Polymer production apparatus and method for producing a polymer

Abstract

A polymer production system (1) includes a first supply unit (112) that supplies a first fluid (A1) containing a first polymerizable compound; a second supply unit (122) that supplies a second fluid (A2) containing a second polymerizable compound; a first junction unit (J1) that joins the first fluid (A1) and the second fluid (A2) to produce a first joined fluid (B); a first pipe-type mixing unit (20) that is disposed on a downstream side of the first junction unit (J1), the first pipe-type mixing unit (20) promoting mixing of the first joined fluid (B) in a radial direction to produce a first pipe-mixed fluid (C); and a first variation alleviating unit (30) that is connected to the first pipe-type mixing unit, the first variation alleviating unit (30) producing a first produced fluid (D) by reducing a variation in viscosity of the first pipe-mixed fluid (C) in an axial direction.

Description

Technical Field

[0001] This invention relates to polymer manufacturing systems and methods for manufacturing polymers. More specifically, this invention relates to polymer manufacturing systems capable of continuously manufacturing polymers and methods for manufacturing polymers using such systems. Background Technology

[0002] Conventionally, as a method for manufacturing polymers such as polyamide acid, there is a known method that involves mixing a first fluid and a second fluid in a mixing tank and further mixing the mixed fluid using a tubular mixer (see, for example, Patent Document 1). In the tubular mixer, the mixed fluid is driven by a pump and is stirred while moving axially along the tube.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 62-214912 Summary of the Invention

[0006] The problem the invention aims to solve

[0007] In tubular mixers, homogenization is achieved through mixing in the radial direction of the tube. However, due to the small residence time distribution within the tubular mixer, the viscosity variation of the mixed fluid generated in the axial direction of the tube is maintained. In addition polymerization reactions, the higher the molecular weight of the resulting polymer, the more precisely the mixing ratio of the raw materials needs to be adjusted. Therefore, while low-viscosity polymers can be stably obtained in addition polymerization reactions based on tubular mixers, it is difficult to continuously obtain high-viscosity polymers of 1000 poise or higher while maintaining a stable viscosity. For polymers whose viscosity varies over time, there is a problem in obtaining films of consistent thickness during film formation. To address this issue, it is considered to install a stirring tank or similar device downstream of the tubular mixer to eliminate viscosity variations. However, this increases equipment costs. Furthermore, there is the problem of air bubbles being entrained in the polymer solution, requiring degassing before film formation.

[0008] In order to solve this problem, in-depth research was conducted, and it was found that in the past, in order to reduce the required time and product loss, the residence time in the liquid delivery line of the polymer was preferably short. However, by deliberately setting a part with a longer residence time in the polymer liquid delivery line, the viscosity of the obtained polymer can be significantly reduced over time, thus completing the invention.

[0009] The object of this invention is to provide a polymer manufacturing system and method capable of continuously and stably obtaining desired polymers with minimal viscosity variation over time. Another object of this invention is to provide a polymer manufacturing system and method capable of reducing the rate of exceeding specifications by minimizing the variation in the properties of the resulting polymer during a continuous polymer manufacturing process.

[0010] Solution for solving the problem

[0011] The specific means used to solve the above problems include the following implementation methods.

[0012] <1>. A polymer manufacturing system that uses a first fluid and a second fluid as raw materials to manufacture a polymer, the first fluid comprising a first polymerizable compound having addition polymerization properties, the second fluid comprising a second polymerizable compound having addition polymerization properties, and undergoing addition polymerization with the first polymerizable compound, wherein the polymer manufacturing system comprises: a first supply unit for supplying the first fluid; a second supply unit for supplying the second fluid; a first confluence unit for confluencing the first fluid and the second fluid to generate a first confluence fluid; a first tubular mixing unit disposed downstream of the first confluence unit, the first tubular mixing unit enhancing radial mixing of the first confluence fluid to generate a first tubular mixed fluid; and a first variation mitigation unit disposed downstream of the first tubular mixing unit, the first variation mitigation unit generating a first generating fluid by reducing axial variation of the properties of the first tubular mixed fluid.

[0013] <2>. The polymer manufacturing system according to <1>, wherein the polymer manufacturing system further comprises a first measuring unit, the first measuring unit acquiring first reaction information relating to physical quantities and / or composition of any one or more of the first confluence fluid, the first pipe mixing fluid, and the first generating fluid.

[0014] <3>. The polymer manufacturing system according to <2>, wherein the first measuring unit has one or more devices selected from the group consisting of a viscometer, a thermometer, a pressure gauge, a pump pressure gauge, an absorbance meter, an infrared spectrometer, a near-infrared spectrometer, a densitometer, a colorimeter, a refractive index meter, a spectrophotometer, a conductivity meter, a turbidimeter, an ultrasonic sensor, and a fluorescence X-ray analysis device.

[0015] <4>. The polymer manufacturing system according to <2>, wherein the polymer manufacturing system further comprises a first temperature control unit for adjusting the temperature of any one or more of the first fluid, the second fluid, the first confluence fluid, the first pipe mixing fluid, and the first generating fluid.

[0016] <5>. The polymer manufacturing system according to any one of <1> to <4>, wherein the first variation mitigation section is composed of one or more tubular members, and the total average residence time of each of the tubular members is 7 minutes or more.

[0017] <6>. The polymer manufacturing system according to any one of <1> to <4>, wherein the first variation buffer is a piping in which the average residence time of the fluid flowing inside is 7 minutes or more.

[0018] <7>. The polymer manufacturing system according to any one of <1> to <4>, wherein a first tubular mixing fluid measuring unit is provided between the first tubular mixing section and the first variation mitigation section, the first tubular mixing fluid measuring unit acquiring first tubular mixing fluid reaction information related to the physical quantity and / or composition of the first tubular mixing fluid, and a first generating fluid measuring unit is further provided at the outlet of the first variation mitigation section or downstream of the outlet, the first generating fluid measuring unit acquiring first generating fluid reaction information related to the physical quantity and / or composition of the first generating fluid, wherein the volume of the first variation mitigation section is 0.5 to 100 times the volume of the first tubular mixing section.

[0019] <8>. The polymer manufacturing system according to any one of <1> to <4>, wherein the volume of the first variation mitigation section is 5 to 100 times the volume of the first tubular mixing section.

[0020] <9>. The polymer manufacturing system according to any one of <1> to <4>, wherein the first variation buffer section is a piping with a residence time of 3 minutes or more for the fluid passing through the fastest flow path.

[0021] <10>. The polymer manufacturing system according to any one of <1> to <4>, wherein the first variation mitigation section is composed of one or more tubular members, the cross-sectional average flow velocity of the fluid flowing inside the tubular members is 0.01 m / s or less, and the total length of each of the tubular members is 0.7 m or more.

[0022] <11>. The polymer manufacturing system according to any one of <1> to <10>, wherein, when using 4×cross-sectional area / wet perimeter as the representative length, the Reynolds number of the fluid flowing inside the first variation buffer section is 2100 or less.

[0023] <12>. The polymer manufacturing system according to <1>, wherein the first variable mitigation section does not have a driven agitator and the fluid forms an open channel.

[0024] <13>. According to the polymer manufacturing system described in <1>, it takes more than 10 minutes from the time the fluid flows out through the fastest flow path until 70% of the fluid flowing into the first variation buffer flows out.

[0025] <14>. A polymer manufacturing system according to any one of <1> to <13>, wherein the first polymerizable compound and the second polymerizable compound satisfy any one of (a) to (c) below to manufacture polyamic acid as the polymer.

[0026] (a) One of the first polymerizable compound and the second polymerizable compound is a tetracarboxylic dianhydride, and the other is a diamine.

[0027] (b) One of the first polymerizable compound and the second polymerizable compound is an anhydride-terminated polyamic acid or an amino-terminated polyamic acid, and the other is a diamine or a tetracarboxylic dianhydride.

[0028] (c) One of the first polymerizable compound and the second polymerizable compound is an anhydride-terminated polyamic acid or an amino-terminated polyamic acid, and the other is an amino-terminated polyamic acid or an anhydride-terminated polyamic acid.

[0029] <15>. The polymer manufacturing system according to <14>, wherein the polymer manufacturing system further comprises an imidization section for imidizing the manufactured polyamic acid, thereby manufacturing a polyimide as said polymer.

[0030] <16>. The polymer manufacturing system according to <4>, wherein the first measuring unit acquires first reaction information of any one or more fluids selected from the first confluence fluid, the first pipe mixing fluid, and the first generating fluid, and the polymer manufacturing system further comprises a control unit that controls any one or more operations selected from the group consisting of fluid supply from the first supply unit, fluid supply from the second supply unit, and temperature adjustment from the first temperature control unit based on the acquired first reaction information.

[0031] <17>. The polymer manufacturing system according to <4>, wherein the first measuring unit acquires the first reaction information of the first confluence fluid and / or the first reaction information of the first pipe mixing fluid, the polymer manufacturing system further comprises a control unit that predicts the properties of the first generating fluid based on the acquired first reaction information, and controls any one or more operations selected from the group consisting of fluid supply from the first supply unit, fluid supply from the second supply unit, and temperature adjustment from the first temperature control unit based on the predicted properties of the first generating fluid.

[0032] <18>. A method for manufacturing a polymer, wherein the polymer manufacturing system described in any one of <1> to <17> is used.

[0033] <19>. A method for manufacturing a polyamic acid solution and / or a polyimide, wherein the polymer manufacturing system described in any one of <1> to <17> is used.

[0034] The effects of the invention

[0035] According to the present invention, a polymer manufacturing system and method are available that can continuously and stably produce desired polymers with minimal viscosity variation over time. Furthermore, a polymer manufacturing system and method are available that can reduce the rate of exceeding specifications during continuous polymer manufacturing by incorporating simple and inexpensive mechanisms for reducing variations in polymer properties. Attached Figure Description

[0036] Figure 1 This is a diagram illustrating the polymer manufacturing system in the first embodiment.

[0037] Figure 2 This is a diagram illustrating the polymer manufacturing system in the second embodiment.

[0038] Figure 3 This is a diagram illustrating the polymer manufacturing system in the third embodiment. Detailed Implementation

[0039] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

[0040] The first to third embodiments are examples of polymer manufacturing systems having a first tubular mixing section and a first variable mitigation section.

[0041] <First Embodiment>

[0042] pass Figure 1 This describes the polymer manufacturing system in the first embodiment. Figure 1 This is a diagram illustrating the polymer manufacturing system in the first embodiment.

[0043] First, an overview of the polymer manufacturing system 1 in the first embodiment will be described.

[0044] Polymer manufacturing system 1 is a manufacturing system that uses a first fluid A1 and a second fluid A2 as raw materials to manufacture a polymer. The first fluid A1 contains a first polymerizable compound that has addition polymerization properties, and the second fluid A2 contains a second polymerizable compound that also has addition polymerization properties. The first embodiment is an example of a polymer manufacturing system in which a first tubular mixing section and a first variation mitigation section are continuously provided.

[0045] Here, the first tubular mixing section refers to a tubular mixing section that homogenizes radial properties while allowing fluid to flow. Furthermore, the first variation mitigation section refers to a structural section capable of reducing axial variation by actively generating a residence time distribution that utilizes differences in flow velocity based on the traces in the flow path.

[0046] The following is an example illustrating the following situation: one of the first polymerizable compound and the second polymerizable compound is a tetracarboxylic dianhydride, and the other is a diamine, used to manufacture polyamic acid as a polymer. More specifically, the following situation illustrates the following: the first polymerizable compound contained in the first fluid A1 is a tetracarboxylic dianhydride, and the second polymerizable compound contained in the second fluid A2 is a diamine, used to manufacture polyamic acid as a polymer.

[0047] There are no particular restrictions on the tetracarboxylic dianhydride used; the same substances used in conventional polyimide synthesis can be employed. Specific examples of tetracarboxylic dianhydrides include: 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 1,3-bis(2,3-dicarboxyphenoxy)phenyl dianhydride, 1,4-bis(2,3-dicarboxyphenoxy)phenyl dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, and 2,2',6,6'-biphenyltetracarboxylic dianhydride. Aromatic tetracarboxylic anhydrides include anhydrides such as naphthalene-1,2,4,5-tetracarboxylic dianhydride, anthracene-2,3,6,7-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, and 2,2-bis(4-hydroxyphenyl)propane dibenzoate-3,3',4,4'-tetracarboxylic dianhydride; aliphatic tetracarboxylic dianhydrides such as butane-1,2,3,4-tetracarboxylic dianhydride; alicyclic tetracarboxylic dianhydrides such as cyclobutane-1,2,3,4-tetracarboxylic dianhydride; and heterocyclic tetracarboxylic dianhydrides such as thiophene-2,3,4,5-tetracarboxylic dianhydride and pyridine-2,3,5,6-tetracarboxylic dianhydride. Tetracarboxylic dianhydrides can be used alone or in combination of two or more.

[0048] As the solvent for fluid A1, solvents capable of dissolving tetracarboxylic dianhydride and polyamic acid can be used. Specific examples of solvents include: amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolinone, and acetanilide; cyclic ester solvents such as γ-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; alcohol solvents such as methanol, ethanol, and isopropanol; and aromatic hydrocarbon solvents such as toluene and xylene. Among these, amide solvents, cyclic ester solvents, and ether solvents with high solubility for polyamic acid are preferred. A single solvent can be used, or two or more solvents can be mixed. For example, the solubility of polyamic acid can be improved by mixing a solvent with low solubility in polyamic acid, such as acetone, ethyl acetate, methyl ethyl ketone, toluene, or xylene, with a highly polar alcohol solvent.

[0049] Fluid A1 may contain small amounts of tertiary amines such as trimethylamine and triethylamine, or acetic acid, in order to improve the solubility of tetracarboxylic dianhydride or to enhance its reactivity with diamines.

[0050] There are no particular restrictions on the diamine used; the same substances used in conventional polyimide synthesis can be employed. 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'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-methylene-bis(2-chloroaniline), 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'- Aromatic diamines include diaminodiphenyl sulfide, 2,6-diaminotoluene, 2,4-diaminochlorobenzene, 1,2-diaminoanthraquinone, 1,4-diaminoanthraquinone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, and 4,4'-diaminobibenzyl; aliphatic diamines include 1,2-diaminoethane, 1,4-diaminobutane, tetramethylenediamine, and 1,10-diaminododecane; alicyclic diamines include 1,4-diaminocyclohexane, 1,2-diaminocyclohexane, bis(4-aminocyclohexyl)methane, and 4,4'-diaminodicyclohexylmethane; heterocyclic diamines include 3,4-diaminopyridine; etc. Diamines can be used alone or in combination of two or more.

[0051] As the solvent for the second fluid A2, solvents that dissolve diamines and polyamic acids can be used. Specific examples of solvents include: amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolinone, and acetanilide; cyclic ester solvents such as γ-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; alcohol solvents such as methanol, ethanol, and isopropanol; and aromatic hydrocarbon solvents such as toluene and xylene. Among these, amide solvents, cyclic ester solvents, and ether solvents with high solubility for polyamic acids are preferred. A single solvent can be used, or two or more solvents can be mixed. For example, the solubility of polyamic acids can be improved by mixing highly polar alcohol solvents with solvents with low solubility for polyamic acids, such as acetone, ethyl acetate, methyl ethyl ketone, toluene, and xylene.

[0052] Fillers that form 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 dioxide, anhydrous dicalcium phosphate, calcium pyrophosphate, calcium carbonate, silica, alumina, barium sulfate, zirconium oxide, kaolin, talc, clay, and mica, as well as organic particles composed of acrylics, styrene, etc. Additionally, inorganic or organic particles added to modify other properties of the polyimide film, such as strength and thermal conductivity, may also be dispersed.

[0053] like Figure 1 As shown, the polymer manufacturing system 1 is configured such that a first fluid A1 and a second fluid A2, serving as raw materials, are merged and mixed at a first confluence section J1 to generate a first confluence fluid B. The first confluence fluid B is stirred in a first tubular mixing section 20, thereby generating a first tubular mixed fluid C in which the concentrations of each component in the radial direction of the tube are equal. Next, the viscosity variation in the axial direction of the first tubular mixed fluid C is reduced by a first variation mitigation section 30 to obtain a first generated fluid D, thereby producing a polyamic acid (polymer) with minimal viscosity variation over time.

[0054] In addition, the polymer manufacturing system 1 has a liquid delivery line L connecting the first tank 11 and the second tank 12 (described later) to the outlet of the first variable mitigation section 30.

[0055] The polymerization reaction takes place in either the first tubular mixing section 20 or the first variation mitigation section 30, or in both. The polymerization reaction may end completely at the outlet of the first tubular mixing section 20, or the reaction may be essentially incomplete at the outlet of the first tubular mixing section 20, with most of the reaction occurring in the first variation mitigation section 30. Alternatively, the polymerization reaction does not necessarily need to end completely at the outlet of the first variation mitigation section 30; the reaction may also occur in a downstream piping or buffer tank. However, to obtain a polymer with stable properties, it is preferable that the polymerization reaction is at least 80% complete at the outlet of the first variation mitigation section 30, and more preferably that the polymerization reaction is at least 80% complete at the outlet of the first tubular mixing section 20.

[0056] Next, the specific structure of polymer manufacturing system 1 will be described.

[0057] like Figure 1 As shown, the polymer manufacturing 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, a first supply pump 112 (first supply section), a second supply pump 122 (second supply section), a first confluence section J1, a first tubular mixing section 20, a first variable damping section 30, a liquid delivery line L, and a control section 200. The liquid delivery line L includes a first liquid delivery section L1, a second liquid delivery section L2, a third liquid delivery section L3, a fourth liquid delivery section L4, and a fifth liquid delivery section L5. Furthermore, the polymer manufacturing system 1 includes a first flow measurement section 113, a second flow measurement section 123, a first tubular mixed fluid measurement section 222 (first measurement section), and a first generated fluid measurement section 322 (first measurement section).

[0058] The first tank 11 contains a first fluid A1, in which a first polymerizable compound is dissolved, the first polymerizable compound having addition polymerization properties. In this embodiment, the first tank 11 contains a first fluid A1 in which tetracarboxylic acid dianhydride is dissolved. The first fluid A1 contained in the first tank 11 is supplied to the first confluence section J1 via the first delivery section L1.

[0059] The first liquid delivery section L1 is a pipeline connecting the first tank 11 and the first junction J1. Between the first tank 11 and the first junction J1 in the first liquid delivery section L1, a first tank on / off valve 111, a first supply pump 112 and a first flow measurement unit 113 are arranged sequentially from the upstream side to the downstream side.

[0060] The first tank opening and closing valve 111 is located near the bottom of the first tank 11 in the first liquid delivery section L1, and opens and closes the first liquid delivery section L1 on the upstream side of the first supply pump 112.

[0061] The first supply pump 112 supplies the first fluid A1 contained in the first tank 11 to the first confluence J1. The first supply pump 112 ejects the first fluid A1 at a predetermined flow rate. For example, the first supply pump 112 is adjusted to supply the first fluid A1 under conditions that allow polyamic acid to have the desired properties.

[0062] In this embodiment, the first supply pump 112 is a metering pump.

[0063] In this embodiment, polyamic acid with desired properties is obtained 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 (described later). Therefore, the supply accuracy of the first fluid A1 and the second fluid A2 is preferably high. In this embodiment, the first supply pump 112 is a metering pump, and the second supply pump 122 (described later) is also a metering pump.

[0064] A fixed displacement pump is a positive displacement pump that delivers a fixed volume of fluid with high precision. Examples of fixed displacement pumps include, for example, extrusion-type reciprocating pumps such as plunger pumps and rotary pumps such as gear pumps with gears.

[0065] The first flow measurement unit 113 measures the flow rate of the first fluid A1 downstream of the first supply pump 112 in the first liquid delivery unit L1. In this embodiment, the first flow measurement unit 113 is disposed between the first supply pump 112 and the first confluence unit J1. The first flow measurement unit 113 outputs the measured flow rate of the first fluid A1 to the control unit 200, which will be described later.

[0066] The second tank 12 contains a second fluid A2, in which a second polymerizable compound is dissolved. This second polymerizable compound has addition polymerizability and undergoes addition polymerization with the first polymerizable compound. In this embodiment, the second tank 12 contains a second fluid A2 containing a dissolved diamine. The second fluid A2 contained in the second tank 12 is supplied to the first confluence section J1 via the second delivery section L2.

[0067] The second liquid delivery section L2 is a pipeline connecting the second tank 12 and the first junction J1. Between the second tank 12 and the first junction J1 in the second liquid delivery section L2, a second tank on / off valve 121, a second supply pump 122 and a second flow measurement unit 123 are arranged sequentially from the upstream side to the downstream side.

[0068] The second tank opening and closing valve 121 is located near the bottom of the second tank 12 in the second liquid delivery section L2, and opens and closes the second liquid delivery section L2 on the upstream side of the second supply pump 122.

[0069] The second supply pump 122 supplies the second fluid A2 contained in the second tank 12 to the first confluence J1. The second supply pump 122 ejects the second fluid A2 at a predetermined flow rate. For example, the second supply pump 122 is adjusted to supply the second fluid A2 under conditions that allow polyamic acid to have the desired properties.

[0070] In this embodiment, for the same reasons as the first supply pump 112 described above, the second supply pump 122 is a metering pump.

[0071] The second flow measurement unit 123 measures the flow rate of the second fluid A2 downstream of the second supply pump 122 in the second liquid delivery unit L2. In this embodiment, the second flow measurement unit 123 is disposed between the second supply pump 122 and the first junction J1. The second flow measurement unit 123 outputs the measured flow rate of the second fluid A2 to the control unit 200, which will be described later.

[0072] The first confluencement section J1 is disposed downstream of the first supply pump 112 and downstream of the second supply pump 122. The first confluencement section J1 merges the first fluid A1 and the second fluid A2 to generate a first confluence fluid B. In the first confluencement section J1, the first fluid A1 and the second fluid A2 merge in a state where they do not come into contact with gas. The first confluencement section J1 is composed of a confluence valve that merges the first fluid A1 supplied by the first supply pump 112 and the second fluid A2 supplied by the second supply pump 122.

[0073] The first tubular mixing section 20 is disposed downstream of the first confluence section J1. The first tubular mixing section 20 stirs the first confluence fluid B in a state where the first confluence fluid B is not in contact with the gas, and at the outlet of the first tubular mixing section 20, the concentration of each component is the same in the radial direction of the tube, thereby generating the first tubular mixed fluid C.

[0074] The first tubular mixing section 20 comprises a tubular reactor consisting of two tubes extending in a predetermined direction. The first tubular mixing section 20 has a first tubular mixing and stirring section 21 disposed radially inward and a first tubular mixing and temperature regulating section 22 (first temperature regulating section) disposed radially outward. The first tubular mixing section 20 is configured to allow the first converging fluid B to flow for a desired residence time.

[0075] The first tubular mixing and stirring unit 21 stirs the first confluent fluid B. In this embodiment, the first tubular mixing and stirring unit 21 stirs the first confluent fluid B after it has been adjusted to a temperature suitable for the polymerization reaction by the first tubular mixing and temperature control unit 22.

[0076] The first tubular mixing unit 21 is configured, for example, as a static mixer including a static mixer, nozzle, or throttling orifice, or as a driven mixer including a centrifugal pump, vortex pump, and stirring blades. It is preferable to configure it to include a static mixer, and more preferably, it is configured to include a static mixer. In addition, a tube with an inserted twisted band (see [Fig. 19] of Japanese Patent Application Publication No. 2003-314982) can also achieve the same stirring-promoting effect as a static mixer, but a static mixer can achieve a better stirring-promoting effect, so it is preferred.

[0077] There is no particular limitation on the type of static mixer; examples include the 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. Among these, the Kenics mixer type static mixer has a simple construction and therefore no wasted space, making it a preferred choice.

[0078] The first tubular mixing and temperature control unit 22 is a piping section disposed radially outside the first tubular mixing and stirring unit 21. The first tubular mixing and temperature control unit 22 controls (e.g., cools) the first confluent fluid B flowing in the first tubular mixing and stirring unit 21 to a desired temperature condition. In the first tubular mixing and temperature control unit 22, the first confluent fluid B is adjusted to a temperature suitable for the polymerization reaction and flows in the first tubular mixing and stirring unit 21.

[0079] The generated first pipe mixed fluid C is supplied to the first variation mitigation section 30 via the fourth liquid delivery section L4.

[0080] The first tube mixed fluid measuring unit 222 acquires first tube mixed fluid reaction information (first reaction information) related to the viscosity of the first tube mixed fluid C between the first tube type mixing unit 20 and the first variation mitigation unit 30 in the fourth liquid delivery unit L4. Since the polymerization reaction occurs through stirring in the first tube type mixing stirring unit 21, the viscosity increases; therefore, the viscosity information is valid as reaction information. The first tube mixed fluid measuring unit 222 outputs the acquired viscosity information of the first tube mixed fluid C to the control unit 200, which will be described later.

[0081] Furthermore, the first tube mixed fluid measuring unit 222 also acquires first tube mixed fluid reaction information (first reaction information) related to the temperature of the first tube mixed fluid C between the first tube type mixing unit 20 and the first fluctuation mitigation unit 30 in the fourth liquid delivery unit L4. The polymerization reaction is carried out by stirring within the first tube type mixing stirring unit 21, but the reaction rate varies depending on the temperature; therefore, temperature information is effective as reaction information. The first tube mixed fluid measuring unit 222 outputs the acquired temperature information of the first tube mixed fluid C to the control unit 200, which will be described later.

[0082] The first variation mitigation section 30 is disposed downstream of the first tubular mixing section 20. The first variation mitigation section 30 is composed of a double tube, having a first variation mitigation piping section 31 disposed radially inner and a first variation mitigation temperature regulating section 32 (first temperature regulating section) disposed radially outer. In this embodiment, the first variation mitigation temperature regulating section 32 is used to adjust the temperature to a temperature suitable for the polymerization reaction of the first tubular mixed fluid C.

[0083] In the first variation mitigation piping section 31, the axial viscosity variation of the first pipe mixed fluid C is reduced by the residence time distribution generated by the radial velocity difference as the first pipe mixed fluid C flows within the first variation mitigation piping section 31, thereby stabilizing the properties of the outflowing first generating fluid D. For example, in the case of laminar flow within a circular pipe, the fluid passing through the center of the pipe has the fastest flow velocity and the shortest residence time. On the other hand, the fluid passing through the pipe wall has an extremely slow flow velocity, and therefore a very long residence time. By utilizing this difference in residence time based on the trajectory, axial variation in properties can be mitigated.

[0084] To achieve sufficient viscosity variation mitigation in the first variation mitigation piping section 31, the first pipe mixed fluid C preferably flows in laminar flow within the first variation mitigation piping section 31. For laminar flow within the first variation mitigation piping section 31, using 4 × cross-sectional area / wetted perimeter as the representative length d, the Reynolds number (ρud / μ) calculated from the viscosity μ, cross-sectional average velocity u, and density ρ is preferably 2100 or less, more preferably 0.00001 or more and 1000 or less. Furthermore, when the solution viscosity is low, the guiding interval until flow development is long, thus preventing effective velocity distribution; therefore, a higher viscosity of the first pipe mixed fluid C flowing within the first variation mitigation piping section 31 is preferable. Specifically, the viscosity of the first pipe mixed fluid C flowing in the first variable mitigation piping section 31 is preferably 0.1 poise or more and 100,000 poise or less under the temperature conditions during flow, more preferably 1 poise or more and 10,000 poise or less, and even more preferably 5 poise or more and 5,000 poise or less.

[0085] The first variation mitigation piping section 31 includes piping with a sufficiently long average residence time. Here, the average residence time is the value obtained by dividing the volume of the piping by the volumetric flow rate of the first pipe-mixed fluid C. A longer average residence time in the first variation mitigation piping section 31 results in a greater stabilization effect on the viscosity of the first generating fluid D flowing out of the first variation mitigation piping section 31. Therefore, the greater the axial variation in the properties of the first mixed fluid C flowing out of the first pipe-type mixing section 20, the longer the average residence time of the first variation mitigation piping section 31 is preferred.

[0086] Specifically, for example, when a Newtonian fluid flows in laminar flow within a first variable-mitigation piping section 31, which is a straight pipe with a circular cross-section, the viscosity variation at the outlet of the first variable-mitigation piping section 31 decreases by 56% when the average residence time of the first variable-mitigation piping section 31 is 3 minutes, by 74% when the average residence time is 7 minutes, and by 81% when the average residence time is 11 minutes. Here, the reduction in viscosity variation refers to the percentage reduction in the difference between the maximum and minimum viscosity values ​​at the outlet of the first variable-mitigation piping section 31 relative to the difference between the maximum and minimum viscosity values ​​at the inlet of the first variable-mitigation piping section 31.

[0087] exist Figure 1 The diagram shows a structure with only one first variation mitigation piping section 31, but the first variation mitigation piping section 31 can also be a structure consisting of two or more tubular members connected by a joint or the like. In this case, the total average residence time of each of the two or more tubular members constituting the first variation mitigation piping section 31 is preferably 7 minutes or more. The longer the average residence time of the first variation mitigation piping section 31, the greater the effect of reducing viscosity variation; however, in order to minimize the loss of the generated polymer, it is preferable to keep the total average residence time to be 300 minutes or less.

[0088] The fluid flowing within the first variation mitigation piping section 31 is not limited to Newtonian fluids. In the case of non-Newtonian fluids, the velocity distribution changes under the influence of shear, resulting in a different residence time distribution. Therefore, the rate of reduction in viscosity variation differs from that of Newtonian fluids. Consequently, it is preferable to take into account the rheology of the fluid flowing within the first variation mitigation piping section 31 when designing its average residence time. For example, in the case of pseudoplastic fluids with a residence time distribution smaller than that of Newtonian fluids, it is preferable to have a longer average residence time in the first variation mitigation piping section 31.

[0089] In the first variation mitigation piping section 31, if the variation has a shorter cycle than the average residence time, it can be mitigated; however, if the variation has a longer cycle than the average residence time, it is difficult to mitigate. Therefore, it is preferable that the average residence time of the first variation mitigation piping section 31 is sufficiently long compared to the average variation cycle of the first pipe mixed fluid C that may be generated at the outlet of the first pipe-type mixing section 20. Here, the average variation cycle refers to the average time from when the viscosity of the first pipe mixed fluid C at the outlet of the first pipe-type mixing section 20 reaches a maximum value until it reaches a minimum value and then reaches a maximum value again. The average residence time of the first variation mitigation piping section 31 is preferably more than one time the average variation cycle of the first pipe mixed fluid C at the outlet of the first pipe-type mixing section 20, and more preferably more than two times.

[0090] In order to ensure that the first variation mitigation piping section 31 has an appropriate average residence time according to the viscosity variation of the first tube mixed fluid C, the volume of the first variation mitigation piping section 31 is preferably 0.5 to 100 times the volume of the first tube type mixing and stirring section 20, more preferably 5 to 100 times.

[0091] Furthermore, the first variation mitigation piping section 31 mitigates viscosity variations by distributing residence time based on differences in flow velocity. Since the flow velocity is extremely slow at the pipe wall, a sufficient viscosity variation mitigation effect can be achieved by designing the fluid passing through the fastest flow path to have a sufficiently long residence time. The fastest flow path refers to, for example, the path that always passes through the center of the cross-section in a laminar flow within a circular pipe. When tracer particles and colorants are placed across the entire cross-section of the inlet of the first variation mitigation piping section 31, the time required for the tracer particles and colorants to initially exit the outlet of the first variation mitigation piping section 31 is approximately the same as the residence time of the fluid passing through the fastest flow path. Specifically, for example, when a Newtonian fluid flows laminarly within the first variation mitigation piping section 31, which is a straight pipe with a circular cross-section, the viscosity variation at the outlet of the first variation mitigation piping section 31 is reduced by 72% when the residence time of the fluid passing through the fastest flow path is 3 minutes. In the first variation mitigation piping section 31, the longer the residence time of the fluid passing through the fastest flow path, the greater the effect of reducing viscosity variation. However, in order to suppress the loss of the generated polymer, it is more preferable to make the total residence time of the fluid passing through the fastest flow path 150 minutes or less.

[0092] If the average residence time of the first variable mitigation piping section 31 is the same, then regardless of the cross-sectional area, length, and flow rate of the first pipe mixed fluid C flowing within the first variable mitigation piping section 31, the viscosity stabilization effect of the first generated fluid D will be the same. However, when the cross-sectional area of ​​the first variable mitigation piping section 31 is small and the length is long, the pressure loss of the first pipe mixed fluid C flowing through the first variable mitigation piping section 31 is large, thus requiring piping with higher pressure resistance, increasing equipment costs. Therefore, it is preferable to increase the cross-sectional area of ​​the first variable mitigation piping section 31 to some extent and shorten its length. Specifically, it is preferable to set the cross-sectional area to be 0.01 m / s or less and the length to be 0.7 m or more; more preferably, it is preferable to set the cross-sectional average flow velocity to be 0.00001 m / s or more and 0.003 m / s or less, and the length to be 0.7 m or more and 60 m or less. The cross-sectional average velocity mentioned here refers to the 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 variable mitigation piping section 31. Furthermore, when the first variable mitigation piping section 31 is a structure consisting of two or more tubular members connected by a joint or the like, the total length of each of the two or more tubular members is 0.7 m or more and 60 m or less.

[0093] To reduce equipment costs, a hollow cylindrical pipe is preferably used for the first fluctuation mitigation piping section 31. However, the shape of the first fluctuation mitigation piping section 31 is not particularly limited, as long as it produces a distribution in residence time based on the velocity distribution in the cross-sectional direction when the mixed fluid C flows through the first pipe. Specifically, it can have an internal structure, can use piping with bends such as elbows, and the cross-section does not have to be circular. In addition, valves, sensors, etc., can also be installed in the middle of the first fluctuation mitigation piping section 31.

[0094] In order to obtain a first generated fluid D that does not contain air bubbles, the first variation mitigation piping section 31 is preferably transported in a state where the fluid does not come into contact with the gas. However, it is not limited to this; if air bubbles are not entrained into the first pipe mixed fluid C, a gas phase may also exist inside the first variation mitigation piping section 31.

[0095] The first variation mitigation piping section 31 is provided between the first pipe mixed fluid measuring section 222 and the first generating fluid measuring section 322. The first variation mitigation piping section 31 is preferably a cylindrical pipe with the same inner diameter from its upstream end to its downstream end in the flow direction of the first pipe mixed fluid C. The length of the first variation mitigation piping section 31 is preferably 5 times or more and 1000 times or less of its inner diameter. The inner diameter of the first variation mitigation piping section 31 is preferably 0.5 times or more and 10 times or less of the inner diameter of the fourth liquid delivery section L4 located upstream. Furthermore, since the first pipe mixed fluid C flows in the first variation mitigation piping section 31 with its internal space completely filled, the radial velocity difference of the first pipe mixed fluid C is relatively large.

[0096] The first temperature-regulating and mitigating unit 32 is a piping section disposed radially outside the first temperature-regulating and mitigating piping section 31. The first temperature-regulating and mitigating unit 32 regulates (e.g., cools) the temperature of the first pipe mixed fluid C flowing in the first temperature-regulating and mitigating piping section 31 to a desired temperature condition. In the first temperature-regulating and mitigating unit 32, the first pipe mixed fluid C is adjusted to a temperature suitable for the polymerization reaction and flows in the first temperature-regulating and mitigating piping section 31.

[0097] In the first tubular mixing section 20 and the first variation mitigation section 30 described above, the first tubular mixing section 20 is disposed in the pre-stage and the first variation mitigation section 30 is disposed in the post-stage. Thus, when there is a viscosity variation in the axial direction of the tube in the first tubular mixing section 20 in the pre-stage, the viscosity variation in the axial direction of the tube can be significantly reduced in the first variation mitigation section 30 in the post-stage.

[0098] For example, when viscosity variations along the pipe axially occur in the generated fluid due to changes in the ratio of the first fluid A1 to the second fluid A2, it is difficult to generate radial velocity distribution in the first tubular mixing section 20, which has an internal stirring structure, and thus the viscosity variations along the pipe axially cannot be eliminated. In contrast, by placing the first tubular mixing section 20 in the pre-stage and the first variation mitigation section 30 in the post-stage, after the radial properties are homogenized by the first tubular mixing section 20 in the pre-stage, the first variation mitigation section 30 in the post-stage delivers the liquid in a manner that has a distribution in residence time. As a result, the viscosity variations along the pipe axially of the first tubular mixed fluid C, which cannot be eliminated in the first tubular mixing section 20 in the pre-stage, can be significantly reduced in the post-stage first variation mitigation section 30.

[0099] The first generated fluid measuring unit 322 is located at or downstream of the outlet of the first variation mitigation unit 30, and acquires first generated fluid reaction information (first reaction information) related to the viscosity of the first generated fluid D in the fifth liquid delivery unit L5. Since the viscosity increases due to the polymerization reaction, the viscosity information is valid as reaction information. The first generated fluid measuring unit 322 outputs the acquired viscosity information of the first generated fluid to the control unit 200, which will be described later.

[0100] In addition, the first generating fluid measuring unit 322 also acquires first generating fluid reaction information (first reaction information) related to the temperature of the first generating fluid D in the fifth liquid delivery unit L5. Since the polymerization reaction rate varies with temperature, temperature information is valid as reaction information. The first generating fluid measuring unit 322 outputs the acquired temperature information of the first generating fluid to the control unit 200, which will be described later.

[0101] Furthermore, the first tube mixing fluid measuring unit 222 and the first generating fluid measuring unit 322 of this embodiment are examples of measuring units that acquire reaction information related to physical quantities and / or composition of any one or more of the first tube mixing fluid C and the first generating fluid D.

[0102] The measuring unit is not limited to the first pipe mixing fluid measuring unit 222 and the first generating fluid measuring unit 322 of this embodiment (type of physical quantity and / or composition, measurement method). The measuring unit may also include one or more devices selected from, for example, a viscometer, thermometer, pressure gauge, pump pressure gauge, absorbance meter, infrared spectrometer, near-infrared spectrometer, densitometer, colorimeter, refractive index meter, spectrophotometer, conductivity meter, turbidimeter, and fluorescence X-ray analysis device. The measuring unit acquires one or more reaction information of the measured object related to the physical quantity and / or composition, and outputs the acquired reaction information to the control unit 200 described later.

[0103] Alternatively, a buffer tank (not shown) can be installed downstream of the fifth liquid delivery line L5 to contain the first generated fluid D. The buffer tank may be, for example, a tank that contains the raw material fluid when polyimide is manufactured by imidizing polyamic acid, which is a polymer.

[0104] In the case of manufacturing polyimide using the polymer manufacturing system 1 in this embodiment, the polymer manufacturing system 1 further includes an imidization section for imidizing polyamic acid. The imidization section (not shown) imidizes polyamic acid, for example, by a thermal imidization method involving thermal dehydration and ring closure, or a chemical imidization method using a dehydrating agent and an imidization accelerator.

[0105] Furthermore, when manufacturing polyimide in polymer manufacturing system 1, it is also possible to configure the system so that no buffer tank is provided, and the liquid is fed from the first variation buffer section 30 to the imidization section. However, it is more preferable to temporarily contain the polyamic acid in a buffer tank.

[0106] The control unit 200 is described below. The first supply pump 112, the second supply pump 122, the first tubular mixing temperature control unit 22, the first variable temperature control unit 32, the first flow measurement unit 113, the second flow measurement unit 123, the first tubular mixed fluid measurement unit 222, and the first generating fluid measurement unit 322 are electrically connected to the control unit 200. Furthermore, in this specification, illustrations of control lines leading from the control unit 200 to each pump, each temperature control unit, and each measurement unit are omitted.

[0107] The control unit 200 controls each supply pump 112 and 122 based on the flow values ​​measured by each flow measurement unit 113 and 123.

[0108] The control unit 200 controls, for example, the mass ratio of the first polymerizable compound contained in the first fluid A1 to the second polymerizable compound contained in the second fluid A2 within a predetermined range by controlling the first supply pump 112 and / or the second supply pump 122. This mass ratio is, for example, set to obtain polyamic acid with desired properties. Furthermore, the control unit 200 controls the reaction rate of the polymerization reaction within a predetermined range by controlling the temperature conditions of the first tubular mixing temperature control unit 22 and / or the first variable easing temperature control unit 32.

[0109] The control unit 200 controls one or more of the following operations based on the first reaction information obtained by the first tube mixing fluid measuring unit 222 and / or the first generating fluid measuring unit 322: the supply of the first supply pump 112, the supply of the second supply pump 122, the temperature adjustment of the first tube mixing temperature control unit 22, and the temperature adjustment of the first variable easing temperature control unit 32.

[0110] Next, the operation of the polymer manufacturing system 1 (polyamic acid manufacturing system) in the first embodiment will be described.

[0111] First, in the polymer manufacturing system 1, by starting operation, the first supply pump 112 supplies a first fluid A1, and the second supply pump 122 supplies a second fluid A2. Here, the ejection flow rates of the first supply pump 112 and the second supply pump 122 are controlled by the control unit 200 to supply the first fluid A1 and the second fluid A2 in a desired ratio. Thus, the first fluid A1 and the second fluid A2 are supplied to the first confluence section J1. In the first confluence section 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 combined and mixed to generate a first confluence fluid B.

[0112] The first confluence fluid B generated in the first confluence section J1 is supplied to the first tubular mixing section 20 through the supply operation of the first supply pump 112 and the second supply pump 122.

[0113] In the first tubular mixing section 20, the first confluent fluid B is stirred to change its radially uneven concentration and other properties into a radially uniform concentration and other properties, thereby generating the first tubular mixed fluid C. In the case where the first tubular mixing section 20 is a static mixer or similar static mixer, the first confluent fluid B is stirred only by the flow of liquid. Here, in the first tubular mixing section 20, the first confluent fluid B moves axially along the tube without generating a large velocity distribution; therefore, if there is a viscosity variation of the first confluent fluid B along the axial direction of the tube, this variation cannot be eliminated.

[0114] The first tubular mixed fluid C generated in the first tubular mixing section 20 is transported in the fourth liquid delivery section L4 and supplied to the first variation mitigation section 30.

[0115] In the first variation mitigation section 30, the first tube mixed fluid C is introduced, and the fluid is continuously supplied in a manner that distributes the residence time of the first tube mixed fluid C through radial velocity distribution. This allows for a significant reduction in the viscosity variation of the first tube mixed fluid C along the tube's axial direction, which cannot be eliminated in the preceding first tube-type mixing section 20, within the subsequent first variation mitigation section 30. Therefore, the desired polymer can be obtained continuously and stably.

[0116] Here, during the operation of the polymer manufacturing system 1, the first pipe mixing fluid measuring unit 222 and the first generating fluid measuring unit 322 acquire viscosity information (measurement process).

[0117] The control unit 200 controls each supply pump 112, 122 and each temperature control unit 22, 32 (control process) based on the viscosity information (first reaction information) obtained by the first pipe mixing fluid measuring unit 222 and / or the first generating fluid measuring unit 322. As a result, polyamic acid with the desired properties (temperature, viscosity) can be obtained.

[0118] Knowing the residence time distribution of the first tube mixed fluid C in the first variation mitigation section 30, the first viscosity information is obtained using the first tube mixed fluid measuring unit 222 (measurement process). Based on this, the time-dependent viscosity change of the first generated fluid D at the outlet of the first variation mitigation section 30 can be predicted (prediction process). The predicted viscosity can also be used to control each supply pump 112, 122 and each temperature control unit 22, 32 (control process). For example, if a Hagen-Poiseuille flow is formed in the first variation mitigation section 30 due to laminar flow, the radial velocity distribution can be calculated, and thus the residence time distribution can be known. Therefore, for the viscosity of the first tube mixed fluid C obtained by the first tube mixed fluid measuring unit 222, when a time-moving average weighted by the residence time distribution is calculated, a predicted value of the viscosity of the first generated fluid D at the outlet of the first variation mitigation section 30 can be obtained.

[0119] If the residence time distribution of the first mixed fluid C in the first variation mitigation section 30 is unknown, it is possible to perform an actual measurement on the time-dependent viscosity changes at the inlet and outlet of the first variation mitigation section 30, and model the reduction effect of viscosity variation based on the first variation mitigation section 30, thereby predicting the viscosity shift of the first generated fluid D. For example, a first-order delay function can be used in the modeling.

[0120] When operating conditions are controlled based on viscosity information acquired by the first mixing fluid measuring unit 222, which varies considerably, there is a risk of oscillation. On the other hand, when operating conditions are controlled based on viscosity information acquired by the first generating fluid measuring unit 322, oscillation is less likely to occur due to the stable viscosity, but it is time-consuming and therefore prone to exceeding limits. Therefore, the following approach is effective: predict the viscosity of the first generating fluid D at the outlet of the first variation mitigation unit 30 based on the viscosity information acquired by the first mixing fluid measuring unit 222, and control it accordingly.

[0121] In addition, during the operation of the polymer manufacturing system 1, the first pipe mixing fluid measuring unit 222 and the first generating fluid measuring unit 322 acquire temperature information (measurement process).

[0122] The control unit 200 controls the temperature adjustment conditions (control process) of the first tube-type mixing temperature control unit 22 and / or the first variable easing temperature control unit 32 based on the temperature information (first reaction information) obtained by the first tube mixing fluid measuring unit 222 and / or the first generating fluid measuring unit 322. As a result, polyamic acid with the desired properties (temperature, viscosity) can be obtained.

[0123] The polymer manufacturing system 1 of this embodiment achieves the following effects.

[0124] The polymer manufacturing 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; a first confluence section J1 that merges the first fluid A1 and the second fluid A2 to generate a first confluence fluid B; a first tubular mixing section 20 disposed downstream of the first confluence section J1 that agitates the first confluence fluid B to homogenize radial viscosity variations, thereby generating a first tubular mixed fluid C; and a first variation mitigation section 30 disposed downstream of the first tubular mixing section 20 that reduces axial non-uniformity of the properties of the first tubular mixed fluid C to generate a first generated fluid D.

[0125] In this invention, since the first tubular mixed fluid C, which is mixed in the first tubular mixing section 20 disposed in the preceding stage, is homogenized in the first variation mitigation section 30 disposed in the following stage, the viscosity variation 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 of the preceding stage, can be eliminated in the first variation mitigation section 30 of the following stage, and a polymer solution can be obtained continuously and stably.

[0126] Especially when manufacturing high-viscosity polymers, the pressure loss of the high-viscosity solution passing through the tubular mixer is significant. Therefore, the pump needs a high ejection pressure, resulting in poor metering of the liquid. Consequently, it is difficult to obtain polymers with stable viscosity using only a tubular mixer. Therefore, the present invention is particularly effective, for example, in manufacturing high-viscosity polymers with a viscosity of 1000 poise or higher.

[0127] Furthermore, in the polymer manufacturing system 1, based on the first reaction information obtained by the first tube mixing fluid measuring unit 222 and / or the first generating fluid measuring unit 322, one or more of the following operations are controlled: the supply of the first supply pump 112, the supply of the second supply pump 122, the temperature adjustment of the first tube mixing temperature control unit 22, and the temperature adjustment of the first temperature fluctuation mitigation unit 32. As a result, a polymer with desired properties (temperature, viscosity) can be obtained.

[0128] Furthermore, in this embodiment, it is described that one of the first polymerizable compound and the second polymerizable compound is a tetracarboxylic acid dianhydride and the other is a diamine, and polyamic acid is produced as a polymer, but it is not limited to this.

[0129] For example, it is also possible to manufacture polyamic acid as a polymer by making one of the first and second polymeric compounds an anhydride-terminated polyamic acid (prepolymer) or an amino-terminated polyamic acid (prepolymer), and the other a diamine or tetracarboxylic dianhydride. In this case, when one of the first and second polymeric compounds is an anhydride-terminated polyamic acid, the other is a diamine. Alternatively, when one of the first and second polymeric compounds is an amino-terminated polyamic acid, the other is a tetracarboxylic dianhydride.

[0130] Alternatively, for example, one of the first and second polymerizable compounds may be an anhydride-terminated or amino-terminated polyamic acid, and the other may be an amino-terminated or an anhydride-terminated polyamic acid, thereby manufacturing a polyamic acid as a polymer. In this case, when one of the first and second polymerizable compounds is an anhydride-terminated polyamic acid, the other is an amino-terminated polyamic acid.

[0131] <Second Implementation>

[0132] pass Figure 2 The polymer manufacturing system in the second embodiment is described. Figure 2 This is a diagram illustrating the polymer manufacturing system in the second embodiment. Furthermore, the same reference numerals are used to denote structural parts that are the same as in the first embodiment.

[0133] In this embodiment, the first variation mitigation unit 30 is disposed downstream of the first tubular mixing unit 20. The first variation mitigation unit 30 includes a cylindrical first variation mitigation tank 31a without a mixer and a first variation mitigation temperature control unit 32 (first temperature control unit) disposed outside the first variation mitigation tank 31a. In this embodiment, the first variation mitigation temperature control unit 32 is used to adjust the first tubular mixed fluid C to a temperature suitable for the polymerization reaction.

[0134] In the first variation mitigation tank 31a, the residence time distribution generated by the velocity difference between the vertical and horizontal directions is used to reduce the viscosity variation in the axial direction (flow direction of the fluid) of the first pipe mixed fluid C, thereby stabilizing the properties of the outflowing first generating fluid D and mitigating the axial variation of the properties of the first pipe mixed fluid C.

[0135] In the first variation mitigation tank 31a, an open channel is formed, through which the first pipe-mixed fluid C flows in from the upper part in a vertical direction, and the first generated fluid D flows out from the lower part. By making the first variation mitigation tank 31a an open channel, the pressure on the inflow side of the first pipe-mixed fluid C becomes the pressure of the gas phase. Therefore, compared to the case where the first pipe-type mixing section 20 is followed by a pipeline, the ejection pressure of the first supply pump 112 and the ejection pressure of the second supply pump 122 can be reduced, which is excellent. The gas phase can be maintained at a constant pressure using an inactive gas or the like.

[0136] The shape of the first variable mitigation tank 31a is not particularly limited, but a structure that does not easily create useless space is preferred; specifically, a cylindrical tank is preferred. If the ratio of the diameter D to the height L (L / D) of the cylindrical tank is too small, the fluid will not flow sufficiently in the horizontal direction, and short circuits are likely to occur. Therefore, L / D is preferably 0.5 or more. On the other hand, if L / D is too large, it is difficult to install the device. Therefore, L / D is preferably 10 or less. Thus, 0.5 to 10 is preferred.

[0137] The inlet of the first fluctuation mitigation tank 31a can be located on the wall or as an insertion tube. If it is an insertion tube, it is preferable that the inlet is positioned such that it is held in the liquid surface or that the fluid flows along the wall surface, thereby preventing air bubbles from entering. The outlet of the first fluctuation mitigation tank 31a is preferably located where the entire outlet is immersed in the liquid to prevent air bubbles from entering.

[0138] In terms of management, it is preferable that the inflow rate of the first mixing fluid C into the first variation buffer tank 31a is the same as the outflow rate of the first generating fluid D, but this can also be varied. For example, the outflow rate of the first generating fluid D can be controlled so that the liquid level in the first variation buffer tank 31a is within a predetermined range.

[0139] When the liquid level is low, gas phase may be entrained at the outlet. Therefore, it is preferable that the amount of the first pipe mixed fluid C in the first fluctuation mitigation tank 31a is more than 20% of the volume of the first fluctuation mitigation tank 31a. When the liquid level is high, the flow in the first fluctuation mitigation tank 31a changes from open channel flow to pipe flow or becomes a transitional state between open channel flow and pipe flow, which may cause pressure fluctuations in the first fluctuation mitigation tank 31a. Therefore, it is preferable that the amount of the first pipe mixed fluid C in the first fluctuation mitigation tank 31a is less than 80% of the volume of the first fluctuation mitigation tank 31a. Therefore, it is preferable to control the amount of the first pipe mixed fluid C in the first fluctuation mitigation tank 31a to 20% to 80% of the volume of the first fluctuation mitigation tank 31a.

[0140] When the first fluctuation mitigation tank 31a is a cylindrical tank, the angle between the central axis and the mounting surface is preferably set to 75° or less to reduce the risk of air bubble entrapment. On the other hand, when the angle is too small, the liquid level refresh is slower; therefore, the angle between the central axis of the first fluctuation mitigation tank 31a and the mounting surface is preferably 45° or more. Therefore, the angle between the central axis of the first fluctuation mitigation tank 31a and the mounting surface is preferably set to 45° to 75°.

[0141] The first variation mitigation tank 31a is configured such that the average residence time is sufficiently long. Here, the average residence time refers to the value obtained by dividing the volume of the solution in the first variation mitigation tank 31a by the volumetric flow rate of the first tube mixing fluid C. A longer average residence time in the first variation mitigation tank 31a results in a greater stabilization effect on the viscosity of the first generated fluid D flowing out of the first variation mitigation tank 31a. Therefore, the greater the axial variation in the properties of the first mixed fluid C flowing out of the first tube-type mixing section 20, the longer the average residence time in the first variation mitigation tank 31a is preferred. The residence time is preferably 3 minutes or more, more preferably 7 minutes or more, and even more preferably 10 minutes or more. The longer the average residence time in the first variation mitigation tank 31a, the greater the reduction effect on viscosity variation; however, in order to minimize the loss of the generated polymer, it is more preferable that the total average residence time be 300 minutes or less.

[0142] In order to ensure that the first variation easing tank 31a has an appropriate average residence time according to the viscosity variation of the first tube mixed fluid C, the volume of the solution in the first variation easing tank 31a is preferably 0.5 to 100 times the volume of the first tube type mixing and stirring section 20, more preferably 5 to 100 times.

[0143] The shape of the first fluctuation mitigation tank 31a is not particularly limited. Specifically, it may also have an internal structure. In addition, sensors or the like may be installed in the first fluctuation mitigation tank 31a.

[0144] The interior of the first variation mitigation tank 31a is an open channel. For the first pipe mixed fluid C that flows in from the inlet located on the upper side, there is a difference in the flow velocity of the first pipe mixed fluid C in the vertical and horizontal directions within the first variation mitigation tank 31a, which in turn creates a difference in the residence time within the first variation mitigation tank 31a. Therefore, it can mitigate the axial variation of the first variation mitigation tank 31a.

[0145] The first temperature regulation and temperature control unit 32 regulates (e.g., cools) the first pipe mixed fluid C flowing in the first temperature regulation tank 31a to the desired temperature conditions.

[0146] In the first tubular mixing section 20 and the first variation mitigation section 30 described above, the first tubular mixing section 20 is disposed in the pre-stage and the first variation mitigation section 30 is disposed in the post-stage. Thus, when there is a viscosity variation in the axial direction of the tube in the first tubular mixing section 20 in the pre-stage, the viscosity variation in the axial direction of the tube can be significantly reduced in the first variation mitigation section 30 in the post-stage.

[0147] Next, the operation of the polymer manufacturing system 1 (polyamic acid manufacturing system) in the second embodiment will be described.

[0148] In the first variation mitigation section 30, the first tube mixed fluid C is introduced, and the fluid is continuously supplied in a manner that distributes the residence time of the first tube mixed fluid C through the residence time distribution generated by the velocity difference between the vertical and horizontal directions. This allows for a significant reduction in the viscosity variation of the first tube mixed fluid C along the tube's axial direction, which cannot be eliminated in the preceding first tube-type mixing section 20, within the subsequent first variation mitigation section 30. Therefore, the desired polymer can be obtained continuously and stably.

[0149] <Third Implementation>

[0150] pass Figure 3 The polymer manufacturing system in the third embodiment is described. Figure 3 This diagram illustrates the polymer manufacturing system in the third embodiment. Furthermore, the same reference numerals are used to denote the same structural parts as in the first and second embodiments.

[0151] In this embodiment, the first variation mitigation section 30 is disposed downstream of the first tubular mixing section 20 and is designed such that the fluids simultaneously flowing into the first variation mitigation section 30 exit from the first variation mitigation section 30 with a longer time difference due to a larger residence time distribution. Specifically, it is designed to produce a residence time distribution such that it takes more than 10 minutes from the time the fluid with the fastest flow velocity trace exits until 70% of the fluid simultaneously flowing into the first variation mitigation section 30 has exited. This larger residence time distribution promotes axial homogenization of the first tubular mixed fluid C, resulting in a first generated fluid D with less viscosity variation over time.

[0152] The fastest flow trajectory refers to, for example, the trajectory that tracer particles and colorants initially follow when they flow out of the outlet of the first variation buffer section 30, covering the entire cross-section of the inlet of the first variation buffer section 30. Furthermore, "it takes more than 10 minutes from the time the fluid flows out through the fastest flow trajectory until 70% of the fluid simultaneously flowing into the first variation buffer section 30 has flowed out" means, for example, that when tracer particles and colorants are placed in the entire cross-section of the inlet of the first variation buffer section 30, it takes more than 10 minutes from the time the tracer particles and colorants initially flow out of the outlet of the first variation buffer section 30 until 70% of the tracer particles and colorants have flowed out. This can be evaluated using a turbidimeter, spectrophotometer, etc.

[0153] The greater the residence time distribution of the first pipe mixed fluid C within the first variation mitigation section 30, the greater the effect of reducing viscosity variation. However, if the residence time distribution is too large, a larger device is required, increasing equipment costs. Therefore, it is preferable to design the first variation mitigation section 30 in a manner that achieves an appropriate residence time distribution. Specifically, it is more preferable to design it such that the time from the exit of the fluid through the fastest flow path until 70% of the fluid simultaneously flowing into the first variation mitigation section 30 has exited is within 360 minutes.

[0154] As a configuration for the first variation mitigation section 30 to achieve a larger residence time distribution, for example, a configuration can be provided in which the mixed fluid C in the first pipe merges after branching into multiple flow paths with different residence times. In this case, the first variation mitigation section 30 has a first variation mitigation branch section J2 (first branch section) that branches the incoming fluid into multiple flow paths, and a first variation mitigation merging section J3 (second merging section) that merges the fluids flowing in the multiple flow paths downstream of the flow direction of the multiple flow paths after branching through the first variation mitigation branch section J2.

[0155] exist Figure 3 The structure shown is configured such that the first variation mitigation section 30 distributes the first tube mixed fluid C to two flow paths with different residence times at the first variation mitigation branch section J2 (first branch section), and merges them again into one flow path at the first variation mitigation confluence section J3 (second confluence section). The two flow paths of the first variation mitigation section 30 are composed of double pipes, having a first variation mitigation piping section 31 and a second variation mitigation piping section 33 arranged radially inward, and a first variation mitigation temperature control section 32 (first temperature control section) and a second variation mitigation temperature control section 34 (first temperature control section) arranged radially outward. In this embodiment, the first variation mitigation temperature control section 32 and the second variation mitigation temperature control section 34 are used to adjust the first tube mixed fluid C to a temperature suitable for the polymerization reaction.

[0156] There are no particular limitations on the shape of the piping constituting the first fluctuation mitigation section 30. For example, as described above, the first fluctuation mitigation section can be configured to have a first branch section that branches the fluid flowing inside into two or more different flow paths and a first fluctuation mitigation converging section (second converging section) that rejoins the branched flow paths. It can also have an internal structure, and can use piping that is bent by elbows or the like. The cross-section does not have to be circular. In addition, valves, sensors, etc., can be installed in the middle of the first fluctuation mitigation piping section 31. Alternatively, by using a separator or the like, the interior of a single piping can be divided to form two or more flow paths with different residence times.

[0157] In the first variation mitigation section 30, in addition to generating a residence time distribution through a combination of flow paths with different residence times, a residence time distribution can also be generated using radial velocity differences within the same flow path. For example, in the case of laminar flow within a circular pipe, the fluid passing through the center of the pipe has the fastest velocity and the shortest residence time. On the other hand, the fluid passing through the pipe wall has an extremely slow velocity, and therefore a very long residence time. Within a single flow path, such differences in residence time based on the trace can also mitigate axial variation in characteristics.

[0158] To achieve sufficient viscosity variation mitigation through radial velocity differences within the same flow path, the first pipe mixed fluid C preferably flows in laminar flow within the piping. For laminar flow within the first variation mitigation piping section 31 and / or the second variation mitigation piping section 33, using 4 × cross-sectional area / wetted perimeter as the representative length d, the Reynolds number (ρud / μ) calculated from the viscosity μ, cross-sectional average velocity u, and density ρ is preferably 2100 or less, more preferably 0.00001 or more and 1000 or less. Furthermore, when the solution viscosity is low, the guiding interval until flow development is long, thus failing to effectively generate velocity distribution; therefore, a higher viscosity of the first pipe mixed fluid C flowing within the first variation mitigation piping section 31 and / or the second variation mitigation piping section 33 is preferable. Specifically, the viscosity of the first pipe mixed fluid C flowing in the first variation mitigation piping section 31 and / or the second variation mitigation piping section 33 is preferably 0.1 poise or more and 100,000 poise or less under the temperature conditions during flow, more preferably 1 poise or more and 10,000 poise or less, and even more preferably 5 poise or more and 5,000 poise or less.

[0159] exist Figure 3The example shown is of the first variation mitigation section 30 consisting of two flow paths with different residence times, but it is not limited to this. As described above, if a residence time distribution of more than 10 minutes is required from the outflow of fluid through the fastest flow path until 70% of the fluid simultaneously flowing into the first variation mitigation section 30 flows out, the first variation mitigation section 30 may not contain branch sections and confluence sections, and may consist of only one pipe. On the other hand, if the flow inside the first variation mitigation section 30 is turbulent, or if the radial velocity difference is small due to the influence of the internal structure, the first variation mitigation section 30 may also be constructed with three or more branched pipes in order to actively generate a residence time distribution.

[0160] In the first variation mitigation piping section 31 and the second variation mitigation piping section 33, if the variation has a shorter cycle than the average residence time, it can be mitigated; however, if the variation has a longer cycle than the average residence time, it is difficult to mitigate. Therefore, it is preferable that the combined average residence time of the first variation mitigation piping section 31 and the second variation mitigation piping section 33 is sufficiently long compared to the average variation cycle of the first pipe mixed fluid C that may be generated at the outlet of the first pipe mixing section 20. Here, the average residence time refers to the value obtained by dividing the total volume of the flow path by the volumetric flow rate of the first pipe mixed fluid C. In addition, the average variation cycle refers to the average time from when the viscosity of the first pipe mixed fluid C at the outlet of the first pipe mixing section 20 reaches a maximum value until it reaches a minimum value and then reaches a maximum value again. The sum of the average residence times of the first variation mitigation piping section 31 and the second variation mitigation piping section 33 is preferably more than one time the average variation cycle of the first pipe mixed fluid C at the outlet of the first pipe type mixing section 20, and more preferably more than two times.

[0161] In order to ensure that the first variation mitigation piping section 31 and the second variation mitigation piping section 33 have appropriate average residence times according to the viscosity variation of the first tube mixed fluid C, the total volume of the first variation mitigation piping section 31 and the second variation mitigation piping section 33 is preferably 0.5 to 100 times the volume of the first tube type mixing and stirring section 20.

[0162] In order to obtain a first generating fluid D that does not contain air bubbles, the first variation mitigation piping section 31 and the second variation mitigation piping section 33 are preferably transported in a state where the fluid does not come into contact with the gas. However, it is not limited to this. If air bubbles are not entrained into the first pipe mixed fluid C, a gas phase may also exist inside the first variation mitigation piping section 31 and / or the second variation mitigation piping section 33.

[0163] exist Figure 1In the configuration where the first pipe mixed fluid C branches into two flow paths with different residence times and then merges, the first pipe mixed fluid C flowing into the first variation mitigation section 30 is distributed to the first variation mitigation piping section 31 and the second variation mitigation piping section 33 at the first variation mitigation branch section J2. After being distributed at the first variation mitigation branch section J2, the first pipe mixed fluid C flows towards the first variation mitigation confluence section J3 in the first variation mitigation piping section 31 and the second variation mitigation piping section 33 respectively, merges at the first variation mitigation confluence section J3, and flows out from the first variation mitigation section 30.

[0164] The first temperature-regulating section 32 and the second temperature-regulating section 34 are respectively located radially outside the first temperature-regulating piping section 31 and the second temperature-regulating piping section 33, and regulate (e.g., cool) the first pipe mixed fluid C flowing inside to the desired temperature conditions. In these temperature-regulating sections, the first pipe mixed fluid C is adjusted to a temperature suitable for the polymerization reaction and flows in the first temperature-regulating piping section 31 and the second temperature-regulating piping section 33.

[0165] If the first tube mixed fluid C is not distributed to the multiple flow paths constituting the first variation mitigation section 30 at the desired flow rate due to differences in pressure loss, etc., one or more pumps may be provided in the first variation mitigation section 30 to adjust the flow rate of the first tube mixed fluid C flowing in each flow path. Alternatively, one or more back pressure valves or valves with adjustable opening degrees may be provided in the first variation mitigation section 30 to adjust the pressure loss, thereby distributing the first tube mixed fluid C to each flow path at the desired flow rate.

[0166] In the first tubular mixing section 20 and the first variation mitigation section 30 described above, the first tubular mixing section 20 is disposed in the pre-stage and the first variation mitigation section 30 is disposed in the post-stage. Thus, when there is a viscosity variation in the axial direction of the tube in the first tubular mixing section 20 in the pre-stage, the viscosity variation in the axial direction of the tube can be significantly reduced in the first variation mitigation section 30 in the post-stage.

[0167] Next, the operation of the polymer manufacturing system 1 (polyamic acid manufacturing system) in the third embodiment will be described.

[0168] In the first variation mitigation section 30, the first tube mixed fluid C is introduced, and the residence time of the first tube mixed fluid C is continuously supplied in a distributed state through the effect of radial velocity distribution and / or branching into flow paths with different residence times. As a result, the viscosity variation of the first tube mixed fluid C in the axial direction of the tube, which cannot be eliminated in the preceding first tube mixing section 20, can be significantly reduced in the subsequent first variation mitigation section 30. Therefore, the desired polymer can be obtained continuously and stably.

[0169] Here, during the operation of the polymer manufacturing system 1, the first pipe mixing fluid measuring unit 222 and the first generating fluid measuring unit 322 acquire viscosity information (measurement process).

[0170] The control unit 200 controls each supply pump 112, 122 and each temperature control unit 22, 32, 34 based on viscosity information (first reaction information) obtained by the first pipe mixing fluid measuring unit 222 and / or the first generating fluid measuring unit 322. This allows for the production of polyamic acid with desired properties (temperature, viscosity).

[0171] Knowing the residence time distribution of the first tube mixed fluid C in the first variation mitigation section 30, the first viscosity information is obtained using the first tube mixed fluid measuring unit 222 (measurement process). Based on this, the time-dependent viscosity change of the first generated fluid D at the outlet of the first variation mitigation section 30 can be predicted (prediction process). The predicted viscosity can also be used to control each supply pump 112, 122 and each temperature control unit 22, 32, 34 (control process). For example, if a Hagen-Poiseuille flow is formed in the first variation mitigation section 30 due to laminar flow, the radial velocity distribution can be calculated, and thus the residence time distribution can be known. Therefore, when a time-weighted moving average of the residence time distribution is calculated based on the viscosity of the first tube mixed fluid C obtained by the first tube mixed fluid measuring unit 222, a predicted value of the viscosity of the first generated fluid D at the outlet of the first variation mitigation section 30 can be obtained. Furthermore, if the first variation mitigation section 30 is constructed to branch into two or more flow paths, it is sufficient to consider the average obtained by weighting the residence time distribution of each flow path using the flow rate ratio of each flow path.

[0172] Furthermore, in the polymer manufacturing system 1, based on the first reaction information obtained by the first tube mixing fluid measuring unit 222 and / or the first generating fluid measuring unit 322, control is performed on any one or more of the following operations: the supply of the first supply pump 112, the supply of the second supply pump 122, the temperature adjustment of the first tube mixing temperature control unit 22, the temperature adjustment of the first temperature fluctuation mitigation unit 32, and the temperature adjustment of the second temperature fluctuation mitigation unit 34. As a result, a polymer with desired properties (temperature, viscosity) can be obtained.

[0173] <Variation Example>

[0174] The above describes three implementation methods, but the present invention is not limited to the above implementation methods. The present invention includes modifications and improvements made within the scope of achieving the purpose of the present invention.

[0175] For example, in the above embodiment, the fluid is configured to mix in the first tubular mixing section and the first variation mitigation section. However, this is not a limitation. One or more stages of tubular mixing sections and / or variation mitigation sections may also be provided further downstream of the structure in the above embodiment. In addition, in the third embodiment, an example was described in which the fluids merge into one flow path at the first variation mitigation confluence section J3, but this is not a limitation. For example, the first tubular mixed fluids C, which are distributed into multiple flow paths, may flow independently into a buffer tank or the like located downstream.

[0176] Furthermore, in this embodiment, the case where the first tubular mixing section 20 is composed of a double tube consisting of a first tubular mixing and stirring section 21 and a first temperature adjusting section 22 is described, but it is not limited to this. For example, the first tubular mixing section 20 may be constructed using only the single tube of the first tubular mixing and stirring section 21, and the first tubular mixing and stirring section 21 may be immersed in a temperature-adjusting liquid.

[0177] Furthermore, while the above embodiments describe a polymer manufacturing system for producing polyamic acid or polyimide, the polymers produced are not limited to these. For example, the polymer manufacturing system may also be a system that uses addition polymerizable monomers such as polyurethane monomers or epoxy monomers to manufacture polymers. Additionally, while the above embodiments describe an example of reducing viscosity over time using the first variation mitigation section 30, the property capable of reducing variation is not limited to viscosity; for other physical properties, the first variation mitigation section 30 can also be used to reduce the over-time variation of that property when it occurs.

[0178] In the above embodiment, viscosity information related to viscosity of the first tube mixing fluid C and the first generating fluid D is obtained using a viscosity measurement unit, and the fluid supply amount and / or mixing temperature conditions are controlled based on the obtained viscosity information, but this is not limited to this. For example, absorbance information related to absorbance of the first tube mixing fluid C and the first generating fluid D may also be obtained, and the fluid supply amount and / or mixing temperature conditions may be controlled based on the obtained absorbance information.

[0179] In the above embodiments, an example is shown where the various parts of the polymer manufacturing system are connected using the first liquid delivery line L1, the second liquid delivery line L2, the third liquid delivery line L3, the fourth liquid delivery line L4, and the fifth liquid delivery line L5, but this is not a limitation. For example, the fourth liquid delivery line L4 may not be provided, and the outlet of the first tubular mixing section 20 and the inlet of the first variation mitigation section 30 may be directly connected.

[0180] Furthermore, while the above embodiment describes a method for controlling the temperature of the first tubular mixing section 20 and the temperature of the first temperature fluctuation mitigation section 30, it is not limited to this. For example, a temperature regulating section for the first tubular mixing section 20 and / or a temperature regulating section for the first temperature fluctuation mitigation section 30 is not necessarily required. Alternatively, a temperature regulating section may be provided at any one or more of the first confluence section J1, the first liquid delivery line L1, the second liquid delivery line L2, the third liquid delivery line L3, the fourth liquid delivery line L4, and the fifth liquid delivery line L5.

[0181] Example

[0182] The present invention will be specifically described below through examples, but the present invention is not limited to these examples.

[0183] <Example 1>

[0184] In Example 1, using Figure 1 Polymer manufacturing system 1, as shown, produces polyamic acid. A first fluid A1 is contained in a first tank 11. This first fluid A1 is obtained by dissolving polyamic acid, which is terminally anhydride and is obtained by reacting 4,4'-diaminodiphenyl ether with pyromellitic dianhydride, in N,N-dimethylformamide. Furthermore, a second fluid A2 is contained in a second tank 12. This second fluid A2 is obtained by dissolving p-phenylenediamine in N,N-dimethylformamide.

[0185] First, in the first confluence section 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 combined and mixed to generate a first confluence fluid B. Next, in the first tubular mixing section 20, the first confluence fluid B is stirred in a state where it does not come into contact with the gas, and a first tubular mixed fluid C with uniform properties in the radial direction of the tube flows out from the outlet of the first tubular mixing section 20.

[0186] More specifically, in the first tubular mixing section 20, a Kenics mixer-type static mixer (8 mm inner diameter, 670 mm length) was used to agitate the first confluent fluid B without contacting the gas. By setting the combined supply rate of the first supply pump 112 and the second supply pump 122 to 1.0 cc / s and adjusting the feed ratio of the raw materials using these pumps, a polymer solution of the desired viscosity was obtained. At the outlet of the first tubular mixing section 20, the polymerization reaction ended, resulting in a first tubular mixed fluid with radially similar properties, but according to measurements using an online viscometer, a viscosity variation of approximately 400 poise was observed between the maximum and minimum viscosity values. The average viscosity of the first tubular mixed fluid C was 2100 poise.

[0187] The first variation mitigation section 30 uses a hollow cylindrical tube with an inner diameter of 30 mm and a length of 900 mm. The first tubular mixed fluid C, flowing from the first tubular mixing section 20, flows into the first variation mitigation section 30 at a volumetric flow rate of 1.0 cc / s. Through the velocity distribution generated within the first variation mitigation section 30, axial mixing of the first tubular mixed fluid C is achieved, and a first generated fluid D with an average viscosity of 2100 poise and reduced viscosity variation flows out from the outlet of the first variation mitigation section 30. According to measurements using an online viscometer, the difference between the maximum and minimum viscosity values ​​of the first generated fluid D is approximately 80 poise. Therefore, it can be seen that by providing the first variation mitigation section 30, the viscosity variation of the fluid at the outlet of the first tubular mixing section 20 over time can be significantly reduced.

[0188] <Example 2>

[0189] In Example 2, using Figure 2 Polymer manufacturing system 1, as shown, produces polyamic acid. A first fluid A1 is contained in a first tank 11, which is obtained by dissolving polyamic acid (terminated with an anhydride) obtained through the reaction of 4,4'-diaminodiphenyl ether with pyromellitic dianhydride in N,N-dimethylformamide. A second fluid A2 is contained in a second tank 12, which is obtained by dissolving p-phenylenediamine in N,N-dimethylformamide.

[0190] First, in the first confluence section 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 combined and mixed to generate a first confluence fluid B. Next, in the first tubular mixing section 20, the first confluence fluid B is stirred in a state where it does not come into contact with the gas, and a first tubular mixed fluid C with uniform properties in the radial direction of the tube flows out from the outlet of the first tubular mixing section 20.

[0191] More specifically, using a Kenics mixer-type static mixer (8mm inner diameter, 670mm length), fluid A1 and fluid A2 were combined to form a first combined fluid B, with a total supply rate of 1.0 cc / s for both fluids A1 and A2. Next, in a first tubular mixing section 20, the first combined fluid B was stirred without contact with the gas. From the outlet of the first tubular mixing section 20, a first tubular mixed fluid C with uniform properties in the radial direction of the tube was obtained. At the outlet of the first tubular mixing section 20, the polymerization reaction ended, resulting in a first tubular mixed fluid C with uniform radial properties, but according to measurements using an online viscometer, a viscosity variation of 800 poise was observed between the maximum and minimum viscosity values. The average viscosity of the first tubular mixed fluid C was 1800 poise.

[0192] The first variation mitigation tank 31a, serving as the first variation mitigation section 30, is a cylindrical tank with an inner diameter of 80 mm and a capacity of 500 ml, and is positioned such that the central axis of the cylindrical tank is at a 60° angle to the mounting surface. A portion of the first tubular mixed fluid C flowing out from the first tubular mixing section 20 flows into the first variation mitigation tank 31a from the top at a volumetric flow rate of 0.2 cc / s. Meanwhile, the first generated fluid D flows out from the bottom of the first variation mitigation tank 31a at the same flow rate. The average residence time within the first variation mitigation tank 31a is 11 minutes.

[0193] The axial mixing of the first tubular mixing fluid C is achieved through the flow velocity distribution generated within the first variable mitigation tank 31a, resulting in the discharge of a first generated fluid D with an average viscosity of 1800 poise and minimal viscosity variation. According to measurements from an online viscometer, the difference between the maximum and minimum viscosity of the first generated fluid D is 40 poise. Therefore, by providing the first variable mitigation section 30, the viscosity variation of the fluid at the outlet of the first tubular mixing section 20 over time is significantly reduced.

[0194] <Example 3>

[0195] In Example 3, using Figure 3 Polymer manufacturing system 1, as shown, produces polyamic acid. A first fluid A1 is contained in a first tank 11. This first fluid A1 is obtained by dissolving polyamic acid, which is terminally anhydride and is obtained through the reaction of 4,4'-diaminodiphenyl ether with pyromellitic dianhydride, in N,N-dimethylformamide. Furthermore, a second fluid A2 is contained in a second tank 12. This second fluid A2 is obtained by dissolving p-phenylenediamine in N,N-dimethylformamide.

[0196] First, in the first confluence section 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 combined and mixed to generate a first confluence fluid B. Next, in the first tubular mixing section 20, the first confluence fluid B is stirred in a state where it does not come into contact with the gas, and a first tubular mixed fluid C with uniform properties in the radial direction of the tube flows out from the outlet of the first tubular mixing section 20.

[0197] More specifically, in the first tubular mixing section 20, a Kenics mixer-type static mixer (8 mm inner diameter, 670 mm length) was used to agitate the first confluent fluid B without contacting the gas. By setting the combined supply rate of the first supply pump 112 and the second supply pump 122 to 1.0 cc / s and adjusting the feed ratio of the raw materials using these pumps, a polymer solution of the desired viscosity was obtained. At the outlet of the first tubular mixing section 20, the polymerization reaction ended, resulting in a first tubular mixed fluid with radially similar properties, but according to measurements using an online viscometer, a viscosity variation of approximately 400 poise was observed between the maximum and minimum viscosity values. The average viscosity of the first tubular mixed fluid C was 2100 poise.

[0198] The first variation mitigation section 30 uses a hollow cylindrical tube with an inner diameter of 30 mm and a length of 1000 mm for the first variation mitigation piping section 31, and a hollow cylindrical tube with an inner diameter of 20 mm and a length of 200 mm for the second variation mitigation piping section 33. The configuration is such that it takes 13 minutes from the time the fluid with the fastest flow velocity exits until 70% of the fluid simultaneously flowing into the first variation mitigation section 30 has exited. The first tubular mixed fluid C, flowing from the first tubular mixing section 20, flows into the first variation mitigation section 30 at a volumetric flow rate of 1.0 cc / s. Through the residence time distribution generated within the first variation mitigation section 30, the first tubular mixed fluid C is mixed axially, and a first generated fluid D with an average viscosity of 2100 poise and minimal viscosity variation flows out from the outlet of the first variation mitigation section 30. According to measurements by an online viscometer, the difference between the maximum and minimum viscosity of the first generated fluid D is approximately 80 poise. Therefore, it can be seen that by providing the first variation mitigation section 30, the viscosity variation of the fluid at the outlet of the first tubular mixing section 20 over time can be significantly reduced.

[0199] Explanation of reference numerals in the attached figures

[0200] 1. Polymer manufacturing system; 11. Tank 1; 12. Tank 2; 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. On / off valve for Tank 1; 112. First supply pump (first supply section); 113. First flow measurement section; 121. On / off valve for Tank 2; 122. Second supply pump ( 2nd Supply Section); 123, 2nd Flow Measurement Section; 200, Control Section; 222, 1st Pipe Mixed Fluid Measurement Section (1st Measurement Section); 322, 2nd Generating Fluid Measurement Section (1st Measurement Section); A1, 1st Fluid; A2, 2nd Fluid; B, 1st Merging Fluid; C, 1st Pipe Mixed Fluid; D, 1st Generating Fluid; L, Liquid Delivery Line; L1, 1st Liquid Delivery Line; L2, 2nd Liquid Delivery Line; L3, 3rd Liquid Delivery Line; L4, 4th Liquid Delivery Line; L5, 5th Liquid Delivery Line; J1, 1st Merging Section; J2, 1st Fluctuation Mitigation Branch Section (1st Branch Section); J3, 2nd Fluctuation Mitigation Merging Section (2nd Merging Section).

Claims

1. A polymer manufacturing apparatus comprising using a first fluid and a second fluid as raw materials to manufacture a polymer, the first fluid comprising a first polymerizable compound having addition polymerizability, the second fluid comprising a second polymerizable compound having addition polymerizability, and undergoing addition polymerization with the first polymerizable compound, wherein... The polymer manufacturing apparatus includes: The first supply unit supplies the first fluid; The second supply unit supplies the second fluid; The first confluence section allows the first fluid and the second fluid to merge to generate a first confluence fluid; A first tubular mixing section is disposed downstream of the first confluence section, which enhances radial mixing of the first confluence fluid to generate a first tubular mixed fluid; as well as The first variation mitigation section is disposed downstream of the first tubular mixing section. The first variation mitigation section reduces the axial variation of the mixed fluid in the first tube by generating the residence time distribution of the mixed fluid in the first tube through radial velocity difference, or vertical and horizontal velocity difference, or by branching into multiple flow paths with different residence times and then merging. This generates the first generating fluid.

2. The polymer manufacturing apparatus according to claim 1, wherein, The polymer manufacturing apparatus also includes a first measuring unit that acquires first reaction information relating to the physical quantity and / or composition of any one or more of the first confluence fluid, the first tube mixing fluid, and the first generating fluid.

3. The polymer manufacturing apparatus according to claim 2, wherein, The first measuring unit has one or more devices selected from the group consisting of a viscometer, thermometer, pressure gauge, pump pressure gauge, absorbance meter, infrared spectrometer, near-infrared spectrometer, densitometer, colorimeter, refractive index meter, spectrophotometer, conductivity meter, turbidimeter, ultrasonic sensor and fluorescence X-ray analysis device.

4. The polymer manufacturing apparatus according to claim 2, wherein, The polymer manufacturing apparatus also includes a first temperature control unit for adjusting the temperature of any one or more of the first fluid, the second fluid, the first confluence fluid, the first pipe mixing fluid, and the first generating fluid.

5. The polymer manufacturing apparatus according to any one of claims 1 to 4, wherein, The first variable buffer section is a piping where the average residence time of the fluid flowing inside is more than 3 minutes.

6. The polymer manufacturing apparatus according to any one of claims 1 to 4, wherein, The first variation mitigation section is composed of one or more tubular components. The combined average residence time of each of the tubular components is more than 7 minutes.

7. The polymer manufacturing apparatus according to any one of claims 1 to 4, wherein, A first-tube mixed fluid measuring unit is provided between the first tubular mixing section and the first variation mitigation section. This first-tube mixed fluid measuring unit acquires first-tube mixed fluid reaction information related to the physical quantities and / or composition of the first-tube mixed fluid. A first generating fluid measuring unit is further provided at the outlet of the first variation mitigation section or downstream of the outlet. This first generating fluid measuring unit acquires first generating fluid reaction information related to the physical quantity and / or composition of the first generating fluid. The volume of the first variable mitigation section is 0.5 to 100 times the volume of the first tubular mixing section.

8. The polymer manufacturing apparatus according to any one of claims 1 to 4, wherein, The volume of the first variable mitigation section is 5 to 100 times the volume of the first tubular mixing section.

9. The polymer manufacturing apparatus according to any one of claims 1 to 4, wherein, The first variable buffer section is a piping section in which the residence time of the fluid passing through the fastest flow path is more than 3 minutes.

10. The polymer manufacturing apparatus according to any one of claims 1 to 4, wherein, The first variation mitigation section is composed of one or more tubular components. The cross-sectional average velocity of the fluid flowing inside the tubular member is below 0.01 m / s. The total length of each of the tubular components is 0.7m or more.

11. The polymer manufacturing apparatus according to any one of claims 1 to 4, wherein, When using 4×cross-sectional area / wet perimeter as the representative length, the Reynolds number of the fluid flowing inside the first variable buffer section becomes 2100 or less.

12. The polymer manufacturing apparatus according to claim 1, wherein, The first variable mitigation section does not have a driven agitator, and the fluid forms an open channel.

13. The polymer manufacturing apparatus according to claim 1, wherein, It takes more than 10 minutes from the time the fluid flows out through the fastest flow path until 70% of the fluid flowing into the first variation buffer section flows out.

14. The polymer manufacturing apparatus according to any one of claims 1 to 4, wherein, The first polymerizable compound and the second polymerizable compound satisfy any one of (a) to (c) below to manufacture polyamic acid as the polymer. (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 anhydride-terminated polyamic acid and the other is a diamine, or one is an amino-terminated polyamic acid and the other is a tetracarboxylic dianhydride. (c) One of the first polymerizable compound and the second polymerizable compound is an anhydride-terminated polyamic acid and the other is an amino-terminated polyamic acid.

15. The polymer manufacturing apparatus according to claim 14, wherein, The polymer manufacturing apparatus also includes an imidization section that imidizes the manufactured polyamic acid to produce polyimide as the polymer.

16. The polymer manufacturing apparatus according to claim 4, wherein, The first measuring unit acquires the first reaction information of any one or more of the following fluids: the first confluence fluid, the first pipe mixing fluid, and the first generating fluid. The polymer manufacturing apparatus also includes a control unit that controls one or more operations selected from the group consisting of fluid supply from the first supply unit, fluid supply from the second supply unit, and temperature adjustment from the first temperature control unit, based on the acquired first reaction information.

17. The polymer manufacturing apparatus according to claim 4, wherein, The first measuring unit acquires the first reaction information of the first confluence fluid and / or the first reaction information of the first pipe mixing fluid. The polymer manufacturing apparatus also includes a control unit that predicts the properties of the first generating fluid based on the acquired first reaction information, and controls one or more operations selected from the group consisting of fluid supply from the first supply unit, fluid supply from the second supply unit, and temperature adjustment from the first temperature control unit based on the predicted properties of the first generating fluid.

18. A method for manufacturing a polymer, wherein, Use the polymer manufacturing apparatus according to any one of claims 1 to 17.

19. A method for manufacturing a polyamic acid solution and / or polyimide, wherein, Use the polymer manufacturing apparatus according to any one of claims 1 to 17.

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