a method for producing a polyarylene sulfide polymer in which a dihalo aromatic compound and a sulfidizing agent are reacted under heating in an organic polar solvent, the amount of water in the reaction system is While maintaining a controlled state in the range of 0.05 to 0.5 mol with respect to 1 mol of the solvent, a water-containing sulfidizing agent is introduced into the dihalo-aromatic compound solution under heating to remove the water-containing sulfide agent. A first step in which the reaction is carried out after the introduction or a second step in which the reaction is continued after changing the amount of water in the system to a range of 0.05 mol or less per 1 mol of the solvent. It is described that high-molecular-weight PPS can be produced by setting the conversion in the first step to 60 to 90% and the conversion in the second step to 90% or more by a two-stage polymerization method (for example, a patent). Reference 1 Irradiation) "
[0004]
[Patent Document 1]
JP-A-8-100604 (pages 2-7)
[0005]
[Problems to be solved by the invention]
However, in the above method, it is possible to obtain a polymer having a relatively high molecular weight, but it is necessary to strictly control the amount of water and the reaction rate in the polymerization system. An object of the present invention is to provide a method for efficiently producing a high molecular weight PAS by solving the above problems.
[Means for Solving the Problems]
The present inventors have conducted intensive studies to achieve the above object, and have obtained the following findings (1), (2), (3), and (4).
(1) It is difficult to efficiently produce a high molecular weight PAS simply by controlling only the amount of water in the polymerization system. {Circle around (2)} When a mixture of an alkali metal sulfide and an alkali metal hydrosulfide is used as the sulfidizing agent, side reactions can be suppressed. (3) The reaction rate can be controlled by controlling the content ratio of the remaining sulfidizing agent at the end of the reaction and the amount of water remaining in the reaction system at the end of the reaction to a specific range. {Circle around (4)} By setting the ratio of the remaining dihalo aromatic compound and the sulfidizing agent at the end of the reaction to a specific range, a high molecular weight PAS can be obtained efficiently.
[0006]
The present invention has been made based on these technical findings. That is, the present invention provides a method for producing a polyarylene sulfide, which comprises reacting a dihalo aromatic compound with a sulfidizing agent in an organic polar solvent,
1) The sulfidizing agent is a mixture of an alkali metal sulfide and an alkali metal hydrosulfide,
2) controlling the molar ratio of water in the reaction system at the end of the polymerization reaction to all the sulfidizing agents used in the polymerization (water / sulfide agent) to be less than 1;
3) Production of polyarylene sulfide, wherein the molar ratio of the remaining dihaloaromatic compound to the sulfidizing agent at the end of the polymerization reaction (dihaloaromatic compound / sulfidizing agent) is controlled to be less than 1. Provide a method.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described specifically.
The sulfidizing agent used in the present invention is a mixture of an alkali metal sulfide and an alkali metal hydrosulfide. Examples of the alkali metal sulfide include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, and cesium sulfide. Among these, sodium sulfide and potassium sulfide are preferable, and sodium sulfide is particularly preferable. These alkali metal sulfides may be used alone or in combination of two or more. The alkali metal sulfide may be any of an anhydride, a hydrate, and an aqueous solution. These alkali metal sulfides can also be obtained by reacting an alkali metal hydrosulfide with an alkali metal hydroxide, or by reacting hydrogen sulfide with an alkali metal hydroxide. You may use the thing obtained by making it.
[0008]
Examples of the alkali metal hydrosulfide used in the present invention include, for example, lithium hydrosulfide, sodium hydrosulfide, potassium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide, and the like. Two or more kinds may be used as a mixture. The alkali metal hydrosulfide may be any of an anhydride, a hydrate, and an aqueous solution. Among these, sodium bisulfide and potassium bisulfide are preferred, and sodium bisulfide is particularly preferred. In addition, these alkali metal hydrosulfides may be alkali metal hydrosulfides themselves or those obtained by previously reacting hydrogen sulfide with alkali metal hydroxides. A material obtained by reacting with an oxide may be used. As the alkali metal sulfide and the alkali metal hydrosulfide, those having 1 mol or more of crystallization water per 1 mol of a sulfur atom are preferable in terms of availability. Hereinafter, in the case where a compound having 1 mol or more of water of crystallization with respect to 1 mol of a sulfur atom in an alkali metal sulfide and an alkali metal hydrosulfide is used, it is referred to as a hydrosulfide agent.
[0009]
Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide. These may be used alone or in combination of two or more. May be used in combination. Further, among the above alkali metal hydroxides, lithium hydroxide, sodium hydroxide and potassium hydroxide are preferable, and sodium hydroxide is particularly preferable.
[0010]
The sulfidizing agent used in the present invention is a mixture of an alkali metal sulfide and an alkali metal hydrosulfide, and is obtained by reacting an alkali metal hydroxide with an excess of an alkali metal hydrosulfide as described above. Alternatively, it may be obtained by reacting an alkali metal hydroxide with excess hydrogen sulfide. Alternatively, it may be obtained by reacting an alkali metal sulfide with hydrogen sulfide.
[0011]
In the mixture of the alkali metal sulfide and the alkali metal hydrosulfide, the ratio of the alkali metal sulfide to the alkali metal hydrosulfide is not particularly limited. The range is preferably from 0.02 to 2 mol, more preferably from 0.04 to 1 mol. Within such a range, a polymer having a higher molecular weight can be obtained.
[0012]
The dihaloaromatic compound used in the present invention is a sulfide having an aromatic nucleus and two halo substituents on the nucleus, and a mixture of an alkali metal sulfide and an alkali metal hydrosulfide. There is no particular limitation as long as it can be polymerized through a dehalogenation / sulfurization reaction with an agent. Therefore, the aromatic nucleus may have various substituents which do not inhibit the dehalogenation / sulfidation reaction, in addition to the case where the aromatic nucleus is composed of only the aromatic hydrocarbon.
[0013]
Examples of the dihalo-aromatic compound include compounds represented by the following general formulas (1) to (4).
[Chemical 1]

[0014]
In the general formulas (1) to (4), X represents a halogen atom, Y represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, and 6 to 18 carbon atoms. Represents an aryl group, a carboxyl group, an alkoxycarbonyl group having 1 to 18 carbon atoms, a sodium carboxylate group, a cyano group, an amino group or a nitro group. X is preferably chlorine or bromine.
[0015]
V in the general formula (4) represents a divalent linking group represented by the following structural formulas (5) to (10).
[Chemical formula 2]

(In the formula, R ′ and R ″ each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms.)
[0016]
In the general formula (1), m represents 2 and n represents an integer of 0 to 4. In the general formula (2), a represents 2 and b represents an integer of 0 to 6. In the general formula (3), c represents an integer of 0 to 2, d represents 0 to 2, e represents an integer of 0 to 3, and f represents an integer of 0 to 2, and c and d satisfy c + d = 2. In the general formula (4), g is 0 to 2, h is 0 to 2, and i and j are integers satisfying 0 ≦ i and j ≦ 2.
[0017]
Specific examples of the dihaloaromatic compounds of the general formulas (1) to (4) include p-dihalobenzene, m-dihalobenzene, o-dihalobenzene, 2,5-dihalotoluene, 1,4-dihalonaphthalene, 1- Methoxy-2,5-dihalobenzene, 4,4′-dihalobiphenyl, 3,5-dihalobenzoic acid, 2,4-dihalobenzoic acid, 2,5-dihalonitrobenzene, 2,4-dihalonitrobenzene, 2, , 4-Dihaloanisole, 2,5-dihaloaniline, 3,5-dihaloaniline, p, p'-dihalodiphenylether, 4,4'-dihalobenzophenone, 4,4'-dihalodiphenylsulfone, 4,4 '-Dihalodiphenyl sulphoxide, 4,4'-dihalodiphenyl sulfide, etc., among which p-dihalobenzene, m-dihalobenzene, 4,4'-diha Robenzophenone and 4,4'-dihalodiphenylsulfone are preferred, of which p-dichlorobenzene, m-dichlorobenzene, 4,4'-dichlorobenzophenone and 4,4'-dichlorodiphenylsulfone are particularly preferably used. .
[0018]
A copolymer containing two or more different reaction units can be obtained by an appropriate combination of dihaloaromatic compounds, and the combination is not particularly limited. It is preferable to use p-dichlorobenzene in combination with 4,4'-dichlorobenzophenone or 4,4'-dichlorophenylsulfone, since a PAS excellent in various physical properties can be obtained. Polymerization using p-dihalobenzene in an amount of 70 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more of the dihaloaromatic compound is particularly preferable because PAS having various excellent physical properties can be obtained. PPS, which is a polymer composed of only dihalobenzene, is excellent in various physical properties. Among them, the use of dichlorobenzene is more preferable in terms of productivity and the like.
[0019]
The PAS according to the present invention is a polymer of the above-mentioned dihalo-aromatic compound, and may be used in combination with a monohalo compound to form a terminal of the formed polymer or to control a polymerization reaction or a molecular weight. In order to form a polymer, a polyhalo compound of trihalo or higher can be used in combination. When these monohalo or polyhalo compounds are used in combination, for example, if a small amount of trichlorobenzene is used in combination with dihalobenzene, a branched phenylene sulfide polymer can be obtained, and three or more halogens such as trichlorobenzene can be obtained. Use of a polyhalo compound having an atom as a substituent is useful in increasing the viscosity of the obtained polymer. Further, the amount of the monohalo compound or the polyhalo compound having three or more halogen atoms as a substituent cannot be specified unconditionally because it varies depending on the purpose or reaction conditions, but is preferably 0.1 to 1 mol of the dihalo aromatic compound. Mol% or less, more preferably 0.06 mol% or less. When the amount of the polyhalo compound having three or more halogen atoms as a substituent represented by trichlorobenzene is in the above range, it is preferable because the viscosity can be increased without substantially impairing the linearity of the obtained polymer. Note that both the monohalo compound and the polyhalo compound having three or more halogen atoms as substituents are not necessarily aromatic compounds.
[0020]
The organic polar solvent used in the polymerization reaction of the present invention is an organic polar solvent having no active hydrogen, that is, an aprotic organic polar solvent.
[0021]
The organic polar solvent does not inhibit the polymerization reaction, and the raw material dihalo aromatic compound and S ^2- It is not particularly limited as long as it has a dissolving ability enough to dissolve the sulfidizing agent giving the above to a concentration required for the reaction. Among these, this solvent is usually a polar solvent having a nitrogen atom, an oxygen atom, and a sulfur atom. Further, it is desirable that this solvent does not participate in the dehalogenation / sulfurization reaction similar to the starting dihaloaromatic compound. Thus, for example, it is desirable not to be a haloaromatic hydrocarbon.
[0022]
Since the organic polar solvent is for providing a controlled small amount of water to the polymerization reaction, it is desirable that this water as a solute can be solvated.
[0023]
Further, as is apparent from the production method of the present invention, it is desirable that the boiling point of the organic polar solvent is higher than the boiling point of water. Those satisfying the above conditions include, for example, (1) amides such as hexamethylphosphoric triamide (HMPA), N-methylpyrrolidone (NMP), N-cyclohexylpyrrolidone (NCP), N-methylcaprolactam, (2) etherified polyethylene glycols such as tetramethylurea (TMU), dimethylformamide (DMF), dimethylacetamide (DMA), etc., for example, polyethylene glycol dialkyl ether (polymerization degree up to about 2,000, alkyl group is C ₁ ~ C ₂₀ (3) sulfoxides, for example, tetramethylene sulfoxide, dimethyl sulfoxide (DMSO) and the like. Among the above solvents, N-methylcaprolactam and NMP are particularly preferred because of their high chemical stability.
[0024]
The amount of the organic polar solvent used depends on the type of the solvent used and the amount of water with respect to the solvent in the system, but maintains the viscosity of the reaction system capable of a uniform polymerization reaction, and also maintains a certain level of productivity. In order to do so, the range is preferably 1.0 to 8.0 mol per 1 mol of sulfur atom in the sulfidizing agent used for the polymerization. Further, when productivity is further considered, the range of 1.0 to 6.0 mol per 1 mol of sulfur atom in the sulfidizing agent used in the polymerization is preferable, and the more preferable amount of the solvent used is in the sulfidizing agent used in the polymerization. Is 1.2 to 5.0 mol per 1 mol of sulfur atom.
[0025]
The water for adjusting the water content in the polymerization system or the water content of the water-containing sulfidizing agent only needs to contain one that inhibits the reaction.Therefore, distilled water, ion-exchanged water, etc. Water excluding cations is preferred.
[0026]
The amount of water present in the polymerization reaction of the present invention is preferably as small as possible in order to avoid simultaneous reactions such as hydrolysis reaction. On the other hand, when the polymerization reaction is in a completely anhydrous state, there is a problem that the reaction rate becomes extremely slow. Therefore, the amount of water to be present in the reaction system in the polymerization reaction of the present invention must be less than 1 mol at the end of the polymerization reaction per 1 mol of the sulfidizing agent used in the polymerization. In addition, from the viewpoint that the reaction proceeds smoothly, it is preferable that 0.02 mol or more is present per 1 mol of the sulfidizing agent used in the polymerization. Among these, the range of 0.03 to 0.60 is preferable, and the range of 0.05 to 0.40 is particularly preferable for 1 mol of the sulfidizing agent used for the polymerization. When the above range is satisfied, the controllability of the control of the reaction rate and the increase in the molecular weight can both be more easily achieved.
[0027]
In the present invention, in the production of polyarylene sulfide by reacting a dihalo aromatic compound with a sulfide agent in an organic polar solvent, the sulfide agent is a mixture of an alkali metal sulfide and an alkali metal hydrosulfide, When the molar ratio of water in the reaction system at the end of the reaction to all of the sulfidizing agents used in the polymerization (water / sulfidizing agent) is less than 1, the remaining dihalo-aromatic compound at the end of the polymerization reaction and the sulfidizing agent (Dihalo aromatic compound / sulfidizing agent) is smaller than 1, but the polymerization method is not particularly limited as long as the above characteristics are satisfied. That is, there is no particular limitation on the method of charging the raw materials such as the dihalo aromatic compound, the sulfidizing agent, the organic polar solvent, and water.
[0028]
When the sulfidizing agent is a hydrous sulfidizing agent, dehydration is required to satisfy the characteristics of the production method of the present invention. And the polymerization may be performed separately, or dehydration may be appropriately performed while performing the polymerization.
[0029]
As a method of simultaneously performing dehydration and polymerization, for example, a temperature at which the polymerization reaction can substantially proceed, that is, a temperature of 200 to 300 ° C., preferably 210 to 280 ° C., and more preferably 215 to 260 ° C. The mixture may contain 0.5 mol or less of water with respect to the solvent) and the dihalo-aromatic compound, and the hydrous sulfidizing agent is added at such a rate that the amount of water in the reaction system can be controlled within the above range. After introducing excess water into the mixture to remove excess water outside the system and controlling the amount of water in the reaction system within the above range, the mixture is further heated to a temperature of 200 to 300 ° C, preferably 210 to 280 ° C, for 40 hours. Hereinafter, a method of performing a polymerization reaction by heating preferably for 0.5 to 20 hours, more preferably 1 to 10 hours may be used.
[0030]
As a method of separately performing dehydration and polymerization, for example, the temperature at which the polymerization reaction hardly proceeds, that is, 120 to 200 ° C., preferably 150 to 190 ° C., at an organic polar solvent (0.5 mole to the organic polar solvent) The mixture may contain the following water) and a dihaloaromatic compound, and the sulfidizing agent is introduced into the mixture at such a rate that the amount of water in the reaction system can be controlled to less than 1 mol per 1 mol of the sulfidizing agent. To remove excess water to the outside of the system to control the amount of water in the reaction system to less than 1 mol per 1 mol of the sulfidizing agent, and then to prepare the prepared organic polar solvent, dihalo-aromatic compound and hydrous sulfidizing agent. Is heated to a temperature at which the polymerization reaction substantially proceeds, ie, a temperature of 200 to 300 ° C., preferably 210 to 280 ° C., for 40 hours or less, preferably 0.5 to 20 hours. During, and more preferably it may be a method of performing polymerization reaction by heating for 1 to 10 hours.
[0031]
In addition, as a method of appropriately performing dehydration while performing polymerization, for example, the following method may be mentioned. {Circle around (1)} A sulfide agent is added to an organic polar solvent, preferably in an inert gas atmosphere, and the temperature is raised to 150 ° C. or more, preferably 180 to 250 ° C., at normal pressure, reduced pressure, or increased pressure, to reduce water sulfide. Adjust to 1 to 1.5 mol per 1 mol of the agent, further add a dihalo aromatic compound, and heat to a temperature at which the polymerization reaction proceeds, that is, 200 to 300 ° C, preferably 210 to 280 ° C. The polymerization reaction is performed by heating for 0.1 to 40 hours, preferably 0.5 to 20 hours, more preferably 1 to 10 hours, and continuously, temporarily or intermittently during the polymerization reaction. And controlling the amount of water in the reaction system to less than 1 mol per 1 mol of the sulfidizing agent in the reaction system.
[0032]
{Circle around (2)} An organic polar solvent (which may contain 0.5 mol or less of water with respect to the organic polar solvent) and a dihalo aromatic at a temperature at which the polymerization reaction hardly proceeds, ie, 120 to 200 ° C., preferably 150 to 190 ° C. A mixture of group III compounds is maintained, and a sulfidizing agent is introduced into the mixture at a rate at which the amount of water in the reaction system can be controlled, excess water is removed outside the system, and the amount of water in the reaction system is converted into sulfide in the reaction system. After controlling to less than 1 mol per 1 mol of the agent, a temperature at which the polymerization reaction of the mixture of the prepared organic polar solvent, dihaloaromatic compound and hydrous sulfidizing agent substantially proceeds, that is, 200 to 300 ° C., preferably Is heated to a temperature of 210 to 280 ° C., and is heated for 0.1 to 40 hours, preferably 0.5 to 20 hours, more preferably 1 to 10 hours to perform a polymerization reaction. Polymerization process between the to reduce further more moisture content to remove moisture in continuously or temporarily or intermittently system according to need.
[0033]
{Circle around (3)} An organic polar solvent (0.5 mol or less of water relative to the organic polar solvent) at a temperature at which the polymerization reaction can proceed, at a temperature of 200 to 300 ° C., preferably 210 to 280 ° C., more preferably 215 to 260 ° C. And a mixture of dihaloaromatic compounds is heated, and a water-containing sulfidizing agent is introduced into the mixture at such a rate that the amount of water in the reaction system can be controlled to remove excess water from the system. After controlling the amount of water in the reaction system to be less than 1 mol per 1 mol of the sulfidizing agent in the reaction system, the mixture is further heated to a temperature of 200 to 300 ° C., preferably 210 to 280 ° C. for 40 hours. Hereinafter, the polymerization reaction is preferably performed by heating for 0.5 to 20 hours, more preferably 1 to 10 hours, and while the polymerization reaction is being performed, the water content in the system is continuously, temporarily, or intermittently. To The polymerization method for reducing the water content was removed by.
[0034]
Among the above polymerization methods, a method of appropriately dehydrating while performing polymerization is preferable from the viewpoint of productivity and the like. Among these, the mixture of the organic polar solvent and the dihalo-aromatic compound is heated to a temperature at which the polymerization reaction can substantially proceed, and the water-containing sulfidizing agent is introduced into the mixture at such a rate that the amount of water in the reaction system can be controlled. After removing excess water to the outside of the system and controlling the amount of water in the reaction system, perform the polymerization reaction further.Continuously, temporarily or intermittently as necessary during the polymerization reaction. Preferably, a polymerization method in which the water content in the reaction system is removed to further reduce the water content is preferable. In particular, the water content in the reaction system is reduced to less than 1 mol per 1 mol of the sulfidizing agent in the reaction system throughout the polymerization process. Most preferred is the polymerization method described in (3) above.
[0035]
The rate at which the above-mentioned hydrous sulfidizing agent is introduced is not particularly limited as long as excess water can be removed outside the system so that the amount of water in the reaction system can be controlled within a desired range with respect to 1 mol of the organic polar solvent. There is no. The introduction time varies depending on the amount of water to be controlled, the temperature at the time of introduction, the water content of the hydrated sulfidizing agent and the like, and cannot be unconditionally specified, but the hydrated sulfidizing agent is used for 0.1 to 20 hours, preferably 0.5 to 20 hours. It is preferable to introduce it over 10 hours. Within this time, it is easy to control the amount of water or the temperature of the reaction system, and the productivity is good.
[0036]
In addition, the temperature at which the hydrated sulfidizing agent is introduced also controls the amount of water to be controlled, the rate at which the sulfidedating agent is introduced, the water content of the hydrated sulfidizing agent, or the type of the reaction. If performed, it is recommended to introduce at 120 to 200 ° C, preferably 150 to 190 ° C. In addition, if dehydration and polymerization are carried out simultaneously, the introduction may be carried out at a temperature of 200 to 300 ° C, preferably 210 to 280 ° C, more preferably 215 to 260 ° C.
[0037]
The polymerization reaction is carried out by heating to a temperature of 200 to 300 ° C, preferably 210 to 280 ° C, for 0.1 to 40 hours, preferably 0.5 to 20 hours, more preferably 1 to 10 hours. preferable. Within this range, the reaction proceeds smoothly.
[0038]
The method of removing water during polymerization can be easily performed by controlling the temperature and pressure of the reaction system. That is, the temperature and pressure to be controlled can be easily estimated from the vapor pressure curves of water, the solvent and the dihaloaromatic compound, and a desired amount of water in the system can be obtained by controlling the temperature and pressure.
[0039]
The amount of the dihalo-aromatic compound and the sulfidizing agent used in the production method of the present invention is determined by the molar ratio of the remaining dihalo-aromatic compound and the remaining sulfidizing agent at the end of the polymerization reaction (dihalo-aromatic compound / sulfide). As long as the (agent) is less than 1, there is no particular limitation. For example, as a method for adding a dihalo aromatic compound and a sulfidizing agent, the following methods (a) and (b) are mentioned.
(A) a dihalo-aromatic compound and a sulfide such that the molar ratio of the remaining dihalo-aromatic compound and the remaining sulfide agent at the end of the polymerization reaction (dihalo-aromatic compound / sulfide agent) is less than 1 in advance; The reaction may be carried out by charging with an agent. (B) the dihalo-aromatic compound and the sulfide so that the molar ratio of the remaining dihalo-aromatic compound and the remaining sulfidizing agent at the end of the polymerization reaction (dihalo-aromatic compound / sulfidizing agent) is 1 or more; After the polymerization, the dihalo-aromatic compound is removed out of the system during the polymerization, and the molar ratio of the remaining dihalo-aromatic compound and the remaining sulfidizing agent at the end of the polymerization reaction (dihalo-aromatic compound / (A sulfidizing agent) may be adjusted to be less than 1. Among these, the above (a) is preferable.
[0040]
In any of the above methods (a) and (b), the molar ratio of the remaining dihalo-aromatic compound and the remaining sulfidizing agent at the end of the polymerization reaction (dihalo-aromatic compound / sulfidizing agent) is less than 1. Is essential, and when it is 1 or more, it is not preferable because the high molecular weight of the polymer which is the object of the present invention cannot be achieved. However, if the molecular weight is too small, the molecular weight may decrease due to the decomposition reaction of the polymer. Therefore, it is preferably 0.05 or more. Among them, the molar ratio of the remaining dihalo-aromatic compound and the remaining sulfidizing agent at the end of the polymerization reaction (dihalo-aromatic compound / sulfidizing agent) is particularly preferably in the range of 0.1 to 0.5. When this range is satisfied, a higher molecular weight can be achieved without causing a decomposition reaction.
[0041]
Therefore, in either case of the above method (a) or (b), [(total use of dihalo-aromatic compound (mol))-(dihalo-aromatic compound (mol) removed out of the system)] and [(total use of dihalo-aromatic compound (mol)) The ratio of (sulfidizing agent (mol))-(sulfur content (mol) removed outside the system)] of greater than 0.90 and less than 1 can provide a polymer having excellent physical properties, that is, a polymer having a higher molecular weight. Preferred. When the above range is satisfied, the preferable range of the remaining monomer ratio is easily satisfied, which is preferable. Further, when the above range is 0.92 to 0.99, it is more preferable from the viewpoint of increasing the molecular weight.
[0042]
The residual amount of the dihalo-aromatic compound is usually determined by gas chromatography. The remaining amount of the sulfidizing agent such as alkali metal sulfide and alkali metal hydrosulfide can be determined by, for example, a silver nitrate titration method.
[0043]
In the polymerization reaction of the present invention, a polymerization vessel made of titanium, chromium, zirconium, or the like is used as a liquid contact part, and is usually preferably performed in an atmosphere of an inert gas such as nitrogen, helium, or argon. Nitrogen is preferred from the viewpoint of ease of handling and ease of handling.
[0044]
The reaction pressure is not particularly limited because it depends on the type and amount of the raw materials and the solvent used, the reaction temperature, and the like, and cannot be specified unconditionally. The reaction liquid preparation and polymer formation reaction may be a one-step reaction performed at a constant temperature, a multi-step reaction in which the temperature is increased stepwise, or a method in which the temperature is continuously changed. May be the reaction.
[0045]
In the present invention, in the production of a polyarylene sulfide polymer in which a dihalo aromatic compound is reacted with a sulfide agent in an organic polar solvent, the sulfide agent is a mixture of an alkali metal sulfide and an alkali metal hydrosulfide, When the molar ratio of water in the reaction system at the end of the reaction to all of the sulfidizing agents used in the polymerization (water / sulfidizing agent) is less than 1, the remaining dihalo-aromatic compound at the end of the polymerization reaction and the sulfidizing agent (Dihalo aromatic compound / sulfidizing agent) is smaller than 1, but additional steps such as a pre-treatment step or a post-treatment step may be provided.
[0046]
In the present invention, post-treatment after the completion of the polymerization reaction can be performed by a conventional method. For example, after the completion of the polymerization reaction, the reaction mixture may be used as it is, or may be diluted with water or an organic solvent such as a reaction solvent, an acid or a base may be added if necessary, and the mixture may be filtered off. It can be performed by summing, washing with water, filtering and drying. Alternatively, as an alternative, the reaction mixture as it is, or after adding an acid or a base, is heated under reduced pressure or normal pressure to distill off only the solvent. , And washed once or twice with water or ketones such as acetone or alcohols such as methanol, or an organic solvent such as a reaction solvent, and then, if necessary, neutralized, washed with water, filtered and dried. This can be done by: The temperature at which the above-described washing and filtering operations are performed is not particularly limited. Alternatively, a treatment with a salt such as ammonium chloride may be used instead of the acid or the base.
[0047]
The isolated polymer is dried by heating to a temperature at which a solvent such as water substantially evaporates. Drying may be performed under vacuum, or may be performed in air or in an atmosphere of an inert gas such as nitrogen.
[0048]
Since the polymer obtained by the present invention has a higher molecular weight than conventional PAS, it can be used as it is for various molding materials, but it can be thickened by heat treatment in air or oxygen-enriched air or under reduced pressure. It is possible, and after performing such a thickening operation as necessary, it may be used for various molding materials. Since the heat treatment temperature varies depending on the treatment time and the atmosphere in which the treatment is performed, it cannot be unconditionally specified. If the heat treatment temperature is lower than 180 ° C., the rate of thickening is extremely slow, and the productivity is poor, which is not preferable. The heat treatment may be performed in a molten state at a temperature higher than the melting point of the polymer using an extruder or the like. However, from the viewpoint of the possibility of deterioration of the polymer or workability, it is preferable to carry out the reaction at a temperature higher than the melting point plus 100 ° C.
[0049]
The polymer obtained by the present invention is a molded product excellent in heat resistance, molding processability, dimensional stability, etc. by various melt processing methods such as injection molding, extrusion molding, compression molding, and blow molding as in the conventional PAS. Can be However, in order to further improve the performance such as strength, heat resistance and dimensional stability, it is also possible to use in combination with various fillers as long as the object of the present invention is not impaired. Examples of the filler include a fibrous filler and an inorganic filler.
[0050]
In addition, a small amount of a mold release agent, a colorant, a heat stabilizer, an ultraviolet stabilizer, a foaming agent, a rust inhibitor, a flame retardant, a lubricant, a cup as an additive during the molding process without departing from the object of the present invention. A ring agent can be included. Further, similarly, the following synthetic resins and elastomers can be mixed and used. As these synthetic resins, polyester, polyamide, polyimide, polyetherimide, polycarbonate, polyphenylene ether, polysulfone, polyethersulfone, polyetheretherketone, polyetherketone, polyarylene, polyethylene, polypropylene, polytetrafluoroethylene, Examples include polydifluoroethylene, polystyrene, ABS resin, epoxy resin, silicone resin, phenolic resin, urethane resin, and liquid crystal polymer. Examples of the elastomer include polyolefin-based rubber, fluorine rubber, and silicone rubber.
[0051]
The polymer and its composition of the present invention are excellent in heat resistance, dimensional stability and the like like PPS obtained by a conventional method, and therefore, for example, electric / electronic parts such as connectors, printed boards, sealing molded articles, lamp reflectors・ Automotive parts such as various electrical parts, interior materials such as various buildings, aircrafts and automobiles, or injection molded and compression molded products such as precision parts such as OA equipment parts, camera parts and clock parts, or fibers and films. It can be widely used as extruded and drawn products such as sheets and pipes.
[0052]
【Example】
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited only to these examples.
[0053]
Raw materials used
1. Sulfidizing agent
Hydrous flake sodium sulfide (hereinafter referred to as Na ₂ S xH ₂ Abbreviated as O. Purity-Na ₂ (S: 58.9% by weight, NaSH: 1.3% by weight) produced by Nagao Corporation. Further, hydrated flake sodium bisulfide (hereinafter, NaSH.yH) ₂ Abbreviated as O. Purity-NaSH: 71.2% by weight, Na ₂ S: 2.7% by weight) used Nagao Corporation product.
[0054]
2. solvent
As N-methylpyrrolidone (hereinafter abbreviated as NMP), BASF Japan Ltd. product was used.
[0055]
3. Dihalo aromatic compounds
As the p-dichlorobenzene (hereinafter abbreviated as p-DCB), Hodogaya Chemical Co., Ltd. product was used.
[0056]
4. water
Tap water was distilled and then subjected to ion exchange.
[0057]
5. Sodium hydroxide (hereinafter abbreviated as NaOH)
Wako Pure Chemical Industries, Ltd. reagent was used.
[0058]
6. 1,3,5-trichlorobenzene (hereinafter abbreviated as TCB)
Tokyo Chemical Co., Ltd. reagent was used.
[0059]
Evaluation of the physical properties
The melt viscosity (η) of the obtained polymer was measured using a Capillograph 1B manufactured by Toyo Seiki Co., Ltd. (300 ° C., shear rate 100 / sec, nozzle hole diameter 1 mm, length 10 mm).
[0060]
The molecular weight was measured using a high-temperature gel permeation chromatograph (high-temperature GPC) SSC-7000 manufactured by Senshu Scientific Co., Ltd. (solvent: 1-chloronaphthalene, temperature: 210 ° C., detector: UV detector (360 nm), Sample injection volume: 200 μl (concentration: 0.2% by weight, flow rate 1 ml / min). The molecular weight was calculated in terms of polystyrene, and the comparison was performed using the peak value Mp of the molecular weight distribution.
[0061]
Example 1
735.0 g (5.0 mol) of p-DCB and 1983 g of NMP (20 mol) were placed in a stainless steel (titanium lining) 4-liter autoclave with stirring blades connected to a temperature sensor, a cooling tower, a dropping tank, a dropping pump, and a distillate separation tank. Mol) and water (36.0 g, 2.0 mol) were charged at room temperature, the temperature was raised to 100 ° C. over 20 minutes with stirring under a nitrogen atmosphere, the system was closed, and the temperature was further raised to 220 ° C. over 40 minutes. At that temperature, the internal pressure was controlled to 0.22 MPa and Na ₂ S xH ₂ O 600g, NaSH ・ yH ₂ A mixture of 90 g of O and 170 g of water (Na ₂ S: 4.56 mol, NaSH: 1.28 mol, water content: 50.3 wt%) was added dropwise over 3 hours. During the dropping, a dehydration operation was performed at the same time, water was removed from the system, and p-DCB distilled out together with the water was continuously returned to the autoclave. The dehydration operation and the operation of returning p-DCB were performed until the temperature was raised to 240 ° C, and the system was sealed when the temperature was completed.
[0062]
Thereafter, the temperature was maintained at the same temperature and pressure for 1 hour, and then the internal temperature was raised to 240 ° C. while reducing the internal pressure to 0.17 MPa over 1 hour, and the temperature was maintained for 1 hour to complete the reaction. Cooled to room temperature. The analysis result of the distillate was 450 g of water and 18 g of NMP. As a result, the amount of water in the reaction system at the end of the reaction was 0.18 (mol / mol) with respect to all the sulfidizing agents used. In addition, about the p-DCB, since the whole amount distilled out was returned into the autoclave, the p-DCB removed outside the system was substantially 0. The amount of hydrogen sulfide scattered outside the system was 19 g. Therefore, a substantial molar ratio of the reaction [(p-DCB (mol) charged)-(p-DCB (mol) removed outside the system)] / [(total used sulfidizing agent (mol))-( H removed ₂ S (mol)) was 0.95. A part of the obtained reaction slurry was sampled, the amount of residual DCB was measured by gas chromatography, and the amount of residual sulfidizing agent was measured by silver nitrate titration using an automatic titrator. As a result, the residual DCB: 1.5 mol%, the residual Na ₂ S: 3.5 mol%, remaining NaSH: 4.4 mol%. 200 g of the obtained reaction slurry was poured into 1 liter of water, stirred at 80 ° C. for 1 hour, and then filtered. The cake was again stirred and washed with 500 ml of hot water for 1 hour, and then filtered. This operation was repeated four times, followed by filtration and drying with a hot air drier at 120 ° C. for 10 hours to obtain a white powdery polymer. The melt viscosity of the obtained polymer was 1900 poise, and the molecular weight (Mp) was 42400 (purification method-1). The reaction solvent was distilled off by heating 200 g of the obtained reaction slurry under reduced pressure (-0.08 MPa) to 120 ° C., and 1 liter of water was poured into the residue, followed by stirring at 80 ° C. for 1 hour. After that, the mixture was filtered. The cake was again stirred and washed with 500 ml of hot water for 1 hour, and then filtered. This operation was repeated three times, and 500 ml of water was further added. The mixture was stirred at 200 ° C. for 1 hour, filtered, and dried with a hot air drier at 120 ° C. for 10 hours to obtain a white powdery polymer. The melt viscosity of the obtained polymer was 1940 poise (purification method-2). 100 g of NMP was added to 200 g of the obtained reaction slurry, stirred at 80 ° C. for 1 hour, and then filtered. The cake was again stirred and washed with 500 ml of hot water for 1 hour, and then filtered. This operation was repeated four times, followed by filtration and drying with a hot air drier at 120 ° C. for 10 hours to obtain a white powdery polymer. The melt viscosity of the obtained polymer was 2,360 poise (purification method-3). The results are shown in Table 1.
[0063]
Examples 2 and 3
It carried out similarly to Example 1 on conditions as shown in Table 1. The results are as shown in Table 1.
[0064]
Example 4
The operation was performed in the same manner as in Example 1 except that the dropping time was changed to 5 hours. The results are shown in Table 2.
[0065]
Example 5
The operation was performed in the same manner as in Example 1 except that 0.45 g (0.0025 mol) of TCB was additionally charged before the temperature was raised. The results are shown in Table 2.
[0066]
Example 6
The reaction was carried out in the same manner as in Example 1 except that the charged amount of p-DCB was 750 g (5.1 mol). However, during the dropping, the entire amount of the distilled p-DCB was continuously returned to the autoclave, and in the temperature raising step, the amount of the distilled p-DCB returned to the autoclave was controlled, and 15 g was extracted from the autoclave to the outside of the autoclave. The results are shown in Table 2.
[0067]
Comparative Example 1
Na ₂ S xH ₂ O 668 g, NaSH.yH ₂ The same procedure as in Example 1 was carried out without using O but using 10 g of NaOH and 140 g of water. The composition of the dropped mixture is Na ₂ S: 5.20 mol, NaOH: 0.10 mol, water content: 50.3 wt%. The obtained polymer had a viscosity of 210 poise by the purification method-1, which was lower than that of the examples.
[0068]
Comparative Example 2
Example 4 was carried out in the same manner as in Example 4 except that the controlling pressure at the time of dropping at 220 ° C was 0.55 MPa and the controlling pressure at the time of raising the temperature of 240 ° C was 0.90 MPa. The amount of water at the end of the reaction was 1.13 (mol / mol) with respect to all the sulfidizing agents used. The obtained polymer had a viscosity of 120 poise by the purification method-1 and was lower than that of the examples.
[0069]
Comparative Example 3
The operation was carried out in the same manner as in Example 1 except that the amount of DCB used was 793.8 g (5.4 mol). The remaining monomer was composed of 8.9 mol% of residual DCB and 1 mol of residual Na with respect to 1 mol of charged DCB. ₂ S: 3.2 mol%, residual NaSH: 3.9 mol%. The obtained polymer had a viscosity of 150 poise by the purification method-1, which was lower than that of the examples.
[0070]
[Table 1]

[0071]
[Table 2]

[0072]
In addition, "reaction substantial molar ratio" in Tables 1 and 2 represents a value calculated by the following equation. Reaction substantial molar ratio = [(p-DCB (mol) charged)-(p-DCB (mol) removed outside the system)] / [(total used sulfidizing agent (mol))-(H removed outside the system) ₂ S (mol))
[0073]
【The invention's effect】
According to the production method of the present invention, in an organic polar solvent, in the production of a polyarylene sulfide polymer in which a dihalo aromatic compound is reacted with a sulfidizing agent, an alkali metal sulfide and an alkali metal hydrosulfide are used as the sulfidizing agent. By using a mixture and controlling the water content and the monomer ratio to specific ranges, it is possible to achieve a high molecular weight PAS. Therefore, a product with improved mechanical strength such as toughness can be provided with high productivity.

Claims (7)

In an organic polar solvent, a method for producing a polyarylene sulfide by reacting a dihalo aromatic compound and a sulfide agent,
1) The sulfidizing agent is a mixture of an alkali metal sulfide and an alkali metal hydrosulfide,
2) controlling the molar ratio of water in the reaction system at the end of the polymerization reaction to all the sulfidizing agents used in the polymerization (water / sulfide agent) to be less than 1;
3) Production of polyarylene sulfide, wherein the molar ratio of the remaining dihaloaromatic compound to the sulfidizing agent at the end of the polymerization reaction (dihaloaromatic compound / sulfidizing agent) is controlled to be less than 1 Method. The method for producing a polyarylene sulfide according to claim 1, wherein the sulfidizing agent is a hydrous sulfidizing agent having water of crystallization. A method of controlling the molar ratio of water in the reaction system and the sulfidizing agent at the end of the polymerization reaction (water / sulfidizing agent) to be less than 1
A method of reacting while introducing a hydrous sulfidizing agent into a mixture containing a heated organic polar solvent and a dihaloaromatic compound,
In addition, the introduction rate of the water-containing sulfidizing agent is adjusted so that the water in the reaction system is removed from the reaction mixture so that the amount of water in the reaction system is less than 1 mol with respect to 1 mol of the entire sulfidizing agent used in the polymerization. 3. The method for producing a polyarylene sulfide according to claim 2, wherein the method is a method of adjusting and controlling the temperature. The mixing ratio of the alkali metal sulfide and the alkali metal hydrosulfide in the sulfidizing agent is in the range of 0.04 to 1 mol of the alkali metal hydrosulfide to 1 mol of the alkali metal sulfide. 4. The method for producing a polyarylene sulfide according to 3. [(Total used dihalo aromatic compound (mol)]-(dihalo aromatic compound (mol) removed outside system)] and [(total used sulfidizing agent (mol))-(sulfur component removed outside system (mol The method for producing a polyarylene sulfide according to claim 2 or 3, wherein the ratio of (mol))) is in the range of 0.92 to 0.99. The method for producing a polyarylene sulfide according to any one of claims 1 to 5, wherein the polyarylene sulfide is polyphenylene sulfide. The method for producing a polyarylene sulfide according to any one of claims 1 to 6, wherein the polyarylene sulfide is a polyphenylene sulfide having a branched structure of 0.1 mol% or less.