JP2012188535A - Method for producing acrylonitrile-based polymer - Google Patents
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本発明は、衣料用繊維や炭素繊維用前駆体繊維束等の製造に用いられるアクリロニトリル系ポリマーの製造方法に関する。 The present invention relates to a method for producing an acrylonitrile-based polymer used for production of clothing fibers, carbon fiber precursor fiber bundles, and the like.
一般にアクリロニトリル系ポリマーの工業的製造法としては、水系析出重合法と溶液重合法が知られている。水系析出重合法は、水性媒体中、水溶性重合開始剤を用いて、アクリロニトリルと必要に応じて使用される共重合性成分とからなる単量体を重合する方法であって、重合反応が進行するにつれポリマーが析出する不均一系の重合法である。溶液重合法は、上述の単量体を溶解しうる無機溶媒または有機溶媒中で、該単量体を重合する方法であり、ポリマーも溶媒中に溶解する均一系の重合法である。 In general, an aqueous precipitation polymerization method and a solution polymerization method are known as industrial production methods for acrylonitrile-based polymers. The aqueous precipitation polymerization method is a method of polymerizing a monomer composed of acrylonitrile and a copolymerizable component that is used as necessary using a water-soluble polymerization initiator in an aqueous medium, and the polymerization reaction proceeds. This is a heterogeneous polymerization method in which the polymer is precipitated as it is. The solution polymerization method is a method in which the monomer is polymerized in an inorganic solvent or an organic solvent in which the above-mentioned monomer can be dissolved, and is a homogeneous polymerization method in which the polymer is also dissolved in the solvent.
これらの重合法によって連続重合を行う場合は、水性媒体、無機溶媒または有機溶媒と、重合開始剤と、単量体等の原料成分とは連続的に重合反応器に供給され、攪拌により分散させられながら重合され、連続的に重合反応器から排出される。これらのうち、特に、水系析出重合を連続的に行う水系析出連続重合法は、連続溶液重合法に比べて短い滞在時間で連続生産が可能で、しかも簡便な重合反応器を使用できるため、非常に生産性が優れている。 When performing continuous polymerization by these polymerization methods, an aqueous medium, an inorganic solvent or an organic solvent, a polymerization initiator, and raw material components such as monomers are continuously supplied to the polymerization reactor and dispersed by stirring. Polymerized and continuously discharged from the polymerization reactor. Among these, in particular, the aqueous precipitation continuous polymerization method in which the aqueous precipitation polymerization is continuously performed can be continuously produced in a shorter residence time than the continuous solution polymerization method, and a simple polymerization reactor can be used. Productivity is excellent.
連続重合において重合反応器から排出される重合反応液は、重合転化率が１００％に達しておらず、未反応の単量体を含んでいる。未反応の単量体は洗浄や蒸留によって除去されるが、未反応の単量体が重合反応器外で除去工程までに重合（以下「後重合」とも言う。）すると、分子量分布の広がりや、共重合体を製造している場合には組成分布の広がりが生じる恐れがあり、その成分がポリマー中の不純物となって、毛羽発生など繊維の物性低下に繋がるため、重合反応液が重合反応器外に排出された後、重合停止剤が添加されることが多い。 The polymerization reaction liquid discharged from the polymerization reactor in the continuous polymerization does not reach the polymerization conversion rate of 100% and contains unreacted monomers. Unreacted monomers are removed by washing or distillation, but if unreacted monomers are polymerized by the removal step outside the polymerization reactor (hereinafter also referred to as “post-polymerization”), When a copolymer is produced, the composition distribution may spread, and the components become impurities in the polymer, leading to fiber properties such as fluff generation. A polymerization terminator is often added after being discharged out of the vessel.
しかしながら、重合反応液が重合反応器外に排出されてから添加される重合停止剤が重合を抑制する効果は、単量体によって異なり、主成分の単量体の重合を抑制していれば重合は一旦停止するが、未反応の主成分の単量体を蒸留により除去する工程を含む場合、主成分の単量体が除去された後に少量含まれる共重合成分が重合する恐れがある。 However, the effect of the polymerization terminator added after the polymerization reaction solution is discharged outside the polymerization reactor is different depending on the monomer, and if the polymerization of the main component monomer is suppressed, the polymerization Is temporarily stopped, but in the case of including a step of removing unreacted main component monomer by distillation, there is a possibility that a small amount of the copolymer component is polymerized after the main component monomer is removed.
例えば、アクリロニトリル系ポリマーの連続水系析出において、重合停止剤としてシュウ酸アンモニウム、炭酸水素アンモニウムの混合水溶液を用いる方法が開示されている。
しかしながら、アクリロニトリル単位とアクリルアミド単位、ヒドロキシアルキルエステル基を有するビニル単量体単位の少なくとも１種以上を有するビニル単量体単位とを共重合させ、上記重合停止剤を添加し、未反応のアクリロニトリル単位を気化により除去した場合、これらの重合停止剤のみでは未反応のアクリルアミド単位、ヒドロキシアルキルエステル基を有するビニル単量体単位の重合が充分に抑制されないという問題がある。
For example, a method of using a mixed aqueous solution of ammonium oxalate and ammonium hydrogen carbonate as a polymerization terminator in continuous aqueous precipitation of an acrylonitrile-based polymer is disclosed.
However, an acrylonitrile unit, an acrylamide unit, and a vinyl monomer unit having at least one kind of vinyl monomer unit having a hydroxyalkyl ester group are copolymerized, and the polymerization terminator is added to form an unreacted acrylonitrile unit. Is removed by vaporization, there is a problem that polymerization of unreacted acrylamide units and vinyl monomer units having a hydroxyalkyl ester group is not sufficiently suppressed only by these polymerization terminators.
本発明は上記事情に鑑みてなされたもので、後重合を抑制することにより不純物を削減したアクリロニトリル系ポリマーを、レドックス系触媒を開始剤とした連続重合法にて提供することを課題とする。 This invention is made | formed in view of the said situation, and makes it a subject to provide the acrylonitrile type | system | group polymer which reduced the impurity by suppressing post-polymerization by the continuous polymerization method which used the redox type | system | group catalyst as the initiator.
本発明のアクリロニトリル系ポリマーの製造方法は、重合開始剤としてレドックス系触媒を用い、アクリロニトリル単位が９５〜９９モル％と、共重合成分として、アクリルアミド単位、ヒドロキシアルキルエステル基を有するビニル単量体単位の少なくとも１種以上が１〜５モル％含有する単量体とを重合反応器内の水または溶媒中で重合反応させる工程、
重合反応器から排出された重合反応液に重合禁止剤とキレート剤とを添加する工程、
未反応のアクリロニトリル単位を気化分離させる工程
を有することを特徴とする。
The method for producing an acrylonitrile polymer of the present invention uses a redox catalyst as a polymerization initiator, 95 to 99 mol% of acrylonitrile units, and a vinyl monomer unit having an acrylamide unit and a hydroxyalkyl ester group as a copolymerization component. A step of polymerizing a monomer containing at least one of 1 to 5 mol% in water or a solvent in a polymerization reactor,
Adding a polymerization inhibitor and a chelating agent to the polymerization reaction solution discharged from the polymerization reactor;
It has a step of vaporizing and separating unreacted acrylonitrile units.
前記重合禁止剤がフェノール類、キノン類、ニトロソ化合物、硫黄化合物、ピラゾロン類の少なくとも１種からなり、前記キレート剤がシュウ酸を含む化合物からなることが好ましい。 It is preferable that the polymerization inhibitor is composed of at least one of phenols, quinones, nitroso compounds, sulfur compounds and pyrazolones, and the chelating agent is composed of a compound containing oxalic acid.
前記重合禁止剤の添加量が、未反応の単量体に対して、０．１〜１５質量％であることが好ましい。 It is preferable that the addition amount of the said polymerization inhibitor is 0.1-15 mass% with respect to the unreacted monomer.
前記キレート剤の添加量が、使用した金属イオンに対して２〜１００モル当量であることが好ましい。 It is preferable that the addition amount of the chelating agent is 2 to 100 molar equivalents relative to the metal ions used.
後重合を抑制することにより不純物を削減したアクリロニトリル系ポリマーを、レドックス系触媒を開始剤とした連続重合法にて提供できる。 An acrylonitrile-based polymer with reduced impurities by suppressing post-polymerization can be provided by a continuous polymerization method using a redox catalyst as an initiator.
以下、本発明を詳細に説明する。
本発明のアクリロニトリル系ポリマーの製造方法は、レドックス系触媒を重合開始剤として、アクリロニトリル単位と、アクリルアミド単位、ヒドロキシアルキルエステル基を有するビニル単量体単位の少なくとも１種以上を含有する単量体とを重合反応させる工程、重合反応器から排出された未反応の単量体を含む重合反応液に重合停止剤を添加する工程、未反応のアクリロニトリル単位を気化分離する工程から成る。重合法は特に限定しないが、水性媒体中で単量体を連続的に重合する水系析出連続重合が好ましい。
Hereinafter, the present invention will be described in detail.
The method for producing an acrylonitrile-based polymer of the present invention comprises a monomer containing at least one of an acrylonitrile unit, an acrylamide unit and a vinyl monomer unit having a hydroxyalkyl ester group, using a redox catalyst as a polymerization initiator. A polymerization reaction step, a step of adding a polymerization terminator to a polymerization reaction solution containing unreacted monomers discharged from the polymerization reactor, and a step of vaporizing and separating unreacted acrylonitrile units. The polymerization method is not particularly limited, but aqueous precipitation continuous polymerization in which monomers are continuously polymerized in an aqueous medium is preferable.
重合工程で重合される単量体は、アクリロニトリル単位と、アクリルアミド単位、ヒドロキシアルキルエステル基を有するビニル単量体単位の少なくとも１種以上とを含有する。必要に応じて他のモノマー単位を共重合させてもよい。該アクリロニトリル系ポリマーには、炭素繊維にしたときの共重合成分に起因する欠陥点を少なくし、炭素繊維の品質並びに性能を向上させる目的からアクリロニトリル単位が９５モル％以上含まれることが好ましく、より好ましくは９７．５モル％以上である。 The monomer to be polymerized in the polymerization step contains an acrylonitrile unit, an acrylamide unit, and at least one vinyl monomer unit having a hydroxyalkyl ester group. If necessary, other monomer units may be copolymerized. The acrylonitrile-based polymer preferably contains 95 mol% or more of acrylonitrile units for the purpose of reducing the number of defects caused by copolymerization components when converted into carbon fibers and improving the quality and performance of carbon fibers. Preferably it is 97.5 mol% or more.
また、本発明のアクリロニトリル系ポリマーは、ヒドロキシアルキルエステル基を有するビニル単量体単位を１．０モル％以上含有するのが好ましい。１．０モル％以上であると、紡糸工程における凝固時の繊維内部への水の拡散を緩やかにする効果が得られやすい。さらに、炭素繊維とする場合には、耐炎化工程においてヒドロキシアルキルエステル基を有するビニル単量体単位のカルボン酸２−ヒドロキシアルキル基がカルボン酸基となった際に、耐炎化反応を促進する効果も得られやすくなる。なお、ヒドロキシアルキルエステル基を有するビニル単量体単位の含有量の上限は、耐炎化反応の暴走の抑制や、耐炎化工程でのヒドロキシアルキル基の脱離に伴う炭素化収率の低下を抑える上でも、２．５モル％以下が好ましい。ヒドロキシアルキルエステル基を有するビニル単量体としては、アクリル酸２−ヒドロキシエチル、アクリル酸２−ヒドロキシプロピル、メタクリル酸２−ヒドロキシエチル、メタクリル酸２−ヒドロキシプロピル、イタコン酸ジ−２−ヒドロキシエチル、イタコン酸ジ−２ヒドロキシプロピル等が挙げられる。 Moreover, it is preferable that the acrylonitrile-type polymer of this invention contains 1.0 mol% or more of vinyl monomer units which have a hydroxyalkylester group. When it is 1.0 mol% or more, it is easy to obtain an effect of gradual diffusion of water into the fiber during coagulation in the spinning process. Further, when carbon fiber is used, the effect of promoting the flameproofing reaction when the 2-hydroxyalkyl group of carboxylic acid of the vinyl monomer unit having a hydroxyalkylester group in the flameproofing step becomes a carboxylic acid group. Is also easier to obtain. The upper limit of the content of the vinyl monomer unit having a hydroxyalkyl ester group is to suppress the runaway of the flameproofing reaction and to suppress the decrease in the carbonization yield accompanying the elimination of the hydroxyalkyl group in the flameproofing process. Also in the above, 2.5 mol% or less is preferable. Examples of the vinyl monomer having a hydroxyalkyl ester group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, di-2-hydroxyethyl itaconate, Examples thereof include di-2-hydroxypropyl itaconate.
また、単量体には、アクリルアミド単位が０．５質量％以上含まれることが好ましい。アクリルアミド単位は、得られたポリマー粉体を溶剤に溶解して紡糸原液とし、この紡糸原液を紡糸した際の凝固過程において、凝固を緩慢にする効果がある。そのため、アクリルアミド単位を含有する単量体から製造されたポリマー粉体を用いると、緻密な繊維構造が形成されやすい。よって、例えば、炭素繊維前駆体繊維束を製造する場合などには、単量体中にアクリルアミド単位が含まれることが好ましく、凝固を緩慢にする効果を十分に得るためには、単量体中に０．５質量％以上含まれることが好ましい。 Further, the monomer preferably contains 0.5% by mass or more of acrylamide units. Acrylamide units have the effect of slowing the coagulation in the coagulation process when the obtained polymer powder is dissolved in a solvent to form a spinning stock solution and the spinning stock solution is spun. Therefore, when a polymer powder produced from a monomer containing an acrylamide unit is used, a dense fiber structure is easily formed. Therefore, for example, when producing a carbon fiber precursor fiber bundle, it is preferable that an acrylamide unit is contained in the monomer, and in order to sufficiently obtain the effect of slowing the coagulation, It is preferable that 0.5 mass% or more is contained in.
重合に使用される開始剤はレドックス系触媒を用い、重合反応を促進するために、重合反応器内に微量の金属イオンを添加する。レドックス開始剤とは、酸化剤と還元剤を存在させ、酸化剤と還元剤との間における酸化還元反応によってラジカルを発生する開始剤である。ここに金属イオンを触媒として添加すると、金属イオンを介した酸化還元反応が起こり、開始反応が促進される。レドックス系触媒における酸化剤、還元剤の組合せ、酸化剤と還元剤の供給比率、金属イオン添加量は単量体の組成などに応じて適宜選択できる。 The initiator used for the polymerization uses a redox catalyst, and a small amount of metal ions is added to the polymerization reactor in order to accelerate the polymerization reaction. The redox initiator is an initiator that causes an oxidizing agent and a reducing agent to exist and generates radicals by an oxidation-reduction reaction between the oxidizing agent and the reducing agent. When a metal ion is added here as a catalyst, an oxidation-reduction reaction through the metal ion occurs and the initiation reaction is promoted. The combination of the oxidizing agent and the reducing agent, the supply ratio of the oxidizing agent and the reducing agent, and the metal ion addition amount in the redox catalyst can be appropriately selected according to the composition of the monomer.
水系析出連続重合法で重合する際には、例えば、予め重合反応器に水（水性媒体）を仕込んでおき、そこへ開始剤が溶解した開始剤溶液や単量体を連続的に供給し、攪拌により均一に分散させながら重合を進行させる。
ここで、重合反応器内へ仕込む水の単量体に対する質量比は、単量体の組成などに応じて適宜選択されるが、水／単量体が１．５〜８．０の範囲が好ましい。水／単量体が１．５以上であると、重合反応器内が粘調らず、攪拌困難となりにくく、一方、水／単量体が８．０以下であると、生産性が向上しやすくなる。
When polymerizing by the aqueous precipitation continuous polymerization method, for example, water (aqueous medium) is charged in advance in a polymerization reactor, and an initiator solution and a monomer in which the initiator is dissolved are continuously supplied thereto, Polymerization proceeds while being uniformly dispersed by stirring.
Here, the mass ratio of water charged into the polymerization reactor with respect to the monomer is appropriately selected according to the composition of the monomer, but the range of water / monomer is in the range of 1.5 to 8.0. preferable. When the water / monomer is 1.5 or more, the inside of the polymerization reactor is not viscous and difficult to stir. On the other hand, when the water / monomer is 8.0 or less, productivity is improved. It becomes easy.
重合反応器における単量体の平均滞在時間は、３０分〜１５０分の範囲が好ましい。３０分以上であると重合率が高くしやすくなり、１５０分以下であると生産性が向上しやすくなる。なお、平均滞在時間とは、下記式（１）で定義される。 The average residence time of the monomer in the polymerization reactor is preferably in the range of 30 minutes to 150 minutes. When it is 30 minutes or more, the polymerization rate is easily increased, and when it is 150 minutes or less, the productivity is easily improved. The average stay time is defined by the following formula (1).
平均滞在時間［ｈｒ］＝［重合反応器容量（Ｌ）］／［重合反応器への供給量（Ｌ／ｈｒ）］・・・（１）
ここで供給量とは、単位時間あたりに定常状態時に重合反応器に供給される水性媒体、単量体、開始剤などの総量である。
Average residence time [hr] = [Polymerization reactor capacity (L)] / [Supply amount to polymerization reactor (L / hr)] (1)
Here, the supply amount is the total amount of the aqueous medium, monomer, initiator and the like supplied to the polymerization reactor in a steady state per unit time.
重合反応器内のｐＨ、温度などは、単量体の組成などに応じて適宜選択可能である。必要に応じて、通常用いられる界面活性剤や凝集剤を重合反応器内に供給してもよい。 The pH, temperature, and the like in the polymerization reactor can be appropriately selected according to the monomer composition and the like. If necessary, a commonly used surfactant or flocculant may be supplied into the polymerization reactor.
重合反応器外へ排出された重合反応液には、水に溶解させた重合停止剤を連続的に添加する。重合停止剤にはキレート剤と重合禁止剤を併用する。キレート剤のみでは金属イオンを介さないラジカル発生反応を抑制することができず、重合禁止剤のみでは重合を抑制するために必要な重合禁止剤量が多くなる。 A polymerization terminator dissolved in water is continuously added to the polymerization reaction liquid discharged to the outside of the polymerization reactor. A chelating agent and a polymerization inhibitor are used in combination as the polymerization terminator. The chelating agent alone cannot suppress the radical generation reaction not involving metal ions, and the polymerization inhibitor alone increases the amount of the polymerization inhibitor necessary for suppressing the polymerization.
キレート剤としてはシュウ酸、クエン酸、エチレンジアミン四酢酸、フィチン酸ニトリロ三酢酸、ジエチレントリアミン五酢酸、ヒドロキシエチルエチレンジアミン三酢酸等とそれらの塩類、アセチルアセトン、オキシン、２，２‘−ジピリジル、ｏ−フェナントロリン等が挙げられ、使用量は重合反応液のｐＨ、濃度、添加した金属イオン種等によって異なるが、通常は使用した金属イオンに対して２〜１００００モル当量使用すればよい。このような範囲であれば、重合を充分に抑制することができ、繊維の物性に悪影響を及ぼさない。 Chelating agents include oxalic acid, citric acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid phytate, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid and their salts, acetylacetone, oxine, 2,2'-dipyridyl, o-phenanthroline, etc. The amount used varies depending on the pH and concentration of the polymerization reaction solution, the added metal ion species, and the like, but usually 2 to 10,000 molar equivalents may be used relative to the metal ion used. If it is such a range, superposition | polymerization can fully be suppressed and it does not exert a bad influence on the physical property of a fiber.
重合禁止剤としては安定なラジカルを生成するものであれば良いが、特にヒドロキノン、p-メトキシフェノール、８−ヒドロキシキノリン、クペロン、チオ尿素、ロダンアンモン、４−アミノアンチピリン等が挙げられ、使用量は重合反応液のｐＨ、濃度、添加した開始剤量によって異なるが、通常は未反応の残存単量体に対して０．０１〜１０質量％使用すればよい。このような範囲であれば、後重合を抑制しやすくなり、繊維の物性に悪影響を及ぼさない。 Any polymerization inhibitor may be used as long as it generates a stable radical, and hydroquinone, p-methoxyphenol, 8-hydroxyquinoline, cuperone, thiourea, rhodanammon, 4-aminoantipyrine, and the like are used. Is different depending on the pH and concentration of the polymerization reaction solution and the amount of the added initiator, but usually 0.01 to 10% by mass based on the unreacted residual monomer may be used. If it is such a range, it will become easy to suppress post-polymerization and will not exert a bad influence on the physical property of a fiber.
重合反応液を温度４０〜８０℃、圧力２０〜１０１ｋＰａ（ａ）の範囲内の条件で未反応のアクリロニトリル単位を気化し、重合反応液中の未反応のアクリロニトリル単位が１００ｐｐｍ以下、好ましくは１０ｐｐｍ以下になるまで、未反応のアクリロニトリル単位を気化分離する。 The unreacted acrylonitrile unit is vaporized under the conditions of the temperature of 40 to 80 ° C. and the pressure of 20 to 101 kPa (a) in the polymerization reaction solution, and the unreacted acrylonitrile unit in the polymerization reaction solution is 100 ppm or less, preferably 10 ppm or less. Until unreacted, the unreacted acrylonitrile units are vaporized and separated.
水分除去工程では、重合工程で得られたポリマーが分散している重合反応液を例えば７０℃程度のイオン交換水で洗浄、脱水後、熱風循環型の乾燥機などで乾燥することによって、ポリマー粉体として回収する。こうして回収されたポリマー粉体は、例えばこのポリマー粉体が衣料用繊維や炭素繊維用前駆体繊維束等の繊維製造用途である場合には、溶剤に溶解されて紡糸原液とされ、紡糸される。 In the water removal step, the polymer reaction solution in which the polymer obtained in the polymerization step is dispersed is washed with, for example, ion-exchanged water at about 70 ° C. Collect as a body. The polymer powder collected in this manner is dissolved in a solvent to form a spinning dope, for example, when the polymer powder is used for fiber production such as clothing fibers and precursor fiber bundles for carbon fibers. .
以上説明したように、このようなアクリロニトリル系ポリマーの製造方法によれば、重合を停止させる際に重合禁止剤とキレート剤とを併用し、重合禁止剤がフェノール類、キノン類、ニトロソ化合物、硫黄化合物、ピラゾロン類の少なくとも1種からなり、キレート剤はシュウ酸を含む化合物からなるため、後重合が抑制しやすくなり、不純物を削減したアクリロニトリル系ポリマーを得ることができる。 As described above, according to such a method for producing an acrylonitrile-based polymer, when the polymerization is stopped, a polymerization inhibitor and a chelating agent are used in combination, and the polymerization inhibitor is phenols, quinones, nitroso compounds, sulfur. Since it is composed of at least one of a compound and pyrazolones and the chelating agent is composed of a compound containing oxalic acid, post-polymerization is easily suppressed, and an acrylonitrile-based polymer with reduced impurities can be obtained.
以下、実施例により本発明をさらに具体的に説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to these Examples.
（ポリマー生成の確認）
東ソー製ＨＬＣ−８０２０を使用し、ガードカラムには東ソー製ＴＳＫ−ＧＥＬ ＳｕｐｅｒＨ４０００、カラムには東ソー製ＴＳＫ−ＧＥＬ ＳｕｐｅｒＨ２０００およびＳｕｐｅｒＨ１０００を用い、溶離液には０．２０ｍｏｌ／Ｌ−硝酸ナトリウムの水、アセトニトリル混合溶液（水／アセトニトリル＝９／１）を用いて、未反応のアクリロニトリル単位を気化分離した後の重合反応液のＧＰＣ測定を行い、２０〜２５分に発現するポリマーのピークの有無によりポリマー生成を確認した。
(Confirmation of polymer formation)
Using Tosoh HLC-8020, Tosoh TSK-GEL SuperH4000 as guard column, Tosoh TSK-GEL SuperH2000 and SuperH1000 as column, 0.20 mol / L-sodium nitrate water, acetonitrile as eluent Using a mixed solution (water / acetonitrile = 9/1), GPC measurement of the polymerization reaction solution after vaporization and separation of unreacted acrylonitrile units was performed, and polymer formation was observed depending on the presence or absence of a polymer peak that appeared between 20 and 25 minutes. It was confirmed.
（実施例１）
容量８０リットルのタービン撹拌翼付きアルミニウム製重合釜に、イオン交換水が重合釜オーバーフロー口まで達するよう７６．５リットル入れ、第一硫酸鉄（Ｆｅ２ＳＯ４
・７Ｈ２Ｏ）を０．０１ｇ加え、重合反応液のｐＨが３．０になるように硫酸を用いて調節し、重合釜内の温度を５７℃で保持した。
次に、重合開始３０分前から、単量体に対してレドックス重合開始剤である過硫酸アンモニウムを０．５１×１０−２モル％、亜硫酸水素アンモニウムを１．７６×１０−２モル％、硫酸第一鉄（Ｆｅ２ＳＯ４ ・７Ｈ２Ｏ）を０．３ｐｐｍ、硫酸を０．１×１０−２モル％となるように、それぞれ脱イオン交換水に溶解して連続的に供給し、攪拌速度１８０ｒｐｍ、攪拌動力１．２ｋＷ／ｍ３にて撹拌を行い、重合釜内での単量体の平均滞在時間が７０分になるように設定した。
ついで、重合開始時に、アクリロニトリル単位９８．９モル％、メタクリル酸２−ヒドロキシエチル単位１．１モル％から成る単量体を水／単量体＝３（質量比）となるように、単量体の連続供給を開始した。その後、重合開始１時間後に重合反応温度を５０℃まで下げて温度を保持し、重合釜オーバーフロー口より連続的に重合反応液を取り出した。
重合反応液には、シュウ酸ナトリウム０．４６×１０−２モル％、クペロン０．４６×１０−２モル％をイオン交換水に溶解した重合停止剤水溶液を、重合反応液／重合停止剤水溶液＝９８．５／１．５（質量比）となるように加えた。
さらに、重合反応液１００ｍｌを取り出してろ過し、ろ液を大気圧下８０℃で加熱して蒸留して未反応のアクリロニトリルを気化分離した後、残渣のＧＰＣ測定を行いポリマー生成の有無を確認した。結果を表１に示す。
Example 1
In an aluminum polymerization kettle with a capacity of 80 liters of turbine stirring blades, 76.5 liters of ion-exchanged water reaches the polymerization kettle overflow port, and ferrous sulfate (Fe2SO4
-0.01 g of 7H2O) was added, and the polymerization reaction solution was adjusted with sulfuric acid so that the pH was 3.0, and the temperature in the polymerization vessel was maintained at 57 ° C.
Next, from 30 minutes before the start of polymerization, 0.51 × 10 −2 mol% of ammonium persulfate, which is a redox polymerization initiator, 1.76 × 10 −2 mol% of ammonium bisulfite, sulfuric acid Ferrous iron (Fe2SO4 · 7H2O) was dissolved in deionized water so that the concentration was 0.3 ppm and sulfuric acid was 0.1 × 10 −2 mol%. Stirring was performed at 1.2 kW / m 3 and the average residence time of the monomer in the polymerization kettle was set to 70 minutes.
Next, at the start of polymerization, a monomer comprising 98.9 mol% of acrylonitrile units and 1.1 mol% of 2-hydroxyethyl methacrylate units was added in a single amount so that water / monomer = 3 (mass ratio). Started continuous feeding of the body. Thereafter, 1 hour after the start of polymerization, the polymerization reaction temperature was lowered to 50 ° C. to maintain the temperature, and the polymerization reaction liquid was continuously taken out from the polymerization kettle overflow port.
The polymerization reaction solution, sodium oxalate 0.46 × 10 -2 mol%, a polymerization terminator solution of cupferron 0.46 × 10 -2 mol% was dissolved in deionized water, the polymerization reaction solution / polymerization terminator solution = 98.5 / 1.5 (mass ratio).
Further, 100 ml of the polymerization reaction solution was taken out and filtered, and the filtrate was heated and distilled at 80 ° C. under atmospheric pressure to evaporate and separate unreacted acrylonitrile. Then, the residue was subjected to GPC measurement to confirm the presence or absence of polymer formation. . The results are shown in Table 1.
（実施例２）
重合禁止剤を０．４６×１０−２モル％のヒドロキノンに変更した以外は実施例１と同様にして評価した。結果を表１に示す。
(Example 2)
Evaluation was conducted in the same manner as in Example 1 except that the polymerization inhibitor was changed to 0.46 × 10 −2 mol% of hydroquinone. The results are shown in Table 1.
（実施例３）
重合禁止剤を０．４６×１０−２モル％のｐ−メトキシフェノールに変更した以外は実施例１と同様にして評価した。結果を表１に示す。
(Example 3)
Evaluation was conducted in the same manner as in Example 1 except that the polymerization inhibitor was changed to 0.46 × 10 −2 mol% of p-methoxyphenol. The results are shown in Table 1.
（実施例４）
重合禁止剤を０．４６×１０−２モル％のチオ尿素に変更した以外は実施例１と同様にして評価した。結果を表１に示す。
Example 4
Evaluation was conducted in the same manner as in Example 1 except that the polymerization inhibitor was changed to 0.46 × 10 −2 mol% of thiourea. The results are shown in Table 1.
（実施例５）
重合禁止剤を０．４６×１０−２モル％のロダンアンモンに変更した以外は実施例１と同様にして評価した。結果を表１に示す。
(Example 5)
Evaluation was conducted in the same manner as in Example 1 except that the polymerization inhibitor was changed to 0.46 × 10 −2 mol% of rhodanammon. The results are shown in Table 1.
（実施例６）
重合禁止剤を０．４６×１０−２モル％の４−アミノアンチピリンに変更した以外は実施例１と同様にして評価した。結果を表１に示す。
(Example 6)
Evaluation was conducted in the same manner as in Example 1 except that the polymerization inhibitor was changed to 0.46 × 10 −2 mol% of 4-aminoantipyrine. The results are shown in Table 1.
（比較例１）
重合禁止剤を０．４６×１０−２モル％の炭酸水素アンモニウムに変更した以外は実施例１と同様にして評価した。結果を表１に示す。
(Comparative Example 1)
Evaluation was conducted in the same manner as in Example 1 except that the polymerization inhibitor was changed to 0.46 × 10 −2 mol% ammonium hydrogen carbonate. The results are shown in Table 1.
（比較例２）
クペロンを除いた以外は実施例１と同様にして評価した。結果を表１に示す。
(Comparative Example 2)
Evaluation was performed in the same manner as in Example 1 except that cuperone was excluded. The results are shown in Table 1.
（比較例３）
シュウ酸を除いた以外は実施例１と同様にして反応を行った。結果を表１に示す。
(Comparative Example 3)
The reaction was performed in the same manner as in Example 1 except that oxalic acid was removed. The results are shown in Table 1.
（実施例７〜１２）
アクリルニトリル単位９８．９モル％、メタクリル酸２−ヒドロキシエチル単位１．１モル％を、アクリルニトリル単位９８．０モル％、アクリルアミド単位２．０モル％に変更した以外は実施例１〜６と同様にして評価した。結果を表２に示す。
(Examples 7 to 12)
Examples 1 to 6 except that 98.9 mol% of acrylonitrile units and 1.1 mol% of 2-hydroxyethyl methacrylate units were changed to 98.0 mol% of acrylonitrile units and 2.0 mol% of acrylamide units. Evaluation was performed in the same manner. The results are shown in Table 2.
（比較例４、５）
アクリルニトリル単位９８．９モル％、メタクリル酸２−ヒドロキシエチル単位１．１モル％を、アクリルニトリル単位９８．０モル％、アクリルアミド単位２．０モル％に変更した以外は比較例２、３と同様にして評価した。結果を表２に示す。
(Comparative Examples 4 and 5)
Comparative Examples 2 and 3 except that 98.9 mol% of acrylonitrile units and 1.1 mol% of 2-hydroxyethyl methacrylate units were changed to 98.0 mol% of acrylonitrile units and 2.0 mol% of acrylamide units. Evaluation was performed in the same manner. The results are shown in Table 2.
Claims (4)
重合反応器から排出された重合反応液に重合禁止剤とキレート剤とを添加する工程、
未反応のアクリロニトリル単位を気化分離させる工程
を有するアクリロニトリル系ポリマーの製造方法。 Using a redox catalyst as a polymerization initiator, 95 to 99 mol% of acrylonitrile units, and 1 to 5 mol% of at least one kind of vinyl monomer units having acrylamide units and hydroxyalkyl ester groups as copolymerization components. A step of polymerizing the contained monomer with water or a solvent in a polymerization reactor,
Adding a polymerization inhibitor and a chelating agent to the polymerization reaction solution discharged from the polymerization reactor;
A method for producing an acrylonitrile-based polymer comprising a step of vaporizing and separating unreacted acrylonitrile units.
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