JPS5832619A - Preparation of polyoxymethylene - Google Patents

Preparation of polyoxymethylene

Info

Publication number
JPS5832619A
JPS5832619A JP12972781A JP12972781A JPS5832619A JP S5832619 A JPS5832619 A JP S5832619A JP 12972781 A JP12972781 A JP 12972781A JP 12972781 A JP12972781 A JP 12972781A JP S5832619 A JPS5832619 A JP S5832619A
Authority
JP
Japan
Prior art keywords
paddle
reactor
paddles
trioxane
polyoxymethylene
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
Application number
JP12972781A
Other languages
Japanese (ja)
Other versions
JPS6214163B2 (en
Inventor
Junzo Masamoto
正本 順三
Toshiyuki Iwasako
祝迫 敏之
Toshio Inoue
俊夫 井上
Kazuhiko Matsuzaki
一彦 松崎
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
Original Assignee
Asahi Chemical Industry Co Ltd
Asahi Kasei Kogyo KK
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Asahi Chemical Industry Co Ltd, Asahi Kasei Kogyo KK filed Critical Asahi Chemical Industry Co Ltd
Priority to JP12972781A priority Critical patent/JPS5832619A/en
Publication of JPS5832619A publication Critical patent/JPS5832619A/en
Publication of JPS6214163B2 publication Critical patent/JPS6214163B2/ja
Granted legal-status Critical Current

Links

Landscapes

  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

PURPOSE:To obtain the titled polymer continuously without damaging the inner wall of a reactor and causing the deposition of scale, by polymerizing trioxane by a two barrel cylindrical reactor having two rotating shafts equipped with lamellar paddles having cross sections like a convex lens with their tips cut by symmetrical curved lines of circular arcs. CONSTITUTION:The two rotating shafts 2 and 2' parallel to each other provided with a large number of the paddles 3 and 3' respectively, which are lamellar and have shapes of cross sections like a convex lenses with their tips cut by curved lines of circular arcs symmetrical about the longer axes of the paddles, are used. A reactor having the two rotating shafts put in the two barrel cylindrical cases 1 and 1' equipped with the inner wall face along the circular curved surface of the rotated paddles 3 and 3' is used, trioxane or a mixture of trioxane and a copolymer are introduced from the feed opening 5 to the reactor, each rotating shaft is revolved in the same direction, and the jacket 4 is heated to carry out polymerization. The desired powdery polymer is recovered continuously from the outlet 6.

Description

【発明の詳細な説明】 本発明は、ポリオキシメチレンの製造方法に関し、さら
に詳しくは、トリオキサンを出発主原料として粉末状ポ
リオキシメチレンを連続的に製造するだめの改良方法に
関するものである。
DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polyoxymethylene, and more particularly to an improved method for continuously producing powdered polyoxymethylene using trioxane as the main starting material.

ポリオキシメチレンは、優れた耐摩耗性や摩擦特性を有
し、電気部品、自動車部品、機械部品等に広く利用され
ている工業的に有用なエンジニアリングプラスチックス
である。
Polyoxymethylene is an industrially useful engineering plastic that has excellent wear resistance and friction properties and is widely used in electrical parts, automobile parts, mechanical parts, etc.

このポリオキシメチレンは、これまで触媒の存在下に、
トリオキサンの単独重合させる方法又はトリオキサンと
エチレンオキシドあるいはジオキソラン、ジオキソラン
のような環状ホルマールとの共重合させる方法によシ製
造されている。
This polyoxymethylene has been produced in the presence of a catalyst.
It is produced by homopolymerizing trioxane or by copolymerizing trioxane with ethylene oxide, dioxolane, or a cyclic formal such as dioxolane.

しかしながら、このような方法においては、通常、重合
反応が急激に進行して反応生成物が塊状に固化し、その
後の処理が困難になったシ、副反応や着色を伴うので、
そのような望ましくない事態を避けるために種々の配慮
を払う必要がある。
However, in such a method, the polymerization reaction usually progresses rapidly and the reaction product solidifies into a lump, making subsequent processing difficult, and is accompanied by side reactions and coloring.
Various considerations need to be taken to avoid such undesirable situations.

このため・例えば多量の不活性溶剤の存在下で重合を行
う1いわゆるスラリー重合法が提案されたが1使用後の
溶剤の回収に手間がかかる上に、得られる重合体の分子
量低下をもたらす等の欠点があるため工業的製法として
、必ずしも満足しうるものとはいえない。
For this reason, for example, a so-called slurry polymerization method in which polymerization is carried out in the presence of a large amount of an inert solvent has been proposed, but it is time-consuming to recover the solvent after use, and it also causes a decrease in the molecular weight of the resulting polymer. Due to these drawbacks, it cannot be said to be necessarily satisfactory as an industrial manufacturing method.

したがって、現在のところポリオキシメチレンの製造方
法としては、塊状重合法が主流となっており、これに関
する改良やその製造装置についての改良が数多く提案さ
れている。
Therefore, at present, the bulk polymerization method is the mainstream method for producing polyoxymethylene, and many improvements in this regard and improvements in the production equipment have been proposed.

例えば)反応室が一対のたがいにかみ合う平行スクリュ
一部材の外部境界に沿った長い双胴ケースから構成さ゛
れており、上記スクリュ一部材はそれぞれ同方向に走行
するねじ山を有し、かつ縦軸を中心として同方向に回転
する構造をもつ二軸スクリュー押出型重合反応機を用い
る方法(特公昭47−629号公報)、反応室が一対の
シャフトの外部境界に実質的に沿った長い双胴型ケース
から構う長円形板を有し、その板の長軸端で相手の表面
をなでるようにかみ合う扁平端をもつセルフクリーニン
グ型重合反応機を用いる方法(特開昭51−84890
号公報)などが提案されている。
For example, if the reaction chamber consists of a long double-barreled case along the external boundary of a pair of intermeshing parallel screw members, each of which has threads running in the same direction and has a longitudinal axis. A method using a twin-screw extrusion type polymerization reactor having a structure that rotates in the same direction around a shaft (Japanese Patent Publication No. 47-629), in which the reaction chamber is located substantially along the outer boundary of a pair of shafts. A method using a self-cleaning polymerization reactor having an oval plate held from a mold case and a flat end that engages with the long axis end of the plate so as to stroke the other surface (Japanese Patent Laid-Open No. 51-84890)
Publication No. 2), etc. have been proposed.

しかしながら、第一の二軸スクリュー押出型重合反応機
を珀いる方法は、生成物の粉砕力が弱いので、その移動
に大馬力を必要とし、しばしばスクリューの回転が困難
になる程度まで負荷がかかつて実質的に押出、不能とな
るという欠点を有している。また、第二のセルフクリー
ニング型重合反応機を用いる方法は、長円形板パドルの
長軸の先端が扁平であるためにケーシング内面及びパド
ル表面に付着したスケールをかき取る作用が小さくて反
応機内にスケールが蓄積し、その結果伝熱係数が低下し
て重合熱の除熱速度が小さくなるばかシでなく、シャフ
リ!おしひろげられて余分の力がかかり、トルクアウト
して連続運転が困難となる欠点を有している。
However, the first method using a twin-screw extrusion type polymerization reactor has a weak crushing force for the product, so large horsepower is required to move the product, and the load is often increased to the extent that it becomes difficult to rotate the screw. Previously, it had the disadvantage of being virtually impossible to extrude. In addition, in the second method of using a self-cleaning polymerization reactor, since the tip of the long axis of the oval plate paddle is flat, the effect of scraping off scale adhering to the inner surface of the casing and the paddle surface is small, and it is difficult to clean the inside of the reactor. Don't be fooled by the fact that scale accumulates, resulting in a decrease in the heat transfer coefficient and a reduction in the rate of polymerization heat removal. It has the disadvantage that when it is stretched out, extra force is applied, causing torque out and making continuous operation difficult.

その他、双胴円筒型ケース内に2本のシャフトを平行に
収納し、そのシャフトのおのおのが、凸レンズ型断面を
もち、その長軸方向の画先端が鋭利なエツジを形成し、
かつ長軸を含む面を対称面とする形状をもつ板状のパド
ルを多数有し・それぞれのパドルは、その鋭利な先端が
他軸の相対するパドルの側面及びそれが属する胴体の内
面と僅少な間隙を保って回転するように位置されている
構造をもつセルフクリーニング型重合反応機を用いる方
法(゛特開昭56−3812号公報)、また1パドルが
レンズ形又は頂角で仮想円に内接する擬多角形であり、
その断面の頂角部には対象面をもたない鋭利なスクレー
パーを備えている構造をもつ双胴体のセルフクリーニン
グ型重合反応機を用いる方法(特開昭56−38313
号公報)なども提案されている。これらの方法は、ノ<
ドルの長軸の先端が鋭利であシ、ケーシング及びノくド
ル間の間隙が僅少であることを特徴としており、ケーシ
ング内面及びパドル表面のスケールのかき取り効果が強
くて反応機内のスケール蓄積は小さい。しかしながら、
この方式ではパドル先端が鋭利で、かつケーシングとパ
ドル、パドルとパドル間の間隙が僅少であるために、わ
ずかな中心軸のたわみによってパドル長軸の先端が相手
材を摩耗し、傷つけやすく、そのために取り扱いに細心
の注意を払わなければならないという問題点が残されて
いる。
In addition, two shafts are housed in parallel in a double cylindrical case, each of which has a convex lens-shaped cross section, and the leading edge of the image in the long axis direction forms a sharp edge.
It has many plate-shaped paddles with a plane of symmetry that includes the long axis. Each paddle has a sharp tip that is slightly connected to the side of the opposing paddle on the other axis and the inner surface of the body to which it belongs. A method using a self-cleaning polymerization reactor having a structure in which it rotates while maintaining a certain gap (Japanese Unexamined Patent Publication No. 56-3812), and a method in which one paddle forms a virtual circle with a lens shape or an apex is an inscribed pseudopolygon,
A method using a twin-body self-cleaning polymerization reactor having a sharp scraper with no symmetrical surface at the top corner of its cross section (Japanese Patent Laid-Open No. 56-38313
(No. Publication) have also been proposed. These methods are
The tip of the long axis of the paddle is sharp, and the gap between the casing and the paddle is small, which has a strong scraping effect on scale on the inside of the casing and on the paddle surface, preventing scale accumulation inside the reactor. small. however,
In this method, the paddle tip is sharp and the gaps between the casing and the paddles and between the paddles are small, so the tip of the long paddle shaft easily wears and damages the mating material due to slight deflection of the center shaft. However, there remains the problem that extreme care must be taken when handling them.

本発明者らは、このような従来方法のもつ欠点特に、そ
の反応装置に由来する問題点を克服し、取シ扱いが容易
で、長時間にわたってポリオキシメチレン粉末を連続的
に製造する方法について鋭意研究を重ねた結果、回転軸
に取り付ける・くドルの形状に工夫を加、えることによ
り、その目的を達成しうろことを見出し、本発明をなす
に至った。
The present inventors have developed a method that overcomes the shortcomings of such conventional methods, particularly the problems arising from the reaction equipment, is easy to handle, and can continuously produce polyoxymethylene powder over a long period of time. As a result of extensive research, it was discovered that the object could be achieved by modifying the shape of the paddle attached to the rotating shaft, and the present invention was achieved.

すなわち、本発明は、それぞれに多数のノくドルを備え
た、たがい(平、行な2本の回転軸を各)(ドルの回転
円周面に沿った内壁面を有する双胴円筒型ケース内に収
納した構造をもつ反応器を用い、その一端に設けた供給
口からポリオキシメチレン製造用モノマーを導入し、前
記各−転軸を同二方向に回転させ、対向する各パドル面
及び・くドル面とケース内壁面の間に形成される狭い間
隙でかきまぜながら反応を行わせ、他端に設けられた吐
出口から生成した粉末状ポリオキシメチレンを連続的に
回収する方法において、前記反応器中の各パドルが箋凸
レンズ型断面をもつ板状かつその両先端部を、その断面
がパドル長軸に対し対称的な円弧周面で切欠した形状を
有するものを使用することを特徴とする連続的ポリオキ
7メチレンの製造方法を提供するものである。
That is, the present invention provides a double-bodied cylindrical case having an inner wall surface along the rotating circumferential surface of the dollars (each having two rotating shafts parallel to each other), each of which has a large number of rotating dollars. Using a reactor with a structure housed inside, a monomer for producing polyoxymethylene is introduced from a supply port provided at one end, and each of the rotating shafts is rotated in the same two directions, and each of the opposing paddle surfaces and... In a method in which the reaction is carried out while stirring in a narrow gap formed between the paddle surface and the inner wall surface of the case, and the powdered polyoxymethylene produced is continuously recovered from a discharge port provided at the other end, the reaction is performed. Each paddle in the device is shaped like a plate with a convex lens-shaped cross section, and its both tips are cut out with a circular arc circumferential surface symmetrical with respect to the long axis of the paddle. A method for continuously producing polyoxy7-methylene is provided.

本発明の製造方法に用いる装置においては、双胴円筒型
ケース内に各円筒の中心軸部に多数のパドルを備えた平
行な2本の回転軸が設置され、いずれも同一方向に回転
するように設計される。本発明においては、それらの各
回転軸に取り付けられるパドルは両面凸レンズの断面の
形状をもった板状体で、その両先端部が鋭利なエツジや
平面カットしたような扁平状ではなく、円弧状であって
、側部周面と連続する曲面に形成される。その先端部の
円弧の曲率半径は長軸の長さのμ以下が好ましく、さら
に好ましくはV4〜1/2Gである。曲率半径が長軸の
〃を超えると円弧の曲率はケース内面のそれよりも小さ
くなり、ケース内面のスケールの付着防止効果が低下し
、V2Oより小さくすることは精度的に加工が困難であ
るばかりでなく、摩滅し易いので好ましくない。この円
弧状部の曲率半径は、通常、1個のパドルでは同一条件
でつくられるが、上記範囲内で連続的に変化させること
もできる。パドルの先端部をこのように形成するとき、
ケースの円筒状内面及びパドル表面に付着したスケール
が効果的にかき取られることは全く意外な発見であった
。また、先端部が鋭利でな1く連続−曲面状に形成され
ているので、ケース内面や他のパドル表面をおたがいに
傷つけ合うこともなく、従って操業的にも取り扱いの上
からも従来の欠陥が極めて好都合に克服されることが見
出された。さらに、パドルの最先端は円弧の部分であっ
て、そのため重合生成物は最先端で巻き込まれ、せん断
力を受けて微粉砕され易いことも極めて有利である。
In the apparatus used in the manufacturing method of the present invention, two parallel rotating shafts each having a large number of paddles are installed in the central axis of each cylinder in a double cylindrical case, and both rotate in the same direction. Designed to. In the present invention, the paddles attached to each of these rotating shafts are plate-shaped bodies that have the cross-sectional shape of a double-convex lens, and both ends of the paddles are arcuate, rather than flat with sharp edges or flat cuts. It is formed into a curved surface that is continuous with the side peripheral surface. The radius of curvature of the arc at the tip is preferably less than the length of the major axis, more preferably V4 to 1/2G. If the radius of curvature exceeds the major axis, the curvature of the arc will be smaller than that of the inner surface of the case, and the effect of preventing scale from adhering to the inner surface of the case will decrease, and making it smaller than V2O will simply be difficult to process accurately. However, it is not preferable because it easily wears out. The radius of curvature of this arcuate portion is usually made under the same conditions for one paddle, but it can also be changed continuously within the above range. When forming the tip of the paddle in this way,
It was a completely unexpected discovery that scale adhering to the cylindrical inner surface of the case and the surface of the paddle could be effectively scraped off. In addition, since the tip is not sharp and is formed into a continuous curved surface, there is no possibility of damaging the inner surface of the case or other paddle surfaces. It has been found that this can be overcome very conveniently. Furthermore, it is extremely advantageous that the leading edge of the paddle is an arcuate portion, so that the polymerization product is easily caught up at the leading edge and pulverized by shearing force.

以下、添付図面により本発明の方法において用いられる
反応装置について説明する。
Hereinafter, the reaction apparatus used in the method of the present invention will be explained with reference to the accompanying drawings.

第1図は、本発明の方法において用いられる反応装置の
1例の部分切欠側面図で、第2図は該装置の横断面図で
ある。
FIG. 1 is a partially cutaway side view of an example of a reaction apparatus used in the method of the present invention, and FIG. 2 is a cross-sectional view of the apparatus.

この反応装置は、西洋なし形の断面形状を有する双胴円
部型であって、中央縦方向で連通した異心同径の円筒胴
体1,1′が一体化されたケース内に各円筒の中心軸の
位置に2本の回転軸2,2′  が収納され、胴体の外
側には1個又は複数個に分割された温度制御用ジャケッ
ト4が備えられている0上記2本の回転軸には、凸レン
ズ型断面をもつノくドル3,3′がそれぞれ多数取り付
は固定されている。おのおののパドルは、その長軸方向
の先端部が円弧状で、かつその長軸に対し対称の形状に
形成されている。これらのパドルには、側面がフラット
型のものとヘリカル型のものがあり、反応系の相変化に
対応してそれらのパドルを任意に選択し、組合わせるこ
とができる。
This reactor is a double-cylinder type with a pear-shaped cross-section, and the central axis of each cylinder is housed in a case in which cylindrical bodies 1 and 1' of different centers and the same diameter are connected in the longitudinal direction of the center. Two rotating shafts 2, 2' are housed at the positions, and a temperature control jacket 4 divided into one or more pieces is provided on the outside of the body. A large number of nozzles 3, 3' each having a convex lens-shaped cross section are fixedly mounted. Each paddle has an arcuate distal end in the longitudinal direction, and is formed in a symmetrical shape with respect to the longitudinal axis. These paddles include those with flat sides and those with helical sides, and these paddles can be arbitrarily selected and combined in accordance with the phase change of the reaction system.

パドルの先端面とケース内壁面との間隙は、ノくドルの
長軸の長さの2%以下、特に好ましくは1%以下であり
、一方のパドルの先端面と他方の回転軸に対向して取り
付けられているパドルの凸レンズ状曲面との間隙は、前
記先端面とケース内壁面との間隙の5倍以下、好ましく
は2倍以下にされる。
The gap between the tip surface of the paddle and the inner wall surface of the case is 2% or less, particularly preferably 1% or less, of the length of the long axis of the paddle, and the tip surface of one paddle faces the rotation axis of the other. The gap between the convex lens-shaped curved surface of the paddle attached to the paddle and the convex lens-shaped curved surface is set to be 5 times or less, preferably 2 times or less, the gap between the tip end surface and the inner wall surface of the case.

第2図に示すように、凸レンズ断面型のパドルの長軸方
向の先端部は円弧状に形成され、側部外周面の円弧と連
続的曲線となるようにつくられる。
As shown in FIG. 2, the tip of the paddle having a convex lens cross section in the longitudinal direction is formed into an arc shape, and is formed in a continuous curve with the arc of the outer peripheral surface of the side part.

この先端円弧状部は、所望ならば特に硬い材料を用いる
と七ができる。またパドルの厚さは、そのパドルの長軸
の長さの1/!n −’/+程度にされる。
This tip arc can be made of a particularly hard material if desired. Also, the thickness of the paddle is 1/1/1 of the length of the long axis of the paddle! It is set to about n −'/+.

回転軸に固定されるパドルは、その中央が回転軸と一体
にとり付けられ、各隣り合っているパドルは、その長軸
が一致しないように角度を与えて固定される。その角度
は・通常45°・60°又は90゜が好都合に採用され
る。
The paddles fixed to the rotating shaft are attached at their centers integrally with the rotating shaft, and adjacent paddles are fixed at an angle so that their long axes do not coincide. The angle is usually conveniently 45°, 60° or 90°.

本発明の方法を実施するには、第1図に示す反応装置の
供給口5より連続的にトリオキサンを供給し、回転軸2
,2′を同一方向に回転させ、ジャケット4により温度
を適当に調節する。トリオキサンは、対向するパドル間
及びパドルとケース内壁面との間でかきまぜながら反応
し、回転するパドルによって次第に移動させられて、ケ
ースの他端にある吐出口6から目的重合物質であるポリ
オキシメチレンが微粉末状で取り出される。
To carry out the method of the present invention, trioxane is continuously supplied from the supply port 5 of the reactor shown in FIG.
, 2' are rotated in the same direction, and the temperature is appropriately adjusted by the jacket 4. The trioxane reacts while being stirred between the opposing paddles and between the paddles and the inner wall of the case, and is gradually moved by the rotating paddles to discharge polyoxymethylene, the target polymeric substance, from the discharge port 6 at the other end of the case. is extracted in fine powder form.

本発明の方法は、トリオキサンの単独重合及びトリオキ
サンと他のオキシアルキレンとの共重合に用いられる。
The process of the invention is used for the homopolymerization of trioxane and the copolymerization of trioxane with other oxyalkylenes.

このような共重合に用いられるコモノマーとしては、例
えばエチレンオキシド、1.3−ジオキソラン、ジオキ
ソラン、トリオキソケンなどの環状エーテルや環ホルマ
ールが挙げられる。これらのコモノマーは、トリオキサ
ンと別個でもよいが、あらかじめ混合して反応装置に供
給することができ名。また、共重合体は、主成分である
オキシメチレン主鎖中に炭素数2以上のオキシアルキレ
ン単位が0.1〜20モル%、好マシくは0.4〜lb
モル%含有されるものが一般に広く利用される。′ 重合は、加熱条件下に重合触媒を用いて行われる。重合
反応温度は、一般に60〜130℃の範囲が採用され、
好ましい温度範囲は65〜115℃である。
Examples of comonomers used in such copolymerization include cyclic ethers and ring formals such as ethylene oxide, 1,3-dioxolane, dioxolane, and trioxokene. These comonomers may be used separately from the trioxane, but they can also be mixed beforehand and fed to the reactor. In addition, the copolymer contains 0.1 to 20 mol%, preferably 0.4 to 20 mol%, of oxyalkylene units having 2 or more carbon atoms in the oxymethylene main chain, which is the main component.
Those containing mol% are generally widely used. ' Polymerization is carried out using a polymerization catalyst under heating conditions. The polymerization reaction temperature is generally in the range of 60 to 130°C,
The preferred temperature range is 65-115°C.

また、重合触媒としては通常知られたカチオン重合触媒
が使用できるが、好ましい触媒は三フッ化ホウ素、三フ
ッ化ホウ素水和物、三フッ化ホウ素エーテル配位物であ
り、特に好ましいものは、三フッ化ホウ素ジエチルエー
テル配位物、三フッ化ホウ素ジブチルエーテル配位物で
ある。
Further, as the polymerization catalyst, commonly known cationic polymerization catalysts can be used, but preferred catalysts are boron trifluoride, boron trifluoride hydrate, and boron trifluoride ether coordination products, and particularly preferred ones are: These are boron trifluoride diethyl ether coordination and boron trifluoride dibutyl ether coordination.

また、重合反応系に不活性有機溶剤を加えてもよく、そ
のような溶剤としては無水のへキサン、ヘプタン、シク
ロヘキサン、ベンゼンなどの脂肪族、脂環族及び芳香族
炭化水素類やハロゲン化炭化水素類が好都合に使用され
る。これらの溶剤は原料モノマー及び触媒を溶解しても
しなくてもよいO 本発明の方法によるトリオキサンの連続的塊状重合にお
いては、数センチポイズの低粘度液体モ1) ツマ−が、反応装置中でスラリー、を経て固体重合体と
なる。その際、多数の上記パドルの組合わさった回転混
練シによって効果的に重合体が微粉状固体となり、連続
的に吐出口から排出されるので何らの支障も起らず、ま
た反応装置を損傷することなく長期間、円滑な連続運転
が可能である。
In addition, an inert organic solvent may be added to the polymerization reaction system, and such solvents include aliphatic, alicyclic, and aromatic hydrocarbons such as anhydrous hexane, heptane, cyclohexane, and benzene, and halogenated hydrocarbons. Hydrogens are advantageously used. These solvents may or may not dissolve the raw material monomers and the catalyst. , it becomes a solid polymer. At this time, the polymer is effectively turned into a fine powder solid by the rotary kneading system using a combination of a large number of the above paddles, and is continuously discharged from the discharge port, so there is no problem and there is no damage to the reaction equipment. Smooth continuous operation is possible for long periods of time without any problems.

以下、実施例により本発明をさらに詳細に説明する。Hereinafter, the present invention will be explained in more detail with reference to Examples.

実施例1 第1図に示すような、ケースの外周に温度制御用ジャケ
ットを備えた双胴円筒型反応装置を用いた。この装置は
、胴の内径が200mm 、 L/Dが14で、原料供
給口の直下には、長さIDの送りスクリューが付けられ
ている。まだ第2図に示すようなパドルの長軸の先端部
の円弧は、その曲率半径が長軸の長さの名。のものであ
り、上記送りスクリューにつづいて、パドルが回転逆方
向に順次45゜の角度をなすようにずらせて回転軸にと
りつけられている。また、各パドル先端面と胴内面の間
隙は2m以下に、相対する他軸のパドル面との間隙は4
11Ell以下に設計されている。
Example 1 A double-barreled cylindrical reactor equipped with a temperature control jacket around the outer periphery of the case as shown in FIG. 1 was used. In this device, the inner diameter of the barrel is 200 mm, the L/D is 14, and a feed screw with length ID is attached directly below the raw material supply port. The radius of curvature of the arc at the tip of the long axis of the paddle as shown in Figure 2 is the name of the length of the long axis. Following the feed screw, the paddles are attached to the rotating shaft at an angle of 45 degrees in the opposite direction of rotation. In addition, the gap between the tip of each paddle and the inner surface of the barrel should be 2 m or less, and the gap between the opposing paddle surface of the other shaft should be 4 m or less.
It is designed to be 11El or less.

この重合反応装置に、油状のトリオキサンを毎時401
cy、エチレンオキシドを毎時soo fI及び三フッ
化ホウ素ジブチルエーテル配位化合物とメチラールをシ
クロヘキサン溶液としてトリオキサン1モル当り、それ
ぞれ0.IミIJモル及び1ミリモル供給した。重合温
度をジャケットにより90Cに制御し、パドル先端の回
転周速度を20m/分で操業操作した。吐出口より、未
反応モノマー8%を含む10メツシユバスの微粒子共重
合体が連続的に得られた。この連続運転は、500時間
後においても何ら異常は認められなかった。また、運転
終了後に反応装置の内部を点検したが、ケース内面やパ
ドル側面、先端部には異常は全く認められなかった。
Oily trioxane was added to this polymerization reactor at a rate of 40% per hour.
cy, ethylene oxide per hour soofI and boron trifluoride dibutyl ether coordination compound and methylal in cyclohexane solution per mole of trioxane, each at 0.0. I and IJ moles and 1 mmol were fed. The polymerization temperature was controlled at 90 C using a jacket, and the operation was carried out at a peripheral speed of rotation of the paddle tip at 20 m/min. From the discharge port, 10 mesh baths of fine particle copolymer containing 8% of unreacted monomer were continuously obtained. No abnormality was observed in this continuous operation even after 500 hours. Furthermore, when the inside of the reactor was inspected after the operation was completed, no abnormalities were found on the inner surface of the case, the side surface of the paddle, or the tip.

比較例1 ケースの外周に反応混合物を加熱するだめのジャケット
を有し、一対のシャフトがケース内に水平に固定され、
この各シャフトが、たがいにかみ合う長円形板のパドル
をもち、その長円形板が長軸端で相手の長円形板の表面
をなでるようにかみ合う扁平端を有する連続混合機を反
応装置として用いた。この装置の胴の内径は200am
 、 L/Dは14であった。また装置の内部に取り付
けられた多数の長円形板の組み合せは、実1.施例1の
パドルと同様にし、間隙も同様にした。長円形板先端の
扁平端の回転周速度も20m/分とし、トリオキサン、
エチレンオキシド、重合触媒、メチラールの供給量及び
重合温度などの各条件も実施例1と同様にして運転を開
始した。約40時間後に、装置に断続的に異常音が生じ
、温度が上昇し始めて90℃に一定に維持することが困
難となった。150時間経過したとき、装置の異常音は
ますます大きく連続的となり、突如シェアピンが折損し
てシャフトの回転が止ったために運転を中止した。装置
を分解して点検したところ、装置内部全般にわたり部分
的に大量のスケールが生成していた。
Comparative Example 1 A jacket for heating the reaction mixture was provided around the outer periphery of the case, a pair of shafts were fixed horizontally within the case,
A continuous mixer in which each shaft had paddles of oval plates that engaged with each other, and flat ends that engaged with each other so that the oval plates stroked the surface of the other oval plate at the long axis end was used as a reaction apparatus. . The inner diameter of the body of this device is 200am
, L/D was 14. Moreover, the combination of a large number of oblong plates installed inside the device is actually 1. The paddle was made in the same manner as in Example 1, and the gap was also the same. The rotational peripheral speed of the flat end of the oblong plate was also 20 m/min, and trioxane,
Operation was started under the same conditions as in Example 1, including the supply amounts of ethylene oxide, polymerization catalyst, methylal, and polymerization temperature. After about 40 hours, the device made intermittent abnormal noises and the temperature began to rise, making it difficult to maintain it at a constant level of 90°C. After 150 hours had elapsed, the abnormal noise from the device became louder and more continuous, and the shear pin suddenly broke and the shaft stopped rotating, so the operation was stopped. When the device was disassembled and inspected, large amounts of scale were found to have formed throughout the inside of the device.

比較例2 第1図に示す反応装置を用いた。ケースの内径は200
 I+IffI、 L/Dは14であった。パドルは凸
レンズ型断面の板状であシ、その先端部には鋭利に加工
されている。実施例1と同様のパドルの組み合わせを行
い、各間隙も同様にした。パドル先端の回転周速度を2
’Om/分とし、トリオキサン、エチレンオキシド、重
合触媒、メチラールの供給量及び重合温度などの各条件
も実施例1と同様ばして1璽転を開始した。吐出口より
未反応物9係を含む重合体が得られた。重合体は概して
微粒子であったが、10メツシユふるいを通過しないも
のが40%あった。500時間の連続運転中、時々きし
むような異音が発し、運転終了後、反応装置の内部を点
検したところ、反応装置のL/Dが7に相当する中央部
のケース下部に、パドルの先端の接触に基づくものと思
われる傷あとが見出された。
Comparative Example 2 A reaction apparatus shown in FIG. 1 was used. The inner diameter of the case is 200
I+IffI, L/D was 14. The paddle is plate-shaped with a convex lens-shaped cross section, and its tip is sharply machined. The same paddle combination as in Example 1 was used, and each gap was also the same. The rotational circumferential speed of the paddle tip is 2
One cycle was started under the same conditions as in Example 1, such as supply amount of trioxane, ethylene oxide, polymerization catalyst, methylal, and polymerization temperature. A polymer containing 9 unreacted substances was obtained from the discharge port. The polymer was generally fine particles, but 40% did not pass through a 10 mesh sieve. During continuous operation for 500 hours, an abnormal squeaking noise was occasionally emitted, and when the inside of the reactor was inspected after the operation was completed, it was found that the tip of the paddle was found at the bottom of the case in the center, where L/D of the reactor corresponds to 7. Scars were found that appeared to be caused by contact.

比較例3 第1図に示す反応装置を用いた。ケースの内径は200
■、L/Dは14であった。パドルは凸レンズ型断面の
板状であり、その頂角部には対称面をもたない鋭利なス
クレーパーを備えていた。実施例1と同様のパドルの組
み合わせを行い、各間隙も同様にした。パドル先端の回
転周速度も20m/分とし、トリオキサン、エチレンオ
キシド、重合速度、メチラールの供給量及び重合温度な
どの各条件も実施例1と同様にして運転を開始した。吐
出口より未反応物9%を含む重合体が得られた。
Comparative Example 3 A reaction apparatus shown in FIG. 1 was used. The inner diameter of the case is 200
■, L/D was 14. The paddle was plate-shaped with a convex lens-shaped cross section, and its apex corner was equipped with a sharp scraper without a plane of symmetry. The same paddle combination as in Example 1 was used, and each gap was also the same. Operation was started under the same conditions as in Example 1, such as the peripheral speed of rotation of the paddle tip at 20 m/min, trioxane, ethylene oxide, polymerization rate, methylal supply amount, and polymerization temperature. A polymer containing 9% of unreacted substances was obtained from the discharge port.

重合体は概して微粒子であったが、ioメツシュのふる
いを通過しないものが40%あった。500時間の連続
運転中、時々きしむような異音を発しだ。運転終了後、
反応装置の内部を点検したところ、反応装置のL/Dが
7に相当する中央部のケース下部にパドルの先端の接触
に基づくものと思われる傷あとが見出された。
The polymer was generally fine particles, but 40% did not pass through the io mesh. During 500 hours of continuous operation, it occasionally emitted an unusual squeaking noise. After driving,
When the inside of the reactor was inspected, scratches that appeared to be caused by contact with the tip of the paddle were found on the lower part of the case in the center, where L/D of the reactor corresponds to 7.

【図面の簡単な説明】[Brief explanation of the drawing]

第1図は、本発明の方法において用いられる反。 窓装置の1例の部分切欠側面図、第2図は同装置の横断
面図である。 図中、符号1,1′は胴体、2,2′は回転軸、3.3
′はパドルである。 特許出願人  旭化成工業株式会社 代理人 阿 形  明
FIG. 1 shows the membrane used in the method of the invention. FIG. 2 is a partially cutaway side view of an example of a window device, and FIG. 2 is a cross-sectional view of the device. In the figure, 1 and 1' are the fuselage, 2 and 2' are the rotating shafts, and 3.3
' is a paddle. Patent applicant: Asahi Kasei Industries Co., Ltd. Agent: Akira Agata

Claims (1)

【特許請求の範囲】[Claims] 1 それぞれに多数のパドルを備えたたがいに平行な2
本の回転軸を、各パドルの回転円周面に沿った内壁面を
有する双胴円筒型ケース内に収納した構造をもつ反応器
を用い、その一端に設けた供給口からトリオキサン又は
トリオキサンとコモノマーを導入し、前記各回転軸を同
一方向に回転させ、対向する各パドル面及びパドル面と
ケース内壁面の間に形成される狭い間隙でかきまぜなが
ら反応を行わせ、他端に設けられた吐出口から生成した
粉末状ポリオキシメチレンを連続的に回収する方法にお
いて、前記反応器中の各パドルが、凸レンズ型断面をも
つ板状で、かつその画先端部を、その断面がパドル長軸
に対し対称的な円弧局面で切欠した形状を有するものを
使用することを特徴とする連続的ポリオキシメチレンの
製造方法。
1. 2 parallel to each other, each with a number of paddles.
Using a reactor with a structure in which the rotating shaft of the book is housed in a double-bodied cylindrical case with an inner wall surface along the rotational circumferential surface of each paddle, trioxane or comonomer is supplied from a supply port provided at one end of the reactor. The rotating shafts are rotated in the same direction to cause the reaction to occur while stirring in the opposing paddle surfaces and in the narrow gap formed between the paddle surface and the inner wall of the case. In a method for continuously recovering powdered polyoxymethylene produced from an outlet, each paddle in the reactor is plate-shaped with a convex lens-shaped cross section, and the tip of the image is aligned with the long axis of the paddle. 1. A continuous method for producing polyoxymethylene, characterized in that a polyoxymethylene having a symmetrical circular arc curved shape is used.
JP12972781A 1981-08-19 1981-08-19 Preparation of polyoxymethylene Granted JPS5832619A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP12972781A JPS5832619A (en) 1981-08-19 1981-08-19 Preparation of polyoxymethylene

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP12972781A JPS5832619A (en) 1981-08-19 1981-08-19 Preparation of polyoxymethylene

Publications (2)

Publication Number Publication Date
JPS5832619A true JPS5832619A (en) 1983-02-25
JPS6214163B2 JPS6214163B2 (en) 1987-04-01

Family

ID=15016700

Family Applications (1)

Application Number Title Priority Date Filing Date
JP12972781A Granted JPS5832619A (en) 1981-08-19 1981-08-19 Preparation of polyoxymethylene

Country Status (1)

Country Link
JP (1) JPS5832619A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61238812A (en) * 1985-04-17 1986-10-24 Polyplastics Co Continuous polymerization
JPS6296515A (en) * 1985-05-13 1987-05-06 Polyplastics Co Continuous production of polymer of copolymer of trioxane
US5587298A (en) * 1995-03-02 1996-12-24 Director General Of National Agriculture Research Center, Ministry Of Agriculture, Forestry And Fisheries Bioreactor
US6139804A (en) * 1994-10-27 2000-10-31 Asahi Kasei Kogyo Kabushiki Kaisha Process for production of polyoxymethylene

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5184890A (en) * 1974-10-11 1976-07-24 Celanese Corp
JPS5386794A (en) * 1976-11-29 1978-07-31 Mitsubishi Gas Chem Co Inc Continuous polymerization
JPS5638312A (en) * 1979-09-05 1981-04-13 Mitsubishi Gas Chem Co Inc Preparation of polyacetal
JPS5659842A (en) * 1979-10-22 1981-05-23 Toray Ind Inc Preparation of polyester
JPS5659824A (en) * 1979-10-23 1981-05-23 Mitsubishi Gas Chem Co Inc Continuous polymerization of trioxane

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5184890A (en) * 1974-10-11 1976-07-24 Celanese Corp
JPS5386794A (en) * 1976-11-29 1978-07-31 Mitsubishi Gas Chem Co Inc Continuous polymerization
JPS5638312A (en) * 1979-09-05 1981-04-13 Mitsubishi Gas Chem Co Inc Preparation of polyacetal
JPS5659842A (en) * 1979-10-22 1981-05-23 Toray Ind Inc Preparation of polyester
JPS5659824A (en) * 1979-10-23 1981-05-23 Mitsubishi Gas Chem Co Inc Continuous polymerization of trioxane

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61238812A (en) * 1985-04-17 1986-10-24 Polyplastics Co Continuous polymerization
JPH058725B2 (en) * 1985-04-17 1993-02-03 Polyplastics Kk
JPS6296515A (en) * 1985-05-13 1987-05-06 Polyplastics Co Continuous production of polymer of copolymer of trioxane
JPH0542452B2 (en) * 1985-05-13 1993-06-28 Polyplastics Kk
US6139804A (en) * 1994-10-27 2000-10-31 Asahi Kasei Kogyo Kabushiki Kaisha Process for production of polyoxymethylene
US5587298A (en) * 1995-03-02 1996-12-24 Director General Of National Agriculture Research Center, Ministry Of Agriculture, Forestry And Fisheries Bioreactor

Also Published As

Publication number Publication date
JPS6214163B2 (en) 1987-04-01

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