JP7296273B2 - Polymer production system and polymer production method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polymer production system and a polymer production method. Specifically, the present invention relates to a polymer production system and a polymer production method capable of continuously producing a bubble-free polymer solution by detecting the presence of bubbles in the solution and removing the bubbles. .

Compared to the batch process, the continuous process is advantageous in that it requires less space, is suitable for high-mix low-volume production, and is easy to scale up. In this continuous process, in order to stably perform production, it may be necessary to precisely control the flow rate of the raw material and feed the liquid. However, in the case of continuous liquid phase production, the presence of a gas phase in the process causes pressure fluctuations that cause fluctuations in the flow rate. Therefore, in a continuous process in which a liquid phase is handled, when precise control of the flow rate of the liquid is required, it is necessary to manage so that the gas phase such as air bubbles does not exist in the system.

By the way, in the synthesis of polyamic acid solution, it takes time and effort to adjust the viscosity to the desired value in the conventional batch process. (See, for example, Patent Document 1).

In the polymerization of polyamic acid by polyaddition, the viscosity of the resulting polymer changes greatly due to a slight difference in the ratio of raw materials. It is necessary to control so that there is no gas phase inside. However, Patent Literature 1 does not mention a method for confirming whether a gas phase exists in the process or a method for removing the gas phase if it exists. Therefore, when air bubbles are mixed in, the flow rate of the raw material may fluctuate, and a polyamic acid solution with unstable quality may be produced.

Furthermore, in the polyimide production process, the presence of air bubbles in the polyamic acid solution, which is the precursor of the film, causes pinholes and craters during film formation, resulting in defects and poor appearance. Therefore, in order to produce a film of stable quality, it is important to control the polyamic acid solution during production so that air bubbles are not included.

JP-A-62-214912

Under such circumstances, there is a demand for means for detecting the presence of air bubbles during the continuous process of producing polyamic acid. In addition, if bubbles can be detected and removed automatically when bubbles are present in the solution, it will be possible to reduce the amount of spec-out discarded products, as well as reduce the number of people in manufacturing operations and make them unmanned. .

The present invention provides a polymer production system and a polymer production method that can automatically detect the presence of air bubbles in a solution in order to detect quality defects at an early stage and minimize the amount of waste. intended to provide Further, the present invention provides a polymer production system and a polymer production method capable of continuously and stably producing a polymer solution containing no bubbles by automatically removing the detected bubbles. With the goal.

Specific means for solving the above problems include the following embodiments.

<1> A polymer production system for obtaining a reaction product fluid by continuously mixing two or more raw material fluids,
two or more supply units for supplying each of the two or more source fluids;
a first mixing section for mixing two or more of the raw material fluids supplied from the supply section to obtain a mixed fluid;
Continuously arranged downstream of the first mixing section, continuously mixed without contacting gas by a tubular reactor, and reacting by advancing the chemical reaction of the reaction raw materials contained in the raw material fluid a first reaction section that produces the reaction product fluid containing products;
a first air bubble measurement unit that acquires one or more first measurement information relating to physical quantities for detecting air bubbles in any one or more of the source fluid, the mixed fluid, and the reaction-generated fluid; ,
The polymer production system , wherein the first mixing section is a connecting section of two or more liquid feeding lines through which two or more of the raw material fluids are respectively passed.

<2> The polymer production system according to <1>, further comprising a first defoaming section that removes a gas phase in the fluid based on the first measurement information acquired by the first bubble measuring section.

<3> The first air bubble measurement unit includes an absorption photometer, an infrared spectrometer, a near-infrared spectrometer, a density meter, a color difference meter, a refractometer, a spectrophotometer, a turbidity meter, and an ultrasonic sensor. The polymer production system according to <1> or <2>, comprising one or more selected from the group.

<4> The first air bubble measurement unit includes a light emitting unit that irradiates visible light and/or infrared light to one or more of the raw material fluid, the mixed fluid, and the reaction product fluid, and is irradiated from the light emitting unit, a light receiving unit for receiving visible light and/or infrared rays transmitted through at least one of the raw material fluid, the mixed fluid, and the reaction-generated fluid, and the raw material fluid and the mixed fluid as the first measurement information; , and the polymer production system according to <1> or <2>, wherein the transmittance of visible light and/or infrared light in any one or more of the reaction-generated fluids is measured.

<5> The source fluids are a first solution containing a first polyaddition polymerizable compound and a second solution containing a second polyaddition polymerizable compound that polyadditions with the first polymerizable compound. can be,
The reaction product fluid is a first polymerization solution containing a first polymer produced using the first polymerizable compound and the second polymerizable compound as raw materials,
The supply unit includes a first supply unit that supplies the first solution and a second supply unit that supplies the second solution,
In the first mixing unit, the first solution and the second solution are continuously mixed without contacting gas to generate a first mixed solution,
In the first reaction section, the polymerization reaction between the first polymerizable compound and the second polymerizable compound contained in the first mixed solution is continuously mixed in a tubular reactor without contact with gas. The polymer production system according to any one of <1> to <4>, wherein the first polymerization solution containing the first polymer is produced by proceeding by

<6> one of the first polymerizable compound and the second polymerizable compound is a tetracarboxylic dianhydride and the other is a diamine;
The polymer production system according to <5>, which produces polyamic acid as the first polymer.

<7> One of the first polymerizable compound and the second polymerizable compound is an acid anhydride group-terminated or amino group-terminated polyamic acid, and the other is a diamine or a tetracarboxylic dianhydride,
The polymer production system according to <5>, which produces polyamic acid as the first polymer.

<8> The polymer production system according to <6> or <7>, further comprising an imidization unit that imidizes the produced polyamic acid.

<9> A polymer production system for obtaining a reaction product fluid by continuously mixing two or more raw material fluids,
two or more supply units for supplying each of the two or more source fluids;
a first mixing section for mixing two or more of the raw material fluids supplied from the supply section to obtain a mixed fluid;
Continuously arranged downstream of the first mixing section, continuously mixed without contacting gas by a tubular reactor, and reacting by advancing the chemical reaction of the reaction raw materials contained in the raw material fluid a first reaction section that produces the reaction product fluid containing products;
a first air bubble measurement unit that acquires one or more first measurement information relating to physical quantities for detecting air bubbles in any one or more of the source fluid, the mixed fluid, and the reaction-generated fluid; ,
A method for producing a polymer, wherein the first mixing section uses a polymer production system in which two or more liquid feed lines are connected to each of the two or more raw material fluids.

<10> Use the polymer production system according to <9>, further comprising a first defoaming section that removes a gas phase in the fluid based on the first measurement information acquired by the first bubble measuring section. A method for producing a polymer characterized by:

<11> The first air bubble measurement unit includes an absorption photometer, an infrared spectrometer, a near-infrared spectrometer, a density meter, a color difference meter, a refractometer, a spectrophotometer, a turbidity meter, and an ultrasonic sensor. A method for producing a polymer, comprising using the polymer production system according to <9> or <10>, which comprises one or more selected from the group.

<12> The first air bubble measurement unit includes a light emitting unit that irradiates visible light and/or infrared rays to one or more of the raw material fluid, the mixed fluid, and the reaction product fluid, and is irradiated from the light emitting unit, a light receiving unit for receiving visible light and/or infrared rays transmitted through at least one of the raw material fluid, the mixed fluid, and the reaction-generated fluid, and the raw material fluid and the mixed fluid as the first measurement information; , and the polymer production system according to <9> or <10>, which measures the transmittance of visible light and/or infrared light in any one or more of the reaction-generated fluids. .

<13> The source fluid is a first solution containing a first polyaddition polymerizable compound and a second solution containing a second polyaddition polymerizable compound that polyadditions with the first polymerizable compound. can be,
The reaction product fluid is a first polymerization solution containing a first polymer produced using the first polymerizable compound and the second polymerizable compound as raw materials,
The supply unit includes a first supply unit that supplies the first solution and a second supply unit that supplies the second solution,
In the first mixing unit, the first solution and the second solution are continuously mixed without contacting gas to generate a first mixed solution,
In the first reaction section, the polymerization reaction between the first polymerizable compound and the second polymerizable compound contained in the first mixed solution is continuously mixed in a tubular reactor without contact with gas. A polymer characterized by using the polymer production system according to any one of <9> to <12>, wherein the first polymerization solution containing the first polymer is produced by proceeding by manufacturing method.

<14> one of the first polymerizable compound and the second polymerizable compound is a tetracarboxylic dianhydride and the other is a diamine,
A method for producing a polymer, characterized by using the polymer production system according to <13> for producing a polyamic acid as the first polymer.

<15> One of the first polymerizable compound and the second polymerizable compound is an acid anhydride group-terminated or amino group-terminated polyamic acid, and the other is a diamine or a tetracarboxylic dianhydride,
A method for producing a polymer, characterized by using the polymer production system according to <13> for producing a polyamic acid as the first polymer.

<16> A method for producing a polymer, using the polymer production system according to <14> or <15>, further comprising an imidization unit for imidizing the produced polyamic acid.

According to the present invention, it is possible to provide a polymer production system and a polymer production method that automatically detect the presence of air bubbles in a solution. Further, the present invention provides a polymer production system and a polymer production method capable of continuously and stably obtaining a polymer solution containing no air bubbles by automatically removing the detected air bubbles. can be done.

It is a figure which shows the polymer manufacturing system in 1st Embodiment.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
The first embodiment is an example of a polymer production system, which is an example of a system capable of detecting when bubbles are contained in a solution based on measurement information from a measurement unit provided in a pipeline. is.

<First embodiment>
A polymer manufacturing system according to the first embodiment will be described with reference to FIG. FIG. 1 is a diagram showing a polymer production system according to the first embodiment.

First, an overview of the polymer production system 1 in the first embodiment will be described.
The polymer production system 1 mixes a first solution A1 containing a first polyaddition polymerizable compound and a second solution A2 containing a second polyaddition polymerizable compound in a first mixing section 51 to produce a first By generating the mixed solution B and allowing the polymerization reaction to proceed in the first reaction section 61 to generate the first polymerization solution C, the polyamic acid (first polymer) is manufactured. Furthermore, a first air bubble measurement unit capable of detecting the presence or absence of air bubbles in any one or more of the conduits through which the first solution A1, the second solution A2, the first mixed solution B, and the first polymerized solution C flow. Prepare. As an example, a case of detecting bubbles when they are present in the first solution A1 will be described below.

Next, a specific configuration of the polymer production system 1 will be described.
As shown in FIG. 1, the polymer production system 1 includes a first tank 11, a second tank 12, a first supply pump 21 (first supply section), and a second supply pump 22 (second supply section). , a first mixing section 51 and a first reaction section 61 .

The first tank 11 contains a first solution A1 containing a first polyaddition polymerizable compound. In the present embodiment, the first tank 11 contains a first solution A1 containing tetracarboxylic dianhydride and/or polyamic acid having an acid anhydride terminal.

The second tank 12 contains a second solution A2 containing a second polyaddition polymerizable compound that polyadditions with the first polymerizable compound. In this embodiment, the second tank 12 contains a second solution A2 containing a diamine and/or an amine-terminated polyamic acid.

The tetracarboxylic dianhydride is not particularly limited, and those similar to those used in conventional polyimide synthesis can be used. Specific examples of tetracarboxylic dianhydrides include 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 2, 3,3′,4′-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 1,3-bis(2,3-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(2, 3-dicarboxyphenoxy)benzene dianhydride, 2,3,3′,4′-benzophenonetetracarboxylic dianhydride, 2,2′,3,3′-benzophenonetetracarboxylic dianhydride, 2,2 ',3,3'-biphenyltetracarboxylic dianhydride, 2,2',6,6'-biphenyltetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydrides such as anthracene-2,3,6,7-tetracarboxylic dianhydride and phenanthrene-1,8,9,10-tetracarboxylic dianhydride; butane-1,2, Aliphatic tetracarboxylic dianhydrides such as 3,4-tetracarboxylic dianhydride; Alicyclic tetracarboxylic dianhydrides such as cyclobutane-1,2,3,4-tetracarboxylic dianhydride; Thiophene -heterocyclic tetracarboxylic dianhydrides such as 2,3,4,5-tetracarboxylic dianhydride and pyridine-2,3,5,6-tetracarboxylic dianhydride; Tetracarboxylic dianhydrides may be used alone or in combination of two or more.

The diamine is not particularly limited, and the same diamines as those used in conventional polyimide synthesis can be used. Specific examples of diamines include 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4′-bis(4- aminophenoxy)biphenyl, 1,4'-bis(4-aminophenoxy)benzene, 1,3'-bis(4-aminophenoxy)benzene, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3, 4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-methylene-bis(2-chloroaniline), 3, 3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl sulfide, 2,6'-diaminotoluene, 2,4-diaminochlorobenzene, 1,2-diaminoanthraquinone, 1,4-diaminoanthraquinone , 3,3′-diaminobenzophenone, 3,4′-diaminobenzophenone, 4,4′-diaminobenzophenone, 4,4′-diaminobibenzyl and other aromatic diamines; 1,2-diaminoethane, 1,4- Aliphatic diamines such as diaminobutane, tetramethylenediamine, 1,10-diaminododecane; 1,4-diaminocyclohexane, 1,2-diaminocyclohexane, bis(4-aminocyclohexyl)methane, 4,4'-diaminodicyclohexylmethane alicyclic diamines such as 3,4-diaminopyridine; heterocyclic diamines such as 3,4-diaminopyridine; A diamine may be used individually by 1 type, and may use 2 or more types together.

The polyamic acid is not particularly limited, and the same polyamic acid used before imidization in conventional polyimide synthesis can be used. Specific examples of polyamic acids include polyamic acids obtained by reacting any one or more of the tetracarboxylic dianhydrides described above with one or more of the diamines described above.

As the solvent for the first solution A1 and the second solution A2, a solvent capable of dissolving the polyaddition polymerizable compound used as a raw material is used. Specific examples of solvents include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 2-propanone, 3-pentanone, tetrahydropyrene, epichlorohydrin, acetone, methyl ethyl ketone, tetrahydrofuran. , ethyl acetate, acetanilide, methanol, ethanol, isopropanol, toluene, xylene and the like. A solvent may be used individually by 1 type, and may mix 2 or more types.

The first solution A1 may contain a small amount of a tertiary amine such as trimethylamine or triethylamine in order to increase the solubility of the tetracarboxylic dianhydride or increase the reactivity with the diamine.

The first supply pump 21 (first supply section) supplies the first solution (raw material fluid) A1 contained in the first tank 11 to the first mixing section 51 . The first supply pump 21 supplies the first solution A1 at a predetermined amount. For example, the first supply pump 21 is adjusted so as to supply the first solution A1 under conditions under which polyamic acid (first polymer) having desired properties is obtained.

The second supply pump 22 (second supply section) supplies the second solution (raw material fluid) A2 contained in the second tank 12 to the first mixing section 51 . The second supply pump 22 supplies the second solution A2 at a predetermined amount. For example, the second supply pump 22 is adjusted so as to supply the second solution A2 under conditions under which polyamic acid (first polymer) having desired properties is obtained.

The first solution air bubble measuring unit 31 (first air bubble measuring unit) is installed in a pipeline (first liquid sending line 71) for sending the first solution A1, and measures whether or not air bubbles are present in the first solution A1. Information (first measurement information) on a physical quantity necessary for determining whether or not is acquired. When it is determined that bubbles are present, an operation for removing the bubbles may be performed by the first solution defoaming section 41, which will be described later. Further, a system may be adopted in which the second solution is not supplied to the first mixing section (first defoaming section) 51 and the polymerization reaction is not performed while air bubbles are mixed.

The first air bubble measurement unit 31 includes, for example, an absorption photometer, an infrared spectrometer, a near-infrared spectrometer, a density meter, a color difference meter, a refractometer, a spectrophotometer, a turbidity meter, and an ultrasonic sensor. It is configured with one or more selected from.

When measuring the presence or absence of air bubbles in a solution based on the transmittance of visible light and/or infrared light, the first air bubble measurement unit includes a light emitting unit that emits visible light and/or infrared light, and a light emitting unit that receives visible light and/or infrared light. and the first solution A1 is present between the light-emitting portion and the light-receiving portion. When bubbles are present in the first solution, the ratio of visible light and/or infrared rays absorbed, reflected, and scattered is different from that of a uniform solution due to the influence of the inside of the bubbles and the interface between the bubbles and the solution. Therefore, by measuring the intensity of visible light and/or infrared light received by the light-receiving part with an absorption photometer, an infrared spectrometer, a near-infrared spectrometer, a spectrophotometer, or the like, the number of bubbles in the first solution A1 can be determined. Presence or absence can be determined. Various forms are conceivable for implementation of this configuration. A shaped measuring instrument may be inserted into the pipeline.

In determining the presence or absence of air bubbles based on the visible light and/or infrared transmittance, the wavelength of the visible light and/or infrared light is not particularly limited. If the solution and the bubbles have different transmittances, the bubbles can be detected by varying the transmittance when they pass between the light-emitting section and the light-receiving section. Further, when the solution and bubbles have the same transmittance, the visible light and/or infrared rays are reflected or scattered at the interface between the solution and the bubbles, so the existence of the bubble can be detected as a change in transmittance. Therefore, the wavelength of visible light and/or infrared light may or may not be a wavelength that passes through the first solution A1. Therefore, the optical properties of the first solution A1 are not particularly limited, and may be colorless or colored. Further, the first solution A1 may be transparent, or may be cloudy due to dispersion of solids insoluble in the solvent. In order to obtain sufficient measurement accuracy, it is preferable to adjust the wavelength and intensity of visible light and/or infrared light and the optical path length passing through the first solution A1, taking into account the optical properties of the first solution.

A first solution defoaming section 41 may be provided in the first liquid feeding line 71 . The first solution defoamer 41 has a mechanism for removing air bubbles in the first solution based on the first measurement information. The method for removing air bubbles in the first solution defoaming section 41 is not particularly limited. For example, an in-line defoaming device may be used, and the solution containing air bubbles can be discarded without being sent to the first mixing section 51. You may provide such a flow path. In addition, when the first tank 11 is provided with a vacuum pump or the like so as to be able to deaerate, the flow path is returned to the first tank 11 in order to remove air bubbles by deaeration and then feed the liquid again. may be provided.

The first mixing unit 51 mixes the first solution A1 and the second solution A2 to generate the first mixed solution B. As shown in FIG. The first mixing section 51 is arranged downstream of the first supply pump 21 and the second supply pump 22 . In order to prevent air bubbles from entering the first mixed solution B, the first mixing section 51 is configured to mix the first solution A1 and the second solution A2 without coming into contact with gas. However, it is sufficient that the first mixing section 51 has a structure in which new bubbles do not enter the solution, and the bubbles are mixed upstream of the first mixing section 51 and sent to the first mixing section 51. As for the case, the object of the present invention can be achieved by providing the first air bubble measuring section and/or the first defoaming section downstream of the first mixing section 51, as will be described later.

The first reaction section 61 is arranged continuously downstream of the first mixing section 51 . The first reaction section 61 is a section that allows the polymerization reaction between the first polymerizable compound and the second polymerizable compound contained in the first mixed solution B to proceed. In the first reaction section 61, the polymerization reaction between the first polymerizable compound and the second polymerizable compound contained in the first mixed solution B progresses gradually, and the first polymerized solution C is obtained. The first reaction section 61 stirs the solution in order to advance the reaction of the first mixed solution B sent from the first merging section 51 . In order to prevent air bubbles from entering the first polymerization solution C, the first reaction part preferably mixes without coming into contact with the gas.

The first reaction section 61 includes, for example, a stationary mixer such as a static mixer, a nozzle, orifice, or a driven mixer such as a centrifugal pump, a volute pump, or an in-line mixer having stirring blades. It comprises a mold mixer, more preferably a static mixer. As described above, a pipe with a twist tape inserted therein can also provide a stirring promotion effect in the same manner as a static mixer.

The static mixer is not particularly limited, and examples thereof include static mixers such as Kenics mixer type, Sulzer SMV type, Sulzer SMX type, Tray Hi-mixer type, Komax mixer type, Lightnin mixer type, Ross ISG type, and Bran & Lube mixer type. mentioned. Among these, the Kenics mixer type static mixer is more preferable since it has a simple structure and has no dead space.

In order to stably supply the polymer solution, it is preferable to remove air bubbles upstream of the first mixing section 51 and mix and react the solutions containing no air bubbles. Air bubbles may be included in the solution even on the downstream side of the first mixing section 81 , such as when there is an air pocket in the pipeline on the downstream side. Therefore, on the downstream side of the first mixing unit 51, a first mixed solution bubble measuring unit 33 (first bubble measuring unit), a first reaction solution bubble measuring unit 34 (first defoaming unit), a first reaction solution degassing unit A first bubble measuring part and/or a first defoaming part such as a bubble part 43 (first defoaming part) is provided to detect and/or remove bubbles in the first mixed solution B and/or the first polymerization solution C. It may be possible to do so.

When the polymer production system 1 according to the present embodiment produces polyimide, the polymer production system 1 further includes an imidization section (imidization step) that imidizes the polyamic acid. The imidization unit (not shown) imidizes the polyamic acid by, for example, a thermal imidization method of thermal dehydration ring closure, a chemical imidization method using a dehydrating agent and an imidization accelerator, or the like.

<Specific example of bubble removal in the first embodiment>
A specific example of air bubble removal in the polymer production system 1 will be described below. However, it is not limited to the following specific examples.

(1) Example 1
It is assumed that the presence or absence of air bubbles is measured in the first solution air bubble measurement unit 31 using visible light having a wavelength that sufficiently penetrates the first solution A1. When the transmittance decreases compared to the uniform first solution A1 during liquid feeding, bubbles contained in the first solution A1 pass through the first solution bubble measurement unit 31, and the visible light is scattered, resulting in the transmittance can be judged to have decreased. Therefore, the supply of the second solution A2 by the second supply pump is stopped, and the portion containing bubbles of the first solution A1 is discarded by the first defoaming section. A1 and the second solution A2 may be sent to the first mixing section 51 .

(2) Example 2
It is assumed that the presence or absence of air bubbles is measured in the first solution air bubble measurement unit 31 using visible light having a wavelength that does not pass through the first solution 1 . When the transmittance is higher than that of the uniform first solution A1, the air bubbles contained in the first solution A1 pass through the first solution bubble measurement unit 31, and the optical path length of visible light passing through the first solution A1 is It can be judged that the transmittance increased because the length became shorter. Therefore, the supply of the second solution A2 by the second supply pump is stopped, and the first solution A1 is returned to the first tank 11 by the first defoaming section, degassed in the first tank 11, and then supplied to the first tank again. The solution A1 and the second solution A2 may be sent to the first mixing section 51.

<Modification>
Although the two embodiments have been described above, the present invention is not limited to the above embodiments, and includes modifications, improvements, etc. within the scope of achieving the object of the present invention.

For example, in the above-described first embodiment, the polymer production system is configured to have one reaction section (treatment section), but is not limited to this, and two or more reaction sections (treatment section) ). That is, the polymer production system is not limited to one-stage reaction, and may be one that performs two-stage or more reactions. For example, the polymer production system may be configured to have two or more sets of a mixing section having a mixing stirring section and a reaction section having a reaction stirring section. The polymer production system can adjust the amount of supply and the like in a multistage manner so as to approach the target reaction rate and quality at each reaction section (treatment section).

Further, in the above-described first embodiment, the case where the pipeline for supplying the first solution is provided with the first air bubble measurement unit and/or the first defoaming unit has been described, but the pipeline for supplying the second solution may be provided with the first air bubble measuring section and/or the first defoaming section.

Also, in the above-described embodiments, the polymer production system for producing polyamic acid or polyimide was described, but the polymer to be produced is not limited to these. For example, the polymer production system may produce polymers using polyaddition monomers such as urethane monomers and epoxy monomers.

EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these Examples.

<Example 1>
In Example 1, a method of continuously producing a polyamic acid solution was carried out while monitoring the presence or absence of air bubbles in the first polymerization solution based on changes in visible light transmittance.

A first solution A1 is prepared by dissolving the acid anhydride group-terminated polyamic acid obtained by the reaction of 4,4′-diaminodiphenyl ether and pyromellitic dianhydride in N,N-dimethylformamide. A solution obtained by dissolving phenylenediamine in N,N-dimethylformamide was used as the second solution A2, and a continuous polymerization reaction was carried out to produce a polyamic acid solution. First, the first solution A1 was placed in the first tank 11, and the second solution A2 was placed in the second tank 12. As shown in FIG. At this time, the first solution A1 and the second solution A2 were sufficiently defoamed in advance by gentle stirring and standing, and by reducing the pressure in the tank as necessary.

First, in the first mixing unit 51, the first solution A1 supplied by the first supply pump 21 and the second solution A2 supplied by the second supply pump 22 are mixed to generate the first mixed solution B. bottom.

Next, in the first reaction section 61, the polymerization reaction between the acid anhydride group-terminated polyamic acid and the p-phenylenediamine contained in the first mixed solution B is allowed to proceed to generate the first polymerization solution C containing the polyamic acid. bottom. Specifically, the first mixed solution B was stirred with a Kenics mixer type static mixer (inner diameter: 8 mm, length: 700 mm) so as not to introduce new air bubbles, and the polymerization reaction was allowed to proceed. As a result, a first polymerization solution C having a higher viscosity than the first solution A1 was obtained.

At this time, the first solution A1 in the first tank 11 and the second solution A2 in the second tank 12 do not contain air bubbles. I get involved as Therefore, an in-line spectrophotometer (33, first mixed solution bubble measurement unit (first bubble measurement unit)) is installed in the liquid feed path of the first polymerization solution C, and the presence or absence of bubbles in the first polymerization solution C is measured. made it possible. When the transmittance of visible light at a wavelength of 700 nm was constantly measured during liquid feeding, the visible light transmittance of the solution containing no bubbles at a wavelength of 700 nm and an optical path length of 1 cm was 98.5%. The transmittance decreased to 93.8% when air bubbles were mixed in immediately after the start of liquid feeding. At this time, it was confirmed visually that the effluent contained air bubbles. After a while from the start of liquid feeding, the transmittance increased to the value of the solution containing no air bubbles, and at this time, it was confirmed visually that the effluent contained no air bubbles.

1 polymer production system 11 first tank 12 second tank 21 first supply pump (first supply unit)
22 Second supply pump (second supply unit)
31 first solution air bubble measurement unit (first air bubble measurement unit)
32 second solution air bubble measurement unit (first air bubble measurement unit)
33 First mixed solution bubble measurement unit (first bubble measurement unit)
34 first polymerization solution air bubble measurement unit (first air bubble measurement unit)
41 first solution defoaming section (first defoaming section)
42 Second solution defoaming section (first defoaming section)
43 First polymerization solution defoaming section (first defoaming section)
51 First mixing section 61 First reaction section 71 First liquid sending line 72 Second liquid sending line A1 First solution (raw material fluid)
A2 Second solution (raw material fluid)
B First mixed solution (mixed fluid)
C first polymerization solution (reaction product fluid)

Claims (16)

A polymer production system for obtaining a reaction product fluid by continuously mixing two or more raw material fluids,
two or more supply units for supplying each of the two or more source fluids;
a first mixing section for mixing two or more of the raw material fluids supplied from the supply section to obtain a mixed fluid;
Continuously arranged downstream of the first mixing section, continuously mixed without contacting gas by a tubular reactor, and reacting by advancing the chemical reaction of the reaction raw materials contained in the raw material fluid a first reaction section that produces the reaction product fluid containing products;
a first air bubble measurement unit that acquires one or more first measurement information relating to physical quantities for detecting air bubbles in any one or more of the source fluid, the mixed fluid, and the reaction-generated fluid; ,
The polymer production system , wherein the first mixing section is a connecting section of two or more liquid feeding lines through which two or more of the raw material fluids are respectively passed. 2. The polymer production system according to claim 1, further comprising a first defoaming section that removes a gas phase in the fluid based on the first measurement information acquired by the first bubble measuring section. The first bubble measurement unit is selected from the group consisting of an absorption photometer, an infrared spectrometer, a near-infrared spectrometer, a density meter, a color difference meter, a refractometer, a spectrophotometer, a turbidity meter, and an ultrasonic sensor. 3. The polymer production system according to claim 1 or 2, comprising one or more of The first air bubble measurement unit includes a light emitting unit that irradiates visible light and/or infrared rays to at least one of the raw material fluid, the mixed fluid, and the reaction product fluid, and a light emitting unit that emits light from the light emitting unit, , a light receiving unit that receives visible light and/or infrared light transmitted through at least one of the mixed fluid and the reaction-generated fluid, and the first measurement information includes the source fluid, the mixed fluid, and the 3. The polymer production system according to claim 1 or 2, wherein the transmittance of visible light and/or infrared light in any one or more of the fluids produced by the reaction is measured. The raw material fluid is a first solution containing a first polyaddition polymerizable compound and a second solution containing a second polyaddition polymerizable compound that polyadditions with the first polymerizable compound,
The reaction product fluid is a first polymerization solution containing a first polymer produced using the first polymerizable compound and the second polymerizable compound as raw materials,
The supply unit includes a first supply unit that supplies the first solution and a second supply unit that supplies the second solution,
In the first mixing unit, the first solution and the second solution are continuously mixed without contacting gas to generate a first mixed solution,
In the first reaction section, the polymerization reaction between the first polymerizable compound and the second polymerizable compound contained in the first mixed solution is continuously mixed in a tubular reactor without contact with gas. The polymer production system according to any one of claims 1 to 4, wherein the first polymerization solution containing the first polymer is produced by proceeding by: one of the first polymerizable compound and the second polymerizable compound is a tetracarboxylic dianhydride and the other is a diamine;
6. The polymer production system according to claim 5, wherein polyamic acid is produced as the first polymer. One of the first polymerizable compound and the second polymerizable compound is an acid anhydride group-terminated or amino group-terminated polyamic acid, and the other is a diamine or a tetracarboxylic dianhydride,
6. The polymer production system according to claim 5, wherein polyamic acid is produced as the first polymer. 8. The polymer production system according to claim 6, further comprising an imidization section that imidizes the produced polyamic acid. A polymer production system for obtaining a reaction product fluid by continuously mixing two or more raw material fluids,
two or more supply units for supplying each of the two or more source fluids;
a first mixing section for mixing two or more of the raw material fluids supplied from the supply section to obtain a mixed fluid;
Continuously arranged downstream of the first mixing section, continuously mixed without contacting gas by a tubular reactor, and reacting by advancing the chemical reaction of the reaction raw materials contained in the raw material fluid a first reaction section that produces the reaction product fluid containing products;
a first air bubble measurement unit that acquires one or more first measurement information relating to physical quantities for detecting air bubbles in any one or more of the source fluid, the mixed fluid, and the reaction-generated fluid; ,
A method for producing a polymer, wherein the first mixing section uses a polymer production system in which two or more liquid feed lines are connected to each of the two or more raw material fluids. 10. The polymer production system according to claim 9, further comprising a first defoaming section that removes a gas phase in the fluid based on the first measurement information acquired by the first bubble measuring section. A method for producing a polymer. The first bubble measurement unit is selected from the group consisting of an absorption photometer, an infrared spectrometer, a near-infrared spectrometer, a density meter, a color difference meter, a refractometer, a spectrophotometer, a turbidity meter, and an ultrasonic sensor. 11. A method for producing a polymer, characterized by using the polymer production system according to claim 9 or 10, which is configured to have one or more components. The first air bubble measurement unit includes a light emitting unit that irradiates visible light and/or infrared rays to at least one of the raw material fluid, the mixed fluid, and the reaction product fluid, and a light emitting unit that emits light from the light emitting unit, , a light receiving unit that receives visible light and/or infrared light transmitted through at least one of the mixed fluid and the reaction-generated fluid, and the first measurement information includes the source fluid, the mixed fluid, and the 11. A method for producing a polymer, characterized by using the polymer production system according to claim 9 or 10, wherein the transmittance of visible light and/or infrared light in any one or more of reaction product fluids is measured. The raw material fluid is a first solution containing a first polyaddition polymerizable compound and a second solution containing a second polyaddition polymerizable compound that polyadditions with the first polymerizable compound,
The reaction product fluid is a first polymerization solution containing a first polymer produced using the first polymerizable compound and the second polymerizable compound as raw materials,
The supply unit includes a first supply unit that supplies the first solution and a second supply unit that supplies the second solution,
In the first mixing unit, the first solution and the second solution are continuously mixed without contacting gas to generate a first mixed solution,
In the first reaction section, the polymerization reaction between the first polymerizable compound and the second polymerizable compound contained in the first mixed solution is continuously mixed in a tubular reactor without contact with gas. A polymer characterized by using the polymer production system according to any one of claims 9 to 12, wherein the first polymerization solution containing the first polymer is produced by proceeding by manufacturing method. one of the first polymerizable compound and the second polymerizable compound is a tetracarboxylic dianhydride and the other is a diamine;
14. A method for producing a polymer, wherein the polymer production system according to claim 13 is used to produce polyamic acid as the first polymer. One of the first polymerizable compound and the second polymerizable compound is an acid anhydride group-terminated or amino group-terminated polyamic acid, and the other is a diamine or a tetracarboxylic dianhydride,
14. A method for producing a polymer, wherein the polymer production system according to claim 13 is used to produce polyamic acid as the first polymer. 16. A method for producing a polymer using the polymer production system according to claim 14 or 15, further comprising an imidization unit for imidizing the produced polyamic acid.

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