JP4799015B2 - Method for increasing molecular weight of polyphenylene ether - Google Patents
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本発明はポリフェニレンエーテルの分子量増大方法に関するものである。 The present invention relates to a method for increasing the molecular weight of polyphenylene ether.
ポリフェニレンエーテルは加工性・生産性に優れ、溶融射出成形法や溶融押出成形法などの成形方法により所望の形状の製品・部品を効率よく生産できるため、電気・電子分野、自動車分野、その他の各種工業材料分野、食品・包装分野の製品・部品用の材料として幅広く用いられている。
ポリフェニレンエーテル系樹脂の分子量の調整に関しては従来、重合時の触媒や溶剤等の改善による方法が数多く提案されてきた。例えば、ピリジンー芳香族化合物溶剤中において、二段階の温度で反応させることを特徴とする高分子量のポリフェニレンエーテル系樹脂の合成方法が提案されている（例えば、特許文献１参照。）。また、高い活性の触媒が提案されている（例えば、特許文献２参照。）。しかし、これらの場合重合段階の改善であるため、重合度を高くするとき重合槽内の粘性が上昇してしまい生産が難しくなる、或いはより低い分子量のポリフェニレンエーテルの製造からより高い分子量のポリフェニレンエーテルの製造に切り替えの際、触媒量を変更する必要性や、切り替え途中のポリフェニレンエーテルの分子量が不安定になるなどの問題点が新たに生じてくる。
Polyphenylene ether is excellent in processability and productivity, and can efficiently produce products and parts of a desired shape by molding methods such as the melt injection molding method and melt extrusion molding method. Widely used as a material for products and parts in the industrial materials and food / packaging fields.
Many methods for improving the molecular weight of polyphenylene ether resins have been proposed in the past by improving the catalyst and solvent during polymerization. For example, a method of synthesizing a high molecular weight polyphenylene ether resin characterized by reacting at a two-step temperature in a pyridine-aromatic compound solvent has been proposed (see, for example, Patent Document 1). A highly active catalyst has been proposed (see, for example, Patent Document 2). However, in these cases, since the polymerization stage is improved, when the degree of polymerization is increased, the viscosity in the polymerization tank increases and production becomes difficult, or from the production of a lower molecular weight polyphenylene ether to a higher molecular weight polyphenylene ether When switching to production, new problems arise, such as the need to change the amount of catalyst and the unstable molecular weight of polyphenylene ether during switching.
一方、分子量分布の調整に関しては、重合反応液を加熱処理する方法が提案されている（例えば、特許文献３参照。）。しかし、この場合分布を低分子量側に広げることはできるが高分子量側の分布を調整することはできない。
本発明は、ポリフェニレンエーテルを製造するにあたり重合時の切り替えの煩雑さを低減した、ポリフェニレンエーテルの分子量増大方法を提供することを目的とする。 An object of the present invention is to provide a method for increasing the molecular weight of polyphenylene ether, which reduces the complexity of switching during polymerization in producing polyphenylene ether.
本発明者は、前記課題を解決すべく、ポリフェニレンエーテルの分子量増大方法について鋭意研究を重ねた結果驚くべき事に、まずより低い分子量のポリフェニレンエーテルを製造し、その後加熱処理することで分子量が上昇することを発見し、様々な分子量を持つポリフェニレンエーテルの製造が簡略化可能であることを見出した。これにより煩雑な重合の切り替えを行なわず分子量を調整できる。
即ち、本発明は、
１．有機溶媒とポリフェニレンエーテルの混合物を、７０℃〜２００℃の範囲で１５分以上加熱処理するポリフェニレンエーテルの分子量増大方法であって、加熱処理前のポリフェニレンエーテルが、フェノール化合物を触媒〔但し、式（１）で表される２級アミンは除く。
Ｒ 1 Ｒ 2 ＮＨ （１）
（Ｒ 1 は炭素数１〜２０のアルキル基、置換アルキル基、Ｒ 2 はアリール基、置換アリール基を表す。）〕と酸素含有ガスの存在下で重合して得られ、その重量平均分子量が８００以上２００００以下であるポリフェニレンエーテルであることを特徴とするポリフェニレンエーテルの分子量増大方法、
２．該有機溶媒が、ポリフェニレンエーテルに対する良溶媒と貧溶媒からなることを特徴とする上記１に記載のポリフェニレンエーテルの分子量増大方法、
３．加熱処理前の有機溶媒とポリフェニレンエーテルの混合物がスラリー形態、かつ加熱処理後における有機溶媒とポリフェニレンエーテルの混合物の形態がスラリーであることを特徴とする上記１又は２に記載のポリフェニレンエーテルの分子量増大方法、
４．加熱処理前のポリフェニレンエーテルがフェノール化合物を触媒〔但し、式（１）で表される２級アミンは除く。
Ｒ 1 Ｒ 2 ＮＨ （１）
（Ｒ 1 は炭素数１〜２０のアルキル基、置換アルキル基、Ｒ 2 はアリール基、置換アリール基を表す。）〕と酸素含有ガスの存在下で重合して得られ、重合終了時の重合溶剤の形態がスラリーであり、触媒及び酸素含有ガスを除去した後に該スラリーにポリフェニレンエーテルに対する良溶剤を添加し、スラリー形態を維持したまま不活性ガス雰囲気下で加熱処理することを特徴とする上記１〜３のいずれかに記載のポリフェニレンエーテルの分子量増大方法、
である。
In order to solve the above-mentioned problems, the present inventor has made extensive studies on the method for increasing the molecular weight of polyphenylene ether. As a result, surprisingly, first, a lower molecular weight polyphenylene ether is produced and then heated to increase the molecular weight. It has been found that the production of polyphenylene ethers having various molecular weights can be simplified. Thereby, the molecular weight can be adjusted without performing complicated polymerization switching.
That is, the present invention
1. A method for increasing the molecular weight of polyphenylene ether, wherein a mixture of an organic solvent and polyphenylene ether is heated in a range of 70 ° C. to 200 ° C. for 15 minutes or longer, wherein the polyphenylene ether before the heat treatment is a phenolic compound [provided that the formula ( The secondary amine represented by 1) is excluded.
R 1 R 2 NH (1)
(R 1 represents an alkyl group having 1 to 20 carbon atoms, a substituted alkyl group, R 2 represents an aryl group or a substituted aryl group.)] And an oxygen-containing gas, and has a weight average molecular weight of A method for increasing the molecular weight of polyphenylene ether, which is a polyphenylene ether having a molecular weight of 800 or more and 20000 or less ,
2 . The method for increasing the molecular weight of polyphenylene ether according to 1 above, wherein the organic solvent comprises a good solvent and a poor solvent for polyphenylene ether,
3 . 3. The molecular weight increase of polyphenylene ether according to 1 or 2 above, wherein the mixture of the organic solvent and polyphenylene ether before the heat treatment is in the form of a slurry, and the mixture of the organic solvent and polyphenylene ether after the heat treatment is in the form of a slurry. Method,
4 . The polyphenylene ether before heat treatment catalyzes a phenol compound [however, the secondary amine represented by the formula (1) is excluded.
R 1 R 2 NH (1)
(R 1 represents an alkyl group having 1 to 20 carbon atoms, a substituted alkyl group, and R 2 represents an aryl group or a substituted aryl group.)] And polymerization at the end of the polymerization. The solvent is a slurry, and after removing the catalyst and oxygen-containing gas, a good solvent for polyphenylene ether is added to the slurry, and heat treatment is performed in an inert gas atmosphere while maintaining the slurry form. A method for increasing the molecular weight of the polyphenylene ether according to any one of 1 to 3 ,
It is.
本発明によれば、ポリフェニレンエーテルを有機溶媒中に分散或いは溶解させた混合物を加熱処理することで分子量分布を高分子量側に広くすることができる。また、より低いポリフェニレンエーテルを製造することで、重合の切り替えを行なわず分子量を調整でき、煩雑さを低減することが可能となる。 According to the present invention, the molecular weight distribution can be widened to the high molecular weight side by heat-treating a mixture in which polyphenylene ether is dispersed or dissolved in an organic solvent. Further, by producing a lower polyphenylene ether, it is possible to adjust the molecular weight without switching the polymerization, and to reduce complexity.
本発明について、以下具体的に説明する。
本発明に用いられるポリフェニレンエーテルとはその繰り返し単位としてフェニレンエーテルユニットを含有するものとして定義され、特に限定はない。その代表的なものは一般式（１）
The present invention will be specifically described below.
The polyphenylene ether used in the present invention is defined as containing a phenylene ether unit as its repeating unit, and is not particularly limited. A typical example is the general formula (1).
（式中Ｒ１、Ｒ２、Ｒ３、Ｒ４は各々独立に水素、アルキル基、置換アルキル基、ハロゲン基、アリール基、置換アリール基、フェニル基、置換フェニル基である）で表されるフェニレンエーテルユニットからなっている。代表的な例としては、ポリ（２，６−ジメチル−１，４−フェニレン）エーテル、ポリ（２−メチル−６−エチル１，４−フェニレン）エーテル、ポリ（２，６−ジエチル−１，４−フェニレン）エーテル、ポリ（２−エチル−６−ｎ−プロピル−１，４−フェニレン）エーテル、ポリ（２，６−ジ−ｎ−プロピル−１，４−フェニレン）エーテル、ポリ（２−メチル−６−ｎ−ブチル−１，４−フェニレン）エーテル、ポリ（２−エチル−６−イソプロピル−１，４−フェニレン）エーテル、ポリ（２−メチル−６−クロロエチル−１，４−フェニレン）エーテル、ポリ（２−メチル−６−ヒドロキシエチル−１，４−フェニレン）エーテル、ポリ（２−メチル−６−クロロエチル−１，４−フェニレン）エーテル等のホモポリマーが挙げられる。 (Wherein R 1 , R 2 , R 3 and R 4 are each independently hydrogen, alkyl group, substituted alkyl group, halogen group, aryl group, substituted aryl group, phenyl group or substituted phenyl group). It consists of a phenylene ether unit. Representative examples include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl 1,4-phenylene) ether, poly (2,6-diethyl-1, 4-phenylene) ether, poly (2-ethyl-6-n-propyl-1,4-phenylene) ether, poly (2,6-di-n-propyl-1,4-phenylene) ether, poly (2- Methyl-6-n-butyl-1,4-phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-phenylene) ether, poly (2-methyl-6-chloroethyl-1,4-phenylene) And homopolymers such as ether, poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ether, poly (2-methyl-6-chloroethyl-1,4-phenylene) ether, and the like. It is.
ポリフェニレンエーテル共重合体は、２，６−ジメチルフェノールと２，３，６−トリメチルフェノールとの共重合体あるいはｏ−クレゾールとの共重合体あるいは２，３，６−トリメチルフェノール及びｏ−クレゾールとの共重合体等、ポリフェニレンエーテル構造を主体としてなるポリフェニレンエーテル共重合体等が挙げられる。また、本発明のポリフェニレンエーテル系樹脂中には、本発明の主旨に反しない限り、従来ポリフェニレンエーテル樹脂中に存在させてもよいことが提案されている他の種々のフェニレンエーテルユニットを部分構造として含んでいても構わない。少量共存させてもよい部分構造として提案されているものの例としては、特開平１−２９７４２８号公報及び特開昭６３−３０１２２２号公報に記載されている、２−（ジアルキルアミノメチル）−６−メチルフェニレンエーテルユニットや、２−（Ｎ−アルキル−Ｎ−フェニルアミノメチル）−６−メチルフェニレンエーテルユニット等が挙げられる。 The polyphenylene ether copolymer is a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, a copolymer of o-cresol, or 2,3,6-trimethylphenol and o-cresol. And a polyphenylene ether copolymer mainly composed of a polyphenylene ether structure. In addition, in the polyphenylene ether resin of the present invention, other various phenylene ether units that have been proposed to be allowed to exist in the polyphenylene ether resin as long as they do not contradict the gist of the present invention are used as partial structures. It may be included. Examples of what has been proposed as a partial structure that may coexist in a small amount include 2- (dialkylaminomethyl) -6-6 described in JP-A-1-297428 and JP-A-63-301222. Examples thereof include a methyl phenylene ether unit and a 2- (N-alkyl-N-phenylaminomethyl) -6-methyl phenylene ether unit.
また、ポリフェニレンエーテル樹脂の主鎖中にジフェノキノン等が少量結合したものも含まれる。さらに、例えば特開平２−２７６８２３、特開昭６３−１０８０５９および特開昭５９−５９７２４号公報等に記載されている、炭素−炭素二重結合を持つ化合物により変性されたポリフェニレンエーテルや、特公昭５７−２６５２６号公報、特公昭５５−４０６１５号公報、特開２００３−１２７９６号公報に記載されている二価フェノール化合物も含むことができる。
本発明に用いるポリフェニレンエーテルの分子量としては重量平均分子量で８００〜２００００であることが好ましい。より好ましい範囲は８００〜１５０００、さらに好ましい範囲は８００〜１００００である。本発明の重量平均分子量とは、ゲルパーミエーションクロマトグラフィーにより、標準ポリスチレンの検量線を用いて求めたポリスチレン換算の重量平均分子量である。
Also included are those in which a small amount of diphenoquinone or the like is bonded to the main chain of the polyphenylene ether resin. Furthermore, for example, polyphenylene ethers modified with a compound having a carbon-carbon double bond described in JP-A-2-276823, JP-A-63-108059, JP-A-59-59724, and the like, Dihydric phenol compounds described in JP-A-57-26526, JP-B-55-40615, and JP-A-2003-12796 can also be included.
The molecular weight of the polyphenylene ether used in the present invention is preferably 800 to 20000 in terms of weight average molecular weight. A more preferable range is 800 to 15000, and a further preferable range is 800 to 10,000. The weight average molecular weight of the present invention is a polystyrene equivalent weight average molecular weight determined by gel permeation chromatography using a standard polystyrene calibration curve.
本発明においてはこのようなポリフェニレンエーテルはフェノール化合物を、金属の塩と各種アミンとの組み合わせからなる触媒を用いて酸化重合する方法（例えば特公昭４２−３１５９号公報、特公昭４５−２３５５５号公報、特開昭６４−３３１３１号公報等）で得られる。重合に使用する溶媒はポリフェニレンエーテルに対する良溶媒と貧溶媒の混合物である場合が一般的であるが、これらの比によっては重合の全般にわたってポリフェニレンエーテルの析出を伴わない溶液重合にもなるし、重合後期にポリフェニレンエーテルが析出する沈殿重合にもなる。
本発明によるポリフェニレンエーテルを有機溶媒に分散させた混合物を調整する際、沈殿重合の場合は重合混合物を、またはそれを触媒除去、副生成物除去の処理を施したスラリーを用いる事ができる。溶液重合の場合は重合終了後、重合溶液からポリフェニレンエーテルをポリフェニレンエーテルに対する貧溶媒で析出させた後のスラリー状態の混合物、またはそれを触媒除去、副生成物除去の処理を施したスラリーを用いることができる。
In the present invention, such polyphenylene ether is obtained by oxidative polymerization of a phenol compound using a catalyst comprising a combination of a metal salt and various amines (for example, Japanese Patent Publication No. 42-3159 and Japanese Patent Publication No. 45-23555). JP-A 64-33131). The solvent used for the polymerization is generally a mixture of a good solvent and a poor solvent for polyphenylene ether, but depending on these ratios, the polymerization may be solution polymerization without precipitation of polyphenylene ether throughout the polymerization. It also becomes precipitation polymerization in which polyphenylene ether precipitates in the latter stage.
In preparing the mixture in which the polyphenylene ether according to the present invention is dispersed in an organic solvent, in the case of precipitation polymerization, a polymerization mixture, or a slurry obtained by subjecting it to catalyst removal and by-product removal can be used. In the case of solution polymerization, after polymerization is completed, use a mixture in a slurry state after depositing polyphenylene ether from the polymerization solution with a poor solvent for polyphenylene ether, or a slurry that has been subjected to catalyst removal and byproduct removal treatment. Can do.
本発明によるポリフェニレンエーテルを有機溶媒に溶解させた混合物を調整する際、沈殿重合の場合は重合混合物の触媒除去、副生成物除去の処理を施したスラリーを通常工業的に用いられている遠心分離や濾過などの方法で溶媒から分離乾燥させ、更に乾燥機を用いた乾燥工程において乾燥するという操作で目的のポリフェニレンエーテルを得た後に、ポリフェニレンエーテルに対する良溶媒に溶解させた溶液を用いることができる。溶液重合の場合重合混合物を、またはそれを触媒除去、副生成物除去の処理を施した溶液を用いることができる。 When preparing a mixture in which polyphenylene ether according to the present invention is dissolved in an organic solvent, in the case of precipitation polymerization, a slurry obtained by subjecting the polymerization mixture to catalyst removal and by-product removal treatment is usually used for industrial centrifugation. After obtaining the desired polyphenylene ether by an operation of separating and drying from the solvent by a method such as filtration or drying, and further drying in a drying process using a dryer, a solution dissolved in a good solvent for polyphenylene ether can be used. . In the case of solution polymerization, a polymerization mixture or a solution obtained by subjecting it to catalyst removal and by-product removal can be used.
本発明に使用できるポリフェニレンエーテルに対する良溶媒としては例えば、ベンゼン、トルエン、エチルベンゼン、キシレンなどの芳香族炭化水素、塩化メチレン、クロロホルム、１，２−ジクロロエタン、クロロベンゼン、ジクロロベンゼン等のハロゲン化炭化水素、ニトロベンゼンのようなニトロ化合物が使用でき、またポリフェニレンエーテルに対する貧溶媒としては例えば、メタノール、エタノール、ｍ−プロパノール、イソプロパノール、ｎ−ブタノール、ｓｅｃ−ブタノール、ｔｅｒｔ−ブタノールなどのアルコール類、アセトン、メチルエチルケトンなどのケトン類、テトラヒドロフラン、ジエチルエーテルのようなエーテル類、酢酸エチルなどのエステル類、ジメチルホルムアミドなどのアミド類などを使用することが一般的であるが、特にこれらの例に限定されない。更にこれらの良溶媒と貧溶媒の混合溶媒を使用することができる。 Examples of good solvents for polyphenylene ether that can be used in the present invention include aromatic hydrocarbons such as benzene, toluene, ethylbenzene, and xylene, halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane, chlorobenzene, and dichlorobenzene, Nitro compounds such as nitrobenzene can be used, and examples of the poor solvent for polyphenylene ether include alcohols such as methanol, ethanol, m-propanol, isopropanol, n-butanol, sec-butanol, and tert-butanol, acetone, and methyl ethyl ketone. Ketones, ethers such as tetrahydrofuran and diethyl ether, esters such as ethyl acetate, amides such as dimethylformamide, etc. It is a specific, not particularly limited to these examples. Furthermore, a mixed solvent of these good and poor solvents can be used.
本発明において、基本的に溶媒は望みの加熱処理温度において適切な分子量が得られるように有機溶媒を単独で、もしくはポリフェニレンエーテルの良溶媒、貧溶媒の組み合わせの中から、安全性、経済性、操作性に優れる溶媒を使用すべきである。例えば芳香族炭化水素とアルコールの混合溶媒などがこのましく用いられる。
本発明における加熱処理時のポリフェニレンエーテルの濃度は混合物重量中０．１〜８０ｗｔ％で行なうことが好ましく、特に好ましくは５〜３０ｗｔ％の範囲である。また反応混合物中には、重合に使用した少量の触媒や、触媒除去・副生成物除去の目的で使用した試薬などが含まれていても構わない。
In the present invention, the solvent is basically an organic solvent alone or a combination of a good solvent and a poor solvent of polyphenylene ether so that an appropriate molecular weight can be obtained at a desired heat treatment temperature. A solvent with excellent operability should be used. For example, a mixed solvent of aromatic hydrocarbon and alcohol is preferably used.
In the present invention, the concentration of polyphenylene ether during the heat treatment is preferably 0.1 to 80 wt%, particularly preferably 5 to 30 wt% in the mixture weight. Further, the reaction mixture may contain a small amount of catalyst used for polymerization, a reagent used for the purpose of catalyst removal and byproduct removal, and the like.
加熱処理する温度は溶媒の種類、ポリフェニレンエーテルに対する良溶媒と貧溶媒の組成にもよるが、４０℃〜２００℃の範囲で行なうことが好ましく、より好ましくは４０℃〜１００℃、特に好ましくは４０℃〜８０℃の範囲である。加熱処理する温度が４０℃より低いと、実質的にポリフェニレンエーテルの重量平均分子量は加熱処理前と比較して何等変化しない。また加熱する温度が２００℃より高いとポリフェニレンエーテルが析出している場合、ポリフェニレンエーテルの異常な凝集が起こり、運転不能になる恐れがある。加熱処理する温度は望みの分子量のものが得られるように加熱処理する温度を適切に選択すべきである。 The temperature for the heat treatment depends on the type of solvent and the composition of good and poor solvents for polyphenylene ether, but is preferably in the range of 40 ° C to 200 ° C, more preferably 40 ° C to 100 ° C, and particularly preferably 40 ° C. It is the range of -80 degreeC. When the temperature for the heat treatment is lower than 40 ° C., the weight average molecular weight of the polyphenylene ether is not substantially changed compared to that before the heat treatment. On the other hand, when the heating temperature is higher than 200 ° C., when polyphenylene ether is precipitated, abnormal aggregation of the polyphenylene ether may occur, and operation may be disabled. The temperature for the heat treatment should be appropriately selected so that the desired molecular weight can be obtained.
加熱処理する容器は密閉系、開放系のどちらでも良いが撹拌下で行なうことが好ましく、撹拌機能または液循環装置のついた容器を用いるのが好ましい、またニーダーのような反応器を用いることもできる。加熱処理を行なう時間は加熱処理を行なう温度にもより一概には言えないが、分子量が所望の大きさになるのに十分な時間だけ加熱処理すればよい。加熱処理を行なう雰囲気は安全の面からなるべく不活性ガス雰囲気で行なうことが望ましいが酸素、空気の存在下で処理しても構わない。不活性ガスは一般に窒素、アルゴン、ヘリウムなどが使用される。加熱処理後、ポリフェニレンエーテルと有機溶媒の混合物をそのまま、或いは該混合物にポリフェニレンエーテルの貧溶媒を加えた後、通常工業的に用いられている遠心分離や濾過などの方法で溶媒から分離乾燥させ、さらに各種乾燥機を用いた乾燥工程において乾燥するという操作で目的のポリフェニレンエーテルを得ることが可能である。 The container to be heat-treated may be either a closed system or an open system, but it is preferably carried out with stirring. It is preferable to use a container equipped with a stirring function or a liquid circulation device, or a reactor such as a kneader may be used. it can. Although the time for performing the heat treatment cannot generally be said to the temperature at which the heat treatment is performed, the heat treatment may be performed for a time sufficient for the molecular weight to become a desired size. The atmosphere in which the heat treatment is performed is desirably an inert gas atmosphere as much as possible from the viewpoint of safety, but the treatment may be performed in the presence of oxygen and air. As the inert gas, nitrogen, argon, helium or the like is generally used. After the heat treatment, the mixture of the polyphenylene ether and the organic solvent is left as it is or after the poor solvent of the polyphenylene ether is added to the mixture, and then separated and dried from the solvent by a method such as centrifugation or filtration that is usually used industrially, Furthermore, the target polyphenylene ether can be obtained by an operation of drying in a drying step using various dryers.
次に実施例により本発明を更に詳細に説明するが、本発明はこれらの例によってなんら限定されるべきではない。
なお測定は以下の方法に従って行なった。
（１）重量平均分子量の測定方法
クロロホルムを溶剤としたＧＰＣ測定を行い、予め作成したポリスチレンの分子量と溶出量の関係を表すグラフから重量平均分子量（Ｍｗ）を算出した。
［参考］ポリフェニレンエーテル混合物の製造方法
重合槽底部に酸素含有ガス導入の為のスパージャー、撹拌タービン翼及びバッフル、重合槽上部のベントガスラインに還流冷却器、重合槽側面に第二重合槽へのオーバーフローラインを備えた１．６リットルのジャケット付き第１重合槽に５００ｍｌ／分の流量で窒素ガスを吹き込みながら、０．４３２ｇの塩化第二銅２水和物、１．９０ｇの３５％塩酸、１９．７９ｇのＮ，Ｎ，Ｎ’，Ｎ’−テトラメチルプロパンジアミン、５８．８ｇのキシレン、５２９．３ｇのｎ−ブタノールを入れた。第二重合槽に１０００ｍｌ／分の流量で窒素ガスを吹き込みながら、１５０ｇのキシレン、１３５０ｇのブタノール、１５００ｇのメタノールを入れた。第一原料タンクに５００ｍｌ／分の流量で窒素ガスを吹き込みながら、１．２９６ｇの塩化第二銅２水和物、５．７０ｇの３５％塩酸、４．９５ｇのジ−ｎ−ブチルアミン、５９．３７ｇのＮ，Ｎ，Ｎ’，Ｎ’−テトラメチルプロパンジアミン、１７６．４ｇのキシレン、１５８７．９ｇのｎ−ブタノール、９２８．９ｇの２，６−ジメチルフェノールを入れ、撹拌により液を混合させた。
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention should not be limited at all by these examples.
The measurement was performed according to the following method.
(1) Measuring method of weight average molecular weight GPC measurement using chloroform as a solvent was carried out, and the weight average molecular weight (Mw) was calculated from a graph showing the relationship between the molecular weight and elution amount of polystyrene prepared in advance.
[Reference] Method for producing polyphenylene ether mixture A sparger for introducing oxygen-containing gas at the bottom of the polymerization tank, a stirring turbine blade and baffle, a reflux gas cooler at the vent gas line at the top of the polymerization tank, and a second polymerization tank at the side of the polymerization tank 0.432 g of cupric chloride dihydrate, 1.90 g of 35% hydrochloric acid, while blowing nitrogen gas at a flow rate of 500 ml / min into a 1.6 liter jacketed first polymerization tank equipped with an overflow line, 19.79 g N, N, N ′, N′-tetramethylpropanediamine, 58.8 g xylene, 529.3 g n-butanol were charged. While nitrogen gas was blown into the second polymerization tank at a flow rate of 1000 ml / min, 150 g of xylene, 1350 g of butanol and 1500 g of methanol were added. While blowing nitrogen gas at a flow rate of 500 ml / min into the first raw material tank, 1.296 g of cupric chloride dihydrate, 5.70 g of 35% hydrochloric acid, 4.95 g of di-n-butylamine, 59. 37 g of N, N, N ′, N′-tetramethylpropanediamine, 176.4 g of xylene, 1587.9 g of n-butanol and 928.9 g of 2,6-dimethylphenol were added, and the liquid was mixed by stirring. It was.
さらに、プランジャーポンプより第一重合槽及び第二重合槽の何れにも送液できるライン、撹拌タービン翼及び槽上部のベントガスラインに還流冷却器を備えた２．０リットルの第二原料タンクに１００ｍｌ／分の流量で窒素ガスを吹き込みながら、１２００ｇのメタノールを入れた。尚、第一原料タンク及び第二原料タンクへの仕込み液は重合に供することで減量するため、その都度上記液組成のものを追加添加した。
次いで激しく撹拌した第一重合槽へ、第一原料タンクより１２．１６ｇ／分の流量で重合溶液を供給するのと同時に、第一重合槽へ２３８ｍｌ／分の速度で酸素をスパージャーより導入を始めた。更に、第一重合槽より第二重合槽へのオーバーフローが開始されると同時に、第二原料タンクより第二重合槽へ７．８４ｇ／分の流量でメタノールを添加し、更に２５７ｍｌ／分の速度で酸素をスパージャーより導入を始めた。その後３８時間重合を継続させ、ポリフェニレンエーテルと有機溶媒からなるポリフェニレンエーテル混合物を得た。
In addition, a 2.0 liter second raw material tank equipped with a line that can be fed from the plunger pump to both the first polymerization tank and the second polymerization tank, a stirring turbine blade, and a vent gas line at the top of the tank with a reflux condenser. While blowing nitrogen gas at a flow rate of 100 ml / min, 1200 g of methanol was added. In addition, in order to reduce the amount of liquid charged into the first raw material tank and the second raw material tank by being subjected to polymerization, the liquid composition having the above liquid composition was added each time.
Next, the polymerization solution is supplied from the first raw material tank to the vigorously stirred first polymerization tank at a flow rate of 12.16 g / min. At the same time, oxygen is introduced into the first polymerization tank from the sparger at a rate of 238 ml / min. I started. Furthermore, simultaneously with the start of overflow from the first polymerization tank to the second polymerization tank, methanol is added from the second raw material tank to the second polymerization tank at a flow rate of 7.84 g / min, and a rate of 257 ml / min is further added. At that point, oxygen was introduced from the sparger. Thereafter, the polymerization was continued for 38 hours to obtain a polyphenylene ether mixture comprising polyphenylene ether and an organic solvent.
［実施例１］
参考例で得られたポリフェニレンエーテル混合物にエチレンジアミン四酢酸３カリウム塩（同仁化学研究所製試薬）の１０％水溶液を添加し、４０℃に温めた。次いでハイドロキノン（和光純薬社製試薬）を少量ずつ添加し、スラリー状のポリフェニレンエーテルが白色となるまで、４０℃での保温を続けた。終了後、濾過して、濾残の湿潤ポリフェニレンエーテルをメタノール洗浄溶媒に投入し、４０℃で撹拌を行なった。続いて再び濾過し、濾残にメタノールをふりかけ洗浄し湿潤ポリフェニレンエーテルを得た。次いで１１０℃で真空乾燥し、乾燥ポリフェニレンエーテルを得た。得られた乾燥ポリフェニレンエーテルの重量平均分子量は５７３０であった。
次いで、重合槽底部にガス導入の為のスパージャー、撹拌タービン翼及びバッフル、重合槽上部のベントガスラインに還流冷却器を備えた１．５リットルのジャケット付き重合槽に６００ｍｌ／分の流量で窒素ガスを吹き込みながら、乾燥ポリフェニレンエーテル８０ｇ、貧溶媒としてメタノール１８７．５ｇ、ｎ−ブタノール６７．０ｇを仕込み激しく撹拌し、良溶媒としてキシレン１３．４ｇを加えた。さらに、激しく撹拌しながらキシレン３２０ｇを除々に添加した。重合槽中のポリフェニレンエーテル混合物はスラリー形態であった。その後窒素雰囲気下において７０℃で１時間加熱処理を行なった。
加熱処理後、室温にまで冷却し、得られたポリフェニレンエーテル混合物に貧溶媒であるメタノールを４８０ｇ添加し濾過を行ない、濾残を１１０℃で真空乾燥しポリフェニレンエーテルを得た。乾燥したポリフェニレンエーテルを用いて重量平均分子量の測定を行なった。結果を表１に示した。
[Example 1]
A 10% aqueous solution of ethylenediaminetetraacetic acid tripotassium salt (a reagent manufactured by Dojindo Laboratories) was added to the polyphenylene ether mixture obtained in Reference Example, and the mixture was warmed to 40 ° C. Subsequently, hydroquinone (a reagent manufactured by Wako Pure Chemical Industries, Ltd.) was added little by little, and the temperature was kept at 40 ° C. until the slurry polyphenylene ether became white. After completion, the mixture was filtered, and the residual wet polyphenylene ether was added to a methanol washing solvent and stirred at 40 ° C. Subsequently, the mixture was filtered again, and the residue was sprinkled with methanol to obtain wet polyphenylene ether. Subsequently, it vacuum-dried at 110 degreeC and the dry polyphenylene ether was obtained. The weight average molecular weight of the obtained dry polyphenylene ether was 5730.
Next, nitrogen was introduced at a flow rate of 600 ml / min into a 1.5 liter jacketed polymerization tank equipped with a sparger for introducing gas at the bottom of the polymerization tank, a stirring turbine blade and baffle, and a reflux gas condenser at the vent gas line at the top of the polymerization tank. While blowing gas, 80 g of dry polyphenylene ether, 187.5 g of methanol as a poor solvent, and 67.0 g of n-butanol were charged and stirred vigorously, and 13.4 g of xylene was added as a good solvent. Further, 320 g of xylene was gradually added with vigorous stirring. The polyphenylene ether mixture in the polymerization vessel was in the form of a slurry. Thereafter, heat treatment was performed at 70 ° C. for 1 hour in a nitrogen atmosphere.
After the heat treatment, the mixture was cooled to room temperature, 480 g of methanol as a poor solvent was added to the obtained polyphenylene ether mixture, filtration was performed, and the residue was vacuum dried at 110 ° C. to obtain polyphenylene ether. The weight average molecular weight was measured using dried polyphenylene ether. The results are shown in Table 1.
［実施例２］
キシレン３２０ｇの代わりにトルエン３２０ｇとした以外の操作は実施例１と同様に行なった。結果を表１に示した。
[Example 2]
The same procedure as in Example 1 was performed except that 320 g of toluene was used instead of 320 g of xylene. The results are shown in Table 1.
［実施例３］
空気雰囲気下で行なう以外の操作は実施例１と同様に行なった。結果を表１に示した。
[Example 3]
Operations other than those performed in an air atmosphere were performed in the same manner as in Example 1. The results are shown in Table 1.
［実施例４］
参考例で得られたポリフェニレンエーテル混合物にエチレンジアミン四酢酸３カリウム塩（同仁化学研究所製試薬）の１０％水溶液を添加し、４０℃に温めた。その後ハイドロキノン（和光純薬社製試薬）を少量ずつ添加し、スラリー状のポリフェニレンエーテルが白色となるまで、４０℃での保温を続けた。次いで重合槽底部にガス導入の為のスパージャー、撹拌タービン翼及びバッフル、重合槽上部のベントガスラインに還流冷却器を備えた１．５リットルのジャケット付き第１重合槽に６００ｍｌ／分の流量で窒素ガスを吹き込みながら、ポリフェニレンエーテル混合物３４７．９ｇを仕込み激しく撹拌した。さらに、激しく撹拌しながらキシレン３２０ｇを除々に添加した。重合槽中の混合物はスラリー形態であった。その後窒素雰囲気下で７０℃で１時間加熱処理を行なった。加熱処理後室温にまで冷却し、得られたポリフェニレンエーテル混合物に貧溶媒であるメタノールを４８０ｇ添加し濾過を行ない、濾残を１１０℃で真空乾燥しポリフェニレンエーテルを得た。乾燥したポリフェニレンエーテルを用いて重量平均分子量の測定を行なった。結果を表１に示した。
[Example 4]
A 10% aqueous solution of ethylenediaminetetraacetic acid tripotassium salt (a reagent manufactured by Dojindo Laboratories) was added to the polyphenylene ether mixture obtained in Reference Example, and the mixture was warmed to 40 ° C. Thereafter, hydroquinone (a reagent manufactured by Wako Pure Chemical Industries, Ltd.) was added little by little, and the temperature was kept at 40 ° C. until the slurry polyphenylene ether became white. Next, a sparger for introducing gas at the bottom of the polymerization tank, a stirring turbine blade and baffle, and a 1.5 liter jacketed first polymerization tank equipped with a reflux condenser in the vent gas line at the top of the polymerization tank at a flow rate of 600 ml / min. While blowing nitrogen gas, 347.9 g of a polyphenylene ether mixture was charged and stirred vigorously. Further, 320 g of xylene was gradually added with vigorous stirring. The mixture in the polymerization vessel was in the form of a slurry. Thereafter, heat treatment was performed at 70 ° C. for 1 hour in a nitrogen atmosphere. After the heat treatment, the mixture was cooled to room temperature, 480 g of methanol as a poor solvent was added to the obtained polyphenylene ether mixture, filtration was performed, and the residue was vacuum dried at 110 ° C. to obtain polyphenylene ether. The weight average molecular weight was measured using dried polyphenylene ether. The results are shown in Table 1.
［実施例６］
参考例で得られたポリフェニレンエーテル混合物にエチレンジアミン四酢酸３カリウム塩（同仁化学研究所製試薬）の１０％水溶液を添加し、４０℃に温めた。次いでハイドロキノン（和光純薬社製試薬）を少量ずつ添加し、スラリー状のポリフェニレンエーテルが白色となるまで、４０℃での保温を続けた。終了後、濾過して、濾残の湿潤ポリフェニレンエーテルをメタノール洗浄溶媒に投入し、４０℃で撹拌を行なった。続いて再び濾過し、濾残にメタノールをふりかけ洗浄し湿潤ポリフェニレンエーテルを得た。次いで１１０℃で真空乾燥し、乾燥ポリフェニレンエーテルを得た。得られた乾燥ポリフェニレンエーテルの重量平均分子量は５４９０であった。
次いで重合槽底部にガス導入の為のスパージャー、撹拌撹拌タービン翼及びバッフル、重合槽上部のベントガスラインに還流冷却器を備えた１．５リットルのジャケット付き重合槽に６００ｍｌ／分の流量で窒素ガスを吹き込みながら、乾燥ポリフェニレンエーテル２５ｇ、トルエン５００ｇを仕込み激しく撹拌しポリフェニレンエーテルをトルエン溶媒に溶解させ、ポリフェニレンエーテル溶液を得た。その後窒素雰囲気下において８０℃で２時間加熱処理を行なった。加熱処理後室温にまで冷却し、得られたポリフェニレンエーテル溶液に貧溶媒であるメタノールを７５０ｇ添加し濾過を行ない、濾残を１１０℃で真空乾燥しポリフェニレンエーテルを得た。乾燥したポリフェニレンエーテルを用いて重量平均分子量の測定を行なった。結果を表１に示した。
[Example 6]
A 10% aqueous solution of ethylenediaminetetraacetic acid tripotassium salt (a reagent manufactured by Dojindo Laboratories) was added to the polyphenylene ether mixture obtained in Reference Example, and the mixture was warmed to 40 ° C. Subsequently, hydroquinone (a reagent manufactured by Wako Pure Chemical Industries, Ltd.) was added little by little, and the temperature was kept at 40 ° C. until the slurry polyphenylene ether became white. After completion, the mixture was filtered, and the residual wet polyphenylene ether was added to a methanol washing solvent and stirred at 40 ° C. Subsequently, the mixture was filtered again, and the residue was sprinkled with methanol to obtain wet polyphenylene ether. Subsequently, it vacuum-dried at 110 degreeC and the dry polyphenylene ether was obtained. The resulting dry polyphenylene ether had a weight average molecular weight of 5490.
Next, a sparger for introducing gas at the bottom of the polymerization tank, a stirring and stirring turbine blade and baffle, a 1.5 liter jacketed polymerization tank equipped with a reflux condenser in the vent gas line at the top of the polymerization tank, and nitrogen at a flow rate of 600 ml / min. While blowing gas, 25 g of dry polyphenylene ether and 500 g of toluene were charged and stirred vigorously to dissolve the polyphenylene ether in a toluene solvent to obtain a polyphenylene ether solution. Thereafter, heat treatment was performed at 80 ° C. for 2 hours in a nitrogen atmosphere. After the heat treatment, the mixture was cooled to room temperature, 750 g of a poor solvent methanol was added to the obtained polyphenylene ether solution, filtration was performed, and the residue was vacuum dried at 110 ° C. to obtain polyphenylene ether. The weight average molecular weight was measured using dried polyphenylene ether. The results are shown in Table 1.
［比較例１］
参考例で得られたポリフェニレンエーテル混合物にエチレンジアミン四酢酸３カリウム塩（同仁化学研究所製試薬）の１０％水溶液を添加し、４０℃に温めた。次いでハイドロキノン（和光純薬社製試薬）を少量ずつ添加し、スラリー状のポリフェニレンエーテルが白色となるまで、４０℃での保温を続けた。終了後、濾過して、濾残の湿潤ポリフェニレンエーテルをメタノール洗浄溶媒に投入し、４０℃で撹拌を行なった。続いて再び濾過し、濾残にメタノールをふりかけ洗浄し湿潤ポリフェニレンエーテルを得た。次いで１１０℃で真空乾燥し、乾燥ポリフェニレンエーテルを得た。得られた乾燥ポリフェニレンエーテルの重量平均分子量は５７３０であった。
次いで、重合槽底部にガス導入の為のスパージャー、撹拌タービン翼及びバッフル、重合槽上部のベントガスラインに還流冷却器を備えた１．５リットルのジャケット付き重合槽に６００ｍｌ／分の流量で窒素ガスを吹き込みながら、乾燥ポリフェニレンエーテル８０ｇ、貧溶媒としてメタノール１８７．５ｇ、ｎ−ブタノール６７．０ｇを仕込み激しく撹拌し、良溶媒としてキシレン１３．４ｇを加えた。さらに、激しく撹拌しながらキシレン３２０ｇを除々に添加した。重合槽中の混合物はスラリー形態であり、操作は室温で行なった。次いで、貧溶媒であるメタノールを４８０ｇ添加後濾過し、濾残を１１０℃で真空乾燥しポリフェニレンエーテルを得た。乾燥したポリフェニレンエーテルを用いて重量平均分子量の測定を行なった。結果を表１に示した。
[Comparative Example 1]
A 10% aqueous solution of ethylenediaminetetraacetic acid tripotassium salt (a reagent manufactured by Dojindo Laboratories) was added to the polyphenylene ether mixture obtained in Reference Example, and the mixture was warmed to 40 ° C. Subsequently, hydroquinone (a reagent manufactured by Wako Pure Chemical Industries, Ltd.) was added little by little, and the temperature was kept at 40 ° C. until the slurry polyphenylene ether became white. After completion, the mixture was filtered, and the residual wet polyphenylene ether was added to a methanol washing solvent and stirred at 40 ° C. Subsequently, the mixture was filtered again, and the residue was sprinkled with methanol to obtain wet polyphenylene ether. Subsequently, it vacuum-dried at 110 degreeC and the dry polyphenylene ether was obtained. The weight average molecular weight of the obtained dry polyphenylene ether was 5730.
Next, nitrogen was introduced at a flow rate of 600 ml / min into a 1.5 liter jacketed polymerization tank equipped with a sparger for introducing gas at the bottom of the polymerization tank, a stirring turbine blade and baffle, and a reflux gas cooler in the vent gas line at the top of the polymerization tank. While blowing gas, 80 g of dry polyphenylene ether, 187.5 g of methanol as a poor solvent, and 67.0 g of n-butanol were charged and stirred vigorously, and 13.4 g of xylene was added as a good solvent. Further, 320 g of xylene was gradually added with vigorous stirring. The mixture in the polymerization tank was in the form of a slurry, and the operation was performed at room temperature. Subsequently, 480 g of methanol which is a poor solvent was added, followed by filtration. The residue was vacuum dried at 110 ° C. to obtain polyphenylene ether. The weight average molecular weight was measured using dried polyphenylene ether. The results are shown in Table 1.
［比較例２］
キシレン３２０ｇの代わりにトルエン３２０ｇとした以外の操作は比較例１と同様に行なった。結果を表１に示した。
[Comparative Example 2]
The same operation as in Comparative Example 1 was performed except that 320 g of toluene was used instead of 320 g of xylene. The results are shown in Table 1.
［比較例３］
参考例で得られたポリフェニレンエーテル混合物にエチレンジアミン四酢酸３カリウム塩（同仁化学研究所製試薬）の１０％水溶液を添加し、４０℃に温めた。次いでハイドロキノン（和光純薬社製試薬）を少量ずつ添加し、スラリー状のポリフェニレンエーテルが白色となるまで、４０℃での保温を続けた。終了後、濾過して、濾残の湿潤ポリフェニレンエーテルをメタノール洗浄溶媒に投入し、４０℃で撹拌を行なった。続いて再び濾過し、濾残にメタノールをふりかけ洗浄し湿潤ポリフェニレンエーテルを得た。次いで１１０℃で真空乾燥し、乾燥ポリフェニレンエーテルを得た。得られた乾燥ポリフェニレンエーテルの重量平均分子量は５４９０であった。
次いで重合槽底部にガス導入の為のスパージャー、撹拌撹拌タービン翼及びバッフル、重合槽上部のベントガスラインに還流冷却器を備えた１．５リットルのジャケット付き重合槽に６００ｍｌ／分の流量で窒素ガスを吹き込みながら、乾燥ポリフェニレンエーテル２５ｇ、トルエン５００ｇを仕込み激しく撹拌しポリフェニレンエーテルをトルエン溶媒に溶解させ、ポリフェニレンエーテル溶液を得た。操作は室温で行なった。得られたポリフェニレンエーテル溶液に貧溶媒であるメタノールを７５０ｇ添加し濾過を行ない、濾残を１１０℃で真空乾燥しポリフェニレンエーテルを得た。乾燥したポリフェニレンエーテルを用いて重量平均分子量の測定を行なった。結果を表１に示した。
[Comparative Example 3]
A 10% aqueous solution of ethylenediaminetetraacetic acid tripotassium salt (a reagent manufactured by Dojindo Laboratories) was added to the polyphenylene ether mixture obtained in Reference Example, and the mixture was warmed to 40 ° C. Subsequently, hydroquinone (a reagent manufactured by Wako Pure Chemical Industries, Ltd.) was added little by little, and the temperature was kept at 40 ° C. until the slurry polyphenylene ether became white. After completion, the mixture was filtered, and the residual wet polyphenylene ether was added to a methanol washing solvent and stirred at 40 ° C. Subsequently, the mixture was filtered again, and the residue was sprinkled with methanol to obtain wet polyphenylene ether. Subsequently, it vacuum-dried at 110 degreeC and the dry polyphenylene ether was obtained. The resulting dry polyphenylene ether had a weight average molecular weight of 5490.
Next, a sparger for introducing gas at the bottom of the polymerization tank, a stirring and stirring turbine blade and baffle, a 1.5 liter jacketed polymerization tank equipped with a reflux condenser in the vent gas line at the top of the polymerization tank, and nitrogen at a flow rate of 600 ml / min. While blowing gas, 25 g of dry polyphenylene ether and 500 g of toluene were charged and stirred vigorously to dissolve the polyphenylene ether in a toluene solvent to obtain a polyphenylene ether solution. The operation was performed at room temperature. To the obtained polyphenylene ether solution, 750 g of a poor solvent methanol was added and filtered, and the residue was vacuum dried at 110 ° C. to obtain polyphenylene ether. The weight average molecular weight was measured using dried polyphenylene ether. The results are shown in Table 1.
本発明により、ポリフェニレンエーテルの分子量を簡便に増大可能となるため、重合時の切り替えの煩雑さを低減し、様々な分子量のポリフェニレンエーテルを製造することができる。 According to the present invention, since the molecular weight of polyphenylene ether can be easily increased, the complexity of switching during polymerization can be reduced, and polyphenylene ethers having various molecular weights can be produced.
Claims (4)
Ｒ 1 Ｒ 2 ＮＨ （１）
（Ｒ 1 は炭素数１〜２０のアルキル基、置換アルキル基、Ｒ 2 はアリール基、置換アリール基を表す。）〕と酸素含有ガスの存在下で重合して得られ、その重量平均分子量が８００以上２００００以下であるポリフェニレンエーテルであることを特徴とするポリフェニレンエーテルの分子量増大方法。 A method for increasing the molecular weight of polyphenylene ether, wherein a mixture of an organic solvent and polyphenylene ether is heated in a range of 70 ° C. to 200 ° C. for 15 minutes or longer, wherein the polyphenylene ether before the heat treatment is a phenolic compound [provided that the formula ( The secondary amine represented by 1) is excluded.
R 1 R 2 NH (1)
(R 1 represents an alkyl group having 1 to 20 carbon atoms, a substituted alkyl group, R 2 represents an aryl group or a substituted aryl group.)] And an oxygen-containing gas, and has a weight average molecular weight of A method for increasing the molecular weight of polyphenylene ether, which is a polyphenylene ether having a molecular weight of 800 or more and 20000 or less .
Ｒ 1 Ｒ 2 ＮＨ （１）
（Ｒ 1 は炭素数１〜２０のアルキル基、置換アルキル基、Ｒ 2 はアリール基、置換アリール基を表す。）〕と酸素含有ガスの存在下で重合して得られ、重合終了時の重合溶剤の形態がスラリーであり、触媒及び酸素含有ガスを除去した後に該スラリーにポリフェニレンエーテルに対する良溶剤を添加し、スラリー形態を維持したまま不活性ガス雰囲気下で加熱処理することを特徴とする請求項１〜３のいずれかに記載のポリフェニレンエーテルの分子量増大方法。 The polyphenylene ether before heat treatment catalyzes a phenol compound [however, the secondary amine represented by the formula (1) is excluded.
R 1 R 2 NH (1)
(R 1 represents an alkyl group having 1 to 20 carbon atoms, a substituted alkyl group, and R 2 represents an aryl group or a substituted aryl group.)] And polymerization at the end of the polymerization. The solvent is a slurry, and after removing the catalyst and the oxygen-containing gas, a good solvent for polyphenylene ether is added to the slurry, and heat treatment is performed in an inert gas atmosphere while maintaining the slurry. Item 4. The method for increasing the molecular weight of polyphenylene ether according to any one of Items 1 to 3 .
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