JP2003292528A - Method for recovering unreacted monomer component at polymerization of acrylonitrile-based monomer and polymerization system - Google Patents
Method for recovering unreacted monomer component at polymerization of acrylonitrile-based monomer and polymerization systemInfo
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- monomer component
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、水系懸濁重合によ
るアクリル系共重合体の重合時に残留するモノマー成分
の回収方法とアクリル系共重合体の重合システムに関
し、特に未反応の前記モノマー成分を重合時の原料モノ
マーとして回収し、循環利用する未反応モノマー成分の
効率的な回収方法とそのアクリル系共重合体の重合シス
テムに関する。TECHNICAL FIELD The present invention relates to a method of recovering a monomer component remaining during polymerization of an acrylic copolymer by aqueous suspension polymerization and a polymerization system of the acrylic copolymer, and more particularly to a method for recovering the unreacted monomer component. The present invention relates to an efficient method for recovering an unreacted monomer component that is recovered as a raw material monomer at the time of polymerization and reused, and a polymerization system for an acrylic copolymer.
【０００２】[0002]
【従来の技術】アクリル繊維は、羊毛に似た優れた嵩高
性、風合、染色鮮明性等の性質を有し、広範囲の用途に
利用されている。また、このアクリル繊維は、炭素繊維
の原料としても多用されている。その紡糸法には、原料
となるアクリル系共重合体を有機溶媒、又は無機溶媒に
溶解する溶解工程を経て、湿式紡糸法、乾式紡糸法又は
半乾式紡糸法によりステ−プル又はフィラメントとされ
る。この原料となるアクリロニトリル系共重合体は、ア
クリロニトリルモノマーとそれと共重合可能なアクリル
酸エステル、メタクリル酸エステル、酢酸ビニル、アク
リルアミドなどの非イオン性のコモノマーとをラジカル
重合させることにより製造される。2. Description of the Related Art Acrylic fibers have excellent bulkiness, texture, and dyeing clarity similar to wool, and are used in a wide range of applications. Further, this acrylic fiber is also frequently used as a raw material for carbon fiber. In the spinning method, a staple or filament is formed by a wet spinning method, a dry spinning method, or a semi-dry spinning method through a dissolution step of dissolving the raw material acrylic copolymer in an organic solvent or an inorganic solvent. . The acrylonitrile-based copolymer as the raw material is produced by radically polymerizing an acrylonitrile monomer and a nonionic comonomer such as an acrylic acid ester, a methacrylic acid ester, vinyl acetate or acrylamide which is copolymerizable therewith.
【０００３】アクリロニトリル系共重合体の製造は、水
を反応媒体として、連続懸濁重合方式を採用することが
多い。この連続懸濁重合方式では、原料タンク及びモノ
マー回収工程よりアクリロニトリルのモノマーとコモノ
マーとが個別に計量され、モノマー調製タンクに供給さ
れる。調製タンク内のモノマー仕込組成は、製造するポ
リマーの共重合組成により、アクリロニトリルとコモノ
マーの反応性比を考慮して、一定値に厳密に設定する必
要がある。For the production of an acrylonitrile copolymer, a continuous suspension polymerization system is often adopted with water as a reaction medium. In this continuous suspension polymerization method, the acrylonitrile monomer and the comonomer are individually measured from the raw material tank and the monomer recovery step and supplied to the monomer preparation tank. The monomer charge composition in the preparation tank must be strictly set to a constant value in consideration of the reactivity ratio of acrylonitrile and comonomer depending on the copolymerization composition of the polymer to be produced.
【０００４】重合釜には、調製されたアクリロニトリル
とコモノマー、水、触媒などとともに、重合開始剤が添
加されて重合が行われる。このときの重合開始剤として
は、一般的に無機系開始剤が使用される。無機系開始剤
としては、例えば過硫酸アンモニウム−亜硫酸水素ナト
リウム−硫酸第一鉄の酸化−還元系の組合せが多く使わ
れており、上記コモノマーを含むアクリロニトリルを主
成分とするモノマー成分が、反応媒体として作用する硫
酸酸性水を使用して重合反応すると、数十ミクロンの粒
子状の重合体が形成され、水性分散液の状態でアクリロ
ニトリル系重合体が得られる。A polymerization initiator is added to the polymerization kettle together with the prepared acrylonitrile, comonomer, water, catalyst and the like to carry out polymerization. As the polymerization initiator at this time, an inorganic initiator is generally used. As the inorganic initiator, for example, a combination of ammonium persulfate-sodium hydrogen sulfite-ferrous sulfate oxidation-reduction system is often used, and a monomer component containing acrylonitrile as a main component containing the above comonomer is used as a reaction medium. Polymerization reaction using active sulfuric acid water forms a polymer in the form of particles of several tens of microns, and an acrylonitrile polymer is obtained in the state of an aqueous dispersion.
【０００５】重合釜から取り出した重合体に、重合停止
剤を添加し反応を停止させる。アクリロニトリル系重合
体を水系懸濁重合で製造する場合の重合停止剤として
は、反応系の酸性水溶液を中和する機能を保持すること
が必要であり、シュウ酸ナトリウム、重炭酸ナトリウ
ム、エチレンジアミン４酢酸２ナトリウム塩などの電解
質水溶液が用いられる。また、貯蔵中や輸送中において
アクリロニトリルのモノマーの重合を禁止すべく、通
常、原料モノマーに、例えばｐ- メトキシフェノールな
どの重合禁止剤が予め添加されている。A polymerization terminator is added to the polymer taken out from the polymerization kettle to stop the reaction. As a polymerization terminator for producing an acrylonitrile-based polymer by aqueous suspension polymerization, it is necessary to maintain the function of neutralizing the acidic aqueous solution of the reaction system. Sodium oxalate, sodium bicarbonate, ethylenediamine tetraacetic acid. An aqueous electrolyte solution such as a disodium salt is used. In order to inhibit the polymerization of the acrylonitrile monomer during storage and transportation, a polymerization inhibitor such as p-methoxyphenol is usually added to the raw material monomer in advance.
【０００６】重合反応の重合停止剤は、通常、アクリロ
ニトリル系重合体を水系懸濁重合方式で製造する際に使
用されるものであれば問題はない。重合体水溶液に重合
停止剤を添加した後、未反応単量体の回収を行う。未反
応単量体の回収方法としては重合体水溶液を直接蒸留し
たのち、気化して分離した未反応モノマー成分と水がコ
ンデンサーに送られ凝縮し、モノマー／水の溶液とな
る。この溶液をデカンターによりモノマー成分と水とに
分離する。分離したモノマー成分は重合釜に戻される。
一方、重合体中に残った水分は通常の乾燥方式によって
取り除かれる。There is no problem as long as the polymerization terminator for the polymerization reaction is usually used when the acrylonitrile polymer is produced by the aqueous suspension polymerization method. After adding the polymerization terminator to the polymer aqueous solution, the unreacted monomer is recovered. As a method of recovering the unreacted monomer, the polymer aqueous solution is directly distilled, and then the unreacted monomer component separated by vaporization and water are sent to a condenser and condensed to form a monomer / water solution. This solution is separated into a monomer component and water by a decanter. The separated monomer component is returned to the polymerization kettle.
On the other hand, the water remaining in the polymer is removed by a usual drying method.
【０００７】[0007]
【発明が解決しようとする課題】ところで、硫酸酸性水
中でアルリロニトリル系重合体が重合されるとき、重合
開始剤である過硫酸アンモニウム−亜硫酸水素ナトリウ
ム−硫酸第一鉄の組合せは、次のとおり遊離基へと分解
される。
（ＮＨ4 ）2 Ｓ2 Ｏ8 →２ＮＨ4 + ＋Ｓ2 Ｏ8 2-
ＮａＨＳＯ3 →Ｎａ+ ＋ＨＳＯ3 -
ＦｅＳＯ4 →Ｆｅ2+＋ＳＯ4 2-
レドックス触媒による重合開始反応は、
Ｓ2 Ｏ8 2-＋Ｆｅ2+→ＳＯ4 2-＋ＳＯ4 ＋Ｆｅ3+
ＨＳＯ3 - ＋Ｆｅ3+→ＨＳＯ3 ・＋Ｆｅ2+
と進行し、このとき亜硫酸と二酸化硫黄とは、
Ｈ+ ＋ＨＳＯ3 - ⇔ Ｈ2 ＳＯ3 ⇔ＳＯ2 ＋Ｈ2 Ｏ
の関係を保って平衡状態を維持する。When the arylonitrile polymer is polymerized in sulfuric acid-acidified water, the combination of the polymerization initiator ammonium persulfate-sodium bisulfite-ferrous sulfate is as follows. Decomposes into free radicals. (NH 4) 2 S 2 O 8 → 2NH 4 + + S 2 O 8 2- NaHSO 3 → Na + + HSO 3 - FeSO 4 → Fe 2+ + polymerization initiation by SO 4 2-redox catalysts, S 2 O 8 2 - + Fe 2+ → SO 4 2+ SO 4 + Fe 3+ HSO 3+ Fe 3+ → HSO 3 · + Fe 2+ and progress, and this time sulfite and sulfur dioxide, H + + HSO 3 - ⇔ H 2 SO 3 Maintain the equilibrium state by maintaining the relationship of ⇔ SO 2 + H 2 O.
【０００８】重合開始剤として重合釜に添加された亜硫
酸水素ナトリウム（ＮａＨＳＯ3 ）のうち、使用されな
かった遊離基が酸性雰囲気下で一部ＳＯ2 となり、蒸留
塔にてモノマー／水と一緒にコンデンサーへと送られ
る。ＳＯ2 及びモノマー／水が凝縮される際に、水に溶
けてＨＳＯ3 - となって、これが重合開始剤として働
き、アクリロニトリル系のモノマー成分を重合させてし
まう。Of the sodium bisulfite (NaHSO 3 ) added to the polymerization kettle as a polymerization initiator, some of the unused free radicals become SO 2 under acidic atmosphere, and together with the monomer / water in the distillation column. It is sent to the condenser. When SO 2 and the monomer / water are condensed, they are dissolved in water to become HSO 3 − , which acts as a polymerization initiator to polymerize the acrylonitrile-based monomer component.
【０００９】このようにして、デカンターで分離される
回収モノマーには重合が起こっているものが多く含まれ
るようになり、重合釜に戻すにあたって様々な問題が発
生する。すなわち、既述したとおり、重合釜に投入され
る前の調製タンク内のモノマー仕込組成は、アクリロニ
トリルとコモノマーの反応性比を考慮して、一定値に厳
密に設定する必要がある。As described above, the recovered monomer separated by the decanter contains a large amount of those which have undergone polymerization, and causes various problems in returning to the polymerization kettle. That is, as described above, the monomer charge composition in the preparation tank before being charged into the polymerization kettle must be strictly set to a constant value in consideration of the reactivity ratio of acrylonitrile and comonomer.
【００１０】したがって、この重合工程にあっては、回
収モノマーの品質により、原料モノマーの仕込組成、
水、触媒の供給量、重合温度などのポリマーの共重合組
成、重合度、重合度分布に微妙な影響をあたえることに
なる。一方、モノマー回収工程で回収されるモノマー成
分（アルリロニトリル／コモノマー）に重合を終了した
ポリマーが混入していると、その混入量は一定とはなら
ず、刻々変化する。しかも、連続重合工程において前記
回収モノマーの混入量を算出することは極めて困難であ
り、仮にその算出が可能であったとしても、その算出量
に応じて調製タンクへの原料モノマー類の投入量を、前
述のように、厳密に調製しなければならなくなり、実施
は到底無理である。更に、モノマーの回収工程に固形の
重合体が混入していると、詰まりが発生しやすくなる。Therefore, in this polymerization step, depending on the quality of the recovered monomer, the charge composition of the raw material monomer,
It has a delicate influence on the copolymerization composition of the polymer such as water, the supply amount of the catalyst, the polymerization temperature, the degree of polymerization, and the degree of polymerization distribution. On the other hand, when the polymer that has been polymerized is mixed in the monomer component (allylonitrile / comonomer) recovered in the monomer recovery step, the mixed amount is not constant and changes every moment. Moreover, it is extremely difficult to calculate the mixed amount of the recovered monomer in the continuous polymerization step, and even if the calculated amount can be calculated, the amount of the raw material monomers to be added to the preparation tank should be adjusted according to the calculated amount. As mentioned above, it has to be strictly prepared, and its implementation is impossible. Furthermore, if a solid polymer is mixed in the monomer recovery step, clogging is likely to occur.
【００１１】本発明は、こうした課題を解決すべくなさ
れたものであり、具体的にはモノマー回収工程で回収さ
れるモノマー成分に、凝縮後の重合により生成された重
合体が混入すること防止し、アクリロニトリル系重合体
の純粋なモノマー成分だけを回収できるモノマー回収方
法とアクリロニトリル系重合体の重合システムとを提供
するを目的としている。The present invention has been made to solve these problems, and specifically, prevents the polymer produced by the polymerization after condensation from being mixed into the monomer component recovered in the monomer recovery step. An object of the present invention is to provide a monomer recovery method capable of recovering only a pure monomer component of an acrylonitrile polymer and a polymerization system for an acrylonitrile polymer.
【００１２】[0012]
【課題を解決するための手段及び作用効果】本発明者ら
は、アルリロニトリル系のモノマーが、蒸留塔を経てコ
ンデンサーによる凝縮中に或いは凝縮後に重合すること
を抑えようとするには、要は凝縮後のモノマー／水の混
合液中に遊離して存在するＨＳＯ3 - を安定化する物質
に変化させることが必要であり、ここに重合禁止剤を添
加すれば重合体の生成はなくなると考えた。この重合禁
止剤を加える場合、モノマー成分が十分凝縮し液化した
段階で添加することが考えられる。また、この添加には
重合禁止剤溶液を別途調製して添加することもできる。
禁止剤を添加しない場合は、十分な冷却を行い、重合反
応を生じさせなければよい。MEANS FOR SOLVING THE PROBLEMS AND EFFECTS OF EFFECT OF THE INVENTION The inventors of the present invention are required to suppress polymerization of an arylonitrile-based monomer during or after condensation by a condenser via a distillation column. Needs to be converted into a substance that stabilizes HSO 3 − existing in the monomer / water mixture after condensation to stabilize it, and if a polymerization inhibitor is added to this, the formation of a polymer will disappear. Thought. When the polymerization inhibitor is added, it may be considered to be added when the monomer components are sufficiently condensed and liquefied. Further, for this addition, a polymerization inhibitor solution can be separately prepared and added.
When no inhibitor is added, sufficient cooling may be performed so that the polymerization reaction does not occur.
【００１３】しかるに、気化したモノマー成分が十分に
凝縮し液化した段階で重合禁止剤を添加しても、相変わ
らず重合体が生成されていることがある。また、冷却に
より凝縮し液化したモノマー成分の重合を抑えようとす
ると、その冷却配管設備が必要となる。本発明者らは、
更に検討を進めたところ、コンデンサーに導入されるモ
ノマー成分が重合を開始するのは、気化したモノマー成
分が凝縮し液化し始めた瞬間において既に重合反応が開
始している可能性があるという事実に着目した。その結
果、本発明に到達したものである。However, even if the polymerization inhibitor is added when the vaporized monomer component is sufficiently condensed and liquefied, the polymer may still be produced. Further, in order to suppress the polymerization of the monomer component condensed and liquefied by cooling, the cooling piping equipment is required. We have
As a result of further study, the fact that the monomer component introduced into the condenser starts the polymerization is due to the fact that the polymerization reaction may have already started at the moment when the vaporized monomer component begins to condense and liquefy. I paid attention. As a result, the present invention has been reached.
【００１４】本発明の第１の基本構成は、アルリロニト
リル系重合体の水系懸濁重合工程で発生するモノマー成
分の回収方法であって、重合工程で得られるモノマー／
ポリマー／水の混合物を蒸留してモノマーと水とをポリ
マーから気化分離させること、及び気化したモノマーと
水を凝縮させてモノマー成分を回収することを備えてな
り、気化工程から凝縮工程への移行時に微量の重合禁止
剤を添加することを含んでなることを特徴とするアクリ
ロニトリル系モノマー成分の回収方法にある。A first basic constitution of the present invention is a method for recovering a monomer component generated in an aqueous suspension polymerization process of an arylonitrile polymer, wherein a monomer obtained in the polymerization process is
Comprising distilling the polymer / water mixture to vaporize and separate the monomer and water from the polymer, and condensing the vaporized monomer and water to recover the monomer component, the transition from the vaporization step to the condensation step. A method for recovering an acrylonitrile-based monomer component is characterized by comprising adding a trace amount of a polymerization inhibitor at times.
【００１５】すなわち、本発明では重合工程で得られる
モノマー／ポリマー／水の混合物を蒸留してモノマー成
分と水をポリマーから気化分離させ、気化したモノマー
と水を凝縮させてモノマー成分を回収するにあたり、モ
ノマー成分と水の気化工程から凝縮工程へと移行すると
き、例えば凝縮工程の入口で微量の重合禁止剤を添加す
る。このときの添加は、重合禁止剤を単独で又は他の物
質と混合させて、霧状に噴霧し、或いは滴下することに
より行う。この重合禁止剤はモノマー成分と水とに混ざ
り合って下流側に運ばれ、モノマー成分と水とが凝縮さ
れて液化した段階で、重合開始剤として機能するＨＳＯ
3 - と結合して、安定物質に変化し、モノマー成分の重
合を停止させる。That is, in the present invention, the monomer / polymer / water mixture obtained in the polymerization step is distilled to vaporize and separate the monomer component and water from the polymer, and the vaporized monomer and water are condensed to recover the monomer component. At the time of shifting from the vaporization step of the monomer components and water to the condensation step, for example, a small amount of a polymerization inhibitor is added at the inlet of the condensation step. The addition at this time is performed by spraying the polymerization inhibitor alone or in a mixture with other substances, and spraying or dropping. This polymerization inhibitor mixes with the monomer component and water and is carried to the downstream side. When the monomer component and water are condensed and liquefied, HSO that functions as a polymerization initiator
3 - combine with, changed to stable material, to stop the polymerization of the monomer component.
【００１６】前記重合工程で得られる重合生成物は、通
常、モノマー／ポリマー／水の比率２〜７％／１０〜３
５％／５８〜８８％の範囲にあり、且つＳＯ2 源が０．
０２〜０．２０％含有されている。添加される重合禁止
剤の添加量は、凝縮工程で得られる前記モノマー成分に
対する重量比で４〜１５０ｐｐｍであることが好まし
い。４ｐｐｍより少ないと添加量が少なすぎて、残留す
るＳＯ2 源と十分に反応できず僅かであっても重合が起
こってしまう。１５０ｐｐｍを越えると、回収されるモ
ノマー成分中に余分な重合禁止剤が残って混入し、重合
反応時に使用する開始剤が余剰に必要となる。また重合
反応の制御に影響を及ぼす可能性がある。The polymerization product obtained in the above-mentioned polymerization step usually has a monomer / polymer / water ratio of 2 to 7% / 10 to 3
In the range of 5% / 58 to 88%, and SO 2 source 0.
The content is 02 to 0.20%. The addition amount of the polymerization inhibitor to be added is preferably 4 to 150 ppm as a weight ratio with respect to the monomer component obtained in the condensation step. If it is less than 4 ppm, the amount of addition is too small to sufficiently react with the remaining SO 2 source, and even a slight amount thereof causes polymerization. If it exceeds 150 ppm, an extra polymerization inhibitor remains and is mixed in the recovered monomer component, and an excess of an initiator used during the polymerization reaction is required. It may also affect the control of the polymerization reaction.
【００１７】前記凝縮工程で得られた前記モノマー成分
に対して重量比で２０〜１００ｐｐｍの重合禁止剤を添
加し、この重合禁止剤が添加された前記モノマー成分
を、重合工程で残留する未反応の上記モノマー成分に対
して２０〜１５０％の重量比で添加することが好まし
い。この場合、凝縮工程に添加される最終的な重合禁止
剤の量は前述とほぼ等しいが、重合禁止剤の調製設備を
別途設ける必要がなくなり、凝縮工程で得られた前記モ
ノマー成分に直接重合禁止剤を添加して、これを凝縮工
程に導入するため次第に希釈され、凝縮して完全に液化
するモノマー成分に含有する重合体の量は無視できる程
度の極く微量となり、これを調製タンクに戻しても、同
タンクにおける原料モノマー成分の仕込組成の調製に格
別の操作は不要となる。20 to 100 ppm by weight of a polymerization inhibitor is added to the monomer component obtained in the condensation step, and the monomer component added with the polymerization inhibitor is left unreacted in the polymerization step. It is preferable to add it in a weight ratio of 20 to 150% with respect to the above-mentioned monomer component. In this case, the final amount of the polymerization inhibitor added to the condensation step is almost the same as that described above, but it is not necessary to provide a separate preparation facility for the polymerization inhibitor, and the monomer component obtained in the condensation step is directly inhibited from polymerization. The amount of the polymer contained in the monomer component, which is gradually diluted by adding the agent and introduced into the condensation step and condensed and completely liquefied, becomes negligible and returned to the preparation tank. However, no special operation is required for the preparation of the feed composition of the raw material monomer components in the same tank.
【００１８】前記重合工程で得られる重合生成物が、モ
ノマー／ポリマー／水の比率２〜７％／１０〜３５％／
５８〜８８％であって、且つＳＯ2 源が０．０２〜０．
２０％含有されており、重量比で２０〜１００ｐｐｍの
重合禁止剤を含むアクリロニトリルの原料モノマーを、
凝縮工程で得られた上記モノマー成分に対して２０〜１
５０％の重量比で添加することもできる。The polymerization product obtained in the above-mentioned polymerization step has a monomer / polymer / water ratio of 2 to 7% / 10 to 35% /
A 58 to 88%, and SO 2 source from 0.02 to 0.
Acrylonitrile raw material monomer containing 20% by weight and containing 20 to 100 ppm by weight of a polymerization inhibitor,
20 to 1 with respect to the above-mentioned monomer components obtained in the condensation step
It is also possible to add it in a weight ratio of 50%.
【００１９】この場合も、凝縮工程に添加される最終的
な重合禁止剤の添加量は前述の場合とほぼ等しいが、元
々アクリロニトリルの原料モノマーに添加されている重
合禁止剤を同原料モノマーとともに凝縮工程に導入する
ようにしている。このため配管などが容易であり、重合
禁止剤の調製設備を別途設ける必要がなくなる。しかも
重合禁止剤の添加量を容易に設定することが可能であ
る。Also in this case, the final amount of the polymerization inhibitor added to the condensation step is almost the same as in the above-mentioned case, but the polymerization inhibitor originally added to the raw material monomer of acrylonitrile is condensed with the same raw material monomer. I am trying to introduce it into the process. Therefore, piping and the like are easy, and it is not necessary to separately provide a facility for preparing the polymerization inhibitor. Moreover, it is possible to easily set the addition amount of the polymerization inhibitor.
【００２０】また、本発明の第２の基本構成は、水系懸
濁重合方式によるアクリロリトリル系重合体の重合シス
テムであって、重合部と、同重合部に連結される蒸留部
と、同蒸留部に連結される凝縮器とを備え、前記蒸留部
に連結される凝縮部の気体導入口近傍に、重合禁止剤の
導入口を更に有してなることを特徴とするアクリロリト
リル系重合体の重合システムにある。このシステムによ
れば、上記アクリロニトリル系の重合体の重合時におけ
る未反応モノマー成分の回収方法による重合禁止剤の添
加が確実に且つ容易に行えるようになる。A second basic constitution of the present invention is a polymerization system of an acrylonitrile polymer by an aqueous suspension polymerization method, which comprises a polymerization section, a distillation section connected to the polymerization section, And a condenser connected to the distillation section, further comprising an inlet for the polymerization inhibitor in the vicinity of the gas inlet of the condenser connected to the distillation section. It is in a combined polymerization system. According to this system, it becomes possible to reliably and easily add the polymerization inhibitor by the method of recovering the unreacted monomer component during the polymerization of the acrylonitrile-based polymer.
【００２１】この発明にあって、前記重合禁止剤の導入
口が、上記凝縮工程後に配されるモノマー成分と水との
分離工程のモノマー導出路と連結され、前記重合禁止剤
の導入口と前記分離工程のモノマー導出路との間に重合
禁止剤の導入部を設けることができる。この場合、モノ
マー成分と水との分離工程から導出されるモノマー成分
の一部が凝縮工程に戻されることになる。この戻される
途中に重合禁止剤の導入部から添加すべき重合禁止剤が
導入される。凝縮工程を経た未反応のモノマー成分及び
水に混在する重合開始剤として機能するＨＳＯ3 - 源は
再び凝縮工程に戻されるが、その戻される途中で重合禁
止剤の一部により安定化し、同時に凝縮工程に新たに導
入される同重合禁止剤により気化して導入されたモノマ
ー／水／ＳＯ2 のＳＯ2 と反応して安定化させる。これ
が繰り返されるうち、凝縮工程により凝縮して液化する
モノマー成分と水は高純度で安定化する。In the present invention, the introduction port of the polymerization inhibitor is connected to the monomer outlet passage of the separation step of separating the monomer component and water arranged after the condensation step, and the introduction port of the polymerization inhibitor and the An introduction part of the polymerization inhibitor can be provided between the monomer derivation path of the separation step. In this case, a part of the monomer component derived from the step of separating the monomer component and water is returned to the condensation step. During this returning, the polymerization inhibitor to be added is introduced from the introduction section of the polymerization inhibitor. HSO 3 functions as a polymerization initiator mixed in with the unreacted monomer component, and water passing through the condensation step - but returned to the source again condensation step, stabilized by a portion of the polymerization inhibitor in the course to the back, at the same time condensing It is stabilized by reacting with the introduced monomer / water / SO 2 of SO 2 which is vaporized by the polymerization inhibitor newly introduced into the process. While this is repeated, the monomer component and water that are condensed and liquefied in the condensation step are stabilized with high purity.
【００２２】更に本発明にあっては、前記重合禁止剤の
導入口を、前記重合禁止剤を含有するアクリロニトリル
の原料モノマーの供給源と連結するように構成すること
もできる。原料モノマーには、貯蔵時又は輸送時に重合
しないように予め所定の量の重合禁止剤が添加されてい
る。この発明では、そうした原料モノマーを凝縮工程の
重合禁止剤導入口に連結させている。かかる構成によ
り、凝縮工程に導入される重合禁止剤の添加量の調整制
御が容易となり、しかも原料モノマーの供給部と重合禁
止剤の導入口との間の配管も簡単にできる。Further, in the present invention, the introduction port of the polymerization inhibitor may be connected to the supply source of the raw material monomer of acrylonitrile containing the polymerization inhibitor. A predetermined amount of a polymerization inhibitor is added to the raw material monomer in advance so as not to polymerize during storage or transportation. In the present invention, such a raw material monomer is connected to the polymerization inhibitor introduction port in the condensation step. With such a configuration, adjustment control of the addition amount of the polymerization inhibitor to be introduced into the condensation step is facilitated, and moreover, piping between the supply unit of the raw material monomer and the introduction port of the polymerization inhibitor can be simplified.
【００２３】[0023]
【発明の実施の形態】以下、本発明の代表的な実施の形
態を図面に基づいて詳細に説明する。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, typical embodiments of the present invention will be described in detail with reference to the drawings.
【００２４】本発明は、水系懸濁重合方式によるアクリ
ロニトリル系重合体の製造時に発生する未反応のモノマ
ー成分を原料モノマーの調製タンクに戻すべく効率的に
回収する技術に関する。図１は、その重合・回収工程を
全てを模式的に示している。まず、主原料であるアクリ
ロニトリルの貯留槽１から計量ポンプ２ａを介してモノ
マー調製タンク３に、アクリロニトリルが計量されなが
ら所定量投入される。本実施形態では、前記貯蔵槽１に
貯蔵されるアクリロニトリルには貯蔵中に重合を起こさ
ないように、重量比で２０〜１００ｐｐｍのｐ- メトキ
シフェノールが添加されている。重合禁止剤としては、
前記ｐ- メトキシフェノールの他に、ハイドロキノン、
ｐ- ｔ- ブチルカテコール、ジフェニルピクリルヒドラ
ジル、ベンゾキノン、ガルビノキシル、１，３，５−ト
リフェニルフェルダジルなどが使用できる。The present invention relates to a technique for efficiently recovering unreacted monomer components generated during the production of an acrylonitrile polymer by an aqueous suspension polymerization method so as to return them to a raw material monomer preparation tank. FIG. 1 schematically shows all the polymerization / recovery steps. First, a predetermined amount of acrylonitrile is charged into the monomer preparation tank 3 from the storage tank 1 of acrylonitrile, which is a main raw material, via the measuring pump 2a. In the present embodiment, 20 to 100 ppm by weight of p-methoxyphenol is added to the acrylonitrile stored in the storage tank 1 so as not to cause polymerization during storage. As a polymerization inhibitor,
In addition to the p-methoxyphenol, hydroquinone,
p-t-Butylcatechol, diphenylpicrylhydrazyl, benzoquinone, galvinoxyl, 1,3,5-triphenylferdazyl and the like can be used.
【００２５】前記モノマー調製タンク３には、更にアク
リロニトリルと共重合する第２成分であるコモノマー
が、同じく計量されながら所定の割合で投入されるとと
もに、重合時に未反応のまま重合反応釜４から送り出さ
れたモノマー成分が戻される。モノマー調製タンク３で
調製された粘調な原料液は、次の計量ポンプ２ｂを介し
て重合反応釜４へと送り込まれる。この重合反応釜４に
は、そのほかに必要量の純水が供給され、同時に重合開
始剤及び各種の助剤が添加される。In the monomer preparation tank 3, a comonomer, which is a second component which is copolymerized with acrylonitrile, is further charged at a predetermined ratio while being metered, and is sent out from the polymerization reaction kettle 4 in an unreacted state during the polymerization. The recovered monomer component is returned. The viscous raw material liquid prepared in the monomer preparation tank 3 is sent to the polymerization reaction kettle 4 via the next metering pump 2b. In addition to this, a required amount of pure water is supplied to the polymerization reaction vessel 4, and at the same time, a polymerization initiator and various auxiliary agents are added.
【００２６】本発明では重合開始剤として、無機系レド
ックス開始剤を使用している。無機系レドックス開始剤
としては、通常の酸化剤、還元剤の中から選ぶことがで
きる。酸化剤と還元剤との組合せからなるレドックスの
場合、代表的なものは、酸化剤としては過硫酸アンモニ
ウム、過硫酸カリウム、過硫酸ナトリウム等の通常使用
されるものであり、還元剤は亜硫酸ナトリウム、亜硫酸
アンモニウム、亜硫酸水素ナトリウム、亜硫酸水素アン
モニウム、チオ硫酸ナトリウム、チオ硫酸アンモニウ
ム、亜二チオン酸ナトリウム、ナトリウムホルムアルデ
ヒドスルフォキシレ−ト、Ｌ−アルコルビン酸、デキス
トロ−ズ等の通常使用されているものである。硫酸第一
鉄又は硫酸銅などの化合物も組合せて使用できる。その
中で、過硫酸アンモニウム−亜硫酸水素ナトリウム（ア
ンモニウム）−硫酸第一鉄の組合せが好ましい。還元剤
と酸化剤の比率はどんな割合でも可能であるが、重合を
より効率よく進めるうえで還元剤と酸化剤との当量比を
１〜４にすることが好ましい。In the present invention, an inorganic redox initiator is used as a polymerization initiator. The inorganic redox initiator can be selected from ordinary oxidizing agents and reducing agents. In the case of a redox composed of a combination of an oxidizing agent and a reducing agent, typical ones are commonly used ones such as ammonium persulfate, potassium persulfate and sodium persulfate as the oxidizing agent, and the reducing agent is sodium sulfite, Commonly used substances such as ammonium sulfite, sodium hydrogen sulfite, ammonium hydrogen sulfite, sodium thiosulfate, ammonium thiosulfate, sodium dithionite, sodium formaldehyde sulfoxylate, L-alcorbic acid and dextrozee. is there. Compounds such as ferrous sulfate or copper sulfate can also be used in combination. Among them, the combination of ammonium persulfate-sodium hydrogen sulfite (ammonium) -ferrous sulfate is preferable. Any ratio of the reducing agent and the oxidizing agent is possible, but it is preferable to set the equivalent ratio of the reducing agent and the oxidizing agent to 1 to 4 in order to promote the polymerization more efficiently.
【００２７】本実施形態で用いられるアクリロニトリル
系重合体は、アクリロニトリルモノマーの他にこれと共
重合可能なモノオレフィン性モノマーとからなる繰り返
し単位からなるものであってもよい。ここでアクリロニ
トリル系重合体は、少なくとも６０重量％のアクリロニ
トリルモノマーから構成される必要がある。アクリロニ
トリルモノマーの含有量が６０重量％未満であると、ア
クリロニトリル系合成繊維が本来有する繊維機能を保有
することができないためである。ここで共重合可能なモ
ノオレフィン性モノマーとしては、例えばアクリル酸、
メタクリル酸及びそれらのエステル、アクリルアミド、
酢酸ビニル、スチレン、塩化ビニル、塩化ビニリデン、
無水マレイン酸、Ｎ−置換マレインイミド、ブタジエ
ン、イソプレン等を挙げることができる。また、Ｐ−ス
ルフォニルメタリルエ−テル、メタリルスルフォン酸、
アリルスルフォン酸、スチレンスルフォン酸、２−アク
リルアミド−２−メチルプロパンスルフォン酸、２−ス
ルフォエチルメタクリレ−ト及びこれらの塩も共重合可
能なモノマーとして使用できる。The acrylonitrile polymer used in this embodiment may be composed of a repeating unit composed of an acrylonitrile monomer and a monoolefinic monomer copolymerizable therewith. Here, the acrylonitrile-based polymer must be composed of at least 60% by weight of acrylonitrile monomer. This is because if the content of the acrylonitrile monomer is less than 60% by weight, the acrylonitrile synthetic fiber cannot have the original fiber function. Examples of the copolymerizable mono-olefinic monomer here include acrylic acid,
Methacrylic acid and their esters, acrylamide,
Vinyl acetate, styrene, vinyl chloride, vinylidene chloride,
Examples thereof include maleic anhydride, N-substituted maleimide, butadiene, isoprene and the like. In addition, P-sulfonyl methallyl ether, methallyl sulfonic acid,
Allyl sulfonic acid, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, 2-sulfoethyl methacrylate and salts thereof can also be used as the copolymerizable monomer.
【００２８】アクリロニトリル系モノマーの重合は、次
のような条件で行う。すなわち、重合反応温度は３０〜
８０℃にすることが好ましい。重合温度が８０℃を超え
るとアクリロニトリルが蒸発し、反応系外へ離散し、重
合転化率が低下する。また３０℃未満では重合速度が低
下し、生産性が低下するばかりでなく、重合安定性を損
なう。重合媒体としての水はイオン交換水を使用するこ
とが好ましい。さらにモノマーに対するイオン交換水の
割合（以下、水／モノマー比という）は如何なる比率で
も可能であるが、好ましくは水／モノマー比は１．０〜
５．０の範囲である。重合反応釜内でのモノマーの平均
滞在時間は、アクリロニトリル系重合体を水系懸濁重合
方式で製造する際に採用される通常の時間でよい。重合
反応釜内での水素イオン濃度は使用される触媒がすみや
かに酸化・還元反応を起こす範囲であればよく、好まし
くはｐＨ２．０〜３．５の酸性領域がよい。The acrylonitrile-based monomer is polymerized under the following conditions. That is, the polymerization reaction temperature is 30 to
It is preferably 80 ° C. When the polymerization temperature exceeds 80 ° C., acrylonitrile evaporates and is dispersed outside the reaction system, and the polymerization conversion rate decreases. On the other hand, if the temperature is lower than 30 ° C., not only the polymerization rate is lowered and the productivity is lowered, but also the polymerization stability is impaired. It is preferable to use ion-exchanged water as the polymerization medium. Further, the ratio of ion-exchanged water to the monomer (hereinafter referred to as water / monomer ratio) can be any ratio, but the water / monomer ratio is preferably 1.0 to
It is in the range of 5.0. The average residence time of the monomer in the polymerization reaction kettle may be a normal time employed when the acrylonitrile polymer is produced by the aqueous suspension polymerization method. The hydrogen ion concentration in the polymerization reaction vessel may be within a range in which the catalyst used promptly causes an oxidation / reduction reaction, and preferably has an acidic region of pH 2.0 to 3.5.
【００２９】重合反応釜４から取り出した重合体に、重
合停止剤を添加し反応を停止させる。重合反応の停止剤
は通常アクリロニトリル系重合体を水系懸濁重合で製造
する際に使用されるものであれば限定されない。重合体
水溶液に重合停止剤を添加した後、未反応モノマーの回
収を行う。未反応モノマーの回収方法としては重合体水
溶液を直接蒸留する方法が採用される。本実施形態にあ
っては、重合反応釜４で重合された重合体水溶液は、図
２に示すように、重合反応釜４から取り出されたのち、
蒸留塔５に導入される。蒸留塔５では、重合体とモノマ
ー／水とに分離されるとともに、モノマー／水の混合液
は蒸留塔５で蒸留されて気化し、コンデンサー６に導入
されて凝縮し未反応のモノマー成分と水の混合液とな
る。コンデンサー６で液化されたモノマー成分と水との
混合液はデカンター７を介して分離され、モノマー成分
は回収モノマータンク８を介して重合反応釜４に戻され
る。A polymerization terminator is added to the polymer taken out of the polymerization reaction kettle 4 to stop the reaction. The termination agent for the polymerization reaction is not particularly limited as long as it is usually used when an acrylonitrile polymer is produced by aqueous suspension polymerization. After adding the polymerization terminator to the polymer aqueous solution, the unreacted monomer is recovered. As a method of recovering unreacted monomers, a method of directly distilling an aqueous polymer solution is adopted. In the present embodiment, the polymer aqueous solution polymerized in the polymerization reaction kettle 4 is taken out from the polymerization reaction kettle 4 as shown in FIG.
It is introduced into the distillation column 5. In the distillation tower 5, the polymer and the monomer / water are separated, and the mixed solution of the monomer / water is distilled in the distillation tower 5 to be vaporized and introduced into the condenser 6 to be condensed and unreacted monomer component and water. It becomes a mixed solution of. The mixed liquid of the monomer component liquefied in the condenser 6 and water is separated via the decanter 7, and the monomer component is returned to the polymerization reaction kettle 4 via the recovery monomer tank 8.
【００３０】ところで、気化してコンデンサー６に送り
込まれる混合気体には、モノマー成分及び水の他に、僅
かではあるがＳＯ2 が混入している。このＳＯ2 は凝縮
して液化した水に溶けると、既述したとおり、同じく水
に混入したモノマー成分の重合開始剤として機能する。
従って、この反応を回避するには、コンデンサー６に送
り込まれる混合気体が凝縮して液化する以前、好ましく
はコンデンサー６に送り込まれた直後に、重合禁止剤を
添加することが肝要である。コンデンサー６に導入され
る以前に重合禁止剤を添加すると、重合禁止剤の一部が
蒸留塔５の上流側に流れる可能性があって、その添加量
が一定しないため、添加量の調整が難しくなる。By the way, in the mixed gas which is vaporized and sent to the condenser 6, a small amount of SO 2 is mixed in addition to the monomer component and water. When this SO 2 is dissolved in water that is condensed and liquefied, it functions as a polymerization initiator for the monomer component that is also mixed in water, as described above.
Therefore, in order to avoid this reaction, it is important to add the polymerization inhibitor before the mixed gas fed into the condenser 6 is condensed and liquefied, preferably immediately after being fed into the condenser 6. If the polymerization inhibitor is added before it is introduced into the condenser 6, a part of the polymerization inhibitor may flow to the upstream side of the distillation column 5, and the addition amount is not constant, which makes it difficult to adjust the addition amount. Become.
【００３１】図２は、本発明による前記重合禁止剤の添
加の仕方の一例を示している。本発明にあっては、必要
な量の重合禁止剤をコンデンサー６の混合気体導入口の
近傍に直接導入することもできるが、本実施形態ではコ
ンデンサー６の混合気体導入口６ａの近傍に別途形成さ
れた重合禁止剤の導入口６ｂとアクリロニトリルの貯留
槽１とを配管１０ａで連結し、必要量のアクリロニトリ
ルのバージン原料をコンデンサー６に送り込むようにし
ている。FIG. 2 shows an example of how to add the polymerization inhibitor according to the present invention. In the present invention, the required amount of the polymerization inhibitor may be directly introduced in the vicinity of the mixed gas introduction port of the condenser 6, but in the present embodiment, it is separately formed in the vicinity of the mixed gas introduction port 6a of the condenser 6. The introduction port 6b of the polymerization inhibitor thus produced and the storage tank 1 for acrylonitrile are connected by a pipe 10a, and a necessary amount of virgin raw material for acrylonitrile is fed to the condenser 6.
【００３２】アクリロニトリルのバージン原料には、既
述したように、所定の重量比（２０〜１００ｐｐｍ）で
重合禁止剤が添加されている。従って、前述のごとく、
コンデンサー６の重合禁止剤の導入口６ｂに、貯留槽１
に貯留されているアクリロニトリルのバージン原料の必
要量をコンデンサー６に送り込むことにより、結果的
に、必要量の重合禁止剤が導入されることになる。As described above, the polymerization inhibitor is added to the virgin raw material of acrylonitrile at a predetermined weight ratio (20 to 100 ppm). Therefore, as mentioned above,
At the inlet 6b of the polymerization inhibitor of the condenser 6, the storage tank 1
By sending the required amount of the acrylonitrile virgin raw material stored in the condenser 6 to the condenser 6, as a result, the required amount of the polymerization inhibitor is introduced.
【００３３】通常、前記重合工程で得られる重合生成物
は、モノマー／ポリマー／水の比率が、それぞれ重量割
合で２〜７％／１０〜３５％／５８〜８８％の範囲にあ
る。また、このとき重合生成物には重合開始剤として機
能するＳＯ2 源が０．０２〜０．２０％含有されてい
る。本実施形態によるアクリロニトリルの原料モノマー
を、凝縮工程で得られた上記モノマー成分の含有量に応
じて２０〜１５０％の重量比をもって添加する。Usually, the polymerization product obtained in the above-mentioned polymerization step has a monomer / polymer / water ratio in the range of 2 to 7% / 10 to 35% / 58 to 88% by weight. Further, at this time, the polymerization product contains 0.02 to 0.20% of an SO 2 source which functions as a polymerization initiator. The acrylonitrile raw material monomer according to the present embodiment is added in a weight ratio of 20 to 150% according to the content of the monomer component obtained in the condensation step.
【００３４】図３は、本発明による前記重合禁止剤の添
加の仕方の他の例を示している。本実施形態ではコンデ
ンサー６とデカンター７との間に配される配管９から分
岐管１０ｂを分岐させて、コンデンサー６の混合気体導
入口６ａの近傍に別途形成された重合禁止剤の導入口６
ｂに分岐管１０ｂで接続している。この分岐管１０ｂに
は重合禁止剤の導入口６ｃが形成され、分岐管１０ｂに
は重合禁止剤導入口６ｃを介して重合禁止剤が供給され
る。このときの重合禁止剤の供給は、重合禁止剤を単独
で供給してもよいし、或いは前述のごとくアクリロニト
リルの原料モノマーを供給するようにしてもよい。この
ときの、重合禁止剤の添加量は、コンデンサー６で凝縮
して液化したモノマー成分に対して重量比で２０〜１５
０％添加する。FIG. 3 shows another example of the method of adding the polymerization inhibitor according to the present invention. In the present embodiment, a branch pipe 10b is branched from a pipe 9 arranged between the condenser 6 and the decanter 7, and a polymerization inhibitor introduction port 6 separately formed in the vicinity of the mixed gas introduction port 6a of the condenser 6 is provided.
It is connected to b by the branch pipe 10b. A polymerization inhibitor introduction port 6c is formed in the branch pipe 10b, and the polymerization inhibitor is supplied to the branch pipe 10b through the polymerization inhibitor introduction port 6c. As for the supply of the polymerization inhibitor at this time, the polymerization inhibitor may be supplied alone, or as described above, the raw material monomer of acrylonitrile may be supplied. At this time, the amount of the polymerization inhibitor added is 20 to 15 by weight ratio with respect to the monomer component condensed and liquefied in the condenser 6.
Add 0%.
【００３５】次に、上述のモノマー成分回収システムを
使ったモノマー成分の回収を実施例に基づいて具体的に
説明する。
（実施例１）水系懸濁重合によるアクリロニトリルと酢
酸ビニルの共重合で得られたモノマー／ポリマー／水の
比率が３％／２２％／７５％（重量比) からなり、且つ
ＳＯ 2 源として亜硫酸水素ナトリウム０．０７５〜０．
０１２５％（重量比) 含有する混合物を蒸留塔に供給し
て、塔頂より得られるモノマー１．２ｔ／ｈｒに対して
重合禁止剤p-メトキシフェノールを４０ｐｐｍ（重量
比) 含む原料モノマー（アクリロニトリル）を１２０％
（重量比) 添加した。原料モノマーは多管式コンデンサ
ー内の導入側で噴霧して添加した。６ヶ月間上記の条件
を継続した後でも、多管式コンデンサーの原料モノマー
の噴霧液が通過する管内範囲における詰まりは見らず、
且つ回収したモノマー成分に重合体は殆ど混在していな
かった。Next, the above-mentioned monomer component recovery system is used.
Specific recovery of used monomer components based on examples
explain.
(Example 1) Acrylonitrile and vinegar by aqueous suspension polymerization
Monomer / polymer / water obtained by copolymerization of vinyl acrylate
The ratio is 3% / 22% / 75% (weight ratio), and
SO 2Sodium bisulfite 0.075-0.
The mixture containing 0125% (weight ratio) was fed to the distillation column.
Then, for 1.2 t / hr of monomer obtained from the top of the column,
Polymerization inhibitor p-methoxyphenol 40ppm (weight
120% of raw material monomer (acrylonitrile) containing
(Weight ratio) Added. Raw material monomer is a multi-tube condenser
It was added by spraying on the introduction side inside. 6 months above conditions
Even after continuing, the raw material monomer of the multi-tube condenser
No clogging in the pipe range where the spray liquid of
In addition, almost no polymer was mixed in the recovered monomer component.
won.
【００３６】（比較例１）コンデンサー内での原料モノ
マーの噴霧を行わないこと以外は実施例１と同様の方法
で行った場合、６ヶ月間上記の条件を継続した後では多
管式コンデンサー内に詰まりが多く見られた。また多管
式コンデンサー以降のデカンターのモノマー層において
も重合物の混入が多かった。Comparative Example 1 In the same manner as in Example 1 except that the raw material monomer was not sprayed in the condenser, after the above conditions were continued for 6 months, There were a lot of jams. In addition, a large amount of polymer was mixed in the monomer layer of the decanter after the multi-tube condenser.
【００３７】以上のとおり、本発明によれば蒸留により
気化されたモノマー成分と水との混合気体をコンデンサ
ーで凝縮し液化したのち、水を分離してモノマー成分を
回収するに際して、コンデンサーの前記混合気体の導入
口近傍に重合禁止剤を導入するようにしたため、添加さ
れた重合禁止剤により混合成分が液化する段階でモノマ
ー成分の重合が禁止されるようになり、回収モノマー成
分に混在する重合体が減少する。As described above, according to the present invention, after a mixed gas of a monomer component vaporized by distillation and water is condensed and liquefied by a condenser, water is separated and a monomer component is recovered. Since the polymerization inhibitor was introduced near the gas introduction port, the polymerization of the monomer component became prohibited at the stage where the mixed component was liquefied by the added polymerization inhibitor, and the polymer mixed in the recovered monomer component Is reduced.
【図１】本発明のモノマー回収装置を備えたアクリロニ
トリル系重合体の重合システムを示す工程図である。FIG. 1 is a process diagram showing a polymerization system of an acrylonitrile-based polymer provided with a monomer recovery device of the present invention.
【図２】本発明の代表的な実施の形態であるモノマー回
収工程の工程図である。FIG. 2 is a process drawing of a monomer recovery process that is a typical embodiment of the present invention.
【図３】本発明の他の実施の形態であるモノマー回収工
程の工程図である。FIG. 3 is a process drawing of a monomer recovery process which is another embodiment of the present invention.
１ アクリロニトリルの貯留槽 ２ａ，２ｂ 計量ポンプ ３ モノマー調製タンク ４ 重合反応釜 ５ 蒸留塔 ６ コンデンサー ６ａ 混合気体導入口 ６ｂ，６ｃ 重合禁止剤導入口 ７ デカンター ８ 回収モノマータンク ９，１０ａ 配管 １０ｂ 分岐管 1 Acrylonitrile storage tank 2a, 2b metering pump 3 Monomer preparation tank 4 polymerization reactor 5 distillation tower 6 condenser 6a Mixed gas inlet 6b, 6c Polymerization inhibitor inlet 7 Decanter 8 Recovery monomer tank 9,10a piping 10b Branch pipe
Claims (7)
合工程で発生するモノマー成分の回収方法であって、 重合工程で得られるモノマー／ポリマー／水の混合物を
蒸留してモノマー成分と水とをポリマーから気化分離さ
せること、及び気化したモノマー成分と水とを凝縮させ
てモノマー成分を回収することを備えてなり、 気化工程から凝縮工程への移行時に微量の重合禁止剤を
添加することを含んでなることを特徴とするアクリロニ
トリル系モノマー成分の回収方法。1. A method for recovering a monomer component generated in an aqueous suspension polymerization step of an arylonitrile polymer, wherein a monomer / polymer / water mixture obtained in the polymerization step is distilled to obtain a monomer component and water. Is separated from the polymer by vaporization, and the monomer component is recovered by condensing the vaporized monomer component and water, and adding a trace amount of a polymerization inhibitor at the time of transition from the vaporization process to the condensation process. A method for recovering an acrylonitrile-based monomer component, which comprises:
モノマー／ポリマー／水の比率２〜７％／１０〜３５％
／５８〜８８％であって、且つＳＯ2 源が０．０２〜
０．２０％含有されており、 前記凝縮工程で得られるモノマー成分に対する重量比で
４〜１５０ｐｐｍの重合禁止剤を添加することを含んで
なる請求項１に記載の回収方法。2. The polymerization product obtained in the polymerization step,
Monomer / Polymer / Water ratio 2-7% / 10-35%
A / 58 to 88%, and SO 2 source 0.02
The recovery method according to claim 1, wherein the content of the polymerization inhibitor is 0.20%, and the method further comprises adding a polymerization inhibitor in a weight ratio of 4 to 150 ppm with respect to the monomer component obtained in the condensation step.
分に対して重量比で２０〜１００ｐｐｍの重合禁止剤を
添加すること、 重合禁止剤が添加された前記モノマー成分を、凝縮工程
に導入されるモノマー成分に対して２０〜１５０％の重
量比で添加することを含んでなる請求項２に記載の回収
方法。3. Adding a polymerization inhibitor in a weight ratio of 20 to 100 ppm to the monomer component obtained in the condensation step, and introducing the monomer component to which the polymerization inhibitor is added into the condensation step. The method according to claim 2, further comprising adding the monomer component in a weight ratio of 20 to 150%.
モノマー／ポリマー／水の比率２〜７％／１０〜３５％
／５８〜８８％であって、且つＳＯ2 源が０．０２〜
０．２０％含有されており、 重量比で２０〜１００ｐｐｍの重合禁止剤を含むアクリ
ロニトリルの原料モノマーを、凝縮工程で得られた上記
モノマー成分に対する２０〜１５０％の重量比で添加す
ることを含んでなる請求項１に記載の回収方法。4. The polymerization product obtained in the polymerization step is
Monomer / Polymer / Water ratio 2-7% / 10-35%
A / 58 to 88%, and SO 2 source 0.02
Acrylonitrile raw material monomer containing 0.20% by weight and containing a polymerization inhibitor of 20 to 100 ppm by weight is added in a weight ratio of 20 to 150% with respect to the monomer component obtained in the condensation step. The recovery method according to claim 1, wherein
ル系重合体の重合システムであって、 重合部と、同重合部に連結される蒸留部と、同蒸留部に
連結される凝縮器とを備え、 前記蒸留部に連結される凝縮部の気体導入口近傍に、重
合禁止剤の導入口を更に有してなることを特徴とするア
クリロリトリル系重合体の重合システム。5. A polymerization system for an acrylonitrile polymer by an aqueous suspension polymerization method, comprising a polymerization section, a distillation section connected to the polymerization section, and a condenser connected to the distillation section. A polymerization system for an acrylonitrile polymer, further comprising an inlet for a polymerization inhibitor in the vicinity of the gas inlet of the condensing unit connected to the distillation unit.
程後に配されるモノマー／水の分離工程のモノマー導出
口と連結され、前記重合禁止剤の導入口と前記分離工程
のモノマー導出口との間に重合禁止剤の導入部を有して
なる請求項５記載の重合システム。6. An inlet for the polymerization inhibitor is connected to a monomer outlet for the monomer / water separation step arranged after the condensation step, and the inlet for the polymerization inhibitor and the monomer outlet for the separation step are provided. 6. The polymerization system according to claim 5, further comprising a polymerization inhibitor introduction part between and.
剤を含有するアクリロニトリルの原料モノマー供給源と
連結されてなる請求項５記載の重合システム。7. The polymerization system according to claim 5, wherein the introduction port of the polymerization inhibitor is connected to a source monomer source of acrylonitrile containing the polymerization inhibitor.
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| JP2002102813A JP3768167B2 (en) | 2002-04-04 | 2002-04-04 | Recovery method and polymerization system of unreacted monomer components during polymerization of acrylonitrile monomers |
| CNB031215610A CN100432048C (en) | 2002-04-04 | 2003-03-31 | Recovery method and polymerization system of non-reaction monomer in polymerization of acrylic monomer |
Applications Claiming Priority (1)
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|---|---|---|---|
| JP2002102813A JP3768167B2 (en) | 2002-04-04 | 2002-04-04 | Recovery method and polymerization system of unreacted monomer components during polymerization of acrylonitrile monomers |
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| JP3768167B2 JP3768167B2 (en) | 2006-04-19 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006225414A (en) * | 2005-02-15 | 2006-08-31 | Mitsubishi Rayon Co Ltd | Recovering method and recovering system of unreacted monomer component in polymerization of acrylonitrile monomer |
| KR20180070294A (en) * | 2016-12-16 | 2018-06-26 | 주식회사 엘지화학 | Method for separating non-reacted monomer from mixture comprising non-reacted monomer |
| WO2022055104A1 (en) * | 2020-09-11 | 2022-03-17 | 주식회사 엘지화학 | Nitrile-based monomer recovery method and recovery apparatus |
| US11512153B2 (en) | 2018-12-18 | 2022-11-29 | Lg Chem, Ltd. | Method of preparing aromatic vinyl compound-vinyl cyanide compound polymer and apparatus for preparing the same |
| CN115894760A (en) * | 2022-11-11 | 2023-04-04 | 广东石油化工学院 | Demonomerization tower and application thereof in preparation of polyolefin elastomer |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106317296B (en) * | 2015-06-18 | 2018-07-06 | 中国石油化工股份有限公司 | For the MONOMER RECOVERY technique of dry acrylic fiber |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3650975B2 (en) * | 1995-07-28 | 2005-05-25 | 日本エクスラン工業株式会社 | Process for producing improved acrylonitrile polymer melt |
-
2002
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2003
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006225414A (en) * | 2005-02-15 | 2006-08-31 | Mitsubishi Rayon Co Ltd | Recovering method and recovering system of unreacted monomer component in polymerization of acrylonitrile monomer |
| KR20180070294A (en) * | 2016-12-16 | 2018-06-26 | 주식회사 엘지화학 | Method for separating non-reacted monomer from mixture comprising non-reacted monomer |
| KR102142550B1 (en) | 2016-12-16 | 2020-08-07 | 주식회사 엘지화학 | Method for separating non-reacted monomer from mixture comprising non-reacted monomer |
| US11512153B2 (en) | 2018-12-18 | 2022-11-29 | Lg Chem, Ltd. | Method of preparing aromatic vinyl compound-vinyl cyanide compound polymer and apparatus for preparing the same |
| WO2022055104A1 (en) * | 2020-09-11 | 2022-03-17 | 주식회사 엘지화학 | Nitrile-based monomer recovery method and recovery apparatus |
| CN115894760A (en) * | 2022-11-11 | 2023-04-04 | 广东石油化工学院 | Demonomerization tower and application thereof in preparation of polyolefin elastomer |
| CN115894760B (en) * | 2022-11-11 | 2024-04-30 | 广东石油化工学院 | De-monomer tower and application thereof in preparation of polyolefin elastomer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1448386A (en) | 2003-10-15 |
| JP3768167B2 (en) | 2006-04-19 |
| CN100432048C (en) | 2008-11-12 |
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