JP2000281799A - Preparation of polyphenylene ether resin particulate - Google Patents
Preparation of polyphenylene ether resin particulateInfo
- Publication number
- JP2000281799A JP2000281799A JP11088994A JP8899499A JP2000281799A JP 2000281799 A JP2000281799 A JP 2000281799A JP 11088994 A JP11088994 A JP 11088994A JP 8899499 A JP8899499 A JP 8899499A JP 2000281799 A JP2000281799 A JP 2000281799A
- Authority
- JP
- Japan
- Prior art keywords
- polyphenylene ether
- polymerization reaction
- reaction solution
- polymerization
- aqueous dispersion
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ポリフェニレンエ
ーテルの製造方法に関する。詳しくは造粒時に平均粒径
のそろった粒子状のポリフェニレンエーテルの製造方法
に関する。The present invention relates to a method for producing polyphenylene ether. More specifically, the present invention relates to a method for producing particulate polyphenylene ether having a uniform average particle size during granulation.
【０００２】[0002]
【従来の技術】ポリフェニレンエーテルは、フェノール
化合物を銅、マンガン、あるいはコバルトを含有する酸
化カップリング重合触媒を用い、芳香族系溶剤、あるい
は芳香族系溶剤と非溶剤の混合溶媒中で酸素の存在下で
重合し得られる。反応後のポリフェニレンエーテル溶液
は反応停止操作および触媒除去操作後、ポリフェニレン
エーテルの非溶媒中に投入され造粒される。2. Description of the Related Art Polyphenylene ether is obtained by using an oxidative coupling polymerization catalyst containing a phenol compound with copper, manganese, or cobalt, and the presence of oxygen in an aromatic solvent or a mixed solvent of an aromatic solvent and a non-solvent. It is polymerized below. After the reaction is stopped and the catalyst is removed, the polyphenylene ether solution after the reaction is charged into a non-solvent of polyphenylene ether and granulated.
【０００３】しかしながら、ポリフェニレンエーテル製
造工程の造粒には、多量の非溶媒が必要となりまた溶媒
の回収にも多量のエネルギーが必要となる。さらにこの
ようにして造粒されたポリフェニレンエーテルの粒子は
微細な粉末の割合が多く、後工程に飛散や成形時のホッ
パーから押し出し機の食い込み不良といった問題が発生
していた。[0003] However, a large amount of non-solvent is required for the granulation in the polyphenylene ether production process, and a large amount of energy is required to recover the solvent. Furthermore, the particles of the polyphenylene ether granulated in this manner have a large proportion of fine powder, and there have been problems such as scattering in a subsequent step and poor penetration of an extruder from a hopper during molding.
【０００４】これらの問題点を解決するため、種々の検
討が行われている。例えば、非溶媒を用いずにポリフェ
ニレンエーテル溶液を水中に分散させ造粒する検討（Ｕ
ＳＰ−４２６３４２６）がおこなわれているが、造粒時
に粒子が会合して著しく大きな塊となってしまい後工程
の取り扱いが非常に難しくなってしまう。また造粒時の
粒径の増大化検討は、造粒方法（特公昭４５−５８７、
特公昭６０−２３６９６）、微小粒子の粒径増加方法
（特公昭５５−１７７７５、特開昭６３−２４３１２
９）、粒径増大補助剤の検討（特開昭６２−１７２０２
２）などが挙げられる。Various studies have been made to solve these problems. For example, a study of dispersing and granulating a polyphenylene ether solution in water without using a non-solvent (U
(SP-4263426), however, the particles are associated with each other at the time of granulation to form a remarkably large mass, which makes handling of the subsequent process very difficult. In addition, the study of increasing the particle size during granulation was conducted using a granulation method (Japanese Patent Publication No. 45-587,
JP-B-60-23696), a method for increasing the particle size of fine particles (JP-B-55-17775, JP-A-63-24243)
9), Examination of particle size increasing auxiliary agent (JP-A-62-17202)
2) and the like.
【０００５】しかしながら、上記に提案された方法だけ
では、造粒後のポリフェニレンエーテル粉末に微細な粉
末の割合が多く含まれ、先に挙げた問題点を全て解決す
るには不十分であった。[0005] However, the method proposed above alone is not sufficient to solve all of the above-mentioned problems because the granulated polyphenylene ether powder contains a large proportion of fine powder.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、従来のよう
な欠点を克服して、ポリフェニレンエーテル溶液から効
率よく、しかも平均粒径のそろったポリフェニレンエー
テルの製造方法を提供することである。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for efficiently producing polyphenylene ether having a uniform average particle size from a polyphenylene ether solution by overcoming the conventional disadvantages.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、上記事情
に鑑み、鋭意検討を行った結果、ポリフェニレンエーテ
ルが均一に溶解した重合反応液を水と混合し、かつ混合
溶液の少なくとも一部を湿式粉砕器に循環し粉砕するこ
とにより、造粒時に平均粒径のそろったポリフェニレン
エーテル粒子が得られることを見い出し、本発明を完成
するに至った。Means for Solving the Problems In view of the above circumstances, the present inventors have made intensive studies, and as a result, mixed a polymerization reaction solution in which polyphenylene ether was uniformly dissolved with water, and at least a part of the mixed solution. Was circulated through a wet pulverizer and pulverized to obtain polyphenylene ether particles having a uniform average particle size during granulation, thereby completing the present invention.
【０００８】即ち、本発明は、（Ａ）金属塩とアミンか
らなる錯体触媒の存在下、ポリフェニレンエーテルの良
溶媒、または良溶媒と非溶媒との混合溶媒を用いて、１
種あるいは２種以上のフェノール化合物を酸化重合させ
ポリフェニレンエーテルが均一に溶解した重合反応液を
製造し、（Ｂ）得られた重合反応液に、重合停止剤、ま
たは重合停止剤と還元剤とを接触させ触媒を除去した重
合反応液に、（Ｃ）触媒を除去した重合反応液を、水に
添加し攪拌して水分散液とし、攪拌もしくは水分散液を
循環しながら加温することにより脱溶媒して造粒するに
際し、（Ｄ）水分散液の少なくとも一部を湿式粉砕機に
循環し粉砕するポリフェニレンエーテル樹脂粉粒体の製
造方法である。That is, the present invention provides a method for preparing a polyphenylene ether using a good solvent or a mixed solvent of a good solvent and a non-solvent in the presence of (A) a complex catalyst comprising a metal salt and an amine.
One or more phenolic compounds are oxidatively polymerized to produce a polymerization reaction solution in which polyphenylene ether is uniformly dissolved, and (B) a polymerization terminator or a polymerization terminator and a reducing agent are added to the obtained polymerization reaction solution. To the polymerization reaction solution from which the catalyst has been removed by contact, the polymerization reaction solution from which the catalyst (C) has been removed is added to water and stirred to form an aqueous dispersion, which is then removed by heating while stirring or circulating the aqueous dispersion. (D) A method for producing polyphenylene ether resin powder particles in which at least a part of an aqueous dispersion is circulated and pulverized in a wet pulverizer when granulating with a solvent.
【０００９】[0009]
【発明の実施の形態】本発明におけるポリフェニレンエ
ーテルは、一般式（１）で表される化合物から酸化重合
によって誘導されるものである。BEST MODE FOR CARRYING OUT THE INVENTION The polyphenylene ether in the present invention is derived from a compound represented by the general formula (1) by oxidative polymerization.
【化１】 （式中、Ｒ1 、Ｒ2 、Ｒ3 及び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、フェニル基又は置換フェニル基
である。）Embedded image (In the formula, R 1 , R 2 , R 3 and R 4 are each independently hydrogen, an alkyl group, a substituted alkyl group, a halogen group, an aryl group, a substituted aryl group, a phenyl group or a substituted phenyl group.)
【００１０】代表的なポリフェニレンエーテルは、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
ーテル等のホモポリマー、また２，６−ジメチルフェノ
ールに共重合体成分として２，３，６−トリメチルフェ
ノールおよびｏ−クレゾールの１種あるいは両方を組み
合わせたポリフェニレンエーテル共重合体等が挙げられ
る。Representative polyphenylene ethers 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-)
Homopolymers such as phenylene) ether, poly (2-methyl-6-chloroethyl-1,4-phenylene) ether and poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ether; Polyphenylene ether copolymers obtained by combining dimethylphenol with one or both of 2,3,6-trimethylphenol and o-cresol as copolymer components are exemplified.
【００１１】また、本発明のポリフェニレンエーテルに
は、本発明の主旨に反さない限り、従来ポリフェニレン
エーテル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
んでいてもよい。例えば、特開平１−２９７４２８号公
報及び特開昭６３−３０１２２２号公報に記載の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
ト等や、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が挙げられる。さらに、
炭素−炭素二重構造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（例えば特開平２−２７６８２３号
公報、特開昭６３−１０８０５９号公報、特開昭５９−
５９７２４号公報）も含むことができる。The polyphenylene ether of the present invention contains, as a partial structure, various other phenylene ether units which have been proposed to be allowed to exist in the polyphenylene ether so far as they do not contradict the gist of the present invention. You may go out. For example, Japanese Patent Application Laid-Open Nos. 1-297428 and 63-301222 disclose 2-
(Dialkylaminomethyl) -6-methylphenylene ether unit, 2- (N-alkyl-N-phenylaminomethyl) -6-methylphenylene ether unit, and a small amount of diphenoquinone or the like bonded in the main chain of polyphenylene ether resin What was done. further,
Polyphenylene ether modified with a compound having a carbon-carbon double structure (for example, JP-A-2-276823, JP-A-63-108059, JP-A-59-1984)
59724).
【００１２】本発明に用いるポリフェニレンエーテル樹
脂の分子量は３０℃クロロホルム中の固有粘度が０．１
〜０．７であるのが好ましい。更に好ましくは０．２〜
０．６の範囲にあるポリフェニレンエーテルが本発明の
効果が著しく現れる。The polyphenylene ether resin used in the present invention has a molecular weight of 30.degree.
Preferably it is ~ 0.7. More preferably 0.2 to
A polyphenylene ether in the range of 0.6 remarkably exerts the effect of the present invention.
【００１３】本発明のポリフェニレンエーテルは、例え
ば、特公昭４２−３１９５号公報、特公昭４５−２３５
５５号公報、特開昭６４−３３１３１号公報等に例示さ
れるように、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される。
重合溶媒は、例えばポリフェニレンエーテルの良溶媒で
あるベンゼン、トルエン、キシレン等の芳香族炭化水
素、ジクロロメタン、クロロホルム、ジクロルベンゼン
等のハロゲン化炭化水素、ニトロベンゼン等のニトロ化
合物等が挙げられる。The polyphenylene ether of the present invention is disclosed in, for example, JP-B-42-3195 and JP-B-45-235.
As exemplified in JP-A-55-33, JP-A-64-33131 and the like, a phenol compound is oxidatively polymerized using a catalyst comprising a combination of a metal salt and various amines.
Examples of the polymerization solvent include aromatic hydrocarbons such as benzene, toluene, and xylene, which are good solvents for polyphenylene ether, halogenated hydrocarbons such as dichloromethane, chloroform, and dichlorobenzene, and nitro compounds such as nitrobenzene.
【００１４】また、前記の良溶媒にポリフェニレンエー
テルの非溶媒であるメタノール、エタノール等のアルコ
ール類、ヘキサン、ヘプタン等の脂肪族炭化水素類、ア
セトン、メチルエチルケトン等のケトン類、酢酸エチル
等のエステル類、ジメチルホルムアミド等のアミド類等
を任意の割合および組成で混合し重合溶媒として用いる
ことができる。重合溶媒中の非溶媒の割合が多くなると
重合中にポリフェニレンエーテルが析出してくる沈澱重
合となるが、本発明では重合後にポリフェニレンエーテ
ルが析出しない溶液重合が溶液の移送や反応停止工程あ
るいは触媒分離工程等におけるハンドリングの点で好ま
しい。The above-mentioned good solvents include non-solvents of polyphenylene ether, such as alcohols such as methanol and ethanol, aliphatic hydrocarbons such as hexane and heptane, ketones such as acetone and methyl ethyl ketone, and esters such as ethyl acetate. And amides such as dimethylformamide and the like can be mixed in an arbitrary ratio and composition and used as a polymerization solvent. When the proportion of non-solvent in the polymerization solvent increases, polyphenylene ether precipitates during the polymerization, resulting in precipitation polymerization.However, in the present invention, solution polymerization in which the polyphenylene ether does not precipitate after the polymerization is performed by transferring the solution, stopping the reaction, or separating the catalyst. It is preferable in terms of handling in the process and the like.
【００１５】本発明におけるポリフェニレンエーテルが
均一に溶解した重合反応液はポリフェニレンエーテル重
合後のポリマー含有溶液であり、ポリフェニレンエーテ
ルの濃度は重量で５〜７０％、好ましくは１０〜５０％
の範囲である。また、ポリフェニレンエーテル重合反応
液は加熱等による濃縮工程により、任意の濃度に調整す
る事も可能である。重合反応液にはポリフェニレンエー
テルのほかに重合触媒や、触媒除去のための薬品、副生
成物除去のための薬品等が含まれていてもかまわない。The polymerization reaction solution in which polyphenylene ether is uniformly dissolved in the present invention is a polymer-containing solution after polyphenylene ether polymerization, and the concentration of polyphenylene ether is 5 to 70% by weight, preferably 10 to 50%.
Range. The concentration of the polyphenylene ether polymerization reaction solution can be adjusted to an arbitrary concentration by a concentration step by heating or the like. The polymerization reaction solution may contain, in addition to polyphenylene ether, a polymerization catalyst, a chemical for removing the catalyst, a chemical for removing by-products, and the like.
【００１６】本発明において、ポリフェニレンエーテル
重合反応液は、攪拌機付きで、かつ湿式粉砕機を通る循
環経路付きの槽において、水とバッチあるいは連続的に
混合される。攪拌機は同方向あるいは往復回転いずれで
もかまわず、また、水とポリフェニレンエーテル重合反
応液の混合液の一部は湿式粉砕機を経由して槽内を循環
する。湿式粉砕機は溶液内の固形成分を粉砕できる構造
のものが良く、例えば、相川鉄工（株）製のゴラトール
（商品名）や小松ゼノア（株）製のディスインテグレー
ター（商品名）等の構造を持つものが好ましい。湿式粉
砕機を循環させない場合は、ポリフェニレンエーテル重
合液が造粒する際に粒子の会合が起きて著しく大きな塊
ができてしまうので好ましくない。In the present invention, the polyphenylene ether polymerization reaction solution is mixed batchwise or continuously with water in a tank equipped with a stirrer and having a circulation path passing through a wet mill. The stirrer may be rotated in the same direction or reciprocatingly, and a part of the mixture of the water and the polyphenylene ether polymerization reaction solution is circulated in the tank via a wet pulverizer. The wet crusher preferably has a structure capable of crushing solid components in a solution. For example, a structure such as Golator (trade name) manufactured by Aikawa Iron Works Co., Ltd. or Disintegrator (trade name) manufactured by Komatsu Zenoa Co., Ltd. is used. Having one is preferred. If the wet pulverizer is not circulated, it is not preferable because particles are associated with each other when the polyphenylene ether polymerization liquid is granulated, resulting in an extremely large lump.
【００１７】ポリフェニレンエーテル重合反応液／水の
重量比は０．０１〜１の範囲でおこなわれるが、好まし
くは０．１〜０．５の範囲でおこなわれる。造粒は１段
あるいは２段以上の直列に連結した槽でおこなわれ、温
度４０〜１００℃の範囲で脱溶剤される。２段以上直列
に連結した槽で造粒する場合、各槽の温度は４０〜１０
０℃の範囲で任意に選べばよいが、少なくとも１槽は本
発明記載の攪拌機付きで、かつ湿式粉砕機を通る循環経
路付きの槽としなければならい。槽内の滞留時間は１〜
１２０分必要で、造粒されたポリフェニレンエーテルは
連続あるいはバッチで遠心分離機や真空ろ過等により固
液分離される。The weight ratio of the polyphenylene ether polymerization reaction liquid / water is in the range of 0.01 to 1, but preferably in the range of 0.1 to 0.5. Granulation is performed in one or two or more series-connected tanks, and the solvent is removed at a temperature in the range of 40 to 100 ° C. When granulating in two or more stages connected in series, the temperature of each tank is 40 to 10
It may be arbitrarily selected within the range of 0 ° C., but at least one tank must be a tank provided with the stirrer according to the present invention and provided with a circulation path passing through the wet mill. The residence time in the tank is 1 to
After 120 minutes, the granulated polyphenylene ether is solid-liquid separated continuously or batchwise by a centrifuge or vacuum filtration.
【００１８】固液分離後、湿潤した造粒ポリフェニレン
エーテルは８０℃〜２００℃で不活性ガス雰囲気あるい
は空気雰囲気等の酸素存在下で連続的またはバッチで乾
燥させられる。不活性ガスは一般に、窒素、アルゴン、
ヘリウム等が使用される。乾燥条件に規定はないが、乾
燥後のポリフェニレンエーテル粒子の５０％重量平均径
は０．２〜２ｍｍの範囲にあることが好ましい。それよ
り平均粒径が小さいと後工程における飛散や成形時のホ
ッパーから押し出し機の食い込み不良が発生し、粒径が
大きいとポリフェニレンエーテルと他樹脂と溶融混練の
際に均一に混ぜる事ができない混練不良の問題が起き
る。After solid-liquid separation, the wet granulated polyphenylene ether is dried continuously or batchwise at 80 ° C. to 200 ° C. in the presence of oxygen such as an inert gas atmosphere or an air atmosphere. Inert gases are generally nitrogen, argon,
Helium or the like is used. Although the drying conditions are not specified, the 50% weight average diameter of the polyphenylene ether particles after drying is preferably in the range of 0.2 to 2 mm. If the average particle size is smaller than this, scattering in the post-process or poor penetration of the extruder from the hopper at the time of molding will occur, and if the particle size is larger, it will not be possible to mix uniformly with polyphenylene ether and other resins during melt kneading. Bad problems arise.
【００１９】本発明方法によれば、乾燥後の固形化ポリ
フェニレンエーテル樹脂の平均粒径が０．２〜２ｍｍ、
嵩比重が０．３〜０．６ｇ／ｃｃのものが得られるた
め、押出機によって溶融混練してペレット化する際に、
食い込み不良とか未溶融部分が残るなどのトラブルもな
く、成形材料として好適に使用することが可能である。According to the method of the present invention, the solidified polyphenylene ether resin after drying has an average particle size of 0.2 to 2 mm,
Since a bulk specific gravity of 0.3 to 0.6 g / cc is obtained, when melt-kneading with an extruder and pelletizing,
It can be suitably used as a molding material without troubles such as poor biting or unmelted portions remaining.
【００２０】[0020]
【実施例】以下に具体例により本発明を説明するが、本
発明は、これらの実施例によって何ら限定される物では
い。EXAMPLES The present invention will be described below with reference to specific examples, but the present invention is not limited to these examples.
【００２１】下記の操作にて得られたポリフェニレンエ
ーテル粒子は窒素を５Ｎｍ3/ｈで流しながら１３５〜１
４０℃で６時間以上乾燥して、ポリフェニレンエーテル
の乾粉を得、乾粉粒子の粒度分布、平均粒径及び１００
μｍ以下の粒子の割合を測定した。粒度分布及び１４０
メッシュパスの１００μｍ以下の粒子の割合は、ＪＩＳ
規格（ＪＩＳ Ｚ８８０１）に準じて行った。１０、１
８．５、６０、１２０、１４０、２８０メッシュの篩を
用い、ＴＮＫ篩振動機（タナカ化学機器社製）を用いて
１０分間振動し篩をかけることで測定した。また、平均
粒径は５０％重量平均径により求めた。The polyphenylene ether particles obtained by the following operation were supplied to the polymer at 135 to 1 while flowing nitrogen at 5 Nm 3 / h.
After drying at 40 ° C. for 6 hours or more, a dry powder of polyphenylene ether was obtained.
The proportion of particles less than μm was measured. Particle size distribution and 140
The ratio of particles having a size of 100 μm or less in the mesh path is determined according to JIS.
The measurement was performed according to the standard (JIS Z8801). 10, 1
Using a sieve of 8.5, 60, 120, 140, or 280 mesh, it was measured by vibrating for 10 minutes using a TNK sieve vibrator (manufactured by Tanaka Chemical Instruments) and sieving. The average particle size was determined from a 50% weight average diameter.
【００２２】押出機による押出試験は、池貝鉄工（株）
製２軸押出機（ＰＣＭ−３０）を用い、乾燥後のポリフ
ェニレンエーテル粉体４０重量部とスチレン系樹脂（電
気化学工業（株）製、商品名HI-UM-301 ）６０重量部を
ミキサーでよく混合した後、溶融混練しストランドを切
断してペレット状の樹脂組成物のペレットを得た。押し
出し機のストランド中に発生するの不完全溶融のポリフ
ェニレンエーテル樹脂を目視で観察し混練不良を判定し
た。The extrusion test by the extruder was performed by Ikegai Iron Works Co., Ltd.
Using a twin-screw extruder (PCM-30), 40 parts by weight of dried polyphenylene ether powder and 60 parts by weight of a styrene resin (trade name: HI-UM-301, manufactured by Denki Kagaku Kogyo KK) using a mixer. After mixing well, the mixture was melt-kneaded and the strand was cut to obtain pellets of the resin composition in the form of pellets. The incompletely melted polyphenylene ether resin generated in the strands of the extruder was visually observed to determine a kneading defect.
【００２３】実施例１ 臭化第二銅２ｋｇをジブチルアミン３５ｋｇ、トルエン
８００ｋｇ、に溶解させた。この触媒溶液に、２，６−
ジメチルフェノール２００ｋｇをトルエン５００ｋｇに
溶かした溶液を加えた。これらの混合液を反応器内に
て、酸素を供給しながら４０℃で重合を３時間行った。
反応停止後、水と接触させて反応液から触媒を除去し、
ポリフェニレンエーテルが均一に溶解した重合反応液を
得た。このポリフェニレンエーテル重合反応液を攪拌し
ながら９０℃の温水中に添加した。この時ポリフェニレ
ンエーテル重合反応液／水の重量比は０．１であった。
この水分散液を９０℃に保ちつつ、湿式粉砕機（商品
名：ゴラトール）に全水分散液の２０倍／時間の量で循
環して湿式粉砕を１時間行った後、水分散液を抜き出し
た。固液分離後、乾燥したポリフェニレンエーテル粉体
の粒度を振動篩で測定した。平均粒径は０．６６ｍｍ、
嵩比重は０．３９であった。押し出し機試験をおこなっ
たところ混練不良は認められなかった。Example 1 2 kg of cupric bromide was dissolved in 35 kg of dibutylamine and 800 kg of toluene. 2,6-
A solution prepared by dissolving 200 kg of dimethylphenol in 500 kg of toluene was added. These mixed solutions were polymerized in a reactor at 40 ° C. for 3 hours while supplying oxygen.
After the reaction is stopped, the catalyst is removed from the reaction solution by contacting with water,
A polymerization reaction solution in which polyphenylene ether was uniformly dissolved was obtained. This polyphenylene ether polymerization reaction solution was added to warm water at 90 ° C. while stirring. At this time, the weight ratio of the polyphenylene ether polymerization reaction liquid / water was 0.1.
The aqueous dispersion was circulated through a wet pulverizer (trade name: Golator) at a rate of 20 times / hour of the total aqueous dispersion while the aqueous dispersion was maintained at 90 ° C., and wet-pulverized for 1 hour. Was. After the solid-liquid separation, the particle size of the dried polyphenylene ether powder was measured with a vibration sieve. The average particle size is 0.66 mm,
The bulk specific gravity was 0.39. When an extruder test was conducted, no kneading defects were found.
【００２４】実施例２ ポリフェニレンエーテル重合反応液／水の重量比は０．
００５、かつ湿式粉砕機（商品名：ゴラトール）に全水
分散液の２０倍／時間の量で循環した以外は実施例１と
同じ方法により乾燥ポリフェニレンエーテル粉体を得
た。平均粒径は０．４８ｍｍ、嵩比重は０．３２であっ
た。押し出し機試験をおこなったところ混練不良は認め
られなかった。Example 2 The weight ratio of the polyphenylene ether polymerization reaction solution / water was 0.1%.
Dry polyphenylene ether powder was obtained in the same manner as in Example 1, except that the mixture was circulated through a wet pulverizer (trade name: Golator) at a rate of 20 times / hour of the total aqueous dispersion. The average particle size was 0.48 mm, and the bulk specific gravity was 0.32. When an extruder test was conducted, no kneading defects were found.
【００２５】比較例１ ポリフェニレンエーテル重合反応液／水の重量比は０．
１、かつ湿式粉砕機（商品名：ゴラトール）に全水分散
液を循環させなかった以外は実施例１と同じ方法により
乾燥ポリフェニレンエーテル粉体を得た。ポリフェニレ
ンエーテル粉体の粒径は９０重量％以上が１０メッシュ
以上であり、嵩比重は０．２７であった。押し出し機試
験をおこなったところ混練不良が認められた。Comparative Example 1 The weight ratio of the polyphenylene ether polymerization reaction solution / water was 0.1%.
1 and a dry polyphenylene ether powder was obtained in the same manner as in Example 1 except that the whole aqueous dispersion was not circulated through a wet pulverizer (trade name: Golator). The particle size of the polyphenylene ether powder was 10 mesh or more at 90% by weight or more, and the bulk specific gravity was 0.27. When an extruder test was performed, kneading defects were found.
【００２６】[0026]
【発明の効果】本発明の方法によれば、ポリフェニレン
エーテル製造の造粒時に、ポリフェニレンエーテルが均
一に溶解した重合反応液を水と混合し、かつ混合溶液の
少なくとも一部を湿式粉砕器に循環し粉砕することによ
り、平均粒径のそろったポリフェニレンエーテル粒子を
造粒できる。According to the method of the present invention, at the time of granulation in the production of polyphenylene ether, a polymerization reaction solution in which polyphenylene ether is uniformly dissolved is mixed with water, and at least a part of the mixed solution is circulated to a wet mill. Then, polyphenylene ether particles having a uniform average particle diameter can be granulated.
フロントページの続き (72)発明者 山田 健二 三重県四日市市日永東二丁目４番16号 三 菱瓦斯化学株式会社四日市工場内 Ｆターム(参考） 4F070 AA52 AC12 AE28 DA42 DA44 DA45 DC07 DC08 4J005 AA24 AA26 BB02 BC00 Continuation of the front page (72) Inventor Kenji Yamada 2-4-1, Hinagahigashi 2-chome, Yokkaichi-shi, Mie F-term (reference) 4F070 AA52 AC12 AE28 DA42 DA44 DA45 DC07 DC08 4J005 AA24 AA26 BB02 BC00
Claims (6)
の存在下、ポリフェニレンエーテルの良溶媒、または良
溶媒と非溶媒との混合溶媒を用いて、１種あるいは２種
以上のフェノール化合物を酸化重合させポリフェニレン
エーテルが均一に溶解した重合反応液を製造し、（Ｂ）
得られた重合反応液に、重合停止剤、または重合停止剤
と還元剤とを接触させ触媒を除去した重合反応液に、
（Ｃ）触媒を除去した重合反応液を、水に添加し攪拌し
て水分散液とし、攪拌もしくは水分散液を循環しながら
加温することにより脱溶媒して造粒するに際し、（Ｄ）
水分散液の少なくとも一部を湿式粉砕機に循環し粉砕す
ることを特徴とするポリフェニレンエーテル樹脂粉粒体
の製造方法。1. A phenol compound of one kind or two or more kinds using a good solvent of polyphenylene ether or a mixed solvent of a good solvent and a non-solvent in the presence of (A) a complex catalyst comprising a metal salt and an amine. (B) preparing a polymerization reaction solution in which polyphenylene ether is uniformly dissolved by oxidative polymerization;
To the obtained polymerization reaction solution, a polymerization terminator, or a polymerization reaction solution obtained by contacting a polymerization terminator and a reducing agent to remove a catalyst,
(C) The polymerization reaction solution from which the catalyst has been removed is added to water and stirred to form an aqueous dispersion, and the solvent is removed by stirring or heating while circulating the aqueous dispersion to form a granule.
A method for producing polyphenylene ether resin particles, wherein at least a part of the aqueous dispersion is circulated through a wet pulverizer and pulverized.
用いられるポリフェニレンエーテル良溶媒がベンゼン、
トルエン及びキシレンからなる群から選ばれる少なくと
も１種である請求項１記載のポリフェニレンエーテル樹
脂粉粒体の製造方法。2. The polyphenylene ether good solvent used in the polyphenylene ether polymerization reaction solution is benzene,
The method for producing a polyphenylene ether resin powder according to claim 1, which is at least one selected from the group consisting of toluene and xylene.
用いられる錯体触媒の金属塩が銅、マンガン又はコバル
トからなる群から選ばれる少なくとも１種である請求項
１記載のポリフェニレンエーテル樹脂粉粒体の製造方
法。3. The method for producing polyphenylene ether resin particles according to claim 1, wherein the metal salt of the complex catalyst used in the polyphenylene ether polymerization reaction solution is at least one selected from the group consisting of copper, manganese and cobalt.
水の重量比が０．０１〜１．０の範囲にある請求項１記
載のポリフェニレンエーテル樹脂粉粒体の製造方法。4. A polymerization reaction solution of polyphenylene ether /
The method for producing a polyphenylene ether resin powder according to claim 1, wherein the weight ratio of water is in the range of 0.01 to 1.0.
環量が全水分散液の１〜３０倍／時間である請求項１記
載のポリフェニレンエーテル樹脂粉粒体の製造方法。5. The method for producing a polyphenylene ether resin powder according to claim 1, wherein the circulation amount of the aqueous dispersion in the granulation step to the wet mill is 1 to 30 times / hour of the total aqueous dispersion.
樹脂の平均粒径が０．２〜２ｍｍ、嵩比重が０．３〜
０．６ｇ／ｃｃである請求項１記載のポリフェニレンエ
ーテル樹脂粉粒体の製造方法。6. The solidified polyphenylene ether resin after drying has an average particle diameter of 0.2 to 2 mm and a bulk specific gravity of 0.3 to 0.3.
The method for producing a polyphenylene ether resin powder according to claim 1, wherein the amount is 0.6 g / cc.
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|---|---|---|---|
| JP08899499A JP4214336B2 (en) | 1999-03-30 | 1999-03-30 | Method for producing polyphenylene ether resin powder |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08899499A JP4214336B2 (en) | 1999-03-30 | 1999-03-30 | Method for producing polyphenylene ether resin powder |
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|---|---|
| JP2000281799A true JP2000281799A (en) | 2000-10-10 |
| JP4214336B2 JP4214336B2 (en) | 2009-01-28 |
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| JP08899499A Expired - Fee Related JP4214336B2 (en) | 1999-03-30 | 1999-03-30 | Method for producing polyphenylene ether resin powder |
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| WO2003064499A1 (en) * | 2002-02-01 | 2003-08-07 | Asahi Kasei Chemicals Corporation | Method for precipitation of polyphenylene ether |
| JP2005509071A (en) * | 2001-11-12 | 2005-04-07 | ゼネラル・エレクトリック・カンパニイ | Production method of poly (arylene ether) and poly (arylene ether) produced by the method |
| WO2007139172A1 (en) * | 2006-05-25 | 2007-12-06 | Mitsubishi Gas Chemical Company, Inc. | Method for producing phenylene ether oligomer |
| JP2009221403A (en) * | 2008-03-18 | 2009-10-01 | Asahi Kasei Chemicals Corp | Method for producing polyphenylene ether |
| WO2012050138A1 (en) | 2010-10-13 | 2012-04-19 | 旭化成ケミカルズ株式会社 | Polyphenylene ether powder and polyphenylene ether composition |
| US20130231430A1 (en) | 2010-10-13 | 2013-09-05 | Asahi Kasei Chemicals Corporation | Polyphenylene ether, resin composition, and molded body of resin composition |
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| JPWO2003064499A1 (en) * | 2002-02-01 | 2005-05-26 | 旭化成ケミカルズ株式会社 | Precipitation method of polyphenylene ether |
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| WO2012050138A1 (en) | 2010-10-13 | 2012-04-19 | 旭化成ケミカルズ株式会社 | Polyphenylene ether powder and polyphenylene ether composition |
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