JPS617332A - Production of high molecular weight polyarylene sulfide - Google Patents
Production of high molecular weight polyarylene sulfideInfo
- Publication number
- JPS617332A JPS617332A JP59126725A JP12672584A JPS617332A JP S617332 A JPS617332 A JP S617332A JP 59126725 A JP59126725 A JP 59126725A JP 12672584 A JP12672584 A JP 12672584A JP S617332 A JPS617332 A JP S617332A
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- water
- melt viscosity
- sulfide
- alkali metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
Description
【発明の詳細な説明】
発明の背景
技術分野
本発明は、高分子量のポリアリーレンスルフィド（以下
、ＰＡＳという）を製造する方法に関する。さらに具体
的には、本発明は、アルカリ金属硫化物とシバａ芳香族
化合物との反応の実施の仕方に主要な特徴を有するＰＡ
Ｓの製造法に関する。BACKGROUND OF THE INVENTION Technical Field The present invention relates to a method for producing high molecular weight polyarylene sulfide (hereinafter referred to as PAS). More specifically, the present invention provides PAs having a key feature in the manner in which the reaction between an alkali metal sulfide and a Ciba aromatic compound is carried out.
This invention relates to a method for producing S.
近年、電子機器部材、自動車部品などとしてますます高
い耐熱性の熱可塑性樹脂が要求されてきている。In recent years, there has been an increasing demand for thermoplastic resins with higher heat resistance for use in electronic equipment components, automobile parts, and the like.
ＰＡＳもその要求に応え得る樹脂としての性質を有して
いるが、このボリフェニＶンスルフィドに代表されるＰ
ＡＳは分子量の充分高いものが得られ難いという事情が
あるために、フィルム、シ−ト、繊維などに成形加工す
るのが極めて難かしいということやその成形物が極めて
脆弱であるという大きな問題点があった。PAS also has properties as a resin that can meet these demands, but
Since it is difficult to obtain AS with a sufficiently high molecular weight, it is extremely difficult to mold it into films, sheets, fibers, etc., and the molded products are extremely brittle, which is a major problem. was there.
本発明はこれらの問題点を解決すべく顕著に高分子量の
ＰＡＳを安価に製造する方法を提供するものである。The present invention aims to solve these problems by providing a method for producing PAS with a significantly high molecular weight at low cost.
従来技術
ＰＡＳの代表的な製造方法としては、Ｎ−メチルピロリ
ドン等の有機アミド溶媒中でジハロ芳香族化合物と硫化
ナトリウムとを反応させる方法が特公昭ｔｉ−ｓ−３３
ｔｅ号公報に開示されている。しかし、この方法で製造
されたＰＡＳは分子量および溶融粘度が低くて、フィル
ム、シート、繊維などには成形加工することが困難であ
った。Conventional technology A typical method for producing PAS is a method in which a dihaloaromatic compound and sodium sulfide are reacted in an organic amide solvent such as N-methylpyrrolidone.
It is disclosed in the TE publication. However, PAS produced by this method has a low molecular weight and low melt viscosity, making it difficult to mold it into films, sheets, fibers, and the like.
このようなところから、高重合度のＰＡＳを得るために
、上記の方法を改善した方法が種々提案されている。最
も代表的な特公昭！；２− ／ココｐ。From this point of view, in order to obtain PAS with a high degree of polymerization, various methods have been proposed that are improved from the above methods. The most representative Tokko Akira! ;2-/cocop.
号公報記載のものでは、上記反応系に重合助剤としてア
ルカリ金属カルボン酸塩を用いている。この方法によれ
ば重合助剤の添加量がアルカリ金属硫化物に対して等モ
ル程度必要とされておシ、さらによシ高重合度のＰＡＳ
を得るためには種々の重合助剤のうちでも高価な酢酸リ
チウムや安息香酸ナトリウムを多量に使用することが必
要であシ、従って結果的にＰＡＳの製造コストが増大し
て工業的に不利となると思われる。また、この方法では
、重合反応後のＰＡＳ回収時の処理排水に多量の有機酸
等が混入することになって公害上の問題を生ずるおそれ
があシ、これを防止するためには多大の費用を必要とす
ることなど、経済的見地から大きな問題があると思われ
る。In the method described in the above publication, an alkali metal carboxylate is used as a polymerization aid in the reaction system. According to this method, the amount of polymerization aid added is required to be approximately equimolar to the alkali metal sulfide.
In order to obtain PAS, it is necessary to use large amounts of expensive lithium acetate and sodium benzoate among various polymerization aids, which results in an increase in the production cost of PAS, which is industrially disadvantageous. It seems that it will be. In addition, with this method, there is a risk that a large amount of organic acids, etc. will be mixed into the treated wastewater when PAS is recovered after the polymerization reaction, causing a pollution problem, and it will cost a lot of money to prevent this. There seems to be a major problem from an economic standpoint, such as the need for
単に溶融粘度ないし分子量が高ければよいのであれば、
ＰＡＲを軽度に酸化して架橋構造を導入する方法が利用
できよう。しかし、この方法で得られる高分子量ＰＡＳ
は線状性がないので、曳糸性および製膜性が不良である
。If the melt viscosity or molecular weight is simply high, then
A method of introducing a crosslinked structure by mildly oxidizing PAR may be used. However, the high molecular weight PAS obtained by this method
Since there is no linearity, the stringability and film forming properties are poor.
発明の概要
要旨
本発明者らは上記の点に鑑み、溶融粘度が高くてしかも
線状のＰＡＲを、アルカリ金属カルボン酸塩等の重合助
剤を使用することなしに、安価に製造する方法を見出す
べくアルカリ金属硫化物とジハロ芳香族化合物との単純
重合系での重合メカニズムを詳細に検討した結果、重合
の諸条件中で特に共存水の量と重合温度とを重合前段と
重合後段で顕著に異ならせることによって、助剤を用い
ることなしに著しく高分子量のＰＡＳを製造することが
できることを思いかけずに見出して本発明に到達した。SUMMARY OF THE INVENTION In view of the above points, the present inventors have developed a method for manufacturing linear PAR with high melt viscosity at low cost without using a polymerization aid such as an alkali metal carboxylate. As a result of a detailed study of the polymerization mechanism in a simple polymerization system of an alkali metal sulfide and a dihaloaromatic compound, we found that among the various polymerization conditions, the amount of coexisting water and the polymerization temperature are particularly significant in the pre-polymerization stage and the post-polymerization stage. The present invention was achieved by unexpectedly discovering that it is possible to produce PAS with a significantly high molecular weight without using any auxiliaries by varying the .
すなわち、本発明による溶融粘度がｔｏｏｏボイズ以上
のポリアリーレンスルフィドの製造性は、有機アミド溶
媒中でアルカリ金属硫化物とジハロ芳香族化合物とを反
応させてポリアリーレンスルフィドを得る方法において
、この反応を少なくとも下記の二段階で行なうこと、を
特徴とするものである。That is, the productivity of polyarylene sulfide having a melt viscosity of too boys or more according to the present invention is achieved by reacting an alkali metal sulfide and a dihaloaromatic compound in an organic amide solvent to obtain a polyarylene sulfide. The method is characterized in that it is carried out in at least the following two steps.
（１） アルカリ金属硫化物ｌそル当ｐｏ、ｚ−２．
参モルの水が存在する状態で、／ＩＩ〜コＪｊ’Ｃの温
度で反応を行なって、溶融粘度！〜３００ボイズのポリ
アリーレンスルフィドをジハロ芳香族化合物の転化率Ｓ
Ｏ〜りｊモルチで生成させる工程、（２）アルカリ金属
硫化物１モル当シコ、！〜７．０そルの水が存在する状
態となるように水を添加すると共に２ｐｔ−コタ０℃の
温度に昇温して、上記の反応を継続する工程。(1) Alkali metal sulfide, z-2.
The reaction is carried out in the presence of about mol of water at a temperature of /II to Jj'C, and the melt viscosity is ! Conversion rate S of polyarylene sulfide with ~300 voids to dihaloaromatic compound
A step of producing it with O~rij morch, (2) 1 mole of alkali metal sulfide,! Adding water so that ~7.0 liters of water is present, raising the temperature to 2 pt-0°C, and continuing the above reaction.
効果
本発明では、前段重合後に水を追加すると共に、温度を
上昇させて所定の含水量と温度で後段重合を行なうこと
によシ、前段重合をそのまま継続したのでは到底得られ
ない１０００ボイズ以上の高い溶融粘度を有するＰＡＳ
を得ることに成功したものである。この方法は、特別の
助剤を必要としない極めて簡素なものであるため、助剤
の使用に基く前記の諸問題は画然に存在せず、経済−に
も優れている。得られるＰＡＲが高溶融粘度でかつ線状
であるため、一般成型品は勿論のこと、すぐれた繊維フ
ィルムを得ることができる。Effects In the present invention, water is added after the first stage polymerization, and the temperature is raised to perform the second stage polymerization at a predetermined water content and temperature. PAS with high melt viscosity of
It was successfully obtained. Since this method is extremely simple and does not require any special auxiliary agents, the above-mentioned problems caused by the use of auxiliary agents do not exist, and it is also economical. Since the obtained PAR has a high melt viscosity and is linear, not only general molded products but also excellent fiber films can be obtained.
更に１本発明によれば、重合終了後ＰＡＳは顆粒状で得
られるため、分離、洗滌等の後処理も容易であると共に
樹脂材料としてベレット化工程度が不要であるという利
点も得られる。すなわち、本発明のもう一つの特徴とも
言うべきことは、パール状のＰＡＲが得られることであ
る０本発明の方法でも攪拌条件などが適切でないと非球
状のものが得られることもあるが、多くの場合は得られ
るＰＡＳは非常に粒径のそろつた真球に近い′り一ル状
のものである。パール状ＰＡＳの形成される状態を調べ
てみると、驚ろくべきことに、後段重合終了後に反応系
を冷却する過程で造粒されるのではなく、後段重合の比
較的初期に溶融したＰＡＳがパール状に造粒され、この
粒子内で反応が進んで溶融粘度が上るにつれて、粒子同
志が融着しない程度にまで硬化してくることがわかった
。このような知見は、従来未知であったと思料されるも
のである。Furthermore, according to the present invention, since the PAS is obtained in the form of granules after polymerization, post-treatments such as separation and washing are easy, and there is also the advantage that a pelletizing step is not necessary as a resin material. That is, another feature of the present invention is that pearl-like PARs can be obtained. Even with the method of the present invention, non-spherical PARs may be obtained if the stirring conditions are not appropriate. In many cases, the obtained PAS is a linear shape that is close to a perfect sphere and has a very uniform particle size. When we investigated the state in which pearl-like PAS was formed, we surprisingly found that PAS was not granulated during the process of cooling the reaction system after the completion of the post-polymerization, but rather that the PAS was molten at a relatively early stage of the post-polymerization. It was found that the particles were granulated into pearls, and as the reaction progressed within the particles and the melt viscosity increased, the particles hardened to the extent that they did not fuse together. Such knowledge is thought to have been previously unknown.
これまで、ＰＡＲの重合においては、重合系中に水が多
量に存在すると加水分解岬の望ましくない反応が起ると
されておシ、系中の共存水量を減らすことに努力が払わ
れてきた。通常は、高溶融粘度のＰＡＲを得るためには
、アルカリ金属硫化物１モル当り共存水１モル〜λモル
におさえられていた。本発明の方法のように、重合途中
で生成ＰＡＳの溶融粘度が極めて低い段階で多量の水を
添加し、且つ重合温度を高めて更に重合を継続させる方
法は未だかつて提案されていなかった。共存水に対する
当業者らのこれまでの考え方からすれば、本発明の方法
はまさに画期的なものと言うことができる。Until now, in the polymerization of PAR, it has been believed that the presence of a large amount of water in the polymerization system causes undesirable hydrolysis reactions, and efforts have been made to reduce the amount of coexisting water in the system. . Usually, in order to obtain a PAR with a high melt viscosity, the amount of coexisting water is limited to 1 mol to λ mol per 1 mol of alkali metal sulfide. As in the method of the present invention, a method in which a large amount of water is added during polymerization at a stage when the melt viscosity of the produced PAS is extremely low, and the polymerization temperature is raised to further continue the polymerization has never been proposed. Considering the conventional thinking of those skilled in the art regarding coexisting water, the method of the present invention can be said to be truly revolutionary.
本発明によるＰＡＳの製造法は、アルカリ金属硫化物と
ジハロ芳香族化合物との反応を特定の条件の下で実施す
ることからなるものである。The method for producing PAS according to the invention consists in carrying out the reaction of an alkali metal sulfide with a dihaloaromatic compound under specific conditions.
アルカリ金属硫化物
本発明で用いられるアルカリ金属硫化物には、硫化リチ
ウム、硫化ナトリウム、硫化カリウム、硫化ルビジウム
、硫化セシウムおよびこれらの混合物が包含される。こ
れらのアルカリ金属硫化物は、水和物または水性混合物
として、あるいは無水の形で、用いることができる。Alkali Metal Sulfides The alkali metal sulfides used in the present invention include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide, and mixtures thereof. These alkali metal sulfides can be used as hydrates or aqueous mixtures or in anhydrous form.
これらのアルカリ金属硫化物の中では、硫化ナトリウム
が最も安価であって工業的には好ましい。Among these alkali metal sulfides, sodium sulfide is the cheapest and is industrially preferred.
なお、アルカリ金属硫化物中に微量存在することあるべ
きアルカリ金属型硫化物やアルカリ金属チオ硫酸塩と反
応させるために、少量のアルカリ金属水酸化物を併用し
てこれら不純物を除去ないし硫化物への変換を計ること
ができる。In addition, in order to react with alkali metal type sulfides and alkali metal thiosulfates, which should exist in trace amounts in alkali metal sulfides, a small amount of alkali metal hydroxide is used in combination to remove these impurities or convert them into sulfides. It is possible to measure the conversion of
ジハロ芳香族化合物
本発明で使用されるジハロ芳香族化合物としては１例え
ば特開昭３９−２２２．２Ａ号公報に記載されているよ
うなジハロ芳香族化合物があり得る。Dihaloaromatic compound The dihaloaromatic compound used in the present invention may include, for example, a dihaloaromatic compound as described in JP-A-39-222.2A.
特に、 Ｐ−シクロルペンゼ／、ｍ−ジクロルベンゼン
、コ、！−ジクａルトルエン、ｐ−ジブロムベンゼン、
／、４！−ジクミルナフタリン、ｌ−メトキシーコ、！
−ジクロルベンゼン、参、参′−ジクロルビフェニル、
３．ｊ−ジクロル安息香１１、ｐ、ｐ’−ジクロルジフ
ェニルエーテル、Ｊ、Ｊ’−ジクロルジフェニルスフ！
／７ｐ７、Ｊ、Ｊ’−ジクロルジフェニルスルフオキシ
ドｓ Ｊ、 ｓ’−シｐロルジフェニルなどが好ましい
。なかでも、ｐ−ジクロルベンゼンに代表されるパラジ
ハロペンゼ／を主成分とするものが好ましい。In particular, P-cyclopenze/, m-dichlorobenzene,! - dikaltoluene, p-dibromobenzene,
/, 4! -Dicumylnaphthalene, l-methoxyco,!
-dichlorobenzene, dichlorobenzene, dichlorobiphenyl,
3. j-dichlorobenzoin 11, p,p'-dichlordiphenyl ether, J,J'-dichlordiphenyl sulfate!
/7p7, J, J'-dichlorodiphenyl sulfoxide s J, s'-dichlorodiphenyl and the like are preferred. Among these, those containing paradihalopense/, typified by p-dichlorobenzene, as a main component are preferred.
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
。例えば、ｐ−ジクロルベンゼンとｍ−ジクミルベンゼ
ン若しくはＰＩｐ’−ジクロルジフェニルスルフォンと
を組合せて使用すれば、物を得ることができる。By appropriately selecting combinations of dihaloaromatic compounds, copolymers containing two or more different reactive units can be obtained. For example, products can be obtained by using a combination of p-dichlorobenzene and m-dicumylbenzene or PIp'-dichlorodiphenylsulfone.
なお、本発明によるＰＡＲ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てもよい）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
てもよい）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１〜口またはポリハロ誘
導体として当業者にとって自明であろう。へ体的には、
たとえば、ジクロルベンゼンに若干量のトリクロルベン
ゼンを組合せて使用すれば、分枝をもったフェニレンス
ルフィド重合体ヲ得ることができる。もっとも、繊維、
フィルム等を得るには、ＰＡＳは実質的に線状であるこ
とが好ましく、分枝の程度は少ないことが好ましい。The PAR according to the present invention is a polymer of the above-mentioned dihaloaromatic compound, but a monohalo compound (not necessarily an aromatic compound) may be used to form the terminal end of the resulting polymer or to control the polymerization reaction or molecular weight. It is also possible to use together a polyhalo compound (not necessarily an aromatic compound) having more than trihalo in order to form a branched or crosslinked polymer. Specific examples when these monohalo or polyhalo compounds are aromatic compounds will be obvious to those skilled in the art as mono- or polyhalo derivatives of the above specific examples. Physically,
For example, by using dichlorobenzene in combination with a small amount of trichlorobenzene, a branched phenylene sulfide polymer can be obtained. However, fiber
In order to obtain a film or the like, the PAS is preferably substantially linear and preferably has a low degree of branching.
重合溶媒
本発明の重合反応において使用する有機アミド溶媒とし
ては、Ｎ−メチルピロリドン（ＮＭＰ）、Ｎ−エチルピ
ロリドン、Ｎ、Ｎ−ジメチルホルムアミド、Ｎ、Ｎ−ジ
メチルアセトアミド、Ｎ−メチルカプロラクタム、テト
ラメチル尿素、ヘキサメチルりん酸トリアミド等及びこ
れらの混合物をあげることができる。これらのうちでは
、Ｎ−メチルピロリドンが特に好ましい。重合溶媒とし
ての有機アミドは、非プロトン化合物であることが望ま
しい。Polymerization Solvent The organic amide solvent used in the polymerization reaction of the present invention includes N-methylpyrrolidone (NMP), N-ethylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylcaprolactam, and tetramethyl. Mention may be made of urea, hexamethyl phosphate triamide, etc., and mixtures thereof. Among these, N-methylpyrrolidone is particularly preferred. The organic amide used as the polymerization solvent is preferably an aprotic compound.
有機アミド溶媒の使用量は、アルカリ金属硫化物１モル
あたりＱ、コ〜ｊリットルの範囲が好ましいｊ
重合
（１）定義
本発明による重合は、重合反応系に存在する水の量およ
び反応温度に関して異なる少なくとも二段階で行なわれ
る。ここで、「少なくとも二段階」ということは、この
二段階の組合せに基因する本発明の効果が実現される限
シ、これらの二工程の前、後または中間に補助的な工程
を附加してもよいことを意味するものである。The amount of the organic amide solvent to be used is preferably in the range of Q, co to J liters per mole of alkali metal sulfide. It is carried out in at least two different stages. Here, "at least two steps" means that an auxiliary step may be added before, after, or in the middle of these two steps, as long as the effect of the present invention based on the combination of these two steps is achieved. It also means something good.
（２）前段重合
さて、本発明での第一の工程では、換言すれば前段重合
では、アルカリ金属硫化物１モル当シ、０．２モル〜λ
、μモルの水を含む重合反応系で、ｉｒｏ℃〜２３！
”Ｃの温度で、重合反応系中のジハロ芳香族化合物の転
化率がＳＯモルチ〜りｔモルチになるまで重合を行なつ
て、溶融粘度！〜３００ボイズのＰＡＳを得る（本発明
において溶融粘度は３ｉ。(2) First-stage polymerization Now, in the first step of the present invention, in other words, in the first-stage polymerization, 0.2 mol to λ per 1 mol of alkali metal sulfide
, a polymerization reaction system containing μmol of water at iro℃~23!
Polymerization is carried out at a temperature of "C" until the conversion rate of the dihaloaromatic compound in the polymerization reaction system becomes SO mole - t mole to obtain a PAS with a melt viscosity of ~300 voids (in the present invention, the melt viscosity is is 3i.
℃で剪断速度２００ （秒） で測定したものであるこ
とは前記したところである〕。℃ and a shear rate of 200 seconds].
実施に際しては、先ず、有機アミド溶媒に、望ましくは
不活性ガス雰囲気下に、常温〜／３０℃の範囲でアルカ
リ金属硫化物およびジハロ芳香族化合物を加えて、所定
の温度に昇温して反応させる。In carrying out the process, first, an alkali metal sulfide and a dihaloaromatic compound are added to an organic amide solvent at a temperature ranging from room temperature to 30°C, preferably under an inert gas atmosphere, and the reaction is carried out by raising the temperature to a predetermined temperature. let
ここで、アルカリ金属硫化物中の含有水量が所定の量よ
シ少ない場合には、必要量を添加補充する。Here, if the amount of water contained in the alkali metal sulfide is less than the predetermined amount, the necessary amount is added and replenished.
多過ぎる場合には、当業者らにとつて公知の方法、すな
わち、ジハロ芳香族化合物を添加する前に溶媒（および
アルカリ金属硫化物）を７３０℃から、２１Ｏ℃程度ま
で昇温しながら常圧下に水の不必要量を系外に追い出す
。この際、水を除去し過ぎた場合には、不足分を添加補
充すればよい。重合系の共存水量は仕込みアルカリ金属
硫化物１モル当シ、０．！モル〜コ、参モルの範囲であ
る。特に、／、０モル〜λ、Ｏモルの範囲は高分子量の
ＰＡＳを得やすい。０，１モル未満では生成ＰＡＳの分
解等望ましくない反応が起るし、一方コ、参モルを超過
する場合にも重合速度が著しく小さくなったシ、系が分
解したシするおそれがあるので、いずれも好ましくない
。If the amount is too high, use a method known to those skilled in the art, that is, heat the solvent (and alkali metal sulfide) from 730°C to about 210°C under normal pressure before adding the dihaloaromatic compound. Remove unnecessary amounts of water from the system. At this time, if too much water is removed, the missing amount can be replenished. The amount of coexisting water in the polymerization system is 0.00% per mole of charged alkali metal sulfide. ! The range is from mol to ko, and from mol to mol. In particular, it is easy to obtain a high molecular weight PAS in the range of /, 0 mol to λ, O mol. If it is less than 0.1 mole, undesirable reactions such as decomposition of the produced PAS will occur, while if it exceeds 0.1 mole, the polymerization rate may be significantly reduced or the system may be decomposed. Neither is preferable.
前段重合は、１ｔ−ｏ℃乃至２３５℃で行なわれる。The first stage polymerization is carried out at a temperature of 1 to 235°C.
温度が低すぎると速度が遅すぎるし、２３４ｒ ”Ｃを
こえると生成ＰＡＳ（および溶媒）が分解を起し易くて
溶融粘度の極めて低いＰＡＳＬか得られない。If the temperature is too low, the speed is too slow, and if it exceeds 234r''C, the generated PAS (and solvent) tends to decompose, making it impossible to obtain PASL with extremely low melt viscosity.
ジハロ芳香族化合物の使用量はアルカリ金属硫化物１モ
ル白シＯ０２モル〜／、１モルの範囲が望ましく、特に
Ｏｏりｔモルルミ、ｏｒモルの範囲が高分子量のＰＡＳ
を得るのに好ましい。Ｏ，タモル未満または／、１モル
を超過する場合は、加工に適した高粘度のＰＡＳを得難
いので好ましくない。The amount of the dihaloaromatic compound to be used is desirably in the range of 2 to 1 mole per mol of the alkali metal sulfide, and in particular, the range of 0 to 1 mole is particularly suitable for high molecular weight PAS.
preferred for obtaining. If the amount is less than 0.0 mol or/more than 1 mol, it is not preferable because it is difficult to obtain a PAS with a high viscosity suitable for processing.
前段重合の終点、すなわち前段重合から後段重合に切シ
換える時点は、系内のジハロ芳香族化合物の転化率が３
ｏモルチ〜９８モルチに達した時点である。転化率がＳ
Ｏモルチ未満では後段重合の際分解等望ましくない反応
が起る。逆に、転化率がりｊモルチな超過すると、後′
段重合を行なつても高重合度のＰＡＳを得難い。転化率
ｎモルチ〜り！モル係程度が、室穴に高重合度のＰＡＳ
が得られるので好ましい。At the end point of the first-stage polymerization, that is, at the time of switching from the first-stage polymerization to the second-stage polymerization, the conversion rate of the dihaloaromatic compound in the system is 3.
This is the point when it reaches 98 molti. Conversion rate is S
If the amount is less than 0 molar, undesirable reactions such as decomposition occur during the subsequent polymerization. On the other hand, if the conversion rate exceeds the
Even if stage polymerization is performed, it is difficult to obtain PAS with a high degree of polymerization. Conversion rate n morchiri! PAS with a high degree of polymerization has a molar coefficient in the chamber hole.
This is preferable because it provides the following.
ここで、ジハロ芳香族化合物の転化率は、以下の式で算
出したものである。Here, the conversion rate of the dihaloaromatic compound is calculated using the following formula.
Ｃ） ジハロ芳香族化合物（ＤＭＡと略記する）をアル
カリ金属硫化物よシモル比で過剰に添加した場合
（ロ）（イ）以外の場合
前段重合から後段重合への切換え時点で、ＰＡＳの溶融
粘度は！ポイズ以上かつＪＯＯボイズ以下であるべきで
ある。ｌＯボイズ以上かつ２００ボイズ以下であれば、
溶融粘度１０００ボイズ以上の高重合度のＰＡＳを得る
のによシ適している。ｊボイズ未満では後段重合時に共
存水量を増すか重合温度を下げる必要があるので、重合
系の分解および反応速度の低下が起ル易い。ＪＯＯボ４
ズを超えると、共存水量を減らすか重合温度を上げる必
要があシ、それぞれポリマー収率の低下および重合系の
分解が起るので好ましくない。C) When a dihaloaromatic compound (abbreviated as DMA) is added in excess at a smol ratio relative to the alkali metal sulfide (b) In cases other than (b), the melt viscosity of PAS changes at the time of switching from the first stage polymerization to the second stage polymerization. teeth! It should be more than poise and less than JOO boise. If it is more than lO bois and less than 200 bois,
It is suitable for obtaining PAS with a high degree of polymerization and a melt viscosity of 1000 voids or more. If it is less than j voids, it is necessary to increase the amount of coexisting water or lower the polymerization temperature during the subsequent polymerization, which tends to cause decomposition of the polymerization system and a decrease in the reaction rate. JOO Bo 4
If the amount exceeds the above, it is necessary to reduce the amount of coexisting water or raise the polymerization temperature, which is not preferable because the polymer yield decreases and the polymerization system decomposes, respectively.
（３） 後段重合
本発明での第二の重合では、換言すれば後段重合では、
前段重合スラリーに水を添加して重合系中の全水量な仕
込アルカリ金属硫化物１モル当シ−２，５モル〜７．０
モルにし、コ≠！℃〜コタ０℃に昇温して、重合を継続
する。後段重合によつて溶融粘度１０００ポイズ以上の
ＰＡＳが得られる。(3) Post-stage polymerization In the second polymerization in the present invention, in other words, in the post-stage polymerization,
Water is added to the first stage polymerization slurry to give a total amount of water in the polymerization system of 2.5 to 7.0 moles per mole of alkali metal sulfide charged.
Make it a mole, Ko≠! The temperature is raised to 0°C to 0°C to continue polymerization. PAS having a melt viscosity of 1000 poise or more can be obtained by the post-polymerization.
系中の全水量が２．３モル未満、または７．０モルを超
過すると、生成ＰＡＲの溶融粘度が低下する。When the total amount of water in the system is less than 2.3 moles or more than 7.0 moles, the melt viscosity of the produced PAR decreases.
特に、３．ｊモル〜！、０モルの範囲で後段重合を行な
うと、高溶融粘度のＰＡＳが得られ易いので好ましい。In particular, 3. jmol~! It is preferable to carry out the post-stage polymerization in the range of 0 mol, since it is easy to obtain PAS with a high melt viscosity.
また、重合温度が、２１１ｊ ’Ｃ未満では低溶融粘度
のＰＡ８１．か得られない。一方、コタｏ”ｃを越える
と、生成ＰＡＢや重合溶媒が分解するおそれがある。特
に、２１０℃〜２７０℃の範囲が高溶融粘度のＰＡＳが
得られ易いので好ましい。Furthermore, when the polymerization temperature is lower than 211j'C, PA81. or not obtained. On the other hand, if the temperature exceeds o''c, there is a risk that the produced PAB and the polymerization solvent will decompose.In particular, a temperature range of 210°C to 270°C is preferable because PAS with a high melt viscosity can be easily obtained.
本発明での後段重合段階は前段で生成したＰＡＳの単な
る分別・造粒の工程ではなく、前段ＰＡＳに著るしい溶
融粘度の上昇を起させるためのものである。従−て、後
段重合の重合時間はこの点から定まるのであシ、具体的
には０．２−に時間程度ということになる。重合時間が
短かすぎると低溶融粘度のＰＡＳＬか得られず、逆圧長
すぎても系の分解が起る。好ましい重合時間は／−／、
１時間、特に好ましい重合時間は３〜ｉｏ時間、である
。The latter polymerization step in the present invention is not simply a step of fractionating and granulating the PAS produced in the earlier stage, but is a step for causing the former PAS to significantly increase in melt viscosity. Therefore, the polymerization time of the latter stage polymerization is determined from this point, and specifically, it is about 0.2 hours. If the polymerization time is too short, PASL with a low melt viscosity cannot be obtained, and if the reverse pressure is too long, the system will decompose. The preferred polymerization time is /-/,
1 hour, particularly preferred polymerization time is 3 to io hours.
前段重合から後段重合への切換えは、前段重合で得られ
たスラリーを別の反応容器に移して後段重合条件に服さ
せることによって行なってもよいし、前段重合と後段重
合とを同一の反応容器中で重合条件を変更することによ
つて行なつてもよい。Switching from the first stage polymerization to the second stage polymerization may be carried out by transferring the slurry obtained in the first stage polymerization to another reaction vessel and subjecting it to the second stage polymerization conditions, or the first stage polymerization and the second stage polymerization may be performed in the same reaction vessel. This may also be carried out by changing the polymerization conditions within the process.
水を添加する時機は、前段重合後で後段重合の温度に昇
温開始前か、昇温途中か、あるいは後段重合の温度に昇
温直後がよい。共存水の少ない状態で後段重合の温度に
長時間保ったのち水を添加したのでは、高溶融粘度のＰ
ＡＳが得られないので好ましくない。The timing for adding water is preferably after the first stage polymerization and before the start of raising the temperature to the second stage polymerization temperature, during the temperature rise, or immediately after the temperature rise to the second stage polymerization temperature. If water is added after keeping the post-polymerization temperature for a long time with little coexisting water, P with a high melt viscosity will result.
This is not preferred because AS cannot be obtained.
（４）後処理
本発明の重合方法における後処理は、常法によ−て行な
うことができる。すなわち、後段重合反応の終了後、冷
却した生成物スラリーをそのままあるいは水分などで稀
釈してからｒ別し、水洗ｒ過を繰シ返して乾燥すること
によｊＤ、ＰＡＳを得ることができる。(4) Post-treatment Post-treatment in the polymerization method of the present invention can be carried out by conventional methods. That is, after the completion of the second-stage polymerization reaction, jD and PAS can be obtained by separating the cooled product slurry as it is or diluting it with water or the like, washing with water, filtering, and drying repeatedly.
生成ＰＡＳ
本発明の方法によシ得られるＰＡｓは、１０００ボイズ
以上の高溶融粘度をもちかつ実質的に線状なので、強靭
な耐熱性フィルム、シート、繊維等に極めて容易に成形
加工することができる。さらにまた、このＰＡＳは射出
成形、押出成形、回転成形などによって種々のモールド
物に加工することができるが、これは肉厚のものであっ
てもクラックが人シ難い。Produced PAS The PAs obtained by the method of the present invention have a high melt viscosity of 1000 voids or more and are substantially linear, so they can be extremely easily molded into tough heat-resistant films, sheets, fibers, etc. can. Furthermore, this PAS can be processed into various molded products by injection molding, extrusion molding, rotary molding, etc., but even if it is thick, it is difficult to crack.
更に本発明の重合体にカーボン黒、炭酸カルシウム粉末
、シリカ粉末、酸化チタン粉末等の粉末状充填材、又は
炭素繊維、ガラス繊維、アスベスト、ポリアラミド線維
な′どの繊維状充填剤を充填して使用することができる
。Furthermore, the polymer of the present invention may be filled with powder fillers such as carbon black, calcium carbonate powder, silica powder, titanium oxide powder, or fibrous fillers such as carbon fiber, glass fiber, asbestos, and polyaramid fiber. can do.
本発明はまたポリカーボネート、ポリフェニレンオキシ
ド、ポリスルフォン、ポリアリーレン、ポリアセタール
、ポリイミド、ポリアミド、ポリエステル、ボリスチレ
ノ、ＡＢＳなどの合成樹脂の一種以上を混合して使用す
ることもできる。The present invention can also use a mixture of one or more synthetic resins such as polycarbonate, polyphenylene oxide, polysulfone, polyarylene, polyacetal, polyimide, polyamide, polyester, polystyrene, and ABS.
実験例
実施例／
（１）前段重合
吃すットルオートクＶ−プにＮ−メチルーーービロリド
ン（以下ＮＭＰと略記する）／／、ＯＫｆとａｔ、Ｏ２
重量％のＮａ２Ｓを含むＮａ２８ ｊ水塩結晶（長屋ソ
ータ社ｆ１１） ４７，２３２Ｋｐ（Ｎａ、２＋８とし
てコｊ、０モル）を仕込、窒素雰囲気下に約２時間かけ
て攪拌しながら徐々に２０３℃まで昇温して、水／、１
１！〜、Ｎ Ｍ Ｐ ／、２４ｍ９および０．ｉｔモル
０Ｈ２８を留出させた。Experimental Examples/ (1) N-methyl-pyrrolidone (hereinafter abbreviated as NMP) //, OKf, at, O2 in the first stage polymerization tank
47,232 Kp (Na, 2+8 as coj, 0 mol) of Na28j hydrate crystals (Nagaya Sota Co., Ltd. f11) containing % Na2S by weight were charged and gradually heated to 203°C with stirring for about 2 hours under a nitrogen atmosphere. Water/, 1
1! ~, N M P /, 24 m9 and 0. It mole 0H28 was distilled off.
この場合、系中の水の量はＮａ２８１モル当シ約／、４
モルになっている。In this case, the amount of water in the system is about 281 moles of Na/4
It has become a mole.
／ＪＯ”Ｃ，まで冷却したのち、パラジクロルベンゼン
（以下ｐ−ＤＣＢと略記する）Ｊ、ｊり〜（λφ、４Ｉ
−λモル）とＮＭＰｊ、／７Ｋｐとを加えてコ１０℃で
ｉｏ時間重合させて、前段重合パラ！ｊ−（８−／ ）
を得た。/JO”C, and then paradichlorobenzene (hereinafter abbreviated as p-DCB) J,jri~(λφ,4I
-λ mol) and NMPj, /7Kp were added and polymerized at 10°C for io hours to complete the first stage polymerization. j-(8-/)
I got it.
スラリー中の残存ｐ−Ｄ’ＣＢ量をガスクロマトグラフ
法によって求め、前記の転化率を算出する式（ロ）に従
ってｐ −ＤＣＢの転化率を求めた。転化率は２裏Ｏモ
ルチであやだ。The amount of p-D'CB remaining in the slurry was determined by gas chromatography, and the conversion rate of p-DCB was determined according to the formula (b) for calculating the conversion rate. The conversion rate is between 2 and 10%.
スラリー１００１をとシ、そのまま吸引ｒ過して液状成
分を除去した。次いで、固形分を約ｌＫ９の脱イオン水
中に分散させ、再度吸引ｒ過して、生成ＰＰＳを洗浄し
た。この様な操作を３回くシ返したのち、１００℃で２
時間乾燥して（空気雰囲気下）、ポリフエニレンスルフ
イド（ｐｐｓ）粉を得た。これを予熱なしに３λＯ℃で
３０秒間溶融プレスして得たプレスシートについて、高
化式フローテスター（高滓製作所製）を用いて３１０℃
（予熱５分）で溶融粘度を測定した。剪断速度−ＺＯＯ
５ａｃ−１に換算してＩＯｊボイズでありた。Slurry 1001 was filtered and filtered under suction to remove liquid components. The solids were then dispersed in approximately 1K9 of deionized water and filtered again with suction to wash away the PPS produced. After repeating this operation three times, it was heated to 100℃ for two
After drying for hours (under air atmosphere), polyphenylene sulfide (pps) powder was obtained. The pressed sheet obtained by melt pressing this at 3λO℃ for 30 seconds without preheating was heated to 310℃ using a Koka type flow tester (manufactured by Takasu Seisakusho).
(preheated for 5 minutes) to measure the melt viscosity. Shear rate-ZOO
It was IOj boys in terms of 5ac-1.
（２）後段重合
スラリー（１９−／）７ｊ’４Ｃ１１（仕込Ｎａ２Ｓ
１モル相当）をｌリットルオートクン−プに仕込み、水
ｊシコＩ（全水量として先ｊ＃ｃル／Ｎｉ２８１モルに
なる）を添加し、窒素雰囲気下に２１０℃に昇温して１
０時間重合させた。ｐ −ＤＣＢの転化率はブタ６０チ
であった。冷却後、孔目寸法約０，１ｍの篩で−く−ル
状ｐｐｓをＮＭＰ、ＰＰ８オリゴマー等から篩別した。(2) Post-polymerization slurry (19-/) 7j'4C11 (prepared Na2S
(equivalent to 1 mole) was placed in a 1 liter autoclave, water (total amount of water equals 281 moles of Ni) was added, and the temperature was raised to 210°C under a nitrogen atmosphere to give 1 mol of Ni.
Polymerization was carried out for 0 hours. The conversion rate of p-DCB was 60 cm. After cooling, the pore-like pps was sieved from NMP, PP8 oligomer, etc. using a sieve having a hole size of about 0.1 m.
次いで、脱イオン水でくシ返し洗浄したのち、１００℃
で３時間乾燥して、下記のような粒度分布（水篩法によ
る）をもつＰＰＳを得た。Next, after rinsing with deionized water, heat at 100°C.
After drying for 3 hours, PPS with the following particle size distribution (based on the water sieve method) was obtained.
収率は約評チでありた。ここで言う収率とは、重合上ツ
マ−が全て高重合度のＰＡＳに転化したと仮定した量（
理論量）に対する回収されたパール状ＰＡＳの割合であ
る。The yield was approx. The yield mentioned here refers to the amount (
This is the ratio of recovered pearl-like PAS to the theoretical amount).
粒径０．３１ ｍ以下 ０ 重量％ｐ ｏ、
３ｔ〜０．グ２ ０．コ 〃Ｉ Ｑ、≠コ〜ｏ
、’ｙｉ ｉ３．ｚ ｐｌ ０．７／〜／
、００ ｊＪ、コ 〃Ｉ １＋００〜１．≠
１３≠、１ １１ １、弘／ｍ以上 Ｏ〃
得られたパール状ＰＰＳの見掛比重は弘３１１７ｄｉで
あった。また、溶融粘度はｚｑｏｏボイズであった。Particle size 0.31 m or less 0 wt% po,
3t~0. G2 0. Ko 〃I Q,≠Ko〜o
,'yi i3. zpl 0.7/~/
, 00 jJ, Ko 〃I 1+00~1. ≠
13≠, 1 11 1, Hiro/m or more O〃 The apparent specific gravity of the obtained pearl-like PPS was Hiro 3117 di. Moreover, the melt viscosity was zqoo voids.
実施例コ〜ｊ
８−／のスラリーを用いて実施例１と同一の操作で重合
時間を／ −／！ｉ時間の範囲で変えて後段重合を行な
った（実施例λ〜り。また、Ｓ−／のスラリーを用い、
添加水分の量を変えて共存水量としてＨ２０／Ｎ轟２Ｓ
モル比３．０−３，０の範囲で後段重合を行なった（実
施例６〜ｔ）。いずれの場合にも、溶融粘度の高いパー
ル状のＰＰＳが得られた。結果は、まとめて表−コに示
す通シである。Example Co~j Using the slurry of 8-/, the polymerization time was changed to /-/! in the same manner as in Example 1. Post-polymerization was carried out by changing the time within the range of i (Examples λ to 1).Also, using a slurry of S-/,
H20/N Todoroki 2S as coexisting water amount by changing the amount of added water
Post-stage polymerization was carried out at a molar ratio in the range of 3.0-3.0 (Examples 6 to t). In either case, pearl-like PPS with high melt viscosity was obtained. The results are summarized in Table C.
実施例り〜１９
実施例１の前段重合とほぼ同様の方法によシ、モル比（
ｐ−ＤＣＢ／Ｎａ２８モル比）、共存水量（１２０／Ｎ
峠Ｓモル比）、仕込濃度（ＮＭＰ／Ｋｐ中のＮａ２Ｓモ
ル数）、重合温度、重合時間を変えて。Example 19 The molar ratio (
p-DCB/Na28 molar ratio), amount of coexisting water (120/N
(S mole ratio), charging concentration (number of moles of Na2S in NMP/Kp), polymerization temperature, and polymerization time.
各種前段スラリー（Ｓ−λ〜７．５−１０〜／４Ａ）を
得た。それぞれについて転化率および生成ＰＰＳの溶融
粘度を求めた。重合条件、結果は、表−１に示した通り
である。Various pre-stage slurries (S-λ~7.5-10~/4A) were obtained. The conversion rate and melt viscosity of the produced PPS were determined for each. The polymerization conditions and results are as shown in Table 1.
次に、これらのスラリーを用い、後段重合条件を表−２
に示すように変えて、後段重合を行なった。結果は、表
−２に示す通シであった。いずれの場合にも、高溶融粘
度でほとんどの場合−々−ル状の粒子を得ることができ
た。Next, using these slurries, the post-polymerization conditions are shown in Table 2.
The second stage polymerization was carried out with the following changes. The results were as shown in Table-2. In all cases, it was possible to obtain particles of high melt viscosity and in most cases a round shape.
比較例１
前段重合スラリー（Ｂ −／ ） ７１≠ｔｔｔ！ｔｉ
リツトルオートクレーブに仕込み、水は添加せずに、窒
素雰囲気下に２！Ｏ℃で１０時間後段重合を行なつた。Comparative Example 1 First-stage polymerization slurry (B −/ ) 71≠ttt! Ti
Place in a little autoclave and place under nitrogen atmosphere without adding water! Post-polymerization was carried out at 0° C. for 10 hours.
冷却後、吸引ｒ過してｐｐｓをＮＭＰから分、離した。After cooling, the pps was separated from the NMP by suction filtration.
次いで、このＰＰＳを脱イオン水でくシ返し洗浄したの
ち、１００℃で！時間乾燥して、微粉状のポリマーを得
たう収率りｔチ、溶融粘度１０ボイズ、見掛比重はｌ−
Ｍ／ｄｉであった（結果を表コにまとめである）。Next, this PPS was washed repeatedly with deionized water, and then heated at 100℃! After drying for a few hours, a fine powder polymer was obtained with a yield of t, a melt viscosity of 10 voids, and an apparent specific gravity of l-
M/di (the results are summarized in Table 1).
比較例コ
前段重合スラリー（Ｓ−ｉ）ｙｚ４！ｉを７リツトルオ
ートクレープに仕込み、水を／／！０．２ ＪｉＦ添加
しく全水量ｒ、ｏモル）、窒素雰囲気下に、２ｊｊ ’
Ｃで１０時間後段重合を行なった。Comparative example first stage polymerization slurry (S-i)yz4! Put i into a 7 liter autoclave and add water//! 0.2 JiF (total amount of water r, o mol) added, under nitrogen atmosphere, 2jj'
Post-polymerization was carried out at C for 10 hours.
冷却後、比較例１と同様にしてｐｐｓを回収した。細か
い砂状のポリマーが得られた。収率り７チ、溶融粘度は
≠１０ボイズであシ、後段重合で水が多すぎると溶融粘
度が高くならないことが判る（結果を表２に示しである
）。After cooling, pps was collected in the same manner as in Comparative Example 1. A fine sandy polymer was obtained. The yield was 7 cm, and the melt viscosity was ≠10 voids, indicating that the melt viscosity did not increase if too much water was added in the post-polymerization (the results are shown in Table 2).
比較例３ 共存水の量をＮａ２Ｓ １モル当シコ、ｊモルとした。Comparative example 3 The amount of coexisting water was defined as j moles per mole of Na2S.
以外は、実施例１とほとんど同じ手順で−ｉｏ℃で１０
時間重合を行なって、前段重合スラＶ−＜５−ｔ）を得
た。転化率ｒｙ、ｒｔｓ、前段ＰＰＳの溶融粘度はｊボ
イズ以下であった（結果を表１にまとめである）。Except for this, the procedure was almost the same as in Example 1, and the temperature was 10°C at -io°C.
Polymerization was carried out for a period of time to obtain a pre-polymerized slurry (V-<5-t). The conversion rate ry, rts, and melt viscosity of the first-stage PPS were below jboise (the results are summarized in Table 1).
このスラリー７７０ｇをｌリットルオートクン −プに
仕込み、水３６１１を追加して、窒素雰囲気下に２２０
℃で１０時間後段重合を行なって、顆粒状のＰｐｓを得
た。収率７♂チ、ｐｐｓの溶融粘度はＩＩＪＯポイズで
あつた。前段重合の水量が少なすぎると溶融粘度が高く
ならず、また後段重合後のスラリーは悪臭がして分解ぎ
みであった（結果を表λにまとめである）。Pour 770 g of this slurry into a 1 liter auto pump, add 3611 g of water, and heat it under nitrogen atmosphere for 220 g.
Post-polymerization was carried out at °C for 10 hours to obtain granular Pps. The yield was 7♂H, and the melt viscosity of pps was IIJO poise. If the amount of water in the first stage polymerization was too small, the melt viscosity could not be increased, and the slurry after the second stage polymerization had a bad odor and was on the verge of decomposition (the results are summarized in Table λ).
比較例≠
辺リットルオートクレーブにＮＭＰ／シｏＫＰ、ｐｔ、
ｏコ重量％のＮａ２８を含むＮａ２８ Ｊ水塩結晶４Ａ
、０７ Ｑ （Ｎａ２８として、２屹０毛ル）、ｐ−Ｄ
ＣＢ！、７０１〜（２１，２０モル）を仕込み、水抜き
せずに窒素雰囲気下に２１０℃でに時間反応させて、前
段重合スラ９−（Ｓ−タ）を得た。転化率は、ｒｊ、Ｏ
チ、前段で得られたｐｐｓの溶融粘度はｊポイズ以下で
あった（結果を表７にまとめである）。Comparative example ≠ NMP/SioKP, pt, in side liter autoclave
Na28 J water salt crystal 4A containing o% by weight of Na28
, 07 Q (as Na28, 2 tons 0 hairs), p-D
CB! , 701-(21.20 mol) were charged and reacted at 210° C. for a period of time in a nitrogen atmosphere without draining water to obtain a pre-polymerization slurry 9-(S-ta). The conversion rate is rj, O
H. The melt viscosity of the pps obtained in the first stage was less than j poise (the results are summarized in Table 7).
このスラリー（Ｓ−タ）ｆｆＪｌｌをｌリットルオート
クン−プに仕込み、窒素雰囲気下に、２！０℃で１０時
間後段重合を行なったところ、分解が起って、重合は進
行しなかった。少量得られた顆粒状ＰＰＳの溶融粘度は
、Ｊボイズ以下であった（結果を表コにまとめである゛
）。When this slurry (S-ta) ffJll was charged into a 1 liter autoclave and post-polymerization was carried out at 2!0° C. for 10 hours in a nitrogen atmosphere, decomposition occurred and the polymerization did not proceed. The melt viscosity of the granular PPS obtained in a small amount was below J-Boise (the results are summarized in Table 1).
比較例！
比較例≠で得た前段重合スラ！Ｊ−（８−５’）ｒｓａ
、９を７リツトルオートクレープに仕込み、水は添加
せずに、窒素雰囲気下に、２１０℃で更に３０時間重合
を行ない、結局、Ｎａ２８１モル当シ約ｚ、ｉモルの共
存水の存在下に、２１０℃で通算３ｏ時間重合を行なっ
たところ、反応液は悪臭がして分解していた。少量回収
されたＰＰＳの溶融粘度は、９ボイズ以下であった。Comparative example! First-stage polymerization slurry obtained in Comparative Example≠! J-(8-5')rsa
. When polymerization was carried out at 210° C. for a total of 3 hours, the reaction solution gave off a bad odor and was decomposed. The melt viscosity of the small amount of PPS recovered was 9 voids or less.
比較例６
前段重合スラリー（，５−ｔ）ｒりざ１１ （Ｎａ２Ｓ
仕込量１２λモル相当）をｌリットルオートクレーブに
仕込み、窒素雰囲気下に２！ｔＯ℃に昇温して！時間重
合を行なって、反応を完結させた。冷却後、００．９を
サンプリングし、転化率を算出する式（イ）に従−て転
化率および生成ｐｐｓの溶融粘度を求めた。Comparative Example 6 First-stage polymerization slurry (,5-t) r Riza 11 (Na2S
Charged amount (equivalent to 12λ moles) was charged into a 1 liter autoclave and placed in a nitrogen atmosphere for 2 hours. Raise the temperature to tO℃! Polymerization was carried out for a period of time to complete the reaction. After cooling, 00.9 was sampled, and the conversion rate and the melt viscosity of the pps produced were determined according to the formula (a) for calculating the conversion rate.
転化率タタ、２モルチ
ｐｐｓの溶融粘度ｒ、２ボイズ
次いで、残シのスラリーに水ｊ７．ｔｌｉを添加しく全
量で先ｊモル）、窒素雰囲気下に、２．７０℃に再昇温
して、 ｉｏ時間反応させて、砂状ないし顆粒状のｐｐ
ｓを得た。収率６５チ、見掛比重３／Ｉ／ｄｌ、溶融粘
度り００ボイズであつた。粒度分布は、次に示す通シで
あった。Conversion rate tata, melt viscosity r of 2 mol pps, 2 voids, then water j7. tli (total amount of J mol) was heated again to 2.70°C under a nitrogen atmosphere, and reacted for io hours to form sandy or granular pp.
I got s. The yield was 65 cm, the apparent specific gravity was 3/I/dl, and the melt viscosity was 00 voids. The particle size distribution was as shown below.
粒径０．ＩＯｒ ｔｘ以下 Ｏ重量価ｙ ｏ、
ｉｏｚ〜Ｑ、３！ コ≠、３ １１ ０．３！ｒ
〜Ｏ０≠コ １２．７ １＃０．グ＋２−０．７
１ ≠３．！〃粒径０．７１〜／、００
１０Ｊ重量％１ １．ＤＯ〜１．≠／
ｊ、０ ／’１ ／、ｌ１１ｗ５以上
３＃７〃前段重合で転化率が余りに大となると、本発
明の条件４で後段重合しても溶融粘度は大とならない。Particle size 0. IOr tx or less O weight value y o,
ioz~Q, 3! Ko≠, 3 11 0.3! r
~O0≠ko 12.7 1#0. g+2-0.7
1 ≠ 3. ! 〃Particle size 0.71~/,00
10J weight%1 1. DO~1. ≠／
j, 0 /'1 /, l11w5 or more
3#7 If the conversion rate becomes too high in the first stage polymerization, the melt viscosity will not increase even if the second stage polymerization is performed under condition 4 of the present invention.
実施例ｍ
１０リツトルオートクレーブにＮＭＰ弘ｈｏｏｐと、ｌ
／−ぶ、０ノ重量％のＮａ２Ｓを含むＮ轟２Ｓ！水塩結
晶ｌｔりＪ、９（Ｎａ２Ｓとしてｉｏモル）とを仕込み
、窒素雰囲気下に徐々に２０２℃まで昇温しながら水６
１１３１１、ＮＭＰＩＩ／７１および０．Ｊ／ モｋｆ
） Ｈ２Ｏを留出させた。この場合、系中の水の量はＮ
ａ２８１モル当シ約１．３３モルである。ｉｓｏ℃まで
冷却後、ｐ−ＤＣＢ／≠３２１ （ｐ−ＤＣＢ／Ｎ息２
Ｓモル比１，０／／／、ＯＯ）とＮＭＰ７６コＩとを加
え、２１０℃で１０時間重合を行なって、前段重合スラ
リーな得た。これを少量サンプリングして調べたところ
、転化率はりＪ、３％、生成ＰＰＳの溶融粘度は約１０
０ボイズであった。Example m In a 10 liter autoclave, add NMP Hiro hoop and l
/-bu, N Todoroki 2S containing 0% by weight of Na2S! Water salt crystals were charged with J,9 (io mol as Na2S), and while gradually heating up to 202°C in a nitrogen atmosphere, water was added with 6
11311, NMPII/71 and 0. J/ Mokf
) H2O was distilled off. In this case, the amount of water in the system is N
It is about 1.33 mol per 281 mol of a. After cooling to iso℃, p-DCB/≠321 (p-DCB/N breath 2
S molar ratio 1,0///, OO) and NMP76 were added, and polymerization was carried out at 210° C. for 10 hours to obtain a pre-polymerization slurry. When a small amount of this was sampled and investigated, the conversion rate was 3%, and the melt viscosity of the PPS produced was approximately 10.
There was 0 voice.
次いで、この前段重合スラリーを冷却せずＫ、水ψＡｎ
を窒素で圧入しく全水量として、Ｎａ２８１モル当り６
０モルになる）、８０℃に昇温して１０時間後段重合を
行なつた。ｐ −ＤＣＢの転化率はりＺ≠係であった。Next, this first-stage polymerization slurry was heated with K and water ψAn without being cooled.
is injected with nitrogen and the total amount of water is 6 per mole of Na28.
0 mol), the temperature was raised to 80° C., and post-polymerization was carried out for 10 hours. The conversion rate of p-DCB was Z≠.
以下、実施例１と同様に−く一ル状のＰＰＳを回収した
。ポリマー収率Ｉｒｔチ、溶融粘度７４！００ボイズで
あった。Thereafter, a pellet-shaped PPS was collected in the same manner as in Example 1. The polymer yield was IRt1, and the melt viscosity was 74!00 voids.
比較例７
前段重合スラリー（Ｓ−／ ） ｙｚ４Ｌｉをｌリット
ルオートクン−プに仕込み、水は添加せずに（全水量は
Ｎａ２Ｂ １モル当＃）１．６モル）、窒素雰囲気下に
２ｊＯ”Ｃ，に昇温して１時間重合を継続して、反応を
完結させた。次いで、冷却せずに、水！２．２１１を窒
素ガスで圧入した。温度は一旦約２２０℃まで低下した
が、更に加熱して８０℃まで回復したところで、ただち
に加熱を中止した。実施例１と同様の操作で回収を行な
って、顆粒状（非球状）のｐｐｓを得た。ｐ −ＤＣＢ
の転化率りＰ、Ｊ％、収率７０’％、ＰＰ８の溶融粘度
２４０ボイズであった。なお、得られたｐｐｓの粒度分
布は、比較例乙のものに類似していた。Comparative Example 7 First-stage polymerization slurry (S-/) yz4Li was charged into a 1 liter autoclave, and 2jO'' was added in a nitrogen atmosphere without adding water (total water amount was 1.6 mol per 1 mol of Na2B). C., and polymerization was continued for 1 hour to complete the reaction.Next, without cooling, water !2.211 was pressurized with nitrogen gas.The temperature was once lowered to about 220°C, but After further heating and the temperature recovered to 80°C, the heating was immediately stopped. Recovery was carried out in the same manner as in Example 1 to obtain granular (non-spherical) pps.p-DCB
The conversion rate was P, J%, the yield was 70'%, and the melt viscosity of PP8 was 240 boids. The particle size distribution of the obtained pps was similar to that of Comparative Example B.
比較例ｔ
Ｎａ２Ｂ １モル当１）／、４モルのＨ２Ｏを含む条件
で２１０℃／１０時間の重合を行なって得たスラリー（
Ｓ−／）７！４！１１をｌリットルオートクレーブに仕
込み、水１４２ｇ（全水量としてＮａ２８１モル当シク
、！モルになる）を添加し、窒素雰囲気下に室温から、
２１０℃まで約１時間かけて昇温した。−２１０’Ｃに
到達後、ただちに冷却した。ｐ −ＤＣＢの転化率はｙ
ｙｒ４であった。以下、実施例１と同様に後処理を行な
った。顆粒状（非球状）のｐｐｓが得られた。ポリマー
収率は約Ａ＃ｉ溶融粘度はｇｏ。Comparative Example t Slurry obtained by polymerization at 210°C/10 hours under conditions containing 1)/1 mole of Na2B/1 mole of H2O (
S-/) 7!4!11 was placed in a liter autoclave, 142 g of water (total amount of water equal to 281 mol of Na, ! mol) was added, and the mixture was heated from room temperature under a nitrogen atmosphere.
The temperature was raised to 210°C over about 1 hour. After reaching -210'C, it was immediately cooled. The conversion rate of p-DCB is y
It was yr4. Thereafter, post-treatment was performed in the same manner as in Example 1. Granular (non-spherical) pps were obtained. Polymer yield is approximately A#i. Melt viscosity is go.
ボイズであった。It was Boyz.
実施例２ノ
実施例１と全く同じ条件で前段重合を行ない、−２ｊＯ
℃で１０時間後段重合を行なった。次いで、攪拌を止め
たまま、２ｊＯ℃に３０分間保ったのち、攪拌を止めた
状態で約２時間かけて室温まで冷却した。Example 2 The first stage polymerization was carried out under exactly the same conditions as in Example 1, and -2jO
Post-polymerization was carried out at °C for 10 hours. Next, the mixture was kept at 2JO<0>C for 30 minutes while stirring was stopped, and then cooled to room temperature over about 2 hours while stirring was stopped.
以下、実施例１と全く同様の後処理を行なって、はぼパ
ール状のＰＰＳを得た。収率ｒ３チ、溶溶融度よ弘００
ボイズであった。Thereafter, the same post-treatment as in Example 1 was carried out to obtain pearl-like PPS. Yield r3chi, melting degree 000
It was Boyz.
得られたＰＰ８０粒度分布は実施例１とほぼ同じであシ
、個々の粒子は偏平になつたシ融着したシしていなかっ
た。従って、パール状の粒子は後段重合後の冷却の過程
でできてくるのではなく、後段重合中に形成されて、徐
々に融着しない程度に硬化していくものと考えられる。The particle size distribution of the obtained PP80 was almost the same as in Example 1, and the individual particles were not flattened or fused together. Therefore, it is considered that the pearl-like particles are not formed during the cooling process after the post-polymerization, but are formed during the post-polymerization and gradually harden to the extent that they do not fuse.
手続補正側 昭和５９年７月２３日procedural amendment side July 23, 1980
Claims (1)
化合物とを反応させてポリアリーレンスルフィドを得る
方法において、この反応を少なくとも下記の二段階で行
なうことを特徴とする、溶融粘度が１０００ボイズ以上
のポリアリーレンスルフィドの製造法（ただし、本発明
において溶融粘度は３１０℃で剪断速度２００（秒）＾
−１で測定したものである）。 （１）アルカリ金属硫化物１モル当り０．５〜２．４モ
ルの水が存在する状態で、１８０〜２３５℃の温度で反
応を行なって、溶融粘度５〜３００ボイズのポリアリー
レンスルフィドをジハロ芳香族化合物の転化率５０〜９
８モル％で生成させる工程、（２）アルカリ金属硫化物
１モル当り２．５〜７．０モルの水が存在する状態とな
るように水を添加すると共に２４５〜２９０℃の温度に
昇温して、上記の反応を継続する工程。[Claims] A method for obtaining polyarylene sulfide by reacting an alkali metal sulfide and a dihaloaromatic compound in an organic amide solvent, characterized in that the reaction is carried out in at least the following two steps: A method for producing polyarylene sulfide having a viscosity of 1000 voids or more (however, in the present invention, the melt viscosity is 310°C and the shear rate is 200 (seconds)^
-1). (1) In the presence of 0.5 to 2.4 moles of water per mole of alkali metal sulfide, a reaction is carried out at a temperature of 180 to 235°C to convert polyarylene sulfide with a melt viscosity of 5 to 300 voids into dihalogen. Conversion rate of aromatic compounds 50-9
(2) adding water so that 2.5 to 7.0 mol of water exists per 1 mol of alkali metal sulfide and raising the temperature to 245 to 290°C; and continuing the above reaction.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59126725A JPS617332A (en) | 1984-06-20 | 1984-06-20 | Production of high molecular weight polyarylene sulfide |
| US06/746,252 US4645826A (en) | 1984-06-20 | 1985-06-18 | Process for production of high to ultra-high molecular weight linear polyarylenesulfides |
| DE8585107575T DE3584692D1 (en) | 1984-06-20 | 1985-06-19 | METHOD FOR PRODUCING LINEAR POLY (ARYLENE SULFIDES) WITH HIGH TO ULTRA-HIGH MOLECULAR WEIGHT. |
| CA000484413A CA1236642A (en) | 1984-06-20 | 1985-06-19 | Process for production of high to ultra-high molecular weight linear polyarylenesulfides |
| EP85107575A EP0166368B1 (en) | 1984-06-20 | 1985-06-19 | Process for production of high to ultra-high molecular weight linear polyarylenesulfides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59126725A JPS617332A (en) | 1984-06-20 | 1984-06-20 | Production of high molecular weight polyarylene sulfide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS617332A true JPS617332A (en) | 1986-01-14 |
| JPS6333775B2 JPS6333775B2 (en) | 1988-07-06 |
Family
ID=14942324
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59126725A Granted JPS617332A (en) | 1984-06-20 | 1984-06-20 | Production of high molecular weight polyarylene sulfide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS617332A (en) |
Cited By (49)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6176529A (en) * | 1984-09-21 | 1986-04-19 | Toyo Soda Mfg Co Ltd | Granular polyarylene sulfide and its production |
| JPS62232437A (en) * | 1986-04-02 | 1987-10-12 | Toto Kasei Kk | Production of polyphenylene sulfide resin |
| JPS62240359A (en) * | 1986-03-11 | 1987-10-21 | Kureha Chem Ind Co Ltd | Polyarylene thioether composition |
| JPS6339926A (en) * | 1986-08-04 | 1988-02-20 | Kureha Chem Ind Co Ltd | Production of polyarylene sulfide |
| JPS63137822A (en) * | 1986-11-29 | 1988-06-09 | Kureha Chem Ind Co Ltd | Extrusion molding method for polyphenylene sulfide |
| JPS63305131A (en) * | 1987-06-06 | 1988-12-13 | Idemitsu Petrochem Co Ltd | Production of arylene sulfide copolymer |
| WO1988009881A1 (en) * | 1987-06-04 | 1988-12-15 | Nippon Seiko Kabushiki Kaisha | Plastic retainer for bearing |
| DE3890466T1 (en) * | 1987-06-04 | 1989-05-24 | Nippon Seiko Kk | PLASTIC HOLDER FOR A WAREHOUSE |
| US4840986A (en) * | 1987-03-06 | 1989-06-20 | Tosoh Corporation And Toso Susteel Co., Ltd. | Process for producing a polyarylene sulfide |
| JPH01299826A (en) * | 1988-05-26 | 1989-12-04 | Kureha Chem Ind Co Ltd | Production of crosslinked polyarylene sulfide polymer |
| US4894419A (en) * | 1987-05-15 | 1990-01-16 | Kureha Kagaku Kogyo K.K. | Biaxially-stretched film made of poly(arylene sulfide) resin composition and production process thereof |
| US4910294A (en) * | 1988-06-20 | 1990-03-20 | Idemitsu Petrochemical Company Limited | Two-stage process for production of polyarylene sulfides with lithium compound |
| US4976825A (en) * | 1986-04-28 | 1990-12-11 | Kureha Kagaku Kogyo Kabushiki Kaisha | Process for recovering N-methylpyrrolidone by plural distillations |
| US4976908A (en) * | 1987-12-28 | 1990-12-11 | Kureha Kagaku Kogyo K. K. | Poly(arylene sulfide) sheet production process |
| JPH0350237A (en) * | 1989-07-17 | 1991-03-04 | Idemitsu Petrochem Co Ltd | Production of polyarylene sulfide |
| US5013823A (en) * | 1988-12-02 | 1991-05-07 | Kureha Kagaku Kogyo K.K. | Poly(arylene sulfide) sheet and production process thereof |
| US5126430A (en) * | 1988-08-04 | 1992-06-30 | Idemitsu Petrochemical Company Limited | Process for preparing polyarylene sulfides with metal salt of hydroxycarboxylic acid |
| US5194580A (en) * | 1988-08-05 | 1993-03-16 | Idemitsu Petrochemical Co., Ltd. | Process for preparing polyarylene sulfides under reduced pressure |
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| JPS6176529A (en) * | 1984-09-21 | 1986-04-19 | Toyo Soda Mfg Co Ltd | Granular polyarylene sulfide and its production |
| JPH0433299B2 (en) * | 1984-09-21 | 1992-06-02 | Tosoo Kk | |
| JPS62240359A (en) * | 1986-03-11 | 1987-10-21 | Kureha Chem Ind Co Ltd | Polyarylene thioether composition |
| JPH0548786B2 (en) * | 1986-03-11 | 1993-07-22 | Kureha Chemical Ind Co Ltd | |
| JPS62232437A (en) * | 1986-04-02 | 1987-10-12 | Toto Kasei Kk | Production of polyphenylene sulfide resin |
| JPH0534373B2 (en) * | 1986-04-02 | 1993-05-21 | Toto Kasei Kk | |
| US4976825A (en) * | 1986-04-28 | 1990-12-11 | Kureha Kagaku Kogyo Kabushiki Kaisha | Process for recovering N-methylpyrrolidone by plural distillations |
| JPS6339926A (en) * | 1986-08-04 | 1988-02-20 | Kureha Chem Ind Co Ltd | Production of polyarylene sulfide |
| JPS63137822A (en) * | 1986-11-29 | 1988-06-09 | Kureha Chem Ind Co Ltd | Extrusion molding method for polyphenylene sulfide |
| US4840986A (en) * | 1987-03-06 | 1989-06-20 | Tosoh Corporation And Toso Susteel Co., Ltd. | Process for producing a polyarylene sulfide |
| US5006605A (en) * | 1987-05-15 | 1991-04-09 | Kureha Kagaku Kogyo K.K. | Biaxially-stretched film made of poly(arylene sulfide) resin composition and production process thereof |
| US4894419A (en) * | 1987-05-15 | 1990-01-16 | Kureha Kagaku Kogyo K.K. | Biaxially-stretched film made of poly(arylene sulfide) resin composition and production process thereof |
| DE3890466T1 (en) * | 1987-06-04 | 1989-05-24 | Nippon Seiko Kk | PLASTIC HOLDER FOR A WAREHOUSE |
| US5590225A (en) * | 1987-06-04 | 1996-12-31 | Nippon Seiko Kabushiki Kaisha | Plastic holder for bearing |
| GB2217395B (en) * | 1987-06-04 | 1991-10-16 | Nippon Seiko Kk | Rolling element holder for a rolling bearing or rolling clutch. |
| WO1988009881A1 (en) * | 1987-06-04 | 1988-12-15 | Nippon Seiko Kabushiki Kaisha | Plastic retainer for bearing |
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| US4976908A (en) * | 1987-12-28 | 1990-12-11 | Kureha Kagaku Kogyo K. K. | Poly(arylene sulfide) sheet production process |
| US5115092A (en) * | 1987-12-28 | 1992-05-19 | Kureha Kagaku Kogyo | Poly(arylene sulfide) sheet |
| JPH01299826A (en) * | 1988-05-26 | 1989-12-04 | Kureha Chem Ind Co Ltd | Production of crosslinked polyarylene sulfide polymer |
| US4910294A (en) * | 1988-06-20 | 1990-03-20 | Idemitsu Petrochemical Company Limited | Two-stage process for production of polyarylene sulfides with lithium compound |
| US5126430A (en) * | 1988-08-04 | 1992-06-30 | Idemitsu Petrochemical Company Limited | Process for preparing polyarylene sulfides with metal salt of hydroxycarboxylic acid |
| US5194580A (en) * | 1988-08-05 | 1993-03-16 | Idemitsu Petrochemical Co., Ltd. | Process for preparing polyarylene sulfides under reduced pressure |
| US5013823A (en) * | 1988-12-02 | 1991-05-07 | Kureha Kagaku Kogyo K.K. | Poly(arylene sulfide) sheet and production process thereof |
| US5100593A (en) * | 1988-12-02 | 1992-03-31 | Kureha Kagaku Kogyo K.K. | Poly(arylene sulfide) sheet and production process thereof |
| JPH0672185B2 (en) * | 1989-07-17 | 1994-09-14 | 出光石油化学株式会社 | Method for producing polyarylene sulfide |
| JPH0350237A (en) * | 1989-07-17 | 1991-03-04 | Idemitsu Petrochem Co Ltd | Production of polyarylene sulfide |
| US5223557A (en) * | 1989-12-28 | 1993-06-29 | Kureha Kagaku Kogyo K.K. | Electronic device sealing resin compositions and sealed electronic devices |
| US5360890A (en) * | 1991-08-14 | 1994-11-01 | Tosoh Corporation | Refining of polyarylene sulfides |
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| JPH07312325A (en) * | 1995-05-12 | 1995-11-28 | Kureha Chem Ind Co Ltd | Capacitor |
| EP0839851A3 (en) * | 1996-10-31 | 2001-08-29 | Tonen Chemical Corporation | Process for the preparation of polyarylene sulfide |
| US6600009B2 (en) | 1996-10-31 | 2003-07-29 | Dainippon Ink And Chemicals, Incorporated | Process for the preparation of polyarylene sulfide |
| US7632915B2 (en) | 2002-12-27 | 2009-12-15 | Kureha Corporation | Production process and washing method of poly(arylene sulfide), and purification process of organic solvent used in washing |
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| US7767783B2 (en) | 2003-01-21 | 2010-08-03 | Kureha Corporation | Poly (arylene sulfide) and production process thereof |
| WO2007129721A1 (en) | 2006-05-10 | 2007-11-15 | Toray Industries, Inc. | Biaxially oriented polyarylene sulfide film |
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