Polymer manufacturing system and polymer manufacturing method

Abstract

To provide a system of producing a polymer capable of continuously and stably producing a required polymer, and a method of producing a polymer.SOLUTION: A system of producing a polymer 1 includes: a first feed part 112 for feeding a first fluid A1 containing a first polymerizable compound; a second feed part 122 for feeding a second fluid A2 containing a second polymerizable compound; a first confluence part J1 for joining the first fluid A1 and the second fluid A2 to generate a first confluence fluid B; a first pipe-type mixing part 20 arranged on the downstream side of the first confluence part J1 for advancing mixing in a radial direction of the first confluence fluid B to generate a first pipe mixed fluid C; and a first variation-moderating part 30 connected the first pipe-type mixing part for reducing variation of a viscosity in an axial direction of the first pipe mixed fluid C to generate a first generated fluid D.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a polymer production system and a method for producing a polymer. Specifically, the present invention relates to a polymer production system capable of continuously producing a polymer and a method for producing a polymer using the polymer production system.

Background Art

[0002] Conventionally, as a method for producing a polymer such as polyamic acid (polyamide acid), for example, a production method in which a first fluid and a second fluid are mixed in a mixing tank and the mixed fluid is further mixed in a tubular tube mixer is known (see, for example, Patent Document 1). In the tube mixer, the mixed fluid is passed by driving a pump, so that the mixed fluid is stirred while being moved in the axial direction of the tube.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] In a tubular mixer, homogenization occurs through mixing in the radial direction of the tube, but because the distribution of residence time within the tubular mixer is small, viscosity fluctuations of the mixed fluid in the axial direction of the tube are retained. In polyaddition reactions, the higher the molecular weight of the polymer produced, the more precisely the mixing ratio of the raw materials needs to be adjusted. Therefore, while low-viscosity polymers can be stably obtained in polyaddition reactions using a tubular mixer, it has been difficult to continuously obtain high-viscosity polymers, such as those with a viscosity of 1000 poise or more, with stable viscosity. With polymers whose viscosity fluctuates over time, there was a problem in that a film of consistent thickness could not be obtained when forming a film. To solve this, it is conceivable to eliminate viscosity fluctuations by installing a stirring tank or the like downstream of the tubular mixer, but this would increase equipment costs, and the polymer solution would entrain air bubbles, requiring degassing before film formation.

[0005] As a result of diligent research to solve these problems, we discovered that while conventionally, a short residence time in the liquid transfer line for the generated polymer is preferable to minimize required time and product loss, intentionally creating a section with a longer residence time in the polymer liquid transfer line can significantly reduce the time-dependent fluctuation in the viscosity of the resulting polymer, thus completing the invention.

[0006] The present invention aims to provide a polymer manufacturing system and method that can continuously and stably obtain a desired polymer with minimal viscosity fluctuations over time. Another objective of the present invention is to provide a polymer manufacturing system and method that can reduce the specification out rate by reducing the range of variation in the properties of the polymer produced during continuous polymer manufacturing. [Means for solving the problem]

[0007] The following embodiments are specific means for solving the above problems. <1> A polymer manufacturing system for producing polymers using a first fluid containing a polyadditive first polymerizable compound and a second fluid containing a polyadditive second polymerizable compound that polyadditively adds to the first polymerizable compound as raw materials, A first supply unit that supplies the first fluid, A second supply unit that supplies the second fluid, A first confluence unit that combines the first fluid and the second fluid to generate a first combined fluid, A first tubular mixing section is located downstream of the first confluence section and promotes radial mixing of the first confluence fluid to generate a first tubular mixed fluid, A polymer manufacturing system comprising: a first fluctuation mitigation unit disposed downstream of the first tubular mixing unit, which generates a first product fluid by reducing fluctuations in the axial properties of the first tubular mixed fluid.

[0008] <2> The system further comprises a first measuring unit for acquiring first reaction information relating to physical quantities and / or composition in one or more of the first confluence fluid, the first pipe mixed fluid, and the first generated fluid. <1> Polymer manufacturing system as described above.

[0009] <3> The first measuring unit comprises one or more selected from the group consisting of a viscometer, thermometer, pressure gauge, pump pressure gauge, absorbance meter, infrared spectrometer, near-infrared spectrometer, densimeter, colorimeter, refractometer, spectrophotometer, conductivity meter, turbidimeter, ultrasonic sensor, and X-ray fluorescence analyzer. <2> Polymer manufacturing system as described above.

[0010] <4> The system further comprises a first temperature control unit for adjusting the temperature of one or more of the first fluid, the second fluid, the first confluence fluid, the first pipe mixed fluid, and the first generated fluid. <2> Polymer manufacturing system as described above.

[0011] <5> The aforementioned first fluctuation mitigation section is a pipe in which the average residence time of the fluid flowing inside is 3 minutes or more. <1> ~ <4> A polymer manufacturing system as described in any of the following.

[0012] <6> The first fluctuation mitigation section is composed of one or more tubular members, The sum of the average residence times of each of the tubular members is 7 minutes or more. <1> ~ <4> A polymer manufacturing system as described in any of the following.

[0013] <7> A first tube-mixed fluid measuring unit for acquiring first tube-mixed fluid reaction information relating to the physical quantities and / or composition of the first tube-mixed fluid is provided between the first tube-type mixing unit and the first fluctuation mitigation unit. A first product fluid measuring unit for acquiring first product fluid reaction information relating to the physical quantities and / or composition of the first product fluid is further provided at or downstream of the outlet of the first fluctuation mitigation unit. The volume of the first fluctuation mitigation section is 0.5 to 100 times the volume of the first tubular mixing section. <1> ~ <4> A polymer manufacturing system as described in any of the following.

[0014] <8> The volume of the first fluctuation-mitigating section is 5 to 100 times the volume of the first tubular mixing section. <1> ~ <4> A system for producing the polymer described in any one of the items.

[0015] <9> The aforementioned first fluctuation mitigation section is a pipe in which the residence time of the fluid that has passed through the fastest flow path is 3 minutes or more. <1> ~ <4> A polymer manufacturing system as described in any of the following.

[0016] <10> The first fluctuation mitigation section is composed of one or more tubular members, The cross-sectional average flow velocity of the fluid flowing inside the tubular member is 0.01 m / s or less. The piping consists of tubular members whose combined lengths are 0.7 m or more. <1> ~ <4> A polymer manufacturing system as described in any of the following.

[0017] <11> The first fluctuation mitigation section is such that the Reynolds number of the fluid flowing inside is 2100 or less when 4 × cross-sectional area / immersion length is used as the characteristic length. <1> ~ <10> A polymer manufacturing system as described in any of the following.

[0018] <12> The first polymerizable compound and the second polymerizable compound satisfy any of the following conditions (a) to (c), and polyamic acid is produced as the polymer. <1> ~ <11> A polymer manufacturing system as described in any of the following. (a) Of the first polymerizable compound and the second polymerizable compound, one is a tetracarboxylic dianhydride and the other is a diamine. (b) Among the first polymerizable compound and the second polymerizable compound, one is a polyamic acid having an acid anhydride terminal or an amino group terminal, and the other is a diamine or a tetracarboxylic dianhydride. (c) Among the first polymerizable compound and the second polymerizable compound, one is a polyamic acid having an acid anhydride terminal or an amino group terminal, and the other is a polyamic acid having an amino group terminal or an acid anhydride terminal.

[0019] <13>. The polymer production system according to <12>, further comprising an imidization unit for imidizing the produced polyamic acid, and producing a polyimide as the polymer.

[0020] <14>. The first measurement unit acquires the first reaction information in any one or more of the first combined fluid, the first pipe mixed fluid, and the first generated fluid. The polymer production system according to <4>, further comprising a control unit that controls any one or more selected from the group consisting of fluid supply in the first supply unit, fluid supply in the second supply unit, and temperature adjustment in the first temperature control unit based on the acquired first reaction information.

[0021] <15>. The first measurement unit acquires the first reaction information in the first combined fluid and / or the first pipe mixed fluid. Predict the properties of the first generated fluid based on the acquired first reaction information, and based on the predicted properties of the first generated fluid, control any one or more selected from the group consisting of fluid supply in the first supply unit, fluid supply in the second supply unit, and temperature adjustment in the first temperature control unit. The polymer production system according to <4>, further comprising a control unit.

[0022] <16>. A method for producing a polymer using the polymer production system according to any one of <1> to <15>.

[0023] <17>. A method for producing a polyamic acid solution and / or a polyimide using the polymer production system according to any one of <1> to <15>. [Effects of the Invention]

[0024] According to the present invention, it is possible to provide a polymer manufacturing system and method that can continuously and stably obtain a desired polymer with little viscosity fluctuation over time. Furthermore, in the continuous production of polymers, by providing a simple and inexpensive mechanism to reduce fluctuations in polymer properties, it is possible to provide a polymer manufacturing system and method that can reduce the specification out rate. [Brief explanation of the drawing]

[0025] [Figure 1] This figure shows the polymer manufacturing system in the first embodiment. [Modes for carrying out the invention]

[0026] Embodiments of the present invention will be described in detail below with reference to the drawings. The first embodiment is an example of a polymer manufacturing system comprising a first tubular mixing section and a first fluctuation mitigation section.

[0027] <First Embodiment> Figure 1 illustrates the polymer manufacturing system in the first embodiment. Figure 1 is a diagram showing the polymer manufacturing system in the first embodiment.

[0028] First, an overview of the polymer manufacturing system 1 in the first embodiment will be described. Polymer manufacturing system 1 is a manufacturing system for producing polymers using a first fluid A1 containing a polyadditive first polymerizable compound and a second fluid A2 containing a polyadditive second polymerizable compound as raw materials. The first embodiment is an example of a polymer manufacturing system in which a first tubular mixing section and a first fluctuation mitigation section are provided in succession.

[0029] Here, the first tubular mixing section refers to a tubular mixing section that homogenizes the radial properties while the fluid flows through it. The first fluctuation mitigation section refers to a structural section that can reduce fluctuations in axial properties by actively generating a residence time distribution that utilizes the difference in flow velocity due to the trajectory in the flow path.

[0030] In the following, as an example, we will describe a case in which one of the first polymerizable compound and the second polymerizable compound is a tetracarboxylic dianhydride and the other is a diamine, and polyamic acid is produced as a polymer. More specifically, we will describe a case in which 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, and polyamic acid is produced as a polymer.

[0031] The tetracarboxylic dianhydride is not particularly limited, and the same types used in conventional polyimide synthesis can be used. Specific examples of tetracarboxylic dianhydrides include 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 2,3,3',4'-biphenyl tetracarboxylic dianhydride, pyromellitic acid dianhydride, 1,3-bis(2,3-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(2,3-dicarboxyphenoxy)benzene dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-biphenyl tetracarboxylic dianhydride, 2,2',6,6'-biphenyl tetracarboxylic dianhydride, naphthalene-1,2,4, Examples include aromatic tetracarboxylic dianhydrides such as 5-tetracarboxylic dianhydride, anthracene-2,3,6,7-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, and 2,2-bis(4-hydroxyphenyl)propanedibenzoate-3,3',4,4'-tetracarboxylic acid 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 may be used individually or in combination of two or more.

[0032] As the solvent for the first fluid A1, a solvent that dissolves tetracarboxylic dianhydride and polyamic acid is used. Specific examples of solvents include amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and acetanilide; cyclic ester solvents such as γ-butyrolactone; linear 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, which have high solubility for polyamic acid, are preferred. The solvent may be used alone or two or more may be mixed. For example, it is possible to improve the solubility of polyamic acids by mixing them with highly polar alcohol-based solvents, such as acetone, ethyl acetate, methyl ethyl ketone, toluene, and xylene, which have relatively low solubility for polyamic acids.

[0033] The first fluid A1 may contain small amounts of tertiary amines such as trimethylamine and triethylamine, or acetic acid, in order to increase the solubility of tetracarboxylic dianhydride or to increase its reactivity with diamines.

[0034] The diamine is not particularly limited, and the same diamines used in conventional polyimide synthesis can be used. Specific examples of diamines include 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-bis(4-aminophenoxy)biphenyl, 1,4'-bis(4-aminophenoxy)benzene, 1,3'-bis(4-aminophenoxy)benzene, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-methylene-bis(2-chloroaniline), 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'- Examples include aromatic diamines such as 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 such as 1,2-diaminoethane, 1,4-diaminobutane, tetramethylenediamine, and 1,10-diaminododecane; alicyclic diamines such as 1,4-diaminocyclohexane, 1,2-diaminocyclohexane, bis(4-aminocyclohexyl)methane, and 4,4'-diaminodicyclohexylmethane; and heterocyclic diamines such as 3,4-diaminopyridine. Diamines may be used individually or in combination of two or more.

[0035] As the solvent for the second fluid A2, a solvent that dissolves diamine and polyamic acid is used. Specific examples of solvents include amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and acetanilide; cyclic ester solvents such as γ-butyrolactone; linear 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, which have high solubility for polyamic acid, are preferred. The solvent may be used alone or as a mixture of two or more. For example, it is possible to improve the solubility of polyamic acids by mixing them with highly polar alcohol-based solvents, such as acetone, ethyl acetate, methyl ethyl ketone, toluene, and xylene, which have relatively low solubility for polyamic acids.

[0036] The first fluid A1 and / or the second fluid A2 may contain a filler that acts as a lubricant for the polyimide film. Examples of lubricants include inorganic particles such as titanium dioxide, discalcium phosphate anhydride, calcium pyrophosphate, calcium carbonate, silicon dioxide, alumina, barium sulfate, zirconia, kaolin, talc, clay, and mica, as well as organic particles composed of acrylic acids, styrenes, etc. In addition, inorganic or organic particles may be dispersed to alter other properties of the polyimide film, such as its strength and thermal conductivity.

[0037] As shown in Figure 1, the polymer manufacturing system 1 is configured to produce a first combined fluid B by combining and mixing the raw materials, the first fluid A1 and the second fluid A2, in the first confluence section J1, and then stirring the first combined fluid B in the first tubular mixing section 20 to produce a first tubular mixed fluid C in which the concentration of each component in the radial direction of the tube is uniform. Subsequently, the axial viscosity fluctuation of the first tubular mixed fluid C is reduced in the first fluctuation mitigation section 30 to obtain a first generated fluid D, thereby producing a polyamic acid (polymer) with little viscosity fluctuation over time.

[0038] Furthermore, the polymer manufacturing system 1 has a liquid supply line L connecting the first tank 11 and the second tank 12 (described later) to the outlet of the first fluctuation mitigation section 30.

[0039] The polymerization reaction proceeds in either the first tubular mixing section 20 or the first fluctuation easing section 30, or both. The polymerization reaction may be completely finished at the outlet of the first tubular mixing section 20, or the reaction may have hardly progressed at the outlet of the first tubular mixing section 20, with the majority of the reaction proceeding in the first fluctuation easing section 30. Furthermore, it is not necessarily required that the polymerization reaction be completely finished at the outlet of the first fluctuation easing section 30; the reaction may also proceed in piping or a cushion tank provided downstream of the first fluctuation easing section 30. However, in order to obtain a polymer with stable properties, it is preferable to design the system so that 80% or more of the polymerization reaction is completed at the outlet of the first fluctuation easing section 30, and it is even more preferable to design the system so that 80% or more of the polymerization reaction is completed at the outlet of the first tubular mixing section 20.

[0040] Next, we will describe the specific configuration of polymer manufacturing system 1. As shown in Figure 1, the polymer manufacturing system 1 includes a first tank 11, an on-off valve 111 for the first tank, a second tank 12, an on-off valve 121 for the second tank, a first supply pump 112 (first supply unit), a second supply pump 122 (second supply unit), a first confluence unit J1, a first tubular mixing unit 20, a first fluctuation mitigation unit 30, a liquid supply line L, and a control unit 200. The liquid supply line L has a first liquid supply unit L1, a second liquid supply unit L2, a third liquid supply unit L3, a fourth liquid supply unit L4, and a fifth liquid supply unit L5. The polymer manufacturing system 1 also includes a first flow rate measuring unit 113, a second flow rate measuring unit 123, a first tubular mixed fluid measuring unit 222 (first measuring unit), and a first generated fluid measuring unit 322 (first measuring unit).

[0041] The first tank 11 contains a first fluid A1 in which a polyadditive first polymerizable compound is dissolved. In this embodiment, the first tank 11 contains a first fluid A1 in which a tetracarboxylic dianhydride is dissolved. The first fluid A1 contained in the first tank 11 is supplied to the first confluence J1 via the first fluid delivery section L1.

[0042] The first liquid supply section L1 is a line connecting the first tank 11 and the first junction section J1. Between the first tank 11 and the first junction section J1 in the first liquid supply section L1, the first tank on / off valve 111, the first supply pump 112, and the first flow rate measuring section 113 are arranged in this order from upstream to downstream.

[0043] The first tank on / off valve 111 is located near the bottom of the first tank 11 in the first liquid supply section L1 and opens and closes the first liquid supply section L1 on the upstream side of the first supply pump 112.

[0044] 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 discharges 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 yield polyamic acid with desired properties.

[0045] In this embodiment, the first supply pump 112 is configured as a metering pump. In this embodiment, a polyamic acid with desired properties is obtained by controlling the supply of a first fluid A1 supplied by a first supply pump 112 and a second fluid A2 supplied by a second supply pump 122, which will be described later. For this reason, it is preferable that the supply accuracy of the first fluid A1 and the second fluid A2 is high, and in this embodiment, the first supply pump 112 is configured as a metering pump, and the second supply pump 122, which will be described later, is also configured as a metering pump.

[0046] A metering pump is a positive displacement pump that repeatedly delivers a fixed amount of fluid with high precision. Examples of metering pumps include plunger pumps and other push-type reciprocating pumps; and gear pumps and other rotary pumps equipped with gears.

[0047] The first flow rate measuring unit 113 measures the flow rate of the first fluid A1 downstream of the first supply pump 112 in the first fluid delivery unit L1. In this embodiment, the first flow rate measuring unit 113 is located between the first supply pump 112 and the first confluence unit J1. The first flow rate measuring unit 113 outputs the measured flow rate of the first fluid A1 to the control unit 200, which will be described later.

[0048] The second tank 12 contains a second fluid A2 in which a polyadditive second polymerizable compound is dissolved and polyadditively added to the first polymerizable compound. In this embodiment, the second tank 12 contains a second fluid A2 in which a diamine is dissolved. The second fluid A2 contained in the second tank 12 is supplied to the first confluence J1 via the second fluid delivery section L2.

[0049] The second liquid supply section L2 is a line connecting the second tank 12 and the first confluence section J1. Between the second tank 12 and the first confluence section J1 in the second liquid supply section L2, the second tank on / off valve 121, the second supply pump 122, and the second flow rate measuring section 123 are arranged in this order from upstream to downstream.

[0050] The second tank on / off valve 121 is located near the bottom of the second tank 12 in the second liquid supply section L2 and opens and closes the second liquid supply section L2 upstream of the second supply pump 122.

[0051] 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 discharges 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 yield polyamic acid with desired properties. In this embodiment, the second supply pump 122 is configured as a metering pump for the same reasons as the first supply pump 112 described above.

[0052] The second flow rate measuring unit 123 measures the flow rate of the second fluid A2 downstream of the second supply pump 122 in the second fluid delivery unit L2. In this embodiment, the second flow rate measuring unit 123 is located between the second supply pump 122 and the first confluence unit J1. The second flow rate measuring unit 123 outputs the measured flow rate of the second fluid A2 to the control unit 200, which will be described later.

[0053] The first confluence section J1 is located downstream of the first supply pump 112 and the second supply pump 122. The first confluence section J1 combines the first fluid A1 and the second fluid A2 to produce the first combined fluid B. In the first confluence section J1, the first fluid A1 and the second fluid A2 are combined without contact with gas. The first confluence section J1 is composed of a confluence valve that combines the first fluid A1 supplied by the first supply pump 112 and the second fluid A2 supplied by the second supply pump 122.

[0054] The first tubular mixing section 20 is located downstream of the first confluence section J1. The first tubular mixing section 20 stirs the first confluence fluid B without contact with the gas, and generates the first tubular mixed fluid C by making the concentration of each component uniform in the radial direction of the pipe at the outlet of the first tubular mixing section 20.

[0055] The first tubular mixing section 20 includes a tubular reactor composed of a double tube extending in a predetermined direction. The first tubular mixing section 20 has a first tubular mixing and stirring section 21 located radially inward and a first tubular mixing and temperature control section 22 (first temperature control section) located radially outward. The first tubular mixing section 20 is configured so that the first confluence fluid B flows through with a desired residence time.

[0056] The first tubular mixing and stirring unit 21 stirs the first combined fluid B. In this embodiment, the first tubular mixing and stirring unit 21 stirs the first combined fluid B, which has been adjusted to a temperature suitable for the polymerization reaction by the first tubular mixing temperature control unit 22.

[0057] The first tubular mixing and stirring section 21 is composed of, for example, stationary mixers such as a static mixer, nozzle, or orifice, and driven mixers such as a centrifugal pump, volute pump, or inline mixer having stirring blades. Preferably, it is composed of stationary mixers, and more preferably, it is composed of a static mixer. Although a tube with a twisted tape inserted inside (see Figure 19 in Japanese Patent Publication No. 2003-314982, etc.) can also provide a stirring-promoting effect similar to that of a static mixer, a static mixer is preferred because it provides a more effective stirring-promoting effect.

[0058] Static mixers are not particularly limited and include, for example, 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 is preferred because its simple structure eliminates dead space.

[0059] The first tubular mixing and temperature control unit 22 is a piping section located radially outside the first tubular mixing and stirring unit 21. The first tubular mixing and temperature control unit 22 controls the temperature of the first combined fluid B flowing through the first tubular mixing and stirring unit 21 to a desired temperature condition (for example, by cooling it). In the first tubular mixing and temperature control unit 22, the first combined fluid B is adjusted to a temperature suitable for the polymerization reaction and flows through the first tubular mixing and stirring unit 21.

[0060] The generated first pipe mixed fluid C is supplied to the first fluctuation mitigation unit 30 via the fourth fluid delivery unit L4.

[0061] The first pipe mixed fluid measuring unit 222 acquires first pipe mixed fluid reaction information (first reaction information) regarding the viscosity of the first pipe mixed fluid C between the first pipe-type mixing unit 20 and the first fluctuation mitigation unit 30 in the fourth liquid delivery unit L4. Since the polymerization reaction proceeds as the fluid is stirred in the first pipe-type mixing and stirring unit 21, causing the viscosity to increase, the viscosity information is useful as reaction information. The first pipe mixed fluid measuring unit 222 outputs the acquired viscosity information of the first pipe mixed fluid C to the control unit 200, which will be described later.

[0062] Furthermore, the first pipe mixed fluid measurement unit 222 also acquires first pipe mixed fluid reaction information (first reaction information) regarding the temperature of the first pipe mixed fluid C between the first pipe-type mixing unit 20 and the first fluctuation mitigation unit 30 in the fourth liquid delivery unit L4. The polymerization reaction proceeds as the fluid is stirred in the first pipe-type mixing and stirring unit 21, but since the reaction rate of the polymerization reaction differs depending on the temperature, the temperature information is useful as reaction information. The first pipe mixed fluid measurement unit 222 outputs the acquired temperature information of the first pipe mixed fluid C to the control unit 200, which will be described later.

[0063] The first fluctuation mitigation section 30 is located downstream of the first tubular mixing section 20. The first fluctuation mitigation section 30 is composed of a double pipe and includes a first fluctuation mitigation piping section 31 located radially inward and a first fluctuation mitigation temperature control section 32 (first temperature control section) located radially outward. In this embodiment, the first fluctuation mitigation temperature control section 32 adjusts the temperature of the first pipe mixed fluid C to a temperature suitable for the polymerization reaction.

[0064] In the first fluctuation-mitigating piping section 31, the residence time distribution resulting from the radial velocity difference when the first pipe-mixed fluid C flows through the first fluctuation-mitigating piping section 31 reduces the axial viscosity fluctuation of the first pipe-mixed fluid C and stabilizes the properties of the outflowing first generated fluid D. For example, when flowing laminarly through 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 along the pipe wall has an extremely slow flow velocity and a very long residence time. This difference in residence time due to the streamline can mitigate axial property fluctuations.

[0065] In order to obtain a sufficient viscosity fluctuation mitigation effect in the first fluctuation mitigation piping section 31, it is preferable that the first pipe mixed fluid C flows laminarly through the first fluctuation mitigation piping section 31. In order for the fluid to flow laminarly through the first fluctuation mitigation piping section 31, it is preferable that the Reynolds number (ρud / μ), calculated from viscosity μ, average cross-sectional flow velocity u, and density ρ, when 4 × cross-sectional area / immersion length is used as the representative length d, be 2100 or less, and more preferably between 0.00001 and 1000. Furthermore, if the solution viscosity is low, the preparatory phase before the flow develops is long, making it difficult to effectively generate a velocity distribution. Therefore, it is preferable that the viscosity of the first pipe mixed fluid C flowing through the first fluctuation mitigation piping section 31 be relatively high. Specifically, the viscosity of the first pipe mixed fluid C flowing through the first fluctuation-mitigating piping section 31 is preferably 0.1 poise or more and 100,000 poise or less at the temperature during flow, more preferably 1 poise or more and 10,000 poise or less, and more preferably 5 poise or more and 5,000 poise or less.

[0066] The first fluctuation-mitigating 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. The longer the average residence time of the first fluctuation-mitigating piping section 31, the greater the viscosity stabilization effect of the first generated fluid D flowing out of the first fluctuation-mitigating piping section 31. Therefore, the greater the axial fluctuation in the properties of the first mixed fluid C flowing out of the first pipe-type mixing section 20, the more preferable it is to increase the average residence time of the first fluctuation-mitigating piping section 31.

[0067] Specifically, for example, when a Newtonian fluid flows laminarly through the first fluctuation-mitigating piping section 31, which is a straight pipe with a circular cross-section, the viscosity fluctuation at the outlet of the first fluctuation-mitigating piping section 31 decreases by 56% when the average residence time of the first fluctuation-mitigating piping section 31 is 3 minutes, decreases by 74% when the average residence time is 7 minutes, and decreases by 81% when the average residence time is 11 minutes. However, the reduction in viscosity fluctuation described here refers to the percentage decrease in the difference between the maximum and minimum viscosity values ​​at the outlet of the first fluctuation-mitigating piping section 31 relative to the difference between the maximum and minimum viscosity values ​​at the inlet of the first fluctuation-mitigating piping section 31.

[0068] Figure 1 shows a configuration with only one first fluctuation-mitigating piping section 31, but the first fluctuation-mitigating piping section 31 may be a structure in which two or more tubular members are connected by joints or the like. In that case, it is preferable that the sum of the average residence times of the two or more tubular members constituting the first fluctuation-mitigating piping section 31 be 7 minutes or more. The longer the average residence time of the first fluctuation-mitigating piping section 31, the greater the effect of reducing viscosity fluctuations, but in order to minimize the loss of the generated polymer, it is more preferable to keep the sum of the average residence times to 300 minutes or less.

[0069] The fluid flowing through the first fluctuation-mitigating piping section 31 is not limited to a Newtonian fluid. However, in the case of a non-Newtonian fluid, the velocity distribution changes due to the effect of shear, and the residence time distribution differs, so the reduction rate of viscosity fluctuations differs from that of a Newtonian fluid. Therefore, when designing the average residence time of the first fluctuation-mitigating piping section 31, it is advisable to consider the rheology of the fluid flowing through the first fluctuation-mitigating piping section 31. For example, in the case of a pseudoplastic fluid, which has a smaller residence time distribution than a Newtonian fluid, it is preferable to make the average residence time of the first fluctuation-mitigating piping section 31 longer.

[0070] The first fluctuation mitigation piping section 31 can mitigate fluctuations with a short period compared to the average residence time, but it is less effective at mitigating fluctuations with a long period compared to the average residence time. Therefore, it is preferable to make the average residence time of the first fluctuation mitigation piping section 31 sufficiently longer than the average fluctuation period of the first pipe-mixed fluid C that may occur at the outlet of the first pipe-type mixing section 20. However, the average fluctuation period referred to here means 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, then once reaches a minimum value, and then reaches a maximum value again. It is preferable that the average residence time of the first fluctuation mitigation piping section 31 be at least one time, and more preferably at least two times, the average fluctuation period of the first pipe-mixed fluid C at the outlet of the first pipe-type mixing section 20.

[0071] In order to ensure that the first fluctuation-mitigating piping section 31 has an appropriate average residence time in response to viscosity fluctuations of the first pipe-mixed fluid C, the volume of the first fluctuation-mitigating piping section 31 is preferably 0.5 to 100 times the volume of the first pipe-type mixing and stirring section 20, and more preferably 5 to 100 times.

[0072] Furthermore, the first fluctuation mitigation piping section 31 mitigates viscosity fluctuations through the distribution of residence times due to differences in flow velocity. Since the flow velocity is extremely slow near the pipe wall, a sufficient viscosity fluctuation mitigation effect can also be obtained by designing the piping section so that the residence time of the fluid passing through the fastest flow velocity trail is sufficiently long. The fastest flow velocity trail refers to the trail that always passes through the center of the cross-section, for example, when flowing laminarly in a circular pipe. When tracer particles or colorants are placed throughout the entire cross-section of the inlet of the first fluctuation mitigation piping section 31, the time required for the tracer particles or colorants to first flow out of the outlet of the first fluctuation mitigation piping section 31 roughly coincides with the residence time of the fluid passing through the fastest flow velocity trail. Specifically, for example, when a Newtonian fluid flows laminarly in the first fluctuation mitigation piping section 31, which is a straight pipe with a circular cross-section, if the residence time of the fluid passing through the fastest flow velocity trail is 3 minutes, the viscosity fluctuation at the outlet of the first fluctuation mitigation piping section 31 will be reduced by 72%. In the first fluctuation-mitigating piping section 31, the longer the residence time of the fluid passing through the fastest flow path, the greater the viscosity fluctuation reduction effect. However, in order to minimize the loss of the generated polymer, it is more preferable to keep the total residence time of the fluid passing through the fastest flow path 150 minutes or less.

[0073] If the average residence time of the first fluctuation mitigation piping section 31 is similar, the viscosity stabilization effect of the first generated fluid D will be similar regardless of the cross-sectional area, length, and flow rate of the first pipe mixed fluid C flowing through the first fluctuation mitigation piping section 31. However, if the cross-sectional area of ​​the first fluctuation mitigation piping section 31 is small and the length is long, the pressure loss when the first pipe mixed fluid C flows through the first fluctuation mitigation piping section 31 will be large, requiring high-pressure resistant piping, which will increase equipment costs. Therefore, it is preferable to increase the cross-sectional area of ​​the first fluctuation mitigation piping section 31 to a certain extent and shorten its length. Specifically, it is preferable to have a length of 0.7 m or more with a cross-sectional area such that the average cross-sectional flow velocity is 0.01 m / s or less, and it is more preferable to have a length of 0.7 m or more with an average cross-sectional flow velocity of 0.00001 m / s or more and 0.003 m / s or less. However, the average cross-sectional flow velocity described herein is the value obtained by dividing the volumetric flow rate of the first pipe mixed fluid C by the cross-sectional area of ​​the first fluctuation-mitigating piping section 31. Furthermore, if the first fluctuation-mitigating piping section 31 is made up of two or more tubular members connected by joints or the like, the sum of the lengths of the two or more tubular members shall be between 0.7m and 60m.

[0074] For the first fluctuation mitigation piping section 31, it is preferable to use a hollow cylindrical pipe in order to reduce equipment costs. However, the shape of the first fluctuation mitigation piping section 31 is not particularly limited as long as the residence time is distributed by the velocity distribution in the cross-sectional direction when the first pipe mixed fluid C flows through it. Specifically, it may have an internal structure, or it may be a pipe bent by an elbow or the like, and the cross-section does not have to be circular. In addition, valves, sensors, etc. may be installed in the middle of the first fluctuation mitigation piping section 31.

[0075] The first fluctuation-mitigating piping section 31 is preferably supplied without contact with gas in order to obtain the first generated fluid D which does not contain air bubbles. However, it is not limited to this, and a gas phase may be present inside the first fluctuation-mitigating piping section 31 as long as air bubbles are not entrained in the first pipe-mixed fluid C.

[0076] The first fluctuation mitigation piping section 31 is provided between the first pipe mixed fluid measuring section 222 and the first generated fluid measuring section 322. Preferably, the first fluctuation mitigation piping section 31 is a cylindrical pipe having the same inner diameter from the upstream end to the downstream end in the flow direction of the first pipe mixed fluid C. Preferably, the length of the first fluctuation mitigation piping section 31 is 5 to 1000 times the inner diameter. Preferably, the inner diameter of the first fluctuation mitigation piping section 31 is 0.5 to 10 times the inner diameter of the fourth fluid supply section L4 located upstream. In addition, in the first fluctuation mitigation piping section 31, the first pipe mixed fluid C flows with the internal space filled with the first pipe mixed fluid C, so the difference in flow velocity of the first pipe mixed fluid C in the radial direction becomes large.

[0077] The first temperature-controlled variable mitigation unit 32 is a piping section located radially outside the first temperature-controlled variable mitigation piping section 31. The first temperature-controlled variable mitigation unit 32 controls the temperature of the first pipe-mixed fluid C flowing through the first temperature-controlled variable mitigation piping section 31 to a desired temperature condition (for example, by cooling it). In the first temperature-controlled variable mitigation unit 32, the first pipe-mixed fluid C is adjusted to a temperature suitable for the polymerization reaction and flows through the first temperature-controlled variable mitigation piping section 31.

[0078] In the first tubular mixing section 20 and the first fluctuation mitigation section 30 described above, by arranging the first tubular mixing section 20 in the preceding stage and the first fluctuation mitigation section 30 in the succeeding stage, if there is a viscosity fluctuation in the axial direction of the tube in the preceding first tubular mixing section 20, the viscosity fluctuation in the axial direction of the tube can be significantly reduced in the succeeding first fluctuation mitigation section 30.

[0079] For example, if the viscosity of the fluid generated by a change in the ratio of the first fluid A1 and the second fluid A2 changes in the axial direction of the pipe, the first tubular mixing section 20, which has a structure for stirring inside, does not easily generate a radial velocity distribution, and therefore cannot eliminate the viscosity fluctuation of the mixed fluid in the axial direction of the pipe. In contrast, by placing the first tubular mixing section 20 in the preceding stage and the first fluctuation mitigation section 30 in the subsequent stage, the radial properties are made uniform in the preceding first tubular mixing section 20, and then the fluid is delivered with a distribution of residence time in the subsequent first fluctuation mitigation section 30. This makes it possible to significantly reduce the viscosity fluctuation of the first mixed fluid C in the axial direction of the pipe, which could not be eliminated in the preceding first tubular mixing section 20, in the subsequent first fluctuation mitigation section 30.

[0080] The first generated fluid measuring unit 322 is located at or downstream of the outlet of the first fluctuation mitigation unit 30 and acquires first generated fluid reaction information (first reaction information) regarding the viscosity of the first generated fluid D in the fifth fluid delivery unit L5. Since viscosity increases as the polymerization reaction proceeds, viscosity information is useful 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.

[0081] Furthermore, the first product fluid measurement unit 322 also acquires first product fluid reaction information (first reaction information) related to the temperature of the first product fluid D in the fifth liquid delivery unit L5. Since the reaction rate of the polymerization reaction differs depending on the temperature, temperature information is useful as reaction information. The first product fluid measurement unit 322 outputs the acquired temperature information of the first product fluid to the control unit 200, which will be described later.

[0082] In this embodiment, the first pipe mixed fluid measuring unit 222 and the first generated fluid measuring unit 322 are examples of measuring units that acquire reaction information regarding physical quantities and / or composition in one or more of the first pipe mixed fluid C and the first generated fluid D.

[0083] The measurement unit is not limited to the first pipe mixed fluid measurement unit 222 and the first generated fluid measurement unit 322 (type of physical quantity and / or composition, measurement method) of this embodiment. The measurement unit may have one or more selected from the group consisting of, for example, a viscometer, thermometer, pressure gauge, pump pressure gauge, absorbance meter, infrared spectrometer, near-infrared spectrometer, densimeter, colorimeter, refractometer, spectrophotometer, conductivity meter, turbidimeter, and X-ray fluorescence analyzer. The measurement unit acquires one or more reaction information regarding the physical quantity and / or composition of the object to be measured and outputs the acquired reaction information to the control unit 200, which will be described later.

[0084] A cushion tank (not shown) may be provided downstream of the fifth liquid transfer line L5 to contain the first product fluid D. The cushion tank may, for example, be used to contain the raw material fluid when producing polyimide by imidizing polyamic acid, which is a polymer.

[0085] In this embodiment, when the polymer manufacturing system 1 produces polyimide, the polymer manufacturing system 1 further comprises an imidation unit that imidizes polyamic acid. The imidation unit (not shown) imidizes polyamic acid by, for example, a thermal imidation method that thermally dehydrates and ring-closes the polyamic acid, or a chemical imidation method that uses a dehydrating agent and an imidation accelerator.

[0086] Furthermore, when the polymer manufacturing system 1 produces polyimide, it may be configured so that the liquid is transferred from the first fluctuation mitigation section 30 to the imidation section without providing a cushion tank. However, it is more preferable to temporarily store the polyamic acid in a cushion tank.

[0087] The control unit 200 will now be described. The control unit 200 is electrically connected to the first supply pump 112, the second supply pump 122, the first tubular mixing temperature control unit 22, the first fluctuation mitigation temperature control unit 32, the first flow rate measuring unit 113, the second flow rate measuring unit 123, the first tubular mixed fluid measuring unit 222, and the first generated fluid measuring unit 322. In this specification, the control lines from the control unit 200 to each pump, each temperature control unit, and each measuring unit are not shown in the diagram.

[0088] The control unit 200 controls each supply pump 112, 122 based on the flow rate values ​​measured by each flow rate measuring unit 113, 123. The control unit 200 controls, for example, the first supply pump 112 and / or the second supply pump 122 so that the molar ratio of the first polymerizable compound contained in the first fluid A1 to the second polymerizable compound contained in the second fluid A2 is within a predetermined range. The above molar ratio is set, for example, so that a polyamic acid with desired properties can be obtained. The control unit 200 also controls, for example, the temperature conditions of the first tubular mixing temperature control unit 22 and / or the first fluctuation mitigation temperature control unit 32 so that the reaction rate of the polymerization reaction is within a predetermined range.

[0089] The control unit 200 controls one or more of the following based on the first reaction information obtained by the first pipe mixed fluid measuring unit 222 and / or the first generated fluid measuring unit 322: supply from the first supply pump 112, supply from the second supply pump 122, temperature adjustment in the first pipe-type mixed temperature control unit 22, and temperature adjustment in the first fluctuation mitigation temperature control unit 32.

[0090] Next, the operation of the polymer manufacturing system 1 (polyamic acid manufacturing system) in the first embodiment will be described. First, in the polymer manufacturing system 1, upon starting operation, the first supply pump 112 supplies the first fluid A1, and the second supply pump 122 supplies the second fluid A2. Here, the discharge flow rates of the first supply pump 112 and the second supply pump 122 are controlled by the control unit 200 so that the first fluid A1 and the second fluid A2 are supplied in a desired ratio. As a result, 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 produce the first confluence fluid B.

[0091] The first combined fluid B generated in the first confluence section J1 is supplied to the first tubular mixing section 20 by being transported through the third liquid delivery section L3 by the supply operation of the first supply pump 112 and the second supply pump 122.

[0092] In the first tubular mixing section 20, the first confluence fluid B is stirred to make its properties, such as concentration, uniform in the radial direction, thereby generating the first tubular mixed fluid C. If the first tubular mixing section 20 is a stationary mixer such as a static mixer, the first confluence fluid B is stirred simply by being passed through it. In this case, in the first tubular mixing section 20, the first confluence fluid B moves along the axial direction of the pipe without a wide velocity distribution, so if there is a fluctuation in the viscosity of the first confluence fluid B along the axial direction of the pipe, it cannot be resolved.

[0093] The first pipe-mixed fluid C generated in the first pipe-type mixing section 20 is transported through the fourth liquid delivery section L4 and supplied to the first fluctuation mitigation section 30.

[0094] In the first fluctuation mitigation section 30, the first pipe mixed fluid C is introduced and continuously supplied while the residence time of the first pipe mixed fluid C is distributed by the radial velocity distribution. As a result, the viscosity fluctuations in the axial direction of the pipe of the first pipe mixed fluid C, which cannot be eliminated in the preceding first pipe-type mixing section 20, can be significantly reduced in the subsequent first fluctuation mitigation section 30. Therefore, the desired polymer can be obtained continuously and stably.

[0095] During the operation of the polymer manufacturing system 1 described above, the first pipe mixed fluid measuring unit 222 and the first produced fluid measuring unit 322 acquire viscosity information (measurement step). The control unit 200 controls each supply pump 112, 122 and each temperature control unit 22, 32 based on viscosity information (first reaction information) obtained by the first pipe mixed fluid measuring unit 222 and / or the first generated fluid measuring unit 322 (control step). This makes it possible to obtain polyamic acid with the desired properties (temperature, viscosity).

[0096] If the residence time distribution of the first pipe-mixed fluid C in the first fluctuation mitigation section 30 is known, the first pipe-mixed fluid measuring unit 222 can acquire first viscosity information (measurement step), and based on this, the time-dependent change in viscosity of the first generated fluid D at the outlet of the first fluctuation mitigation section 30 can be predicted (prediction step). Based on the viscosity predicted in this way, each supply pump 112, 122 and each temperature control unit 22, 32 may be controlled (control step). For example, if laminar flow occurs within the first fluctuation mitigation section 30 and Hagen-Poiseuille flow is formed, the radial velocity distribution can be calculated, and therefore the residence time distribution can be determined. Accordingly, by calculating a time-moving average weighted by the residence time distribution for the viscosity of the first pipe-mixed fluid C acquired by the first pipe-mixed fluid measuring unit 222, a predicted value of the viscosity of the first generated fluid D at the outlet of the first fluctuation mitigation section 30 can be obtained.

[0097] If the distribution of residence time of the first pipe mixed fluid C in the first fluctuation mitigation section 30 is unknown, the viscosity change of the first generated fluid D may be predicted by first measuring the viscosity change over time at the inlet and outlet of the first fluctuation mitigation section 30, and then modeling the effect of the first fluctuation mitigation section 30 in reducing viscosity fluctuations based on the results. For example, a first-order lag function can be used for modeling.

[0098] Controlling operating conditions based on viscosity information from the first pipe mixed fluid measuring unit 222, which experiences large fluctuations, carries the risk of hunting. On the other hand, controlling operating conditions based on viscosity information from the first generated fluid measuring unit 322 is less prone to hunting because the viscosity is stable, but it is more likely to exceed specifications due to the long wasted time. Therefore, it is effective to predict the viscosity of the first generated fluid D at the outlet of the first fluctuation mitigation unit 30 based on the viscosity information from the first pipe mixed fluid measuring unit 222 and control the system based on that prediction.

[0099] Furthermore, during the operation of the polymer manufacturing system 1 described above, the first pipe mixed fluid measuring unit 222 and the first product fluid measuring unit 322 acquire temperature information (measurement process). The control unit 200 controls the temperature adjustment conditions in the first tubular mixing temperature control unit 22 and / or the first fluctuation mitigation temperature control unit 32 based on the temperature information (first reaction information) obtained by the first tubular mixing fluid measuring unit 222 and / or the first generated fluid measuring unit 322 (control step). This makes it possible to obtain polyamic acid with the desired properties (temperature, viscosity).

[0100] The polymer manufacturing system 1 of this embodiment provides the following effects. 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 combines the first fluid A1 and the second fluid A2 to produce a first combined fluid B, a first tubular mixing section 20 located downstream of the first confluence section J1 that stirs the first combined fluid B to equalize the radial viscosity fluctuations and produce a first tubular mixed fluid C, and a first fluctuation mitigation section 30 located downstream of the first tubular mixing section 20 that reduces axial irregularities in the properties of the first tubular mixed fluid C and produces a first generated fluid D.

[0101] In this invention, the first pipe-mixed fluid C, which is mixed in the first pipe-type mixing section 20 located in the preceding stage, is homogenized in the axial direction in the first fluctuation mitigation section 30 located in the subsequent stage. As a result, fluctuations in the viscosity of the first pipe-mixed fluid C in the axial direction of the pipe, which cannot be eliminated in the first pipe-type mixing section 20 located in the preceding stage, can be eliminated in the first fluctuation mitigation section 30 located in the subsequent stage, and a polymer solution can be obtained continuously and stably.

[0102] In particular, when producing high-viscosity polymers, the pressure loss when the high-viscosity solution passes through a tubular mixer becomes large, requiring a high discharge pressure from the pump, which impairs the quantitative accuracy of the liquid being delivered. Therefore, it is difficult to obtain polymers with stable viscosity using only a tubular mixer. Accordingly, the present invention is particularly effective when producing high-viscosity polymers, for example, with a viscosity of 1000 poise or more.

[0103] Furthermore, in the polymer production system 1, based on the first reaction information obtained by the first pipe-mixed fluid measuring unit 222 and / or the first product fluid measuring unit 322, one or more of the following are controlled: supply from the first supply pump 112, supply from the second supply pump 122, temperature adjustment in the first pipe-type mixing temperature control unit 22, and temperature adjustment in the first fluctuation mitigation temperature control unit 32. This makes it possible to obtain a polymer with desired properties (temperature, viscosity).

[0104] In this embodiment, we have described a case where one of the first polymerizable compound and the second polymerizable compound is a tetracarboxylic dianhydride and the other is a diamine, and polyamic acid is produced as the polymer, but the invention is not limited to this. For example, polyamic acid may be produced as a polymer by using a polyamic acid (prepolymer) with an acid anhydride group or amino group terminus as one of the first polymerizable compound and the second polymerizable compound, and a diamine or tetracarboxylic dianhydride as the other. In this case, if one of the first polymerizable compound and the second polymerizable compound is a polyamic acid with an acid anhydride group terminus, the other is a diamine. Also, if one of the first polymerizable compound and the second polymerizable compound is a polyamic acid with an amino group terminus, the other is a tetracarboxylic dianhydride. Furthermore, for example, one of the first polymerizable compound and the second polymerizable compound may be a polyamic acid with an acid anhydride group terminus or an amino group terminus, and the other may be a polyamic acid with an amino group terminus or an acid anhydride group terminus, and the polyamic acid may be produced as a polymer. In this case, if one of the first polymerizable compound and the second polymerizable compound is a polyamic acid with an acid anhydride group terminus, the other is a polyamic acid with an amino group terminus.

[0105] <Variation> Although one embodiment has been described above, the present invention is not limited to the above embodiment, and any modifications, improvements, etc., within the scope that can achieve the objectives of the present invention are included in the present invention.

[0106] For example, in the first embodiment described above, the fluids are mixed in the first tubular mixing section and the first fluctuation mitigation section. However, the system is not limited to this. Further downstream of the configuration of the first embodiment, one or more tubular mixing sections and / or fluctuation mitigation sections may be provided.

[0107] Furthermore, although this embodiment describes a case where the first tubular mixing section 20 is composed of a double pipe consisting of a first tubular mixing and stirring section 21 and a first temperature control section 22, it is not limited to this. For example, the first tubular mixing section 20 may be composed of a single pipe consisting only of the first tubular mixing and stirring section 21, and this first tubular mixing and stirring section 21 may be immersed in a liquid for temperature control. Similarly, although a case where the first fluctuation mitigation section 30 is composed of a double pipe has been described, it is not limited to this.

[0108] Furthermore, although the above-described embodiments described a polymer manufacturing system for producing polyamic acid or polyimide, the polymers to be produced are not limited to these. For example, the polymer manufacturing system may produce polymers using polyadditive monomers such as urethane monomers or epoxy monomers. Also, although the above-described embodiments described an example in which the time-dependent fluctuation of viscosity is reduced by the first fluctuation mitigation unit 30, the properties that can have their fluctuations reduced are not limited to viscosity, and the first fluctuation mitigation unit 30 can also reduce fluctuations in other physical properties that occur over time.

[0109] In the above-described embodiment, viscosity information relating to the viscosity of the first pipe mixed fluid C and the first generated fluid D was acquired by the viscosity measuring unit, and the amount of fluid supplied and / or the temperature conditions of the mixture were controlled based on the acquired viscosity information. However, the embodiment is not limited to this. For example, absorbance information relating to the absorbance of the first pipe mixed fluid C and the first generated fluid D may be acquired, and the amount of fluid supplied and / or the temperature conditions of the mixture may be controlled based on the acquired absorbance information.

[0110] In the above-described embodiment, an example was shown in which each part of the polymer manufacturing system is connected by the first liquid supply line L1, the second liquid supply line L2, the third liquid supply line L3, the fourth liquid supply line L4, and the fifth liquid supply line L5, but the system is not limited thereto. For example, the fourth liquid supply line L4 may be omitted, and the outlet of the first tubular mixing section 20 and the inlet of the first fluctuation mitigation section 30 may be directly connected.

[0111] Furthermore, while the above-described embodiment mentions a method for controlling the temperature of the first tubular mixing section 20 and the first fluctuation mitigation section 30, the invention is not limited thereto. For example, a temperature control unit for the first tubular mixing section 20 and / or the first fluctuation mitigation section 30 is not necessarily required, and a temperature control unit may be provided in 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. [Examples]

[0112] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[0113] <Example 1> In Example 1, polyamic acid was produced using a polymer production system 1 having the structure shown in Figure 1. The first tank 11 contained a first fluid A1, which was obtained by dissolving polyamic acid with acid anhydride at the end, obtained by the reaction of 4,4'-diaminodiphenyl ether and pyromellitic dianhydride, in N,N-dimethylformamide. The second tank 12 contained a second fluid A2, which was obtained by dissolving p-phenylenediamine in N,N-dimethylformamide.

[0114] First, at 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 were combined and mixed to produce the first confluence fluid B. Next, at the first tubular mixing section 20, the first confluence fluid B was stirred without contact with gas, and the first tubular mixed fluid C, which had uniform properties in the radial direction of the pipe, flowed out of the outlet of the first tubular mixing section 20.

[0115] More specifically, a Kenics mixer-type static mixer (8 mm inner diameter, 670 mm length) was used as the first tubular mixing section 20 to stir the first combined fluid B without contact with the gas. The total supply rate from the first supply pump 112 and the second supply pump 122 was set to 1.0 cc / s, and a polymer solution of the desired viscosity was obtained by adjusting the supply ratio of the raw materials from these pumps. At the outlet of the first tubular mixing section 20, the polymerization reaction was complete, and a first tubular mixed fluid C with uniform radial properties was obtained. However, measurements using an online viscometer showed viscosity fluctuations with a difference of approximately 400 poise between the maximum and minimum viscosity values. The average viscosity of the first tubular mixed fluid C was 2100 poise.

[0116] A hollow cylindrical tube with an inner diameter of 30 mm and a length of 900 mm was used as the first fluctuation mitigation section 30. The first pipe-mixed fluid C that flowed out from the first pipe-type mixing section 20 was introduced into the first fluctuation mitigation section 30 at a volumetric flow rate of 1.0 cc / s. Due to the flow velocity distribution generated within the first fluctuation mitigation section 30, axial mixing of the first pipe-mixed fluid C proceeded, and the first generated fluid D with an average viscosity of 2100 poise and reduced viscosity fluctuations flowed out from the outlet of the first fluctuation mitigation section 30. From measurements using an online viscometer, the difference between the maximum and minimum viscosity values ​​of the first generated fluid D was approximately 80 poise. Therefore, it was found that the time-dependent viscosity fluctuation of the fluid at the outlet of the first pipe-type mixing section 20 can be significantly reduced by providing the first fluctuation mitigation section 30. [Explanation of Symbols]

[0117] 1. A derivative manufacturing system. 11 Tank No. 1 12 Tank No. 2 20 1st tube type mixing section 21 1st tube type mixing and stirring section 22 1st tube type mixing temperature control section (1st temperature control section) 30. First Fluctuation Mitigation Section 31. First Fluctuation Mitigation Piping Section 32. First temperature mitigation unit (first temperature control unit) 111 Shut-off valve for the first tank 112 First supply pump (first supply unit) 113 1st flow rate measurement section 121 Shut-off valve for the second tank 122 Second supply pump (second supply unit) 123 2nd flow rate measurement section 200 Control Unit 222 1st tube mixed fluid measurement section (1st measurement section) 322 Second generated fluid measurement section (first measurement section) A1 1st fluid A2 2nd fluid B 1st confluence fluid C 1st pipe mixed fluid D 1st generation fluid L liquid delivery line L1 First liquid delivery line L2 Second liquid delivery line L3 Third liquid delivery line L4 4th liquid delivery line L5 Fifth liquid delivery line J1 1st confluence

Claims

1. A polymer production system for producing a polymer using a first fluid containing a polyadditive first polymerizable compound and a second fluid containing a polyadditive second polymerizable compound that polyadditively adds to the first polymerizable compound as raw materials, A first supply unit that supplies the first fluid, A second supply unit that supplies the second fluid, A first confluence unit that combines the first fluid and the second fluid to generate a first combined fluid, A first tubular mixing section is located downstream of the first confluence section and promotes radial mixing of the first confluence fluid to generate a first tubular mixed fluid, The system comprises a first fluctuation mitigation unit, which is located downstream of the first tubular mixing unit and generates a first generated fluid by reducing fluctuations in the axial properties of the first tubular mixed fluid, The first fluctuation mitigation section is such that the Reynolds number of the fluid flowing inside is 2100 or less when 4 × cross-sectional area / immersion length is used as the characteristic length. Polymer manufacturing system.

2. The system further comprises a first measuring unit for acquiring first reaction information relating to physical quantities and / or composition in one or more of the first confluence fluid, the first pipe mixed fluid, and the first generated fluid. A polymer production system according to claim 1.

3. The first measuring unit includes one or more selected from the group consisting of a viscometer, thermometer, pressure gauge, pump pressure gauge, absorbance meter, infrared spectrometer, near-infrared spectrometer, densimeter, colorimeter, refractometer, spectrophotometer, conductivity meter, turbidimeter, ultrasonic sensor, and X-ray fluorescence analyzer. A polymer production system according to claim 2.

4. The system further comprises a first temperature control unit for adjusting the temperature of one or more of the first fluid, the second fluid, the first confluence fluid, the first pipe mixed fluid, and the first generated fluid. A polymer production system according to claim 2.

5. The first fluctuation mitigation section is a pipe in which the average residence time of the fluid flowing inside is 3 minutes or more. A polymer manufacturing system according to any one of claims 1 to 4.

6. The first fluctuation mitigation section is composed of one or more tubular members, The sum of the average residence times of each of the tubular members is 7 minutes or more. A polymer manufacturing system according to any one of claims 1 to 4.

7. A first tube-mixed fluid measuring unit for acquiring first tube-mixed fluid reaction information relating to the physical quantities and / or composition of the first tube-mixed fluid is provided between the first tube-type mixing unit and the first fluctuation mitigation unit. A first product fluid measuring unit for acquiring first product fluid reaction information relating to the physical quantities and / or composition of the first product fluid is further provided at or downstream of the outlet of the first fluctuation mitigation unit. The volume of the first fluctuation mitigation section is 0.5 to 100 times the volume of the first tubular mixing section. A polymer manufacturing system according to any one of claims 1 to 4.

8. The volume of the first fluctuation mitigation section is 5 to 100 times the volume of the first tubular mixing section. A polymer manufacturing system according to any one of claims 1 to 4.

9. The first fluctuation mitigation section is a pipe in which the residence time of the fluid that has passed through the fastest flow path is 3 minutes or more. A polymer manufacturing system according to any one of claims 1 to 4.

10. The first fluctuation mitigation section is composed of one or more tubular members, The average cross-sectional flow velocity of the fluid flowing inside the tubular member is 0.01 m / s or less. The piping consists of tubular members whose combined lengths are 0.7 m or more. A polymer manufacturing system according to any one of claims 1 to 4.

11. The first polymerizable compound and the second polymerizable compound satisfy any of the following (a) to (c), and polyamic acid is produced as the polymer. A polymer manufacturing system according to any one of claims 1 to 10. (a) Of the first polymerizable compound and the second polymerizable compound, one is a tetracarboxylic dianhydride and the other is a diamine. (b) Of the first polymerizable compound and the second polymerizable compound, one is a polyamic acid with an acid anhydride or amino group terminus, and the other is a diamine or a tetracarboxylic dianhydride. (c) Of the first polymerizable compound and the second polymerizable compound, one is a polyamic acid with an acid anhydride terminus or an amino group terminus, and the other is a polyamic acid with an amino group terminus or an acid anhydride terminus.

12. The system further comprises an imidation unit for imidizing the manufactured polyamic acid, thereby producing polyimide as the polymer. The polymer production system according to claim 11.

13. The first measuring unit acquires first reaction information in one or more of the first confluence fluid, the first pipe mixed fluid, and the first generated fluid. The system further includes a control unit that controls one or more selected from the group consisting of fluid supply in the first supply unit, fluid supply in the second supply unit, and temperature control in the first temperature control unit, based on the acquired first reaction information. A polymer production system according to claim 4.

14. The first measuring unit acquires the first reaction information in the first confluence fluid and / or the first pipe mixed fluid, The system further includes a control unit that predicts the properties of the first generated fluid based on the acquired first reaction information, and controls one or more selected from the group consisting of fluid supply in the first supply unit, fluid supply in the second supply unit, and temperature adjustment in the first temperature control unit, based on the predicted properties of the first generated fluid. A polymer production system according to claim 4.

15. A method for producing a polymer using the polymer production system described in any one of claims 1 to 14.

16. A method for producing a polyamic acid solution and / or polyimide using the polymer production system described in any one of claims 1 to 14.

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