JP5289719B2

JP5289719B2 - Polymerization reaction control method and polymerization reaction control apparatus

Info

Publication number: JP5289719B2
Application number: JP2007068580A
Authority: JP
Inventors: 紳介杉浦; 孝司豊岡
Original assignee: Nitto Denko Corp
Current assignee: Nitto Denko Corp
Priority date: 2007-03-16
Filing date: 2007-03-16
Publication date: 2013-09-11
Anticipated expiration: 2027-03-16
Also published as: JP2008231150A

Description

本発明は、粘着剤等に使用されるポリマーを合成する際の重合反応を制御する重合反応制御方法及び重合反応制御装置であって、特に、重合反応の終了までに滴下する溶剤の総滴下量が予め設定された目標量となるように外浴の温度を制御する重合反応制御方法及び重合反応制御装置に関する。 The present invention relates to a polymerization reaction control method and a polymerization reaction control device for controlling a polymerization reaction when a polymer used for an adhesive or the like is synthesized, and in particular, a total dripping amount of a solvent dropped before the completion of the polymerization reaction The present invention relates to a polymerization reaction control method and a polymerization reaction control apparatus for controlling the temperature of an outer bath so that the temperature reaches a preset target amount.

従来より、粘着剤等に使用されるポリマーを合成する際には、攪拌槽内に予め投入したモノマーに開始剤を滴下してモノマー混合物を重合反応させることにより合成する。その際、重合反応の再現性を向上させるためには、重合温度（以下、内浴温度）について、目標温度からの差異を小さくすることが極めて重要である。
その為、重合反応に伴う重合発熱量を適宜除熱する必要があるが、以下に代表される２種類の方法を用いてそれを実施している。
（１）攪拌槽外側に設置した冷却ジャケットとの熱交換を行うことにより重合発熱量を除熱する方法（例えば、特開２００４−２５６７３４号公報参照）。
操作パラメーター：外浴冷媒温度、攪拌翼回転数（熱伝達効率）
（２）重合温度より低温度の溶剤（あるいは分散媒）の系内への滴下を行うことにより重合発熱量を除熱する方法。
操作パラメーター：溶剤滴下量、滴下タイミング
特開２００４−２５６７３４号公報 Conventionally, when synthesizing a polymer used for an adhesive or the like, the polymer is synthesized by dropping an initiator into a monomer charged in advance in a stirring tank to cause a monomer mixture to undergo a polymerization reaction. At that time, in order to improve the reproducibility of the polymerization reaction, it is extremely important to reduce the difference from the target temperature with respect to the polymerization temperature (hereinafter referred to as the inner bath temperature).
Therefore, it is necessary to appropriately remove the heat generated by the polymerization accompanying the polymerization reaction, but this is carried out using two types of methods represented below.
(1) A method of removing heat of polymerization heat by performing heat exchange with a cooling jacket installed outside the stirring tank (see, for example, JP-A-2004-256734).
Operating parameters: Outer bath refrigerant temperature, stirring blade rotation speed (heat transfer efficiency)
(2) A method of removing heat generated by polymerization by dropping a solvent (or dispersion medium) having a temperature lower than the polymerization temperature into the system.
Operation parameters: amount of solvent dripping, dripping timing
JP 2004-256734 A

上記２つの方法の内、制御を開始し、実際の除熱効果が現れるまでの遅れ時間が短い（温調レスポンスが高い）のは、（２）の低温溶剤滴下による方法である。
特に、重合が進んで液粘度が増加すると、内浴側の境膜が増大するので、（１）の方法では温調レスポンスが著しく低下し、内浴温度を好適に制御できなくなり、（２）の方法に基づく制御が重要となる。従って、特に高粘度となるような重合を行う場合には、外浴温度設定値及び攪拌速度設定値をあらかじめ決定した値で固定し、大まかに除熱をしておき、それでも除熱できない発熱分を溶剤滴下によって除熱する高精度な温度制御を実施することが必要となる。 Of the above two methods, the delay time until the actual heat removal effect appears after the start of control is short (the temperature control response is high) is the method of (2) by low temperature solvent dropping.
Particularly, when the polymerization proceeds and the liquid viscosity increases, the boundary film on the inner bath side increases, so that the temperature control response is remarkably reduced by the method (1), and the inner bath temperature cannot be suitably controlled. (2) Control based on this method is important. Therefore, when performing polymerization that results in a particularly high viscosity, the outer bath temperature set value and the stirring speed set value are fixed at predetermined values, and heat is roughly removed. It is necessary to carry out highly accurate temperature control that removes heat by dripping solvent.

ここで、上記（２）の除熱方法における溶剤の具体的な滴下方法としては、更に以下の２つの方法がある。
（ｉ）内浴温度の閾値を段階的に決定しておき、その各閾値を超えた場合に、定量の溶剤を反応系内に滴下する方法。
（ｉｉ）内浴温度、及び内浴温度変化率を関数とした、最適溶剤滴下量の算出式をあらかじめ実験などにより求めておき、算出された量の溶剤を反応系内に滴下する方法。 Here, there are the following two methods as specific methods for dropping the solvent in the heat removal method (2).
(I) A method in which threshold values for the inner bath temperature are determined stepwise, and when each threshold value is exceeded, a fixed amount of solvent is dropped into the reaction system.
(Ii) A method in which an equation for calculating the optimum amount of solvent dripping using the inner bath temperature and the rate of change in the inner bath temperature as a function is obtained in advance by experiments or the like, and the calculated amount of the solvent is dripped into the reaction system.

上記（ｉ）及び（ｉｉ）の方法を用いることによって、内浴温度を目標温度付近に好適に制御することが可能である。しかし、上記いずれの滴下方法をとったとしても、総滴下量にバラつきが生じ、この結果、得られるポリマーの物性（分子量）にバラつきが生じるという問題が生じていた。 By using the methods (i) and (ii) above, it is possible to suitably control the inner bath temperature near the target temperature. However, even if any of the above dropping methods is employed, the total dropping amount varies, and as a result, the physical property (molecular weight) of the obtained polymer varies.

この溶剤総滴下量がポリマー分子量に影響を与える原因としては、溶剤そのものが重合反応の連鎖移動剤としての効果も持っていることや、滴下によりモノマー濃度を低下させる（分子量はモノマー濃度に依存）こと等が挙げられる。そして、実際に重合に用いた溶剤の総滴下量と生成されたポリマー分子量は、図１０に示すような相関が得られることが分かっている。
従って、所望のポリマー物性を得るには、溶剤の総滴下量を常に一定範囲内に抑える必要がある。
しかし、実際の生産現場では、攪拌槽内の溶存酸素濃度のバラツキから、溶剤の総滴下量にバラツキが生じることとなっていた。即ち、溶存酸素濃度のバラツキから反応阻害効果が変化することによって、重合速度、発熱挙動、溶剤の総滴下量がそれぞれ変化し、その結果、ポリマー分子量が変化する。そして、ポリマー分子量の変化が所定の範囲を超えた場合には、異常ロットとなり、製品の歩留まり低下にも繋がるといったケースも起こる。 The reason why the total amount of solvent dripped affects the molecular weight of the polymer is that the solvent itself has an effect as a chain transfer agent for the polymerization reaction, and the monomer concentration is lowered by dripping (the molecular weight depends on the monomer concentration). And so on. Then, it is known that a correlation as shown in FIG. 10 is obtained between the total dripping amount of the solvent actually used for polymerization and the generated polymer molecular weight.
Therefore, in order to obtain desired polymer properties, it is necessary to keep the total amount of solvent dripped within a certain range.
However, in actual production sites, the total amount of solvent dropped varies due to variations in dissolved oxygen concentration in the stirring tank. That is, when the reaction inhibition effect changes due to the variation in dissolved oxygen concentration, the polymerization rate, the exothermic behavior, and the total dripping amount of the solvent change, and as a result, the polymer molecular weight changes. When the change in the molecular weight of the polymer exceeds a predetermined range, an abnormal lot may occur, leading to a decrease in product yield.

そして、上記の攪拌槽内の溶存酸素濃度のバラツキには、以下の要因が考えられる。
窒素置換条件バラツキ、開始剤投入時の酸素混入、重合温度（反応液温度）バラツキ、各種モノマー中に含まれる禁止剤濃度バラツキ、その他不純物混入濃度バラツキ、滴下溶剤の温度、滴下溶剤内の溶存酸素濃度である。
これら要因が、重合速度を変化させる要因として働き、その結果、冷却のために滴下する溶剤の量が変化してしまう。 And the following factors can be considered for variation in the dissolved oxygen concentration in said stirring tank.
Nitrogen substitution condition variation, oxygen mixing at the time of initiator addition, polymerization temperature (reaction liquid temperature) variation, concentration variation of inhibitor contained in various monomers, other impurity contamination concentration variation, dropping solvent temperature, dissolved oxygen in dropping solvent Concentration.
These factors work as factors for changing the polymerization rate, and as a result, the amount of the solvent dropped for cooling changes.

そこで、上記問題に対する改善策としては、以下の２つの方法がある。
（Ｉ）上記に挙げた要因を全て反応に影響しないよう、すべての生産ロットにおいて、計測管理する方法。
（ＩＩ）上記バラツキ発生要因が反応に影響したとしても、溶剤を一定の量及び間隔で滴下し続け、他制御因子にて、内浴温度を制御する方法。 Therefore, there are the following two methods for improving the above problem.
(I) A method of measuring and managing all production lots so that all the above-mentioned factors do not affect the reaction.
(II) A method in which the internal bath temperature is controlled by another control factor while the solvent is continuously dropped at a constant amount and interval even if the above-described variation generation factor affects the reaction.

しかしながら、（Ｉ）の方法については、バッチ方式の生産設備では、複数台の設備が導入されているケースも多く、これらすべての生産設備において、上記要因を計測・制御することは非常に難しくコスト増に繋がり、非現実的である（計測機のメンテナンスを含める）。
一方、（ＩＩ）の方法について、ここでの他制御因子とは、外浴温度設定値及び攪拌翼回転数の設定値が挙げられるが、冒頭に上げたように、これらは、時定数が大きく、詳細な温度制御ができない。 However, with regard to the method (I), there are many cases where multiple production facilities are introduced in batch-type production facilities, and it is very difficult to measure and control the above factors in all these production facilities. This is unrealistic (including maintenance of measuring instruments).
On the other hand, with respect to the method (II), examples of other control factors here include the outer bath temperature set value and the set value of the stirring blade rotation speed. As described above, these have large time constants. Detailed temperature control is not possible.

本発明は前記従来における問題点を解消するためになされたものであり、重合途中の溶剤の積算滴下量により、各種バラツキ要因による反応への影響度を代替的に定量化し、更に、反応終了時の総滴下量を予測することにより、重合反応の再現性を向上させつつポリマーの物性（分子量）のバラつきを防止した重合反応制御方法及び重合反応制御装置を提供することを目的とする。 The present invention has been made to solve the above-described problems in the prior art, and by quantifying the degree of influence on the reaction due to various variation factors by the cumulative amount of solvent in the middle of polymerization, and at the end of the reaction It is an object of the present invention to provide a polymerization reaction control method and a polymerization reaction control apparatus that prevent variations in physical properties (molecular weight) of a polymer while improving the reproducibility of the polymerization reaction by predicting the total amount of dripping.

前記目的を達成するため本願の請求項１に係る重合反応制御方法は、モノマー混合物を攪拌槽内に投入して重合反応によりポリマーを合成する過程で、攪拌槽の外浴温度を制御すると共に、溶剤を攪拌槽内に滴下することにより重合反応を制御する重合反応制御方法において、重合反応中における所定のタイミングで重合開始からの前記溶剤の積算滴下量を算出し、重合反応終了時までに予め設定された総滴下量の溶剤を滴下するように前記算出された溶剤の積算滴下量に基づいて外浴の温度を制御し、前記溶剤の積算滴下量を算出するタイミングは、温度が異なる複数種類の前記溶剤を用いて重合反応を行い、前記用いた溶剤の種類毎に重合開始から所定時間毎の前記溶剤の積算滴下量と重合反応終了までの総滴下量との相関を求めた場合に、前記相関が所定高さ以上で且つ重合開始から最も早いタイミングを前記溶剤の積算滴下量を算出するタイミングとすることを特徴とする。 In order to achieve the above object, the polymerization reaction control method according to claim 1 of the present application controls the outer bath temperature of the stirring tank in the course of synthesizing the polymer by the polymerization reaction by introducing the monomer mixture into the stirring tank, In a polymerization reaction control method for controlling a polymerization reaction by dropping a solvent into a stirring vessel, an integrated dropping amount of the solvent from the start of polymerization is calculated at a predetermined timing during the polymerization reaction, and the polymerization reaction is completed in advance by the end of the polymerization reaction. The temperature of the outer bath is controlled based on the calculated cumulative dropping amount of the solvent so as to drop the total dropping amount of the solvent, and the timing for calculating the cumulative dropping amount of the solvent is a plurality of types with different temperatures. When the polymerization reaction is carried out using the solvent, and the correlation between the total amount of dripping of the solvent and the total amount of dripping from the start of polymerization to the end of the polymerization reaction is determined for each type of solvent used. , Wherein the correlation is a timing to calculate an integrated dropping amount of the solvent the earliest timing from and polymerization initiator at least a predetermined height.

また、請求項２に係る重合反応制御方法は、請求項１に記載の重合反応制御方法において、前記溶剤の積算滴下量に基づく外浴の温度の制御量を以下のようにして求める、異なる温度の複数種類の溶剤を用いて重合反応を行い、重合開始から所定時間後に外浴温度を変更し、前記用いた溶剤の種類毎に変更した外浴温度の温度差と重合反応終了までの総滴下量とをそれぞれ算出し、目標の総滴下量となる温度差と外浴温度の変更時点までの溶剤の積算滴下量との関係から外浴の温度の制御量を求めることを特徴とする。 Further, the polymerization reaction control method according to claim 2 is the polymerization reaction control method according to claim 1, wherein the temperature difference of the outer bath based on the cumulative dripping amount of the solvent is determined as follows. The polymerization reaction is performed using a plurality of types of solvents, and the outer bath temperature is changed after a predetermined time from the start of the polymerization, and the temperature difference of the outer bath temperature changed for each type of the solvent used and the total dropwise addition until the end of the polymerization reaction The control amount of the temperature of the outer bath is obtained from the relationship between the temperature difference that becomes the target total dripping amount and the cumulative dripping amount of the solvent up to the time of changing the outer bath temperature.

また、請求項３に係る重合反応制御装置は、モノマー混合物を攪拌する攪拌槽と、前記攪拌槽の外浴の温度を制御する外浴温度制御手段と、溶剤を前記攪拌槽内に滴下する滴下手段と、を有し、モノマー混合物を攪拌槽内に投入して重合反応によりポリマーを合成する過程で、前記外浴温度制御手段により外浴温度を制御すると共に、前記滴下手段で溶剤を攪拌槽内に滴下することにより重合反応を制御する重合反応制御装置において、重合反応中における所定のタイミングで重合開始からの前記溶剤の積算滴下量を算出する滴下量算出手段を備え、前記外浴温度制御手段は重合反応終了時までに予め設定された総滴下量の溶剤を滴下するように前記滴下量算出手段で算出された溶剤の積算滴下量に基づいて外浴の温度を制御し、前記滴下量算出手段による溶剤の積算滴下量を算出するタイミングは、温度が異なる複数種類の前記溶剤を用いて重合反応を行い、前記用いた溶剤の種類毎に重合開始から所定時間毎の前記溶剤の積算滴下量と重合反応終了までの総滴下量との相関を求めた場合に、前記相関が所定高さ以上で且つ重合開始から最も早いタイミングを前記溶剤の積算滴下量を算出するタイミングとすることを特徴とする。 Further, the polymerization reaction control device according to claim 3 includes a stirring tank for stirring the monomer mixture, an outer bath temperature control means for controlling the temperature of the outer bath of the stirring tank, and a dropping for dropping the solvent into the stirring tank. Means, and in the process of synthesizing the polymer by polymerization reaction by introducing the monomer mixture into the stirring tank, the outer bath temperature is controlled by the outer bath temperature control means, and the solvent is stirred by the dropping means. In the polymerization reaction control apparatus for controlling the polymerization reaction by dripping in, provided with a dripping amount calculating means for calculating the cumulative dripping amount of the solvent from the start of polymerization at a predetermined timing during the polymerization reaction, the outer bath temperature control It means to control the temperature of the outer bath based on the integrated dropping amount of solvent calculated by the dropping amount calculation means to dropping the total dropping amount of the solvent which is previously set by the time the polymerization reaction was completed, the dropping amount The timing for calculating the cumulative dripping amount of the solvent by the dispensing means is that the polymerization reaction is performed using a plurality of types of the solvents having different temperatures, and the cumulative dripping of the solvent is performed every predetermined time from the start of the polymerization for each type of the solvent used. When the correlation between the amount and the total dripping amount until the end of the polymerization reaction is obtained, the correlation is equal to or higher than a predetermined height and the earliest timing from the start of polymerization is the timing for calculating the cumulative dripping amount of the solvent. And

また、請求項４に係る重合反応制御装置は、請求項４に記載の重合反応制御装置において、前記外浴温度制御手段による溶剤の積算滴下量に基づく外浴の温度の制御量を以下のようにして求める、異なる温度の複数種類の溶剤を用いて重合反応を行い、重合開始から所定時間後に外浴温度を変更し、前記用いた溶剤の種類毎に変更した外浴温度の温度差と重合反応終了までの総滴下量とをそれぞれ算出し、目標の総滴下量となる温度差と外浴温度の変更時点までの溶剤の積算滴下量との関係から外浴の温度の制御量を求めることを特徴とする。 The polymerization reaction control device according to claim 4, in a polymerization reaction control device according to claim 4, the following control of the temperature of the outer bath based on accumulated dropping amount of the solvent by the outer bath temperature control means The polymerization reaction is carried out using a plurality of types of solvents at different temperatures, the outer bath temperature is changed after a predetermined time from the start of polymerization, and the temperature difference between the outer bath temperature and the polymerization changed for each type of solvent used. Calculate the total dripping amount until the end of the reaction, and obtain the control amount of the temperature of the outer bath from the relationship between the temperature difference that becomes the target total dripping amount and the cumulative dripping amount of the solvent until the change of the outer bath temperature. It is characterized by.

前記構成を有する請求項１に係る重合反応制御方法では、重合反応中における所定のタイミングで重合開始からの溶剤の積算滴下量を算出し、重合反応終了時までに予め設定された総滴下量の溶剤を滴下するように算出された溶剤の積算滴下量に基づいて外浴の温度を制御するので、重合途中の溶剤の積算滴下量により、溶存酸素濃度等の各種バラツキ要因による反応への影響度を代替的に定量化し、更に、反応終了時の総滴下量を予測することにより、重合反応の再現性を向上させつつポリマーの物性（分子量）のバラつきを防止することができる。
また、異なる温度の複数種類の溶剤を用いて重合反応を行い、用いた溶剤の種類毎に重合開始から所定時間毎の溶剤の積算滴下量と重合反応終了までの総滴下量との相関を求め、相関が所定高さ以上で且つ重合開始から最も早いタイミングを溶剤の積算滴下量を算出するタイミングとして求めるので、外浴温度の制御を行う際に外浴の温度設定幅を小さくでき、オーバーシュート等の制御による外乱の影響を小さくできる。 In the polymerization reaction control method according to claim 1 having the above-described configuration, the cumulative dripping amount of the solvent from the start of polymerization is calculated at a predetermined timing during the polymerization reaction, and the total dripping amount set in advance by the end of the polymerization reaction is calculated. Since the temperature of the outer bath is controlled based on the cumulative amount of solvent calculated so that the solvent is dropped, the degree of influence on the reaction due to various dispersion factors such as dissolved oxygen concentration, depending on the cumulative amount of solvent added during polymerization Alternatively, by quantifying the amount and predicting the total dropping amount at the end of the reaction, it is possible to improve the reproducibility of the polymerization reaction and prevent variations in the physical properties (molecular weight) of the polymer.
In addition, the polymerization reaction is performed using multiple types of solvents at different temperatures, and the correlation between the total amount of solvent dropped from the start of polymerization to the end of the polymerization reaction and the total amount of dripping is determined for each type of solvent used. Since the correlation is equal to or higher than a predetermined height and the earliest timing from the start of polymerization is calculated as the timing for calculating the cumulative dripping amount of the solvent, the temperature setting range of the outer bath can be reduced and the overshoot can be reduced when controlling the outer bath temperature. It is possible to reduce the influence of disturbance due to such control.

また、請求項２に係る重合反応制御方法では、異なる温度の複数種類の溶剤を用いて重合反応を行い、重合開始から所定時間後に外浴温度を変更し、用いた溶剤の種類毎に変更した外浴温度の温度差と重合反応終了までの総滴下量とをそれぞれ算出し、目標の総滴下量となる温度差と外浴温度の変更時点までの溶剤の積算滴下量との関係から外浴の温度の制御量を求めるので、外浴温度の制御を行うことにより溶剤の総滴下量を常に一定範囲内に抑えることができ、所望のポリマー物性を得ることが可能となる。 Moreover, in the polymerization reaction control method according to claim 2, the polymerization reaction is performed using a plurality of types of solvents at different temperatures, the outer bath temperature is changed after a predetermined time from the start of the polymerization, and is changed for each type of solvent used. Calculate the temperature difference of the outer bath temperature and the total dripping amount until the completion of the polymerization reaction, and calculate the outer bath from the relationship between the temperature difference that becomes the target total dripping amount and the cumulative dripping amount of the solvent until the change of the outer bath temperature. Therefore, by controlling the outer bath temperature, the total dripping amount of the solvent can be always kept within a certain range, and desired polymer physical properties can be obtained.

また、請求項３に係る重合反応制御装置では、重合反応中における所定のタイミングで重合開始からの溶剤の積算滴下量を算出し、重合反応終了時までに予め設定された総滴下量の溶剤を滴下するように算出された溶剤の積算滴下量に基づいて外浴の温度を制御するので、重合途中の溶剤の積算滴下量により、溶存酸素濃度等の各種バラツキ要因による反応への影響度を代替的に定量化し、更に、反応終了時の総滴下量を予測することにより、重合反応の再現性を向上させつつポリマーの物性（分子量）のバラつきを防止することができる。
また、異なる温度の複数種類の溶剤を用いて重合反応を行い、用いた溶剤の種類毎に重合開始から所定時間毎の溶剤の積算滴下量と重合反応終了までの総滴下量との相関を求め、相関が所定高さ以上で且つ重合開始から最も早いタイミングを溶剤の積算滴下量を算出するタイミングとして求めるので、外浴温度の制御を行う際に外浴の温度設定幅を小さくでき、オーバーシュート等の制御による外乱の影響を小さくできる。 In the polymerization reaction control apparatus according to claim 3 , the cumulative dropping amount of the solvent from the start of the polymerization is calculated at a predetermined timing during the polymerization reaction, and the total dropping amount of the solvent set in advance by the end of the polymerization reaction is calculated. Since the temperature of the outer bath is controlled based on the cumulative amount of solvent calculated to be dripped, the cumulative amount of solvent in the middle of polymerization substitutes the degree of influence on the reaction due to various dispersion factors such as dissolved oxygen concentration. By quantitatively quantifying and predicting the total dropping amount at the end of the reaction, it is possible to prevent variations in the physical properties (molecular weight) of the polymer while improving the reproducibility of the polymerization reaction.
In addition, the polymerization reaction is performed using multiple types of solvents at different temperatures, and the correlation between the total amount of solvent dropped from the start of polymerization to the end of the polymerization reaction and the total amount of dripping is determined for each type of solvent used. Since the correlation is equal to or higher than a predetermined height and the earliest timing from the start of polymerization is calculated as the timing for calculating the cumulative dripping amount of the solvent, the temperature setting range of the outer bath can be reduced and the overshoot can be reduced when controlling the outer bath temperature. It is possible to reduce the influence of disturbance due to such control.

また、請求項４に係る重合反応制御装置では、異なる温度の複数種類の溶剤を用いて重合反応を行い、重合開始から所定時間後に外浴温度を変更し、前記用いた溶剤の種類毎に変更した外浴温度の温度差と重合反応終了までの総滴下量とをそれぞれ算出し、目標の総滴下量となる温度差と外浴温度の変更時点までの溶剤の積算滴下量との関係から外浴の温度の制御量を求めるので、外浴温度の制御を行うことにより溶剤の総滴下量を常に一定範囲内に抑えることができ、所望のポリマー物性を得ることが可能となる。 In the polymerization reaction control apparatus according to claim 4 , the polymerization reaction is performed using a plurality of types of solvents at different temperatures, the outer bath temperature is changed after a predetermined time from the start of the polymerization, and is changed for each type of the solvent used. The temperature difference between the outer bath temperatures and the total dripping amount until the end of the polymerization reaction are calculated, respectively, and it is excluded from the relationship between the temperature difference that becomes the target total dripping amount and the cumulative dripping amount of the solvent until the change of the outer bath temperature. Since the control amount of the bath temperature is obtained, the total dripping amount of the solvent can be always kept within a certain range by controlling the outer bath temperature, and desired polymer physical properties can be obtained.

以下、本発明に係る重合反応制御方法及び重合反応制御装置について具体化した実施形態に基づき図面を参照しつつ詳細に説明する。先ず、本実施形態に係る重合反応制御装置１について図１に基づき説明する。図１は本実施形態に係る重合反応制御装置１の要部を示す概略側面図である。 DETAILED DESCRIPTION Hereinafter, a polymerization reaction control method and a polymerization reaction control device according to the present invention will be described in detail with reference to the drawings based on specific embodiments. First, the polymerization reaction control apparatus 1 according to this embodiment will be described with reference to FIG. FIG. 1 is a schematic side view showing a main part of a polymerization reaction control device 1 according to this embodiment.

図１に示すように、本実施形態に係る重合反応制御装置１は、投入したモノマー混合物からポリマーを合成する攪拌機２と、攪拌機２を構成する攪拌槽３に溶剤（本実施形態では冷却水）を滴下する滴下槽４と、攪拌槽３の外浴温度、溶剤の滴下等を制御する制御部５と、種々の条件の入力設定や操作を行う操作部６から基本的に構成されている。 As shown in FIG. 1, a polymerization reaction control apparatus 1 according to this embodiment includes a stirrer 2 that synthesizes a polymer from a charged monomer mixture, and a solvent (cooling water in this embodiment) in a stirrer 3 that constitutes the stirrer 2. Is basically composed of a dripping tank 4 for dripping, an outer bath temperature of the stirring tank 3, a controller 5 for controlling the dripping of the solvent, and the like, and an operation section 6 for performing input setting and operation of various conditions.

以下、各構成について具体的に説明する。尚、滴下槽４は本発明の滴下手段に、制御部５は外浴温度制御手段、滴下量算出手段にそれぞれ相当する。 Each configuration will be specifically described below. The dropping tank 4 corresponds to the dropping means of the present invention, and the control unit 5 corresponds to the outer bath temperature control means and the dropping amount calculation means.

攪拌機２は、底部が椀状をした攪拌槽３と、攪拌槽３の中心部の上方から片持ち支持された回転軸７と、回転軸７に取り付けられた攪拌翼８とから構成されている。この回転軸７は、図示しない回転駆動手段に連接されており、図中のＹ軸回りに回転する。また、攪拌槽３の外周には攪拌槽３内で行われる重合反応の重合温度（攪拌槽３内の内浴温度）を制御するための温度調節手段であるジャケット９が付設されている。 The stirrer 2 includes a stirring tank 3 having a bowl-like bottom, a rotating shaft 7 that is cantilevered from above the center of the stirring tank 3, and a stirring blade 8 attached to the rotating shaft 7. . The rotation shaft 7 is connected to a rotation driving means (not shown) and rotates around the Y axis in the drawing. A jacket 9 is attached to the outer periphery of the stirring tank 3 as temperature adjusting means for controlling the polymerization temperature of the polymerization reaction performed in the stirring tank 3 (inner bath temperature in the stirring tank 3).

また、攪拌槽３は上蓋１０に対してコンデンサ１１が立設されている。コンデンサ１１は重合反応にともなって蒸発した水分を冷却して水に戻すとともに、攪拌槽３内に供給して不要となった窒素（Ｎ_２）を排出する。尚、窒素は、攪拌槽３の下部と上部に接続された配管を介して、その近傍に配備された図示しない窒素タンクから適時・適量供給される。また、底部には内浴の温度を検出する温度センサＳ１が取り付けられている。 Further, the stirring tank 3 is provided with a condenser 11 with respect to the upper lid 10. The condenser 11 cools and returns the water evaporated in accordance with the polymerization reaction to water, and discharges unnecessary nitrogen (N ₂ ) supplied to the stirring tank 3. Nitrogen is supplied in a timely and appropriate amount from a nitrogen tank (not shown) disposed in the vicinity thereof through a pipe connected to the lower and upper portions of the stirring tank 3. A temperature sensor S1 for detecting the temperature of the inner bath is attached to the bottom.

一方、ジャケット９は、温度調節用流体を供給・排出循環させるための配管Ｒ１が上・下部に連通接続されている。この配管Ｒ１のジャケット入口側（図１では下部）には熱交換器１５が設けられている。熱交換器１５は攪拌槽３内の温度を上昇させるために、配管Ｒ１に循環する水温を上昇させ、温水をジャケット９へと供給する。また、熱交換器１５には、バルブＶ１を開放することにより蒸気が供給される配管Ｒ２が連通接続されている。更に、配管Ｒ１には、攪拌槽３を冷却するために配管Ｒ１を循環する温水または冷却水を排出するためのバルブＶ２が設けられているとともに、バルブＶ２を開放して温水などを排出したときに新たな冷却水を供給するための配管Ｒ３がバルブＶ３を介して配管Ｒ１に連通接続されている。 On the other hand, the jacket 9 is connected to the upper and lower portions of a pipe R1 for supplying and discharging the temperature adjusting fluid. A heat exchanger 15 is provided on the jacket inlet side (lower part in FIG. 1) of the pipe R1. The heat exchanger 15 raises the temperature of the water circulating in the pipe R <b> 1 in order to raise the temperature in the stirring tank 3, and supplies the hot water to the jacket 9. Further, the heat exchanger 15 is connected to a pipe R2 through which steam is supplied by opening the valve V1. Further, the pipe R1 is provided with a valve V2 for discharging hot water or cooling water circulating through the pipe R1 in order to cool the stirring tank 3, and when the valve V2 is opened to discharge hot water or the like. A pipe R3 for supplying new cooling water to the pipe R1 is connected to the pipe R1 through a valve V3.

また、温度調節用流体をジャケット９に供給する側の配管Ｒ１（図１ではジャケット９の下部近傍）には外浴の入口温度を検出する温度センサＳ２が設けられている。一方、排出する側（図１ではジャケット９の上部近傍）には外浴の出口温度を検出する温度センサＳ３と、ジャケット９を循環する循環水の流量を検出するジャケット循環水流量計Ｆ１とがそれぞれ設けられている。 In addition, a temperature sensor S2 for detecting the inlet temperature of the outer bath is provided on the pipe R1 (in the vicinity of the lower portion of the jacket 9 in FIG. 1) on the side for supplying the temperature adjusting fluid to the jacket 9. On the other hand, on the discharge side (in the vicinity of the upper part of the jacket 9 in FIG. 1), there are a temperature sensor S3 for detecting the outlet temperature of the outer bath and a jacket circulating water flow meter F1 for detecting the flow rate of circulating water circulating through the jacket 9. Each is provided.

滴下槽４は、所定の温度および所定の溶存酸素濃度に調整された溶剤（本実施形態では冷却水）が蓄えられている。また、その外周には、溶剤の温度を一定に保持するジャケット２１が付設されている。また、滴下槽４の内部には内浴の温度（冷却水の温度）を検出する温度センサＳ４が配置されている。そして、ジャケット２１には、温度センサＳ４によって検出された冷却水の温度に基づいて、適時に設定変更された冷却水が循環する。尚、溶存酸素濃度については、滴下槽４から供給される過程で、酸素を供給してスタテックミキサなどで攪拌し、その濃度レベルを適時に調節してもよい。 The dripping tank 4 stores a solvent (cooling water in this embodiment) adjusted to a predetermined temperature and a predetermined dissolved oxygen concentration. A jacket 21 for keeping the temperature of the solvent constant is attached to the outer periphery. Further, a temperature sensor S4 for detecting the temperature of the inner bath (cooling water temperature) is disposed inside the dropping tank 4. The jacket 21 is circulated with the cooling water whose setting is changed in a timely manner based on the temperature of the cooling water detected by the temperature sensor S4. As for the dissolved oxygen concentration, in the process of being supplied from the dropping tank 4, oxygen may be supplied and stirred with a static mixer or the like to adjust the concentration level in a timely manner.

また、滴下槽４の上下部には配管が連通接続されており、それぞれの配管から窒素（Ｎ２）が供給される。そして、滴下槽４に窒素を供給し滴下槽４内の酸素を排気管から排出する窒素置換を行う。 In addition, piping is connected to the upper and lower portions of the dropping tank 4, and nitrogen (N2) is supplied from each piping. Then, nitrogen replacement is performed in which nitrogen is supplied to the dropping tank 4 and oxygen in the dropping tank 4 is discharged from the exhaust pipe.

更に、滴下槽４は、バルブＶ４を備えた配管Ｒ４を介して攪拌槽３と連通接続されている。そして、滴下槽４の溶剤は、後述する制御部５の制御によりバルブＶ４が開閉操作されることで攪拌槽３に所定量が滴下される。なお、配管Ｒ４には、攪拌槽３に供給される溶剤の滴下量を検出する溶剤流量計Ｆ２が取り付けられている。 Furthermore, the dripping tank 4 is connected to the stirring tank 3 through a pipe R4 provided with a valve V4. Then, a predetermined amount of the solvent in the dropping tank 4 is dropped into the stirring tank 3 by opening and closing the valve V4 under the control of the control unit 5 described later. Note that a solvent flow meter F2 that detects the dripping amount of the solvent supplied to the stirring tank 3 is attached to the pipe R4.

制御部５は攪拌槽３の外浴温度や溶剤の滴下を制御することによって重合反応制御装置１で行われる重合反応を制御する制御手段であり、回路基板上に配置され予め設定されたプログラムに従って制御動作を行うＣＰＵ、並びに記憶手段であるＲＯＭやＲＡＭ等を備える。また、制御部５にはポリマー合成条件に応じた外浴の温度の制御量及び制御タイミング、溶剤を攪拌槽３に滴下する量及びタイミング等の種々の設定条件が操作部６から予め入力設定されて、ＲＡＭ等のメモリに記憶されている。そして、記憶された各種条件と各センサからの測定結果に基づいて後述のように外浴温度や溶剤の滴下を制御する。 The control unit 5 is a control unit that controls the polymerization reaction performed in the polymerization reaction control device 1 by controlling the outer bath temperature of the stirring tank 3 and the dropping of the solvent, and is arranged on the circuit board according to a preset program. A CPU that performs control operations and ROM, RAM, and the like, which are storage means, are provided. In addition, various setting conditions such as the control amount and control timing of the temperature of the outer bath according to the polymer synthesis conditions and the amount and timing of dropping the solvent into the stirring tank 3 are input and set to the control unit 5 from the operation unit 6 in advance. And stored in a memory such as a RAM. And based on the various conditions memorize | stored and the measurement result from each sensor, outer bath temperature and dripping of a solvent are controlled as mentioned later.

次に、上記構成を有する重合反応制御装置１の重合反応制御方法について説明する。
先ず、攪拌機２の攪拌槽３に予め用意したモノマー溶液を抽入する。また、滴下槽４に滴下用溶剤を抽入する。その後、ジャケット９及びジャケット２１を循環させる温度調節用流体の温度を調整し、攪拌槽３及び滴下槽４の外浴の温度を目標温度（攪拌槽３を５９℃、滴下槽４を１５℃）に温調する。
次に、それぞれ任意の窒素流量にて、モノマー溶液や溶剤をバブリングして窒素置換を行う。規定の時間だけ窒素置換を実施後、液相部よりの窒素送入を止め、気相部よりの送入に切り替える。そして、内浴温度が安定していることを確認後、重合開始剤を投入する。
その後、攪拌槽３の外浴設定温度を５９℃に固定した状態で待機し、内浴温度が上昇して重合反応が開始されたことを確認したと同時に制御部５による重合反応の制御を開始する。
重合反応の制御が開始されると、先ず、攪拌槽３の外浴温度を４０℃に設定し、１０分経過後に２０℃に設定し、１５０分経過後から反応終了（１８０分経過）までは５０℃に設定する。
一方で、攪拌槽３の内浴温度が６０℃以上となると、バルブＶ４を開放し、滴下槽４からの溶剤の滴下を行う。ここで、溶剤の滴下は内浴温度が６０℃未満となるまで、１０ｋｇの溶剤を１２０ｓｅｃかけて繰り返し滴下することにより行われる。
また、重合反応の開始から３０分経過した際に、３０分経過時点での溶剤の積算滴下量ｎ[kg]を算出し、更に算出した積算滴下量ｎを予め事前実験を行うことにより求めた下記の演算式（１）に代入することによって外浴の温度の制御量（外浴の設定温度の補正量）ΔＳＶを算出する。
ΔＳＶ[℃]＝−０．２８５ｎ×１２．５５５・・・（１）
そして、算出したΔＳＶを設定温度に加算した温度により、それ以後の外浴の温度を設定する（例えば、ΔＳＶ＝２℃と算出された場合には、重合反応の開始から１５０分が経過するまでは現在の設定温度を２℃上昇させた２２℃へと外浴温度を新たに設定し直し、１５０分経過後から反応終了までは５２℃に設定する）。それによって、反応終了までに滴下される溶剤の総滴下量を予め設定した目標値とすることができる。 Next, a polymerization reaction control method of the polymerization reaction control device 1 having the above configuration will be described.
First, a monomer solution prepared in advance is drawn into the stirring tank 3 of the stirrer 2. Further, a dropping solvent is drawn into the dropping tank 4. Thereafter, the temperature of the temperature adjusting fluid circulating through the jacket 9 and the jacket 21 is adjusted, and the temperatures of the outer baths of the stirring tank 3 and the dropping tank 4 are set to the target temperature (the stirring tank 3 is 59 ° C., the dropping tank 4 is 15 ° C.). Adjust the temperature.
Next, nitrogen substitution is performed by bubbling a monomer solution or a solvent at an arbitrary nitrogen flow rate. After carrying out nitrogen substitution for a specified time, stop nitrogen feeding from the liquid phase part and switch to feeding from the gas phase part. Then, after confirming that the inner bath temperature is stable, a polymerization initiator is added.
After that, the apparatus was on standby with the set temperature of the outer bath of the stirring tank 3 fixed at 59 ° C., and it was confirmed that the inner bath temperature was increased and the polymerization reaction was started, and at the same time, the control of the polymerization reaction by the control unit 5 was started. To do.
When the control of the polymerization reaction is started, the outer bath temperature of the stirring tank 3 is first set to 40 ° C., set to 20 ° C. after 10 minutes, and from 150 minutes to the end of the reaction (180 minutes). Set to 50 ° C.
On the other hand, when the inner bath temperature of the stirring tank 3 is 60 ° C. or higher, the valve V4 is opened and the solvent from the dropping tank 4 is dropped. Here, the dropping of the solvent is performed by repeatedly dropping 10 kg of the solvent over 120 seconds until the inner bath temperature becomes less than 60 ° C.
Further, when 30 minutes have elapsed from the start of the polymerization reaction, the cumulative drop amount n [kg] of the solvent at the point of 30 minutes was calculated, and the calculated cumulative drop amount n was obtained by conducting a preliminary experiment in advance. By substituting into the following equation (1), the control amount of the outer bath temperature (correction amount of the set temperature of the outer bath) ΔSV is calculated.
ΔSV [° C.] = − 0.285 n × 12.555 (1)
Then, the temperature of the outer bath after that is set by the temperature obtained by adding the calculated ΔSV to the set temperature (for example, when ΔSV = 2 ° C. is calculated, 150 minutes have elapsed from the start of the polymerization reaction). (2), the outside bath temperature is newly set to 22 ° C., which is increased by 2 ° C., and is set to 52 ° C. after 150 minutes until the end of the reaction. Thereby, the total amount of solvent dripped before the end of the reaction can be set to a preset target value.

続いて、前記構成を有する本実施形態に係る重合反応制御装置１の重合反応制御に係る各処理について図２及び図３に基づき説明する。図２は本実施形態に係る重合反応制御装置１の攪拌槽３の外浴温度制御プログラムのフローチャートである。図３は本実施形態に係る重合反応制御装置１の溶剤の滴下制御プログラムのフローチャートである。尚、攪拌槽３の外浴温度制御プログラムは、攪拌槽３内に重合開始剤が投入され、内浴温度が上昇して重合反応が開始されたことを確認したと同時に開始される。また、図２及び図３にフローチャートで示されるプログラムは、制御部５が備えているＲＡＭやＲＯＭに記憶されており、ＣＰＵにより実行される。 Next, each process related to the polymerization reaction control of the polymerization reaction control apparatus 1 according to this embodiment having the above-described configuration will be described with reference to FIGS. FIG. 2 is a flowchart of an outer bath temperature control program of the stirring tank 3 of the polymerization reaction control apparatus 1 according to this embodiment. FIG. 3 is a flowchart of the solvent dropping control program of the polymerization reaction control apparatus 1 according to this embodiment. The outer bath temperature control program for the stirring tank 3 is started at the same time as confirming that the polymerization initiator has been introduced into the stirring tank 3 and the inner bath temperature has risen to initiate the polymerization reaction. 2 and FIG. 3 are stored in the RAM or ROM provided in the control unit 5 and executed by the CPU.

ここで、図２に示すように攪拌槽３の外浴温度制御プログラムのフローチャートは、２つのフローチャートによって基本的に構成される。一方は、重合反応の開始から所定時間の経過に伴って攪拌槽３の外浴の設定温度を変更する基本制御フローチャートであり、他方は、所定のタイミングでの溶剤の積算滴下量に基づいて、その後の外浴の設定温度に補正を加える設定温度補正制御フローチャートである。 Here, as shown in FIG. 2, the flowchart of the outer bath temperature control program of the stirring tank 3 is basically constituted by two flowcharts. One is a basic control flowchart for changing the set temperature of the outer bath of the stirring tank 3 as the predetermined time elapses from the start of the polymerization reaction, and the other is based on the cumulative amount of solvent dropped at a predetermined timing, It is a preset temperature correction control flowchart which adds correction | amendment to the preset temperature of the subsequent outer bath.

先ず、外浴温度制御プログラムでは、ステップ（以下、Ｓと略記する）１において制御部５は、重合反応開始からの経過時間を示すタイマＴＭ１の計測を開始する。次に、Ｓ２で制御部５は、熱交換器１５やバルブＶ１〜Ｖ３の開度を制御して攪拌槽３の外浴温度ＳＶの設定温度をＴ１（℃）に設定する。ここで、本実施形態ではＴ１は基本的に４０℃であるが、後述するＳ１４の処理によって設定温度が補正された場合には補正された後の設定温度へと設定されることとなる。 First, in the outer bath temperature control program, in step (hereinafter abbreviated as S) 1, the control unit 5 starts measuring the timer TM1 indicating the elapsed time from the start of the polymerization reaction. Next, in S2, the control unit 5 controls the opening degree of the heat exchanger 15 and the valves V1 to V3 to set the set temperature of the outer bath temperature SV of the stirring tank 3 to T1 (° C.). Here, in this embodiment, T1 is basically 40 ° C., but when the set temperature is corrected by the process of S14 described later, it is set to the set temperature after correction.

続いて、Ｓ３で制御部５はタイマＴＭ１の示す重合反応開始からの経過時間がｔ１となったか否か判定される。尚、本実施形態では、ｔ１は１０分とする。そして、重合反応開始からの経過時間がｔ１となったと判定された場合（Ｓ３：ＹＥＳ）にはＳ４へと移行する。一方、重合反応開始からの経過時間がｔ１となっていないと判定された場合（Ｓ３：ＮＯ）には、ｔ１を経過するまで待機する。 Subsequently, in S3, the control unit 5 determines whether or not the elapsed time from the start of the polymerization reaction indicated by the timer TM1 has reached t1. In the present embodiment, t1 is 10 minutes. When it is determined that the elapsed time from the start of the polymerization reaction has become t1 (S3: YES), the process proceeds to S4. On the other hand, when it is determined that the elapsed time from the start of the polymerization reaction is not t1 (S3: NO), the process waits until t1 elapses.

Ｓ４で制御部５は、熱交換器１５やバルブＶ１〜Ｖ３の開度を制御して攪拌槽３の外浴温度ＳＶの設定温度をＴ２（℃）に設定する。ここで、本実施形態ではＴ２は基本的に２０℃であるが、後述するＳ１４の処理によって設定温度が補正された場合には補正された後の設定温度へと設定されることとなる。 In S4, the control unit 5 controls the opening degree of the heat exchanger 15 and the valves V1 to V3 to set the set temperature of the outer bath temperature SV of the stirring tank 3 to T2 (° C.). Here, in this embodiment, T2 is basically 20 ° C., but when the set temperature is corrected by the process of S14 described later, it is set to the corrected set temperature.

続いて、Ｓ５で制御部５はタイマＴＭ１の示す重合反応開始からの経過時間がｔ２となったか否か判定される。尚、本実施形態では、ｔ２は１５０分とする。そして、重合反応開始からの経過時間がｔ２となったと判定された場合（Ｓ５：ＹＥＳ）にはＳ６へと移行する。一方、重合反応開始からの経過時間がｔ２となっていないと判定された場合（Ｓ５：ＮＯ）には、ｔ２を経過するまで待機する。 Subsequently, in S5, the control unit 5 determines whether or not the elapsed time from the start of the polymerization reaction indicated by the timer TM1 has reached t2. In this embodiment, t2 is 150 minutes. When it is determined that the elapsed time from the start of the polymerization reaction has become t2 (S5: YES), the process proceeds to S6. On the other hand, when it is determined that the elapsed time from the start of the polymerization reaction is not t2 (S5: NO), the process waits until t2.

Ｓ６で制御部５は、熱交換器１５やバルブＶ１〜Ｖ３の開度を制御して攪拌槽３の外浴温度ＳＶの設定温度をＴ３（℃）に設定する。ここで、本実施形態ではＴ３は基本的に５０℃であるが、後述するＳ１４の処理によって設定温度が補正された場合には補正された後の設定温度へと設定されることとなる。 In S6, the control unit 5 controls the opening degree of the heat exchanger 15 and the valves V1 to V3 to set the set temperature of the outer bath temperature SV of the stirring tank 3 to T3 (° C.). Here, in this embodiment, T3 is basically 50 ° C., but when the set temperature is corrected by the process of S14 described later, it is set to the corrected set temperature.

続いて、Ｓ７で制御部５はタイマＴＭ１の示す重合反応開始からの経過時間が、重合反応の終了する１８０分となったか否か判定される。尚、本実施形態では重合反応が終了するまでの時間を１８０分としているが、その時間はポリマーの製造条件によって異なる。そして、重合反応開始からの経過時間が１８０分となったと判定された場合（Ｓ７：ＹＥＳ）には当該外浴温度制御プログラムを終了する。一方、重合反応開始からの経過時間が１８０分となっていないと判定された場合（Ｓ７：ＮＯ）には、１８０分を経過するまで待機する。 Subsequently, in S7, the control unit 5 determines whether or not the elapsed time from the start of the polymerization reaction indicated by the timer TM1 has reached 180 minutes when the polymerization reaction ends. In this embodiment, the time until the completion of the polymerization reaction is 180 minutes, but this time varies depending on the polymer production conditions. If it is determined that the elapsed time from the start of the polymerization reaction is 180 minutes (S7: YES), the outer bath temperature control program is terminated. On the other hand, when it is determined that the elapsed time from the start of the polymerization reaction is not 180 minutes (S7: NO), the process waits until 180 minutes have elapsed.

また、外浴温度制御プログラムでは、Ｓ１１において制御部５はタイマＴＭ１の示す重合反応開始からの経過時間がｔｎとなったか否か判定される。尚、本実施形態ではｔｎは３０分とするが、このｔｎの値は後述する事前実験によって求められるものである。そして、重合反応開始からの経過時間がｔｎとなったと判定された場合（Ｓ１１：ＹＥＳ）にはＳ１２へと移行する。一方、重合反応開始からの経過時間がｔｎとなっていないと判定された場合（Ｓ１１：ＮＯ）には、ｔｎを経過するまで待機する。 In the outer bath temperature control program, in S11, the control unit 5 determines whether or not the elapsed time from the start of the polymerization reaction indicated by the timer TM1 has reached tn. In this embodiment, tn is 30 minutes, but the value of tn is obtained by a preliminary experiment described later. When it is determined that the elapsed time from the start of the polymerization reaction has become tn (S11: YES), the process proceeds to S12. On the other hand, when it is determined that the elapsed time from the start of the polymerization reaction is not tn (S11: NO), the process waits until tn elapses.

Ｓ１２で制御部５は、溶剤流量計Ｆ２の検出結果に基づいて、ｔｎ経過時点での滴下槽４からの溶剤の積算滴下量ｎを算出する。 In S12, the control unit 5 calculates the cumulative dropping amount n of the solvent from the dropping tank 4 at the time when tn has elapsed, based on the detection result of the solvent flow meter F2.

次に、Ｓ１３で制御部５は、前記Ｓ１２で算出した積算滴下量ｎを予め事前実験で求めた下記の演算式（１）に代入することによって外浴の温度の制御量（補正量）ΔＳＶを算出する。
ΔＳＶ[℃]＝−０．２８５ｎ×１２．５５５・・・（１） Next, in step S13, the control unit 5 substitutes the integrated drop amount n calculated in step S12 into the following arithmetic expression (1) obtained in advance in advance, thereby controlling the temperature (control amount) ΔSV of the temperature of the outer bath. Is calculated.
ΔSV [° C.] = − 0.285 n × 12.555 (1)

更に、Ｓ１４で制御部５は、前記Ｓ１３で算出したΔＳＶを設定温度に加算した温度により、それ以後の外浴の温度Ｔ１〜Ｔ３を補正する。例えば、本実施形態においてΔＳＶ＝２℃と算出された場合には、重合反応の開始から１５０分が経過するまでは現在の設定温度を２℃上昇させた２２℃へと外浴温度を新たに設定し直し、前記Ｓ６では外浴温度を５２℃に設定する。また、本実施形態においてΔＳＶ＝−１．５℃と算出された場合には、重合反応の開始から１５０分が経過するまでは現在の設定温度を１．５℃下降させた１８．５℃へと外浴温度を新たに設定し直し、前記Ｓ６では外浴温度を４８．５℃に設定する。このように外浴の設定温度を補正することによって、反応終了までに滴下される溶剤の総滴下量を予め設定した目標値とすることができる。 Further, in S14, the control unit 5 corrects the subsequent temperatures T1 to T3 of the outer bath with the temperature obtained by adding ΔSV calculated in S13 to the set temperature. For example, when ΔSV = 2 ° C. is calculated in the present embodiment, the outer bath temperature is newly increased to 22 ° C. by increasing the current set temperature by 2 ° C. until 150 minutes have elapsed from the start of the polymerization reaction. In step S6, the outer bath temperature is set to 52 ° C. In the present embodiment, when ΔSV = −1.5 ° C. is calculated, the current set temperature is decreased by 1.5 ° C. to 18.5 ° C. until 150 minutes have elapsed from the start of the polymerization reaction. The outer bath temperature is newly set, and the outer bath temperature is set to 48.5 ° C. in S6. Thus, by correcting the set temperature of the outer bath, the total amount of solvent dripped before the end of the reaction can be set to a preset target value.

続いて、図３に示す溶剤の滴下制御プログラムでは、先ずＳ２１において制御部５は、温度センサＳ１により攪拌槽３の内浴温度を検出する。次に、Ｓ２２で制御部５は前記Ｓ２１で検出した内浴温度がＴ４（例えば６０℃）以上であるか否か判定される。 Subsequently, in the solvent dropping control program shown in FIG. 3, first, in S <b> 21, the controller 5 detects the inner bath temperature of the stirring tank 3 by the temperature sensor S <b> 1. Next, in S22, the controller 5 determines whether or not the inner bath temperature detected in S21 is equal to or higher than T4 (for example, 60 ° C.).

そして、内浴温度がＴ４以上であると判定された場合（Ｓ２２：ＹＥＳ）にはＳ２３へと移行し、バルブＶ４が開放されて溶剤の滴下が開始される。尚、溶剤の滴下はＡｋｇ（例えば１０ｋｇ）の溶剤がその後にｔ３秒かけて滴下される。一方、内浴温度がＴ４未満であると判定された場合（Ｓ２２：ＮＯ）には、Ｓ２６へと移行する。 When it is determined that the inner bath temperature is equal to or higher than T4 (S22: YES), the process proceeds to S23, the valve V4 is opened, and the dropping of the solvent is started. The solvent is dropped by adding A kg (for example, 10 kg) of solvent over a period of t3 seconds. On the other hand, when it is determined that the inner bath temperature is lower than T4 (S22: NO), the process proceeds to S26.

その後、Ｓ２４では制御部５は、溶剤の滴下開始からの経過時間を示すタイマＴＭ２の計測を開始する。そして、Ｓ２５で制御部５はタイマＴＭ２の示す溶剤の滴下開始からの経過時間がｔ３となったか否か判定される。尚、本実施形態では、ｔ３は１２０秒とする。そして、溶剤の滴下開始からの経過時間がｔ３となったと判定された場合（Ｓ２５：ＹＥＳ）にはＳ２６へと移行する。一方、溶剤の滴下開始からの経過時間がｔ３となっていないと判定された場合（Ｓ２５：ＮＯ）には、ｔ３を経過するまで待機する。 Thereafter, in S24, the control unit 5 starts measuring the timer TM2 indicating the elapsed time from the start of the dropping of the solvent. In S25, the control unit 5 determines whether or not the elapsed time from the start of dropping of the solvent indicated by the timer TM2 has reached t3. In the present embodiment, t3 is 120 seconds. And when it determines with the elapsed time from the dripping start of a solvent having become t3 (S25: YES), it transfers to S26. On the other hand, when it is determined that the elapsed time from the start of the dropping of the solvent is not t3 (S25: NO), the process waits until t3 elapses.

次に、Ｓ２６で制御部５はタイマＴＭ１の示す重合反応開始からの経過時間が、重合反応の終了する１８０分を経過したか否か判定される。尚、本実施形態では重合反応が終了するまでの時間を１８０分としているが、その時間はポリマーの製造条件によって異なる。そして、重合反応開始からの経過時間が１８０分を経過したと判定された場合（Ｓ２６：ＹＥＳ）には当該溶剤の滴下制御プログラムを終了する。一方、重合反応開始からの経過時間が１８０分を経過していないと判定された場合（Ｓ２６：ＮＯ）にはＳ２１へと戻り、再度、攪拌槽３の内浴温度の検出が行われる。 Next, in S26, the control unit 5 determines whether the elapsed time from the start of the polymerization reaction indicated by the timer TM1 has passed 180 minutes when the polymerization reaction ends. In this embodiment, the time until the completion of the polymerization reaction is 180 minutes, but this time varies depending on the polymer production conditions. When it is determined that the elapsed time from the start of the polymerization reaction has passed 180 minutes (S26: YES), the solvent dropping control program is terminated. On the other hand, when it is determined that the elapsed time from the start of the polymerization reaction has not passed 180 minutes (S26: NO), the process returns to S21, and the inner bath temperature of the stirring tank 3 is detected again.

続いて、上記Ｓ１１で判定される溶剤の積算滴下量を算出するタイミングである反応開始時間からの経過時刻ｔｎを求める為の事前実験１と、前記Ｓ１３で外浴温度の制御量を算出する際に用いる上記（１）の演算式を求める為の事前実験２について説明する。 Subsequently, in the preliminary experiment 1 for obtaining the elapsed time tn from the reaction start time, which is the timing for calculating the cumulative amount of solvent determined in S11, and in calculating the control amount of the outer bath temperature in S13. A preliminary experiment 2 for obtaining the arithmetic expression (1) used in the above will be described.

〔事前実験１〕
事前実験１では、図１に示す重合反応制御装置１を用い、温度の異なる４種類の溶剤Ａ〜Ｄ（溶剤Ａ：１５℃、溶剤Ｂ：２０℃、溶剤Ｃ：２５℃、溶剤Ｄ：３０℃）を滴下することにより攪拌槽３の内浴温度を調整し、攪拌槽３内にあるモノマー混合物を重合反応させ、ポリマーを合成することにより行う。尚、攪拌槽３の外浴温度は既に説明したＳ１〜Ｓ７の処理（図２）に従って制御部５により制御される。また、溶剤の滴下は既に説明したＳ２１〜Ｓ２６の処理（図３）に従って制御部５により制御される。 [Preliminary experiment 1]
In the preliminary experiment 1, the polymerization reaction control apparatus 1 shown in FIG. 1 was used, and four types of solvents A to D having different temperatures (solvent A: 15 ° C., solvent B: 20 ° C., solvent C: 25 ° C., solvent D: 30 C.) is added dropwise to adjust the inner bath temperature of the stirring vessel 3, polymerize the monomer mixture in the stirring vessel 3, and synthesize the polymer. In addition, the outer bath temperature of the stirring tank 3 is controlled by the control part 5 according to the process (FIG. 2) of S1-S7 already demonstrated. Further, the dropping of the solvent is controlled by the control unit 5 in accordance with the processes of S21 to S26 already described (FIG. 3).

先ず、事前実験１を行うに際して、それぞれ任意の窒素流量にて、攪拌槽３をバブリングして窒素置換を行う。そして、窒素置換を４時間行った後、液相部よりの窒素送入を止め、気相部よりの送入に切り替える。そして、内浴温度が安定していることを確認後、重合開始剤を投入する。
そして、前記Ｓ１〜Ｓ７の処理（図２）に従って攪拌槽３の外浴温度を制御し、前記Ｓ２１〜Ｓ２６の処理（図３）に従って溶剤の滴下を制御する。図４は上記条件でポリマーの合成を行った結果、重合反応の開始から終了までの各時刻での溶剤の積算滴下量を、実験に用いた溶剤Ａ〜Ｄ毎に示した図である。 First, when the preliminary experiment 1 is performed, nitrogen is substituted by bubbling the stirring tank 3 at an arbitrary nitrogen flow rate. And after nitrogen substitution is performed for 4 hours, the nitrogen feeding from the liquid phase part is stopped, and it switches to the feeding from the gas phase part. Then, after confirming that the inner bath temperature is stable, a polymerization initiator is added.
Then, the outer bath temperature of the agitation tank 3 is controlled according to the processing of S1 to S7 (FIG. 2), and the dropping of the solvent is controlled according to the processing of S21 to S26 (FIG. 3). FIG. 4 is a graph showing the cumulative amount of solvent dripped at each time from the start to the end of the polymerization reaction for each of the solvents A to D used in the experiment as a result of polymer synthesis under the above conditions.

次に、重合時間１０分毎に反応開始から３０分までの溶剤の積算滴下量と最終の総滴下量とをプロットし、相関性が所定高さ以上（本実施形態では、決定係数Ｒ２が０．９以上）で、且つ重合反応の開始からの時間が最も早い時間を求める。図５は重合反応の開始から１０分後の溶剤の積算滴下量とその後に反応終了まで要した総滴下量を、実験に用いた溶剤Ａ〜Ｄ毎に示した図、図６は重合反応の開始から２０分後の溶剤の積算滴下量とその後に反応終了まで要した総滴下量を、実験に用いた溶剤Ａ〜Ｄ毎に示した図、図７は重合反応の開始から３０分後の溶剤の積算滴下量とその後に反応終了まで要した総滴下量を、実験に用いた溶剤Ａ〜Ｄ毎に示した図である。 Next, the cumulative drop amount of solvent and the final total drop amount from the start of reaction to 30 minutes after the start of the reaction are plotted every 10 minutes, and the correlation is not less than a predetermined level (in this embodiment, the determination coefficient R2 is 0). .9 or more) and the earliest time from the start of the polymerization reaction is obtained. FIG. 5 is a graph showing the cumulative amount of solvent added 10 minutes after the start of the polymerization reaction and the total amount of dripping required thereafter until the end of the reaction, for each of the solvents A to D used in the experiment, and FIG. FIG. 7 shows the cumulative amount of solvent dropped 20 minutes after the start and the total amount of dripping required until the end of the reaction for each of the solvents A to D used in the experiment. FIG. 7 shows the result after 30 minutes from the start of the polymerization reaction. It is the figure which showed the total dripping amount required until the completion | finish of reaction after the total dripping amount of a solvent for every solvent AD used for experiment.

先ず、重合反応開始から１０分経過時点での溶剤の積算滴下量と総滴下量の相関性について図５に基づいて求める。図５に示すように、各プロットに基づいて決定された回帰直線はｙ＝１２．９２ｘ＋２１４．９６となる。そして、実測データとの差異に基づいて算出された決定係数Ｒ２は０．３７となる。 First, the correlation between the cumulative dripping amount of the solvent and the total dripping amount after 10 minutes from the start of the polymerization reaction is determined based on FIG. As shown in FIG. 5, the regression line determined based on each plot is y = 12.92x + 214.96. The determination coefficient R2 calculated based on the difference from the actual measurement data is 0.37.

次に、重合反応開始から２０分経過時点での溶剤の積算滴下量と総滴下量の相関性について図６に基づいて求める。図６に示すように、各プロットに基づいて決定された回帰直線はｙ＝９．９０ｘ＋９７．６３となる。そして、実測データとの差異に基づいて算出された決定係数Ｒ２は０．８３となる。 Next, the correlation between the cumulative dripping amount of the solvent and the total dripping amount after 20 minutes from the start of the polymerization reaction is determined based on FIG. As shown in FIG. 6, the regression line determined based on each plot is y = 9.90x + 97.63. The determination coefficient R2 calculated based on the difference from the actual measurement data is 0.83.

更に、重合反応開始から３０分経過時点での溶剤の積算滴下量と総滴下量の相関性について図７に基づいて求める。図７に示すように、各プロットに基づいて決定された回帰直線はｙ＝５．３９ｘ＋１１０．１９となる。そして、実測データとの差異に基づいて算出された決定係数Ｒ２は０．９１となる。
従って、相関性が所定高さ以上（本実施形態では、決定係数Ｒ２が０．９以上）で、且つ重合反応の開始からの時間が最も早い時間は、重合反応開始から３０分経過時点であることが求められる。 Furthermore, the correlation between the cumulative dripping amount of the solvent and the total dripping amount after 30 minutes from the start of the polymerization reaction is determined based on FIG. As shown in FIG. 7, the regression line determined based on each plot is y = 5.39x + 110.19. The determination coefficient R2 calculated based on the difference from the actual measurement data is 0.91.
Therefore, the correlation is not less than a predetermined level (in this embodiment, the determination coefficient R2 is not less than 0.9), and the earliest time from the start of the polymerization reaction is the time when 30 minutes have elapsed from the start of the polymerization reaction. Is required.

そして、求められた時刻（重合反応開始から３０分経過時）を、上記Ｓ１１で判定される溶剤の積算滴下量を算出するタイミングである反応開始時間からの経過時刻ｔｎとする。また、このとき得られたポリマーの分子量を測定しておき、図１０に示す溶剤の総滴下量とポリマー分子量の相関から、所望の分子量が得られる最適な溶剤の総滴下量を導出する。尚、本実施形態では最適な溶剤の総滴下量が３５０ｋｇと導出されたとして、以下に事前実験２の説明を行う。 And let the calculated | required time (at the time of 30-minute progress from a polymerization reaction start) be the elapsed time tn from the reaction start time which is a timing which calculates the cumulative dripping amount of the solvent determined by said S11. Further, the molecular weight of the polymer obtained at this time is measured, and the optimum total dripping amount of the solvent for obtaining a desired molecular weight is derived from the correlation between the total dripping amount of the solvent and the polymer molecular weight shown in FIG. In the present embodiment, assuming that the optimum total amount of the solvent dropped is 350 kg, the preliminary experiment 2 will be described below.

〔事前実験２〕
事前実験２では、事前実験１と同様に図１に示す重合反応制御装置１を用い、温度の異なる４種類の溶剤Ａ〜Ｄ（溶剤Ａ：１５℃、溶剤Ｂ：２０℃、溶剤Ｃ：２５℃、溶剤Ｄ：３０℃）を滴下することにより攪拌槽３の内浴温度を調整し、攪拌槽３内にあるモノマー混合物を重合反応させ、ポリマーを合成することにより行う。尚、攪拌槽３の外浴温度は既に説明したＳ１〜Ｓ７の処理（図２）に従って制御部５により制御される。また、溶剤の滴下は既に説明したＳ２１〜Ｓ２６の処理（図３）に従って制御部５により制御される。
更に、事前実験２における攪拌槽３の外浴温度の制御については、事前実験１で求めたｔｎの時刻（重合反応開始から３０分経過時）で、以降の攪拌槽３の外浴の設定温度を−４℃、−２℃、±０、＋２℃、＋４℃変更する。
ここで、図８は上記条件でポリマーの合成を行った結果、重合反応開始からｔｎ（３０分）経過時点での外浴温度変化量と重合反応の終了までに要した溶剤の総滴下量を、実験に用いた溶剤Ａ〜Ｄ毎に示した図である。 [Preliminary experiment 2]
In the preliminary experiment 2, similarly to the preliminary experiment 1, the polymerization reaction control apparatus 1 shown in FIG. 1 is used, and four types of solvents A to D (solvent A: 15 ° C., solvent B: 20 ° C., solvent C: 25 having different temperatures) are used. C., solvent D: 30.degree. C.) is added dropwise to adjust the inner bath temperature of the stirring tank 3, polymerize the monomer mixture in the stirring tank 3, and synthesize the polymer. In addition, the outer bath temperature of the stirring tank 3 is controlled by the control part 5 according to the process (FIG. 2) of S1-S7 already demonstrated. Further, the dropping of the solvent is controlled by the control unit 5 in accordance with the processes of S21 to S26 already described (FIG. 3).
Further, regarding the control of the outer bath temperature of the stirring tank 3 in the preliminary experiment 2, the set temperature of the outer bath of the subsequent stirring tank 3 at the time of tn obtained in the preliminary experiment 1 (30 minutes after the start of the polymerization reaction). Are changed by -4 ° C, -2 ° C, ± 0, + 2 ° C, and + 4 ° C.
Here, FIG. 8 shows the result of synthesizing the polymer under the above conditions. As a result, the amount of change in the outer bath temperature after the start of the polymerization reaction and the total dripping amount of the solvent required until the end of the polymerization reaction are shown. It is the figure shown for every solvent AD used for experiment.

先ず、図８に基づいて溶剤Ａを用いた場合の各プロットを参照し、回帰直線を求めると、ｙ＝１９．５ｘ＋２７２．８となる。そして、回帰直線に基づいて最適な溶剤の総滴下量である３５０ｋｇを滴下する為の外浴の温度変化を以下の演算式（２）で求める。
（３５０−２７２．８）／１９．５＝３．９６[℃]・・・（２）
従って、溶剤Ａを用いた場合にはｔｎ経過時点で以降の外浴温度を３．９６℃上昇させることにより、重合反応の終了までに要する溶剤の総滴下量を３５０ｋｇとすることが可能であることが分かる。 First, referring to each plot in the case of using the solvent A based on FIG. 8 and finding a regression line, y = 19.5x + 272.8. Then, based on the regression line, the temperature change of the outer bath for dropping 350 kg which is the optimum total dripping amount of the solvent is obtained by the following calculation formula (2).
(350-272.8) /19.5=3.96 [° C.] (2)
Therefore, when the solvent A is used, the total amount of the solvent required to complete the polymerization reaction can be 350 kg by increasing the subsequent bath temperature by 3.96 ° C. after elapse of tn. I understand that.

次に、図８に基づいて溶剤Ｂを用いた場合の各プロットを参照し、回帰直線を求めると、ｙ＝２０．３ｘ＋３１１．０となる。そして、回帰直線に基づいて最適な溶剤の総滴下量である３５０ｋｇを滴下する為の外浴の温度変化を以下の演算式（３）で求める。
（３５０−３１１．０）／２０．３＝１．９２[℃]・・・（３）
従って、溶剤Ｂを用いた場合にはｔｎ経過時点で以降の外浴温度を１．９２℃上昇させることにより、重合反応の終了までに要する溶剤の総滴下量を３５０ｋｇとすることが可能であることが分かる。 Next, referring to each plot in the case of using the solvent B based on FIG. 8, the regression line is obtained, and y = 20.3x + 311.0. Then, based on the regression line, the temperature change of the outer bath for dropping 350 kg which is the optimum total dripping amount of the solvent is obtained by the following arithmetic expression (3).
(350-311.0) /20.3=1.92 [° C.] (3)
Therefore, when the solvent B is used, the total amount of the solvent required to complete the polymerization reaction can be 350 kg by raising the subsequent outer bath temperature by 1.92 ° C. after the time tn has elapsed. I understand that.

次に、図８に基づいて溶剤Ｃを用いた場合の各プロットを参照し、回帰直線を求めると、ｙ＝２６．３ｘ＋３７０．０となる。そして、回帰直線に基づいて最適な溶剤の総滴下量である３５０ｋｇを滴下する為の外浴の温度変化を以下の演算式（４）で求める。
（３５０−３７０．０）／２６．３＝−０．７６[℃]・・・（４）
従って、溶剤Ｃを用いた場合にはｔｎ経過時点で以降の外浴温度を０．７６℃下降させることにより、重合反応の終了までに要する溶剤の総滴下量を３５０ｋｇとすることが可能であることが分かる。 Next, referring to each plot when the solvent C is used based on FIG. 8, the regression line is obtained, and y = 26.3x + 370.0. Then, based on the regression line, the temperature change of the outer bath for dropping 350 kg which is the optimum total dropping amount of the solvent is obtained by the following calculation formula (4).
(350−370.0) /26.3=−0.76 [° C.] (4)
Therefore, when the solvent C is used, the total amount of the solvent required to complete the polymerization reaction can be reduced to 350 kg by lowering the subsequent outer bath temperature by 0.76 ° C. at the time when tn has elapsed. I understand that.

更に、図８に基づいて溶剤Ｄを用いた場合の各プロットを参照し、回帰直線を求めると、ｙ＝２４．１ｘ＋３９７．３となる。そして、回帰直線に基づいて最適な溶剤の総滴下量である３５０ｋｇを滴下する為の外浴の温度変化を以下の演算式（５）で求める。
（３５０−３９７．３）／２４．１＝−１．９６[℃]・・・（５）
従って、溶剤Ｃを用いた場合にはｔｎ経過時点で以降の外浴温度を１．９６℃下降させることにより、重合反応の終了までに要する溶剤の総滴下量を３５０ｋｇとすることが可能であることが分かる。 Further, referring to each plot when the solvent D is used based on FIG. 8, the regression line is obtained and y = 24.1x + 397.3. Then, based on the regression line, the temperature change of the outer bath for dropping 350 kg which is the optimum total dropping amount of the solvent is obtained by the following arithmetic expression (5).
(350-397.3) /24.1=-1.96 [° C.] (5)
Therefore, when the solvent C is used, the total amount of the solvent required to complete the polymerization reaction can be reduced to 350 kg by lowering the subsequent outer bath temperature by 1.96 ° C. after the time tn has elapsed. I understand that.

次に、この最適な溶剤の総滴下量（３５０ｋｇ）となる外浴の温度制御量ΔＳＶとｔｎ経過時（重合反応開始から３０分経過時）での溶剤の積算滴下量をプロットする。図９は溶剤の総滴下量を３５０ｋｇとする為の外浴の温度制御量ΔＳＶと重合反応開始から３０分経過時での溶剤の積算滴下量を、実験に用いた溶剤Ａ〜Ｄ毎に示した図である。 Next, the temperature control amount ΔSV of the outer bath to be the optimum total dripping amount of the solvent (350 kg) and the cumulative dripping amount of the solvent when tn has elapsed (30 minutes after the start of the polymerization reaction) are plotted. FIG. 9 shows the temperature control amount ΔSV of the outer bath for setting the total dripping amount of the solvent to 350 kg and the cumulative dripping amount of the solvent after 30 minutes from the start of the polymerization reaction for each of the solvents A to D used in the experiment. It is a figure.

ここで、図９に基づいて各溶剤Ａ〜Ｄのプロットを参照し、回帰直線を求めると、ｙ＝−０．２８５ｘ＋１２．５５５となる。この式が上記（１）の演算式に相当するものであり、重合反応開始からｔｎ経過時点での積算滴下量を代入することにより、ｔｎ経過時点で行う外浴の温度制御量ΔＳＶを算出することが可能となる。 Here, referring to the plots of the respective solvents A to D based on FIG. 9, the regression line is obtained, and y = −0.285x + 12.555. This equation corresponds to the above equation (1), and the temperature control amount ΔSV of the outer bath performed at the time point tn is calculated by substituting the integrated dripping amount at the time point tn after the start of the polymerization reaction. It becomes possible.

従って、以上に説明した事前実験１により、図２のＳ１１で判定される溶剤の積算滴下量を算出するタイミングである反応開始時間からの経過時刻ｔｎが求まり、事前実験２により、Ｓ１３で外浴温度の制御量を算出する際に用いる上記（１）の演算式が求まる。 Therefore, by the preliminary experiment 1 described above, an elapsed time tn from the reaction start time, which is the timing for calculating the cumulative dripping amount of the solvent determined in S11 of FIG. 2, is obtained. The arithmetic expression (1) used when calculating the temperature control amount is obtained.

以上詳細に説明した通り、本実施形態に係る重合反応制御装置１及び重合反応制御方法では、重合開始剤が攪拌槽３に投入され、重合反応が開始されたことを確認したと同時に制御部５による重合反応の制御を開始する。重合反応の制御では、重合反応の開始からｔｎ（本実施形態では３０分）が経過した際に、ｔｎ経過時点での溶剤の積算滴下量ｎ[kg]を算出し（Ｓ１２）、更に算出した積算滴下量ｎを予め事前実験１、２を行うことにより求めた演算式（１）に代入することによって、外浴の温度の制御量ΔＳＶを算出する（Ｓ１３）。そして、算出したΔＳＶを設定温度に加算した温度により、それ以後の外浴の温度を設定する（Ｓ１４）とことにより、反応終了までに滴下される溶剤の総滴下量を予め設定した目標値とするので、重合途中の溶剤の積算滴下量により、溶存酸素濃度等の各種バラツキ要因による反応への影響度を代替的に定量化することができる。更に、反応終了時の総滴下量を予測することにより、重合反応の再現性を向上させつつポリマーの物性（分子量）のバラつきを防止することができる。
また、事前実験１、２では異なる温度の複数種類の溶剤Ａ〜Ｄを用いて重合反応を行い、重合開始から所定時間後に外浴温度を変更し、用いた溶剤の種類毎に変更した外浴温度の温度差と重合反応終了までの総滴下量とをそれぞれ算出し、目標の総滴下量となる温度差と外浴温度の変更時点までの溶剤の積算滴下量との関係から外浴の温度の制御量を求める。それにより、外浴温度の制御を行うことにより溶剤の総滴下量を常に一定範囲内に抑えることができ、所望のポリマー物性を得ることが可能となる。
更に、事前実験１、２では異なる温度の複数種類の溶剤を用いて重合反応を行い、用いた溶剤の種類毎に重合開始から所定時間毎の溶剤の積算滴下量と重合反応終了までの総滴下量との相関を求め、相関が所定高さ以上で且つ重合開始から最も早いタイミングを溶剤の積算滴下量を算出するタイミングとして求める。それにより、外浴温度の制御を行う際に外浴の温度設定幅を小さくでき、オーバーシュート等の制御による外乱の影響を小さくできる。 As described above in detail, in the polymerization reaction control device 1 and the polymerization reaction control method according to the present embodiment, the control unit 5 simultaneously confirms that the polymerization initiator is charged into the stirring tank 3 and the polymerization reaction is started. Control of the polymerization reaction is started. In the control of the polymerization reaction, when tn (30 minutes in the present embodiment) has elapsed from the start of the polymerization reaction, the cumulative drop amount n [kg] of the solvent at the time tn has been calculated (S12) and further calculated. By substituting the integrated dropping amount n into the arithmetic expression (1) obtained by performing the preliminary experiments 1 and 2 in advance, the control amount ΔSV of the temperature of the outer bath is calculated (S13). Then, by setting the calculated ΔSV to the set temperature, the temperature of the outer bath thereafter is set (S14), so that the total amount of solvent dripped before the end of the reaction is set to a preset target value. Therefore, the degree of influence on the reaction due to various variation factors such as dissolved oxygen concentration can be quantified alternatively by the cumulative amount of solvent dropped during the polymerization. Furthermore, by predicting the total dropping amount at the end of the reaction, it is possible to prevent variations in the physical properties (molecular weight) of the polymer while improving the reproducibility of the polymerization reaction.
In the preliminary experiments 1 and 2, the polymerization reaction is performed using a plurality of types of solvents A to D at different temperatures, the outer bath temperature is changed after a predetermined time from the start of polymerization, and the outer bath is changed for each type of solvent used. Calculate the temperature difference of the temperature and the total dripping amount until the end of the polymerization reaction, and calculate the temperature of the outer bath from the relationship between the temperature difference that becomes the target total dripping amount and the cumulative dripping amount of the solvent until the change of the outer bath temperature. Determine the amount of control. Thereby, by controlling the outer bath temperature, the total dripping amount of the solvent can always be kept within a certain range, and desired polymer physical properties can be obtained.
Furthermore, in the preliminary experiments 1 and 2, the polymerization reaction is performed using a plurality of types of solvents at different temperatures, and for each type of solvent used, the total amount of solvent dropped from the start of polymerization to the end of the polymerization reaction every predetermined time. The correlation with the amount is obtained, and the earliest timing at which the correlation is equal to or higher than a predetermined height and the start of polymerization is obtained as the timing for calculating the cumulative amount of solvent dripped. Thereby, the temperature setting range of the outer bath can be reduced when controlling the outer bath temperature, and the influence of disturbance due to control of overshoot and the like can be reduced.

尚、本発明は前記実施形態に限定されるものではなく、本発明の要旨を逸脱しない範囲内で種々の改良、変形が可能であることは勿論である。
例えば、本実施形態では事前実験１で溶剤の積算滴下量を算出するタイミングを求める際に、溶剤の積算滴下量と総滴下量の相関性を示す決定係数Ｒ^２が０．９以上であることを条件としたが、決定係数Ｒ^２が０．８以上であることを条件としても良い。 Note that the present invention is not limited to the above-described embodiment, and various improvements and modifications can be made without departing from the scope of the present invention.
For example, when the present embodiment to determine the timing to calculate the cumulative dropping amount of the solvent in the pre Experiment 1, it determines the coefficient R ² indicating the correlation of the integrated dropwise and total dropping amount of the solvent is 0.9 or more the was a condition may be the condition that the coefficient of determination R ² is 0.8 or more.

本実施形態に係る重合反応制御装置の要部を示す概略側面図である。It is a schematic side view which shows the principal part of the polymerization reaction control apparatus which concerns on this embodiment. 本実施形態に係る重合反応制御装置の攪拌槽の外浴温度制御プログラムのフローチャートである。It is a flowchart of the outer bath temperature control program of the stirring tank of the polymerization reaction control device according to the present embodiment. 本実施形態に係る重合反応制御装置の溶剤の滴下制御プログラムのフローチャートである。It is a flowchart of the dripping control program of the solvent of the polymerization reaction control apparatus which concerns on this embodiment. 事前実験１で重合反応の開始から終了までの各時刻での溶剤の積算滴下量を、実験に用いた溶剤Ａ〜Ｄ毎に示した図である。It is the figure which showed the cumulative dripping amount of the solvent at each time from the start of a polymerization reaction to completion | finish in the prior experiment 1 for every solvent AD used for experiment. 事前実験１で重合反応の開始から１０分後の溶剤の積算滴下量とその後に反応終了まで要した総滴下量を、実験に用いた溶剤Ａ〜Ｄ毎に示した図である。It is the figure which showed the integrated dripping amount of the solvent 10 minutes after the start of the polymerization reaction in the prior experiment 1, and the total dripping amount required until the completion of the reaction for each of the solvents A to D used in the experiment. 事前実験１で重合反応の開始から２０分後の溶剤の積算滴下量とその後に反応終了まで要した総滴下量を、実験に用いた溶剤Ａ〜Ｄ毎に示した図である。It is the figure which showed the integrated dripping amount of the solvent 20 minutes after the start of the polymerization reaction in the prior experiment 1, and the total dripping amount required until the completion of the reaction for each of the solvents A to D used in the experiment. 事前実験１で重合反応の開始から３０分後の溶剤の積算滴下量とその後に反応終了まで要した総滴下量を、実験に用いた溶剤Ａ〜Ｄ毎に示した図である。It is the figure which showed the integrated dripping amount of the solvent 30 minutes after the start of a polymerization reaction in prior experiment 1, and the total dripping amount required until the completion of reaction for every solvent AD used for experiment. 事前実験２で重合反応開始から３０分経過時点での外浴温度変化と重合反応の終了までに要した溶剤の総滴下量を、実験に用いた溶剤Ａ〜Ｄ毎に示した図である。It is the figure which showed the total dripping amount of the solvent required for the external bath temperature change and the completion | finish of a polymerization reaction at the time of 30-minute progress in the prior experiment 2 for every solvent AD used for experiment. 事前実験２で溶剤の総滴下量を３５０ｋｇとする為の外浴の温度変化ΔＳＶと重合反応開始から３０分経過時での溶剤の積算滴下量を、実験に用いた溶剤Ａ〜Ｄ毎に示した図である。The temperature change ΔSV of the outer bath and the cumulative amount of solvent dripping after 30 minutes from the start of the polymerization reaction are shown for each of the solvents A to D used in the experiment in order to set the total dripping amount of the solvent to 350 kg in the preliminary experiment 2. It is a figure. 重合に用いた溶剤の総滴下量と生成されたポリマー分子量の相関を示した図である。It is the figure which showed the correlation of the total dripped amount of the solvent used for superposition | polymerization, and the produced | generated polymer molecular weight.

１重合反応制御装置
２攪拌機
３攪拌槽
４滴下槽
５制御部
９ジャケット DESCRIPTION OF SYMBOLS 1 Polymerization reaction control apparatus 2 Stirrer 3 Stirrer tank 4 Dripping tank 5 Control part 9 Jacket

Claims

Polymerization reaction control method for controlling the polymerization reaction by controlling the outer bath temperature of the stirring tank and dropping the solvent into the stirring tank in the course of synthesizing the polymer by the polymerization reaction by introducing the monomer mixture into the stirring tank In
Calculate the cumulative dropping amount of the solvent from the start of polymerization at a predetermined timing during the polymerization reaction,
Control the temperature of the outer bath based on the calculated cumulative amount of solvent dripped so that a preset total amount of solvent dripped by the end of the polymerization reaction ,
The timing for calculating the cumulative dripping amount of the solvent is as follows:
A polymerization reaction is performed using a plurality of types of the solvents having different temperatures, and the correlation between the total amount of the solvent dropped from the start of polymerization to the end of the polymerization reaction and the completion of the polymerization reaction is determined for each type of the solvent used. When asked
The polymerization reaction control method, wherein the correlation is equal to or higher than a predetermined height and the earliest timing from the start of polymerization is set as the timing for calculating the cumulative amount of the solvent .

In the polymerization reaction control method according to claim 1,
A control amount of the temperature of the outer bath based on the cumulative dripping amount of the solvent is determined as follows.
A polymerization reaction is performed using a plurality of types of solvents at different temperatures, the outer bath temperature is changed after a predetermined time from the start of polymerization, and the temperature difference between the outer bath temperature changed for each of the used solvents and the end of the polymerization reaction are changed. Calculate the total dripping amount,
A polymerization reaction control method characterized in that a control amount of a temperature of an outer bath is obtained from a relationship between a temperature difference that becomes a target total dripping amount and an integrated dripping amount of a solvent up to a change time of the outer bath temperature.

A stirring tank for stirring the monomer mixture;
Outer bath temperature control means for controlling the temperature of the outer bath of the stirring tank;
Dropping means for dropping the solvent into the stirring tank,
In the process of putting the monomer mixture into the stirring tank and synthesizing the polymer by the polymerization reaction, the outer bath temperature is controlled by the outer bath temperature control means, and the solvent is dropped into the stirring tank by the dropping means. In the polymerization reaction control device for controlling the reaction,
A dropping amount calculating means for calculating the cumulative dropping amount of the solvent from the start of polymerization at a predetermined timing during the polymerization reaction;
The outer bath temperature control means controls the temperature of the outer bath based on the cumulative drop amount of the solvent calculated by the drop amount calculation means so as to drop a preset total drop amount of the solvent by the end of the polymerization reaction. And
The timing for calculating the cumulative amount of solvent dripped by the dripping amount calculating means is as follows:
A polymerization reaction is performed using a plurality of types of the solvents having different temperatures, and the correlation between the total amount of the solvent dropped from the start of polymerization to the end of the polymerization reaction and the completion of the polymerization reaction is determined for each type of the solvent used. When asked
The polymerization reaction control apparatus characterized in that the correlation is equal to or higher than a predetermined height and the earliest timing from the start of polymerization is set as the timing for calculating the cumulative dripping amount of the solvent .

In the polymerization reaction control device according to claim 3 ,
Obtaining the control amount of the temperature of the outer bath based on the cumulative dripping amount of the solvent by the outer bath temperature control means as follows:
A polymerization reaction is performed using a plurality of types of solvents at different temperatures, the outer bath temperature is changed after a predetermined time from the start of polymerization, and the temperature difference between the outer bath temperature changed for each of the used solvents and the end of the polymerization reaction are changed. Calculate the total dripping amount,
A polymerization reaction control apparatus for obtaining a control amount of a temperature of an outer bath from a relationship between a temperature difference that becomes a target total dripping amount and an accumulated dripping amount of a solvent up to a change time of the outer bath temperature.