JP2020090600A - Polymer production system, and production method - Google Patents

Abstract

To provide a polymer production system capable of obtaining an intended polymer continuously and stably, and a production method.SOLUTION: The polymer production system 1 produces a polymer from a first solution A1 containing a polyadditionable first polymerizable compound, and a second solution A2 containing a polyadditionable second polymerizable compound as raw materials, and includes: a first supplying part 15 for supplying the first solution A1; a second supplying part 16 for supplying the second solution A2; a first flow-through stirring vessel type mixing part 20 for producing a first stirring vessel mixed solution B by stirring to proceed polymerization reaction in such a state that the first solution A1 and the second solution A2 contact a gas and continuously performing the acceptance of the first solution A1 and the second solution A2, and the discharge of the first stirring vessel mixed solution B; a third supplying part 22 for supplying the first stirring vessel mixed solution B; and a tubular mixing part 30 disposed on a downstream side of the first flow-through stirring vessel type mixing part 20, and for producing a tube mixed solution C by stirring the first stirring vessel mixed solution B to further proceed polymerization reaction.SELECTED DRAWING: Figure 1

Description

The present invention relates to a polymer manufacturing system and manufacturing method. More specifically, the present invention relates to a polymer production system and a production method capable of continuously producing a polymer.

Conventionally, as a method for producing a polymer such as polyamic acid, a batch-type production method utilizing a stirring tank has been known.
Further, as a continuous polyamic acid (polyamic acid) production method, for example, a method of producing a polyamic acid using a tube reactor is known (see, for example, Patent Document 1).

JP, 2006-249380, A

In a batch-type method for producing a polymer such as polyamic acid, there is a significant increase in viscosity, and the appropriate stirring blade and stirring conditions differ depending on the viscosity.Therefore, effective stirring in polymerization using a single batch reactor There was a problem that could not be done. In a large stirring tank, there was a remarkable temperature rise at the beginning of the reaction, and the quality sometimes deteriorated. When the polymerization is carried out by a batch process, the residual solution in the reaction tank may affect the reaction of the next batch, and a difference in quality between batches may easily occur. Therefore, there is a problem that it is difficult to obtain a desired polymer continuously and stably.

On the other hand, when polyamic acid or the like is produced in the tube of a tube reactor in a closed state, the viscosity increase of the solution is small, and the purpose of producing fine particles which does not require highly accurate control of the monomer ratio is relatively easy to achieve. However, in the case of producing a polyamic acid having a high viscosity in a closed tube, since the pressure loss in the tube is large, an expensive pump capable of supplying the raw material at a high supply pressure (high discharge pressure) is required. In addition, when a desired polyamic acid having a high viscosity is produced in a closed tube by mixing the first solution and the second solution, it is necessary to strictly control the monomer ratio. It is necessary to use expensive pumps that can supply the liquid with high accuracy.
When a low-precision pump with a low supply pressure is used, a sufficient flow rate (production amount) cannot be ensured due to the low discharge pressure, and the supply pressure of each pump is adjusted to adjust the first solution and the second solution. It is difficult to adjust the mixing ratio of. Therefore, when producing a highly viscous polyamic acid in a sealed tube without using an expensive pump, there is a problem that it is difficult to continuously and stably obtain a desired polymer.

An object of the present invention is to provide a polymer production system and a production method capable of continuously and stably obtaining a desired polymer.

Specific means for solving the above problems include the following embodiments.
<1> A polymer production system for producing a polymer using as a raw material a first solution containing a polyadditive first polymerizable compound and a second solution containing a polyadditive second polymerizable compound,
A first supply unit for supplying the first solution;
A second supply unit for supplying the second solution;
The first solution and the second solution are stirred in a state of being in contact with a gas to allow a polymerization reaction to proceed, thereby producing a first stirred tank mixed solution, and receiving the first solution and the second solution and A first flow type stirring tank type mixing section for continuously taking out the first stirring tank mixed solution;
A third supply unit for supplying the first stirred tank mixed solution;
And a tube type mixing section which is disposed on the downstream side of the first flow type stirring tank type mixing section and which generates a tube mixed solution by further stirring the first stirring tank mixed solution to further advance the polymerization reaction. Polymer manufacturing system.

<2> The polymer production system according to <1>, wherein the first supply unit and/or the second supply unit includes a metering pump.

<3> A fourth supply unit that supplies a third solution containing a polyadditive third polymerizable compound,
It is arranged between the first flow type stirring tank type mixing section and the tube type mixing section, and the first stirring tank mixed solution and the third solution are stirred in a state of being in contact with gas to proceed a polymerization reaction. A second flow-type stirring tank type, in which a second stirring tank mixed solution is generated by performing the above, and the first stirring tank mixed solution and the third solution are continuously received and the second stirring tank mixed solution is taken out continuously. A mixing section,
A fifth supply unit for supplying the second stirred tank mixed solution,
The said tube type mixing part is a polymer manufacturing system as described in <1> or <2> which produces|generates the said tube mixed solution by stirring the said 2nd stirring tank mixed solution and further advancing a polymerization reaction.

<4> The polymer production system according to <3>, wherein the third supply unit and/or the fourth supply unit includes a metering pump.

<5> A measurement unit that acquires reaction information about a physical quantity and/or a composition in any one or more of the first stirred tank mixed solution and the tube mixed solution,
Any one of <1> to <4>, further comprising: a control unit that controls the supply in the first supply unit and/or the second supply unit based on the reaction information acquired by the measurement unit. The polymer production system according to 1.

<6> The measuring unit includes a viscometer, a pressure gauge, a pump pressure gauge, an absorptiometer, an infrared spectrometer, a near infrared spectrometer, a density meter, a color difference meter, a refractometer, a spectrophotometer, a conductivity meter, and a turbidity meter. The polymer production system according to <5>, which comprises one or two or more selected from the group consisting of a densitometer and a fluorescent X-ray analyzer.

<7> The first polymerizable compound and the second polymerizable compound satisfy any of the following (a) to (c), and a polyamic acid is produced as the polymer according to <1> or <2>. Polymer manufacturing system.
(A) Of the first polymerizable compound and the second polymerizable compound, one is tetracarboxylic dianhydride and the other is diamine.
(B) Of the first polymerizable compound and the second polymerizable compound, one is a polyamic acid having an acid anhydride group terminal or an amino group terminal, and the other is a diamine or a tetracarboxylic acid dianhydride.
(C) Of the first polymerizable compound and the second polymerizable compound, one is a polyamic acid having an acid anhydride group terminal or an amino group terminal and the other is a polyamic acid having an amino group terminal or an acid anhydride group terminal. Is.

<8> The first polymerizable compound and the second polymerizable compound satisfy any of the following (a) to (c), the third polymerizable compound is tetracarboxylic dianhydride or diamine, The polymer production system according to <3> or <4>, which produces a polyamic acid as a polymer.
(A) Of the first polymerizable compound and the second polymerizable compound, one is tetracarboxylic dianhydride and the other is diamine.
(B) Of the first polymerizable compound and the second polymerizable compound, one is a polyamic acid having an acid anhydride group terminal or an amino group terminal, and the other is a diamine or a tetracarboxylic acid dianhydride.
(C) Of the first polymerizable compound and the second polymerizable compound, one is a polyamic acid having an acid anhydride group terminal or an amino group terminal and the other is a polyamic acid having an amino group terminal or an acid anhydride group terminal. Is.

<9> A polyamic acid in which the first polymerizable compound and the second polymerizable compound satisfy any of the following (a) to (c), and the third polymerizable compound has an acid anhydride group terminal or an amino group terminal. And the polymer production system according to <3> or <4>, which produces a polyamic acid as the polymer.
(A) Of the first polymerizable compound and the second polymerizable compound, one is tetracarboxylic dianhydride and the other is diamine.
(B) Of the first polymerizable compound and the second polymerizable compound, one is a polyamic acid having an acid anhydride group terminal or an amino group terminal, and the other is a diamine or a tetracarboxylic acid dianhydride.
(C) Of the first polymerizable compound and the second polymerizable compound, one is a polyamic acid having an acid anhydride group terminal or an amino group terminal and the other is a polyamic acid having an amino group terminal or an acid anhydride group terminal. Is.

<10> The polymer production system according to any one of <7> to <9>, further including an imidization unit that imidizes the produced polyamic acid, and producing a polyimide as the polymer.

<11> A method for producing a polymer, which comprises producing a polymer using a first solution containing a polyadditive first polymerizable compound and a second solution containing a polyadditive second polymerizable compound as raw materials. ,
A first supplying step of supplying the first solution,
A second supply step of supplying the second solution;
In the first flow type stirring tank type mixing section, the first solution and the second solution are stirred in a state of being in contact with gas to promote a polymerization reaction to generate a first stirring tank mixed solution, A first stirring tank mixing step of continuously receiving one solution and the second solution and taking out the first stirring tank mixed solution;
A third supply step of supplying the first stirred tank mixed solution,
A tube mixing step of producing a tube mixed solution by further advancing the polymerization reaction by stirring the first stirred tank mixed solution in the tube type mixing section.

<12> The method for producing a polymer according to <11>, wherein in the first supply step and/or the second supply step, the first solution and/or the second solution is supplied by a metering pump.

<13> A fourth supply step of supplying a third solution containing a polyadditive third polymerizable compound,
In the second circulation type stirring tank type mixing section, the first stirring tank mixed solution and the third solution are stirred in a state of being in contact with gas to allow the polymerization reaction to proceed to generate a second stirring tank mixed solution. A second stirring tank mixing step of continuously receiving the first stirring tank mixed solution and the third solution and taking out the second stirring tank mixed solution,
And a fifth supplying step of supplying the second stirred tank mixed solution,
In the pipe mixing step, the method for producing a polymer according to <11> or <12>, in which the pipe mixed solution is produced by stirring the second stirred tank mixed solution to further advance a polymerization reaction.

<14> The method for producing a polymer according to <13>, wherein in the third supply step and/or the fourth supply step, the first stirred tank mixed solution and/or the third solution is supplied by a metering pump. ..

<15> A measurement step of acquiring reaction information regarding a physical quantity and/or a composition in any one or more of the first stirred tank mixed solution and the tube mixed solution,
Any one of <11>-<14> which further includes a control step of controlling the supply in the first supply step and/or the second supply step based on the reaction information acquired in the measurement step. The method for producing a polymer according to item 1.

<16> In the measurement step, a viscometer, a pressure gauge, a pump pressure gauge, an absorptiometer, an infrared spectrometer, a near-infrared spectrometer, a density meter, a color difference meter, a refractometer, a spectrophotometer, a conductivity meter, and a turbidity meter. The method for producing a polymer according to <15>, wherein the reaction information is acquired by one or more selected from the group consisting of a thermometer and a fluorescent X-ray analyzer.

<17> The first polymerizable compound and the second polymerizable compound satisfy any one of the following (a) to (c), and produce a polyamic acid as the polymer described in <11> or <12>. Method for producing polymer.
(A) Of the first polymerizable compound and the second polymerizable compound, one is tetracarboxylic dianhydride and the other is diamine.
(B) Of the first polymerizable compound and the second polymerizable compound, one is a polyamic acid having an acid anhydride group terminal or an amino group terminal, and the other is a diamine or a tetracarboxylic acid dianhydride.
(C) Of the first polymerizable compound and the second polymerizable compound, one is a polyamic acid having an acid anhydride group terminal or an amino group terminal and the other is a polyamic acid having an amino group terminal or an acid anhydride group terminal. Is.

<18> The first polymerizable compound and the second polymerizable compound satisfy any of the following (a) to (c), and the third polymerizable compound is tetracarboxylic dianhydride or diamine, The method for producing a polymer according to <13> or <14>, wherein a polyamic acid is produced as the polymer.
(A) Of the first polymerizable compound and the second polymerizable compound, one is tetracarboxylic dianhydride and the other is diamine.
(B) Of the first polymerizable compound and the second polymerizable compound, one is a polyamic acid having an acid anhydride group terminal or an amino group terminal, and the other is a diamine or a tetracarboxylic acid dianhydride.
(C) Of the first polymerizable compound and the second polymerizable compound, one is a polyamic acid having an acid anhydride group terminal or an amino group terminal and the other is a polyamic acid having an amino group terminal or an acid anhydride group terminal. Is.

<19> The first polymerizable compound and the second polymerizable compound satisfy any of the following (a) to (c), and the third polymerizable compound is an acid anhydride group terminal or an amino group terminal polyamic acid. And the method for producing a polymer according to <13> or <14>, wherein a polyamic acid is produced as the polymer.
(A) Of the first polymerizable compound and the second polymerizable compound, one is tetracarboxylic dianhydride and the other is diamine.
(B) Of the first polymerizable compound and the second polymerizable compound, one is a polyamic acid having an acid anhydride group terminal or an amino group terminal, and the other is a diamine or a tetracarboxylic acid dianhydride.
(C) Of the first polymerizable compound and the second polymerizable compound, one is a polyamic acid having an acid anhydride group terminal or an amino group terminal and the other is a polyamic acid having an amino group terminal or an acid anhydride group terminal. Is.

<20> The method for producing a polymer according to any one of <17> to <19>, further including an imidization step of imidizing the produced polyamic acid to produce a polyimide as the polymer.

According to the present invention, it is possible to provide a polymer production system and a production method capable of continuously and stably obtaining a desired polymer.

It is a figure which shows the polymer manufacturing system in 1st Embodiment. It is a figure which shows the polymer manufacturing system in 2nd Embodiment.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
The first embodiment is an example of a polymer production system including a first flow type stirring tank type mixing section and a tube type mixing section, and in the case where no solution is added in the middle of the liquid feeding line L. The second embodiment includes a first flow type stirring tank type mixing unit, a second flow type stirring tank type mixing unit and a pipe type mixing unit, and polymer production in the case of adding a solution in the middle of the liquid feeding line L. It is an example of a system.

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

First, the outline of the polymer production system 1 in the first embodiment will be described.
The polymer production system 1 is a production system for producing a polymer using a first solution A1 containing a polyadditive first polymerizable compound and a second solution A2 containing a polyadditive second polymerizable compound as raw materials. Is. The first embodiment is an example of a polymer production system in which a first flow type stirring tank type mixing section and a tube type mixing section are continuously provided.

Here, the “(first) flow type stirring tank type mixing section” means a mixing section having a stirring tank type reactor for performing mixing while continuously receiving and taking out the solution. Further, the “tubular mixing section” means a mixing section having a tubular reactor for mixing while circulating a solution.

Hereinafter, as an example, a case where one of the first polymerizable compound and the second polymerizable compound is a tetracarboxylic acid dianhydride and the other is a diamine and a polyamic acid is produced as a polymer will be described. More specifically, the first polymerizable compound contained in the first solution A1 is a tetracarboxylic acid dianhydride, the second polymerizable compound contained in the second solution A2 is a diamine, and a polyamic acid is used as a polymer. The case of manufacturing is explained.

The tetracarboxylic dianhydride is not particularly limited, and the same ones used in conventional polyimide synthesis can be used. Specific examples of the tetracarboxylic dianhydride include 3,3′,4,4′-benzophenone tetracarboxylic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, and 3,3′,4′-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 1,3-bis(2,3-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(2,2 3-dicarboxyphenoxy)benzene dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 2,2 ',3,3'-biphenyltetracarboxylic dianhydride, 2,2',6,6'-biphenyltetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, Aromatic tetracarboxylic dianhydrides such as anthracene-2,3,6,7-tetracarboxylic dianhydride and phenanthrene-1,8,9,10-tetracarboxylic dianhydride; butane-1,2, Aliphatic tetracarboxylic dianhydrides such as 3,4-tetracarboxylic dianhydride; alicyclic tetracarboxylic dianhydrides such as cyclobutane-1,2,3,4-tetracarboxylic dianhydride; thiophene Heterocyclic tetracarboxylic dianhydrides such as -2,3,4,5-tetracarboxylic dianhydride and pyridine-2,3,5,6-tetracarboxylic dianhydride; and the like. The tetracarboxylic dianhydrides may be used alone or in combination of two or more.

As the solvent of the first solution A1, a solvent in which tetracarboxylic dianhydride is dissolved is used. Specific examples of the solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 2-propanone, 3-pentanone, tetrahydropyrene, epichlorohydrin, acetone, methyl ethyl ketone, tetrahydrofuran. , Ethyl acetate, acetanilide, methanol, ethanol, isopropanol, toluene, xylene and the like. As the solvent, one type may be used alone, or two or more types may be mixed.

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

The diamine is not particularly limited, and those similar to those used in conventional polyimide synthesis can be used. Specific examples of the diamine 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'-diaminodiphenyl sulfide, 2,6-diaminotoluene, 2,4-diaminochlorobenzene, 1,2-diaminoanthraquinone, 1,4-diaminoanthraquinone, Aromatic diamines such as 3,3′-diaminobenzophenone, 3,4′-diaminobenzophenone, 4,4′-diaminobenzophenone and 4,4′-diaminobibenzyl; 1,2-diaminoethane, 1,4-diamino Aliphatic diamines such as butane, tetramethylenediamine, 1,10-diaminododecane; 1,4-diaminocyclohexane, 1,2-diaminocyclohexane, bis(4-aminocyclohexyl)methane, 4,4′-diaminodicyclohexylmethane, etc. Alicyclic diamines; and heterocyclic diamines such as 3,4-diaminopyridine; The diamine may be used alone or in combination of two or more.

As the solvent of the second solution A2, a solvent in which diamine is dissolved is used. Specific examples of the solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 2-propanone, 3-pentanone, tetrahydropyrene, epichlorohydrin, acetone, methyl ethyl ketone, tetrahydrofuran. , Ethyl acetate, acetanilide, methanol, ethanol, isopropanol and the like. As the solvent, one type may be used alone, or two or more types may be mixed.

As shown in FIG. 1, in the polymer production system 1, the first solution A1 and the second solution A2, which are raw materials, are stirred in a state of being in contact with a gas in the first flow-type stirring tank type mixing section 20 to carry out a polymerization reaction. The first stirred tank mixed solution B is produced by advancing the mixture, and the first stirred tank mixed solution B is stirred in the tubular mixing section 30 to further advance the polymerization reaction to produce the tube mixed solution C. It is configured to produce an acid (polymer).

Further, the polymer production system 1 has a liquid feed line L connecting a first tank 11 and a second tank 12 described later to the cushion tank 40.

Subsequently, a specific configuration of the polymer production system 1 will be described.
As shown in FIG. 1, the polymer production system 1 includes a first tank 11, a first tank opening/closing valve 111, a second tank 12, a second tank opening/closing valve 121, and a first supply pump 15 ( 1st supply part), 2nd supply pump 16 (2nd supply part), 1st flow type stirring tank type mixing part 20, 1st stirring tank opening/closing valve 21, 3rd supply pump 22 (3rd) A supply unit), a tubular mixing unit 30, a cushion tank 40, a liquid supply line L, and a control unit 200. The liquid delivery line L described above includes a first liquid delivery unit L1, a second liquid delivery unit L2, a third liquid delivery unit L3, and a fourth liquid delivery unit L4. Moreover, the polymer production system 1 includes a first flow rate measurement unit 151, a second flow rate measurement unit 161, a third flow rate measurement unit 221, a first viscosity measurement unit 222, and a second viscosity measurement unit 322. Have.

The first tank 11 stores a first solution A1 containing a polyadditive first polymerizable compound. In the present embodiment, the first tank 11 stores the first solution A1 containing tetracarboxylic dianhydride. The first solution A1 contained in the first tank 11 is supplied to the first flow-type stirring tank type mixing unit 20 via the first liquid feeding unit L1.

The 1st liquid sending part L1 is a line which connects the 1st tank 11 and the 1st flow type stirring tank type mixing part 20. The first tank opening/closing valve 111, the first supply pump 15, and the first flow rate measuring unit 151 are provided between the first tank 11 and the first flow-type stirring tank type mixing unit 20 in the first liquid feeding unit L1. , Are arranged in this order from the upstream side to the downstream side.

The first tank opening/closing valve 111 is arranged near the lower side of the first tank 11 in the first liquid feeding unit L1, and opens/closes the first liquid feeding unit L1 on the upstream side of the first supply pump 15.

The first supply pump 15 (first supply unit) supplies the first solution A1 contained in the first tank 11 to the first circulation type stirring tank type mixing unit 20. The first supply pump 15 discharges the first solution A1 at a predetermined flow rate. For example, the first supply pump 15 is adjusted so as to supply the first solution A1 under the condition that a polyamic acid having a desired property is obtained.

In the present embodiment, the first supply pump 15 is a metering pump. The metering pump is a positive displacement pump, which pumps a fixed amount of solution repeatedly with high accuracy. Examples of the metering pump include an extrusion type reciprocating pump such as a plunger pump; a rotary pump such as a gear pump provided with gears; and the like.

The first flow rate measurement unit 151 measures the flow rate of the first solution A1 on the downstream side of the first supply pump 15 in the first liquid feeding unit L1. In the present embodiment, the first flow rate measuring unit 151 is arranged between the first supply pump 15 and the first flow-type stirring tank type mixing unit 20. The first flow rate measurement unit 151 outputs the measured flow rate of the first solution A1 to the control unit 200 described below.

The second tank 12 stores a second solution A2 containing a polyadditive second polymerizable compound. In the present embodiment, the second tank 12 stores the second solution A2 containing diamine. The second solution A2 contained in the second tank 12 is supplied to the first flow-type stirring tank type mixing unit 20 via the second liquid feeding unit L2.

The second liquid feeding unit L2 is a line that connects the second tank 12 and the first flow-type stirring tank type mixing unit 20. A second tank opening/closing valve 121, a second supply pump 16, and a second flow rate measuring unit 161 are provided between the second tank 12 and the first flow type stirring tank type mixing unit 20 in the second liquid feeding unit L2. , Are arranged in this order from the upstream side to the downstream side.

The second tank opening/closing valve 121 is arranged near the lower part of the second tank 12 in the second liquid sending section L2, and opens and closes the second liquid sending section L2 on the upstream side of the second supply pump 16.

The second supply pump 16 (second supply unit) supplies the second solution A2 contained in the second tank 12 to the first flow-type stirring tank type mixing unit 20. The second supply pump 16 discharges the second solution A2 at a predetermined flow rate. For example, the second supply pump 16 is adjusted to supply the second solution A2 under the condition that a polyamic acid having a desired property is obtained.
In the present embodiment, the second supply pump 16 is a metering pump, like the first supply pump 15 described above.

The second flow rate measurement unit 161 measures the flow rate of the second solution A2 on the downstream side of the second supply pump 16 in the second liquid feeding unit L2. In the present embodiment, the second flow rate measuring unit 161 is arranged between the second supply pump 16 and the first flow type stirring tank type mixing unit 20. The second flow rate measurement unit 161 outputs the measured flow rate of the second solution A2 to the control unit 200 described later.

The first flow type stirring tank type mixing unit 20 is arranged on the downstream side of the first supply pump 15 and the second supply pump 16. The 1st circulation type stirring tank type|mold mixing part 20 produces|generates the 1st stirring tank mixed solution B by stirring the 1st solution A1 and the 2nd solution A2 in a state which is in contact with gas, and advancing a polymerization reaction. The first circulation type stirring tank type mixing unit 20 continuously receives the first solution A1 and the second solution A2 and takes out the first stirring tank mixed solution B. In the present embodiment, after the polymerization reaction of the first polymerizable compound and the second polymerizable compound proceeds in the first flow-type stirring tank type mixing section 20, the polymerization reaction further proceeds in the tube type mixing section 30. By doing so, the desired polymer can be continuously and stably obtained without using an expensive pump with high discharge pressure and high precision.

The first flow type stirring tank type mixing unit 20 includes a stirring tank type reactor 201 and a plurality of first stirring blades 202 (first stirring members). The reactor 201 is composed of a stirring tank provided with a temperature control jacket. The first stirring blade 202 stirs the first solution A1 and the second solution A2 introduced into the reactor 201 to generate the first stirring tank mixed solution B. In the present embodiment, the first flow type stirring tank type mixing unit 20 is arranged at the front stage of the first flow type stirring tank type mixing unit 20 and the pipe type mixing unit 30 which are continuously provided. Since the solution has a low viscosity, the stirring member for low viscosity is used as the first stirring blade 202. Examples of the low-viscosity stirring member include an inclined paddle.

The stirring member used for the first stirring blade 202 of the first flow type stirring tank type mixing unit 20 is not particularly limited, but one having high vertical circulation of the reaction solution and high mixing performance is preferable. Below, an example of a stirring member used in a low viscosity region, a medium viscosity region, and a high viscosity region is shown. However, these stirring members are examples, and the stirring members are not limited thereto.

In a relatively low viscosity region where the viscosity of the reaction solution is about several centipoise, a stirring blade such as an inclined paddle blade or a turbine blade is used as the stirring member.
In addition, in the medium viscosity region where the viscosity of the reaction solution is in the range of several tens to hundreds of poises, examples of the stirring member include Maxblend blades, full-zone blades, Sun-Meller blades, and Hi-Fi mixer blades.
Further, in the high viscosity region where the viscosity of the reaction solution is about several hundred poises, examples of the stirring member include anchor blades; helical ribbon blades; screw blades; wide paddle blades; log bone blades.

In the first flow type stirring tank type mixing section 20 described above, the reaction is performed while continuously receiving the first solution A1 and the second solution A2 and taking out the first stirring tank mixed solution B in the open state. The first solution A1 and the second solution A2 supplied to the vessel 201 are stirred by the first stirring blade 202. The first stirred tank mixed solution B generated by stirring the first solution A1 and the second solution A2 is supplied to the tubular mixing section 30 via the third liquid feeding section L3.

The third liquid feeding unit L3 is a line that connects the first flow type stirring tank type mixing unit 20 and the pipe type mixing unit 30. Between the first flow type stirring tank type mixing unit 20 and the pipe type mixing unit 30 in the third liquid feeding unit L3, the first stirring tank opening/closing valve 21, the third supply pump 22, and the third flow rate measuring unit. 221 are arranged in this order from the upstream side to the downstream side.

The first stirring tank opening/closing valve 21 is arranged near the lower portion of the first flow-type stirring tank type mixing section 20 in the third liquid feeding section L3, and on the upstream side of the third supply pump 22, the third liquid feeding section L3. Open and close. The control unit 200 described below controls the opening/closing operation of the first stirring tank opening/closing valve 21 and the discharge flow rate of the third supply pump 22 to allow the solution to stay in the first flow-type stirring tank mixing unit 20 for a residence time. To control.

The third supply pump 22 (third supply unit) supplies the first stirring tank mixed solution B housed in the first flow-type stirring tank mixing unit 20 to the tubular mixing unit 30. The third supply pump 22 discharges the first stirred tank mixed solution B at a predetermined flow rate. If necessary, an inline defoaming device may be installed upstream of the third supply pump 22.
In the present embodiment, the third supply pump 22 needs only to be able to push the first stirred tank mixed solution B into the tube-type mixing section 30 and continuously withdraw the tube mixed solution C, and to supply with high accuracy. Not required. Therefore, unlike the first supply pump 15 and the second supply pump 16 described above, the third supply pump 22 does not have to be a metering pump. It is not excluded that the third supply pump 22 is a metering pump, and the third supply pump 22 may be a metering pump.

The third flow rate measurement unit 221 measures the flow rate of the first stirred tank mixed solution B on the downstream side of the third supply pump 22 in the third liquid feeding unit L3. In the present embodiment, the third flow rate measuring unit 221 is arranged between the third supply pump 22 and the tubular mixing unit 30. The third flow rate measurement unit 221 outputs the measured flow rate of the first stirred tank mixed solution B to the control unit 200 described later.

The first viscosity measuring unit 222 acquires the viscosity information of the first stirred tank mixed solution B between the third flow rate measuring unit 221 and the tubular mixing unit 30 in the third liquid feeding unit L3. Since the viscosity increases as the polymerization reaction progresses, the viscosity information is effective information as reaction information. The first viscosity measuring unit 222 outputs the acquired viscosity information of the first stirred tank mixed solution B to the control unit 200 described later.

The tubular mixing section 30 is arranged downstream of the first flow-type stirring tank type mixing section 20 and downstream of the third supply pump 22. The tubular mixing unit 30 produces the tubular mixed solution C by stirring the first stirred tank mixed solution B to further advance the polymerization reaction.

In the tubular mixing section 30, the polymerization reaction in the first stirred tank mixed solution B further proceeds, and the tubular mixed solution C is obtained. The viscosity of the tube mixed solution C is higher than that of the first stirred tank mixed solution B because the polymerization reaction of the tube mixed solution C is more advanced than that of the first stirred tank mixed solution B. The tube mixed solution C is sent to the cushion tank 40.

The tubular mixing section 30 is configured to include a tubular reactor configured by a double tube extending in a predetermined direction. The tubular mixing section 30 has a tubular mixing and stirring section 31 arranged inside in the radial direction and a temperature adjusting section 32 arranged outside in the radial direction. The tubular mixing section 30 is formed so that the first stirred tank mixed solution B flows for a desired residence time.

The tubular mixing and stirring unit 31 stirs the first stirring tank mixed solution B. In the present embodiment, the tubular mixing/stirring section 31 stirs the first stirring tank mixed solution B adjusted to a temperature suitable for the polymerization reaction by the temperature adjusting section 32.

The tubular mixing/stirring unit 31 is configured to include, for example, a static mixer, a static mixer such as a nozzle or an orifice, or a driving mixer such as a centrifugal pump, a centrifugal pump, or an in-line mixer having stirring blades, preferably The static mixer is included, and more preferably, the static mixer is included. It should be noted that a pipe having twist tapes inserted therein (see [FIG. 19] of JP 2003-314982 A) can also obtain the stirring promotion effect as with the static mixer, but the static mixer has a more stirring promotion effect. Is preferred, which is preferable.

The static mixer is not particularly limited, and examples thereof include a Kenics mixer type, a Sulzer SMV type, a Sulzer SMX type, a Tray Hi-mixer type, a Komax mixer type, a Lightnin mixer type, a Ross ISG type, and a Bran & Luber type mixer. Can be mentioned. Among them, the Kenics mixer type static mixer is more preferable because it has no dead space because of its simple structure.

The temperature adjusting unit 32 is a pipe unit arranged outside the tubular mixing and stirring unit 31 in the radial direction. The temperature adjusting unit 32 adjusts the temperature of the first stirred tank mixed solution B flowing through the tubular mixing and stirring unit 31 to a desired temperature condition (for example, cooling). In the temperature adjusting unit 32, the first stirring tank mixed solution B is adjusted to a temperature suitable for the polymerization reaction and is circulated in the tubular mixing and stirring unit 31.

In the tube type mixing unit 30 described above, the tube mixed solution C is generated by further advancing the polymerization reaction of the first stirred tank mixed solution B. The generated pipe mixed solution C is supplied to the cushion tank 40 via the fourth liquid sending section L4.

The second viscosity measuring unit 322 acquires the viscosity information of the pipe mixed solution C between the fourth flow rate measuring unit 321 and the cushion tank 40 in the fourth liquid feeding unit L4. Since the viscosity increases as the polymerization reaction progresses, the viscosity information is effective information as reaction information. The second viscosity measuring unit 322 outputs the acquired viscosity information of the tube mixed solution C to the control unit 200 described later.

The first viscosity measuring unit 222 and the second viscosity measuring unit 322 of the present embodiment acquire reaction information regarding the physical quantity and/or the composition in any one or more of the first stirred tank mixed solution B and the pipe mixed solution C. It is an example of a measurement unit.

The measurement unit is not limited to the first viscosity measurement unit 222 and the second viscosity measurement unit 322 (physical quantity and/or composition type, measurement method) of the present embodiment. The measuring unit includes, for example, a viscometer, a pressure gauge, a pump pressure gauge, an absorptiometer, an infrared spectrometer, a near infrared spectrometer, a density meter, a color difference meter, a refractometer, a spectrophotometer, a conductivity meter, and a turbidimeter. , And one or more selected from the group consisting of the X-ray fluorescence analyzer. The measurement unit acquires one or more pieces of reaction information regarding the physical quantity and/or the composition of the measurement target, and outputs the acquired reaction information to the control unit 200 described below.

The cushion tank 40 stores the tube mixed solution C from the tube type mixing section 30. The cushion tank 40 is, for example, a tank that stores a raw material solution when a polyimide is produced by imidizing a polyamic acid that is a polymer.

When the polymer production system 1 in the present embodiment produces a polyimide, the polymer production system 1 further includes an imidization unit that imidizes a polyamic acid. The imidization unit (not shown) imidizes the polyamic acid by, for example, a thermal imidization method of thermally dehydrating and ring-closing, a chemical imidization method using a dehydrating agent and an imidization promoter, and the like.

When the polymer production system 1 produces polyimide, the cushion tank 40 may be omitted, and liquid may be fed from the tubular mixing section 30 to the imidization section. However, as described above, it is preferable to temporarily store the polyamic acid in the cushion tank 40.

The control unit 200 will be described. The control unit 200 includes a first supply pump 15, a second supply pump 16, a first flow rate measurement unit 151, a second flow rate measurement unit 161, a first stirring tank opening/closing valve 21, a third supply pump 22, and a third flow rate. The measurement unit 221, the first viscosity measurement unit 222, and the second viscosity measurement unit 322 are electrically connected. In this specification, illustration of control lines from the control unit 200 to each pump, each measurement unit, and each valve is omitted.

The control unit 200 controls the supply pumps 15, 16, 22 based on the flow rate values measured by the flow rate measurement units 151, 161, 221.
The control unit 200 controls the first supply pump 15 and/or the second supply pump 16, for example, so that the first polymerizable compound contained in the first solution A1 and the second polymerizable compound contained in the second solution A2. The molar ratio with the compound is controlled to be within a predetermined range. The above molar ratio is set, for example, so that a polyamic acid having desired properties can be obtained.

The control unit 200 includes the first viscosity information (first reaction information) acquired by the first viscosity measurement unit 222 (measurement unit) and/or the second viscosity information acquired by the second viscosity measurement unit 322 (measurement unit). The supply in the first supply pump 15 and/or the second supply pump 16 is controlled based on the (second reaction information).

Next, the operation of the polyamic acid production system 1 in the first embodiment will be described.
First, in the polyamic acid production system 1, by starting the operation, the first supply pump 15 supplies the first solution A1 (first supply step), and the second supply pump 16 supplies the second solution A2 ( Second supply step). Here, the discharge flow rates of the first supply pump 15 and the second supply pump 16 are controlled by the control unit 200 so as to supply the first solution A1 and the second solution A2 at a desired ratio. As a result, the first solution A1 and the second solution A2 are supplied to the first flow type stirring tank type mixing unit 20.

In the first circulation type stirring tank type mixing section 20, the first solution A1 and the second solution A2 are stirred by the first stirring blade 202 in a state of being in contact with gas to allow the polymerization reaction to proceed, whereby the first stirring tank A mixed solution B is generated (first stirring tank mixing step). The first stirring blade 202 is a stirring member for low viscosity. In the first flow type stirring tank type mixing unit 20, the reception of the first solution A1 and the second solution A2 and the taking out of the first stirring tank mixed solution B are continuously performed. The first supply pump 15 and the second supply pump 16 are agitated in a state in which the first solution A1 and the second solution A2 are in contact with gas in the first flow-type agitation tank type mixing unit 20 arranged on the downstream side. Composed of a metering pump, without the need for high supply pressure.

The first stirring tank mixed solution B generated in the first flow type stirring tank type mixing section 20 is fed to the third liquid feeding section L3 by the feeding operation of the third feeding pump 22, and is fed to the tubular mixing section 30. Is supplied (third supplying step).

In the tube-type mixing unit 30, the tube-mixed solution C is generated by further advancing the polymerization reaction of the first stirred tank mixed solution B (tube-mixing step). In the tubular mixing section 30, the first stirred tank mixed solution B is stirred to further advance the polymerization reaction. When the tubular mixing unit 30 is a static mixer such as a static mixer, the first stirring tank mixed solution B is simply passed and stirred.

The tube mixed solution C generated in the tube type mixing section 30 is supplied to the cushion tank 40 after being sent to the fourth solution sending section L4.

Here, during the operation of the polymer production system 1 described above, the first viscosity measurement unit 222 and the second viscosity measurement unit 322 acquire viscosity information (measurement step).
The control unit 200 includes the first viscosity information (first reaction information) acquired by the first viscosity measurement unit 222 (measurement unit) and/or the second viscosity information acquired by the second viscosity measurement unit 322 (measurement unit). The supply in the first supply pump 15 and/or the second supply pump 16 is controlled based on the (second reaction information) (control step). Thereby, a polyamic acid having desired properties (viscosity) can be obtained.

Here, for example, the method for producing the polyamic acid in the present embodiment may be a part of the method for producing the polyimide. In this case, the method for producing a polyimide further includes an imidization step of imidizing the polyamic acid.
When the polymer production system 1 produces polyimide, the cushion tank 40 may be omitted, and liquid may be fed from the tubular mixing section 30 to the imidization section. However, as described above, it is preferable to temporarily store the polyamic acid in the cushion tank 40.

According to the polymer production system 1 of this embodiment, the following effects are exhibited.
The polymer production system 1 produces a polymer by using a first solution A1 containing a polyadditive first polymerizable compound and a second solution A2 containing a polyadditive second polymerizable compound as raw materials, 1st supply part 15 which supplies 1 solution A1, 2nd supply part 16 which supplies 2nd solution A2, 1st solution A1 and 2nd solution A2 are agitated in the state of contacting gas, and a polymerization reaction is carried out. The first flow tank type mixing tank type mixing in which the first stirring tank mixed solution B is generated by advancing, and the first solution A1 and the second solution A2 are continuously received and the first stirring tank mixed solution B is taken out. Part 20, a third supply part 22 for supplying the first stirred tank mixed solution B, and a downstream side of the first flow type stirred tank mixed part 20, and the first stirred tank mixed solution B is stirred to polymerize. And a tubular mixing section 30 for producing a tubular mixed solution C by further advancing the reaction. In this way, in the first flow type stirring tank type mixing unit 20 arranged in the preceding stage, the polymerization reaction is allowed to proceed in a temporarily open state, so that a high discharge pressure or a highly accurate expensive pump is not used. The raw material can be stably supplied by the first supply pump 15 and the second supply pump 16, and the viscosity and concentration of the polymer can be stabilized. Further, since the heat generation due to the polymerization reaction becomes steady by advancing the polymerization reaction stepwise, it is possible to stabilize the viscosity and concentration of the polymer by easily controlling the temperature. Therefore, it is possible to continuously and stably obtain a desired polymer without using an expensive pump.

In addition, in the polymer production system 1, the first supply pump 15 and/or the second supply pump 16 is configured to include a metering pump. In the present embodiment, since the polymerization reaction is allowed to proceed in a temporarily open state by the first flow type stirring tank type mixing unit 20 arranged in the preceding stage, a metering pump (first By using the first supply pump 15 and/or the second supply pump 16), the first solution A1 and/or the second solution A2 can be easily supplied. Moreover, since it is not necessary to use a high-precision pump, the mixing ratio of the first solution A1 and the second solution A2 can be easily adjusted. Therefore, it is possible to continuously and stably obtain a desired polymer.

Further, in the polymer production system 1, the first viscosity information (first reaction information) acquired by the first viscosity measurement unit 222 (measurement unit) and/or the second viscosity measurement unit 322 (measurement unit) acquired. The supply in the first supply pump 15 and/or the second supply pump 16 is controlled based on the second viscosity information (second reaction information). Thereby, a polymer having desired properties (viscosity) can be obtained.

In the present embodiment, one of the first polymerizable compound and the second polymerizable compound is a tetracarboxylic acid dianhydride, the other is a diamine, and a case of producing a polyamic acid as a polymer has been described. It is not limited to this.
For example, one of the first polymerizable compound and the second polymerizable compound is a polyamic acid (prepolymer) having an acid anhydride group terminal or an amino group terminal, and the other is a diamine or tetracarboxylic acid dianhydride, and a polymer is obtained. You may make it produce a polyamic acid. In this case, one of the first polymerizable compound and the second polymerizable compound is a polyamic acid having an acid anhydride group terminal, and the other is a diamine. When one of the first polymerizable compound and the second polymerizable compound is an amino group-terminated polyamic acid, the other is a tetracarboxylic dianhydride.
In addition, for example, of the first polymerizable compound and the second polymerizable compound, one is a polyamic acid having an acid anhydride group terminal or an amino group terminal and the other is a polyamic acid having an amino group terminal or an acid anhydride group terminal. You may make it produce a polyamic acid as a united body. In this case, one of the first polymerizable compound and the second polymerizable compound is a polyamic acid having an acid anhydride group terminal, and the other is a polyamic acid having an amino group terminal.

<Second Embodiment>
Next, referring to FIG. 2, a polymer production system according to the second embodiment will be described. FIG. 2 is a diagram showing a polymer production system according to the second embodiment. The second embodiment is mainly different from the first embodiment in that the third solution A3 is additionally supplied in the middle of the liquid transfer line L of the first embodiment. In addition, in the second embodiment, detailed description of the same configuration as the first embodiment will be omitted.

A polymer production system 1A according to the second embodiment will be described with reference to FIG.
In the polymer production system 1A of the second embodiment, the second flow type stirring tank type mixing unit 50 is arranged in the middle of the liquid feeding line L, and the third solution A3 is supplied in the second flow type stirring tank type mixing unit 50. Additional supply.
In the polymer production system 1A of the second embodiment, the first stirring tank mixed solution B generated by the first circulation type stirring tank type mixing unit 20 of the first embodiment and the third solution A3 as the raw material are secondly distributed. The second stirring tank mixed solution D is generated by agitating the polymerization stirring tank type mixing section 50 in a state of being in contact with gas to proceed the polymerization reaction, and the second stirring tank mixing solution D is stirred in the tube type mixing section 30. By further advancing the polymerization reaction, a tube mixed solution E is generated to produce a polyamic acid (polymer).

As shown in FIG. 2, the polymer production system 1A has, in addition to the configuration of the polymer production system 1 of the first embodiment, a second flow type stirring tank type mixing section 50 and a second stirring tank opening/closing valve 51. And a fifth supply pump 52 (fifth supply unit) and a fifth flow rate measurement unit 521. The polymer production system 1A further includes a third tank 13, a third tank opening/closing valve 131, an additional solution supply pump 17 (fourth supply section), and an additional solution flow rate measurement section 171. .. In addition, the liquid transfer line L further includes a fifth liquid transfer section L5 and a sixth liquid transfer section L6. Further, the polymer production system 1A further includes a third viscosity measuring unit 522.

The second flow type stirring tank type mixing unit 50 is connected to the downstream end of the third liquid feeding unit L3 of the first embodiment. The second stirred tank mixed solution D generated in the second flow type stirred tank type mixing section 50 is supplied to the tube type mixing section 30 described in the first embodiment via the fifth liquid feeding section L5.

In the second flow type stirring tank type mixing unit 50, the first stirring tank mixed solution B generated by the first flow type stirring tank type mixing unit 20 is supplied, and the third solution A3 is additionally supplied. The third solution A3 is stored in the third tank 13, and the third solution A3 is supplied to the second flow-type stirring tank type mixing unit 50 via the sixth liquid feeding unit L6.

The third tank 13 contains a third solution A3 containing a polyadditive third polymerizable compound. When the first polymerizable compound and the second polymerizable compound satisfy any of the following (a) to (c), the third polymerizable compound may be a tetracarboxylic acid dianhydride or a diamine. It may be a polyamic acid having a physical group terminal or an amino group terminal.
(A) Of the first polymerizable compound and the second polymerizable compound, one is tetracarboxylic dianhydride and the other is diamine.
(B) Of the first polymerizable compound and the second polymerizable compound, one is a polyamic acid having an acid anhydride group terminal or an amino group terminal, and the other is a diamine or a tetracarboxylic acid dianhydride.
(C) Of the first polymerizable compound and the second polymerizable compound, one is a polyamic acid having an acid anhydride group terminal or an amino group terminal, and the other is a polyamic acid having an amino group terminal or an acid anhydride group terminal. ..

The third polymerizable compound is appropriately selected so that the desired polyamic acid (polymer) is produced. For example, when the first polymerizable compound is tetracarboxylic dianhydride or acid anhydride group-terminated polyamic acid and the second polymerizable compound is diamine or amino group-terminated polyamic acid, the first polymerizable compound is If the amount is large, the third polymerizable compound is a diamine or amino group-terminated polyamic acid, and if the amount is large, the third polymerizable compound is a tetracarboxylic acid dianhydride or an acid anhydride group-terminated polyamic acid. Is.

The third tank opening/closing valve 131, the additional solution supply pump 17, and the additional solution flow rate measurement section 171 are provided on the upstream side between the third tank 13 and the tubular mixing section 30 in the sixth liquid sending section L6. Are arranged in this order from the downstream side.

The third tank opening/closing valve 131 is arranged near the third tank 13 in the sixth liquid sending section L6 and opens and closes the sixth liquid sending section L6 on the upstream side of the additional solution supply pump 17.

The additional solution supply pump 17 (fourth supply section) supplies the third solution A3 stored in the third tank 13 to the second flow-type stirring tank type mixing section 50. The additional solution supply pump 17 discharges the third solution A3 at a predetermined flow rate. For example, the additional solution supply pump 17 is adjusted to supply the third solution A3 under the condition that a polyamic acid having a desired property is obtained. The supply amount of the additional solution supply pump 17 can be set according to the properties and composition of the second stirred tank mixed solution D.
In the present embodiment, the additional solution supply pump 17 is composed of a metering pump, like the first supply pump 15 of the above-described first embodiment.

In the second embodiment, the supply of the third solution A3 additionally supplied by the additional solution supply pump 17 and the first stirring tank mixed solution B supplied by the third supply pump 22 should be controlled. Then, a polyamic acid having a desired property is obtained. Therefore, it is preferable that the supply accuracy of the third solution A3 and the first stirred tank mixed solution B is high. In the second embodiment, the additional solution supply pump 17 is configured as a metering pump, and the third supply pump 22 is also It consists of a metering pump.

The additional solution flow rate measuring unit 171 measures the flow rate of the third solution A3 on the downstream side of the additional solution supply pump 17 in the sixth liquid sending unit L6. In the present embodiment, the additional solution flow rate measuring unit 171 is arranged between the third tank 13 and the second flow-type stirring tank type mixing unit 50. The additional solution flow rate measuring unit 171 outputs the measured flow rate of the third solution A3 to the control unit 200A described later.
The second flow-type stirring tank type mixing unit 50 is arranged on the downstream side of the additional solution flow rate measuring unit 171.

The second flow type stirred tank type mixing unit 50 stirs the first stirred tank mixed solution B and the third solution A3 in a state of being in contact with a gas to allow the polymerization reaction to proceed, whereby the second stirred tank mixed solution D is obtained. To generate. The second flow type stirring tank type mixing unit 50 continuously receives the first stirring tank mixed solution B and the third solution A3 and takes out the second stirring tank mixed solution D.

In the second flow type stirring tank type mixing section 50, the polymerization reaction in the first stirring tank mixed solution B and the third solution A3 proceeds, and the second stirring tank mixed solution D is obtained. The viscosity of the second stirred tank mixed solution D is higher than that of the first stirred tank mixed solution B because the polymerization reaction of the second stirred tank mixed solution D is more advanced than that of the first stirred tank mixed solution B. The second stirred tank mixed solution D is sent to the tubular mixing section 30.

The second circulation type stirring tank type mixing unit 50 includes a stirring tank type reactor 501 and a plurality of second stirring blades 502 (second stirring members). The reactor 501 is composed of a stirring tank provided with a temperature control jacket. The second stirring blade 502 stirs the first stirring tank mixed solution B and the third solution A3 introduced into the reactor 501 to generate the second stirring tank mixed solution D. The second stirring blade 302 is a stirring member suitable for stirring a solution having a viscosity higher than that of the first stirring blade 202 of the first flow-type stirring tank type mixing unit 20. In the present embodiment, since the second flow type stirring tank type mixing unit 50 is arranged on the downstream side of the first flow type stirring tank type mixing unit 20 and the solution has a high viscosity, the second stirring blade is used. As 502, a stirring member having a higher viscosity than the first stirring blade 202 of the first flow type stirring tank type mixing unit 20 is used. As the stirring member for the viscosity higher than that of the first stirring blade 202 of the first flow type stirring tank type mixing section 20, for example, a helical ribbon blade can be cited.

The stirring member used for the second stirring blade 502 of the second flow type stirring tank type mixing unit 50 is not particularly limited, but one having high vertical circulation of the reaction solution and high mixing performance is preferable. As an example of the stirring member used in the low-viscosity region, the medium-viscosity region, and the high-viscosity region, the same stirring member as that shown in the first embodiment can be mentioned.

As the second stirring blade 502 in the present embodiment, for example, a stirring member for medium viscosity region may be used, or a stirring member for high viscosity region may be used. When a stirring member for the medium viscosity region is used for the second stirring blade 502 of the present embodiment, for example, a stirring member for the low viscosity region may be used as the first stirring blade 202. When a stirring member for the high viscosity region is used for the second stirring blade 502 of the present embodiment, for example, a stirring member for the low viscosity region may be used as the first stirring blade 202, and a medium viscosity Area stirring members may be used.

In the second flow type stirring tank type mixing unit 50 described above, in the open state, reception of the first stirring tank mixed solution B and the third solution A3 and removal of the second stirring tank mixed solution D are continuously performed. Meanwhile, the first stirring tank mixed solution B and the third solution A3 supplied to the reactor 501 are stirred by the second stirring blade 502. The 2nd stirring tank mixed solution D produced by stirring the 1st stirring tank mixed solution B and the 3rd solution A3, and advancing a polymerization reaction is demonstrated in 1st Embodiment via the 5th liquid sending part L5. It is supplied to the tubular mixing section 30.

The fifth liquid feeding unit L5 is a line that connects the second flow type stirring tank type mixing unit 50 and the pipe type mixing unit 30. A second stirring tank opening/closing valve 51, a fifth supply pump 52 (fifth supply section), between the second flow type stirring tank type mixing section 50 and the tube mixing section 30 in the fifth liquid feeding section L5. The fifth flow rate measurement unit 521 is arranged in this order from the upstream side to the downstream side.

The second stirring tank opening/closing valve 51 is arranged near the lower portion of the second flow-type stirring tank type mixing section 50 in the fifth liquid feeding section L5, and on the upstream side of the fifth supply pump 52, the fifth liquid feeding section L5. Open and close. The control unit 200A, which will be described later, controls the opening/closing operation of the second stirring tank opening/closing valve 51 and the discharge flow rate of the fifth supply pump 52 so that the solution stays in the second flow-type stirring tank type mixing unit 50 for a residence time. To control.

The fifth supply pump 52 supplies the second stirring tank mixed solution D housed in the second flow type stirring tank mixing section 50 to the tube mixing section 30. The fifth supply pump 52 discharges the second stirred tank mixed solution D at a predetermined flow rate. If necessary, an inline defoaming device may be installed upstream of the fifth supply pump 52.
In the present embodiment, the fifth supply pump 52 pushes the second stirred tank mixed solution D into the tubular mixing section 30 to transfer the tube mixed solution E, similarly to the third supply pump 22 of the first embodiment described above. It suffices if it can be continuously extracted, and high-precision supply is not required. Therefore, unlike the first supply pump 15 and the second supply pump 16 described above, the fifth supply pump 52 does not have to be a metering pump. It is not excluded that the fifth supply pump 52 is a metering pump, and the fifth supply pump 52 may be a metering pump.

The fifth flow rate measuring unit 521 measures the flow rate of the second stirred tank mixed solution D on the downstream side of the fifth supply pump 52 in the fifth liquid feeding unit L5. In the present embodiment, the fifth flow rate measurement unit 521 is arranged between the fifth supply pump 52 and the tubular mixing unit 30. The fifth flow rate measurement unit 521 outputs the measured flow rate of the second stirred tank mixed solution D to the control unit 200A described later.

The third viscosity measuring unit 522 acquires the viscosity information of the second stirred tank mixed solution D between the fifth flow rate measuring unit 521 and the tubular mixing unit 30 in the fifth liquid feeding unit L5. Since the viscosity increases as the polymerization reaction progresses, the viscosity information is effective information as reaction information. The third viscosity measuring unit 522 outputs the acquired viscosity information of the second stirred tank mixed solution D to the control unit 200A described later.

In addition, the 3rd viscosity measurement part 522 of this embodiment is related with the physical quantity and/or composition in the 2nd stirring tank mixed solution D similarly to the 1st viscosity measurement part 222 and the 2nd viscosity measurement part 322 of 1st Embodiment. It is an example of a measurement unit that acquires reaction information.

The control unit 200A will be described. In addition to the configuration connected to the control unit 200 of the first embodiment, the control unit 200A includes an additional solution supply pump 17 (fourth supply unit), a fifth supply pump 52 (fifth supply unit), and an additional solution. Flow rate measuring unit 171, fifth flow rate measuring unit 521, second stirring tank opening/closing valve 51, third viscosity measuring unit 522, and second viscosity measuring unit 322 are electrically connected. In the present specification, illustration of control lines from the control unit 200A to each pump, each measurement unit, and each valve is omitted.

The control unit 200A includes the first viscosity information (first reaction information) acquired by the first viscosity measurement unit 222 (measurement unit) and the second viscosity information (first reaction information) acquired by the second viscosity measurement unit 322 (measurement unit). 2 reaction information) and/or based on the third viscosity information (third reaction information) acquired by the third viscosity measurement unit 522 (measurement unit), in the third supply pump 22 and/or the additional solution supply pump 17 Control supply. Thereby, a polyamic acid having desired properties (viscosity) can be obtained.
Note that the control unit 200A also has the function of the control unit 200 in the first embodiment, but detailed description of portions common to the control unit 200 will be omitted.

Next, the operation of the polymer production system 1A according to the second embodiment will be described. The description of the same operation as that of the polymer production system 1 in the first embodiment is omitted.
In the polymer production system 1A, the first stirring tank mixed solution B generated in the first flow type stirring tank type mixing unit 20 described in the first embodiment is supplied to the third liquid by the supply operation of the third supply pump 22. The part L3 is fed and supplied to the second flow type stirring tank type mixing part 50 (third supplying step).
Further, the additional solution supply pump 17 supplies the third solution A3 to the second flow type stirring tank type mixing section 50 (fourth supply step).

Here, the third supply pump 22 and the additional solution supply pump 17 have the first viscosity information (first reaction information) and the second viscosity measurement unit 322 (measurement) acquired by the first viscosity measurement unit 222 (measurement unit). Part) based on the second viscosity information (second reaction information) and/or the third viscosity measuring unit 522 (measuring unit) based on the third viscosity information (third reaction information), the first stirring The mutual discharge flow rates are controlled by the control unit 200A so that the tank mixed solution B and the third solution A3 are supplied at a desired ratio. The discharge flow rate of the additional solution supply pump 17 is controlled by the control unit 200A so as to supply the third solution A3 at a desired ratio.

In the second flow type stirred tank type mixing unit 50, the second stirred tank mixed solution D is generated by advancing the polymerization reaction of the first stirred tank mixed solution B and the third solution A3 (second stirred tank mixing Process).

The second stirred tank mixed solution D is fed by the fifth feeding pump 52 to the fifth liquid feeding section L5 and is fed to the tubular mixing section 30 (fifth feeding step). In the tube type mixing section 30, the tube mixing solution E is generated by further advancing the polymerization reaction of the second stirring tank mixed solution D and the third solution A3 (tube mixing step). The tube mixed solution E generated in the tube type mixing section 30 is supplied to the cushion tank 40 after being sent to the fourth solution sending section L4.

According to the polymer production system 1A of the present embodiment, the following effects are exhibited in addition to the effects of the first embodiment described above.
The polymer production system 1A includes an additional solution supply pump 17 for supplying a third solution A3 containing a polyadditive third polymerizable compound, a first flow type stirring tank type mixing section 20, and a tube type mixing section 30. And the first stirring tank mixed solution B and the third solution A3 are stirred in a state of being in contact with gas to allow the polymerization reaction to proceed, thereby producing the second stirring tank mixed solution D and the first stirring tank. A second flow type stirring tank type mixing section 50 for continuously receiving the tank mixing solution B and the third solution A3 and taking out the second stirring tank mixing solution D, and supplying the second stirring tank mixing solution D 5 supply pump 52 is further provided, and the tubular mixing section 30 produces the tubular mixed solution E by stirring the second stirred tank mixed solution D to further advance the polymerization reaction. As a result, by additionally supplying the third solution A3 in the second flow type stirring tank type mixing section 50, a polymer having desired properties can be obtained.

Further, in the polymer production system 1A, the first viscosity information (first reaction information) obtained by the first viscosity measuring unit 222 (measuring unit) and/or the second viscosity measuring unit 322 (measuring unit) obtained. The supply in the third supply pump 22 and/or the additional solution supply pump 17 is controlled based on the second viscosity information (second reaction information). Thereby, a polymer having desired properties (viscosity) can be obtained.

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

For example, in the above-described embodiment, the polymer production system is configured to perform two-stage mixing in the first flow-type stirring tank type mixing section and the tubular mixing section in the first embodiment, and in the second embodiment. The first flow type stirring tank type mixing unit, the second flow type stirring tank type mixing unit, and the tube type mixing unit were configured to perform three-stage mixing. However, it is not limited to this. You may have the structure which mixes 4 or more steps. That is, the polymer production system is not limited to a system in which two-stage and three-stage mixing is performed, and may be a system in which four or more stages of mixing are performed. For example, in the polymer production system, one or more stages of the flow type stirring tank type mixing unit or the pipe type mixing unit are provided between the first flow type stirring tank type mixing unit 20 and the pipe type mixing unit 30. Alternatively, a single stage or a plurality of stages of a flow type stirring tank type mixing unit or a pipe type mixing unit may be provided on the downstream side of the pipe type mixing unit. The polymer production system is designed so that the desired polymer can be continuously and stably prepared without using a high discharge pressure or a high-precision and expensive pump by temporarily opening the flow-type stirring tank type mixing section. It is possible to obtain.

Moreover, in the above-mentioned embodiment, although the polymer manufacturing system which manufactures polyamic acid or a polyimide was demonstrated, the polymer manufactured is not limited to these. For example, the polymer production system may be one that produces a polymer using a polyaddition monomer such as a urethane monomer or an epoxy monomer.

Moreover, in the above-described embodiment, the viscosity measuring unit acquires the viscosity information regarding the viscosities of the first stirred tank mixed solution B, the tube mixed solutions C and E, and/or the second stirred tank mixed solution D, and the acquired viscosity. Although the residence time was controlled and the supply amounts of the solutions A1, A2 and A3 were controlled based on the information, the present invention is not limited to this. For example, the absorbance information regarding the absorbance of the first stirring tank mixed solution B, the tube mixed solutions C and E, and/or the second stirring tank mixed solution D is acquired, and the residence time is controlled based on the acquired absorbance information. The supply amounts of the solutions A1, A2 and A3 may be controlled.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

<Example 1>
In Example 1, a polyamic acid was produced using the polymer production system 1 having the structure shown in FIG. In the first tank 11, a first solution prepared by dissolving a polyamic acid having an acid anhydride group terminal obtained by the reaction of 4,4′-diaminodiphenyl ether and pyromellitic dianhydride in N,N-dimethylformamide. A1 was housed. Further, the second tank 12 contained the second solution A2 in which p-phenylenediamine was dissolved in N,N-dimethylformamide. The first flow type stirring tank type mixing section 20 was a stirring tank having a jacket for temperature control, and the first stirring blade 202 was an inclined paddle. A Kenics mixer type static mixer was used as the tube type mixing unit 30.

First, in the first flow type stirring tank type mixing unit 20, the first solution A1 supplied by the first supply pump 15 and the second solution A2 supplied by the second supply pump 16 are mixed and reacted, A one-stirred tank mixed solution B was produced. Then, the first stirred tank mixed solution B supplied by the third supply pump 22 is continuously supplied to the tubular mixing section 30, and further reaction is allowed to proceed in the tubular mixing section 30. Continuously withdrawing was performed by extruding, and 900 poise of tube mixed solution C was continuously obtained.

<Example 2>
In Example 2, a polyamic acid was produced using the polymer production system 1A having the structure shown in FIG. In the first tank 11, a first solution prepared by dissolving a polyamic acid having an acid anhydride group terminal obtained by the reaction of 4,4′-diaminodiphenyl ether and pyromellitic dianhydride in N,N-dimethylformamide. A1 was housed. Further, the second tank 12 contained the second solution A2 in which p-phenylenediamine was dissolved in N,N-dimethylformamide. Further, the third tank 13 contained a third solution A3 in which p-phenylenediamine was dissolved in N,N-dimethylformamide. The first flow type stirring tank type mixing section 20 was a stirring tank having a jacket for temperature control, and the first stirring blade 202 was an inclined paddle. The second circulation type stirring tank type mixing section 50 is a stirring tank having a jacket for temperature control, and the second stirring blade 502 is a helical ribbon blade. A Kenics mixer type static mixer was used as the tube type mixing unit 30.

First, in the first flow type stirring tank type mixing unit 20, the first solution A1 supplied by the first supply pump 15 and the second solution A2 supplied by the second supply pump 16 are mixed and reacted, A one-stirred tank mixed solution B was produced. Then, the first stirred tank mixed solution B supplied by the third supply pump 22 and the third solution A3 supplied by the additional solution supply pump 17 are continuously supplied to the second flow type stirred tank type mixing unit 50. Then, the second stirred tank mixed solution D is generated, and the second stirred tank mixed solution D supplied by the fifth supply pump 52 is continuously supplied to the tubular mixing section 30, and further reaction is performed in the tubular mixing section 30. Was continuously carried out, and extraction was continuously carried out by extrusion by the supply of the fifth supply pump 52 to continuously obtain 3500 poises of the tube mixed solution E.

1, 1A Polymer Manufacturing System 15 First Supply Pump (First Supply Section)
16 Second supply pump (second supply section)
17 Supply pump for additional solution (4th supply part)
20 1st flow type stirring tank type mixing section 22 3rd supply pump (3rd supply section)
30 Tube Type Mixing Section 50 Second Flow Stirring Tank Type Mixing Section 52 Fifth Supply Pump (Fifth Supply Section)
200, 200A Control unit 222 First viscosity measuring unit 322 Second viscosity measuring unit A1 First solution A2 Second solution A3 Third solution B First stirring tank mixed solution C Tube mixed solution D Second stirring tank mixed solution E Tube mixed Solution L liquid transfer line

Claims (20)

A polymer production system for producing a polymer using a first solution containing a polyadditive first polymerizable compound and a second solution containing a polyadditive second polymerizable compound as raw materials,
A first supply unit for supplying the first solution;
A second supply unit for supplying the second solution;
The first solution and the second solution are stirred in a state of being in contact with a gas to allow a polymerization reaction to proceed, thereby producing a first stirred tank mixed solution, and receiving the first solution and the second solution and A first flow type stirring tank type mixing section for continuously taking out the first stirring tank mixed solution;
A third supply unit for supplying the first stirred tank mixed solution;
And a tube type mixing section which is disposed on the downstream side of the first flow type stirring tank type mixing section and which generates a tube mixed solution by further stirring the first stirring tank mixed solution to further advance the polymerization reaction. Polymer manufacturing system. The polymer production system according to claim 1, wherein the first supply unit and/or the second supply unit includes a metering pump. A fourth supply part for supplying a third solution containing a polyadditive third polymerizable compound,
It is arranged between the first flow type stirring tank type mixing section and the tube type mixing section, and the first stirring tank mixed solution and the third solution are stirred in a state of being in contact with gas to proceed a polymerization reaction. A second flow-type stirring tank type, in which a second stirring tank mixed solution is generated by performing the above, and the first stirring tank mixed solution and the third solution are continuously received and the second stirring tank mixed solution is taken out continuously. A mixing section,
A fifth supply unit for supplying the second stirred tank mixed solution,
The polymer production system according to claim 1 or 2, wherein the tubular mixing section produces the tubular mixed solution by stirring the second stirred tank mixed solution to further advance a polymerization reaction. The polymer manufacturing system according to claim 3, wherein the third supply unit and/or the fourth supply unit includes a metering pump. A measurement unit that acquires reaction information regarding a physical quantity and/or composition in any one or more of the first stirred tank mixed solution and the tube mixed solution;
The control part which controls the supply in the said 1st supply part and/or said 2nd supply part based on the reaction information acquired by the said measurement part, It further comprises any one of Claims 1-4. Polymer manufacturing system. The measuring unit includes a viscometer, a pressure gauge, a pump pressure gauge, an absorptiometer, an infrared spectrometer, a near infrared spectrometer, a density meter, a color difference meter, a refractometer, a spectrophotometer, a conductivity meter, a turbidimeter, The polymer production system according to claim 5, wherein the polymer production system comprises one or more selected from the group consisting of a fluorescent X-ray analyzer. The polymer production system according to claim 1 or 2, wherein the first polymerizable compound and the second polymerizable compound satisfy any of the following (a) to (c) and produce a polyamic acid as the polymer.
(A) Of the first polymerizable compound and the second polymerizable compound, one is tetracarboxylic dianhydride and the other is diamine.
(B) Of the first polymerizable compound and the second polymerizable compound, one is a polyamic acid having an acid anhydride group terminal or an amino group terminal, and the other is a diamine or a tetracarboxylic acid dianhydride.
(C) Of the first polymerizable compound and the second polymerizable compound, one is a polyamic acid having an acid anhydride group terminal or an amino group terminal and the other is a polyamic acid having an amino group terminal or an acid anhydride group terminal. Is. The first polymerizable compound and the second polymerizable compound satisfy any of the following (a) to (c), the third polymerizable compound is tetracarboxylic acid dianhydride or diamine, as the polymer The polymer production system according to claim 3, which produces a polyamic acid.
(A) Of the first polymerizable compound and the second polymerizable compound, one is tetracarboxylic dianhydride and the other is diamine.
(B) Of the first polymerizable compound and the second polymerizable compound, one is a polyamic acid having an acid anhydride group terminal or an amino group terminal, and the other is a diamine or a tetracarboxylic acid dianhydride.
(C) Of the first polymerizable compound and the second polymerizable compound, one is a polyamic acid having an acid anhydride group terminal or an amino group terminal and the other is a polyamic acid having an amino group terminal or an acid anhydride group terminal. Is. The first polymerizable compound and the second polymerizable compound satisfy any of the following (a) ~ (c), the third polymerizable compound is an acid anhydride group terminal or amino group terminal polyamic acid, The polymer production system according to claim 3 or 4, which produces polyamic acid as the polymer.
(A) Of the first polymerizable compound and the second polymerizable compound, one is tetracarboxylic dianhydride and the other is diamine.
(B) Of the first polymerizable compound and the second polymerizable compound, one is a polyamic acid having an acid anhydride group terminal or an amino group terminal, and the other is a diamine or a tetracarboxylic acid dianhydride.
(C) Of the first polymerizable compound and the second polymerizable compound, one is a polyamic acid having an acid anhydride group terminal or an amino group terminal and the other is a polyamic acid having an amino group terminal or an acid anhydride group terminal. Is. The polymer production system according to any one of claims 7 to 9, further comprising an imidization part for imidizing the produced polyamic acid, and producing polyimide as the polymer. A method for producing a polymer, which comprises producing a polymer using a first solution containing a polyadditive first polymerizable compound and a second solution containing a polyadditive second polymerizable compound as raw materials,
A first supplying step of supplying the first solution,
A second supply step of supplying the second solution;
In the first flow type stirring tank type mixing section, the first solution and the second solution are stirred in a state of being in contact with gas to promote a polymerization reaction to generate a first stirring tank mixed solution, A first stirring tank mixing step of continuously receiving one solution and the second solution and taking out the first stirring tank mixed solution;
A third supply step of supplying the first stirred tank mixed solution,
A tube mixing step of producing a tube mixed solution by further advancing the polymerization reaction by stirring the first stirred tank mixed solution in the tube type mixing section. The method for producing a polymer according to claim 11, wherein in the first supply step and/or the second supply step, the first solution and/or the second solution is supplied by a metering pump. A fourth supplying step of supplying a third solution containing a polyadditive third polymerizable compound,
In the second circulation type stirring tank type mixing section, the first stirring tank mixed solution and the third solution are stirred in a state of being in contact with gas to allow the polymerization reaction to proceed to generate a second stirring tank mixed solution. A second stirring tank mixing step of continuously receiving the first stirring tank mixed solution and the third solution and taking out the second stirring tank mixed solution,
And a fifth supplying step of supplying the second stirred tank mixed solution,
The method for producing a polymer according to claim 11 or 12, wherein in the tube mixing step, the tube mixed solution is produced by stirring the second stirred tank mixed solution to further advance a polymerization reaction. The method for producing a polymer according to claim 13, wherein in the third supply step and/or the fourth supply step, the first stirred tank mixed solution and/or the third solution is supplied by a metering pump. A measurement step of obtaining reaction information regarding a physical quantity and/or composition in any one or more of the first stirred tank mixed solution and the tube mixed solution;
The control process which controls the supply in the said 1st supply process and/or said 2nd supply process based on the reaction information acquired by the said measurement process, It further contains any one of Claims 11-14. A method for producing the polymer. In the measuring step, a viscometer, a pressure gauge, a pump pressure gauge, an absorptiometer, an infrared spectrometer, a near infrared spectrometer, a density meter, a color difference meter, a refractometer, a spectrophotometer, a conductivity meter, a turbidimeter, 16. The method for producing a polymer according to claim 15, wherein the reaction information is acquired by one or more selected from the group consisting of an X-ray fluorescence analyzer. The method for producing a polymer according to claim 11 or 12, wherein the first polymerizable compound and the second polymerizable compound satisfy any of the following (a) to (c), and a polyamic acid is produced as the polymer. ..
(A) Of the first polymerizable compound and the second polymerizable compound, one is tetracarboxylic dianhydride and the other is diamine.
(B) Of the first polymerizable compound and the second polymerizable compound, one is a polyamic acid having an acid anhydride group terminal or an amino group terminal, and the other is a diamine or a tetracarboxylic acid dianhydride.
(C) Of the first polymerizable compound and the second polymerizable compound, one is a polyamic acid having an acid anhydride group terminal or an amino group terminal and the other is a polyamic acid having an amino group terminal or an acid anhydride group terminal. Is. The first polymerizable compound and the second polymerizable compound satisfy any of the following (a) to (c), the third polymerizable compound is tetracarboxylic acid dianhydride or diamine, as the polymer The method for producing a polymer according to claim 13 or 14, which comprises producing a polyamic acid.
(A) Of the first polymerizable compound and the second polymerizable compound, one is tetracarboxylic dianhydride and the other is diamine.
(B) Of the first polymerizable compound and the second polymerizable compound, one is a polyamic acid having an acid anhydride group terminal or an amino group terminal, and the other is a diamine or a tetracarboxylic acid dianhydride.
(C) Of the first polymerizable compound and the second polymerizable compound, one is a polyamic acid having an acid anhydride group terminal or an amino group terminal and the other is a polyamic acid having an amino group terminal or an acid anhydride group terminal. Is. The first polymerizable compound and the second polymerizable compound satisfy any of the following (a) ~ (c), the third polymerizable compound is an acid anhydride group terminal or amino group terminal polyamic acid, The method for producing a polymer according to claim 13 or 14, wherein a polyamic acid is produced as the polymer.
(A) Of the first polymerizable compound and the second polymerizable compound, one is tetracarboxylic dianhydride and the other is diamine.
(B) Of the first polymerizable compound and the second polymerizable compound, one is a polyamic acid having an acid anhydride group terminal or an amino group terminal, and the other is a diamine or a tetracarboxylic acid dianhydride.
(C) Of the first polymerizable compound and the second polymerizable compound, one is a polyamic acid having an acid anhydride group terminal or an amino group terminal and the other is a polyamic acid having an amino group terminal or an acid anhydride group terminal. Is. The method for producing a polymer according to claim 17, further comprising an imidization step of imidizing the produced polyamic acid to produce a polyimide as the polymer.

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