JPH05132503A - Spray polymerization method and nozzle for spray polymerization - Google Patents
Spray polymerization method and nozzle for spray polymerizationInfo
- Publication number
- JPH05132503A JPH05132503A JP32400591A JP32400591A JPH05132503A JP H05132503 A JPH05132503 A JP H05132503A JP 32400591 A JP32400591 A JP 32400591A JP 32400591 A JP32400591 A JP 32400591A JP H05132503 A JPH05132503 A JP H05132503A
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- JP
- Japan
- Prior art keywords
- nozzle
- liquid
- circular pipe
- spray
- polymerization
- 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.)
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、有機不飽和カルボン酸
又はその塩を主成分とするモノマー溶液をレドックス系
重合開始剤を使用して噴霧重合する方法、特に高吸水性
樹脂の製造に適した噴霧重合法及び噴霧重合用ノズルに
関するものである。FIELD OF THE INVENTION The present invention is suitable for a method of spray-polymerizing a monomer solution containing an organic unsaturated carboxylic acid or a salt thereof as a main component by using a redox type polymerization initiator, and particularly suitable for producing a super absorbent polymer. The present invention also relates to a spray polymerization method and a spray polymerization nozzle.
【0002】[0002]
【従来の技術】有機不飽和カルボン酸又はその塩を主成
分とするモノマーから高吸水性樹脂を製造する方法とし
ては逆相懸濁法が主流であり、一部で溶液重合法も用い
られている。これらの方法では乾燥とか粉砕とかの後工
程を必要とし、また逆相懸濁法では粒径100μm以下
の微粒子も生成するので製品の均質化及び取扱上の問題
もある。2. Description of the Related Art As a method for producing a super absorbent polymer from a monomer containing an organic unsaturated carboxylic acid or its salt as a main component, a reverse phase suspension method is the mainstream, and a solution polymerization method is also partially used. There is. These methods require subsequent steps such as drying and pulverization, and the inverse phase suspension method also produces fine particles having a particle size of 100 μm or less, which causes problems in homogenization and handling of products.
【0003】特公昭32−10196号には、アクリル
酸、メタクリル酸、イタコン酸などの水溶性塩からなる
モノマーの水溶液を過硫酸アルカリ金属塩又は過硫酸ア
ンモニウム触媒の存在下300〜900F(149〜4
82℃)に加熱したガス媒質中に噴霧させる重合法が記
載されている。噴霧方法としてはスプレーガンとか回転
円盤とかが例示され、予めモノマーの水溶液と触媒を混
合してから回転円盤に供給する方法又はモノマー水溶液
と開始剤溶液を直前に混合して回転円盤に供給する方法
についても述べている。Japanese Patent Publication No. 32-10196 discloses an aqueous solution of a monomer consisting of a water-soluble salt such as acrylic acid, methacrylic acid or itaconic acid in the presence of an alkali metal persulfate or ammonium persulfate catalyst at 300 to 900 F (149 to 4).
A polymerization process is described in which the gas medium heated to 82 ° C. is atomized. Examples of the spraying method include a spray gun and a rotating disk, and a method of previously mixing an aqueous solution of a monomer and a catalyst and then supplying the same to a rotating disk, or a method of immediately mixing an aqueous monomer solution and an initiator solution and supplying the same to a rotating disk. Is also mentioned.
【0004】特開昭49−105889号には、有機不
飽和カルボン酸又はその塩を、有機ハイドロパーオキサ
イドと還元剤からなるレドックス系重合開始剤を使用し
て水への不溶解分の生成を伴わない噴霧重合法が記載さ
れ、噴霧機としては回転円盤型、圧力ノズル型、二流体
ノズル型等があるが、長時間運転を行う上からは単量体
と重合開始剤溶液は別個の導管から供給する方が好まし
く、回転円盤型のように複数の導管から供給される液が
円盤内で短時間に混合されるものが望ましいと述べてい
る。In JP-A-49-105889, an organic unsaturated carboxylic acid or a salt thereof is used to form an insoluble component in water by using a redox polymerization initiator composed of an organic hydroperoxide and a reducing agent. A spray polymerization method that does not accompany is described, and there are a rotating disk type, a pressure nozzle type, a two-fluid nozzle type, etc. as the atomizer, but from the viewpoint of long-term operation, the monomer and the polymerization initiator solution are separate conduits. It is described that the liquid supplied from a plurality of conduits is preferably mixed in the disk in a short time, such as a rotating disk type.
【0005】特開平2−64106号には水溶性エチレ
ン性不飽和モノマーを主成分とする溶液を水蒸気又は水
蒸気と少なくとも一種の重合に実質的に不活性を示す気
体を混合してなる気相中に供給し該気相中で重合させる
吸水性樹脂の製造法が、また特開平2−138306号
には前記方法においてモノマー濃度が少なくとも20重
量%の溶液を気相に供給し、しかも気相の相対湿度30
%以上の条件下で重合させる吸水性樹脂の製造法が開示
され、予めラジカル重合開始剤を混合したモノマーを、
アトマイザー、スプレーノズル(圧力ノズル)を用いて
40〜180℃の気相中に噴霧することにより平均粒径
100〜400μm程度の粒子状高吸水性樹脂を得てい
る。Japanese Patent Laid-Open No. 64-64106 discloses a gas phase prepared by mixing a solution containing a water-soluble ethylenically unsaturated monomer as a main component with water vapor or water vapor and at least one gas which is substantially inert to polymerization. And a method of producing a water-absorbent resin in which the polymerization is carried out in the gas phase. In JP-A-2-138306, a solution having a monomer concentration of at least 20% by weight is supplied to the gas phase, and Relative humidity 30
%, A method for producing a water-absorbent resin to be polymerized under the conditions is disclosed, and a monomer preliminarily mixed with a radical polymerization initiator,
By spraying in a gas phase at 40 to 180 ° C. using an atomizer and a spray nozzle (pressure nozzle), a particulate super absorbent resin having an average particle size of about 100 to 400 μm is obtained.
【0006】噴霧の前に重合性モノマーと重合開始剤を
混合するケースでは原理的にノズルの内部で重合が開始
される危険性を持っている。特に長時間運転を行う場合
には必ず滞留時間分布ができ、ノズル内での重合反応が
進行する危険性が高く問題である。さらに、重合反応は
発熱反応であるので僅かでも反応が起き始めれば、暴走
的に進行してノズルの閉塞を引き起こす。また特開昭4
9−105889号に開示されるモノマーと重合開始剤
溶液を別個の導管から回転円盤に供給する方法は、モノ
マーと重合開始剤が円盤上で混合されるため、滞留時間
分布が生じ、重合反応が円盤上で開始される危険性があ
り、長時間運転は難しい。In the case where the polymerizable monomer and the polymerization initiator are mixed before spraying, there is a risk that the polymerization is initiated inside the nozzle in principle. In particular, when operating for a long time, there is always a residence time distribution, and there is a high risk of the polymerization reaction proceeding in the nozzle, which is a problem. Further, since the polymerization reaction is an exothermic reaction, if the reaction starts to occur even a little, it progresses in a runaway manner and causes clogging of the nozzle. In addition, Japanese Patent Laid-Open No. 4
In the method disclosed in 9-105889 in which a monomer and a polymerization initiator solution are supplied to a rotating disk through separate conduits, the monomer and the polymerization initiator are mixed on the disk, so that a residence time distribution occurs and the polymerization reaction There is a risk of starting on a disc, and it is difficult to drive for a long time.
【0007】[0007]
【発明が解決しようとする課題】本発明は、有機不飽和
カルボン酸又はその塩を主成分とするモノマー溶液をレ
ドックス系重合開始剤を使用して噴霧重合する方法に関
するもので、噴霧機における重合を防止し、長時間の連
続運転を可能にする噴霧重合法及び噴霧重合用ノズルを
提供することを目的とする。The present invention relates to a method of spray-polymerizing a monomer solution containing an organic unsaturated carboxylic acid or a salt thereof as a main component by using a redox type polymerization initiator. It is an object of the present invention to provide a spray polymerization method and a spray polymerization nozzle that prevent the above and enable continuous operation for a long time.
【0008】[0008]
【課題を解決するための手段】本発明に関わる噴霧重合
法は、有機不飽和カルボン酸又はその塩を主成分とする
モノマー溶液をレドックス系重合開始剤を使用して噴霧
重合するに際して、レドックス系重合開始剤を構成する
酸化剤と還元剤の内の一方をモノマー溶液に添加した第
1液を第1の液用ノズルに供給し、酸化剤と還元剤の内
の他方はモノマー溶液を加え又は加えずに第2液として
第2の液用ノズルに供給し、第1及び第2の液用ノズル
の出口で第1液及び第2液が混合するように噴出させて
気相中で重合反応を行わせることを特徴とする。The spray polymerization method according to the present invention is a redox-based method for spray-polymerizing a monomer solution containing an organic unsaturated carboxylic acid or a salt thereof as a main component by using a redox-based polymerization initiator. A first liquid obtained by adding one of an oxidizing agent and a reducing agent constituting a polymerization initiator to a monomer solution is supplied to the first liquid nozzle, and the other of the oxidizing agent and the reducing agent is added with a monomer solution or It is supplied as a second liquid to the second liquid nozzle without being added, and is jetted so that the first liquid and the second liquid are mixed at the outlets of the first and second liquid nozzles to carry out the polymerization reaction in the gas phase. It is characterized by performing.
【0009】高吸水性樹脂を製造するためのモノマー溶
液としては、アクリル酸、メタクリル酸、マレイン酸、
イタコン酸又はそれらの塩など、有機不飽和カルボン酸
又はその塩の水溶液或は混合水溶液が用いられる。特に
好ましいのはアクリル酸又はその塩である。有機不飽和
カルボン酸の塩としては、アンモニウム塩、アルカリ金
属塩、アルカリ土類金属塩が挙げられ、特にナトリウ
ム、カリウム、アンモニウムのアクリレート又はメタク
リレートである。さらに、アクリルアミド、メタクリル
アミドや、アクリル酸エステルなどのような共重合可能
な単量体を共存させても良い。水溶液中の有機不飽和カ
ルボン酸又はその塩の合計の濃度は20重量%以上、好
ましくは25重量%以上である。吸水性能向上のため架
橋剤をモノマー重量に対し0.5重量%以下添加しても
良い。As a monomer solution for producing the super absorbent polymer, acrylic acid, methacrylic acid, maleic acid,
An aqueous solution or a mixed aqueous solution of an organic unsaturated carboxylic acid or a salt thereof such as itaconic acid or a salt thereof is used. Particularly preferred is acrylic acid or its salt. Examples of the salts of organic unsaturated carboxylic acids include ammonium salts, alkali metal salts and alkaline earth metal salts, particularly sodium, potassium and ammonium acrylates or methacrylates. Further, a copolymerizable monomer such as acrylamide, methacrylamide, or acrylic acid ester may coexist. The total concentration of organic unsaturated carboxylic acids or salts thereof in the aqueous solution is 20% by weight or more, preferably 25% by weight or more. In order to improve the water absorption performance, a cross-linking agent may be added in an amount of 0.5% by weight or less based on the weight of the monomer.
【0010】重合開始剤としては重合反応時間が短いこ
とからレドックス系を用いる。レドックス系重合開始剤
を構成する酸化剤及び還元剤の組合わせは通常良く知ら
れたものが使用できる。例えばH2 O2 とl−アスコル
ビン酸又はアミン類との組合わせが挙げられる。As the polymerization initiator, a redox system is used because the polymerization reaction time is short. As the combination of the oxidizing agent and the reducing agent which constitute the redox type polymerization initiator, those well known in general can be used. For example, a combination of H 2 O 2 and 1-ascorbic acid or amines can be mentioned.
【0011】噴霧した液滴が落下しながら重合する気相
のガスとしては窒素、ヘリウム、炭酸ガス等の重合に不
活性なものが好ましいが、空気でもよい。また、水蒸気
のみの場合を含め、ガス中の湿度には特に制限はない。
ガスの温度条件は室温以上、200℃以下、望ましくは
150℃以下である。ガスの流れ方向は向流、並流のど
ちらでも良いが、滞留時間を長くする必要がある場合は
向流(反重力方向)の方がよい。The gas phase gas which polymerizes while the sprayed droplets fall is preferably nitrogen, helium, carbon dioxide gas or the like which is inert to the polymerization, but may be air. Moreover, there is no particular limitation on the humidity in the gas, including the case of using only steam.
The temperature condition of the gas is room temperature or higher and 200 ° C. or lower, preferably 150 ° C. or lower. The gas flow direction may be either countercurrent or parallel flow, but countercurrent (anti-gravitational direction) is better when the residence time needs to be lengthened.
【0012】噴霧された液滴の粒径、従って重合した樹
脂の粒径を制御する方法としては、ノズルの内径又は外
径を変える方法と、第1液及び第2液の流量又は両液が
混合する場所に噴射するガスの流量を変える方法とがあ
る。前者の場合、ノズルでの液の線速度が大きいときは
内径が小さい方がノズルより出る液柱が細くなり小さい
粒径の液滴を生じる。また液の線速が小さいときは外径
が小さい方が液滴に働く表面張力が小さくなるので小さ
い粒径の液滴を生じる。後者の場合は、平均粒径百μm
オーダーの樹脂が得られ、噴射するガス量が多い方が小
さい平均粒径の樹脂を生じる。As a method of controlling the particle size of the sprayed droplets, and hence the particle size of the polymerized resin, the method of changing the inner diameter or the outer diameter of the nozzle and the flow rate of the first liquid and the second liquid or both liquids are used. There is a method of changing the flow rate of the gas injected to the mixing place. In the former case, when the linear velocity of the liquid at the nozzle is high, the smaller the inner diameter, the narrower the liquid column that exits from the nozzle, and the smaller the droplet size. Further, when the linear velocity of the liquid is small, the smaller the outer diameter is, the smaller the surface tension acting on the liquid droplets is, so that liquid droplets having a small particle diameter are generated. In the latter case, the average particle size is 100 μm
A resin of the order is obtained, and a resin having a smaller average particle diameter is produced when the amount of injected gas is larger.
【0013】本発明で使用するノズルの一例は、図1に
示すように、二本の液用ノズル1及び液用ノズル2が並
べて設置され、両方のノズルの先端位置が揃えてある結
束式ノズルである。図2はノズル先端部X−Xにおける
断面図で、液用ノズル1と液用ノズル2が並んでいる状
態を示している。一方の液用ノズルからレドックス系重
合開始剤を構成する酸化剤と還元剤の内の一方をモノマ
ー溶液に添加した第1液を供給し、酸化剤と還元剤の内
の他方はモノマー溶液を加え又は加えずに第2液として
他方の液用ノズルに供給すれば、両方のノズルから噴出
した液滴はノズルの出口で混合し、気相中を落下しなが
ら重合反応を行う。An example of the nozzle used in the present invention is, as shown in FIG. 1, a bundling type nozzle in which two liquid nozzles 1 and 2 are installed side by side, and the tip positions of both nozzles are aligned. Is. FIG. 2 is a cross-sectional view of the nozzle tip portion XX, showing a state in which the liquid nozzle 1 and the liquid nozzle 2 are lined up. From one of the liquid nozzles, the first liquid in which one of the oxidizing agent and the reducing agent constituting the redox polymerization initiator is added to the monomer solution is supplied, and the other of the oxidizing agent and the reducing agent is added to the monomer solution. Alternatively, if the second liquid is supplied to the other liquid nozzle without being added, the droplets ejected from both nozzles are mixed at the outlet of the nozzle, and the polymerization reaction is performed while dropping in the gas phase.
【0014】図3は本発明で使用する他の形式のノズル
を示すもので、一方の液用ノズル1が他方の液用ノズル
2内に内挿されており、両方のノズルの先端位置が揃っ
ている二重式ノズルである。図4はこのノズル先端部Y
−Yにおける断面図を示したものである。FIG. 3 shows another type of nozzle used in the present invention, in which one liquid nozzle 1 is inserted into the other liquid nozzle 2 and the tip positions of both nozzles are aligned. It is a double type nozzle. Figure 4 shows this nozzle tip Y
It is a cross-sectional view taken along line -Y.
【0015】図5は二重式ノズルの他の例を示すもの
で、一方の液用ノズル1が他方の液用ノズル2内に内挿
されており、内挿されているノズル1の先端位置11が
外側のノズル2の先端(先端孔)22より突き出ている
二重式ノズルである。図6はこのノズル先端部Z−Zに
おける断面図を示したものである。FIG. 5 shows another example of the double type nozzle. One liquid nozzle 1 is inserted into the other liquid nozzle 2 and the tip position of the inserted nozzle 1 is shown. Reference numeral 11 is a double nozzle that projects from the tip (tip hole) 22 of the outer nozzle 2. FIG. 6 is a sectional view of the nozzle tip portion ZZ.
【0016】図7は第1液及び第2液が混合する場所に
高速の気流を噴射するタイプのノズルの一例(対向型ノ
ズル)を示すもので、二本の液用ノズル1と2はそれぞ
れの先端の延長線が交差する角度で別個に設置され、そ
れら二本の液用ノズルから噴射された液が交差する位置
に気流を噴射するようにガス用ノズル4が設けられてい
る。FIG. 7 shows an example of a nozzle (opposite type nozzle) of a type for injecting a high-speed air flow to a place where the first liquid and the second liquid are mixed, and the two liquid nozzles 1 and 2 are respectively. The extension lines of the tip ends of the gas nozzles are separately installed at the intersecting angles, and the gas nozzles 4 are provided so as to eject the airflow at the positions where the liquids ejected from the two liquid nozzles intersect.
【0017】図8は第1液及び第2液が混合する場所に
高速の気流を噴射するタイプのノズルの他の例(同心円
型ノズル)を示すもので、ガス用ノズルとして用いられ
る第1の円管5を中心として、第1の円管5の外径より
大きい内径の第2の円管6及び第2の円管6の外径より
大きい内径の第3の円管7が同心円的に重ねられた三重
管構造で、第1の円管と第2の円管との間隙が第1の液
用ノズル1、第2の円管と第3の円管との間隙が第2の
液用ノズル2、第1の円管5の内部がガス用ノズル4を
構成している。第1の円管5の内部がガス用ノズルを構
成することが好ましいが、外側のノズル(第2の円管と
第3の円管との間隙)をガス用ノズルとして使用しても
良い。FIG. 8 shows another example of a nozzle (concentric circle type nozzle) of a type for injecting a high-speed air stream to a place where the first liquid and the second liquid are mixed, which is used as a gas nozzle. A second circular pipe 6 having an inner diameter larger than the outer diameter of the first circular pipe 5 and a third circular pipe 7 having an inner diameter larger than the outer diameter of the second circular pipe 6 are concentrically arranged around the circular pipe 5. In the overlapped triple pipe structure, the gap between the first circular pipe and the second circular pipe is the first liquid nozzle 1, and the gap between the second circular pipe and the third circular pipe is the second liquid pipe. The inside of the gas nozzle 2 and the first circular pipe 5 constitutes a gas nozzle 4. It is preferable that the inside of the first circular pipe 5 constitutes a gas nozzle, but an outer nozzle (a gap between the second circular pipe and the third circular pipe) may be used as a gas nozzle.
【0018】気相に液滴を放出後、落下するまでにほぼ
重合反応を終了させようと考えたとき、10m程度の落
下距離での落下時間は数秒から十数秒である。そのため
噴霧重合法を成功に導くには重合反応の誘導期及び反応
時間の合計を十数秒以下にする必要がある。従ってかか
る条件を満たすように、重合開始剤の種類、量、液滴が
落下する気相の温度等を定めれば良い。When it is considered that the polymerization reaction is almost completed before the liquid drops are dropped into the gas phase until they fall, the drop time at a drop distance of about 10 m is several seconds to ten and several seconds. Therefore, in order to make the spray polymerization method successful, the total of the induction period and the reaction time of the polymerization reaction must be 10 seconds or less. Therefore, the type and amount of the polymerization initiator, the temperature of the gas phase in which the liquid drops fall, and the like may be determined so as to satisfy such conditions.
【0019】本発明においては、レドックス系重合開始
剤を構成する酸化剤と還元剤の内のどちらか一方をモノ
マー溶液に添加したものを第1液として使用することが
要件で、他方にはモノマー溶液を加えずに第2液として
使用しても、モノマー溶液を加えたものを第2液として
使用しても良く、それぞれ別個のノズルより噴出させて
ノズルの出口で両溶液を混合し、気相中で重合反応を行
わせる。In the present invention, it is a requirement that one of the oxidizing agent and the reducing agent constituting the redox type polymerization initiator is added to the monomer solution as the first liquid, and the other is the monomer. It may be used as the second liquid without adding the solution, or may be used as the second liquid by adding the monomer solution, and the both solutions are jetted from separate nozzles and mixed at the outlet of the nozzle, Allow the polymerization reaction to take place in phase.
【0020】以下実施例により本発明を具体的に説明す
るが、本発明は下記の実施例に限定されるものではな
い。The present invention will be described in detail with reference to the following examples, but the present invention is not limited to the following examples.
【0021】[0021]
【モノマー溶液調製例】80重量%のアクリル酸水溶液
125重量部に42.6重量%の水酸化ナトリウム水溶
液65.1重量部と架橋剤(N,N′−メチレンビスア
クリルアミド)0.14重量部と、さらに酸化剤として
30重量%の過酸化水素水溶液2.8重量部を加えて溶
液Aを調製した。溶液Aのモノマー濃度は60重量%、
中和度は50モル%であった。これとは別に80重量%
のアクリル酸水溶液125重量部に41.4重量%の水
酸化ナトリウム水溶液67.1重量部と架橋剤(N,
N′−メチレンビスアクリルアミド)0.14重量部を
加え、さらに還元剤としてl−アスコルビン酸0.34
重量部加えて溶液Bを調製した。溶液Bのモノマー濃
度、中和度は溶液Aと同様であった。[Example of preparation of monomer solution] 125 parts by weight of 80% by weight acrylic acid aqueous solution, 65.1 parts by weight of 42.6% by weight sodium hydroxide aqueous solution and 0.14 parts by weight of a cross-linking agent (N, N'-methylenebisacrylamide). Then, 2.8 parts by weight of a 30% by weight aqueous hydrogen peroxide solution was further added as an oxidizing agent to prepare a solution A. The monomer concentration of solution A is 60% by weight,
The degree of neutralization was 50 mol%. Separately 80% by weight
125 parts by weight of the acrylic acid aqueous solution of 61.4 parts by weight of a 41.4% by weight aqueous sodium hydroxide solution and a crosslinking agent (N,
(N'-methylenebisacrylamide) 0.14 parts by weight was added, and 1-ascorbic acid 0.34 was further added as a reducing agent.
Solution B was prepared by adding parts by weight. The monomer concentration and the degree of neutralization of solution B were the same as those of solution A.
【0022】実施例及び比較例においては、これらのモ
ノマー水溶液を45℃に加温して供給した。一方、溶液
重合実験によりモノマー水溶液A及びBを45℃で等量
混合した時の誘導期及び反応時間はそれぞれ約0.5
秒、約2秒であった。In Examples and Comparative Examples, these monomer aqueous solutions were heated to 45 ° C. and supplied. On the other hand, in the solution polymerization experiment, the induction period and the reaction time when the monomer aqueous solutions A and B were mixed in equal amounts at 45 ° C. were each about 0.5.
Seconds, about 2 seconds.
【0023】反応塔内部のガス流速は20cm/秒の上
昇流、ガス温度は45℃とし、下記の比較例・実施例す
べてをこの条件で行った。The gas flow rate inside the reaction tower was 20 cm / sec ascending flow and the gas temperature was 45 ° C., and all the following Comparative Examples and Examples were carried out under these conditions.
【0024】[0024]
【比較例1】A,Bのモノマー水溶液をそれぞれ別の供
給配管により回転円盤に50ml/分の流速で供給し
た。この回転円盤は直径100mmで水平に位置し、7
800rpmで回転していた。運転開始後、数分で円盤
上に重合物が生成し始め、その後重合物の堆積が急速に
発生し運転が困難となったので中止した。[Comparative Example 1] Aqueous solutions of A and B were supplied to the rotating disk through separate supply pipes at a flow rate of 50 ml / min. This rotating disk has a diameter of 100 mm and lies horizontally.
It was spinning at 800 rpm. Polymerization started to form on the disk within a few minutes after the start of the operation, and the accumulation of the polymer rapidly occurred thereafter, which made the operation difficult, so the operation was stopped.
【0025】[0025]
【比較例2】イケウチ製充円錐ノズル1/4MJ050
s316Wを使用し、A,Bのモノマー水溶液それぞれ
25mlずつ合計50mlを供給した。これらの溶液は
ノズル直前で滞留時間約0.2秒のオンライン混合器で
混合後ノズルに供給した。運転開始直後、混合器のとこ
ろで重合反応が起き配管が高粘性物により閉塞されたの
で運転を中止した。[Comparative Example 2] Full-cone nozzle made of ikeuchi 1 / 4MJ050
Using s316W, a total of 50 ml of 25 ml each of A and B monomer aqueous solutions was supplied. These solutions were supplied to the nozzle after mixing with an online mixer having a residence time of about 0.2 seconds immediately before the nozzle. Immediately after the start of operation, a polymerization reaction occurred in the mixer and the pipe was blocked by the highly viscous substance, so the operation was stopped.
【0026】[0026]
【比較例3】液滴化用のガス流体用の入口の他に液体用
に2つの入口を持ち内部で2液の混合ができるタイプの
ノズルを使用し、ガス流体用の入口に窒素ガスを150
Nl/分流し、A,Bの2溶液をそれぞれ120ml/
分でノズルに供給した。2溶液はノズル内部で混合され
た後、液流体用出口から出てガス流体によって液滴に分
散された。ノズル内部での計算上の滞留時間は0.2秒
以下であったが、運転開始後1〜2分でノズル内部に高
粘性物が生成し運転の継続ができなくなった。[Comparative Example 3] In addition to an inlet for gas fluid for forming droplets, a nozzle of a type having two inlets for liquid and capable of mixing two liquids inside is used, and nitrogen gas is used for the inlet for gas fluid. 150
Nl / divided, two solutions of A and B 120ml /
The nozzle was fed in minutes. The two solutions were mixed inside the nozzle, then exited from the liquid fluid outlet, and were dispersed into droplets by the gas fluid. Although the calculated residence time inside the nozzle was 0.2 seconds or less, a highly viscous substance was generated inside the nozzle 1 to 2 minutes after the start of the operation, and the operation could not be continued.
【0027】[0027]
【実施例1】図1に示した2本ノズルを結束したタイプ
で、内径0.7mmの2本のノズルの組み合わせ及び内
径0.4mmの2本のノズルの組み合わせを使用し、
A,Bのモノマー溶液を表1に示す液線速(ノズル先端
速度)でそれぞれ別のノズルに供給して噴霧重合試験を
行った。このノズルは連続運転性能に優れ、1時間以上
の継続運転が可能であった。結果を表1に示す。表1か
ら明らかなように、平均粒径はモノマー溶液の線速には
あまり影響されないが、ノズル先端部分の内径、したが
って断面積とは相関関係がある。Example 1 A type in which the two nozzles shown in FIG. 1 are bundled, and a combination of two nozzles having an inner diameter of 0.7 mm and a combination of two nozzles having an inner diameter of 0.4 mm are used.
A spray polymerization test was performed by supplying the monomer solutions of A and B to the different nozzles at the liquid linear velocities (nozzle tip velocities) shown in Table 1. This nozzle was excellent in continuous operation performance and could be continuously operated for 1 hour or more. The results are shown in Table 1. As is clear from Table 1, the average particle diameter is not so much influenced by the linear velocity of the monomer solution, but has a correlation with the inner diameter of the nozzle tip portion, that is, the cross-sectional area.
【表1】 [Table 1]
【0028】[0028]
【実施例2】図3に示したタイプの二重式ノズルで、外
管の内径が0.9mmのノズル及び外管の内径が0.6
mmのノズルを使用した。内管外壁と外管内壁との間の
開口部(外側ノズル)の断面積と内管の開口部(内側ノ
ズル)の断面積は同一であった。Aのモノマー水溶液を
内側ノズルに、Bのモノマー水溶液を外側ノズルにそれ
ぞれ表2に示す液線速(ノズル先端速度)で供給して噴
霧重合試験を行った。このノズルは連続運転性能に優
れ、1時間以上の継続運転が可能であった。結果を表2
に示す。表2から明らかなように、平均粒径はモノマー
溶液の線速にはあまり影響されないが、ノズル先端部分
の外管の内径、従って断面積とは相関関係がある。[Embodiment 2] A double-type nozzle of the type shown in FIG. 3, in which the outer tube has an inner diameter of 0.9 mm and the outer tube has an inner diameter of 0.6.
A mm nozzle was used. The cross-sectional area of the opening (outer nozzle) between the outer wall of the inner tube and the inner wall of the outer tube was the same as the cross-sectional area of the opening of the inner tube (inner nozzle). A spray polymerization test was carried out by supplying the monomer aqueous solution A to the inner nozzle and the monomer aqueous solution B to the outer nozzle at the liquid linear velocity (nozzle tip velocity) shown in Table 2, respectively. This nozzle was excellent in continuous operation performance and could be continuously operated for 1 hour or more. The results are shown in Table 2.
Shown in. As is clear from Table 2, the average particle diameter is not so much influenced by the linear velocity of the monomer solution, but has a correlation with the inner diameter of the outer tube at the nozzle tip portion, that is, the cross-sectional area.
【表2】 [Table 2]
【0029】[0029]
【実施例3】図5に示したタイプの二重式ノズルで、外
管の内径(孔径)が0.6mm、内管の内径が0.3m
m、内管が外管の孔より出ている長さが0.7mmのノ
ズルを使用し、A,Bのモノマー水溶液又はBのモノマ
ー水溶液と15%過酸化水素H2 O2 水溶液を表3に示
す液線速(ノズル先端速度)でそれぞれ別のノズルに供
給して噴霧重合試験を行った。結果を表3に示す。この
ノズルは連続運転性能に優れ、1時間以上の継続運転が
可能であった。[Embodiment 3] A double type nozzle of the type shown in FIG. 5, in which the outer tube has an inner diameter (hole diameter) of 0.6 mm and the inner tube has an inner diameter of 0.3 m.
m, a nozzle having a length of 0.7 mm in which the inner tube is protruded from the hole of the outer tube is used, and a monomer aqueous solution of A or B or a monomer aqueous solution of B and a 15% hydrogen peroxide H 2 O 2 aqueous solution are used. The spray polymerization test was carried out by supplying the liquid linear velocity (nozzle tip velocity) to different nozzles. The results are shown in Table 3. This nozzle was excellent in continuous operation performance and could be continuously operated for 1 hour or more.
【表3】 [Table 3]
【0030】[0030]
【実施例4】図7に示した対向型ノズル又は図8に示し
た同心円型ノズルを使用して、A,Bのモノマー溶液を
表4に示す条件でそれぞれ別のノズルに供給し、ガス用
ノズルから窒素ガスを供給して噴霧重合試験を行った。
A,Bの2液は供給ラインを出てから混合されると同時
に噴出気流により液滴に分散される。結果を表4に示
す。これらの方法は平均400μm以下の粒子を造るの
に適している。対向型のノズルも同心円型のノズルも連
続運転性能に優れ、1時間以上の継続運転が可能であっ
た。Example 4 Using the facing type nozzle shown in FIG. 7 or the concentric type nozzle shown in FIG. 8, monomer solutions of A and B were supplied to different nozzles under the conditions shown in Table 4 for gas. A spray polymerization test was performed by supplying nitrogen gas from the nozzle.
The two liquids A and B are mixed after they exit the supply line, and at the same time, they are dispersed into droplets by the jet stream. The results are shown in Table 4. These methods are suitable for producing particles with an average diameter of 400 μm or less. Both the opposed type nozzle and the concentric type nozzle were excellent in continuous operation performance and could be continuously operated for 1 hour or more.
【表4】 [Table 4]
【0031】[0031]
【発明の効果】ノズル内部及びノズル上におけるモノマ
ーの重合をなくし、ノズルの閉塞・重合物の堆積を防止
できるので、長期連続運転が可能となり、ノズルの保守
点検・清掃が簡単となる。EFFECTS OF THE INVENTION Since the polymerization of the monomer inside and on the nozzle can be eliminated to prevent the clogging of the nozzle and the accumulation of the polymer, long-term continuous operation becomes possible and the maintenance and cleaning of the nozzle become easy.
【図1】本発明を実施するためのノズルの一例を示す図
である。FIG. 1 is a diagram showing an example of a nozzle for carrying out the present invention.
【図2】図1に示したノズルの断面図である。FIG. 2 is a cross-sectional view of the nozzle shown in FIG.
【図3】本発明を実施するためのノズルの他の例(二重
式ノズル)を示す図である。FIG. 3 is a view showing another example (double type nozzle) of a nozzle for carrying out the present invention.
【図4】図3に示したノズルの断面図である。4 is a cross-sectional view of the nozzle shown in FIG.
【図5】本発明を実施するための二重式ノズルの他の例
を示す図である。FIG. 5 is a view showing another example of a double type nozzle for carrying out the present invention.
【図6】図5に示したノズルの断面図である。6 is a cross-sectional view of the nozzle shown in FIG.
【図7】第1液及び第2液が混合する場所に高速の気流
を噴射するタイプのノズルの一例(対向型ノズル)の断
面図である。FIG. 7 is a cross-sectional view of an example of a nozzle (opposed nozzle) of a type that ejects a high-speed airflow to a place where the first liquid and the second liquid are mixed.
【図8】第1液及び第2液が混合する場所に高速の気流
を噴射するタイプのノズルの他の例(同心円型ノズル)
の断面図である。FIG. 8 is another example of a nozzle of a type that ejects a high-speed air stream to a place where the first liquid and the second liquid are mixed (concentric nozzle).
FIG.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 大原 武 神奈川県横浜市南区別所1−14−1日揮株 式会社横浜事業所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takeshi Ohara 1-1-14, Minami Sanrokusho, Yokohama-shi, Kanagawa JGC Corporation Yokohama Office
Claims (7)
分とするモノマー溶液をレドックス系重合開始剤を使用
して噴霧重合するに際して、レドックス系重合開始剤を
構成する酸化剤と還元剤の内の一方をモノマー溶液に添
加した第1液を第1の液用ノズルに供給し、酸化剤と還
元剤の内の他方はモノマー溶液を加え又は加えずに第2
液として第2の液用ノズルに供給し、第1及び第2の液
用ノズルの出口で第1液及び第2液が混合するように噴
出させて気相中で重合反応を行わせることを特徴とする
噴霧重合法。1. When a monomer solution containing an organic unsaturated carboxylic acid or a salt thereof as a main component is spray-polymerized by using a redox-based polymerization initiator, the redox-based polymerization initiator is mixed with an oxidizing agent and a reducing agent. The first liquid in which one of them is added to the monomer solution is supplied to the nozzle for the first liquid, and the other of the oxidizing agent and the reducing agent is added to the second nozzle without or with the addition of the monomer solution.
The liquid is supplied to the second liquid nozzle, and jetted so that the first liquid and the second liquid are mixed at the outlets of the first and second liquid nozzles to carry out the polymerization reaction in the gas phase. Characteristic spray polymerization method.
並べて設置され、且つ両方の先端位置が揃っている一組
の液用ノズルを使用する請求項1記載の噴霧重合法。2. The spray polymerization method according to claim 1, wherein the first liquid nozzle and the second liquid nozzle are installed side by side, and a set of liquid nozzles in which both tip positions are aligned is used.
内挿されている二重式ノズルを使用する請求項1記載の
噴霧重合法。3. The spray polymerization method according to claim 1, wherein a double type nozzle in which the first liquid nozzle is inserted in the second liquid nozzle is used.
置された二本の液用ノズルを使用し、それら二本の液用
ノズルから噴射された液が交差する位置に気流を噴射す
る請求項1記載の噴霧重合法。4. Use of two liquid nozzles installed separately at an angle at which the extension lines of the tips intersect, and jets an air flow at a position where the liquids jetted from these two liquid nozzles intersect. The spray polymerization method according to claim 1.
管を中心として、第1の円管の外径より大きい内径の第
2の円管及び第2の円管の外径より大きい内径の第3の
円管が同心円的に重ねられた三重管構造で、第1の円管
と第2の円管との間隙を第1の液用ノズル、第2の円管
と第3の円管との間隙を第2の液用ノズルとして使用す
る請求項1記載の噴霧重合法。5. A second circular pipe having an inner diameter larger than the outer diameter of the first circular pipe and an inner diameter larger than the outer diameter of the second circular pipe centering on the first circular pipe used as a gas nozzle. A triple pipe structure in which third circular pipes are concentrically stacked, and a gap between the first circular pipe and the second circular pipe is provided with a first liquid nozzle, a second circular pipe and a third circular pipe. 2. The spray polymerization method according to claim 1, wherein the gap between and is used as a second liquid nozzle.
置された二本の液用ノズルと、液の交差部に気流を噴射
するガス用ノズルを有することを特徴とする重合性モノ
マーの噴霧重合用ノズル。6. A polymerizable monomer comprising: two liquid nozzles, which are separately installed at an angle at which the extension lines of the tips intersect, and a gas nozzle for injecting an air stream at the intersection of the liquids. Spray polymerization nozzle.
管を中心として、第1の円管の外径より大きい内径の第
2の円管及び第2の円管の外径より大きい内径の第3の
円管が同心円的に重ねられた三重管構造で、第1の円管
と第2の円管との間隙が第1の液用ノズル、第2の円管
と第3の円管との間隙が第2の液用ノズルを構成してい
ることを特徴とする重合性モノマーの噴霧重合用ノズ
ル。7. A second circular pipe having an inner diameter larger than the outer diameter of the first circular pipe and an inner diameter larger than the outer diameter of the second circular pipe centering around the first circular pipe used as a gas nozzle. A triple pipe structure in which third circular pipes are concentrically overlapped, and a gap between the first circular pipe and the second circular pipe is a first liquid nozzle, a second circular pipe and a third circular pipe. A nozzle for spray polymerization of a polymerizable monomer, characterized in that a gap between and forms a second liquid nozzle.
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JP32400591A JP3145156B2 (en) | 1991-11-13 | 1991-11-13 | Spray polymerization method and nozzle for spray polymerization |
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JP32400591A JP3145156B2 (en) | 1991-11-13 | 1991-11-13 | Spray polymerization method and nozzle for spray polymerization |
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WO2003011913A1 (en) * | 2001-07-31 | 2003-02-13 | Mitsubishi Chemical Corporation | Method of polymerization and nozzle for use in the polymerization method |
US6590052B2 (en) | 1997-10-28 | 2003-07-08 | Atofina | Process for continuous polymerization with micromixing of reactive fluids |
WO2006011625A1 (en) * | 2004-07-30 | 2006-02-02 | Mitsubishi Chemical Corporation | Liquid absorbing composite body, method for producing same, liquid absorbing article, and nozzle |
JP2010024374A (en) * | 2008-07-22 | 2010-02-04 | Osaka Prefecture Univ | Droplet composition and method for producing the same, polymer composition, and apparatus for producing droplet composition |
US8013087B2 (en) | 2006-10-05 | 2011-09-06 | Basf Se | Method for the production of water absorbent polymer particles by polymerizing drops of a monomer solution |
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- 1991-11-13 JP JP32400591A patent/JP3145156B2/en not_active Expired - Lifetime
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US6892958B2 (en) | 1997-10-28 | 2005-05-17 | Arkema | Process for the continuous polymerization with micromixing of reactive fluids |
US6590052B2 (en) | 1997-10-28 | 2003-07-08 | Atofina | Process for continuous polymerization with micromixing of reactive fluids |
EP1424346A4 (en) * | 2001-07-31 | 2008-05-07 | Mitsubishi Chem Corp | Method of polymerization and nozzle for use in the polymerization method |
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US7288610B2 (en) | 2001-07-31 | 2007-10-30 | Mitsubishi Chemical Corporation | Method of polymerization and nozzle employed in same |
WO2003011913A1 (en) * | 2001-07-31 | 2003-02-13 | Mitsubishi Chemical Corporation | Method of polymerization and nozzle for use in the polymerization method |
WO2006011625A1 (en) * | 2004-07-30 | 2006-02-02 | Mitsubishi Chemical Corporation | Liquid absorbing composite body, method for producing same, liquid absorbing article, and nozzle |
US8013087B2 (en) | 2006-10-05 | 2011-09-06 | Basf Se | Method for the production of water absorbent polymer particles by polymerizing drops of a monomer solution |
US8529805B2 (en) | 2006-10-05 | 2013-09-10 | Basf Se | Method for the production of water absorbent polymer particles by polymerizing drops of a monomer solution |
US10450395B2 (en) | 2006-10-05 | 2019-10-22 | Basf Se | Method for the production of absorbent polymer particles by polymerizing drops of a monomer solution |
JP2010024374A (en) * | 2008-07-22 | 2010-02-04 | Osaka Prefecture Univ | Droplet composition and method for producing the same, polymer composition, and apparatus for producing droplet composition |
EP2907582A1 (en) * | 2014-02-17 | 2015-08-19 | ERBE Elektromedizin GmbH | Method and nozzle for mixing and spraying medical fluids |
JP2015150440A (en) * | 2014-02-17 | 2015-08-24 | エルベ エレクトロメディジン ゲゼルシャフト ミット ベシュレンクテル ハフツングERBE ELEKTROMEDIZIN GmbH | Method and nozzle for mixing and spraying fluids |
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