JP2013071966A - Aqueous solution of ethyleneimine polymer and method for producing the same - Google Patents
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本発明は、エチレンイミン重合体水溶液およびその製造方法に関するものである。さらに詳しくは、本発明は、エチレンイミンを開環重合させるエチレンイミン重合体水溶液の製造方法、並びに、エチレンイミン重合体水溶液に関するものである。 The present invention relates to an aqueous ethyleneimine polymer solution and a method for producing the same. More specifically, the present invention relates to a method for producing an ethyleneimine polymer aqueous solution for ring-opening polymerization of ethyleneimine, and an ethyleneimine polymer aqueous solution.
ポリエチレンイミンは紙加工剤、接着剤、粘着剤、塗料、インキ、繊維処理剤、凝集分離剤、化粧品、トイレタリー、分散剤などの分野で幅広く利用されている。エチレンイミン重合体は、エチレンイミンを重合開始剤の存在下に重合させて得られるが、無溶媒下での重合では、粘度上の問題から、得られるエチレンイミン重合体の重合度は低い。このため、高重合度のエチレンイミン重合体を得るためには、水性媒体中で重合反応を行い、高分子量のエチレンイミン重合体をその水溶液の形態で得ている。例えば、特許文献１には、水性溶液中でポリハロアルカン重合開始剤の存在下、５５℃から８５℃でエチレンイミン水溶液の沸点の範囲の温度でエチレンイミンを重合させてエチレンイミン重合体水溶液を得る方法が記載されている。特許文献２は、モノエタノールアミンを触媒の存在下に分子内脱水反応させて得られる粗エチレンイミンの水性媒体中でポリハロアルカン重合開始剤、例えば、ジクロロエタンの存在下に８０℃で反応することによりエチレンイミン重合体水溶液が得られることが開示されている。特許文献３には、水性媒体中でエチレンイミンを重合してエチレンイミン重合体水溶液を製造するにあたり、エチレンイミンを８０℃以下の温度で重合させ、次いで１００〜１５０℃の温度で熟成することにより、粘度の経時的変化が少なく品質が安定し、また樹脂分が２０〜７０質量％という高濃度のエチレンイミン重合体水溶液が得られることが開示されている。 Polyethyleneimine is widely used in fields such as paper processing agents, adhesives, pressure-sensitive adhesives, paints, inks, fiber treatment agents, aggregating and separating agents, cosmetics, toiletries, and dispersing agents. The ethyleneimine polymer is obtained by polymerizing ethyleneimine in the presence of a polymerization initiator. However, in the polymerization in the absence of a solvent, the degree of polymerization of the resulting ethyleneimine polymer is low due to viscosity problems. For this reason, in order to obtain an ethyleneimine polymer having a high degree of polymerization, a polymerization reaction is carried out in an aqueous medium to obtain a high molecular weight ethyleneimine polymer in the form of an aqueous solution thereof. For example, Patent Document 1 discloses that an ethyleneimine polymer aqueous solution is obtained by polymerizing ethyleneimine in an aqueous solution in the presence of a polyhaloalkane polymerization initiator at a temperature ranging from 55 ° C to 85 ° C in the boiling point of the ethyleneimine aqueous solution. A method is described. Patent Document 2 discloses a reaction in an aqueous medium of crude ethyleneimine obtained by intramolecular dehydration reaction of monoethanolamine in the presence of a catalyst at 80 ° C. in the presence of a polyhaloalkane polymerization initiator, for example, dichloroethane. It is disclosed that an ethyleneimine polymer aqueous solution can be obtained. In Patent Document 3, in the production of an ethyleneimine polymer aqueous solution by polymerizing ethyleneimine in an aqueous medium, ethyleneimine is polymerized at a temperature of 80 ° C. or less, and then aged at a temperature of 100 to 150 ° C. Further, it is disclosed that an aqueous ethyleneimine polymer solution having a high concentration of 20 to 70% by mass with a resin content can be obtained with little change in viscosity with time.
しかしながら、エチレンイミン重合体は製造工程、貯蔵、運搬、使用時など経時的に黄変、さらには褐色に着色しやすいことが問題となった。そのため外観が問題となる用途、例えば食品の包装フィルム用や洗剤用原料、インク、塗料など外観を重視する用途によってはエチレンイミン重合体水溶液の使用制限を受けることがあった。そのため、かかる変色を防止する方法として、下記の方法が知られている。例えば、ポリアリルアミンやポリエチレンイミンの水溶性の混合物に、リン酸、クエン酸、酒石酸などの酸を添加する方法（特許文献４参照）、ポリアミンにホウ素化合物を添加することによる変色防止法（特許文献５参照。）、ポリアミンに、ケイ酸化合物および／または該ポリアミンよりも高い塩基性を有する塩基性化合物を添加することにより変色防止法（特許文献６参照）、着色抑制剤として有機リン酸エステル化合物の添加（特許文献７）が提案されている。 However, the ethyleneimine polymer has been problematic in that it tends to yellow over time, such as during the manufacturing process, storage, transportation, and use, and further easily brown. For this reason, use of an ethyleneimine polymer aqueous solution may be restricted depending on uses in which appearance is a problem, for example, food packaging films, raw materials for detergents, inks, paints, etc. that place importance on appearance. Therefore, the following methods are known as methods for preventing such discoloration. For example, a method of adding an acid such as phosphoric acid, citric acid, and tartaric acid to a water-soluble mixture of polyallylamine and polyethyleneimine (see Patent Document 4), and a method for preventing discoloration by adding a boron compound to polyamine (Patent Document) 5), a silicic acid compound and / or a basic compound having a higher basicity than the polyamine is added to the polyamine to prevent discoloration (see Patent Document 6), and an organic phosphate compound as a coloring inhibitor (Patent Document 7) has been proposed.
しかし、各種の酸、ホウ素化合物、塩基性化合物または有機リン酸エステル化合物等の着色抑制剤は使用時の着色、ラミネートフィルム等の使用製品の着色を抑制する目的としたものであり、また各種抑制剤の添加は純度を低下させる要因となるため、根本的に低着色で高純度のエチレンイミン重合体およびその製造方法が望まれており改善の余地があった。 However, coloring inhibitors such as various acids, boron compounds, basic compounds, or organic phosphate compounds are intended to suppress coloring during use and coloring of products used such as laminate films. Since the addition of the agent causes a decrease in purity, there has been a room for improvement since a radically low-colored and high-purity ethyleneimine polymer and a method for producing the same have been desired.
上記問題点に鑑み、本発明は、着色がなく、長期に保存しても着色の少ない高純度エチレンイミン重合体水溶液及びその製造方法を提供することを目的としている。 In view of the above problems, an object of the present invention is to provide a high-purity ethyleneimine polymer aqueous solution that is not colored and has little coloration even when stored for a long period of time, and a method for producing the same.
本発明者らの研究によれば、前記課題は下記発明により達成できることがわかった。
（１）水性媒体中でエチレンイミンを重合してエチレンイミン重合体水溶液の製造方法であって、酸素濃度２体積％以下の不活性ガス雰囲気下で、重合時の反応溶液温度が４５〜８０℃になるようにエチレンイミンを重合させ、かつ重合中の反応熱を除去する熱媒の温度を４０℃以上で行うことを特徴とするエチレンイミン重合体水溶液の製造方法。
（２）重合反応後に１００〜１５０℃の温度で熟成することを特徴とする（１）記載のエチレンイミン重合体水溶液製造方法。
（３）反応溶液温度が５０〜７０℃になるようにエチレンイミンを重合させ、次いで１１０〜１４０℃の温度で熟成することを特徴とする（１）または（２）記載のエチレンイミン重合体水溶液の製造方法。
（４）（１）から（３）のいずれかに記載の重合を、反応液の最終液量（ｍ３）当りの撹拌機の撹拌動力（ｋＷ）の比率（ＰＶ値＝撹拌動力／最終液量）が０．５ｋＷ／ｍ３以上であることを特徴とする（１）から（３）のいずれかに記載のエチレンイミン重合体水溶液の製造方法。
（５）エチレンイミンを重合して得られたエチレンイミン重合体水溶液の水をさらに蒸留除去してエチレンイミン重合体水溶液を精製する工程を含むことを特徴とする（１）から（４）のいずれかに記載のエチレンイミン重合体水溶液の製造方法。
（６）着色度合いの指標となるハーゼン単位色数が１００以下であることを特徴とするエチレンイミン重合体水溶液。
According to the studies by the present inventors, it has been found that the above problems can be achieved by the following invention.
(1) A method for producing an ethyleneimine polymer aqueous solution by polymerizing ethyleneimine in an aqueous medium, wherein the reaction solution temperature during polymerization is 45 to 80 ° C. in an inert gas atmosphere having an oxygen concentration of 2% by volume or less. A method for producing an ethyleneimine polymer aqueous solution, characterized in that the temperature of a heating medium for polymerizing ethyleneimine and removing reaction heat during polymerization is 40 ° C. or higher.
(2) The method for producing an ethyleneimine polymer aqueous solution according to (1), wherein the polymer is aged at a temperature of 100 to 150 ° C. after the polymerization reaction.
(3) The ethyleneimine polymer aqueous solution according to (1) or (2), wherein the ethyleneimine is polymerized so that the reaction solution temperature is 50 to 70 ° C., and then aged at a temperature of 110 to 140 ° C. Manufacturing method.
(4) A ratio of stirring power (kW) of the stirrer per final liquid volume (m 3 ) of the reaction liquid (PV value = stirring power / final liquid). The method for producing an aqueous ethyleneimine polymer solution according to any one of (1) to (3), wherein the amount is 0.5 kW / m 3 or more.
(5) The method according to any one of (1) to (4), further comprising a step of purifying the ethyleneimine polymer aqueous solution by further removing the water of the ethyleneimine polymer aqueous solution obtained by polymerizing ethyleneimine. A method for producing an aqueous ethyleneimine polymer solution according to claim 1.
(6) An ethyleneimine polymer aqueous solution having a Hazen unit color number of 100 or less as an index of the degree of coloring.
本発明によれば、重合反応後だけでなく、長期に保存しても着色の少ない高純度エチレンイミン重合体水溶液を製造することができる。さらに、本発明の着色の少ない高純度エチレンイミン重合体水溶液は、着色および粘度が経時的に変化が起きないため、品質が安定なエチレンイミン重合体水溶液であり、食品の包装フィルム用や洗剤用原料、インク、塗料などに好適に用いることが可能となる。 According to the present invention, it is possible to produce a high-purity ethyleneimine polymer aqueous solution with little coloration after storage for a long period of time as well as after the polymerization reaction. Furthermore, the highly pure ethyleneimine polymer aqueous solution of the present invention with little coloration is a stable quality ethyleneimine polymer aqueous solution because its coloration and viscosity do not change with time, and is used for food packaging films and detergents. It can be suitably used for raw materials, inks, paints, and the like.
本発明にかかるエチレンイミン重合体水溶液の製造方法は、水性媒体中でエチレンイミンを重合する際に、酸素濃度２体積％以下の不活性ガス雰囲気下で、重合時の反応溶液温度が４５〜８０℃になるようにエチレンイミンを重合させ、かつ重合中の反応熱を除去する熱媒の温度を４０℃以上で行うエチレンイミン重合体水溶液の製造方法である。また、本発明にかかる高純度エチレンイミン重合体水溶液は、ハーゼン単位色数が１００以下であるエチレンイミン重合体水溶液である。 In the method for producing an ethyleneimine polymer aqueous solution according to the present invention, when ethyleneimine is polymerized in an aqueous medium, the reaction solution temperature during polymerization is 45 to 80 in an inert gas atmosphere having an oxygen concentration of 2% by volume or less. This is a method for producing an ethyleneimine polymer aqueous solution in which ethyleneimine is polymerized so that the temperature is 0 ° C., and the temperature of the heating medium for removing heat of reaction during polymerization is 40 ° C. or higher. The high-purity ethyleneimine polymer aqueous solution according to the present invention is an ethyleneimine polymer aqueous solution having a Hazen unit color number of 100 or less.
本発明に用いるエチレンイミンには特に制限はなく、例えば、液相でハロゲン化エチルアミンを濃アルカリにより分子内閉環する方法、モノエタノールアミン硫酸エステルを熱濃アルカリにより分子内閉環する方法（以下、液相法ともいう）、あるいはモノエタノールアミンを触媒的気相分子内脱水反応させる方法（以下、気相法ともいう）により得られるエチレンイミンを用いることができる。 The ethyleneimine used in the present invention is not particularly limited, and examples thereof include a method of intramolecular ring closure of halogenated ethylamine with concentrated alkali in a liquid phase, and a method of intramolecular ring closure of monoethanolamine sulfate with hot concentrated alkali (hereinafter, liquid Ethyleneimine obtained by a catalytic gas phase intramolecular dehydration reaction of monoethanolamine (hereinafter also referred to as a gas phase method) can be used.
気相法により得られるエチレンイミン原料としては、モノエタノールアミンの触媒的分子内脱水反応により得られるエチレンイミン含有反応混合物を簡単な蒸留操作に供して回収した粗エチレンイミンを重合用の原料とすることができる（特許文献２参照）。尚、粗エチレンイミンを重合する場合は、例えば特開２００１−２７０９４１号公報に記載のとおり、エチレンイミン重合体（以下、粗エチレンイミン重合体ということもある。）を簡便な精製操作に供して、工業的に要求される品質基準に適合した高純度ポリエチレンイミンを得ることができる。 As the ethyleneimine raw material obtained by the gas phase method, a crude ethyleneimine recovered by subjecting the ethyleneimine-containing reaction mixture obtained by the catalytic intramolecular dehydration reaction of monoethanolamine to a simple distillation operation is used as a raw material for polymerization. (See Patent Document 2). When polymerizing crude ethyleneimine, for example, as described in JP-A-2001-270941, an ethyleneimine polymer (hereinafter sometimes referred to as crude ethyleneimine polymer) is subjected to a simple purification operation. A high-purity polyethyleneimine that meets industrially required quality standards can be obtained.
前記エチレンイミン含有反応混合物を高度に精製して得られる精製エチレンイミンもエチレンイミン重合体水溶液合成の原料として利用することができる。この場合、前記エチレンイミン含有反応混合物中には、目的物のエチレンイミンのほかに、未反応のモノエタノールアミンや、エチレンイミンのオリゴマー、アセトアルデヒドなどのケトン類、アセトアルデヒドと原料のモノエタノールアミンとが反応して生成するシッフ塩基などの重質不純物や、アンモニア、メチルアミンおよびエチルアミンの軽質アミン類、アセトニトリルなどの軽質不純物が含まれているので、これら不純物を高度の精製工程を経て除去し、しかる後に得られる精製エチレンイミンを重合反応に供するのである。 Purified ethyleneimine obtained by highly purifying the ethyleneimine-containing reaction mixture can also be used as a raw material for the synthesis of an ethyleneimine polymer aqueous solution. In this case, in the ethyleneimine-containing reaction mixture, in addition to the target ethyleneimine, unreacted monoethanolamine, ethyleneimine oligomers, ketones such as acetaldehyde, acetaldehyde and the raw material monoethanolamine It contains heavy impurities such as Schiff base produced by reaction, light amines such as ammonia, methylamine and ethylamine, and acetonitrile, so these impurities are removed through advanced purification steps. The purified ethyleneimine obtained later is subjected to a polymerization reaction.
高度の精製工程を経て得られる精製エチレンイミンを用いてエチレンイミン重合体を製造する技術は、高度の精製工程の実施にともなう生産コストのアップを免れず、工業的に有利とはいえないため、粗エチレンイミンがエチレンイミン原料として好適に用いられる。 The technology for producing an ethyleneimine polymer using purified ethyleneimine obtained through an advanced purification process is not industrially advantageous because it does not escape the increase in production costs associated with the implementation of the advanced purification process. Crude ethyleneimine is suitably used as the ethyleneimine raw material.
重合開始剤としては、エチレンイミンの重合に一般に用いられているものを使用できるが、１，２−ジクロロエタン、１，３−ジクロロプロパン、１，２−ジブロモエタン、クロロホルムなどのポリハロアルカンが好適に用いられる。重合開始剤の使用量は、目的とするエチレンイミン重合体の分子量により適宜選択できる。高分子量エチレンイミン重合体の水溶液を得るためには、エチレンイミンに対して、０．５〜５質量％とするのが好適である。 As the polymerization initiator, those generally used for the polymerization of ethyleneimine can be used, but polyhaloalkanes such as 1,2-dichloroethane, 1,3-dichloropropane, 1,2-dibromoethane, and chloroform are preferably used. Used. The usage-amount of a polymerization initiator can be suitably selected with the molecular weight of the target ethyleneimine polymer. In order to obtain an aqueous solution of a high molecular weight ethyleneimine polymer, the content is preferably 0.5 to 5% by mass with respect to ethyleneimine.
水性媒体としては、通常、水が用いられるが、水溶性有機液体、例えば、メタノール、エタノール、アセトン、ジメチルホルムアミドなどと水との混合物も使用することができる。 As the aqueous medium, water is usually used, but a water-soluble organic liquid, for example, a mixture of methanol, ethanol, acetone, dimethylformamide and the like and water can also be used.
本発明において、エチレンイミンを重合する際には酸素濃度２体積％以下の不活性ガス雰囲気下で行うのが良い。好ましくは酸素濃度１体積％以下、より好ましくは０．５体積％以下である。２体積％を超えるとエチレンイミン重合体水溶液が着色するか、またはその水溶液の保存又は貯蔵中に着色しやすくなる。不活性ガスとしては、特に限定されるものではなく、エチレンイミンに対して反応不活性なガスであれば良く、例えば、窒素、ヘリウム、二酸化炭素、又はアルゴン等を用いることができ、好適には窒素が用いられる。 In the present invention, the polymerization of ethyleneimine is preferably performed in an inert gas atmosphere having an oxygen concentration of 2% by volume or less. The oxygen concentration is preferably 1% by volume or less, more preferably 0.5% by volume or less. When it exceeds 2% by volume, the ethyleneimine polymer aqueous solution is colored, or is easily colored during storage or storage of the aqueous solution. The inert gas is not particularly limited, and may be any gas that is reactive with respect to ethyleneimine. For example, nitrogen, helium, carbon dioxide, or argon can be used, and preferably Nitrogen is used.
本発明においては、エチレンイミンを重合する際、反応溶液温度を４５〜８０℃、好ましくは５０〜７０℃の温度で行う。８０℃を超える温度では、粘度の経時的変化が少なく品質の安定したエチレンイミン重合体水溶液を得ることができない。なお、あまり低い温度では、重合時間が長くなって経済的でない。 In the present invention, when polymerizing ethyleneimine, the reaction solution temperature is 45 to 80 ° C., preferably 50 to 70 ° C. At temperatures exceeding 80 ° C., it is not possible to obtain an ethyleneimine polymer aqueous solution with little quality change with time and stable quality. If the temperature is too low, the polymerization time becomes long and it is not economical.
本発明において、反応熱を除去するために用いる熱媒の温度は４０℃以上に維持しながら重合を行うのが良い。好ましくは４５℃以上、より好ましくは５０℃以上である。熱媒の温度が４０℃より低いとエチレンイミン重合体水溶液の着色しやすい傾向がみられる。熱媒の上限温度は特に制限はなく、前記反応溶液温度より低く、反応温度を制御できる熱媒温度であれば良いが、反応溶液温度との差が小さいと反応時間が伸びて生産性が低下する。 In the present invention, it is preferable to carry out the polymerization while maintaining the temperature of the heat medium used for removing reaction heat at 40 ° C. or higher. Preferably it is 45 degreeC or more, More preferably, it is 50 degreeC or more. When the temperature of the heating medium is lower than 40 ° C., the aqueous ethyleneimine polymer solution tends to be colored easily. The upper limit temperature of the heating medium is not particularly limited and may be any heating medium temperature that is lower than the reaction solution temperature and can control the reaction temperature. However, if the difference from the reaction solution temperature is small, the reaction time is extended and the productivity is lowered. To do.
前記熱媒の温度を維持することにより、エチレンイミンの反応中に反応溶液が局部的に高粘度になることが抑制され、高効率の撹拌により局部滞留がなく均一な重合をさせることができるため、エチレンイミンの反応が均一かつ効率的に行うことができるようになる。熱媒としては、温水、水蒸気または加熱したオイル等が使用でき、工業的には温水および水蒸気が好適に用いられる。 By maintaining the temperature of the heating medium, it is possible to suppress the reaction solution from becoming locally highly viscous during the reaction of ethyleneimine, and uniform polymerization can be achieved without local retention by highly efficient stirring. The reaction of ethyleneimine can be performed uniformly and efficiently. As the heat medium, warm water, steam, heated oil or the like can be used, and warm water and steam are preferably used industrially.
本発明においては、エチレンイミンの重合終了後、好ましくは供給したエチレンイミンの９５％以上が消費された後、反応液を１００〜１５０℃、好ましくは１１０〜１４０℃に昇温して、この温度範囲で熟成させる。１００℃より低い温度では、粘度の経時的変化が少なく品質の安定したエチレンイミン重合体水溶液を得ることができない。また、１５０℃より高い温度では、生成したエチレンイミン重合体の熱分解が起こり、高分子量の重合体が得られないこともある。熟成時間は、通常、１〜２０時間であり、好ましくは２〜１０時間である。また、反応液を熟成温度まで昇温する時間は、通常、０．２〜５時間であり、好ましくは０．５〜３時間である。 In the present invention, after completion of the polymerization of ethyleneimine, preferably after 95% or more of the supplied ethyleneimine has been consumed, the reaction solution is heated to 100 to 150 ° C., preferably 110 to 140 ° C. Aging in range. When the temperature is lower than 100 ° C., an ethyleneimine polymer aqueous solution with little quality change with time and stable quality cannot be obtained. Further, at a temperature higher than 150 ° C., the produced ethyleneimine polymer may be thermally decomposed, and a high molecular weight polymer may not be obtained. The aging time is usually 1 to 20 hours, preferably 2 to 10 hours. The time for raising the temperature of the reaction solution to the aging temperature is usually 0.2 to 5 hours, preferably 0.5 to 3 hours.
本発明におけるエチレンイミンの重合反応の際、重合開始剤およびエチレンイミンは一括して添加してもよいが、発熱反応であるため、温度制御しながらそれぞれ連続的に供給するのがよい。 In the polymerization reaction of ethyleneimine in the present invention, the polymerization initiator and ethyleneimine may be added all at once, but since they are exothermic reactions, it is preferable to supply them continuously while controlling the temperature.
重合反応は常圧、加圧のいずれでもよく、通常、０〜１０ＭＰａＧ、好ましくは０〜２ＭＰａＧで行う。反応液の熟成は、通常、０．０５〜１０ＭＰａＧ、好ましくは０．０５〜１ＭＰａＧの加圧下に行うのがよい。ここで、ＭＰａＧ（メガパスカルゲージ）はゲージ圧力のことである。 The polymerization reaction may be performed under normal pressure or increased pressure, and is usually performed at 0 to 10 MPaG, preferably 0 to 2 MPaG. Aging of the reaction solution is usually carried out under a pressure of 0.05 to 10 MPaG, preferably 0.05 to 1 MPaG. Here, MPaG (megapascal gauge) is a gauge pressure.
重合反応および熟成処理は、回分式（バッチ式）、半回分式、連続流通式などいずれの反応形式によっても行うことができる。連続流通式のように連続的にエチレンイミン重合体を製造する場合は管型反応器等が用いられ、回分式反応の場合は反応器等が使用される。本発明に用いる反応器としては、温度計、撹拌機、冷却装置等を備えた円筒型反応器が好適に用いられる。 The polymerization reaction and the aging treatment can be performed by any reaction system such as a batch system (batch system), a semi-batch system, and a continuous flow system. In the case of continuously producing an ethyleneimine polymer as in the continuous flow method, a tubular reactor or the like is used, and in the case of a batch reaction, a reactor or the like is used. As the reactor used in the present invention, a cylindrical reactor equipped with a thermometer, a stirrer, a cooling device and the like is preferably used.
回分式反応の場合、重合反応の際に、重合物の粘度が高くなるため、除熱、拡散、反応促進のため撹拌機として、工業的にはパドル翼や高粘度用撹拌翼、例えばマックスブレンド翼（住友重機械工業（株）製）などが用いられ、好適にはマックスブレンド翼である。また重合により発生した反応熱を除去できるように熱媒を流すための冷却装置が付いた反応器、例えば外部ジャケット付反応器などが好適に用いられる。ジャケット式除熱の効率化を図るため縦チューブ型冷却器を用いることもでき、エチレンイミンを還流下で重合するのが好適である。 In the case of batch reaction, the viscosity of the polymer is increased during the polymerization reaction, so as a stirrer for heat removal, diffusion, and reaction promotion, industrially paddle blades and high viscosity stirring blades such as Max Blend A wing (manufactured by Sumitomo Heavy Industries, Ltd.) or the like is used, and a max blend wing is preferable. A reactor equipped with a cooling device for flowing a heat medium so that reaction heat generated by the polymerization can be removed, such as a reactor with an external jacket, is preferably used. In order to increase the efficiency of jacket-type heat removal, a vertical tube type cooler can be used, and it is preferable to polymerize ethyleneimine under reflux.
本発明においては、反応液の最終液量（ｍ３）当りの撹拌動力（ｋＷ）で表わされる値、すなわちＰＶ値（撹拌動力／最終液量）を０．５ｋＷ／ｍ３以上で行うのが良く、好ましくは、２ｋＷ／ｍ３以上が好ましい。尚、１０ｋＷ／ｍ３超えるとエネルギーコストが高くなり経済的でない。 In the present invention, the value represented by the stirring power (kW) per final liquid volume (m 3 ) of the reaction liquid, that is, the PV value (stirring power / final liquid volume) is 0.5 kW / m 3 or more. Good, preferably 2 kW / m 3 or more. If it exceeds 10 kW / m 3 , the energy cost increases and it is not economical.
本発明の製法において好ましい形態は、得られたエチレンイミン重合体水溶液の水や水溶性有機液体をさらに蒸発除去してエチレンイミン重合体水溶液を精製する工程を含む形態である。具体的には、例えば、重合反応終了後、反応器内温度が２００℃を超えない温度、好ましくは１００〜１８０℃の範囲の温度で撹拌下にエチレンイミン重合体水溶液から水分を蒸発除去する。水分の蒸発除去の程度（水溶液の濃縮の程度）については特に制限はないが、後述の通り、エチレンイミン重合体水溶液中のエチレンイミン重合体の濃度（樹脂分）は通常２０〜７０質量％であり、好適範囲が３０〜５０質量％であるので、この範囲になるようにエチレンイミン重合体水溶液中の水を蒸発除去すればよい。これにより、気相法で得られた粗エチレンイミン原料とする場合は軽質アミン類、アセトニトリルの含有量がともに１ｐｐｍ以下の高純度エチレンイミン重合体水溶液を得ることができる。なお、蒸発操作は常圧または減圧のいずれでもよいが、減圧下で行う場合には、反応器内圧力を１０〜７００ｍｍＨｇにするのが好ましい。 A preferred form in the production method of the present invention is a form including a step of purifying the ethyleneimine polymer aqueous solution by further evaporating and removing water and water-soluble organic liquid of the obtained ethyleneimine polymer aqueous solution. Specifically, for example, after completion of the polymerization reaction, water is evaporated and removed from the ethyleneimine polymer aqueous solution with stirring at a temperature at which the temperature in the reactor does not exceed 200 ° C., preferably in the range of 100 to 180 ° C. Although there is no restriction | limiting in particular about the degree of evaporation removal of water (degree of concentration of aqueous solution), As mentioned later, the density | concentration (resin content) of the ethyleneimine polymer in ethyleneimine polymer aqueous solution is 20-70 mass% normally. Since the preferred range is 30 to 50% by mass, the water in the ethyleneimine polymer aqueous solution may be removed by evaporation so as to be within this range. Thereby, when using as a crude ethyleneimine raw material obtained by the vapor phase method, a high-purity ethyleneimine polymer aqueous solution in which the contents of light amines and acetonitrile are both 1 ppm or less can be obtained. The evaporation operation may be carried out at normal pressure or reduced pressure, but when carried out under reduced pressure, the pressure in the reactor is preferably 10 to 700 mmHg.
本発明のエチレンイミン重合体水溶液に含まれるエチレンイミン重合体（樹脂分）の濃度は、通常、エチレンイミン重合体水溶液の全質量に対し２０〜７０質量％である。好ましくは４０〜６０質量％、最も好ましくは３０〜５０質量％である。２０質量％以下では製品安定性が低下する傾向がみられる。７０質量％を超えると粘度が高すぎて取り扱いが困難となる。 The concentration of the ethyleneimine polymer (resin component) contained in the ethyleneimine polymer aqueous solution of the present invention is usually 20 to 70% by mass with respect to the total mass of the ethyleneimine polymer aqueous solution. Preferably it is 40-60 mass%, Most preferably, it is 30-50 mass%. When the amount is 20% by mass or less, the product stability tends to decrease. If it exceeds 70% by mass, the viscosity is too high and handling becomes difficult.
本発明のエチレンイミン重合体水溶液は、水以外の媒体を含まないものが最も好ましい形態であるが、例えば、水に対してメタノール、エタノール、アセトン、ジメチルホルムアミドなどが５質量％未満の溶剤が含まれていても良い。 The ethyleneimine polymer aqueous solution of the present invention is most preferably in the form that does not contain a medium other than water. For example, methanol, ethanol, acetone, dimethylformamide, and the like contain less than 5% by mass of solvent with respect to water. It may be.
本発明のエチレンイミン重合体水溶液は不純物の少ない高純度の重合体水溶液でもある。原料のエチレンイミンは特に制限されないが、その原料エチレンイミンの製造方法の種類により含まれる不純物が異なる。前記気相法により得られたエチレンイミンを用いる場合、不純物として原料のモノエタノールアミン、エチレンイミンのオリゴマー、アセトアルデヒドなどのケトン類、アセトアルデヒドと原料のモノエタノールアミンとが反応して生成するシッフ塩基などの重質不純物や、アンモニア、メチルアミンおよびエチルアミンの軽質アミン類、アセトニトリルなどの軽質不純物が含まれるが、エチレンイミン重合体水溶液の重量に対してそれぞれ０．１ｐｐｍ以下、好ましくはそれぞれ０．０５ｐｐｍ以下、より好ましくはそれぞれ０．０１ｐｐｍ以下である。不純物が多いと下記に示す、着色や粘度の経時的変化に悪影響を及ぼす場合がある。これらの不純物はガスクロマトグラフにより測定することができる。 The ethyleneimine polymer aqueous solution of the present invention is also a high-purity polymer aqueous solution with few impurities. The raw material ethyleneimine is not particularly limited, but the impurities contained differ depending on the type of the raw material ethyleneimine production method. When using ethyleneimine obtained by the gas phase method, raw material monoethanolamine, ethyleneimine oligomer, ketones such as acetaldehyde, Schiff base generated by reaction of acetaldehyde with raw material monoethanolamine, etc. Heavy impurities, light amines such as ammonia, methylamine and ethylamine, and light impurities such as acetonitrile, but 0.1 ppm or less, preferably 0.05 ppm or less, respectively, based on the weight of the ethyleneimine polymer aqueous solution. More preferably, each is 0.01 ppm or less. If there are many impurities, the following changes in coloration and viscosity over time may be adversely affected. These impurities can be measured by a gas chromatograph.
前記液相法により得られたエチレンイミンを用いる場合は、エチレンイミンの蒸溜操作に問題がある場合、合成途中で生成する硫酸アルカリ金属塩が不純物として含まれることになる。硫酸アルカリ金属が混入すると着色の原因となることがある。そのため、不純物量は硫酸イオン換算として含有量をエチレンイミン重合体水溶液の重量に対して１．０ｐｐｍ以下、さらには０．１ｐｐｍ以下にすることが好ましい。硫酸イオンはイオンクロマトグラフィーで測定することができる。 When ethyleneimine obtained by the liquid phase method is used, when there is a problem in the distillation operation of ethyleneimine, an alkali metal sulfate salt generated during the synthesis is contained as an impurity. When alkali metal sulfate is mixed, it may cause coloring. Therefore, the impurity content is preferably 1.0 ppm or less, more preferably 0.1 ppm or less with respect to the weight of the ethyleneimine polymer aqueous solution, in terms of sulfate ion. Sulfate ions can be measured by ion chromatography.
本発明のエチレンイミン重合体水溶液に含まれる未反応エチレンイミンは０．１ｐｐｍ以下、好ましくは０．０１ｐｐｍ以下である。未反応エチレンイミンは窒素ガスのバブリング等の公知方法により除去することができるが、前記した重合体（樹脂分）の濃度を調整する工程で、水分を蒸溜で除去する操作の際に同時に未反応エチレンイミンを除去することもできる。未反応エチレンイミンはガスクロマトグラフィーで測定することができる。 The unreacted ethyleneimine contained in the aqueous ethyleneimine polymer solution of the present invention is 0.1 ppm or less, preferably 0.01 ppm or less. Unreacted ethyleneimine can be removed by a known method such as bubbling of nitrogen gas, but in the step of adjusting the concentration of the polymer (resin content), unreacted at the same time as the operation of removing moisture by distillation. Ethyleneimine can also be removed. Unreacted ethyleneimine can be measured by gas chromatography.
本発明のエチレンイミン重合体水溶液に含まれる重合体は、エチレンイミン重合体の平均重量分子量は１，０００〜１，０００，０００（ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）測定、プルラン換算）である。 The polymer contained in the ethyleneimine polymer aqueous solution of the present invention has an average molecular weight of 1,000 to 1,000,000 (gel permeation chromatography (GPC) measurement, pullulan conversion) of the ethyleneimine polymer. is there.
本発明のエチレンイミン重合体水溶液は、ハーゼン単位色数が１００以下のエチレンイミン重合体である。好ましくは、７５以下、より好ましくは５０以下である。ハーゼン単位色数が１００を超えると明らかに着色が感じられるため、食品の包装フィルム用や洗剤用原料、インク、塗料などに用いた場合に外観的影響を与える場合がある。 The ethyleneimine polymer aqueous solution of the present invention is an ethyleneimine polymer having a Hazen unit color number of 100 or less. Preferably, it is 75 or less, more preferably 50 or less. When the number of Hazen unit colors exceeds 100, coloring is clearly felt, and when used in food packaging films, detergent raw materials, inks, paints, etc., the appearance may be affected.
本発明のエチレンイミン重合体水溶液の粘度は、エチレンイミン重合体の樹脂分濃度により異なるが、例えば、樹脂分濃度５０質量％の場合、１０，０００〜２０，０００ｍＰａ・ｓ／２５℃、好ましくは１４，０００〜１８，０００ｍＰａ・ｓ／２５℃である。 The viscosity of the ethyleneimine polymer aqueous solution of the present invention varies depending on the resin concentration of the ethyleneimine polymer. For example, when the resin concentration is 50% by mass, 10,000 to 20,000 mPa · s / 25 ° C., preferably 14,000 to 18,000 mPa · s / 25 ° C.
本発明の方法によれば、上述の物性および組成を有するエチレンイミン重合体水溶液は、保存中の経時変化が少ない安定したエチレンイミン重合体水溶液でもある。特に、着色の変化及び粘度変化の少ないのエチレンイミン重合体水溶液である。 According to the method of the present invention, the ethyleneimine polymer aqueous solution having the above-mentioned physical properties and composition is also a stable ethyleneimine polymer aqueous solution with little temporal change during storage. In particular, it is an ethyleneimine polymer aqueous solution with little color change and viscosity change.
以下、実施例を挙げて本発明を具体的に説明するが、本発明の範囲はこれらの実施例のみに限定されるものではない。なお、ことわりのない場合、本明細書に記載した「ｐｐｍ」、「％」は「質量ｐｐｍ」、「質量％」を示すものとする。
＜着色度の測定＞
ＪＩＳ Ｋ００７１−１「ハーゼン単位色数」に準じて測定した。具体的には、塩化白金酸カリウムと塩化コバルトを所定濃度で溶解し溶液を標準比色液とした。比色管は外径２５ｍｍ、内径２２ｍｍの石英ガラス製のもので底面は平底仕上げしたもの、さらには底面より１３０ｍｍの高さ（約５０ｍｌに相当）に標線があり蓋付きのものを用いた。
標準比色液とエチレンイミン重合体水溶液を各比色管に取り、色を目視で比較しその結果をハーゼン単位色数として表した。
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, the scope of the present invention is not limited only to these Examples. In addition, when there is no notice, "ppm" and "%" which were described in this specification shall show "mass ppm" and "mass%".
<Measurement of coloring degree>
Measured according to JIS K0071-1 “Hazen unit color number”. Specifically, potassium chloroplatinate and cobalt chloride were dissolved at a predetermined concentration, and the solution was used as a standard colorimetric solution. The colorimetric tube was made of quartz glass with an outer diameter of 25 mm and an inner diameter of 22 mm, and the bottom surface was flat-bottomed. .
The standard colorimetric solution and the ethyleneimine polymer aqueous solution were taken in each colorimetric tube, the colors were visually compared, and the result was expressed as the Hazen unit color number.
実施例１＜エチレンイミン重合体水溶液の調製＞
撹拌装置、温度計、エチレンイミンおよび重合開始剤仕込管を備えた容積２リットル（以下、Ｌとも表す）の耐圧反応器を熱媒の温水を６０℃にした水浴槽中に置いた。反応器に水１２００ｇを仕込み、反応溶液温度を５５℃に加熱した後、窒素ガス置換により酸素濃度０．５体積％の雰囲気にし気相法で得られたエチレンイミン８００ｇおよび１，２−ジクロロエタン１３．２ｇ（対エチレンイミン１．６５質量％）を反応温度が８０℃になるように保ちながら、反応器にフィードした。その後、水槽の水温を調節しながら反応温度を７０℃で４時間撹拌したところ、原料エチレンイミンの９８％が反応していた。この間の反応液温度と水浴槽の熱媒温度の差を１０〜２０℃に維持した。
Example 1 <Preparation of aqueous ethyleneimine polymer solution>
A pressure-resistant reactor having a volume of 2 liters (hereinafter also referred to as L) equipped with a stirrer, a thermometer, ethyleneimine, and a polymerization initiator feeding tube was placed in a water bath in which the hot water of the heating medium was 60 ° C. The reactor was charged with 1200 g of water, and the reaction solution temperature was heated to 55 ° C., and then an atmosphere of oxygen volume of 0.5 volume% was made by nitrogen gas substitution to obtain 800 g of ethyleneimine and 1,2-dichloroethane 13 obtained by the gas phase method. .2 g (1.65% by mass with respect to ethyleneimine) was fed to the reactor while maintaining the reaction temperature at 80 ° C. Then, when the reaction temperature was stirred at 70 ° C. for 4 hours while adjusting the water temperature in the water tank, 98% of the raw material ethyleneimine had reacted. The difference between the reaction liquid temperature and the heat medium temperature of the water bath during this period was maintained at 10 to 20 ° C.
その後、水槽をオイル槽に変更し反応液の温度を１２０℃まで３０分で昇温し、温度１２０℃、圧力０．１ＭＰａＧで５時間熟成した。１２０℃に昇温直後の反応液の粘度は５０００ｍＰａ・ｓ／２５℃に達した。熟成中の粘度の変化は見られなかった。エチレンイミン重合体水溶液中の残存エチレンイミンは１ｐｐｍ以下であり、得られたエチレンイミン重合体水溶液中のハーゼン単位色数は５以下であった。 Thereafter, the water tank was changed to an oil tank, and the temperature of the reaction solution was raised to 120 ° C. in 30 minutes, and aged at a temperature of 120 ° C. and a pressure of 0.1 MPaG for 5 hours. The viscosity of the reaction solution immediately after raising the temperature to 120 ° C. reached 5000 mPa · s / 25 ° C. There was no change in viscosity during aging. The residual ethyleneimine in the ethyleneimine polymer aqueous solution was 1 ppm or less, and the Hazen unit color number in the obtained ethyleneimine polymer aqueous solution was 5 or less.
尚、ＰＶ値（撹拌動力（ｋＷ）／最終液量（ｍ３）は２．０ｋＷ／ｍ３で行った。 The PV value (stirring power (kW) / final liquid amount (m 3 ) was 2.0 kW / m 3 .
上記の方法により得られたエチレンイミン重合体水溶液１０００ｇをオイルバス上の攪拌機、蒸気凝縮抜出し器および温度計を備えたフラスコ反応器に仕込み、気相部に窒素ガスを連続添加しながら酸素濃度０．１体積％以下の雰囲気で、常圧にて、１１０℃に加熱して精製を行った。留出水をカットし、樹脂分５０質量％になったところで、分析した結果、残存するエチレンイミンは０・０１ｐｐｍ以下であった。得られた精製エチレンイミン重合体水溶液中のハーゼン単位色数は５以下であった。また、精製後の粘度は１７０００ｍＰａ・ｓ／２５℃であった。
実施例２
温水温度を４５℃に変更した以外は実施例１同様に実施し、エチレンイミン重合体水溶液を得た。精製前後のエチレンイミン重合体水溶液のハーゼン単位色数は５以下であった。精製後のエチレンイミン重合体水溶液の樹脂分が５０質量％になったところで粘度は１６３００ｍＰａ・ｓ／２５℃であった。
実施例３
ＰＶ値（撹拌動力／最終液量）を０．７ｋＷ／ｍ３に変更した以外は実施例１同様に実施し、エチレンイミン重合体水溶液を得た。精製前後のエチレンイミン重合体水溶液のハーゼン単位色数はそれぞれ５以下であった。精製後のエチレンイミン重合体水溶液の樹脂分が５０質量％になったところで粘度は１６８００ｍＰａ・ｓ／２５℃であった。
比較例１
温水温度を３５℃未満（２５℃）に変更して、ＰＶ値（撹拌動力／最終液量）を０．３ｋＷ／ｍ３、酸素濃度２．５体積％で行った以外は実施例１同様に実施し、エチレンイミン重合体水溶液を得た。精製後のハーゼン単位色数は１２０であった。
精製後のエチレンイミン重合体水溶液の樹脂分が５０質量％になったところで粘度は１６１００ｍＰａ・ｓ／２５℃であった。
＜エチレンイミン重合体水溶液の安定性評価＞
実施例１、２、３及び比較例１で得られた精製前のエチレンイミン重合体水溶液を７０℃に保持し、１０日後の経時変化を調べた結果、実施例１、２、３のエチレンイミン重合体水溶液のハーゼン単位色数変化はなかったが、比較例１のエチレンイミン重合体水溶液のハーゼン単位色数は１４０となり、着色の変化が見られた。また、実施例１及び比較例１で得られた水溶液の粘度は、それぞれ１６７００、１６１００、１６０００及び１４９００ｍＰａ・ｓ／２５℃であった。
1000 g of the ethyleneimine polymer aqueous solution obtained by the above method was charged into a flask reactor equipped with a stirrer, a vapor condensing and extracting device and a thermometer on an oil bath, and an oxygen concentration of 0 was added while continuously adding nitrogen gas to the gas phase portion. Purification was carried out by heating to 110 ° C. at normal pressure in an atmosphere of 1% by volume or less. Distilled water was cut and the resin content reached 50% by mass. As a result of analysis, the remaining ethyleneimine was 0.01 ppm or less. The Hazen unit color number in the obtained purified ethyleneimine polymer aqueous solution was 5 or less. The viscosity after purification was 17000 mPa · s / 25 ° C.
Example 2
Except having changed the warm water temperature into 45 degreeC, it implemented similarly to Example 1 and obtained ethyleneimine polymer aqueous solution. The Hazen unit color number of the ethyleneimine polymer aqueous solution before and after purification was 5 or less. When the resin content of the purified ethyleneimine polymer aqueous solution reached 50% by mass, the viscosity was 16300 mPa · s / 25 ° C.
Example 3
Except having changed PV value (stirring power / final liquid amount) into 0.7 kW / m < 3 >, it implemented like Example 1 and obtained ethyleneimine polymer aqueous solution. The Hazen unit color numbers of the ethyleneimine polymer aqueous solutions before and after purification were 5 or less, respectively. When the resin content of the purified ethyleneimine polymer aqueous solution reached 50% by mass, the viscosity was 16800 mPa · s / 25 ° C.
Comparative Example 1
Example 1 except that the hot water temperature was changed to less than 35 ° C. (25 ° C.) and the PV value (stirring power / final liquid amount) was 0.3 kW / m 3 and the oxygen concentration was 2.5 vol%. This was carried out to obtain an ethyleneimine polymer aqueous solution. The Hazen unit color number after purification was 120.
When the resin content of the purified ethyleneimine polymer aqueous solution reached 50% by mass, the viscosity was 16100 mPa · s / 25 ° C.
<Stability evaluation of ethyleneimine polymer aqueous solution>
The ethyleneimine polymer aqueous solution before purification obtained in Examples 1, 2, 3 and Comparative Example 1 was kept at 70 ° C., and the change over time after 10 days was examined. Although there was no change in the Hazen unit color number of the aqueous polymer solution, the Hazen unit color number of the ethyleneimine polymer aqueous solution of Comparative Example 1 was 140, indicating a change in coloring. Moreover, the viscosity of the aqueous solution obtained in Example 1 and Comparative Example 1 was 16700, 16100, 16000, and 14900 mPa · s / 25 ° C., respectively.
実施例１、２、３および比較例１から明らかなように、本発明で得られるエチレンイミン重合体水溶液は、着色の経時的変化がないだけでなく、粘度も経時的な変化もほとんどない、品質の安定なエチレンイミン重合体水溶液であることが判明した。 As is apparent from Examples 1, 2, 3 and Comparative Example 1, the ethyleneimine polymer aqueous solution obtained in the present invention has not only a change in color with time but also a viscosity and a change with time. It turned out to be a stable quality ethyleneimine polymer aqueous solution.
本発明のエチレンイミン重合体水溶液は、紙加工剤、接着剤、粘着剤、塗料、インキ、繊維処理剤、凝集分離剤、化粧品、トイレタリー、分散剤などの分野で安全に利用することができる。 The aqueous ethyleneimine polymer solution of the present invention can be safely used in fields such as paper processing agents, adhesives, pressure-sensitive adhesives, paints, inks, fiber treatment agents, aggregating / separating agents, cosmetics, toiletries, and dispersing agents.
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