JP4711806B2 - Polymer production method and apparatus thereof - Google Patents

Description

  The present invention relates to a polymer production method and an apparatus therefor, and more particularly to a technique for efficiently producing a polymer having an arbitrary molecular weight distribution and gel fraction.

  Conventionally, the following methods have been proposed and implemented in order to obtain a predetermined molecular weight distribution and gel fraction in the course of producing a polymer.

  In the process of producing a polymer by adding a monomer and an initiator to a stirrer, a predetermined amount of a solvent is dropped into a stirring tank to control the polymerization temperature. For example, the actual value of the polymerization temperature in the stirring tank and the actual value of the temperature of the cooling water that has passed through the jacket, which is a cooling means attached to the stirring tank, are detected during the polymer production process, and the deviation between these actual value and the target value. Ask for. When the obtained deviation exceeds a predetermined reference value, a fixed amount of fixed solvent is dropped into the tank (for example, see Patent Document 1).

JP 2003-040910 A

  However, the conventional method has the following problems.

  That is, only the polymerization temperature in the stirring tank is monitored after the polymerization reaction is started, and the state in which the reaction of the polymerization reaction changes is not taken into consideration. That is, even when the polymerization temperature is the same, the reaction rate of the polymerization reaction varies from time to time, and the reaction may be intense or mild. When the polymerization reaction is intense as described above, the polymerization temperature continues to rise without being able to suppress the polymerization reaction even if a fixed amount of the fixed solvent is dropped into the stirring tank. Further, when the polymerization reaction is gentle, the polymerization reaction is excessively suppressed and the polymerization temperature is lowered. Therefore, since the reaction rate cannot be controlled with high accuracy, there is a problem that the polymerization temperature eventually changes so much that the molecular weight distribution and the gel fraction of the polymer vary and the product characteristics are not stable.

  The present invention has been made in view of such circumstances, and provides a polymer production method and apparatus capable of efficiently producing a high-quality polymer having a target molecular weight distribution and gel fraction. The main purpose is to provide.

Accordingly, the present invention has the following configuration in order to achieve such an object.
That is, the first invention is a polymer production method for producing a polymer by performing a polymerization reaction while introducing and mixing an initiator into a monomer previously charged in a tank,
With respect to a reference reaction rate at the time of a polymerization reaction determined in advance according to the polymer to be manufactured, a dripping amount of a solvent that suppresses the polymerization reaction so that the actual reaction rate of the polymer manufacturing process matches the reference reaction rate is as follows: It is adjusted in the manner of,
The actual reaction rate during the polymerization reaction is an internal bath temperature gradient indicating a change in the calorific value per unit time in the tank,
The actual polymerization temperature in the tank is detected by the temperature detection means, and a temperature deviation is determined from the actual polymerization temperature and a reference polymerization temperature determined in advance according to the polymer to be manufactured, and the calorific value per unit time at the actual polymerization temperature. A first process for determining an actual bath temperature gradient indicating a change in
A second step of determining a theoretical bath temperature gradient for correcting the actual bath temperature gradient including the temperature deviation to a reference inner bath temperature gradient indicated by a reference polymerization temperature;
A third step of obtaining a target internal bath temperature gradient change amount from a difference between the theoretical internal bath temperature gradient and the actual internal bath temperature gradient;
Corresponding to the target inner bath temperature gradient change amount based on the correlation function of each polymerization temperature including a plurality of temperature deviations with respect to the reference polymerization temperature and the drop amount of the solvent predetermined in accordance with the inner bath temperature gradient change amount. A fourth process for determining the amount of solvent dripping;
A fifth step of dropping a predetermined amount of the solvent obtained in the fourth step into the tank;
It is characterized by performing by.

(Operation / Effect) According to the present invention, in the process of producing the polymer to be produced, the actual reaction rate is controlled to match the reference reaction rate by adjusting the dropping amount of the solvent that suppresses the polymerization reaction. . As a result, a rapid increase or decrease in the polymerization temperature is suppressed. That is, a high-quality polymer having a target gel fraction can be produced accurately and efficiently.
That is, the actual reaction rate at the time of the polymerization reaction is determined, and the theoretical reaction rate change rate necessary for correcting the actual reaction rate to return to the reference reaction rate is determined. Further, a target reaction rate change rate obtained by removing the influence of the actual reaction rate change rate from the theoretical reaction rate change rate is obtained. That is, the reaction component used for further positively conducting the polymerization reaction from the time when the actual reaction rate is obtained is removed. That is, this target reaction rate change rate allows for a delay time from when the solvent is dropped into the tank until the reaction rate decreases. Then, by calculating the amount of solvent dripping according to this target reaction change rate from the correlation function, the reaction rate is estimated with the expectation of the delay time until the reaction rate drops from the solvent dripping and the future reaction rate increase. It is possible to determine the amount of solvent that can be suppressed so as to match the reference reaction rate.

According to a second invention, in the first invention, for each polymer to be produced, dripping of a solvent necessary to correct the actual internal bath temperature gradient when the reference polymerization temperature is changed to the reference internal bath temperature gradient. The amount of the solvent was determined in advance by repeating the first to fourth steps, and the amount of the solvent dropped in accordance with the actual polymerization temperature and the actual bath temperature gradient detected in the polymer production process was determined in advance. Selection is made with reference to the amount of the solvent dropped, and a predetermined amount of the solvent is dropped into the tank.

(Operation / Effect) According to the present invention, for each polymer to be produced, the dripping amount of the solvent required to correct the actual internal bath temperature gradient when the standard polymerization temperature is changed to the standard internal bath temperature gradient is changed. It is preferable that the first process to the fourth process are repeatedly performed to obtain in advance. By determining the amount of solvent added in advance, in the process of polymer production, the optimum solvent addition to match the actual reaction rate to the reference reaction rate is obtained simply by determining the actual polymerization temperature and the actual bath temperature gradient. The amount can be obtained accurately in a short time.

A fourth invention is a polymer production apparatus for producing a polymer by carrying out a polymerization reaction while mixing an initiator with a monomer,
A stirrer that stirs so as to mix the monomer and the initiator charged in the stirring tank;
A solvent dropping means for storing a solvent for suppressing the polymerization reaction in the stirring tank and dropping the solvent into the stirring tank;
Storage means for storing correlation data between the rate of change of the reaction rate that changes during the polymerization reaction of the polymer to be produced, and the amount of solvent added to correct each reaction rate having the rate of change to the reference reaction rate;
Detection means for detecting a physical quantity resulting from the reaction rate of the polymerization reaction in the stirring tank;
Based on the physical quantity detected by the detection means, a change amount of the reaction rate is obtained, and a calculation means for obtaining a dripping amount of the solvent according to the obtained change amount from the storage means;
Control means for operating the solvent dropping means to drop the solvent dropping amount obtained by the calculating means into the stirring tank;
The control means obtains the dripping amount of the solvent as follows.
The reaction rate is an inner bath temperature gradient indicating a change in the calorific value per unit time in the stirring tank during the polymerization reaction,
The physical quantity detected by the detection means is a polymerization temperature in the stirring tank,
The correlation data stored in the storage means uses the inner bath temperature gradient when the reference polymerization temperature determined for each polymer to be manufactured is changed,
(A) The actual polymerization temperature in the tank is detected by the detection means, and a temperature deviation is obtained from the actual polymerization temperature and a reference polymerization temperature determined in advance according to the polymer to be manufactured, and per unit time at the actual polymerization temperature. The actual bath temperature gradient showing the change in calorific value of
(B) obtaining a theoretical internal bath temperature gradient for correcting the actual internal bath temperature gradient including the temperature deviation to a standard internal bath temperature gradient indicated by a standard polymerization temperature;
(C) A target internal bath temperature gradient change amount is obtained from a difference between the theoretical internal bath temperature gradient and the actual internal bath temperature gradient,
(D) Based on a correlation function of each polymerization temperature including a plurality of temperature deviations with respect to the reference polymerization temperature and a drop amount of the solvent predetermined in accordance with the amount of change in the inner bath temperature gradient, the target inner bath temperature gradient change amount Find the amount of solvent dripping corresponding to
(E) The above (a) to (d) are repeatedly performed to form data and stored in the storage means .

  (Operation / Effect) According to the present invention, the stirrer stirs so as to mix the monomer and the initiator charged in the stirring tank. The solvent dropping means stores a solvent that suppresses the polymerization reaction in the stirring tank, and drops the solvent in the stirring tank. The storage means stores correlation data between the rate of change of the reaction rate that changes during the polymerization reaction of the polymer to be produced and the amount of solvent dripping required to correct each reaction rate having the rate of change to the reference reaction rate. . A detection means detects the physical quantity resulting from the reaction rate of the polymerization reaction in a stirring tank. The calculation means obtains the change amount of the reaction rate based on the physical quantity detected by the detection means, and obtains the dripping amount of the solvent according to the obtained change amount from the storage means. The control means operates the solvent dropping means to drop the solvent dropping amount obtained by the calculating means to the stirring tank. That is, according to this configuration, an optimum amount of the solvent dropped according to the change in the reaction rate is obtained, and the reaction rate is controlled to become the reference reaction rate by dropping this solvent. Therefore, a high quality polymer having a target gel fraction and the like can be produced. That is, the first invention method can be suitably realized.

  In the polymer production method and apparatus according to the present invention, in the course of producing the polymer to be produced, the actual reaction rate can be matched with the reference reaction rate by adjusting the dropping amount of the solvent that suppresses the polymerization reaction. The rise and fall of the polymerization temperature can be accurately suppressed. That is, a polymer having a target gel fraction and molecular weight distribution can be produced accurately and efficiently.

  In this example, when producing the polymer to be produced, the reference reaction rate of the polymerization reaction that serves as a reference is determined, and the solvent is added dropwise to suppress the actual reaction rate during the polymerization reaction so as to maintain the reference reaction rate. A method for adjusting the amount and making it possible to produce a polymer having an arbitrary gel fraction and molecular weight distribution will be described.

  In this embodiment, a case where a polymer is synthesized by batch polymerization by emulsion polymerization will be described as an example.

  For example, butyl acrylate (BA), acrylic acid (AA), or the like is used as a monomer used for emulsion polymerization.

  An azo initiator is used as the initiator. Examples of the azo initiator include 2,2-azobisisobutyronitrile, 2,2-azobis (2-amidinopropane) dihydrochloride, and 2,2′-azobis (N, N′dimethyleneisobutylamidine). And dihydrochloride, 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, azobis (2-methylproionamidine), and the like.

  Examples of the solvent include ethyl acetate.

  Hereinafter, a specific method will be described.

  First, manufacturing conditions (polymerization conditions) for manufacturing a polymer to be manufactured are determined. For example, the standard polymerization temperature is determined for each polymer to be produced, and the reaction rate used as a reference for the polymerization reaction (hereinafter referred to as “reference reaction rate” as appropriate) is determined as the change in the calorific value per unit time in the stirring tank. It is obtained through experiments and simulations.

  In this example, 900 kg of BA as a monomer and 300 kg of ethyl acetate as a solvent were charged in a stirrer equipped with a 3000 L (liter) stirring tank in advance, and the reference polymerization temperature was set to 57.8 ° C. The case of producing a polymer will be described as an example.

  In the production of this polymer, a polymerization reaction is started while mixing a monomer and a solvent previously charged in a stirring tank by rotating a stirring blade. Then, when the inside of the stirring tank reaches a predetermined polymerization temperature, the initiator is charged. Thereafter, a predetermined amount of a solvent is dropped according to the actual polymerization temperature detected when the actual polymerization temperature in the stirring vessel changes with respect to a reference polymerization temperature determined in advance in the polymerization reaction process. In this production process, the actual polymerization temperature in the stirring tank is monitored by a sensor.

  First, before producing the polymer to be produced, the production experiment of the same polymer as the production object is performed, and the inner bath temperature in the stirring tank, that is, the actual polymerization temperature is changed with respect to the preset reference polymerization temperature. The relationship between the amount of dripping when a different amount of solvent is dropped with respect to each polymerization temperature and the amount of heat generated per unit time in the stirring vessel (internal bath temperature gradient change amount) is obtained in advance. In the case of this example, 6 kg, 8 kg, and 11 kg of solvent are dropped to each polymerization temperature. The experimental result is as shown in FIG.

  Further, in this experimental process, as shown in FIG. 2, when the polymerization reaction is started, the polymerization temperature rises, approximates a predetermined reference polymerization temperature, and tends to further increase. That is, it can be seen that the polymerization reaction is promoted, the amount of heat generated per unit time is increased, and the reaction rate is increased. Therefore, in this example, in this reaction process, the inner bath temperature gradient of the stirring tank obtained from the actual polymerization temperature as the reaction rate shown in the practice of FIG. 2 is a reference obtained from a change in the reference polymerization temperature determined in advance by experiments or the like. A predetermined amount of solvent is dropped into the stirring tank so as to coincide with the inner bath temperature gradient.

  In this example, as the change in the reaction rate at the time of dropping the solvent, the calorific value that changes per unit time in the stirring tank is used to obtain the change in the inner bath temperature gradient shown in FIG. Furthermore, using the group of data shown in FIG. 1, as shown in FIG. 3, the relationship with the inner bath temperature that changes in accordance with the change in the inner bath temperature gradient after the dropping of the solvent can be obtained. The relationship is expressed by the following formula (1).

V = 3.1151X ₁ +0.7664 (1)

  Here, the detection result of the actual polymerization temperature in the stirring tank is 59 ° C., and the actual bath temperature gradient V = + 0.2 ° C./determined from the change in the calorific value per unit time when this actual polymerization temperature is detected. The process for obtaining the dripping amount of the solvent necessary for correcting the actual reaction rate in the case of min to the reference reaction rate will be specifically described. The process of detecting the actual polymerization temperature in the agitation tank with a sensor to determine the amount of change in the calorific value per unit time, and further determining the actual bath temperature gradient from this amount of change is the first step of the present invention. included.

<Step S1>
The theoretical bath temperature gradient for correcting the actual reaction rate to the reference reaction rate is obtained. Here, first, a temperature deviation between the reference polymerization temperature and the actual polymerization temperature is obtained. In this case, since the standard polymerization temperature = 57.8 ° C. and the actual polymerization temperature = 59 ° C., the temperature deviation = −1.2 (° C.) from the difference.

Then, using the obtained temperature deviation the above formula (1) Find the theoretical in-bath temperature gradient X _1. In this case, since V = −1.2, the theoretical bath temperature gradient X ₁ = −0.631. The process for obtaining the temperature deviation is included in the first process of the present invention, and the process for obtaining the theoretical bath temperature gradient corresponds to the second process of the present invention.

<Step S2>
When the actual reaction rate is obtained, the actual polymerization temperature exceeds the reference polymerization temperature, so that the polymerization reaction is actively performed and the reaction rate is increased. Here, it is possible to calculate the dropping amount of the solvent based on the theoretical bath temperature gradient obtained in Step 1 and drop it into the stirring tank, but even if the solvent is dropped into the stirring tank, FIG. As shown in FIG. 4, a delay time H occurs from the dropping point D1 until the solvent acts to suppress the reaction rate. Therefore, in this step S2, the reaction component of the polymerization reaction that can occur during the time delay is predicted, and the target internal bath temperature gradient change amount that can remove this reaction component is obtained from the relationship shown in the following equation (2).

  Target bath temperature gradient change = theoretical bath temperature gradient-actual bath temperature gradient (2)

  Therefore, in this embodiment, the theoretical internal bath temperature gradient = −0.631 and the actual internal bath temperature gradient = 0.2, so that the target internal bath temperature gradient change amount = −0.831. That is, the amount of change shown in FIG. 4 from the time when the solvent is dropped to the time when the inner bath temperature gradient has been lowered is obtained. Step S2 corresponds to the third process of the present invention.

<Step S3>
In this step, a correlation function of the dripping amount of the solvent necessary for obtaining the target inner bath temperature gradient change amount according to the change of the inner bath temperature is obtained. For this correlation, the data shown in FIG. 1 acquired in the course of the experiment is used to obtain the relationship shown in FIG. When this actual polymerization temperature was 59 ° C., the function was y = −15.695X ₂ −4.762. Here, y is the dripping amount of the solvent, and X ₂ is the target inner bath temperature gradient change amount. Therefore, when the target internal bath temperature gradient change amount y = −0.831, the solvent dripping amount X ₂ = 8.22 kg. As described above, the dripping amount of the solvent necessary to correct the actual reaction rate at the time when the actual polymerization temperature is detected to the reference reaction rate is obtained.

  Next, a polymer production apparatus capable of realizing the above-described embodiment method will be described.

  FIG. 6 is a schematic configuration diagram illustrating a stirrer that is a polymer manufacturing apparatus according to the present embodiment and a peripheral configuration thereof.

  As shown in FIG. 10, the example apparatus includes a stirrer 1 for synthesizing a polymer from a monomer mixture composed of a monomer and an initiator that are roughly divided, and a solvent storage unit 3 for dropping the solvent into a stirring tank 2 constituting the stirrer 1. , A control unit 4 that comprehensively controls the entire polymerization apparatus including the amount of oxygen present in the agitation tank, the polymerization temperature, and the like, and an operation unit that performs input settings such as various production conditions during polymer production and operation of the entire apparatus It is composed of five. Each configuration will be specifically described below. The control unit 4 corresponds to the control unit of the present invention, and the operation unit 5 corresponds to the setting unit.

  In the stirrer 1, a stirring vessel 2 (lattice blade in FIG. 6) is attached to a stirring tank 2 having a bowl-like bottom and a rotating shaft 5 that is cantilevered from above the center. The rotation shaft 5 is connected to a rotation driving means such as a motor (not shown), and rotates about the Y axis in the drawing. A jacket 7 for controlling the polymerization temperature in the stirring tank is attached to the outer periphery of the stirring tank 2.

  In addition, the stirring tank 2 is provided with a condenser C standing on its upper lid, which cools and returns the water evaporated due to the polymerization reaction to water, and discharges nitrogen that is supplied to the stirring tank and becomes unnecessary. . 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 2.

  Moreover, the temperature sensor S3 which detects the internal bath temperature of the stirring tank 2 is provided. The temperature sensor S3 corresponds to the detection means of the present invention.

  In the jacket 7, a pipe R <b> 1 for supplying and discharging a temperature adjusting fluid such as hot water and cooling water is connected to the upper and lower portions of the jacket 7. In order to increase the temperature in the agitation tank on the jacket inlet side (lower part in FIG. 6) of the pipe R1, there is a heat exchanger 8 for raising the temperature of the water circulating in the pipe R1 so as to supply hot water to the jacket 7, for example. Is provided. A pipe R2 to which steam is supplied by opening the electromagnetic valve V2 is connected to the heat exchanger 8 in communication. The piping R1 is provided with an electromagnetic valve V1 for discharging hot water or cooling water circulating through the piping R1 in order to cool the stirring tank 2, and the electromagnetic valve V1 is opened to discharge hot water or the like. When this is done, a pipe R3 for supplying new cooling water is connected to the pipe R1 through an electromagnetic valve V3.

  A temperature sensor S1 is provided on the pipe R1 on the side for supplying the temperature adjusting fluid to the jacket 7 (in the vicinity of the lower part of the jacket 7 in FIG. 6), and a temperature sensor S2 is provided on the discharge side (in the vicinity of the upper part of the jacket 7 in FIG. 6). A flow meter F1 (left side in FIG. 6) is provided.

  The solvent storage unit 3 stores an amount of initiator that is determined in advance by experiments, simulations, or the like according to the polymer to be manufactured.

  Moreover, the solvent storage part 3 is connected in communication with the agitation tank 2 via a pipe R4 provided with an electromagnetic valve V4. A predetermined amount of the solvent stored in the solvent storage unit 3 is dropped into the agitation tank 2 by opening and closing the electromagnetic valve V4 under the control of the control unit 4 described later. The solvent storage unit 3 is provided with a fuel gauge Z1 that detects a dripping amount of the solvent supplied to the stirring tank 2. In addition, the structure containing the solvent storage part 3 and the electromagnetic valve V4 is corresponded to the solvent dripping means of this invention.

  The control unit 4 includes a storage unit 9 and an arithmetic processing unit 10. In the storage unit 9, the pattern data of the standard reaction rate at the time of the polymerization reaction according to the polymer production conditions and the processes from step S1 to step S3 in the above production method are repeated for each change in the polymerization temperature, as shown in FIG. Correlation data is stored which is a matrix of the amount of solvent dropped determined from the relationship between the inner bath temperature and the inner bath temperature gradient. Various manufacturing conditions such as the timing of dropping the solvent are input and set from the operation unit 5 in advance. The storage unit 9 corresponds to the storage unit of the present invention.

  The arithmetic processing unit 10 is configured to calculate a dripping amount of a solvent for producing a polymer having a target gel fraction based on the initial condition input and set from the operation unit 5.

  In order to calculate the dripping amount of the solvent, the arithmetic processing unit 10 further includes a polymerization temperature change rate calculating unit 11 and a solvent dropping amount calculating unit 12. The arithmetic processing of each unit will be described in detail in the explanation of the operation of the embodiment apparatus. The arithmetic processing unit 10 corresponds to the arithmetic means of the present invention.

  Next, a series of operations for producing a polymer having an arbitrary gel fraction using the example apparatus having the above-described configuration will be described based on the flowchart shown in FIG.

  First, in step S <b> 10, various manufacturing conditions according to the polymer to be manufactured are initialized in the storage unit 9 of the control unit 4 by operating the operation unit 5. In this example, as the production conditions, the respective capacities of the stirring tank 2 and the solvent storage unit 3, the reference pattern of the reference polymerization temperature and the reference reaction rate of the polymer to be manufactured, the input amount of the solvent used for the manufacture, the dropping timing of the solvent, Various conditions such as a target gel fraction are initially set. When the initial setting is completed, the process proceeds to step S20.

  In step S20, stirring of the monomer and solvent charged in the stirring tank 2 is started. Along with the start of stirring, the actual polymerization temperature, which is the inner bath temperature of the stirring tank, is detected by the temperature sensor S3 and transmitted to the control unit 4. The control unit 4 monitors the actual polymerization temperature, and the arithmetic processing unit 10 determines whether the actual polymerization temperature exceeds a preset reference polymerization temperature. In this process, if the actual polymerization temperature does not exceed the reference polymerization temperature, the process of step S20 is repeated, and the process proceeds to step S30 when the actual polymerization temperature exceeds the reference polymerization temperature.

  In step S30, the polymerization temperature change rate calculation unit 11 of the arithmetic processing unit 10 obtains an inner bath temperature gradient as a change in the heat generation amount per unit time from the deviation between the actual polymerization temperature and the reference polymerization temperature. And the solvent dripping calculation part 12 extracts the solvent dripping amount according to the inner-bath temperature gradient and the actual polymerization temperature which were calculated | required previously by performing the correlation calculation previously stored in the memory | storage part 9, and a comparison calculation process.

  In step S <b> 40, the control unit 4 adjusts the opening degree of the electromagnetic valve V <b> 4 and drops a predetermined amount of the solvent extracted by the dropping amount calculation unit 15 into the stirring tank 2.

  In step S50, the control unit 4 counts the time from the next solvent dropping to the next solvent dropping. This counting time is determined in advance by experiments, simulations, and the like, and is the minimum time when the effect of suppressing the polymerization reaction is lost after the solvent is dropped. In this embodiment, the minimum time is set to 2.5 minutes.

  In step S60, when the minimum time of 2.5 minutes is reached, the arithmetic processing unit 10 obtains the inner bath temperature gradient using the actual polymerization temperature continuously detected by the temperature sensor S3. If the obtained inner bath temperature gradient is zero or more, it is determined that the actual reaction rate tends to increase and deviate from the reference reaction rate, and the processing from step S10 is repeated. This process is repeated until the polymer to be manufactured has a predetermined gel fraction. Moreover, in the case of a present Example, the temperature of the cooling solvent circulated through the jacket 7 is adjusted by PID control in the process of producing the polymer.

  As described above, the amount of solvent added to correct the actual reaction rate to the reference reaction rate for each polymerization temperature that changes in the polymerization reaction process is determined according to the relationship between the inner bath temperature gradient and the polymerization temperature. Each time, the amount of the solvent dropped can be easily determined by detecting the actual polymerization temperature by the temperature sensor S3 by obtaining the result by experiments in advance and making it a matrix and storing it in the storage unit 9 as correlation data. In addition, in this example, when calculating the dropping amount of the solvent, a future reaction component that occurs within a delay time from when the solvent is dropped into the stirring tank to when the reaction is suppressed is predicted, and this reaction component is calculated. The dripping amount of the removable solvent is calculated for each polymerization temperature. Therefore, a polymer having an arbitrary gel fraction and molecular weight distribution can be produced accurately and efficiently.

  The present invention is not limited to the embodiment described above, and can be modified as follows.

  (1) In the above embodiment, the batch polymerization by emulsion polymerization has been described as an example. However, the present invention is not limited to this form, and is applicable to dropping polymerization, two-stage polymerization, and homogeneous solution polymerization. be able to.

  (2) In the case of the said Example, it is preferable to control so that the temperature of the solvent stored by the solvent storage part 3 may be kept substantially constant. By comprising in this way, it becomes easy to control reaction rate further.

It is a figure which shows the amount of inner bath temperature gradient changes in the stirring tank acquired by experiment. It is a figure which shows the change of the internal bath temperature gradient in a stirring tank. It is a figure which shows the relationship with the internal bath temperature which changes according to the change of the internal bath temperature gradient after solvent dripping. It is a figure which shows the change of the inner bath temperature gradient at the time of solvent dripping. It is a figure which shows the correlation of the dripping amount of a solvent required in order to obtain the amount of target bath temperature gradient changes. It is a schematic block diagram of the polymer manufacturing apparatus which concerns on an Example. It is a matrix which shows the solvent dripping amount calculated | required from the relationship between an inner bath temperature gradient and an inner bath temperature. It is a flowchart which controls the reaction rate when an Example apparatus is utilized.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Stirrer 2 ... Stirring tank 3 ... Solvent storage part 4 ... Control part 5 ... Operation part 7 ... Jacket 9 ... Memory | storage part 10 ... Arithmetic processing part 11 ... Polymerization temperature change rate calculation part 12 ... Solvent dripping amount calculation part

Claims (4)

In the polymer production method for producing a polymer by performing a polymerization reaction while adding an initiator to a monomer previously charged in a tank and mixing it,
The reference reaction rate at predetermined polymerization reaction according to the production target polymer, hereinafter the dropping amount of inhibiting solvent polymerization reaction so that the actual reaction rate of the polymer production process is identical to the reference reaction rate It is adjusted in the manner of,
The actual reaction rate during the polymerization reaction is an internal bath temperature gradient indicating a change in the calorific value per unit time in the tank,
The actual polymerization temperature in the tank is detected by the temperature detection means, and a temperature deviation is determined from the actual polymerization temperature and a reference polymerization temperature determined in advance according to the polymer to be manufactured, and the calorific value per unit time at the actual polymerization temperature. A first process for determining an actual bath temperature gradient indicating a change in
A second step of determining a theoretical bath temperature gradient for correcting the actual bath temperature gradient including the temperature deviation to a reference inner bath temperature gradient indicated by a reference polymerization temperature;
A third step of obtaining a target internal bath temperature gradient change amount from a difference between the theoretical internal bath temperature gradient and the actual internal bath temperature gradient;
Corresponding to the target inner bath temperature gradient change amount based on the correlation function of each polymerization temperature including a plurality of temperature deviations with respect to the reference polymerization temperature and the drop amount of the solvent predetermined in accordance with the inner bath temperature gradient change amount. A fourth process for determining the amount of solvent dripping;
A fifth step of dropping a predetermined amount of the solvent obtained in the fourth step into the tank;
The polymer production method characterized by performing by this . In the polymer manufacturing method of Claim 1 ,
For each polymer to be produced, the amount of solvent dripping required to correct the actual internal bath temperature gradient when the reference polymerization temperature is changed from the actual internal bath temperature gradient to the standard internal bath temperature gradient is determined from the first process to the fourth process. Repeatedly determining in advance, selecting the amount of solvent dropped according to the actual polymerization temperature detected in the polymer production process and the actual bath temperature gradient with reference to the previously determined amount of solvent dropped, A method for producing a polymer, wherein a predetermined amount of solvent is dropped into a tank. In the polymer manufacturing method of Claim 1 or Claim 2 ,
The polymer production method, wherein the solvent is dropped intermittently at predetermined time intervals. In a polymer production apparatus for producing a polymer by carrying out a polymerization reaction while mixing an initiator with a monomer,
A stirrer that stirs so as to mix the monomer and the initiator charged in the stirring tank;
A solvent dropping means for storing a solvent for suppressing the polymerization reaction in the stirring tank and dropping the solvent into the stirring tank;
Storage means for storing correlation data between the rate of change of the reaction rate that changes during the polymerization reaction of the polymer to be produced, and the amount of solvent added to correct each reaction rate having the rate of change to the reference reaction rate;
Detection means for detecting a physical quantity resulting from the reaction rate of the polymerization reaction in the stirring tank;
Based on the physical quantity detected by the detection means, a change amount of the reaction rate is obtained, and a calculation means for obtaining a dripping amount of the solvent according to the obtained change amount from the storage means;
Control means for operating the solvent dropping means to drop the solvent dropping amount obtained by the calculating means into the stirring tank;
The control means obtains the dripping amount of the solvent as follows.
The reaction rate is an inner bath temperature gradient indicating a change in the calorific value per unit time in the stirring tank during the polymerization reaction,
The physical quantity detected by the detection means is a polymerization temperature in the stirring tank,
The correlation data stored in the storage means uses the inner bath temperature gradient when the reference polymerization temperature determined for each polymer to be manufactured is changed,
(A) The actual polymerization temperature in the tank is detected by the detection means, and a temperature deviation is obtained from the actual polymerization temperature and a reference polymerization temperature determined in advance according to the polymer to be manufactured, and per unit time at the actual polymerization temperature. The actual bath temperature gradient showing the change in calorific value of
(B) obtaining a theoretical internal bath temperature gradient for correcting the actual internal bath temperature gradient including the temperature deviation to a standard internal bath temperature gradient indicated by a standard polymerization temperature;
(C) A target internal bath temperature gradient change amount is obtained from a difference between the theoretical internal bath temperature gradient and the actual internal bath temperature gradient,
(D) Based on a correlation function of each polymerization temperature including a plurality of temperature deviations with respect to the reference polymerization temperature and a drop amount of the solvent predetermined in accordance with the amount of change in the inner bath temperature gradient, the target inner bath temperature gradient change amount Find the amount of solvent dripping corresponding to
(E) A polymer production apparatus characterized in that the above (a) to (d) are repeatedly performed and converted into data and stored in the storage means .

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