JP3868011B2 - Method for producing polyarylene sulfide polymer - Google Patents

Description

【００２５】
ここで各置換基は下記の意味を持つ。
Ｘ：Ｃｌ、Ｂｒ、Ｉ または Ｆ。特に、Ｃｌ及びＢｒより成る群から選ばれた少なくとも１種のハロゲン。
【００２６】
Ｙ：−Ｒ、−ＯＲ、−ＣＯＯＲ、−ＣＯＯＮａ、−ＣＮ及び−ＮＯ₂（Ｒは、 Ｈ、アルキル基、シクロアルキル基、アリール基及びアラルキル基より成る群から選ばれたもの）より成る群から選ばれたもの。ここで、アルキル基又はアルキル基部分は炭素数１〜１８程度、アリール基またはアリール基部分は炭素数６〜１８程度のものがふつうである。
【００２７】
【化２】

（Ｒ'及びＲ''は、Ｈ、アルキル基、シクロアルキル基、アリール基及びアラルキル基より成る群から選ばれたもの）より成る群から選ばれたもの。ここでアルキル基またはアルキル基部分及びアリール基またはアリール基部分は上記と同様に定義される。
【００２８】
式（Ａ）中でｍ及びｎは、それぞれｍ＝２、０≦ｎ≦４の整数。
式（Ｂ）中でａ及びｂは、それぞれａ＝２、０≦ｂ≦６の整数。
式（Ｃ）中でｃ、ｄ、ｅ及びｆは、それぞれ０≦ｃ≦２、０≦ｄ≦２、
ｃ＋ｄ＝２、０≦ｅ、ｆ≦２の整数。
【００２９】
式（Ｄ）中でｇ、ｈ、ｉ及びｊは、それぞれ０≦ｇ≦２、０≦ｈ≦２、
ｇ＋ｈ＝２、０≦ｉ、ｊ≦２の整数。
上記一般式のジハロゲン置換基芳香族化合物の例として、次のようなものがある。
【００３０】
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、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−ジクロルベンゼン、ｍ−ジクロルベンゼン、４，４’−ジクロルベンゾフェノンおよび４，４’−ジクロルジフェニルスルホンは特に好適に使用される。
【００３１】
ジハロ芳香族化合物の適当な選択組合せによって２種以上の異なる反応単位を含む共重合体を得ることができることは前記した通りである。ｐ−ジクロルベンゼンと４，４’−ジクロルベンゾフェノンもしくは４，４’−ジクロルフェニルスルホンとを組み合わせて使用すれば、
【００３２】
【化３】

【００３３】
単位と
【００３４】
【化４】

【００３５】
単位もしくは
【００３６】
【化５】

【００３７】
単位とを含んだ共重合物を得ることができる。
但し、共重合することは可能ではあるが、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ＰＰＳが得られるので好ましい。
【００３８】
本発明で使用するジハロ芳香族化合物の使用量は使用するスルフィド化剤中の硫黄源１モル当たり０．８〜１．３モルの範囲が望ましく、特に０．９〜１．１０モルの範囲が物性の優れたポリマーを得るのに好ましい。
【００３９】
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（必ずしも芳香族化合物でなくともよい）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（必ずしも芳香族化合物でなくともよい）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が芳香族化合物である場合の具体例は、上記具体例のモノハロまたはポリハロ誘導体として当業者にとって自明であろう。具体的には、例えばジハロベンゼンに若干量のトリクロル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る。また、モノハロまたは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０．０５モル以下である。
【００４０】
（溶媒および水）
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。
【００４１】
この溶媒は、本発明重合反応を不当に阻害するものであってはならない。また、この溶媒は、少なくとも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るべきである。従って、この溶媒は、窒素原子、酸素原子および／または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。
【００４２】
本発明で使用する溶媒は、制御された微小の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。
【００４３】
また、本発明の製造方法から明らかなように、使用する溶媒の沸点は水の沸点より高くなければならない
このような溶媒の具体的例を挙げれば、（１）アミド、たとえば、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）、その他、（２）エーテル化ポリエチレングリコールたと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Ｃ₁〜Ｃ₂₀程度）など、（３）スルホキシド、たと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）その他、がある。これらのうちでも、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。
【００４４】
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源１モル当り１．０〜５モルの範囲が好ましい。また、反応容器の容積当たりのポリマーの生産量が大きくするためには、重合に用いるスルフィド化剤中の硫黄源１モル当り１．０〜３．５モルの範囲が好ましく、また、更に好ましい使用溶媒量は同１モル当り１．２〜３．０モルである。
【００４５】
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。
【００４６】
一般に、本発明の重合反応に存在させるべき水分は、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よい。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、有機極性溶媒１モル当たり０．０２〜０．５モル、好ましくは０．０２〜０．３モルである。
（重合）
本発明による重合は、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、好ましくは１５０℃以上に加熱し、含水スルフィド化剤を水が反応混合物から除去され得る速度で導入することにより、反応系内の水分量を該有機極性溶媒１モルに対して０．０２〜０．５モルの範囲にコントロールし、その条件下で進行する。
【００４７】
したがって、本発明方法としては、脱水と重合を別々に行う方法、例えば重合反応が実質的に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上記範囲内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上記範囲内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なう方法でもよい。また脱水と重合を同時に行う方法、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方法でも良い。
【００４８】
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０．０２〜０．５モル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、また生産性もよい。
【００４９】
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。
【００５０】
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。
【００５１】
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窒素が好ましい。
【００５２】
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、反応液の調整及び共重合体の生成反応は一定温度で行なう１段反応でもよいし、段階的に温度を上げていく多段階反応でもよいし、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はない。
【００５３】
重合体の回収は、反応終了時にまず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、ついで缶残固形物を水、アセトン、メチルエチルケトン、アルコール類などの溶媒で１回または２回以上洗浄し、それから中和、水洗、ろ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、反応終了後に反応混合物に水、アセトン、メチルエチルケトン、アルコール類、エーテル類、ハロゲン化炭化水素、芳香族炭化水素、脂肪族炭化水素などの溶媒（使用した重合溶媒に可溶であり、かつ少なくとも生成重合体に対しては貧溶媒であるもの）を沈降剤をして添加して重合体、無機塩等の固体状生成物を沈降させ、それを濾別、洗浄及び乾燥することによって行うこともできる。これらの場合の「洗浄」は、抽出の形で実施することができる。また、反応終了後、反応混合物に反応溶媒（もしくはそれと同等の低分子重合体の溶解度を有する溶媒）を加えて攪拌した後、ろ別して低分子量重合体を除いた後、水、アセトン、メチルエチルケトン、アルコール類などの溶媒で１回または２回以上洗浄し、その後中和、水洗、ろ別および乾燥をすることによっても行うことができる。乾燥は、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行う。乾燥は真空下で行なってもよいし、空気中あるいは窒素のような不活性ガス雰囲気下で行なってもよい。
【００５４】
得られた重合体は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化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なった後、各種成形材料等に利用してもよい。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。熱処理を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。
【００５５】
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。
【００５６】
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。繊維状充填材としては、ガラス繊維、炭素繊維、シランガラス繊維、セラミック繊維、アラミド繊維、金属繊維、チタン酸カリウム、炭化珪素、硫酸カルシウム、珪酸カルシウム等の繊維、ウォラストナイト等の天然繊維等が使用できる。また無機充填材としては、硫酸バリウム、硫酸カルシウム、クレー、バイロフェライト、ベントナイト、セリサイト、ゼオライト、マイカ、雲母、タルク、アタルパルジャイト、フェライト、珪酸カルシウム、炭酸カルシウム、炭酸マグネシウム、ガラスビーズ等が使用できる。
【００５７】
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。
【００５８】
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、寸歩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・各種電装品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、あるいはコンポジット・シート・パイプなどの押出成形・引抜成形などの各種成形加工分野において耐熱性や成形加工性、寸法安定性等の優れた成形材料あるいは繊維、フィルムとして用いられる。
【００５９】
【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。
【００６０】
［参考例１］
使用原料
１．スルフィド化剤（アルカリ金属硫化物）
結晶硫化ナトリウム（５水塩）（以下、Ｎａ₂Ｓ・５Ｈ₂Ｏと略称する）は三協化成（株）製品を使用。
【００６１】
結晶硫化ナトリウム（９水塩）（以下、Ｎａ₂Ｓ・９Ｈ₂Ｏと略称する）は和光純薬（株）製品を使用。
２．溶媒
Ｎ−メチルピロリドン（以下、ＮＭＰと略称する）は三菱化成（株）製品を使用。
【００６２】
３．ジハロ芳香族化合物
ｐ−ジクロルベンゼン（以下、ｐ−ＤＣＢと略称する）は住友化学（株）製品を使用。
【００６３】
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。
〈物性評価〉
得られた重合体の溶融粘度（η）は、高化式フローテスターを用いて測定した（３１６℃、剪断速度１００／秒、ノズル孔径０．５ｍｍ、長さ１．０ｍｍ）。
【００６４】
［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 １２４０ｇ（１２．５モル）、水 ２７．０ｇ（１．５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３０分かけて昇温し系を閉じ、更に１８０℃まで３０分かけて昇温し、その温度で脱水しながら、Ｎａ₂Ｓ・９Ｈ₂Ｏ １２００．９ｇ（５．０モル）を２時間かけて滴下した。滴下中に水と共沸的に留出されるｐ−ＤＣＢは連続的にオートクレーブに返した。Ｎａ₂Ｓ・９Ｈ₂Ｏの滴下が終了した後、１８０℃から２２０℃まで１時間かけて昇温し、その温度で３時間保持した。この後、２５０℃まで１時間かけて昇温し、その温度で１時間保持して反応を終了した。滴下中の留出液の分析をしたところ、水が８０５ｇ、ＮＭＰ２１ｇであった。
【００６５】
得られたスラリーを２０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５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、熱風乾燥器で一晩（１２０℃）乾燥して白色の粉末状のポリマーを５２１ｇ得た。得られたポリマーの溶融粘度は４５０ポイズであった。
【００６６】
また、上記と同じ仕込組成で同一の滴下操作を行い、滴下中の反応混合物を１時間、２時間でサンプリングし、水分含有量をカールフィッシャー法により、メタノール懸濁液中で測定した。また併せて上記反応の最終スラリー中の水分も測定した。その結果、それぞれの水分含有量は溶媒であるＮＭＰに対して、２．７重量％、２．５重量％、２．５重量％であった。
［実施例２］
Ｎａ₂Ｓ・９Ｈ₂Ｏの滴下、及び脱水に要する時間を３時間にして、実施例１と同様に実施した。留出液中の水分は８１８ｇ、ＮＭＰは１２ｇであった。得られたポリマーは５１５ｇ、溶融粘度は４１０ポイズであった。
【００６７】
［実施例３］
Ｎａ₂Ｓ・９Ｈ₂Ｏの滴下、及び脱水に要する時間を１時間にして、実施例１と同様に実施した。留出液中の水分は７７２ｇ、ＮＭＰは４５ｇであった。得られたポリマーは５１０ｇ、溶融粘度は２７０ポイズであった。
【００６８】
［実施例４］
Ｎａ₂Ｓ・９Ｈ₂Ｏ １２００．９ｇの代わりにＮａ₂Ｓ・５Ｈ₂Ｏ ８４０．６ｇ（５．０モル）を用いて、実施例３と同様に実施した。留出液中の水分は４４８ｇ、ＮＭＰは１６ｇであった。得られたポリマーは５１７ｇ、溶融粘度は４４０ポイズであった。
【００６９】
［実施例５］
使用する原料の量をそれぞれｐ−ＤＣＢ ９５５．５ｇ（６．５モル）、ＮＭＰ ９０２ｇ（９．１モル）、水 １８．０ｇ（１．０モル）、Ｎａ₂Ｓ・９Ｈ₂Ｏ１５６１．２ｇ（６．５モル）に変えて実施例２と同様に実施した。留出液中の水分は１０５１ｇ、ＮＭＰは１７ｇであった。得られたポリマーは６７０ｇ、溶融粘度は４００ポイズであった。
【００７０】
［実施例６］
使用する原料の量をそれぞれｐ−ＤＣＢ ５８８ｇ（４．０モル）、ＮＭＰ １３８８ｇ（１４．０モル）、水 ２７．０ｇ（１．５モル）、Ｎａ₂Ｓ・９Ｈ₂Ｏ ９６０．７ｇ（４．０モル）に変えて実施例１と同様に実施した。留出液中の水分は６５１ｇ、ＮＭＰは１５ｇであった。得られたポリマーは４１６ｇ、溶融粘度は３８０ポイズであった。
【００７１】
［実施例７］
Ｎａ₂Ｓ・９Ｈ₂Ｏの滴下、及び脱水に要する時間を３．５時間にして、実施例６と同様に実施した。留出液中の水分は６６５ｇ、ＮＭＰは１０ｇであった。得られたポリマーは４１３ｇ、溶融粘度は３５０ポイズであった。
【００７２】
［実施例８］
使用する原料を水を用いずに、それぞれｐ−ＤＣＢ ７３５ｇ（５．０モル）、ＮＭＰ １２４０ｇ（１２．５モル）、Ｎａ₂Ｓ・９Ｈ₂Ｏ １２００．９ｇ（５．０モル）とし、Ｎａ₂Ｓ・９Ｈ₂Ｏの滴下、及び脱水に要する時間を１．５時間にして、実施例１と同様に実施した。留出液中の水分は７７２ｇ、ＮＭＰは２９ｇであった。得られたポリマーは５１３ｇ、溶融粘度は３５０ポイズであった。
【００７３】
［実施例９］
４リットルオートクレーブにｐ−ＤＣＢ ７３５．０ｇ（５．０モル）、ＮＭＰ １２４０ｇ（１２．５モル）、水 ２７．０ｇ（１．５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３０分かけて昇温し系を閉じ、更に２２０℃まで１時間かけて昇温し、その温度でＮａ₂Ｓ・９Ｈ₂Ｏ １２００．９ｇ（５．０モル）を２時間かけて滴下及び脱水を行った。滴下中に水と共沸的に留出されるｐ−ＤＣＢは連続的にオートクレーブに返した。Ｎａ₂Ｓ・９Ｈ₂Ｏの滴下が終了した後、２２０℃で３時間保持した。この後、２５０℃まで１時間かけて昇温し、その温度で１時間保持して反応を終了した。滴下中の留出液の分析をしたところ、水が８１２ｇ、ＮＭＰ３５ｇであった。反応後のスラリーの処理は実施例１と同様に行った。得られたポリマーは５１８ｇ、溶融粘度は４８０ポイズであった。
【００７４】
［実施例１０］
Ｎａ₂Ｓ・９Ｈ₂Ｏの滴下、及び脱水に要する時間を４時間にして、実施例９と同様に実施した。留出液中の水分は８１５ｇ、ＮＭＰは２２ｇであった。得られたポリマーは５１５ｇ、溶融粘度は５２０ポイズであった。
【００７５】
［比較例１］
使用する原料の量をそれぞれｐ−ＤＣＢ ７３５．０ｇ（５．０モル）、ＮＭＰ １２４０ｇ（１２．５モル）、水 １３５．０ｇ（７．５モル）、Ｎａ₂Ｓ・９Ｈ₂Ｏ １２００．９ｇ（５．０モル）に変えて実施例３と同様に実施した。留出液中の水分は８１２ｇ、ＮＭＰは５７ｇであった。反応後のスラリーは激しい悪臭（分解臭）がしており、ポリマーは得られなかった。
【００７６】
［比較例２］
Ｎａ₂Ｓ・９Ｈ₂Ｏの滴下、及び脱水に要する時間を３時間にして、実施例８と同様に実施した。留出液中の水分は８０８ｇ、ＮＭＰは１８ｇであった。得られたポリマーは４８１ｇ、溶融粘度は８０ポイズであった。
【００７７】
［比較例３］
４リットルオートクレーブにＮａ₂Ｓ・９Ｈ₂Ｏ １２００．９ｇ（５．０モル）、ＮＭＰ ９９１ｇ（１０．０モル）を仕込み、窒素雰囲気下、２０４℃まで昇温することにより水−ＮＭＰ混合物を留去した。留出液中の組成はＮＭＰ１４４ｇ、水６９５ｇ、イオン性硫黄３５ｍｍｏｌであった。ついでこの系を２２０℃まで昇温しｐ−ＤＣＢ ７３５．０ｇ（５．０モル）をＮＭＰ４００ｇに溶かした溶液２時間かけて滴下した。滴下終了後、２２０℃で３時間保持した。この後、２５０℃まで１時間かけて昇温し、その温度で１時間保持して反応を終了した。反応後のスラリーは激しい異臭（分解臭）がし、ポリマーは得られなかった。
【００７８】
以上の実施例、比較例における結果を表１〜表３に示す。
【００７９】
【表１】

【００８０】
【表２】

【００８１】
【表３】

【００８２】
【発明の効果】
本発明の製造方法は、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、そこへ含水スルフィド化剤を水が反応混合物から除去され得る速度で導入すること、そしてその際反応系内の水分量を有機極性溶媒１モルに対して０．０２〜０．５モルの範囲にコントロールすることに特徴があり、この方法によって安定性等の物性に優れたＰＡＳが高い生産性及び再現性をもって提供できる。[0001]
[Industrial application fields]
The present invention relates to a process for producing polyarylene sulfide (hereinafter abbreviated as PAS) represented by polyphenylene sulfide (hereinafter abbreviated as PPS) by reaction of a dihaloaromatic compound such as dihalobenzenes and an alkali metal sulfide. is there. More specifically, the present invention relates to a method for obtaining a highly stable and highly productive PAS by controlling the amount of water in the system during the polymerization reaction to a specific ratio with a relatively simple apparatus. is there.
[0002]
In recent years, more and more heat-resistant thermoplastic resins have been required for electronic and electronic parts, automobile parts, etc., and as a result, they have high heat resistance and other physical properties such as moldability and dimensional stability. PAS typified by excellent PPS is greatly increasing in importance, and the issue is how to increase production with stable physical properties. The present invention provides a method for producing a highly productive and stable physical property PAS.
[0003]
[Prior art]
As a method for producing PAS typified by PPS, conventionally used industrially well (1) Alkali metal sulfides disclosed in US Pat. No. 3,354,129 and the like, particularly crystal water There is a method in which sodium sulfide (hereinafter abbreviated as hydrous sodium sulfide) is heated in a polar solvent to remove the water contained in the hydrous sodium sulfide, and dichlorobenzene is added thereto for thermal polymerization.
[0004]
However, in this method, water is removed by heating in a polymerization solvent in order to remove the moisture of one of the raw materials, hydrous sodium sulfide (including the reaction product of hydrous sodium hydrosulfide and sodium hydroxide). Therefore, it is a. (B) sufficient dehydration is difficult, that is, 1 to 1.5 mol of water remains in the system with respect to 1 mol of a sulfidizing agent such as sodium sulfide, and it is difficult to control the amount of residual water; When the water is distilled, the sulfur content in the metal sulfide is accompanied by loss in the form of hydrogen sulfide or the like, so that the amount of sulfur content in the reaction system fluctuates. In a state where a considerable amount of moisture remains, there are problems such as metal sulfide erodes the reaction vessel and the eluted heavy metal ions hinder the high molecular weight of the produced polymer. In addition, in this method, water remains in the system, so that the molecular weight cannot be increased, or if the amount of solvent used for the sulfidizing agent is reduced, a decomposition reaction occurs or a polymer is obtained with good reproducibility. There was no problem.
[0005]
In addition, (2) JP-A-59-105027 and JP-A-3-35023 disclose that a sulfur source and a dihalogenoaromatic compound are polymerized in an organic polar solvent while dehydrating at normal pressure or under pressure. A method for producing a PAS characterized by the above is disclosed. However, in this method, raw materials are charged all at once, dehydrating while raising the temperature of the reaction system, and further performing the polymerization reaction while continuing dehydration, so when using a hydrate such as an alkali metal sulfide as a sulfur source, At the beginning of the polymerization reaction, 1 mol or more of water is present in the system with respect to 1 mol of the sulfur source. Therefore, when the amount of solvent used is reduced relative to the sulfur source, the amount of water in the system becomes relatively large. For this reason, there have been problems such as a slow reaction rate and a long time for the polymerization reaction, or side reactions such as decomposition reactions.
[0006]
Further, (3) JP-A-4-275334 discloses an aqueous mixture composed of a sulfur source such as an alkali metal sulfide and an organic polar solvent (however, the sulfur source is 0.36 mol or more per 1 mol of the organic polar solvent). A method is disclosed in which dehydration is performed, the dehydration mixture and a polyhalo-substituted aromatic compound are mixed, polymerized, and polymerized while degassing is performed during polymerization to remove by-product water.
[0007]
This method is also substantially the same method as the above (2). Therefore, when the amount of solvent used is reduced with respect to the sulfur source, the amount of water in the system becomes relatively large. For this reason, there have been problems such as a slow reaction rate and a long time for the polymerization reaction, or side reactions such as decomposition reactions.
[0008]
Further, (4) JP-A-5-239210 discloses an aqueous mixture comprising a sulfur source such as an alkali metal sulfide and an organic polar solvent (provided that the molar ratio of the organic polar solvent to the sulfur source is 0.15 / 1 to 1). In the range of up to about 0.9 / 1, and the dehydrated mixture and polyhalo-substituted aromatic compound are mixed and polymerized. Certainly, in this method, the water remaining in the system before polymerization can be controlled to 1 mol or less per mol of the sulfur source, and the production amount per volume of the reactor can be increased. The method involves problems such as corrosion of the reactor when dehydrating an aqueous mixture composed of a sulfur source such as alkali metal sulfide and an organic polar solvent, or the abundance of sulfur in the reaction system due to loss of hydrogen sulfide during dehydration. And the reaction cannot be performed with good reproducibility, and the viscosity of the obtained polymer is not so high as shown in the examples of the publication, which is not sufficient.
[0009]
Further, (5) Japanese Patent Application Laid-Open No. 60-104130 and Japanese Patent Application Laid-Open No. 2-18585527 disclose a mixture of an aromatic dihalide (which may contain a small amount of aromatic tri- or tetrahalide) and an organic solvent. A method for producing a high molecular weight PAS, wherein water-containing alkali metal sulfide is introduced at a rate at which water can be removed from the reaction mixture at 150 ° C. or higher, and a polymerization reaction is carried out in a substantially anhydrous system Is disclosed. Certainly, it is possible to carry out the polymerization reaction in an anhydrous state by this method. However, since the amount of water in the system is dehydrated, the solubility of alkali metal sulfides in the solvent is reduced, and therefore the reaction rate is slowed down, requiring a long time for the polymerization reaction, or side reactions such as decomposition reactions. There were problems such as concurrent occurrence.
[0010]
[Problems to be solved by the invention]
An object of the present invention is to solve the above-mentioned disadvantages of the conventional production method and to provide a method for producing a polymer having excellent reproducibility and excellent physical properties such as stability, with high productivity and economically.
[0011]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above object, the present inventors have made it possible to shorten the reaction time or increase the production amount per volume of the reaction vessel in order to produce PAS with high productivity. For this purpose, it is important to strictly control the amount of water in the polymerization system. If a water-containing sulfiding agent is introduced into a mixture of an organic polar solvent and a dihaloaromatic compound under specific conditions, the amount of water in the reaction system It was found that it can be controlled within a specific range and is effective.
[0012]
That is, the present invention provides a water-containing sulfiding agent in a mixture containing a heated organic polar solvent and a dihaloaromatic compound in the production of a polyarylene sulfide polymer in which a dihaloaromatic compound and a sulfiding agent are reacted in an organic polar solvent. Polyester characterized in that water is introduced at a rate at which it can be removed from the reaction mixture, and the amount of water in the reaction system is controlled in the range of 0.02 to 0.5 moles per mole of the organic polar solvent. A method for producing an arylene sulfide polymer is provided.
[0013]
【Constitution】
In the present invention, the terms “sulfiding agent”, “dihaloaromatic compound”, and “solvent” include cases where each of the mentioned compounds or substances is a mixture within a defined range. Must be understood. For example, the present invention includes a case where the “dihaloaromatic compound” is composed of a plurality of compounds and the produced PAS is a copolymer as one specific example.
[0014]
(Manufacture of polymer)
The process for producing PAS according to the present invention is based on a dehalogenation / sulfurization reaction of a dihaloaromatic compound with a sulfidizing agent.
[0015]
(Hydrosulfide agent)
Examples of the hydrous sulfiding agent used in the present invention include hydrous substances such as alkali metal sulfides, alkali metal hydrosulfides, and mixtures thereof.
[0016]
Examples of the alkali metal sulfide include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, and cesium sulfide. These may be used alone or in combination of two or more. Also good. The alkali metal sulfide may be any of an anhydride, a hydrate, and an aqueous solution. In the case of an anhydride, water must be added to the hydrate before the reaction.
[0017]
Among the alkali metal sulfides, sodium sulfide and potassium sulfide are preferable, and sodium sulfide is particularly preferable.
These alkali metal sulfides can be obtained by reacting an alkali metal hydrosulfide and an alkali metal base, or hydrogen sulfide and an alkali metal base, but those prepared outside the reaction system may also be used.
[0018]
Examples of the alkali metal hydrosulfide include lithium hydrosulfide, sodium hydrosulfide, potassium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide and the like. These may be used alone or in combination of two or more. May be used. The alkali metal hydrosulfide may be any of an anhydride, a hydrate, and an aqueous solution. In the case of an anhydride, water must be added before the reaction to form a hydrate.
[0019]
Among the alkali metal hydrosulfides, sodium hydrosulfide and potassium hydrosulfide are preferable, and sodium hydrosulfide is particularly preferable.
These alkali metal hydrosulfides can be obtained by reacting hydrogen sulfide with an alkali metal base, but those prepared outside the reaction system may also be used.
[0020]
Examples of the alkali metal base include alkali metal hydroxide. Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide and the like. These may be used alone or in combination of two or more. May be used.
[0021]
Among the alkali metal hydroxide compounds, lithium hydroxide, sodium hydroxide, and potassium hydroxide are preferable, and sodium hydroxide is particularly preferable.
In any of the above cases, an alkali metal base may be added in a small excess to remove impurities present in a trace amount in the alkali metal sulfide or alkali metal hydrosulfide.
[0022]
(Dihaloaromatic compounds)
As long as the dihaloaromatic compound corresponding to the monomer to form the skeleton of the aromatic sulfide polymer has an aromatic nucleus and two halo substituents on the nucleus, and an alkali metal sulfide As long as it can be polymerized through a dehalogenation / sulfurization reaction with a sulfidizing agent such as Therefore, the aromatic nucleus may have various substituents that do not inhibit this dehalogenation / sulfurization reaction, in addition to the case of consisting only of aromatic hydrocarbons.
[0023]
Specifically, examples of the dihaloaromatic compound used in the present invention include compounds represented by the following formulas (A) to (D).
[0024]
[Chemical 1]

[0025]
Here, each substituent has the following meaning.
X: Cl, Br, I or F. In particular, at least one halogen selected from the group consisting of Cl and Br.
[0026]
Y: -R, -OR, -COOR, -COONa, -CN and -NO ₂ (R is selected from the group consisting of H, an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group). Here, an alkyl group or an alkyl group part usually has about 1 to 18 carbon atoms, and an aryl group or an aryl group part usually has about 6 to 18 carbon atoms.
[0027]
[Chemical 2]

(R ′ and R ″ are selected from the group consisting of H, an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group). Here, the alkyl group or alkyl group part and the aryl group or aryl group part are defined in the same manner as described above.
[0028]
In the formula (A), m and n are integers of m = 2 and 0 ≦ n ≦ 4, respectively.
In the formula (B), a and b are integers of a = 2 and 0 ≦ b ≦ 6, respectively.
In the formula (C), c, d, e and f are 0 ≦ c ≦ 2, 0 ≦ d ≦ 2,
c + d = 2, 0 ≦ e, f ≦ 2.
[0029]
In the formula (D), g, h, i and j are 0 ≦ g ≦ 2, 0 ≦ h ≦ 2, respectively.
g + h = 2, 0 ≦ i, j ≦ 2.
Examples of the dihalogen-substituted aromatic compound of the above general formula include the following.
[0030]
p-dihalobenzene, m-dihalobenzene, o-dihalobenzene, 2,5-dihalotoluene, 1,4-dihalonaphthalene, 1-methoxy-2,5-dihalobenzene, 4,4'-dihalobiphenyl, 3,5-dihalo Benzoic acid, 2,4-dihalobenzoic acid, 2,5-dihalonitrobenzene, 2,4-dihalonitrobenzene, 2,4-dihaloanisole, p, p'-dihalodiphenyl ether, 4,4'-di Halobenzophenone, 4,4′-dihalodiphenyl sulfone, 4,4′-dihalodiphenyl sulfoxide, 4,4′-dihalodiphenyl sulfide, etc. Among them, p-dihalobenzene, m-dihalobenzene, 4,4 '-Dihalobenzophenone and 4,4'-dihalodiphenyl sulfone are preferred, among which p-dichlorobenzene, m-dichloro Benzene, 4,4'-chloro benzophenone and 4,4' dichlorodiphenylsulfone are particularly preferably used.
[0031]
As described above, a copolymer containing two or more different reactive units can be obtained by appropriately selecting and combining dihaloaromatic compounds. If p-dichlorobenzene and 4,4′-dichlorobenzophenone or 4,4′-dichlorophenylsulfone are used in combination,
[0032]
[Chemical 3]

[0033]
Units and
[0034]
[Formula 4]

[0035]
Unit or
[0036]
[Chemical formula 5]

[0037]
A copolymer containing units can be obtained.
However, although copolymerization is possible, when p-dihalobenzene is polymerized using 70 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more in the dihaloaromatic compound, various physical properties are excellent. Since PPS is obtained, it is preferable.
[0038]
The amount of the dihaloaromatic compound used in the present invention is preferably in the range of 0.8 to 1.3 mol, particularly in the range of 0.9 to 1.10 mol, per mol of the sulfur source in the sulfidizing agent used. It is preferable for obtaining a polymer having excellent physical properties.
[0039]
The PAS according to the present invention is a polymer of the above-mentioned dihaloaromatic compound, but it is not necessarily a monohalo compound (not necessarily an aromatic compound) in order to form the end of the produced polymer or to adjust the polymerization reaction or molecular weight. ) Or a polyhalo compound of trihalo or higher (not necessarily an aromatic compound) can be used in combination to form a branched or crosslinked polymer. Specific examples where these monohalo or polyhalo compounds are aromatic compounds will be apparent to those skilled in the art as the monohalo or polyhalo derivatives of the above specific examples. Specifically, for example, when a slight amount of trichlorobenzene is used in combination with dihalobenzene, a branched phenylene sulfide polymer can be obtained. Further, the amount of monohalo or polyhalo compound used varies depending on the purpose or reaction conditions and cannot be defined unconditionally, but is preferably 0.1 mol or less, more preferably 0.05 mol or less, per 1 mol of the dihaloaromatic compound. is there.
[0040]
(Solvent and water)
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 type organic polar solvent.
[0041]
This solvent should not unduly inhibit the polymerization reaction of the present invention. Further, this solvent is at least a raw material dihaloaromatic compound and S ^2- The sulfidizing agent that gives the water should have a solubility enough to dissolve at a concentration necessary for the reaction. Therefore, this solvent is usually a polar solvent having a nitrogen atom, an oxygen atom and / or a sulfur atom. Furthermore, it is desirable that this solvent is not capable of participating in the same dehalogenation / sulfurization reaction as the raw material dihaloaromatic compound. Thus, for example, it is preferably not a haloaromatic hydrocarbon.
[0042]
Since the solvent used in the present invention is for providing a controlled minute amount of water to the polymerization reaction, it is desirable that the water as a solute can be solvated.
[0043]
Further, as is apparent from the production method of the present invention, the boiling point of the solvent used must be higher than the boiling point of water.
Specific examples of such solvents include: (1) Amides such as hexamethylphosphoric triamide (HMPA), N-methylpyrrolidone (NMP), N-cyclohexylpyrrolidone (NCP), N-methylcaprolactam, tetra Methylurea (TMU), dimethylformamide (DMF), dimethylacetamide (DMA), etc., (2) etherified polyethylene glycol such as polyethylene glycol dialkyl ether (degree of polymerization up to about 2000, alkyl group is C ₁ ~ C ₂₀ (3) sulfoxides such as tetramethylene sulfoxide, dimethyl sulfoxide (DMSO) and others. Among these, N-methylcaprolactam and NMP are particularly preferable because of their high chemical stability.
[0044]
The amount of solvent used varies depending on the type of solvent used and the amount of water relative to the solvent in the system, but the viscosity of the reaction system capable of uniform polymerization reaction is maintained, and in order to maintain a certain level of productivity. Is preferably in the range of 1.0 to 5 moles per mole of sulfur source in the sulfidizing agent used for the polymerization. Further, in order to increase the production amount of the polymer per volume of the reaction vessel, the range of 1.0 to 3.5 mol per 1 mol of the sulfur source in the sulfidizing agent used for the polymerization is preferable, and more preferable use. The amount of solvent is 1.2 to 3.0 mol per mol.
[0045]
The water for adjusting the water content in the polymerization system or the water content of the water-containing sulfidizing agent is not required to contain water that inhibits the reaction. For this reason, distilled water, ion-exchanged water, etc. Water excluding cations is preferred.
[0046]
In general, the amount of water to be present in the polymerization reaction of the present invention is preferably as small as possible in order to avoid the simultaneous occurrence of hydrolysis reactions and the like. On the other hand, when the polymerization reaction is completely anhydrous, there is a problem that the reaction rate becomes remarkably slow. Therefore, the amount of water to be present in the reaction system in the polymerization reaction of the present invention is 0.02 to 0.5 mol, preferably 0.02 to 0.3 mol, per mol of the organic polar solvent.
(polymerization)
The polymerization according to the invention involves reacting by heating a mixture of an organic polar solvent and a dihaloaromatic compound, preferably above 150 ° C., and introducing a hydrous sulfiding agent at a rate at which water can be removed from the reaction mixture. The amount of water in the system is controlled in the range of 0.02 to 0.5 mol with respect to 1 mol of the organic polar solvent, and the process proceeds under the conditions.
[0047]
Therefore, as the method of the present invention, a method of performing dehydration and polymerization separately, for example, a temperature at which the polymerization reaction substantially does not proceed, that is, 120 to 200 ° C., preferably 150 to 190 ° C. And 0.5 mol water or less) and a dihaloaromatic compound mixture is maintained, 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 within the above range. After removing excess water outside the system and controlling the amount of water in the reaction system within the above range, the polymerization reaction proceeds substantially through the mixture of the prepared organic polar solvent, dihaloaromatic compound and hydrous sulfiding agent. 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. During heating to the polymerization reaction may be a method of performing. Further, a method of performing dehydration and polymerization simultaneously, for example, an organic polar solvent (organic polar solvent) at a temperature at which the polymerization reaction can proceed substantially, 200 to 300 ° C., preferably 210 to 280 ° C., more preferably 215 to 260 ° C. The mixture of the dihaloaromatic compound and the dihaloaromatic compound may be heated to mix the water-containing sulfiding agent at a rate at which the amount of water in the reaction system can be controlled within the above range. Into the reaction system, excess water is removed from the system, and the amount of water in the reaction system is controlled within the above range, followed by further heating to a temperature of 200 to 300 ° C, preferably 210 to 280 ° C. The polymerization reaction may be carried out by heating for -40 hours, preferably 0.5-20 hours, more preferably 1-10 hours.
[0048]
The rate at which the water-containing sulfidizing agent is introduced is the rate at which excess water can be removed from the system so that the amount of water in the reaction system can be controlled in the range of 0.02 to 0.5 mol with respect to 1 mol of the organic polar solvent. If there is no restriction in particular. The introduction time varies depending on the moisture content to be controlled, the temperature at the time of introduction, the moisture content of the water-containing sulfidizing agent and the like, and thus cannot be defined unconditionally. However, the water-containing sulfidizing agent is used for 0.1 to 20 hours, preferably 0.5 It is preferable to introduce over 10 hours. Within this time, the water content or temperature of the reaction system can be easily controlled, and the productivity is good.
[0049]
In addition, although it depends on the amount of water that controls the temperature at which the hydrous sulfidizing agent is introduced, the rate at which it is introduced, the water content of the hydrous sulfidizing agent, or the type of reaction, it cannot be defined unconditionally, but dehydration and polymerization are performed separately. If it is carried out, it may be introduced at 120 to 200 ° C., preferably 150 to 190 ° C. If dehydration and polymerization are performed simultaneously, the introduction may be performed at a temperature of 200 to 300 ° C, preferably 210 to 280 ° C, more preferably 215 to 260 ° C.
[0050]
The polymerization reaction is performed by heating to a temperature of 200 to 300 ° C., preferably 210 to 280 ° C., and heating 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.
[0051]
The polymerization reaction of the present invention is preferably carried out in an inert gas atmosphere such as nitrogen, helium, argon, etc. using a polymerization can whose wetted part is made of titanium, chromium, zirconium or the like. Nitrogen is preferable from the viewpoint of easy handling.
[0052]
The reaction pressure is not particularly limited because it depends on the type and amount of the raw material and solvent used, or the reaction temperature and cannot be defined unconditionally.
Further, the reaction liquid preparation and the copolymer formation reaction may be a one-stage reaction performed at a constant temperature, a multi-stage reaction in which the temperature is raised stepwise, or the temperature is continuously changed. There is no need for a formal response.
[0053]
To recover the polymer, at the end of the reaction, the reaction mixture is first left as it is, or after adding an acid or base, it is heated under reduced pressure or normal pressure to distill off only the solvent. It can be carried out by washing once or more with a solvent such as methyl ethyl ketone or alcohol, followed by neutralization, washing with water, filtration and drying. Alternatively, after completion of the reaction, the reaction mixture is soluble in water, acetone, methyl ethyl ketone, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons, aliphatic hydrocarbons and the like (soluble in the polymerization solvent used). And at least a poor solvent for the produced polymer) is added as a precipitating agent to precipitate solid products such as polymers and inorganic salts, which are filtered, washed and dried Can also be done. The “washing” in these cases can be carried out in the form of an extraction. After completion of the reaction, a reaction solvent (or a solvent having a low molecular polymer solubility equivalent to the reaction solvent) is added to the reaction mixture, stirred, filtered to remove the low molecular weight polymer, water, acetone, methyl ethyl ketone, It can also be carried out by washing once or more with a solvent such as alcohol, followed by neutralization, washing with water, filtration and drying. Drying is performed by heating the isolated polymer 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 inert gas atmosphere such as nitrogen.
[0054]
The obtained polymer can be used for various molding materials as it is, but it can be thickened by heat treatment in air or oxygen-enriched air or under reduced pressure, and if necessary, such a thickening operation. After carrying out, it may be used for various molding materials. This heat treatment temperature varies depending on the treatment time and also varies depending on the atmosphere to be treated, so it cannot be specified unconditionally. If the heat treatment temperature is less than 180 ° C., the speed of thickening is very slow and the productivity is poor, which is not preferable. The heat treatment may be performed in a molten state using an extruder or the like above the melting point of the polymer. However, it is preferable to carry out at melting | fusing point plus 100 degrees C or less from the possibility of deterioration of a polymer or workability | operativity.
[0055]
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 case of conventional PAS. Can be. However, in order to further improve performance such as strength, heat resistance, and dimensional stability, it can be used in combination with various fillers as long as the object of the present invention is not impaired.
[0056]
Examples of the filler include a fibrous filler and an inorganic filler. Examples of the fibrous filler include glass fiber, carbon fiber, silane glass fiber, ceramic fiber, aramid fiber, metal fiber, potassium titanate, silicon carbide, calcium sulfate, calcium silicate, and other natural fibers such as wollastonite. Can be used. Inorganic fillers include barium sulfate, calcium sulfate, clay, viroferrite, bentonite, sericite, zeolite, mica, mica, talc, talpulgite, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, glass beads, etc. Can be used.
[0057]
In addition, a small amount of a release agent, a colorant, a heat stabilizer, an ultraviolet stabilizer, a foaming agent, a rust inhibitor, a flame retardant, a lubricant, a cup as long as they do not deviate from the object of the present invention as additives during molding processing A ring agent can be contained. Furthermore, the following synthetic resins and elastomers can also be mixed and used. These synthetic resins include polyester, polyamide, polyimide, polyetherimide, polycarbonate, polyphenylene ether, polysulfone, polyethersulfone, polyetheretherketone, polyetherketone, polyarylene, polyethylene, polypropylene, polytetrafluoroethylene, Examples thereof include poly (difluoroethylene), polystyrene, ABS resin, epoxy resin, silicone resin, phenol resin, urethane resin, liquid crystal polymer, and the like, and examples of the elastomer include polyolefin rubber, fluorine rubber, and silicone rubber.
[0058]
Since the polymer of the present invention and the composition thereof are excellent in heat resistance, dimension stability, etc., as in the case of PPS obtained by a conventional method, for example, electrical / electronic parts such as connectors, printed boards, sealing molded products, lamps, etc. Auto parts such as reflectors and various electrical parts, interior materials such as various buildings and aircraft and automobiles, and precision parts such as OA equipment parts, camera parts and watch parts, injection molding and compression molding, or composite sheets -It is used as a molding material, fiber, or film having excellent heat resistance, molding processability, dimensional stability, etc. in various molding processes such as extrusion molding and pultrusion molding of pipes.
[0059]
【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.
[0060]
[Reference Example 1]
Raw materials used
1. Sulfiding agent (alkali metal sulfide)
Crystalline sodium sulfide (pentahydrate) (hereinafter Na ₂ S ・ 5H ₂ O) is a product of Sankyo Kasei Co., Ltd.
[0061]
Crystalline sodium sulfide (9-hydrate) (hereinafter referred to as Na ₂ S • 9H ₂ O) is a product of Wako Pure Chemical Industries, Ltd.
2. solvent
N-methylpyrrolidone (hereinafter abbreviated as NMP) is a product of Mitsubishi Kasei Co., Ltd.
[0062]
3. Dihaloaromatic compounds
p-Dichlorobenzene (hereinafter abbreviated as p-DCB) is a product of Sumitomo Chemical Co., Ltd.
[0063]
4). water
Use tap water distilled and ion exchanged.
<Evaluation of the physical properties>
The melt viscosity (η) of the obtained polymer was measured using a Koka flow tester (316 ° C., shear rate 100 / sec, nozzle hole diameter 0.5 mm, length 1.0 mm).
[0064]
[Example 1]
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, p-DCB 735.0 g (5.0 mol), NMP 1240 g (12 0.5 mol) and 27.0 g (1.5 mol) of water at room temperature, the temperature was raised to 100 ° C over 30 minutes under stirring in a nitrogen atmosphere, the system was closed, and the temperature was further raised to 180 ° C over 30 minutes. While dehydrating at that temperature, Na ₂ S • 9H ₂ 1200.9 g (5.0 mol) of O was added dropwise over 2 hours. The p-DCB distilled azeotropically with water during the dropping was continuously returned to the autoclave. Na ₂ S • 9H ₂ After the dropping of O was completed, the temperature was raised from 180 ° C. to 220 ° C. over 1 hour, and the temperature was maintained for 3 hours. Then, it heated up to 250 degreeC over 1 hour, and hold | maintained at the temperature for 1 hour, and reaction was complete | finished. When the distillate during the dropping was analyzed, water was 805 g and NMP was 21 g.
[0065]
The obtained slurry was poured into 20 liters of water, stirred at 80 ° C. for 1 hour, and then filtered. The cake was again stirred and washed with 5 liters of hot water for 1 hour and then filtered. This operation was repeated four times, and after filtration, dried in a hot air drier overnight (120 ° C.) to obtain 521 g of a white powdery polymer. The resulting polymer had a melt viscosity of 450 poise.
[0066]
In addition, the same dropping operation was performed with the same charging composition as above, the reaction mixture being dropped was sampled for 1 hour and 2 hours, and the water content was measured in a methanol suspension by the Karl Fischer method. In addition, the water content in the final slurry of the above reaction was also measured. As a result, each water content was 2.7 wt%, 2.5 wt%, and 2.5 wt% with respect to NMP as a solvent.
[Example 2]
Na ₂ S • 9H ₂ The time required for dropping O and dehydrating was 3 hours, and the same procedure as in Example 1 was performed. The water in the distillate was 818 g, and NMP was 12 g. The obtained polymer was 515 g and the melt viscosity was 410 poise.
[0067]
[Example 3]
Na ₂ S • 9H ₂ The time required for dropping O and dehydrating was 1 hour, and the same procedure as in Example 1 was performed. The water content in the distillate was 772 g and NMP was 45 g. The obtained polymer was 510 g and the melt viscosity was 270 poise.
[0068]
[Example 4]
Na ₂ S • 9H ₂ Na instead of 1200.9g O ₂ S ・ 5H ₂ The same operation as in Example 3 was carried out using 840.6 g (5.0 mol) of O. The water in the distillate was 448 g, and NMP was 16 g. The obtained polymer was 517 g, and the melt viscosity was 440 poise.
[0069]
[Example 5]
The amounts of raw materials used were p-DCB 955.5 g (6.5 mol), NMP 902 g (9.1 mol), water 18.0 g (1.0 mol), Na ₂ S • 9H ₂ The same procedure as in Example 2 was carried out except that the amount was changed to O1561.2 g (6.5 mol). The water in the distillate was 1051 g and NMP was 17 g. The obtained polymer was 670 g, and the melt viscosity was 400 poise.
[0070]
[Example 6]
The amounts of raw materials used were p-DCB 588 g (4.0 mol), NMP 1388 g (14.0 mol), water 27.0 g (1.5 mol), Na ₂ S • 9H ₂ The same procedure as in Example 1 was carried out except that O was changed to 960.7 g (4.0 mol). The water in the distillate was 651 g and NMP was 15 g. The obtained polymer was 416 g, and the melt viscosity was 380 poise.
[0071]
[Example 7]
Na ₂ S • 9H ₂ The time required for dropping O and dehydrating was 3.5 hours, and the same procedure as in Example 6 was performed. The water in the distillate was 665 g, and NMP was 10 g. The obtained polymer was 413 g, and the melt viscosity was 350 poise.
[0072]
[Example 8]
The raw materials used were p-DCB 735 g (5.0 mol), NMP 1240 g (12.5 mol), Na, respectively, without using water. ₂ S • 9H ₂ 1200.9 g (5.0 mol) of O, Na ₂ S • 9H ₂ The time required for dropping O and dehydrating was 1.5 hours, and the same procedure as in Example 1 was performed. The water in the distillate was 772 g and NMP was 29 g. The obtained polymer was 513 g and the melt viscosity was 350 poise.
[0073]
[Example 9]
A 4 liter autoclave was charged with 735.0 g (5.0 mol) of p-DCB, 1240 g (12.5 mol) of NMP, and 27.0 g (1.5 mol) of water at room temperature, and stirred at 100 ° C. in a nitrogen atmosphere. The temperature was raised to 30 minutes until the system was closed, and the temperature was further raised to 220 ° C. over 1 hour. ₂ S • 9H ₂ 1200.9 g (5.0 mol) of O was dropped and dehydrated over 2 hours. The p-DCB distilled azeotropically with water during the dropping was continuously returned to the autoclave. Na ₂ S • 9H ₂ After completion of the dropwise addition of O, the mixture was kept at 220 ° C. for 3 hours. Then, it heated up to 250 degreeC over 1 hour, and hold | maintained at the temperature for 1 hour, and reaction was complete | finished. When the distillate during the dropping was analyzed, water was 812 g and NMP was 35 g. The slurry treatment after the reaction was carried out in the same manner as in Example 1. The obtained polymer was 518 g, and the melt viscosity was 480 poise.
[0074]
[Example 10]
Na ₂ S • 9H ₂ The time required for dropping O and dehydrating was 4 hours, and the same procedure as in Example 9 was performed. The water in the distillate was 815 g and NMP was 22 g. The obtained polymer was 515 g and the melt viscosity was 520 poise.
[0075]
[Comparative Example 1]
The amounts of raw materials used were 735.0 g (5.0 mol) of p-DCB, 1240 g (12.5 mol) of NMP, 135.0 g (7.5 mol) of water, Na, respectively. ₂ S • 9H ₂ The same procedure as in Example 3 was carried out except that 1200.9 g (5.0 mol) of O was used. The water in the distillate was 812 g and NMP was 57 g. The slurry after the reaction had a strong malodor (decomposed odor), and no polymer was obtained.
[0076]
[Comparative Example 2]
Na ₂ S • 9H ₂ The time required for dropping O and dehydrating was 3 hours, and the same procedure as in Example 8 was performed. The water in the distillate was 808 g and NMP was 18 g. The obtained polymer was 481 g, and the melt viscosity was 80 poise.
[0077]
[Comparative Example 3]
4 liter autoclave with Na ₂ S • 9H ₂ 1200.9 g (5.0 mol) of O and 991 g (10.0 mol) of NMP were charged, and the mixture was heated to 204 ° C. under a nitrogen atmosphere to distill off the water-NMP mixture. The composition in the distillate was 144 g NMP, 695 g water, and 35 mmol ionic sulfur. Next, the temperature of the system was raised to 220 ° C., and a solution in which 735.0 g (5.0 mol) of p-DCB was dissolved in 400 g of NMP was added dropwise over 2 hours. After completion of dropping, the mixture was kept at 220 ° C. for 3 hours. Then, it heated up to 250 degreeC over 1 hour, and hold | maintained at the temperature for 1 hour, and reaction was complete | finished. The slurry after the reaction had a strong odor (decomposition odor), and no polymer was obtained.
[0078]
The results in the above Examples and Comparative Examples are shown in Tables 1 to 3.
[0079]
[Table 1]

[0080]
[Table 2]

[0081]
[Table 3]

[0082]
【The invention's effect】
The production method of the present invention comprises heating a mixture of an organic polar solvent and a dihaloaromatic compound and introducing a hydrous sulfiding agent thereto at a rate at which water can be removed from the reaction mixture, The amount is controlled in the range of 0.02 to 0.5 mol per 1 mol of organic polar solvent, and this method provides PAS with excellent physical properties such as stability with high productivity and reproducibility. it can.

Claims (6)

In the production of a polyarylene sulfide polymer in which a dihaloaromatic compound and a sulfiding agent are reacted in an organic polar solvent, water is added to the mixture containing the heated organic polar solvent and the dihaloaromatic compound from the reaction mixture. Production of polyarylene sulfide polymer characterized by introducing at a rate that can be removed, and controlling the amount of water in the reaction system in the range of 0.02 to 0.5 mol relative to 1 mol of the organic polar solvent Method. The method according to claim 1, wherein the mixture containing the organic polar solvent and the dihaloaromatic compound is heated to 150 ° C or higher. The production method according to claim 1 or 2, wherein the amount of water in the reaction system is controlled in the range of 0.02 to 0.3 mol with respect to 1 mol of the organic polar solvent. The production method according to claim 1 or 2, wherein the molar ratio of the organic polar solvent and the sulfur source in the hydrous sulfiding agent (solvent / sulfur source) is 1.0 / 1 to 3.5 / 1. The method according to claim 1 or 2, wherein the hydrous sulfiding agent is an aqueous solution of an alkali metal sulfide or a molten liquid of an alkali metal sulfide hydrate. The production method according to any one of claims 1 to 5, wherein the dihaloaromatic compound is a dihalobenzene, and the polyarylene sulfide obtained is polyphenylene sulfide.