JP2000044606A - Production of purified acrylic polymer solution and purification of acrylic polymer solution - Google Patents
Production of purified acrylic polymer solution and purification of acrylic polymer solutionInfo
- Publication number
- JP2000044606A JP2000044606A JP10219239A JP21923998A JP2000044606A JP 2000044606 A JP2000044606 A JP 2000044606A JP 10219239 A JP10219239 A JP 10219239A JP 21923998 A JP21923998 A JP 21923998A JP 2000044606 A JP2000044606 A JP 2000044606A
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- polymer solution
- pressure
- supplied
- packed tower
- solution
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、精製アクリル系重
合体溶液の製造方法、アクリル系重合体溶液の精製方法
に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a purified acrylic polymer solution and a method for purifying an acrylic polymer solution.
【０００２】[0002]
【従来の技術】一般にアクリロニトリルの重合はラジカ
ル重合であり、該重合により工業的にアクリロニトリル
重合体を得るプロセスには、均一系である溶液重合と不
均一系である水系懸濁重合に大別される。2. Description of the Related Art Generally, polymerization of acrylonitrile is radical polymerization. Processes for industrially obtaining an acrylonitrile polymer by the polymerization are roughly classified into solution polymerization which is a homogeneous system and aqueous suspension polymerization which is a heterogeneous system. You.
【０００３】ラジカル重合の反応速度は、一般に反応の
進行が進むにつれて遅くなるので、高転化率を得るため
には、大型の装置、あるいは長い反応時間を必要とし工
業的に不利であるため、転化率を９０％前後で打ち切る
のが経済的にも有利である。このため、重合体溶液は未
反応のモノマーを含んでいるので、未反応のモノマーが
後に続く紡糸工程に持ち込まれると、モノマーが大気中
に排出され、作業環境の悪化を引き起こし、好ましくな
く、未反応モノマーを十分に除去することが必要であ
る。[0003] Since the reaction rate of radical polymerization generally decreases as the reaction proceeds, a large apparatus or a long reaction time is required to obtain a high conversion, which is industrially disadvantageous. It is economically advantageous to cut off the rate at around 90%. For this reason, since the polymer solution contains unreacted monomers, if the unreacted monomers are brought into the subsequent spinning process, the monomers are discharged into the atmosphere, causing a deterioration in the working environment, which is not preferable. It is necessary to sufficiently remove the reactive monomer.
【０００４】一方、溶液重合は均一重合であるため、水
系不均一重合で必要となるポリマーの分離、乾燥、溶解
工程がなく、水系不均一重合に比較して工程が簡略であ
るという利点があるが、溶液重合で製造したアクリル系
重合体溶液は高粘度であるため、未反応モノマーの除去
率を高くすることが比較的困難であるのが現状である。On the other hand, since solution polymerization is homogeneous polymerization, there is no polymer separation, drying and dissolving steps required for aqueous heterogeneous polymerization, and there is an advantage that the process is simpler than aqueous heterogeneous polymerization. However, at present, it is relatively difficult to increase the removal rate of unreacted monomers because the acrylic polymer solution produced by solution polymerization has a high viscosity.
【０００５】従来、溶液重合での未反応モノマーの除去
は、重合を打ち切り、未反応モノマーを含む重合体溶液
を、減圧した脱気槽の内壁に薄膜状にして供給し、未反
応モノマーを除去する方法が一般的であるが、この方法
では未反応モノマーの除去率がそれほど高くなく、除去
率を上げるためには、供給する重合体溶液を高温にする
ことや、脱気槽を高真空にする必要があった。しかし、
前者では製品の着色を引き起こし好ましくなく、後者に
おいても装置が大型になることや、除去率が大きく上が
らないなど、コストの面からも不利である。しかも、こ
の方法を用いて未反応モノマーの除去率を上げると、未
反応モノマーと同時に溶媒の一部も除去され、その結
果、重合体溶液のポリマー濃度が上がりすぎ、粘度も上
昇し、後に続く紡糸工程では、ポリマー濃度が上がりす
ぎると好ましくないことが多く、このために、未反応モ
ノマーを除去した後、重合体溶液のポリマー濃度を適正
にするため、溶媒での希釈が必要な場合もある。また、
除去率が比較的低いままで後に続く紡糸工程に重合体溶
液を持ち込むと、紡糸工程からモノマーが大気に排出さ
れ、この大気排出を減らすためには、紡糸浴の密封化
や、蒸散したモノマーの回収、焼却などいずれも装置が
高価であったり、ランニングコストが高いなどの欠点が
あり、より少ない工程での未反応モノマーの高除去率を
得る抜本策が望まれている。Conventionally, unreacted monomers in solution polymerization are removed by terminating the polymerization and supplying a polymer solution containing unreacted monomers in the form of a thin film to the inner wall of a depressurized degassing tank to remove unreacted monomers. In general, the removal rate of unreacted monomers is not so high.In order to increase the removal rate, the polymer solution to be supplied must be heated to a high temperature, or the degassing tank must be kept at a high vacuum. I needed to. But,
The former is not preferable because it causes coloring of the product, and the latter is disadvantageous also in terms of cost, such as an increase in the size of the apparatus and an increase in the removal rate. Moreover, when the removal rate of the unreacted monomer is increased by using this method, a part of the solvent is also removed at the same time as the unreacted monomer. As a result, the polymer concentration of the polymer solution becomes too high, the viscosity also increases, and the subsequent In the spinning step, it is often not preferable that the polymer concentration is too high. For this reason, after removing unreacted monomers, dilution with a solvent may be necessary to make the polymer concentration of the polymer solution appropriate. . Also,
If the polymer solution is brought into the subsequent spinning process with a relatively low removal rate, the monomer is discharged from the spinning process to the atmosphere.To reduce this air release, the spinning bath must be sealed or the evaporated monomer must be removed. There are drawbacks such as expensive equipment and high running cost for both recovery and incineration, and a drastic measure to obtain a high removal rate of unreacted monomer in fewer steps is desired.
【０００６】特開昭５２−４３８９４号公報には、重合
体溶液からの未反応モノマーの回収方法として、ジメチ
ルスルホキシド、あるいはジメチルホルムアミドの蒸気
を重合体溶液と向流接触させて未反応モノマーの除去を
する方法が開示されているが、この方法を単に実施して
も、未反応モノマーの蒸発率が約９５％程度であった
り、あるいは、ポリマーが適正に濃縮されているか否か
わからない等の問題点があった。また、この特開昭５２
−４３８９４号公報には、充填塔ではなく、棚段の塔を
用いて実施した例が開示されているが、かかる方法をア
クリル系重合体溶液のような高粘度の溶液に使用する
と、塔頂と塔底の圧力損失が大きくなり、ポリマーが適
正に濃縮されることがなく、さらに、重合体溶液の表面
更新が比較的少なく、未反応モノマーの回収率が上がら
ない等、種々好ましくない問題を有するものである。ま
た、充填塔について具体的考察はなされておらず、未反
応モノマーの除去率も大きくできなかったのが実状であ
る。JP-A-52-43894 discloses a method for recovering unreacted monomers from a polymer solution by removing the unreacted monomers by bringing dimethyl sulfoxide or dimethylformamide vapor into countercurrent contact with the polymer solution. However, even if this method is simply performed, there are problems such as an unreacted monomer evaporation rate of about 95%, or it is not known whether the polymer is properly concentrated or not. There was a point. Also, Japanese Patent Application Laid-Open No.
JP-A-43894 discloses an example in which a packed tower is used instead of a packed tower. However, when such a method is used for a high-viscosity solution such as an acrylic polymer solution, the top of the tower is reduced. Pressure loss at the bottom of the column increases, the polymer is not properly concentrated, the surface renewal of the polymer solution is relatively small, and the recovery rate of unreacted monomer does not increase. Have Further, no specific consideration has been made on the packed tower, and the actual situation is that the removal rate of unreacted monomers could not be increased.
【０００７】さらに、特公昭４５−３４８３６号公報に
は、重合体溶液からの未反応モノマーの除去と溶液の濃
縮をする方法が記載されているが、プロセスが複雑で設
備費が高価であり、加熱と冷却を繰り返しエネルギー的
に不利で、さらにランニングコストも高い等の問題点が
あった。Furthermore, Japanese Patent Publication No. 45-34836 discloses a method for removing unreacted monomers from a polymer solution and concentrating the solution, but the process is complicated and the equipment cost is high. There were problems such as repeated heating and cooling, which was disadvantageous in terms of energy, and high running cost.
【０００８】また、本発明者らは、先に、未反応モノマ
ーの除去と重合体溶液をフラッシュ蒸発を利用すること
によって濃縮する方法を提案したが（特願平９−３５４
７６０号）、この技術は、一工程で未反応モノマーの除
去と重合体溶液の濃縮を行うという点で画期的な有効技
術であるが、濃縮された重合体溶液の温度が比較的高
く、これを冷却する装置が必要であることがあり、かか
る冷却装置を必要としない技術の実現も要望されてい
た。The present inventors have previously proposed a method of removing unreacted monomers and concentrating a polymer solution by using flash evaporation (Japanese Patent Application No. 9-354).
No. 760), this technology is a revolutionary effective technology in that the unreacted monomer is removed and the polymer solution is concentrated in one step, but the temperature of the concentrated polymer solution is relatively high, In some cases, a device for cooling this is required, and there has been a demand for a technique that does not require such a cooling device.
【０００９】[0009]
【発明が解決しようとする課題】本発明は、かかる従来
技術の背景に鑑み、溶液重合における重合体溶液から、
未反応モノマーを極めて高い除去率で除去し、実質的に
紡糸工程からのモノマーの大気排出がなく、しかも重合
体溶液を少ない工程で適正な濃度に濃縮する精製アクリ
ル系重合体溶液の製造方法を提供せんとするものであ
る。SUMMARY OF THE INVENTION In view of the background of the prior art, the present invention relates to a method for polymerizing a polymer solution in solution polymerization.
A method for producing a purified acrylic polymer solution that removes unreacted monomers at an extremely high removal rate, practically eliminates atmospheric discharge of monomers from the spinning process, and concentrates the polymer solution to an appropriate concentration in a small number of processes. It will not be provided.
【００１０】また、他の目的は同様な効果を有するアク
リル系重合体溶液の精製方法を提供せんとするものであ
る。Another object of the present invention is to provide a method for purifying an acrylic polymer solution having the same effect.
【００１１】[0011]
【課題を解決するための手段】本発明は、かかる課題を
解決するために、次の構成を有するものである。The present invention has the following structure in order to solve the above-mentioned problems.
【００１２】すなわち、本発明の精製アクリル系重合体
溶液の製造方法は、少なくともアクリロニトリルを含む
モノマーを溶液重合して得られる重合体溶液を、減圧せ
しめた充填塔の上部から供給するとともに、充填塔の下
部から該重合体溶液の溶媒の蒸気を該重合体溶液と向流
接触させるように供給し、充填塔下部から流出する該重
合体溶液を、該充填塔底圧力よりも低い圧力に減圧せし
めた脱気槽に供給することを特徴とするものである。That is, according to the process for producing a purified acrylic polymer solution of the present invention, a polymer solution obtained by solution polymerization of at least a monomer containing acrylonitrile is supplied from the upper portion of a packed column under reduced pressure, The vapor of the solvent of the polymer solution is supplied from the lower portion of the column so as to bring the polymer solution into countercurrent contact with the polymer solution, and the polymer solution flowing out from the lower portion of the packed column is reduced to a pressure lower than the bottom pressure of the packed column. It is supplied to a deaeration tank.
【００１３】また、本発明のアクリル系重合体溶液の精
製方法は、少なくともアクリロニトリルを含むモノマー
を溶液重合して得られる重合体溶液を、減圧せしめた充
填塔の上部から供給するとともに、充填塔の下部から該
重合体溶液の溶媒の蒸気を該重合体溶液と向流接触させ
るように供給し、充填塔下部から流出する該重合体溶液
を、該充填塔底圧よりも低い圧力に減圧せしめた脱気槽
に供給し、精製を行うように構成したことを特徴とする
ものである。In the method for purifying an acrylic polymer solution of the present invention, a polymer solution obtained by solution-polymerizing at least a monomer containing acrylonitrile is supplied from the top of a packed column under reduced pressure, The vapor of the solvent of the polymer solution was supplied from the lower portion so as to be brought into countercurrent contact with the polymer solution, and the polymer solution flowing out from the lower portion of the packed column was reduced to a pressure lower than the bottom pressure of the packed column. It is characterized in that it is configured to supply to a degassing tank and perform purification.
【００１４】[0014]
【発明の実施の形態】以下、本発明について更に詳しく
説明をする。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail.
【００１５】本発明の精製アクリル系重合体溶液の製造
方法は、少なくともアクリロニトリルを含むモノマーを
溶液重合して得られる重合体溶液を、減圧せしめた充填
塔の上部から供給するとともに、充填塔の下部から該重
合体溶液の溶媒の蒸気を該重合体溶液と向流接触させる
ように供給し、そして、該充填塔下部から流出する該重
合体溶液を、該充填塔底圧力よりも低い圧力に減圧せし
めた脱気槽に供給し、重合体溶液中の未反応モノマーを
除去し、さらには重合体溶液の濃縮と冷却をするもので
ある。In the method for producing a purified acrylic polymer solution according to the present invention, a polymer solution obtained by solution polymerization of at least a monomer containing acrylonitrile is supplied from the upper part of a packed tower under reduced pressure, And supplying the vapor of the solvent of the polymer solution in countercurrent contact with the polymer solution, and reducing the polymer solution flowing out from the lower portion of the packed column to a pressure lower than the bottom pressure of the packed column. The unreacted monomer in the polymer solution is supplied to the degassing tank, and the polymer solution is further concentrated and cooled.
【００１６】このような構成とすることによって、本発
明によれば、従来技術に比較して、未反応モノマーの除
去の点で従来技術に劣ることはなく、設備構成の点で充
填塔に供給する重合体溶液の加熱設備を小型化でき、充
填塔から流出する重合体溶液の冷却器が不要でエネルギ
ー的に極めて有利であり、ランニングコストの点でも極
めて有利となるものである。さらに、重合体溶液の品質
という点で熱履歴による重合体溶液の着色防止や重合体
の変質による異物の生成防止に非常に有効であり、本発
明によって重合体溶液中の未反応モノマーの除去と重合
体溶液の濃縮と冷却を実現することができるのである。By adopting such a constitution, according to the present invention, the unreacted monomer is not inferior to the prior art in comparison with the prior art, and is supplied to the packed column in terms of the equipment constitution. The heating equipment for the polymer solution can be miniaturized, and a cooler for the polymer solution flowing out of the packed tower is not required, which is extremely advantageous in terms of energy and extremely advantageous in terms of running costs. Furthermore, in terms of the quality of the polymer solution, it is very effective in preventing coloration of the polymer solution due to heat history and preventing generation of foreign matter due to deterioration of the polymer, and by removing unreacted monomers in the polymer solution according to the present invention. Concentration and cooling of the polymer solution can be realized.
【００１７】すなわち、特に、充填塔下部から流出する
重合体溶液を、該充填塔よりも低い圧力に減圧せしめた
脱気槽に供給することによって、脱気槽で重合体溶液の
溶媒とわずかに残存する未反応モノマーの一部が蒸発
し、この結果、脱気槽から流出する重合体溶液の濃縮と
冷却を同時に達成することができる。これによって、エ
ネルギー的に極めて有利なプロセスが可能となるのであ
る。That is, in particular, by supplying the polymer solution flowing from the lower part of the packed tower to a degassing tank reduced in pressure to a pressure lower than that of the packed tower, the solvent of the polymer solution is slightly mixed with the solvent in the degassing tank. Part of the remaining unreacted monomer evaporates. As a result, the polymer solution flowing out of the degassing tank can be simultaneously concentrated and cooled. This enables a very energetically favorable process.
【００１８】本発明において、充填塔の下部から該重合
体溶液の溶媒の蒸気を該重合体溶液と向流接触させるよ
うに供給するとは、充填塔内での未反応モノマーの分離
帯域における重合体溶液の移動方向と溶媒の蒸気の移動
方向が実質的に反対となるように、溶媒の蒸気を供給す
ることをいう。In the present invention, supplying the vapor of the solvent of the polymer solution from the lower part of the packed tower so as to bring the polymer solution into countercurrent contact with the polymer solution means that the polymer in the separation zone of the unreacted monomer in the packed tower is This refers to supplying the solvent vapor such that the moving direction of the solution and the moving direction of the solvent vapor are substantially opposite.
【００１９】本発明の方法において、用いられるモノマ
ーは、全モノマー中におけるアクリロニトリルの含有量
８０ｍｏｌ％以上のものであることが好ましく、他のエ
チレン性二重結合を有するモノマーを１種以上含んでい
てもよく、他のエチレン性二重結合を有するモノマーに
は、例えば、塩化ビニル等のハロゲン化ビニル；酢酸ビ
ニル等のビニルエステル；アクリル酸、メタクリル酸、
及びこれらのエステルまたは塩；マレイン酸、フマル
酸、及びこれらのエステルまたは無水物；ブタジエン、
クロロプレン、イソプレン等のジエン系単量体；スチレ
ン、アクリロニトリル、ハロゲン化ビニリデン、ビニル
エーテル等を使用することができる。In the method of the present invention, the monomer used preferably has an acrylonitrile content of at least 80 mol% in all the monomers, and contains at least one other monomer having an ethylenic double bond. Other monomers having an ethylenic double bond include, for example, vinyl halides such as vinyl chloride; vinyl esters such as vinyl acetate; acrylic acid, methacrylic acid,
And their esters or salts; maleic acid, fumaric acid, and their esters or anhydrides; butadiene,
Diene monomers such as chloroprene and isoprene; styrene, acrylonitrile, vinylidene halide, vinyl ether and the like can be used.
【００２０】本発明において、重合体溶液の溶媒として
は、ジメチルスルホキシド（以下、「ＤＭＳＯ」と略す
る）、ジメチルホルムアミド、ジメチルアセトアミドな
どの有機溶媒が好ましく使用されるが、本発明は溶媒に
よって限定されるものではない。すなわち、例えば、無
機塩の水溶液でアクリル重合体を溶液重合している場合
は溶媒の蒸気として水蒸気を用いることができる。重合
方法としては、バッチ重合、連続重合のいずれでもよ
く、充填塔の上部から供給される重合体溶液は、その４
５℃における粘度が５０〜１０００ポイズのものである
ことが好ましい。さらに、充填塔の上部から供給される
重合体溶液として、１５〜３０重量％の重合体濃度を有
するとともに、未反応モノマーを１〜８重量％含んでい
るものを用いることが好ましい。In the present invention, as a solvent for the polymer solution, an organic solvent such as dimethyl sulfoxide (hereinafter abbreviated as "DMSO"), dimethylformamide and dimethylacetamide is preferably used, but the present invention is limited by the solvent. It is not something to be done. That is, for example, when the acrylic polymer is solution-polymerized with an aqueous solution of an inorganic salt, steam can be used as the vapor of the solvent. As the polymerization method, either batch polymerization or continuous polymerization may be used.
Preferably, the viscosity at 5 ° C. is 50 to 1000 poise. Furthermore, as the polymer solution supplied from the upper part of the packed tower, it is preferable to use a polymer solution having a polymer concentration of 15 to 30% by weight and containing 1 to 8% by weight of an unreacted monomer.
【００２１】本発明において、充填塔とは塔内に充填物
が充填されている塔のことであり、重合体溶液は一般の
溶液と比較して粘度が非常に高いので、塔内に均一に重
合体溶液を分散させることが比較的困難であり、充填塔
内に均一に重合体溶液を供給するためには、パイプ型、
オリフィス型、トラフ型、ノッチ型、ラダー型、トーナ
メント型等の分散器が適宜使用され得る。また、塔内で
の熱損失を防ぐために、塔内でのこれら分散器や分散器
の導入配管の少なくとも一部を保温することも好ましく
行われる。In the present invention, the packed column is a column in which the packing is packed, and the polymer solution has a very high viscosity as compared with a general solution. It is relatively difficult to disperse the polymer solution, and in order to uniformly supply the polymer solution into the packed tower, a pipe type,
A disperser such as an orifice type, a trough type, a notch type, a ladder type, and a tournament type can be appropriately used. In order to prevent heat loss in the tower, it is preferable to keep at least a part of the disperser and the introduction pipe of the disperser in the tower.
【００２２】また、本発明において、充填塔は、１０〜
３５０ｍ2 ／ｍ3 の比表面積を有する充填物が充填され
ているものを用いるのが好ましい。該充填物が存在して
いることにより、重合体溶液の表面が更新し、未反応モ
ノマーの除去が促進されるからである。該比表面積のさ
らに好ましい範囲は、５０〜２７０ｍ2 ／ｍ3である。Also, in the present invention, the packed tower is preferably 10 to
It is preferable to use one filled with a filler having a specific surface area of 350 m 2 / m 3 . This is because the presence of the filler renews the surface of the polymer solution and promotes removal of unreacted monomers. A more preferable range of the specific surface area is 50 to 270 m 2 / m 3 .
【００２３】このような１０〜３５０ｍ2 ／ｍ3 の比表
面積を有する充填物としては、特に限定されないが、未
反応モノマーの安定した除去の観点からも、圧力損失が
低く充填領域内での気液の偏流が少ないものが好まし
く、材質としては、金属製、プラスチック製、陶器製等
があるが、空隙率と強度の点からも金属製が好ましい。The packing having such a specific surface area of 10 to 350 m 2 / m 3 is not particularly limited, but from the viewpoint of stable removal of unreacted monomers, the pressure loss is low and the gas in the packing region is low. It is preferable that the liquid has a small drift, and the material is metal, plastic, pottery, etc., but metal is also preferable in terms of porosity and strength.
【００２４】さらに、充填塔の下部からは重合体溶液の
溶媒をリボイラー等の加熱器で加熱しその蒸気を充填塔
に供給する。また、リボイラーに供給する溶媒の液量は
多い方が好ましいが、装置、ランニングコストの点か
ら、充填塔に供給する重合体溶液の体積に対して、１〜
５０体積％が好ましい。Further, from the lower part of the packed tower, the solvent of the polymer solution is heated by a heater such as a reboiler and the vapor is supplied to the packed tower. Further, it is preferable that the amount of the solvent supplied to the reboiler is large.
50% by volume is preferred.
【００２５】また、充填塔頂の圧力Ｐｔ（Ｔｏｒｒ）
は、０＜Ｐｔ≦５０の範囲内であることが望ましく、該
範囲以外であると、溶媒の蒸気が高温となり、充填塔か
ら流出する重合体溶液が高温となるので望ましくない。
特に好ましくは、０＜Ｐｔ≦３０の範囲内である。The pressure Pt (Torr) at the top of the packed tower
Is desirably in the range of 0 <Pt ≦ 50. If the value is outside the range, the solvent vapor becomes high in temperature, and the polymer solution flowing out of the packed tower becomes high in temperature.
Particularly preferably, it is in the range of 0 <Pt ≦ 30.
【００２６】また、充填塔頂の圧力Ｐｔ（Ｔｏｒｒ）と
充填塔底の圧力Ｐｂ（Ｔｏｒｒ）が、０＜（Ｐｂ−Ｐ
ｔ）≦１０の関係を満足するように条件を定めるのがよ
い。（Ｐｂ−Ｐｔ）が１０を越えると充填塔内での重合
体溶液の偏流の可能性があり、未反応モノマーの除去の
点で好ましくない。The pressure Pt (Torr) at the top of the packed column and the pressure Pb (Torr) at the bottom of the packed column are 0 <(Pb-P
It is preferable that the conditions are set so as to satisfy the relationship of t) ≦ 10. If (Pb-Pt) exceeds 10, there is a possibility that the polymer solution will drift in the packed tower, which is not preferable in terms of removing unreacted monomers.
【００２７】さらに、充填塔底の圧力Ｐｂ（Ｔｏｒｒ）
と脱気槽の圧力Ｐｄ（Ｔｏｒｒ）は、０＜（Ｐｂ−Ｐ
ｄ）≦３０とするのが好ましく、該（Ｐｂ−Ｐｄ）値
が、３０よりも大きいと、充填塔底の圧力が高くなり充
填塔から流出する重合体溶液の温度が高くなるので好ま
しくない。好ましくは、該値は２〜２０である。また、
充填塔に供給する重合体溶液の温度ｔｉ（℃）と脱気槽
から流出する重合体溶液の温度ｔｏ（℃）は、０＜（ｔ
ｉ−ｔｏ）≦５０とするのが好ましく、該範囲を外れる
と、重合体溶液の過濃縮となってくるので、好ましくな
い。Further, the pressure Pb (Torr) at the bottom of the packed column
And the pressure Pd (Torr) of the degassing tank is 0 <(Pb-P
d) ≦ 30 is preferred, and if the (Pb−Pd) value is larger than 30, the pressure at the bottom of the packed tower increases, and the temperature of the polymer solution flowing out of the packed tower increases, which is not preferred. Preferably, the value is between 2 and 20. Also,
The temperature ti (° C.) of the polymer solution supplied to the packed tower and the temperature to (° C.) of the polymer solution flowing out of the degassing tank are 0 <(t
It is preferable that i-to) ≦ 50. If the ratio is out of the range, the polymer solution becomes excessively concentrated, which is not preferable.
【００２８】さらには、充填塔底の圧力Ｐｂ（Ｔｏｒ
ｒ）が０＜Ｐｂ≦３０であり、かつ、充填塔底の圧力Ｐ
ｂ（Ｔｏｒｒ）と脱気槽の圧力Ｐｄ（Ｔｏｒｒ）が０＜
（Ｐｂ−Ｐｄ）＜３０であるように設定をするのが、最
も重合体溶液の濃縮と冷却が適正に達成できるので好ま
しいものである。充填塔頂の圧力とは、充填物の最上段
部よりも上部で塔本体との空間の圧力であり、充填塔底
圧力とは、充填物の最下部よりも下部で塔本体との空間
の圧力である。Further, the pressure Pb (Torr) at the bottom of the packed tower
r) is 0 <Pb ≦ 30 and the pressure P at the bottom of the packed column is
b (Torr) and deaeration tank pressure Pd (Torr) are 0 <
It is preferable to set (Pb-Pd) <30 because the concentration and cooling of the polymer solution can be most appropriately achieved. The pressure at the top of the packed tower is the pressure in the space above the top of the packing and the space between the tower and the packed body, and the pressure at the bottom of the packed tower is the space below the bottom of the packed material and the space between the body and the tower. Pressure.
【００２９】以下、本発明の精製アクリル系重合体溶液
の製造方法の好ましい一実施態様例を、図１を用いて説
明する。A preferred embodiment of the method for producing a purified acrylic polymer solution of the present invention will be described below with reference to FIG.
【００３０】図１は、本発明の精製アクリル系重合体溶
液の製造方法の一例を示した概略フロー図であり、未反
応モノマーを含む重合体溶液を充填塔１の上部から塔内
に供給する。該充填塔下部に設けられたリボイラー２で
溶媒を加熱しその蒸気を塔内に供給し、溶媒の蒸気と重
合体溶液とを向流接触させ重合体溶液中の未反応モノマ
ーを除去し、溶媒の蒸気と除去したモノマーの混合物を
吸収塔３で有機溶媒に吸収させる。FIG. 1 is a schematic flow chart showing an example of the method for producing a purified acrylic polymer solution of the present invention, in which a polymer solution containing an unreacted monomer is supplied from the top of a packed column 1 into the column. . The solvent is heated by the reboiler 2 provided at the lower part of the packed tower, the vapor is supplied into the tower, the vapor of the solvent is brought into countercurrent contact with the polymer solution, and the unreacted monomer in the polymer solution is removed. The mixture of the vapor and the removed monomer is absorbed in the organic solvent in the absorption tower 3.
【００３１】また、エゼクター４を用いて真空を発生さ
せ、吸収塔３と充填塔１を減圧し、充填塔頂と充填塔底
の圧力差を好ましくは１０Ｔｏｒｒ以下とする。このよ
うにして未反応モノマーを除去し、精製したアクリル系
重合体溶液をポンプ５を用いて抜き出す。ポンプ６で抜
き出した精製アクリル系重合体溶液を充填塔１の塔底の
圧力よりも低い圧力の脱気槽６に送り、主として重合体
溶液の濃縮と冷却を行い、脱気槽６からポンプ７を用い
て抜き出すものである。A vacuum is generated using the ejector 4 to reduce the pressure in the absorption tower 3 and the packed tower 1 so that the pressure difference between the top of the packed tower and the bottom of the packed tower is preferably 10 Torr or less. The unreacted monomer is removed in this way, and the purified acrylic polymer solution is withdrawn using the pump 5. The purified acrylic polymer solution extracted by the pump 6 is sent to the degassing tank 6 having a pressure lower than the pressure at the bottom of the packed tower 1, and the polymer solution is mainly concentrated and cooled. It is extracted using.
【００３２】[0032]
【実施例】以下、実施例により本発明をより具体的に説
明する。The present invention will be described more specifically with reference to the following examples.
【００３３】実施例１ 図１に示したとおりの本発明の精製アクリル系重合体溶
液の製造方法の一例フローにより、下記のとおりに精製
アクリル系重合体溶液を製造した。Example 1 A purified acrylic polymer solution was produced in the following manner according to an example of the method for producing a purified acrylic polymer solution of the present invention as shown in FIG.
【００３４】すなわち、アクリロトリル９３．８ｍｏｌ
％、アクリル酸メチル６ｍｏｌ％、メタリルスルホン酸
ナトリウム０．２ｍｏｌ％を含むモノマーをＤＭＳＯを
溶媒として重合し、未反応モノマーを３．４重量％含む
ポリマー濃度２２．０重量％、４５℃における粘度が１
７０ポイズのアクリル系重合体のＤＭＳＯ溶液を７０℃
で、塔頂圧力１０Torrの充填塔１に供給した。充填塔１
には比表面積１５５ｍ2 ／ｍ3 のステンレス製の充填物
を充填した。塔底からはリボイラー２で加熱したＤＭＳ
Ｏの蒸気を供給量に対して２０重量％を供給した。この
ときの充填塔底圧力は１１Torrであった。塔底より流出
する重合体溶液をポンプ５を用いて抜き出した。塔底よ
り抜き出された重合体溶液のポリマー濃度は２１．２重
量％であり、温度は７４℃であった。That is, 93.8 mol of acrylotrile
%, 6% by mole of methyl acrylate, and 0.2% by mole of sodium methallylsulfonate are polymerized using DMSO as a solvent. Is 1
DMSO solution of 70 poise acrylic polymer at 70 ° C
To the packed column 1 having a top pressure of 10 Torr. Packing tower 1
Was filled with a stainless filler having a specific surface area of 155 m 2 / m 3 . DMS heated by reboiler 2 from the bottom
O vapor was supplied at 20% by weight based on the supply amount. At this time, the pressure at the bottom of the packed tower was 11 Torr. The polymer solution flowing out from the bottom of the column was extracted using a pump 5. The polymer concentration of the polymer solution extracted from the bottom was 21.2% by weight, and the temperature was 74 ° C.
【００３５】ガスクロマトグラフィを用いて、塔底より
抜き出された重合体溶液のモノマー濃度を測定したとこ
ろ、０．０４重量％であった。この塔底より抜き出され
た重合体溶液を４．０Ｔｏｒｒの脱気槽６に導入した。
脱気槽６から抜き出された重合体溶液のポリマー濃度は
２２．４％であり、温度は５８℃であった。The concentration of the monomer in the polymer solution extracted from the bottom of the column was measured by gas chromatography and found to be 0.04% by weight. The polymer solution extracted from the bottom of the tower was introduced into a degassing tank 6 at 4.0 Torr.
The polymer concentration of the polymer solution extracted from the degassing tank 6 was 22.4%, and the temperature was 58 ° C.
【００３６】この結果からわかるように、本発明の方法
によれば、未反応モノマーを極めて高い除去率（９８．
８％（除去前の未反応モノマー量３．４重量％、除去後
の未反応モノマー量０．０４重量％、））で除去するこ
とができた。As can be seen from the results, according to the method of the present invention, an extremely high removal rate of the unreacted monomer (98.
8% (3.4% by weight of unreacted monomer before removal, 0.04% by weight of unreacted monomer after removal)).
【００３７】実施例２ 実施例１と同様のプロセスにおいて、比表面積１９９ｍ
2 ／ｍ3 のステンレス製の充填物を充填した以外は、他
は同様にして、精製アクリル系重合体溶液を製造した。Example 2 In the same process as in Example 1, a specific surface area of 199 m
A purified acrylic polymer solution was produced in the same manner except that a 2 / m 3 stainless steel filler was filled.
【００３８】このときの充填塔底圧力は１２Torrであっ
た。塔底より流出する重合体溶液をポンプ５を用いて抜
き出した。塔底より抜き出された重合体溶液のポリマー
濃度は２１．４重量％であり、温度は７５℃であった。At this time, the pressure at the bottom of the packed tower was 12 Torr. The polymer solution flowing out from the bottom of the column was extracted using a pump 5. The polymer concentration of the polymer solution withdrawn from the bottom was 21.4% by weight, and the temperature was 75 ° C.
【００３９】ガスクロマトグラフィを用いて、塔底より
抜き出された重合体溶液のモノマー濃度を測定したとこ
ろ、０．０２重量％であった。この塔底より抜き出され
た重合体溶液を４Ｔｏｒｒの脱気槽６に導入した。脱気
槽６から抜き出された重合体溶液のポリマー濃度は２
２．４％であり、温度は５８℃であった。The concentration of the monomer in the polymer solution extracted from the bottom of the column was measured by gas chromatography and found to be 0.02% by weight. The polymer solution extracted from the bottom of the tower was introduced into a degassing tank 6 of 4 Torr. The polymer concentration of the polymer solution extracted from the degassing tank 6 is 2
2.4% and the temperature was 58 ° C.
【００４０】この結果からわかるように、本発明の方法
によれば、未反応モノマーを極めて高い除去率（９９．
４％（除去前の未反応モノマー量３．４重量％、除去後
の未反応モノマー量０．０２重量％、））で除去するこ
とができた。As can be seen from the results, according to the method of the present invention, an extremely high removal rate of unreacted monomers (99.
4% (3.4% by weight of unreacted monomer before removal, 0.02% by weight of unreacted monomer after removal)).
【００４１】比較例１ アクリロニトリル９３．８ｍｏｌ％、アクリル酸メチル
６ｍｏｌ％、メタリルスルホン酸ナトリウム０．２ｍｏ
ｌ％をＤＭＳＯを溶媒として重合し、未反応モノマーを
３．５重量％含むポリマー濃度２２．０重量％、４５℃
における粘度が１７０ポイズのアクリル系重合体のＤＭ
ＳＯ溶液を熱交換器で８８℃に加熱し、塔頂圧力１０To
rrの充填塔に供給した。充填塔には比表面積１５５ｍ2
／ｍ3 のステンレス製の充填物を充填した。塔底からは
ＤＭＳＯの蒸気を供給量に対して２０重量％を供給し
た。このときの塔底の圧力は１１Torrであった。塔底よ
り流出する重合体溶液をポンプ５を用いて抜き出した。
塔底より抜き出された重合体溶液のポリマー濃度は２
２．４重量％で、温度は７４℃であり、冷却器を用いて
６０℃に冷却した。ガスクロマトグラフィを用いて、塔
底より抜き出された重合体溶液のモノマー濃度を測定し
たところ、０．０５重量％であった。この結果からわか
るように、この方法によれば、未反応モノマーを高い除
去率（９８．５％（除去前の未反応モノマー量３．４重
量％、除去後の未反応モノマー量０．０４重量％））で
除去できたものの、重合体溶液の濃縮を行うために充填
塔上部から供給する重合体溶液を高温に加熱する必要が
あり、さらに、重合体溶液の熱劣化を防ぐために塔下部
から抜き出した重合体溶液を冷却器を用いて冷却する必
要があった。Comparative Example 1 Acrylonitrile 93.8 mol%, methyl acrylate 6 mol%, sodium methallyl sulfonate 0.2 mol
1% polymerized in DMSO as a solvent, and a polymer concentration of 22.0% by weight containing 3.5% by weight of unreacted monomer,
Of an acrylic polymer having a viscosity of 170 poise at room temperature
The SO solution was heated to 88 ° C with a heat exchanger, and the top pressure was 10 To
rr was fed to the packed tower. The packed tower has a specific surface area of 155 m 2
/ M 3 of stainless steel packing. From the bottom of the tower, 20% by weight of DMSO vapor was supplied to the supply amount. At this time, the pressure at the bottom of the tower was 11 Torr. The polymer solution flowing out from the bottom of the column was extracted using a pump 5.
The polymer concentration of the polymer solution withdrawn from the bottom was 2
At 2.4% by weight, the temperature was 74 ° C. and cooled to 60 ° C. using a cooler. The monomer concentration of the polymer solution extracted from the bottom of the column was measured by gas chromatography, and was found to be 0.05% by weight. As can be seen from this result, according to this method, a high removal rate of unreacted monomer (98.5% (3.4% by weight of unreacted monomer before removal, 0.04% by weight of unreacted monomer after removal) %)), It is necessary to heat the polymer solution supplied from the top of the packed tower to a high temperature in order to concentrate the polymer solution, and from the bottom of the tower to prevent thermal degradation of the polymer solution. It was necessary to cool the extracted polymer solution using a cooler.
【００４２】[0042]
【発明の効果】以上述べた通りの本発明のアクリル系精
製ポリマー溶液の製造方法を用いることにより、重合体
溶液中の未反応モノマーを極めて高い除去率で除去する
ことができるので、本発明者らの各種知見によれば、一
般に、未反応モノマー含有量が０．０５重量％以下の精
製ポリマー溶液を得ることができる。By using the method for producing a purified acrylic polymer solution of the present invention as described above, the unreacted monomer in the polymer solution can be removed at an extremely high removal rate. According to these various findings, generally, a purified polymer solution having an unreacted monomer content of 0.05% by weight or less can be obtained.
【００４３】また、ポリマー濃度を適正な濃度に濃縮さ
せた精製ポリマー溶液を得ることができ、さらに、精製
ポリマー溶液を適正な温度にすることもできる。Further, it is possible to obtain a purified polymer solution in which the polymer concentration is concentrated to a proper concentration, and it is also possible to set the purified polymer solution to a proper temperature.
【００４４】すなわち、ポリマー濃度であれば、概して
濃度２２．１〜２３．０％までに濃縮することができ、
さらに、重合体溶液の温度を６９〜５０℃まで冷却する
ことができる。これらのことは、充填塔に供給する重合
体溶液の温度を一定にし、脱気槽の圧力を調整すること
で比較的容易に達成することができ、重合体溶液を濃縮
するために重合体溶液を高温にする必要がなく、重合体
溶液の熱劣化を防止するという更なる効果をもたらすこ
とが可能なのであり、本発明方法は、実際産業上、極め
て有意義な方法である。That is, if the concentration is a polymer, the concentration can be generally reduced to 22.1 to 23.0%.
Further, the temperature of the polymer solution can be cooled to 69-50C. These can be achieved relatively easily by keeping the temperature of the polymer solution supplied to the packed tower constant and adjusting the pressure of the degassing tank. Does not need to be heated to a high temperature, and a further effect of preventing thermal degradation of the polymer solution can be obtained. Thus, the method of the present invention is actually a very significant method in industry.
【００４５】すなわち、本発明のアクリル系精製ポリマ
ー溶液の製造方法は、溶液重合における未反応モノマー
を含む重合体溶液から、未反応モノマーを極めて高い除
去率で除去するとともに、重合体溶液を適正な濃度への
濃縮と冷却を、同時に達成することができるのである。That is, the method for producing a purified acrylic polymer solution of the present invention removes the unreacted monomer from the polymer solution containing the unreacted monomer in the solution polymerization at an extremely high removal rate, and at the same time, removes the polymer solution from Concentration to concentration and cooling can be achieved simultaneously.
【図１】本発明のアクリル系精製ポリマー溶液の製造方
法を実施するための装置の一例を示す概略図である。FIG. 1 is a schematic view showing an example of an apparatus for performing a method for producing a purified acrylic polymer solution of the present invention.
１：充填塔 ２：リボイラー ３：吸収塔 ４：エゼクター ５：ポンプ ６：脱気槽 ７：ポンプ ８：重合体溶液供給ライン 1: Packing tower 2: Reboiler 3: Absorption tower 4: Ejector 5: Pump 6: Degassing tank 7: Pump 8: Polymer solution supply line
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4J011 DA04 DB28 DB34 HA02 HA03 4J100 AC03Q AE02Q AG04Q AJ02Q AJ09Q AK32Q AL02Q AL34Q AM02P AS02Q AS07Q CA01 CA04 DA09 EA01 FA19 GB05 GB18 GC26 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J011 DA04 DB28 DB34 HA02 HA03 4J100 AC03Q AE02Q AG04Q AJ02Q AJ09Q AK32Q AL02Q AL34Q AM02P AS02Q AS07Q CA01 CA04 DA09 EA01 FA19 GB05 GB18 GC26
Claims (11)
ーを溶液重合して得られる重合体溶液を、減圧せしめた
充填塔の上部から供給するとともに、充填塔の下部から
該重合体溶液の溶媒の蒸気を該重合体溶液と向流接触さ
せるように供給し、充填塔下部から流出する該重合体溶
液を、該充填塔底圧よりも低い圧力に減圧せしめた脱気
槽に供給することを特徴とする精製アクリル系重合体溶
液の製造方法。1. A polymer solution obtained by solution-polymerizing a monomer containing at least acrylonitrile is supplied from an upper portion of a packed tower under reduced pressure, and a vapor of a solvent of the polymer solution is supplied from a lower portion of the packed tower to the polymer. A purified acrylic, which is supplied so as to be brought into countercurrent contact with the coalescing solution, and wherein the polymer solution flowing out from the lower part of the packed tower is supplied to a degassing tank reduced in pressure to a pressure lower than the bottom pressure of the packed tower. A method for producing a polymer solution.
ロニトリルの含有量が８０ｍｏｌ％以上のものであるこ
とを特徴とする請求項１記載の精製アクリル系重合体溶
液の製造方法。2. The method for producing a purified acrylic polymer solution according to claim 1, wherein the content of acrylonitrile in all the monomers is 80 mol% or more.
４５℃における粘度が５０〜１０００ポイズのものであ
ることを特徴とする請求項１または２記載の精製アクリ
ル系重合体溶液の製造方法。3. The process for producing a purified acrylic polymer solution according to claim 1, wherein the polymer solution supplied from the upper part of the packed tower has a viscosity at 45 ° C. of 50 to 1000 poise. Method.
して、１５〜３０重量％の重合体濃度を有するものであ
り、かつ、未反応モノマーを１〜８重量％含んでいるも
のを用いることを特徴とする請求項１、２、または３記
載の精製アクリル系重合体溶液の製造方法。4. A polymer solution supplied from the upper part of the packed tower having a polymer concentration of 15 to 30% by weight and containing 1 to 8% by weight of an unreacted monomer is used. The method for producing a purified acrylic polymer solution according to claim 1, 2, or 3.
面積を有する充填物が充填されているものであることを
特徴とする請求項１、２、３、または４記載の精製アク
リル系重合体溶液の製造方法。5. The purified acrylic according to claim 1, wherein the packed tower is packed with a packing having a specific surface area of 10 to 350 m 2 / m 3. A method for producing a polymer solution.
Ｐｔ≦５０であることを特徴とする請求項１、２、３、
４または５記載の精製アクリル系重合体溶液の製造方
法。6. The pressure Pt (Torr) at the top of the packed tower is 0 <
Pt ≦ 50, wherein Pt ≦ 50.
6. The method for producing a purified acrylic polymer solution according to 4 or 5.
底の圧力Ｐｂ（Ｔｏｒｒ）が、０＜（Ｐｂ−Ｐｔ）≦１
０である請求項１、２、３、４、５または６記載の精製
アクリル系重合体溶液の製造方法。7. The pressure Pt (Torr) at the top of the packed column and the pressure Pb (Torr) at the bottom of the packed column are 0 <(Pb−Pt) ≦ 1.
The method for producing a purified acrylic polymer solution according to claim 1, 2, 3, 4, 5, or 6, which is 0.
の圧力Ｐｄ（Ｔｏｒｒ）が０＜（Ｐｂ−Ｐｄ）≦３０で
ある請求項１、２、３、４、５、６または７記載の精製
アクリル系重合体溶液の製造方法。8. The method according to claim 1, wherein the pressure Pb (Torr) at the bottom of the packed tower and the pressure Pd (Torr) of the degassing tank satisfy 0 <(Pb−Pd) ≦ 30. 8. The method for producing a purified acrylic polymer solution according to 7.
（℃）と脱気槽から流出する重合体溶液の温度ｔｏ
（℃）が０＜（ｔｉ−ｔｏ）≦５０である請求項１、
２、３、４、５、６、７または８記載の精製アクリル系
重合体溶液の製造方法。9. The temperature ti of the polymer solution supplied to the packed tower.
(° C.) and the temperature of the polymer solution flowing out of the degassing tank to
The method according to claim 1, wherein (° C.) satisfies 0 <(ti-to) ≦ 50.
The method for producing a purified acrylic polymer solution according to 2, 3, 4, 5, 6, 7, or 8.
Ｐｂ≦３０であり、かつ、充填塔底の圧力Ｐｂ（Ｔｏｒ
ｒ）と脱気槽の圧力Ｐｄ（Ｔｏｒｒ）が０＜（Ｐｂ−Ｐ
ｄ）＜３０である請求項１、２、３、４、５、６、７、
８または９記載の精製アクリル系重合体溶液の製造方
法。10. The pressure Pb (Torr) at the bottom of the packed tower is 0 <
Pb ≦ 30 and the pressure Pb (Torr
r) and the pressure Pd (Torr) of the deaeration tank are 0 <(Pb-P
d) <30, wherein 1, 2, 3, 4, 5, 6, 7,
10. The method for producing a purified acrylic polymer solution according to 8 or 9.
マーを溶液重合して得られる重合体溶液を、減圧せしめ
た充填塔の上部から供給するとともに、充填塔の下部か
ら該重合体溶液の溶媒の蒸気を該重合体溶液と向流接触
させるように供給し、充填塔下部から流出する該重合体
溶液を、該充填塔底圧よりも低い圧力に減圧せしめた脱
気槽に供給し、精製を行うように構成したことを特徴と
するアクリル系重合体溶液の精製方法。11. A polymer solution obtained by solution-polymerizing a monomer containing at least acrylonitrile is supplied from the upper portion of a packed column under reduced pressure, and the vapor of the solvent of the polymer solution is supplied from the lower portion of the packed column to the polymer. The polymer solution is supplied so as to be brought into countercurrent contact with the coalescing solution, and the polymer solution flowing out from the lower portion of the packed tower is supplied to a degassing tank reduced in pressure to a pressure lower than the bottom pressure of the packed tower to perform purification. A method for purifying an acrylic polymer solution, comprising:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10219239A JP2000044606A (en) | 1998-08-03 | 1998-08-03 | Production of purified acrylic polymer solution and purification of acrylic polymer solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10219239A JP2000044606A (en) | 1998-08-03 | 1998-08-03 | Production of purified acrylic polymer solution and purification of acrylic polymer solution |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000044606A true JP2000044606A (en) | 2000-02-15 |
Family
ID=16732402
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10219239A Pending JP2000044606A (en) | 1998-08-03 | 1998-08-03 | Production of purified acrylic polymer solution and purification of acrylic polymer solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000044606A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180070294A (en) | 2016-12-16 | 2018-06-26 | 주식회사 엘지화학 | Method for separating non-reacted monomer from mixture comprising non-reacted monomer |
| WO2019132470A1 (en) | 2017-12-28 | 2019-07-04 | 주식회사 엘지화학 | Method for separating unreacted monomer from mixed solution comprising unreacted monomer |
| KR20190079833A (en) | 2017-12-28 | 2019-07-08 | 주식회사 엘지화학 | Method for separating non-reacted monomer from mixture comprising non-reacted monomer with reduced energy usage |
-
1998
- 1998-08-03 JP JP10219239A patent/JP2000044606A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180070294A (en) | 2016-12-16 | 2018-06-26 | 주식회사 엘지화학 | Method for separating non-reacted monomer from mixture comprising non-reacted monomer |
| WO2019132470A1 (en) | 2017-12-28 | 2019-07-04 | 주식회사 엘지화학 | Method for separating unreacted monomer from mixed solution comprising unreacted monomer |
| KR20190079832A (en) | 2017-12-28 | 2019-07-08 | 주식회사 엘지화학 | Method for separating non-reacted monomer from mixture comprising non-reacted monomer |
| KR20190079833A (en) | 2017-12-28 | 2019-07-08 | 주식회사 엘지화학 | Method for separating non-reacted monomer from mixture comprising non-reacted monomer with reduced energy usage |
| US11198953B2 (en) | 2017-12-28 | 2021-12-14 | Lg Chem, Ltd. | Method for separating unreacted monomer from mixture solution including unreacted monomer |
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