WO2022196554A1

WO2022196554A1 - Polymer production system and polymer production method

Info

Publication number: WO2022196554A1
Application number: PCT/JP2022/010836
Authority: WO
Inventors: 瑛人竪山; 倶透豊田; 康裕田多; 康祐齊藤
Original assignee: 株式会社カネカ
Priority date: 2021-03-18
Filing date: 2022-03-11
Publication date: 2022-09-22
Also published as: KR20230157305A

Abstract

A polymer production system 1 comprises a first supply unit 112 that supplies a first fluid A1 including a first polymerizable compound, a second supply unit 122 that supplies a second fluid A2 including a second polymerizable compound, a first merging unit J1 that merges the first fluid A1 and the second fluid A2 to generate a first merged fluid B, a first tube-type mixing unit 20 that is arranged downstream of the first merging unit J1 and advances mixing of the first merged fluid B in the radial direction to generate a first tube-type mixed fluid C, and a first fluctuation mitigation unit 30 that is connected to the first tube-type mixing unit and reduces the variation in the viscosity of the first tube-type mixed fluid C in the axial direction to generate a first generated fluid D.

Description

Polymer production system and polymer production method

The present invention relates to a polymer production system and a polymer production method. Specifically, the present invention relates to a polymer production system capable of continuously producing a polymer and a polymer production method using the polymer production system.

Conventionally, as a method for producing a polymer such as polyamic acid (polyamic acid), for example, a first fluid and a second fluid are mixed in a mixing tank, and the mixed fluid is further mixed in a tubular tubular mixer. A manufacturing method is known (see, for example, Patent Document 1). In the tubular mixer, the mixed fluid is agitated while being moved in the axial direction of the tube by driving the pump to pass the mixed fluid.

JP-A-62-214912

In the tubular mixer, homogenization due to mixing progresses in the radial direction of the tube, but because the residence time distribution in the tubular mixer is small, the viscosity fluctuation of the mixed fluid that occurs in the axial direction of the tube is maintained. . In the polyaddition reaction, the higher the molecular weight of the polymer to be produced, the more precisely the mixing ratio of the raw materials must be adjusted. For example, it is difficult to continuously obtain a high-viscosity polymer of 1000 poise or more with a stable viscosity. A polymer whose viscosity fluctuates over time has a problem that a film with a constant thickness cannot be obtained when it is formed into a film. In order to solve this problem, it is conceivable to install a stirring tank or the like downstream of the tubular mixer to eliminate the fluctuation of the viscosity. However, there is a problem that defoaming is required before film formation.

As a result of intensive studies to solve such problems, conventionally, in order to reduce the required time and product loss, it is preferable that the residence time of the liquid transfer line for transferring the generated polymer is short. However, the present inventors have found that by deliberately providing a portion having a long residence time in the polymer feed line, it is possible to greatly reduce the variation in the viscosity of the resulting polymer over time, leading to the completion of the invention.

An object of the present invention is to provide a polymer production system and production method capable of continuously and stably obtaining a desired polymer with little viscosity change over time. Another object of the present invention is to provide a polymer production system and production method capable of reducing the spec out rate by reducing the fluctuation range of the properties of the polymer produced in continuous polymer production. for the purpose of

Specific means for solving the above problems include the following embodiments.
<1>. A first fluid containing a first polyaddition polymerizable compound and a second fluid containing a second polyaddition polymerizable compound that polyadditions with the first polymerizable compound are used as raw materials to produce a polymer. A combined manufacturing system,
a first supply unit that supplies the first fluid;
a second supply unit that supplies the second fluid;
a first merging section for merging the first fluid and the second fluid to generate a first merged fluid;
a first tubular mixing section disposed downstream of the first merging section for promoting radial mixing of the first merged fluid to generate a first tubular mixed fluid;
a first variation mitigation section disposed downstream of the first tubular mixing section and configured to reduce variations in axial properties of the first tubular mixed fluid to generate a first product fluid. manufacturing system.

<2>. According to <1>, further comprising a first measurement unit that acquires first reaction information relating to physical quantities and/or compositions in any one or more of the first merged fluid, the first tube mixed fluid, and the first generated fluid. polymer manufacturing system.

<3>. The first measurement unit includes a viscometer, a thermometer, a pressure gauge, a pump pressure gauge, an absorbance meter, an infrared spectrometer, a near-infrared spectrometer, a density meter, a color difference meter, a refractometer, a spectrophotometer, and a conductivity meter. , having one or more selected from the group consisting of a turbidimeter, an ultrasonic sensor, and a fluorescent X-ray analyzer,
The polymer production system according to <2>.

<4>. further comprising a first temperature control unit for adjusting the temperature of any one or more of the first fluid, the second fluid, the first merged fluid, the first tube mixed fluid, and the first generated fluid,
The polymer production system according to <2>.

<5>. The first fluctuation reducing section is configured by one or more tubular members,
The polymer production system according to any one of <1> to <4>, wherein the total average residence time of each of the tubular members is 7 minutes or longer.

<6>. The polymer production system according to any one of <1> to <4>, wherein the first fluctuation reducing section is a pipe in which an average residence time of fluid flowing therein is 7 minutes or longer.

<7>. a first tube mixed fluid measuring unit for acquiring first tube mixed fluid reaction information related to the physical quantity and/or composition of the first tube mixed fluid is provided between the first tubular mixing unit and the first fluctuation reducing unit; prepared,
further comprising a first generated fluid measurement unit for obtaining first generated fluid reaction information related to the physical quantity and/or composition of the first generated fluid, at the outlet of the first fluctuation mitigation unit or downstream thereof;
The polymer production system according to any one of <1> to <4>, wherein the volume of the first fluctuation reducing section is 0.5 to 100 times the volume of the first tubular mixing section.

<8>. The polymer production system according to any one of <1> to <4>, wherein the volume of the first fluctuation reducing section is 5 to 100 times the volume of the first tubular mixing section.

<9>. The polymer production system according to any one of <1> to <4>, wherein the first fluctuation mitigation section is a pipe in which the fluid that has passed through the trajectory line with the highest flow velocity has a residence time of 3 minutes or longer.

<10>. The first fluctuation reducing section is configured by one or more tubular members,
The cross-sectional average flow velocity of the fluid flowing inside the tubular member is 0.01 m/s or less,
The polymer production system according to any one of <1> to <4>, wherein the total length of each of the tubular members is 0.7 m or longer.

<11>. Any one of <1> to <10>, wherein the Reynolds number of the fluid flowing inside the first fluctuation reducing portion is 2100 or less when 4×cross-sectional area/immersion side length is used as a representative length The described polymer production system.

<12>. The polymer production system according to <1>, wherein the first fluctuation reducing section does not have a driven stirrer and the fluid forms an open channel.

<13>. In <1>, it takes 10 minutes or more after the fluid that has flowed through the trajectory line with the highest flow velocity has flowed out until 70% of the fluid that simultaneously flowed into the first fluctuation damping portion flows out. The described polymer production system.

<14>. <1> to <13>, wherein the first polymerizable compound and the second polymerizable compound satisfy any one of the following (a) to (c), and a polyamic acid is produced as the polymer: Polymer production system.
(a) One of the first polymerizable compound and the second polymerizable compound is a tetracarboxylic dianhydride and the other is a diamine.
(b) One of the first polymerizable compound and the second polymerizable compound is an acid anhydride-terminated or amino group-terminated polyamic acid, and the other is a diamine or a tetracarboxylic dianhydride.
(c) one of the first polymerizable compound and the second polymerizable compound is an acid anhydride-terminated or amino group-terminated polyamic acid, and the other is an amino group-terminated or an acid anhydride-terminated polyamic acid; .

<15>. The polymer production system according to <14>, further comprising an imidization section for imidizing the produced polyamic acid, and producing polyimide as the polymer.

<16>. the first measurement unit acquires the first reaction information in any one or more of the first merged fluid, the first tube mixed fluid, and the first generated fluid;
any one or more selected from the group consisting of fluid supply in the first supply unit, fluid supply in the second supply unit, and temperature adjustment in the first temperature control unit based on the acquired first reaction information; The polymer production system according to <4>, further comprising a controller for controlling.

<17>. The first measuring unit has a measuring step of acquiring the first reaction information in the first merged fluid and/or the first tube mixed fluid,
Based on the obtained first reaction information, the property of the first generated fluid is predicted, and based on the predicted property of the first generated fluid, the fluid supply in the first supply unit and the second supply unit The polymer production system according to <4>, further comprising a control unit that controls at least one selected from the group consisting of fluid supply and temperature adjustment in the first temperature control unit.

<18>. A method for producing a polymer using the polymer production system according to any one of <1> to <17>.

<19>. A method for producing a polyamic acid solution and/or polyimide using the polymer production system according to any one of <1> to <17>.

According to the present invention, it is possible to provide a polymer production system and production method capable of continuously and stably obtaining a desired polymer with little viscosity change over time. Also, in continuous polymer production, a polymer production system and production that can reduce the spec out rate by providing a mechanism with a simple structure and low equipment cost to reduce fluctuations in the properties of the polymer. can provide a method.

It is a figure which shows the polymer manufacturing system in 1st Embodiment. It is a figure which shows the polymer manufacturing system in 2nd Embodiment. It is a figure which shows the polymer manufacturing system in 3rd 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 to third embodiments are examples of a polymer production system that includes a first tubular mixing section and a first fluctuation reducing section.

<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 is a production system for producing a polymer using a first fluid A1 containing a first polyaddition polymerizable compound and a second fluid A2 containing a second polyaddition polymerizable compound as raw materials. is. The first embodiment is an example of a polymer production system in which a first tubular mixing section and a first fluctuation reducing section are provided continuously.

Here, the first tubular mixing section means a tubular mixing section that homogenizes properties in the radial direction while circulating the fluid. In addition, the first variation mitigation section is a structural section that can reduce variations in properties in the axial direction by actively generating a residence time distribution that utilizes the difference in flow velocity due to the trajectory in the flow channel. means

As an example, the case where one of the first polymerizable compound and the second polymerizable compound is a tetracarboxylic dianhydride and the other is a diamine to produce a polyamic acid as a polymer will be described below. More specifically, the first polymerizable compound contained in the first fluid A1 is tetracarboxylic dianhydride, the second polymerizable compound contained in the second fluid A2 is diamine, and the polymer is polyamic acid. will be described.

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, anthracene-2,3,6,7-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, 2,2-bis(4-hydroxyphenyl)propane dibenzoate-3 ,3′,4,4′-tetracarboxylic dianhydride and other aromatic tetracarboxylic dianhydrides; butane-1,2,3,4-tetracarboxylic dianhydride and other aliphatic tetracarboxylic acids dianhydride; alicyclic tetracarboxylic dianhydride such as cyclobutane-1,2,3,4-tetracarboxylic dianhydride; thiophene-2,3,4,5-tetracarboxylic dianhydride, pyridine -heterocyclic tetracarboxylic dianhydrides such as 2,3,5,6-tetracarboxylic dianhydride; Tetracarboxylic dianhydrides may be used alone or in combination of two or more.

As the solvent for the first fluid A1, one that dissolves tetracarboxylic dianhydride and polyamic acid is used. Specific examples of solvents include amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and acetanilide; Cyclic ester solvents such as butyrolactone; chain ester solvents such as ethyl acetate; ketone solvents such as 2-propanone, 3-pentanone, acetone and methyl ethyl ketone; ether solvents such as tetrahydrofuran and dioxolane; and aromatic hydrocarbon solvents such as toluene and xylene; and the like. Among these, amide-based solvents, cyclic ester-based solvents, and ether-based solvents in which the polyamic acid is highly soluble are preferred. A solvent may be used individually by 1 type, and may mix 2 or more types. For example, by mixing a highly polar alcoholic solvent with a solvent in which polyamic acid has relatively low solubility, such as acetone, ethyl acetate, methyl ethyl ketone, toluene, and xylene, the solubility of polyamic acid can be improved. is also possible.

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

The diamine is not particularly limited, and the same ones 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, Aromatic diamines such as 3,3′-diaminobenzophenone, 3,4′-diaminobenzophenone, 4,4′-diaminobenzophenone, 4,4′-diaminobibenzyl; 1,2-diaminoethane, 1,4-diamino Aliphatic diamines such as butane, tetramethylenediamine, and 1,10-diaminododecane; heterocyclic diamines such as 3,4-diaminopyridine; and the like. A diamine may be used individually by 1 type, and may use 2 or more types together.

As the solvent for the second fluid A2, one that dissolves diamine and polyamic acid is used. Specific examples of solvents include amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and acetanilide; Cyclic ester solvents such as butyrolactone; chain ester solvents such as ethyl acetate; ketone solvents such as 2-propanone, 3-pentanone, acetone and methyl ethyl ketone; ether solvents such as tetrahydrofuran and dioxolane; and aromatic hydrocarbon solvents such as toluene and xylene; and the like. Among these, amide-based solvents, cyclic ester-based solvents, and ether-based solvents in which the polyamic acid is highly soluble are preferred. A solvent may be used individually by 1 type, and may mix 2 or more types. For example, by mixing a highly polar alcoholic solvent with a solvent in which polyamic acid has relatively low solubility, such as acetone, ethyl acetate, methyl ethyl ketone, toluene, and xylene, the solubility of polyamic acid can be improved. is also possible.

A filler that serves as a lubricant for the polyimide film may be dispersed in the first fluid A1 and/or the second fluid A2. Examples of lubricants include inorganic particles such as titanium oxide, dicalcium phosphate anhydride, calcium pyrophosphate, calcium carbonate, silicon dioxide, alumina, barium sulfate, zirconia, kaolin, talc, clay, mica, acrylic acids, and styrenes. and the like can be exemplified as organic particles. Further, inorganic particles or organic particles added for the purpose of changing other properties of the polyimide film such as film strength and thermal conductivity may be dispersed.

As shown in FIG. 1, the polymer production system 1 joins and mixes a first fluid A1 and a second fluid A2, which are raw materials, at a first junction J1 to generate a first merged fluid B, By agitating the merged fluid B in the first tubular mixing section 20, a first tubular mixed fluid C in which the concentration of each component in the radial direction of the tube is uniform is generated. Subsequently, by reducing the variation in the axial viscosity of the first tube mixed fluid C in the first variation reducing section 30 to obtain the first generated fluid D, polyamic acid (heavy combined).

In addition, the polymer production system 1 has a liquid feed line L that connects the first tank 11 and the second tank 12 described later to the outlet of the first fluctuation reducing section 30 .

The polymerization reaction proceeds in either or both of the first tubular mixing section 20 and the first fluctuation reducing section 30. The polymerization reaction may be completely completed at the outlet of the first tubular mixing section 20, or the reaction has hardly progressed at the outlet of the first tubular mixing section 20, and the first fluctuation reducing section 30 may Most of the reaction may proceed. In addition, the polymerization reaction does not necessarily have to be completely completed at the outlet of the first fluctuation reducing section 30, and the reaction may proceed even in the pipe or cushion tank provided downstream of the first fluctuation reducing section 30. good. However, in order to obtain a polymer with stable properties, it is preferable to design so that 80% or more of the polymerization reaction is completed at the outlet of the first fluctuation reducing section 30, and the polymerization is performed at the outlet of the first tubular mixing section 20. It is more preferable to design so that the reaction is completed 80% or more.

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 first tank on-off valve 111, a second tank 12, a second tank on-off valve 121, and a first supply pump 112 ( first supply section), a second supply pump 122 (second supply section), a first junction J1, a first tubular mixing section 20, a first fluctuation reducing section 30, a liquid feed line L, A control unit 200 is provided. The liquid feeding line L described above has a first liquid feeding section L1, a second liquid feeding section L2, a third liquid feeding section L3, a fourth liquid feeding section L4, and a fifth liquid feeding section L5. . In addition, the polymer production system 1 includes a first flow rate measurement unit 113, a second flow rate measurement unit 123, a first tube mixed fluid measurement unit 222 (first measurement unit), and a first generated fluid measurement unit 322 (second 1 measuring unit).

The first tank 11 contains the first fluid A1 in which the polyaddition first polymerizable compound is dissolved. In this embodiment, the first tank 11 contains the first fluid A1 in which tetracarboxylic dianhydride is dissolved. The first fluid A1 contained in the first tank 11 is supplied to the first junction J1 via the first liquid feeding section L1.

The first liquid feeding part L1 is a line that connects the first tank 11 and the first junction part J1. A first tank on-off valve 111, a first supply pump 112, and a first flow rate measuring unit 113 are provided between the first tank 11 and the first junction J1 in the first liquid feeding unit L1, from the upstream side to the downstream side. Arranged in this order from side to side.

The first tank on-off valve 111 is arranged in the vicinity of the lower part of the first tank 11 in the first liquid feeding section L1, and opens and closes the first liquid feeding section L1 on the upstream side of the first supply pump 112.

The first supply pump 112 supplies the first fluid A1 contained in the first tank 11 to the first junction J1. The first supply pump 112 discharges the first fluid A1 at a predetermined flow rate. For example, the first supply pump 112 is adjusted so as to supply the first fluid A1 under conditions under which polyamic acid with desired properties is obtained.

In this embodiment, the first supply pump 112 is composed of a metering pump.
In the present embodiment, by controlling the supply of the first fluid A1 supplied by the first supply pump 112 and the second fluid A2 supplied by the second supply pump 122, which will be described later, a desired property can be obtained. Obtain polyamic acid. Therefore, it is preferable that the first fluid A1 and the second fluid A2 are supplied with high accuracy. Configured.

A metering pump is a positive displacement pump that repeatedly pumps out a fixed amount of fluid with high accuracy. Examples of metering pumps include push-type reciprocating pumps such as plunger pumps; rotary pumps such as gear pumps provided with gears; and the like.

The first flow rate measuring unit 113 measures the flow rate of the first fluid A1 on the downstream side of the first supply pump 112 in the first liquid feeding unit L1. In this embodiment, the first flow rate measurement section 113 is arranged between the first supply pump 112 and the first junction J1. The first flow rate measurement unit 113 outputs the measured flow rate of the first fluid A1 to the control unit 200, which will be described later.

The second tank 12 contains the second fluid A2 in which the second polyadditive polymerizable compound that polyadditions with the first polymerizable compound is dissolved. In this embodiment, the second tank 12 contains the second fluid A2 in which diamine is dissolved. The second fluid A2 stored in the second tank 12 is supplied to the first junction J1 via the second liquid feeding section L2.

The second liquid feeding part L2 is a line that connects the second tank 12 and the first junction part J1. A second tank on-off valve 121, a second supply pump 122, and a second flow rate measuring unit 123 are provided between the second tank 12 and the first junction J1 in the second liquid feeding unit L2, from the upstream side to the downstream side. Arranged in this order from side to side.

The second tank on-off valve 121 is arranged in the vicinity of the lower portion of the second tank 12 in the second liquid feeding section L2, and opens and closes the second liquid feeding section L2 on the upstream side of the second supply pump 122.

The second supply pump 122 supplies the second fluid A2 contained in the second tank 12 to the first junction J1. The second supply pump 122 discharges the second fluid A2 at a predetermined flow rate. For example, the second supply pump 122 is adjusted so as to supply the second fluid A2 under conditions under which polyamic acid with desired properties is obtained.
In this embodiment, the second supply pump 122 is a metering pump for the same reason as the first supply pump 112 described above.

The second flow rate measuring section 123 measures the flow rate of the second fluid A2 on the downstream side of the second supply pump 122 in the second liquid feeding section L2. In this embodiment, the second flow rate measurement section 123 is arranged between the second supply pump 122 and the first junction J1. The second flow rate measurement unit 123 outputs the measured flow rate of the second fluid A2 to the control unit 200, which will be described later.

The first junction J1 is arranged downstream of the first supply pump 112 and the second supply pump 122 . The first confluence J1 generates a first merge fluid B by merging the first fluid A1 and the second fluid A2. At the first junction J1, the first fluid A1 and the second fluid A2 are merged without coming into contact with gas. The first junction J1 is configured by a junction valve that joins the first fluid A1 supplied by the first supply pump 112 and the second fluid A2 supplied by the second supply pump 122 .

The first tubular mixing section 20 is arranged downstream of the first junction J1. The first tubular mixing section 20 agitates the first merged fluid B without contacting the gas, and makes the fluid uniform in the radial direction of the tube at the outlet of the first tubular mixing section 20. Thus, the first tube mixed fluid C is generated.

The first tubular mixing section 20 includes a tubular reactor composed of double tubes extending in a predetermined direction. The first tubular mixing section 20 includes a first tubular mixing and stirring section 21 arranged radially inside and a first tubular mixing temperature control section 22 arranged radially outward (first temperature control section ) and The first tubular mixing section 20 is formed so that the first merged fluid B flows for a desired residence time.

The first tubular mixing and stirring part 21 stirs the first merged fluid B. In the present embodiment, the first tubular mixing/agitation section 21 agitates the first combined fluid B adjusted to a temperature suitable for the polymerization reaction by the first tubular mixing/temperature control section 22 .

The first tubular mixing/stirring unit 21 includes, for example, static mixers, nozzles, orifices, and other stationary mixers, centrifugal pumps, volute pumps, and drive-type mixers, such as in-line mixers having stirring blades. It preferably includes a static mixer, and more preferably includes a static mixer. In addition, a pipe with a twist tape inserted (see [Fig. 19] of Japanese Patent Application Laid-Open No. 2003-314982, etc.) can also provide the same agitation promotion effect as a static mixer, but the static mixer has a better agitation promotion effect. is obtained.

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.

The first tubular mixing temperature control section 22 is a piping section arranged radially outside the first tubular mixing stirring section 21 . The first tubular mixing temperature control section 22 adjusts (for example, cools) the temperature of the first merged fluid B flowing through the first tubular mixing and stirring section 21 to a desired temperature condition. In the first tubular mixing temperature control section 22 , the first combined fluid B is adjusted to a temperature suitable for the polymerization reaction, and flows through the first tubular mixing stirring section 21 .

The generated first tube mixed fluid C is supplied to the first fluctuation reducing section 30 via the fourth liquid feeding section L4.

The first pipe mixed fluid measuring unit 222 measures the viscosity of the first pipe mixed fluid C between the first pipe mixing unit 20 and the first fluctuation reducing unit 30 in the fourth liquid feeding unit L4. Reaction information (first reaction information) is acquired. The viscosity information is effective information as the reaction information because the polymerization reaction progresses and the viscosity increases due to the stirring in the first tubular mixing/stirring part 21 . The first pipe mixed fluid measurement unit 222 outputs the acquired viscosity information of the first pipe mixed fluid C to the control unit 200 which will be described later.

In addition, the first pipe mixed fluid measurement unit 222 measures the temperature of the first pipe mixed fluid C between the first pipe mixing unit 20 and the first fluctuation reducing unit 30 in the fourth liquid feeding unit L4. Mixed fluid reaction information (first reaction information) is also acquired. The polymerization reaction proceeds by being stirred in the first tubular mixing/stirring part 21. Since the reaction speed of the polymerization reaction varies depending on the temperature, temperature information is effective information as reaction information. The first pipe mixed fluid measurement unit 222 outputs the obtained temperature information of the first pipe mixed fluid C to the control unit 200 which will be described later.

The first fluctuation reducing section 30 is arranged downstream of the first tubular mixing section 20 . The first fluctuation mitigating section 30 is composed of a double pipe, and includes a first fluctuation mitigating pipe section 31 arranged radially inside and a first fluctuation mitigating temperature control section 32 arranged radially outside (first a temperature control unit); In this embodiment, the temperature is adjusted to a temperature suitable for the polymerization reaction of the mixed fluid C in the first tube by the first fluctuation relaxation temperature control section 32 .

In the first fluctuation mitigating pipe portion 31, the axial viscosity of the first pipe mixed fluid C is controlled by the residence time distribution caused by the difference in velocity in the radial direction when the first pipe mixed fluid C flows through the first fluctuation mitigating pipe portion 31. Fluctuations are reduced, and the properties of the outflowing first generated fluid D are stabilized. For example, in the case of laminar flow in a circular tube, the fluid passing through the center of the tube has the highest flow velocity and the shortest residence time. On the other hand, since the flow velocity of the fluid passing near the pipe wall is extremely low, the residence time is very long. The variation in properties in the axial direction can be mitigated by the difference in residence time due to this trajectory.

In order to obtain a sufficient viscosity fluctuation mitigation effect in the first fluctuation mitigating pipe portion 31, it is preferable that the first pipe mixed fluid C flows in the first fluctuation mitigating pipe portion 31 in a laminar flow. In order to flow in a laminar flow in the first fluctuation relaxation pipe portion 31, when using 4 × cross-sectional area / immersion side length as the representative length d, it is calculated from the viscosity μ, the cross-sectional average flow velocity u, and the density ρ The Reynolds number (ρud/μ) is preferably 2100 or less, more preferably 0.00001 or more and 1000 or less. Further, when the solution viscosity is low, the velocity distribution cannot be effectively generated because the run-up section until the flow develops is long. should have a higher viscosity. Specifically, the viscosity of the first pipe mixed fluid C flowing in the first fluctuation mitigating pipe portion 31 is preferably 0.1 poise or more and 100000 poise or less, more preferably 1 poise or more and 10000 poise or less at the temperature during circulation. More preferably, it is 5 poise or more and 5000 poise or less.

The first fluctuation mitigation pipe section 31 includes a pipe with a sufficiently long average residence time. Here, the average residence time is a value obtained by dividing the volume of the pipe by the volumetric flow rate of the mixed fluid C in the first pipe. The longer the average residence time of the first fluctuation relaxation pipe portion 31 is, the greater the effect of stabilizing the viscosity of the first generated fluid D flowing out from the first fluctuation relaxation pipe portion 31 is. Therefore, it is preferable to lengthen the average residence time of the first fluctuation mitigating pipe portion 31 as the fluctuation of the properties of the first mixed fluid C flowing out from the first tubular mixing portion 20 in the axial direction increases.

Specifically, for example, when the Newtonian fluid flows in a laminar flow in the first fluctuation relaxation pipe portion 31, which is a straight pipe with a circular cross section, the average residence time of the first fluctuation relaxation pipe portion 31 is 3 minutes. , the viscosity fluctuation at the outlet of the first fluctuation mitigating pipe portion 31 is reduced by 56%, the viscosity fluctuation is reduced by 74% when the average residence time is 7 minutes, and the viscosity fluctuation is reduced when the average residence time is 11 minutes. is reduced by 81%. However, the reduction in viscosity fluctuation described here means that the difference between the maximum value and the minimum value of the viscosity at the inlet of the first fluctuation relaxation pipe portion 31 is the maximum value of the viscosity at the outlet of the first fluctuation relaxation pipe portion 31. It means the rate at which the difference between the minimum values decreases.

Although FIG. 1 shows a configuration in which only one first fluctuation relaxation pipe portion 31 is provided, the first fluctuation relaxation pipe portion 31 may have a structure in which two or more tubular members are connected by joints or the like. In that case, it is preferable that the total average residence time of each of the two or more tubular members constituting the first fluctuation mitigating pipe section 31 is 7 minutes or longer. The longer the average residence time of the first fluctuation mitigating pipe section 31, the greater the viscosity fluctuation reduction effect. .

The fluid flowing through the first fluctuation relaxation pipe portion 31 is not limited to a Newtonian fluid. different from the case of Therefore, when designing the average residence time of the first fluctuation mitigating pipe section 31, the rheology of the fluid flowing through the first fluctuation mitigating pipe section 31 should be taken into consideration. For example, in the case of a pseudoplastic fluid whose residence time distribution is smaller than that of a Newtonian fluid, it is preferable to set the average residence time of the first fluctuation relaxation pipe portion 31 longer.

The first fluctuation mitigating pipe section 31 can mitigate fluctuations with a shorter period than the average residence time, but it is difficult to alleviate fluctuations with a longer period than the average residence time. Therefore, it is preferable to make the average residence time of the first fluctuation reducing pipe section 31 sufficiently longer than the average fluctuation period of the first pipe mixed fluid C that can occur at the outlet of the first tubular mixing section 20 . However, the average fluctuation cycle described here is the average of the time from when the viscosity of the first tube mixed fluid C at the outlet of the first tube mixing section 20 reaches a maximum value to when it reaches a minimum value and then reaches a maximum value again. time. The average residence time of the first fluctuation mitigating pipe section 31 is preferably at least 1 time, more preferably at least 2 times the average fluctuation cycle of the first tube mixed fluid C at the outlet of the first tubular mixing section 20. more preferred.

In order to ensure that the first fluctuation relaxation pipe section 31 has an appropriate average residence time according to the viscosity fluctuation of the first pipe mixed fluid C, the volume of the first fluctuation relaxation pipe section 31 is set to the first pipe mixing stirring part It is preferably 0.5 to 100 times the volume of 20, more preferably 5 to 100 times.

In addition, the first fluctuation mitigating pipe section 31 alleviates viscosity fluctuations by the distribution of residence time due to the difference in flow velocity, and since the flow velocity is extremely slow near the pipe wall, A sufficient effect of alleviating viscosity fluctuations can also be obtained by designing the fluid so that its residence time is sufficiently long. The trajectory with the highest flow velocity refers to the trajectory that always passes through the center of the cross section, for example, in the case of laminar flow in a circular tube. When the tracer particles and the coloring agent are put into the entire cross section of the inlet of the first fluctuation mitigating pipe portion 31, the time required for the tracer particles and the coloring agent to first flow out from the outlet of the first fluctuation mitigating pipe portion 31 is It roughly corresponds to the residence time of the fluid passing through the trajectory with the highest velocity. Specifically, for example, when a Newtonian fluid flows in a laminar flow in the first fluctuation mitigating pipe section 31, which is a straight pipe with a circular cross section, the residence time of the fluid passing through the trajectory line with the highest flow velocity is 3 In the case of minutes, the variation in viscosity at the outlet of the first variation relaxation piping section 31 is reduced by 72%. The effect of reducing viscosity fluctuations in the first fluctuation reducing pipe section 31 increases as the residence time of the fluid that has passed through the trajectory line with the highest flow velocity increases. More preferably, the total residence time of the fluid through the fast trajectories is 150 minutes or less.

If the average residence time of the first fluctuation relaxation piping section 31 is about the same, the cross-sectional area and length of the first fluctuation relaxation piping section 31 and the first pipe mixed fluid C flowing through the first fluctuation relaxation piping section 31 are The effect of stabilizing the viscosity of the first generated fluid D is approximately the same regardless of the flow rate. However, if the cross-sectional area of the first fluctuation relaxation pipe portion 31 is small and the length is long, the pressure loss increases when the mixed fluid C in the first pipe flows through the first fluctuation relaxation pipe portion 31, so the pressure resistance is high. Piping is required, and equipment costs are high. Therefore, it is preferable to increase the cross-sectional area of the first fluctuation relaxation pipe portion 31 to some extent and shorten the length. Specifically, it is preferable that the length of the cross-sectional area is 0.7 m or more so that the cross-sectional average flow velocity is 0.01 m / s or less, and the cross-sectional average flow velocity is 0.00001 m / s or more and 0.003 m / s. More preferably, the length is 0.7 m or more and 60 m or less. However, the cross-sectional average flow velocity described here is a value obtained by dividing the volumetric flow rate of the mixed fluid C in the first pipe by the cross-sectional area of the first fluctuation reducing pipe portion 31 . In addition, when two or more tubular members are connected by a joint or the like in the first fluctuation mitigating pipe section 31, the total length of each of the two or more tubular members should be 0.7 m or more and 60 m or less.

It is preferable to use a hollow cylindrical pipe as the first fluctuation mitigation pipe section 31 in order to reduce the equipment cost. However, the shape of the first fluctuation mitigating pipe portion 31 is not particularly limited as long as the residence time has a distribution due to the velocity distribution in the cross-sectional direction when the first pipe mixed fluid C flows. Specifically, it may have a structure inside, may use a pipe bent by an elbow or the like, and may not have a circular cross section. Also, a valve, a sensor, or the like may be installed in the middle of the first fluctuation mitigating pipe section 31 .

In order to obtain the first generated fluid D that does not contain air bubbles, it is preferable that the first fluctuation mitigating pipe section 31 is fed without contacting the gas. However, the present invention is not limited to this, and a gas phase may exist inside the first fluctuation reducing pipe portion 31 as long as air bubbles are not involved in the mixed fluid C in the first pipe.

The first fluctuation mitigation pipe section 31 is provided between the first pipe mixed fluid measurement section 222 and the first generated fluid measurement section 322 . The first fluctuation reducing pipe portion 31 is preferably a cylindrical pipe having the same inner diameter dimension from the end on the upstream side to the end on the downstream side in the flow direction of the mixed fluid C in the first pipe. It is preferable that the length dimension of the first fluctuation mitigating pipe portion 31 is 5 times or more and 1000 times or less the inner diameter dimension. It is preferable that the inner diameter dimension of the first fluctuation reducing pipe portion 31 is 0.5 times or more and 10 times or less the inner diameter dimension of the fourth liquid feeding portion L4 located on the upstream side. In addition, in the first fluctuation mitigating pipe section 31, the first pipe mixed fluid C flows in a state in which the internal space is filled with the first pipe mixed fluid C. Therefore, the flow velocity of the first pipe mixed fluid C in the radial direction is the difference becomes greater.

The first fluctuation mitigation temperature control section 32 is a piping section arranged radially outside the first fluctuation mitigation piping section 31 . The first fluctuation mitigation temperature control section 32 temperature-regulates (for example, cools) the first pipe mixed fluid C flowing through the first fluctuation mitigation piping section 31 to a desired temperature condition. In the first fluctuation relaxation temperature control section 32 , the first pipe mixed fluid C is adjusted to a temperature suitable for the polymerization reaction, and flows through the first fluctuation relaxation piping section 31 .

In the first tubular mixing section 20 and the first fluctuation reducing section 30 described above, the first tubular mixing section 20 is arranged in the front stage and the first fluctuation reducing section 30 is arranged in the rear stage, so that the first When there is variation in viscosity in the axial direction of the tube in the tubular mixing section 20, the variation in viscosity in the axial direction of the tube can be significantly reduced in the subsequent first variation reducing section 30. FIG.

For example, when the viscosity of the fluid produced by the variation in the ratio of the first fluid A1 and the second fluid A2 varies in the axial direction of the tube, the first tube mixing structure has a structure for agitation inside. In the portion 20, the velocity distribution in the radial direction is difficult to occur, and the fluctuation of the viscosity of the mixed fluid in the axial direction of the pipe cannot be eliminated. On the other hand, by arranging the first tubular mixing section 20 in the front stage and arranging the first fluctuation reducing section 30 in the rear stage, the properties in the radial direction are made uniform in the first tubular mixing section 20 in the front stage. After that, by feeding the liquid with a distribution in the residence time in the first fluctuation reducing section 30 in the latter stage, the first tube mixed fluid C that could not be eliminated in the first tubular mixing section 20 in the former stage Fluctuations in viscosity in the axial direction of the pipe can be significantly reduced in the first fluctuation reducing section 30 in the latter stage.

The first generated fluid measuring unit 322 is located at the outlet of the first fluctuation reducing unit 30 or downstream thereof, and is provided with first generated fluid reaction information (first reaction information ). Viscosity information is effective information as reaction information because the viscosity increases as the polymerization reaction progresses. The first generated fluid measurement unit 322 outputs the acquired viscosity information of the first generated fluid to the control unit 200, which will be described later.

The first generated fluid measurement unit 322 also acquires first generated fluid reaction information (first reaction information) regarding the temperature of the first generated fluid D in the fifth liquid feeding unit L5. Since the reaction rate of the polymerization reaction differs depending on the temperature, temperature information is effective information as reaction information. The first generated fluid measurement unit 322 outputs the acquired temperature information of the first generated fluid to the control unit 200, which will be described later.

Note that the first tube mixed fluid measurement unit 222 and the first generated fluid measurement unit 322 of the present embodiment provide reaction information related to the physical quantity and/or composition of at least one of the first tube mixed fluid C and the first generated fluid D. is an example of a measurement unit that acquires

The measurement unit is not limited to the first tube mixed fluid measurement unit 222 and the first generated fluid measurement unit 322 (physical quantity and/or composition type, measurement method) of the present embodiment. The measurement unit includes, for example, a viscometer, a thermometer, a pressure gauge, a pump pressure gauge, an absorbance meter, an infrared spectrometer, a near-infrared spectrometer, a density meter, a color difference meter, a refractometer, a spectrophotometer, a conductivity meter, It may have one or more selected from the group consisting of a turbidimeter and a fluorescent X-ray analyzer. The measurement unit acquires one or more pieces of reaction information relating to the physical quantity and/or composition of the object to be measured, and outputs the acquired reaction information to the control unit 200, which will be described later.

A cushion tank (not shown) may be provided downstream of the fifth liquid feeding line L5 to accommodate the first generated fluid D. The cushion tank serves as a tank for containing a raw material fluid, for example, when polyamic acid, which is a polymer, is imidated to produce polyimide.

When the polymer production system 1 according to the present embodiment produces polyimide, the polymer production system 1 further includes an imidization unit 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.

When the polymer manufacturing system 1 manufactures polyimide, the cushion tank may not be provided, and the liquid may be fed from the first fluctuation reducing section 30 to the imidization section. However, it is more preferable to once store the polyamic acid in a cushion tank.

The control unit 200 will be explained. The control unit 200 includes a first supply pump 112 , a second supply pump 122 , a first tubular mixing temperature control unit 22 , a first fluctuation relaxation temperature control unit 32 , a first flow rate measurement unit 113 , a second flow rate measurement unit 123 . , the first tube mixed fluid measurement unit 222 and the first generated fluid measurement unit 322 are electrically connected. In this specification, illustration of control lines from the control unit 200 to each pump, each temperature control unit, and each measurement unit is omitted.

The control section 200 controls the supply pumps 112 and 122 based on the flow rate values measured by the flow

rate measurement sections

113 and 123, respectively.
The control unit 200 controls, for example, the first supply pump 112 and/or the second supply pump 122, thereby controlling the first polymerizable compound contained in the first fluid A1 and the second polymerizable compound contained in the second fluid A2. The substance amount ratio with the compound is controlled so as to be within a predetermined range. The above substance amount ratio is set, for example, so as to obtain a polyamic acid having desired properties. Further, the control unit 200 controls the temperature conditions of the first tubular mixing temperature control unit 22 and/or the first fluctuation relaxation temperature control unit 32, for example, so that the reaction rate of the polymerization reaction is within a predetermined range. to control.

Based on the first reaction information acquired by the first tube mixed fluid measurement unit 222 and/or the first generated fluid measurement unit 322, the control unit 200 controls the supply of the first supply pump 112 and the supply of the second supply pump 122. , temperature adjustment in the first tubular mixing temperature control section 22 , and temperature adjustment in the first fluctuation mitigation temperature control section 32 .

Next, the operation of the polymer production system 1 (polyamic acid production system) in the first embodiment will be described.
First, in the polymer production system 1, by starting operation, the first supply pump 112 supplies the first fluid A1, and the second supply pump 122 supplies the second fluid A2. Here, the discharge flow rates of the first supply pump 112 and the second supply pump 122 are controlled by the controller 200 so as to supply the first fluid A1 and the second fluid A2 at a desired ratio. As a result, the first fluid A1 and the second fluid A2 are supplied to the first junction J1. In the first merging portion J1, the first fluid A1 supplied by the first supply pump 112 and the second fluid A2 supplied by the second supply pump 122 are merged and mixed to form the first merged fluid B. generated.

The first merged fluid B generated in the first merging portion J1 is sent through the third liquid sending portion L3 by the supply operations of the first supply pump 112 and the second supply pump 122, and is fed to the first tubular mixing portion 20. supplied to

In the first tubular mixing section 20, the first merged fluid B is stirred to make the properties such as concentration uniform in the radial direction, thereby generating the first tubular mixed fluid C. do. When the first tubular mixing section 20 is a static mixer such as a static mixer, the first merged fluid B is stirred only by passing it through. Here, in the first tubular mixing section 20, the first merged fluid B moves in the axial direction of the pipe without causing a wide velocity distribution. If there is a change, it cannot be resolved.

The first pipe mixed fluid C generated in the first tubular mixing section 20 is sent through the fourth liquid sending section L4 and supplied to the first fluctuation reducing section 30 .

In the first fluctuation reducing section 30, the first pipe mixed fluid C is introduced and continuously fed while the residence time of the first pipe mixed fluid C is distributed according to the velocity distribution in the radial direction. As a result, fluctuations in the viscosity of the first pipe mixed fluid C in the axial direction of the tube, which cannot be eliminated in the first tubular mixing section 20 in the preceding stage, can be significantly reduced in the first fluctuation reducing section 30 in the subsequent stage. can. Therefore, a desired polymer can be obtained continuously and stably.

Here, during the operation of the polymer production system 1 described above, the first pipe mixed fluid measuring section 222 and the first produced fluid measuring section 322 acquire viscosity information (measurement step).
Based on the viscosity information (first reaction information) acquired by the first tube mixed fluid measurement unit 222 and/or the first generated fluid measurement unit 322, the control unit 200 controls the supply pumps 112 and 122 and the

temperature controllers

112 and 122. The

parts

22 and 32 are controlled (control process). Thereby, a polyamic acid having desired properties (temperature, viscosity) can be obtained.

When the distribution of the residence time of the first pipe mixed fluid C in the first fluctuation mitigation unit 30 is known, the first pipe mixed fluid measurement unit 222 acquires the first viscosity information (measuring step), and based on this, the first fluctuation A temporal change in the viscosity of the first generated fluid D at the outlet of the relaxation section 30 can be predicted (prediction step). The supply pumps 112 and 122 and the

temperature controllers

22 and 32 may be controlled based on the predicted viscosity (control step). For example, when a laminar flow is formed in the first fluctuation reducing section 30 and a Hagen-Poiseuille flow is formed, the flow velocity distribution in the radial direction can be calculated, so the residence time distribution can be known. Therefore, when the time moving average weighted by the residence time distribution is calculated for the viscosity of the first pipe mixed fluid C acquired by the first pipe mixed fluid measurement unit 222, the first generation at the outlet of the first fluctuation reduction unit 30 An estimate of the viscosity of fluid D is obtained.

When the distribution of the residence time of the first pipe mixed fluid C in the first fluctuation mitigation section 30 is unknown, the change over time of the viscosity at the inlet of the first fluctuation mitigation section 30 and the viscosity at the outlet of the first fluctuation mitigation section 30 may be measured once, and the change in the viscosity of the first generated fluid D may be predicted by modeling the effect of reducing the viscosity variation by the first variation reducing section 30 from the result. For modeling, for example, a first-order lag function or the like can be used.

If the operating conditions are controlled based on the viscosity information from the first pipe mixed fluid measurement unit 222, which fluctuates greatly, hunting may occur. On the other hand, if the operating conditions are controlled based on the viscosity information obtained by the first generated fluid measuring unit 322, the viscosity is stable, so hunting is unlikely, but the dead time is long, so spec-out is likely to occur. Therefore, it is effective to predict the viscosity of the first generated fluid D at the outlet of the first fluctuation reducing section 30 based on the viscosity information obtained by the first tube mixed fluid measuring section 222, and to perform control based thereon. .

In addition, during the operation of the polymer production system 1 described above, the first pipe mixed fluid measurement unit 222 and the first product fluid measurement unit 322 acquire temperature information (measurement step).
Based on the temperature information (first reaction information) acquired by the first tube mixed fluid measurement unit 222 and/or the first generated fluid measurement unit 322, the control unit 200 controls the first tubular mixed temperature control unit 22 and/or Alternatively, the temperature adjustment conditions in the first fluctuation mitigation temperature adjustment section 32 are controlled (control step). Thereby, a polyamic acid having desired properties (temperature, viscosity) can be obtained.

According to the polymer production system 1 of this embodiment, the following effects are obtained.
The polymer production system 1 includes a first supply pump 112 that supplies a first fluid A1 containing a first polymerizable compound, a second supply pump 122 that supplies a second fluid A2 containing a second polymerizable compound, and a first a first merging portion J1 for merging the fluid A1 and the second fluid A2 to generate a first merged fluid B; and a first tubular mixing section 20 that generates the first tubular mixed fluid C by equalizing the fluctuation of the viscosity of the first tubular mixing section 20, and the axis of the first tubular mixed fluid C that is arranged downstream of the first tubular mixing section 20. and a first fluctuation reducing unit 30 that generates the first generated fluid D by reducing the unevenness of the directional property.

In the present invention, the first tubular mixed fluid C mixed in the first tubular mixing section 20 arranged in the preceding stage is made uniform in the axial direction in the first fluctuation reducing section 30 arranged in the subsequent stage. Fluctuations in the viscosity of the first tubular mixed fluid C in the axial direction of the tube, which cannot be eliminated in the first tubular mixing section 20, can be eliminated in the subsequent first fluctuation reducing section 30, and the polymer solution can be continuously supplied. can be stably obtained.

Especially when producing a high-viscosity polymer, the pressure loss increases when the high-viscosity solution passes through the tubular mixer. Therefore, it is difficult to obtain a polymer with stable viscosity using only a tubular mixer. Therefore, the present invention is particularly effective when producing a high-viscosity polymer of, for example, 1000 poise or more.

In addition, in the polymer production system 1, based on the first reaction information acquired by the first tube mixed fluid measurement unit 222 and/or the first produced fluid measurement unit 322, the supply in the first supply pump 112, the second supply Any one or more of supply by the pump 122, temperature adjustment by the first tubular mixing temperature control section 22, and temperature adjustment by the first fluctuation relaxation temperature control section 32 is controlled. Thereby, a polymer having desired properties (temperature, viscosity) can be obtained.

In the present embodiment, one of the first polymerizable compound and the second polymerizable compound is a tetracarboxylic dianhydride and the other is a diamine, and the case of producing a polyamic acid as a polymer was described. It is not limited to this.
For example, among the first polymerizable compound and the second polymerizable compound, one is an acid anhydride group-terminated or amino group-terminated polyamic acid (prepolymer), the other is a diamine or tetracarboxylic dianhydride, and as a polymer You may make it manufacture a polyamic acid. In this case, one of the first polymerizable compound and the second polymerizable compound is an acid anhydride group-terminated polyamic acid, and the other is a diamine. Further, when one of the first polymerizable compound and the second polymerizable compound is an amino group-terminated polyamic acid, the other is a tetracarboxylic dianhydride.
Further, for example, 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 an amino group-terminated or an acid anhydride group-terminated polyamic acid, A polyamic acid may be produced as a coalescence. In this case, one of the first polymerizable compound and the second polymerizable compound is an acid anhydride group-terminated polyamic acid, and the other is an amino group-terminated polyamic acid.

<Second embodiment>
A polymer manufacturing system according to the second embodiment will be described with reference to FIG. FIG. 2 is a diagram showing a polymer production system in the second embodiment. In addition, the same code|symbol is attached|subjected and shown to the component similar to 1st Embodiment.

The first fluctuation reducing section 30 of the present embodiment is arranged downstream of the first tubular mixing section 20 . The first fluctuation damping section 30 includes a cylindrical first fluctuation damping tank 31a without a stirrer, and a first fluctuation damping temperature control section 32 (first temperature control section) arranged outside the first fluctuation damping tank 31a. , have In this embodiment, the temperature of the mixed fluid C in the first tube is adjusted to a temperature suitable for the polymerization reaction by the first fluctuation relaxation temperature control section 32 .

In the first fluctuation reduction tank 31a, the viscosity fluctuation in the first tube mixed fluid C in the axial direction (fluid flow direction) is reduced by the residence time distribution caused by the difference in velocity between the vertical direction and the horizontal direction. The properties of the fluid D can be stabilized, and fluctuations in the properties of the first tube mixed fluid C in the axial direction can be alleviated.

In the first fluctuation mitigation tank 31a, an open channel is formed, in which the first tube mixed fluid C flows in from the upper part in the vertical direction, and the first produced fluid D flows out from the lower part. Since the pressure on the inflow side of the first pipe mixed fluid C becomes the pressure of the gas phase portion by making the first fluctuation mitigation tank 31a an open channel, when the first pipe mixing portion 20 and subsequent ones are pipes, In comparison, it is superior in that the discharge pressures of the first supply pump 112 and the second supply pump 122 can be reduced. The gas phase portion can be kept at a constant pressure with an inert gas or the like.

Although there is no particular limitation on the shape of the first fluctuation mitigation tank 31a, a structure that does not easily create a dead space is preferable, and specifically, a cylindrical tank is preferable. If the ratio (L/D) of the diameter D to the height L of the cylindrical tank is too small, the fluid will not flow sufficiently in the horizontal direction and short-passing will easily occur, so it is preferably 0.5 or more. On the other hand, if the L/D is too large, it becomes difficult to install the apparatus, so it is preferably 10 or less. Therefore, it is preferably 0.5 to 10.

The inlet of the first fluctuation mitigation tank 31a may be installed on the wall surface or may be an insertion pipe. When an insertion tube is used, it is preferable to install the inflow port so that it is held in the liquid surface, or to install it so that the fluid flows along the wall surface to prevent air bubbles from entering. The outflow port of the first fluctuation reduction tank 31a is preferably installed at a position where the entire outflow port is immersed in the liquid in order to prevent air bubbles from entering.

Although it is preferable from a management point of view that the inflow velocity of the first pipe mixed fluid C into the first fluctuation mitigation tank 31a and the outflow velocity of the first generated fluid D are the same, variations may occur. For example, the outflow speed of the first generated fluid D may be controlled so that the liquid level in the first fluctuation reduction tank 31a is within a predetermined range.

If the liquid level is low, the gas phase may be involved at the outlet, so it is preferable to make it 20% or more. When the liquid level is high, the flow in the first fluctuation reducing tank 31a transitions from the open channel flow to the pipe channel flow or between the open channel flow and the pipe channel flow, causing pressure fluctuations in the first fluctuation reducing tank 31a. Since there is a possibility, it is preferable to set it to 80% or less. Therefore, it is preferable to control the amount of the first tube mixed fluid C in the first fluctuation reduction tank 31a to be 20% to 80% of the volume of the first fluctuation reduction tank 31a.

When a cylindrical tank is used as the first fluctuation mitigation tank 31a, it is preferable that the angle formed by the central axis and the installation surface is 75° or less in order to reduce the risk of entrainment of air bubbles. On the other hand, if the angle is too small, the update of the liquid level will be delayed. Therefore, it is preferable that the angle between the central axis of the first fluctuation mitigation tank 31a and the installation surface is 45° to 75°.

The first fluctuation mitigation tank 31a is configured so that the average residence time is sufficiently long. Here, the average residence time is a value obtained by dividing the volume of the solution in the first fluctuation mitigation tank 31a by the volumetric flow rate of the mixed fluid C in the first pipe. The longer the average residence time in the first fluctuation mitigation tank 31a, the greater the effect of stabilizing the viscosity of the first generated fluid D flowing out of the first fluctuation mitigation tank 31a. Therefore, it is preferable to lengthen the average residence time in the first fluctuation mitigation tank 31a as the fluctuation of the properties of the first mixed fluid C flowing out of the first tubular mixing section 20 in the axial direction increases. The residence time is preferably 3 minutes or longer, more preferably 7 minutes or longer, and more preferably 10 minutes or longer. The longer the average residence time in the first fluctuation mitigation tank 31a, the greater the viscosity fluctuation reduction effect.

In order to ensure that the first fluctuation relaxation tank 31a has an appropriate average residence time according to the viscosity fluctuation of the first pipe mixed fluid C, the volume of the solution in the first fluctuation relaxation tank 31a is adjusted to the first tubular mixing stirring part It is preferably 0.5 to 100 times the volume of 20, more preferably 5 to 100 times.

The shape of the first fluctuation mitigation tank 31a is not particularly limited. Specifically, it may have a structure inside. Further, a sensor or the like may be installed in the first fluctuation mitigation tank 31a.

The inside of the first fluctuation mitigation tank 31a is an open channel, and the first pipe mixed fluid C flowing in from the inlet located on the upper side flows vertically and horizontally in the first fluctuation mitigation tank 31a. Since the flow velocity of the first pipe mixed fluid C differs and the residence time in the first fluctuation reducing tank 31a differs, the fluctuation of the properties of the first fluctuation reducing tank 31a in the axial direction can be reduced.

The first fluctuation mitigation temperature control unit 32 temperature-regulates (for example, cools) the first tube mixed fluid C flowing through the first fluctuation mitigation tank 31a to a desired temperature condition.

Next, the operation of the polymer production system 1 (polyamic acid production system) in the second embodiment will be described.

In the first fluctuation reducing section 30, the first pipe mixed fluid C is allowed to flow in, and the residence time of the first pipe mixed fluid C is distributed according to the residence time distribution caused by the difference in velocity between the vertical direction and the horizontal direction. Feed continuously. As a result, fluctuations in the viscosity of the first pipe mixed fluid C in the axial direction of the tube, which cannot be eliminated in the first tubular mixing section 20 in the preceding stage, can be significantly reduced in the first fluctuation reducing section 30 in the subsequent stage. can. Therefore, a desired polymer can be obtained continuously and stably.

<Third Embodiment>
A polymer manufacturing system according to the third embodiment will be described with reference to FIG. FIG. 3 is a diagram showing a polymer production system in the third embodiment. In addition, the same code|symbol is attached|subjected and shown to the component similar to 1st and 2nd embodiment.

The first fluctuation mitigation section 30 of the present embodiment is arranged downstream of the first tubular mixing section 20, and the fluids simultaneously flowing into the first fluctuation mitigation section 30 flow into the first fluctuation mitigation section 30 due to a wide residence time distribution. designed to drain over a long period of time from Specifically, it takes 10 minutes or more from the point at which the fluid flowing through the trajectory line with the highest flow velocity flows out until 70% of the fluid that simultaneously flows into the first fluctuation damping section 30 flows out. It is designed to produce a distribution of residence times. This wide residence time distribution promotes homogenization of the mixed fluid C in the first pipe in the axial direction, making it possible to obtain the first produced fluid D with little variation in viscosity over time.

The trajectory with the highest flow velocity is, for example, when the tracer particles and the colorant are put in the entire cross section of the entrance of the first fluctuation reduction section 30, the tracer particles and the colorant are first from the exit of the first fluctuation reduction section 30. refers to the trajectory through which the flows out. Further, the statement that ``it takes 10 minutes or more from the time the fluid flowing through the trajectory line with the highest flow velocity to flow out until 70% of the fluid that simultaneously flowed into the first fluctuation damping section 30 flows out'' means that For example, when the tracer particles and the coloring agent are put into the entire cross section of the entrance of the first fluctuation reducing section 30, the tracer particles and the coloring agent first flow out from the outlet of the first fluctuation reducing section 30, and then the tracer particles and the coloring agent It means that it takes 10 minutes or more for 70% of the agent to flow out. These can be evaluated by a turbidity meter, an absorption photometer, or the like.

The wider the residence time distribution of the first pipe mixed fluid C in the first fluctuation alleviating section 30, the greater the effect of reducing the viscosity fluctuation. However, if the residence time distribution is made too wide, a large apparatus is required and the equipment cost becomes high. Specifically, 70% of the fluid that simultaneously flowed into the first fluctuation damping section 30 will flow out within 360 minutes after the flow of the fluid that has passed through the trajectory line with the highest flow velocity has flowed out. It is more preferable to design

As a structure of the first fluctuation reducing section 30 for widening the residence time distribution, for example, there is a structure in which the first pipe mixed fluid C is branched into a plurality of flow paths with different residence times and then merged. In this case, the first fluctuation mitigation section 30 includes a first fluctuation mitigation branch section J2 (first branch section) that branches the inflowing fluid into a plurality of flow paths, and a first fluctuation mitigation branch section J2. A first fluctuation mitigation junction J3 (second junction) for joining the fluids flowing through the plurality of flow paths is provided on the downstream side of each of the plurality of flow paths in the fluid flow direction.

In the configuration shown in FIG. 3, the first fluctuation mitigation section 30 distributes the first pipe mixed fluid C to two flow paths having different residence times at the first fluctuation mitigation branch section J2 (first branch section). It has a structure in which it merges into one flow path again at the fluctuation mitigation confluence portion J3 (second confluence portion). The two flow paths of the first fluctuation mitigation section 30 are composed of double pipes, with a first fluctuation mitigation pipe section 31 and a second fluctuation mitigation pipe section 33 arranged radially inside, and a fluctuation relaxation pipe section 33 arranged radially outside. a first fluctuation relaxation temperature control section 32 (first temperature control section) and a second fluctuation relaxation temperature control section 34 (first temperature control section). In the present embodiment, the first pipe mixed fluid C is adjusted to a temperature suitable for the polymerization reaction by the first fluctuation relaxation temperature control section 32 and the second fluctuation relaxation temperature control section 34 .

The shape of the pipe that constitutes the first fluctuation mitigation section 30 is not particularly limited. For example, as described above, the first fluctuation mitigation section includes a first branching section that branches the fluid flowing inside into two or more different flow paths, and a first fluctuation mitigation confluence section (second confluence) where the branched flow paths merge again. (part), may have a structure inside, may use a pipe bent by an elbow or the like, and may not have a circular cross section. Also, a valve, a sensor, or the like may be installed in the middle of the first fluctuation mitigating pipe section 31 . Also, the interior of one pipe may be divided by a partition or the like to form two or more flow paths having different residence times.

In the first fluctuation reducing section 30, in addition to generating a residence time distribution by combining flow paths with different residence times, a residence time distribution may be generated by a radial velocity difference within the same flow path. For example, in the case of laminar flow in a circular tube, the fluid passing through the center of the tube has the highest flow velocity and the shortest residence time. On the other hand, since the flow velocity of the fluid passing near the pipe wall is extremely low, the residence time is very long. Even within one flow path, the variation in properties in the axial direction can be mitigated by such a difference in residence time due to the trajectory.

In order to obtain a sufficient effect of alleviating viscosity fluctuations due to the difference in velocity in the radial direction within the same flow path, it is more preferable for the mixed fluid C in the first pipe to flow in a laminar flow within the pipe. In order to flow in laminar flow in the first fluctuation relaxation pipe portion 31 and / or the second fluctuation relaxation pipe portion 33, when using 4 × cross-sectional area / immersion length as the representative length d, viscosity μ, cross-section The Reynolds number (ρud/μ) calculated from the average flow velocity u and the density ρ is preferably 2100 or less, more preferably 0.00001 or more and 1000 or less. Also, when the viscosity of the solution is low, the velocity distribution cannot be effectively generated because the run-up section until the flow develops is long, so the first fluctuation relaxation pipe part 31 and / or the second fluctuation relaxation pipe part The viscosity of the first pipe mixed fluid C flowing in 33 is preferably high. Specifically, the viscosity of the first pipe mixed fluid C flowing through the first fluctuation mitigating pipe section 31 and/or the second fluctuation mitigating pipe section 33 is preferably 0.1 poise or more and 100000 poise or less at the temperature during circulation. It is preferably 1 poise or more and 10000 poise or less, and more preferably 5 poise or more and 5000 poise or less.

Although FIG. 3 shows an example in which the first fluctuation reducing section 30 is composed of two flow paths with different residence times, it is not limited to this. As described above, due to the radial velocity difference in one flow path, 70% of the fluid simultaneously flowing into the first fluctuation reducing section 30 passes through the trajectory line with the highest flow velocity before flowing out. If there is a residence time distribution that requires 10 minutes or more after the fluid has flowed out, the first fluctuation reducing section 30 may be configured by one pipe without including the branching section and the merging section. On the other hand, when the flow is turbulent inside the first fluctuation reducing portion 30, or when the radial velocity difference is small due to the influence of the internal structure, etc., the residence time distribution is positively generated. One fluctuation reducing section 30 may have a structure in which it branches into three or more pipes.

The first fluctuation mitigation pipe part 31 and the second fluctuation mitigation pipe part 33 can mitigate fluctuations with a shorter period than the average residence time, but they can alleviate fluctuations with a longer period than the average residence time. Hateful. Therefore, compared to the average fluctuation cycle of the first pipe mixed fluid C that can occur at the outlet of the first tubular mixing unit 20, the total average residence time of the first fluctuation reducing pipe portion 31 and the second fluctuation reducing pipe portion 33 is It should preferably be long enough. However, the average residence time mentioned here is a value obtained by dividing the total volume of the flow path by the volumetric flow rate of the mixed fluid C in the first tube. Further, the average fluctuation period is the average of the time from when the viscosity of the first tube mixed fluid C at the outlet of the first tube mixing section 20 reaches a maximum value to when it reaches a minimum value and then reaches a maximum value again. value. The sum of the average residence times of the first fluctuation mitigating pipe portion 31 and the second fluctuation mitigating pipe portion 33 should be at least 1 time the average fluctuation cycle of the first pipe mixed fluid C at the outlet of the first pipe mixing portion 20. is preferable, and more preferably twice or more.

In order for the first fluctuation relaxation pipe portion 31 and the second fluctuation relaxation pipe portion 33 to have an appropriate average residence time according to the viscosity fluctuation of the mixed fluid C in the first pipe, the first fluctuation relaxation pipe portion 31 and the second It is preferable that the total volume of the two fluctuation-mitigating pipe sections 33 is 0.5 to 100 times the volume of the first tubular mixing/stirring section 20 .

In order to obtain the first generated fluid D that does not contain air bubbles, it is preferable that the first fluctuation mitigating pipe section 31 and the second fluctuation mitigating pipe section 33 are fed without contacting gas. However, the present invention is not limited to this, and a gas phase may exist inside the first fluctuation mitigating pipe section 31 and/or the second fluctuation mitigating pipe section 33 as long as air bubbles are not involved in the first pipe mixed fluid C. .

In the structure in FIG. 1 in which the first pipe mixed fluid C is branched into two flow paths with different residence times and then merged, the first pipe mixed fluid C flowing into the first fluctuation reducing section 30 is subjected to the first fluctuation It is distributed to the first fluctuation relaxation piping section 31 and the second fluctuation relaxation piping section 33 at the relaxation branch J2. The first pipe mixed fluid C distributed at the first fluctuation mitigation branch portion J2 flows through the first fluctuation mitigation pipe portion 31 and the second fluctuation mitigation pipe portion 33 toward the first fluctuation mitigation junction J3 side, It merges at the first fluctuation mitigation junction J3 and flows out from the first fluctuation mitigation section 30 .

The first fluctuation mitigation temperature control part 32 and the second fluctuation mitigation temperature control part 34 are pipe parts arranged radially outside the first fluctuation mitigation pipe part 31 and the second fluctuation mitigation pipe part 33, respectively. The temperature of the first tube mixed fluid C flowing through is controlled (for example, cooled) to a desired temperature condition. In these temperature control units, the mixed fluid C in the first tube is adjusted to a temperature suitable for the polymerization reaction, and flows through the first fluctuation relaxation piping section 31 and the second fluctuation relaxation piping section 33 .

When the first pipe mixed fluid C is not distributed at a desired flow rate to each of the plurality of flow paths constituting the first fluctuation reducing section 30 due to the influence of differences in pressure loss, etc., the first fluctuation reducing section 30 has one or more may be provided to adjust the flow rate of the first tube mixed fluid C flowing through each channel. In addition, by providing one or more back pressure valves and valves that can adjust the opening degree in the first fluctuation reducing unit 30 to adjust the pressure loss, the first pipe mixed fluid C is distributed to each flow path at a desired flow rate. You may do so.

Next, the operation of the polymer production system 1 (polyamic acid production system) in the third embodiment will be described.

In the first fluctuation reducing section 30, the first pipe mixed fluid C is allowed to flow in, and the radial velocity distribution and/or the residence time distribution of the first pipe mixed fluid C is distributed by the effect of branching into flow paths with different residence times. Continuously feed the liquid while holding the As a result, fluctuations in the viscosity of the first pipe mixed fluid C in the axial direction of the tube, which cannot be eliminated in the first tubular mixing section 20 in the preceding stage, can be significantly reduced in the first fluctuation reducing section 30 in the subsequent stage. can. Therefore, a desired polymer can be obtained continuously and stably.

temperature controllers

112 and 122. Control the

parts

22, 32, 34 (control process). Thereby, a polyamic acid having desired properties (temperature, viscosity) can be obtained.

When the distribution of the residence time of the first pipe mixed fluid C in the first fluctuation mitigation unit 30 is known, the first pipe mixed fluid measurement unit 222 acquires the first viscosity information (measuring step), and based on this, the first fluctuation A temporal change in the viscosity of the first generated fluid D at the outlet of the relaxation section 30 can be predicted (prediction step). The supply pumps 112, 122 and the

temperature controllers

22, 32, 34 may be controlled based on the predicted viscosity (control step). For example, when a Hagen-Poiseuille flow is formed by laminar flow in the first fluctuation damping section 30, the flow velocity distribution in the radial direction can be calculated, so the residence time distribution can be known. Therefore, if the time moving average weighted by the residence time distribution is calculated from the viscosity of the first pipe mixed fluid C acquired by the first pipe mixed fluid measurement unit 222, the first generation at the outlet of the first fluctuation reduction unit 30 An estimate of the viscosity of fluid D is obtained. In addition, when the first fluctuation reducing section 30 has a structure that branches into two or more flow paths, the average of the residence time distribution of each flow path, weighted by the flow rate ratio of each flow path, may be considered. .

In addition, in the polymer production system 1, based on the first reaction information acquired by the first tube mixed fluid measurement unit 222 and/or the first produced fluid measurement unit 322, the supply in the first supply pump 112, the second supply Any one or more of the supply by the pump 122, the temperature adjustment in the first tubular mixing temperature control section 22, the temperature adjustment in the first fluctuation relaxation temperature control section 32, and the temperature adjustment in the second fluctuation relaxation temperature control section 34 are controlled. Thereby, a polymer having desired properties (temperature, viscosity) can be obtained.

<Modification>
Although the three 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 embodiment, the fluids are mixed in the first tubular mixing section and the first fluctuation reducing section. However, it is not limited to this. A one-stage or multiple-stage tubular mixing section and/or a variation reducing section may be provided further downstream of the configuration of the above-described embodiments. Further, in the third embodiment, an example of merging into one flow path at the first fluctuation mitigation confluence part J3 has been described, but the present invention is not limited to this. Alternatively, the water may flow separately into a cushion tank or the like provided downstream.

In addition, in the present embodiment, the case where the first tubular mixing section 20 is composed of a double tube of the first tubular mixing stirring section 21 and the first temperature adjusting section 22 has been described, but the present invention is limited to this. not a thing For example, the first tubular mixing section 20 may be composed of only the first tubular mixing/stirring section 21 with a single tube, and the first tubular mixing/stirring section 21 may be immersed in the temperature control liquid.

Also, in the above 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. Further, in the above-described embodiment, an example in which the first variation reducing unit 30 reduces the variation in viscosity over time is described, but the property that can reduce variation is not limited to viscosity, and other physical properties can be reduced over time. Even if there is a large fluctuation, it can be reduced by the first fluctuation reducing section 30 .

In the above-described embodiment, the viscosity information about the viscosity of the mixed fluid C in the first tube and the viscosity of the first generated fluid D is acquired by the viscosity measuring unit, and based on the acquired viscosity information, the supply amount of the fluid and/or the mixing temperature Controlled but not limited to conditions. For example, absorbance information relating to the absorbance of the first pipe mixed fluid C and the first product fluid D may be acquired, and the fluid supply amount and/or the temperature conditions for mixing may be controlled based on the acquired absorbance information.

In the above-described embodiment, each part of the polymer production system is connected by the first liquid-feeding line L1, the second liquid-feeding line L2, the third liquid-feeding line L3, the fourth liquid-feeding line L4, and the fifth liquid-feeding line L5. Although an example is shown, it is not limited to this. For example, the outlet of the first tubular mixing section 20 and the inlet of the first fluctuation reducing section 30 may be directly connected without the fourth liquid feeding line L4.

Also, in the above-described embodiment, the method for controlling the temperatures of the first tubular mixing section 20 and the first fluctuation reducing section 30 has been described, but the present invention is not limited to this. For example, the temperature control section of the first tubular mixing section 20 and/or the first fluctuation reducing section 30 is not necessarily required, and the first junction section J1, the first liquid feeding line L1, the second liquid feeding line L2, Any one or more of the third liquid-feeding line L3, the fourth liquid-feeding line L4, and the fifth liquid-feeding line L5 may be provided with a temperature control section.

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 polyamic acid was produced using a polymer production system 1 having a structure as shown in FIG. In the first tank 11, a polyamic acid having an acid anhydride at the end obtained by the reaction of 4,4′-diaminodiphenyl ether and pyromellitic dianhydride was dissolved in N,N-dimethylformamide. It accommodated the first fluid A1. Also, the second tank 12 contained a second fluid A2 in which p-phenylenediamine was dissolved in N,N-dimethylformamide.

First, in the first junction J1, the first fluid A1 supplied by the first supply pump 112 and the second fluid A2 supplied by the second supply pump 122 are merged and mixed to form a first merged fluid B generated. Next, in the first tubular mixing section 20, the first merged fluid B is stirred without coming into contact with gas, and from the outlet of the first tubular mixing section 20, the first mixed fluid B having uniform properties in the radial direction of the tube is discharged. Tube mixed fluid C flowed out.

More specifically, a Kenics mixer type static mixer (inner diameter 8 mm, length 670 mm) was used as the first tubular mixing section 20 to stir the first merged fluid B without contacting the gas. The total amount supplied by the first supply pump 112 and the second supply pump 122 was set to 1.0 cc/s, and a polymer solution having a desired viscosity was obtained by adjusting the material supply ratio of these pumps. At the outlet of the first tubular mixing section 20, the polymerization reaction was completed, and the first tubular mixed fluid C was obtained with uniform properties in the radial direction. and a minimum value difference of about 400 poise. The average viscosity of the mixed fluid C in the first tube was 2100 poise.

A hollow cylindrical tube with an inner diameter of 30 mm and a length of 900 mm was used as the first fluctuation reducing section 30 . The first tubular mixed fluid C flowing out of the first tubular mixing section 20 was allowed to flow into the first fluctuation reducing section 30 at a volumetric flow rate of 1.0 cc/s. Due to the flow velocity distribution generated in the first fluctuation reducing section 30, mixing in the axial direction of the first pipe mixed fluid C proceeds, and the average viscosity from the outlet of the first fluctuation reducing section 30 is 2100 poise, and the viscosity fluctuation of the first generated fluid D flowed out. Measurement by an on-line viscometer revealed that the difference between the maximum value and the minimum value of the viscosity of the first generated fluid D was about 80 poise. Therefore, it was found that the temporal viscosity fluctuation of the fluid at the outlet of the first tubular mixing section 20 can be significantly reduced by providing the first fluctuation reducing section 30 .

<Example 2>
In Example 2, a polyamic acid was produced using a polymer production system 1 having a structure as shown in FIG. In the first tank 11, a first polyamic acid having acid anhydride ends obtained by the reaction of 4,4′-diaminodiphenyl ether and pyromellitic dianhydride was dissolved in N,N-dimethylformamide. Fluid A1 was accommodated. Also, the second tank 12 contained a second fluid A2 in which p-phenylenediamine was dissolved in N,N-dimethylformamide.

More specifically, using a Kenics mixer type static mixer (inner diameter 8 mm, length 670 mm), the first fluid A1 and the second fluid A2 are combined and mixed at a total supply amount of 1.0 cc/s. and the first merged fluid B was generated. Next, in the first tubular mixing section 20, the first merged fluid B is stirred without coming into contact with gas, and from the outlet of the first tubular mixing section 20, the first mixed fluid B having uniform properties in the radial direction of the tube is discharged. A pipe mixed fluid C was obtained. At the outlet of the first tubular mixing section 20, the polymerization reaction was completed, and the first tubular mixed fluid C was obtained with uniform properties in the radial direction. and the minimum value difference is 800 poise. The average viscosity of the mixed fluid C in the first tube was 1800 poise.

A cylindrical tank having an inner diameter of 80 mm and a capacity of 500 ml was used as the first variation mitigation tank 31a of the first variation mitigation unit 30, and the central axis of the cylindrical tank was installed at an angle of 60° to the installation surface. A portion of the first pipe mixed fluid C flowing out from the first tubular mixing section 20 was allowed to flow in from the upper portion of the first fluctuation damping tank 31a at a volumetric flow rate of 0.2 cc/s. Further, the first generated fluid D was caused to flow out at the same flow rate from the bottom portion of the first fluctuation mitigation tank 31a. The average residence time in the first fluctuation mitigation tank 31a was 11 minutes.
Due to the flow velocity distribution generated in the first fluctuation relaxation tank 31a, the axial mixing of the mixed fluid C in the first pipe progresses, and the average value of the viscosity from the outlet of the first fluctuation relaxation tank 31a is 1800 poise, and the viscosity fluctuation The first generated fluid D with a small amount flowed out. Measurement by an on-line viscometer revealed that the difference between the maximum value and the minimum value of the viscosity of the first generated fluid D was 40 poise. Therefore, the temporal viscosity fluctuation of the fluid at the outlet of the first tubular mixing section 20 is significantly reduced by providing the first fluctuation reducing section 30 .

<Example 3>
In Example 3, a polyamic acid was produced using a polymer production system 1 having a structure as shown in FIG. In the first tank 11, a first polyamic acid having acid anhydride ends obtained by the reaction of 4,4′-diaminodiphenyl ether and pyromellitic dianhydride was dissolved in N,N-dimethylformamide. Fluid A1 was accommodated. Also, the second tank 12 contained a second fluid A2 in which p-phenylenediamine was dissolved in N,N-dimethylformamide.

As the first fluctuation relaxation section 30, the first fluctuation relaxation piping section 31 uses a hollow cylindrical tube with an inner diameter of 30 mm and a length of 1000 mm, and the second fluctuation relaxation piping section 33 uses a hollow cylindrical tube with an inner diameter of 20 mm and a length of 200 mm. 13 minutes after the fluid flowing through the trajectory line with the highest flow velocity flows out until 70% of the fluids simultaneously flowing into the first fluctuation damping section 30 flow out. The first tubular mixed fluid C flowing out of the first tubular mixing section 20 was allowed to flow into the first fluctuation reducing section 30 at a volumetric flow rate of 1.0 cc/s. Due to the residence time distribution generated in the first fluctuation reducing section 30, mixing in the axial direction of the first pipe mixed fluid C progresses, and the average value of the viscosity from the outlet of the first fluctuation reducing section 30 is 2100 poise, and the viscosity The first generated fluid D with little fluctuation flowed out. Measurement by an on-line viscometer revealed that the difference between the maximum value and the minimum value of the viscosity of the first generated fluid D was about 80 poise. Therefore, it was found that the temporal viscosity fluctuation of the fluid at the outlet of the first tubular mixing section 20 can be significantly reduced by providing the first fluctuation reducing section 30 .

1 polymer production system 11 first tank 12 second tank 20 first tubular mixing section 21 first tubular mixing stirring section 22 first tubular mixing temperature control section (first temperature control section)
30 First fluctuation mitigation section 31 First fluctuation mitigation piping section 31a First fluctuation mitigation tank 32 First fluctuation mitigation temperature control section (first temperature control section)
33 Second fluctuation mitigation piping section 34 Second fluctuation mitigation temperature control section (first temperature control section)
111 first tank on-off valve 112 first supply pump (first supply unit)
113 First flow rate measurement unit 121 Second tank on-off valve 122 Second supply pump (second supply unit)
123 Second flow measurement unit 200 Control unit 222 First pipe mixed fluid measurement unit (first measurement unit)
322 second generated fluid measurement unit (first measurement unit)
A1 First fluid A2 Second fluid B First merged fluid C First tube mixed fluid D First generated fluid L Liquid sending line L1 First liquid sending line L2 Second liquid sending line L3 Third liquid sending line L4 Fourth sending Liquid line L5 Fifth liquid feeding line J1 First junction J2 First fluctuation mitigation branch (first branch)
J3 Second Fluctuation Mitigation Junction (Second Junction)

Claims

A first fluid containing a first polyaddition polymerizable compound and a second fluid containing a second polyaddition polymerizable compound that polyadditions with the first polymerizable compound are used as raw materials to produce a polymer. A combined manufacturing system,
a first supply unit that supplies the first fluid;
a second supply unit that supplies the second fluid;
a first merging section for merging the first fluid and the second fluid to generate a first merged fluid;
a first tubular mixing section disposed downstream of the first merging section for promoting radial mixing of the first merged fluid to generate a first tubular mixed fluid;
a first fluctuation reducing section disposed downstream of the first tubular mixing section and configured to reduce fluctuations in axial properties of the first tubular mixed fluid to generate a first product fluid;
Polymer production system.
further comprising a first measurement unit that acquires first reaction information relating to physical quantities and/or compositions in any one or more of the first merged fluid, the first tube mixed fluid, and the first generated fluid;
The polymer production system according to claim 1.
The first measurement unit includes a viscometer, a thermometer, a pressure gauge, a pump pressure gauge, an absorbance meter, an infrared spectrometer, a near-infrared spectrometer, a density meter, a color difference meter, a refractometer, a spectrophotometer, and a conductivity meter. , having one or more selected from the group consisting of a turbidimeter, an ultrasonic sensor, and a fluorescent X-ray analyzer,
The polymer production system according to claim 2.
further comprising a first temperature control unit for adjusting the temperature of any one or more of the first fluid, the second fluid, the first merged fluid, the first tube mixed fluid, and the first generated fluid,
The polymer production system according to claim 2.
The first fluctuation mitigation section is a pipe having an average residence time of 3 minutes or more for the fluid flowing inside,
The polymer production system according to any one of claims 1-4.
The first fluctuation reducing section is configured by one or more tubular members,
the total average residence time of each of said tubular members is 7 minutes or more;
The polymer production system according to any one of claims 1-4.
a first tube mixed fluid measuring unit for acquiring first tube mixed fluid reaction information related to the physical quantity and/or composition of the first tube mixed fluid is provided between the first tubular mixing unit and the first fluctuation reducing unit; prepared,
further comprising a first generated fluid measurement unit for obtaining first generated fluid reaction information related to the physical quantity and/or composition of the first generated fluid, at the outlet of the first fluctuation mitigation unit or downstream thereof;
The volume of the first fluctuation reducing section is 0.5 to 100 times the volume of the first tubular mixing section.
The polymer production system according to any one of claims 1-4.
The volume of the first fluctuation reducing section is 5 to 100 times the volume of the first tubular mixing section.
The polymer production system according to any one of claims 1-4.
The first fluctuation mitigation section is a pipe in which the residence time of the fluid that has passed through the trajectory line with the highest flow velocity is 3 minutes or more,
The polymer production system according to any one of claims 1-4.
The first fluctuation reducing section is configured by one or more tubular members,
The cross-sectional average flow velocity of the fluid flowing inside the tubular member is 0.01 m/s or less,
The total length of each of the tubular members is a pipe of 0.7 m or more,
The polymer production system according to any one of claims 1-4.
The Reynolds number of the fluid flowing inside the first fluctuation reducing portion is 2100 or less when using 4 × cross-sectional area / immersion side length as a representative length.
The polymer production system according to any one of claims 1-10.
2. The polymer manufacturing system according to claim 1, wherein the first fluctuation damping section does not have a driven stirrer, and the fluid forms an open channel.
It takes 10 minutes or more after the fluid flowing through the trajectory line with the highest flow velocity flows out until 70% of the fluid that simultaneously flows into the first fluctuation damping section flows out.
The polymer production system according to claim 1.
The first polymerizable compound and the second polymerizable compound satisfy any one of the following (a) to (c), and a polyamic acid is produced as the polymer,
The polymer production system according to any one of claims 1-13.
(a) One of the first polymerizable compound and the second polymerizable compound is a tetracarboxylic dianhydride and the other is a diamine.
(b) One of the first polymerizable compound and the second polymerizable compound is an acid anhydride-terminated or amino group-terminated polyamic acid, and the other is a diamine or a tetracarboxylic dianhydride.
(c) one of the first polymerizable compound and the second polymerizable compound is an acid anhydride-terminated or amino group-terminated polyamic acid, and the other is an amino group-terminated or an acid anhydride-terminated polyamic acid; .
Further comprising an imidization unit for imidizing the produced polyamic acid, producing polyimide as the polymer,
15. The polymer production system according to claim 14.
the first measurement unit acquires the first reaction information in any one or more of the first merged fluid, the first tube mixed fluid, and the first generated fluid;
any one or more selected from the group consisting of fluid supply in the first supply unit, fluid supply in the second supply unit, and temperature adjustment in the first temperature control unit based on the acquired first reaction information; Further comprising a control unit for controlling
The polymer production system according to claim 4.
The first measurement unit acquires the first reaction information in the first merged fluid and/or the first tube mixed fluid,
Based on the obtained first reaction information, the property of the first generated fluid is predicted, and based on the predicted property of the first generated fluid, the fluid supply in the first supply unit and the second supply unit Further comprising a control unit that controls any one or more selected from the group consisting of fluid supply and temperature adjustment in the first temperature control unit,
The polymer production system according to claim 4.
A method for producing a polymer using the polymer production system according to any one of claims 1 to 17.
A method for producing a polyamic acid solution and/or polyimide using the polymer production system according to any one of claims 1 to 17.