JP2021024893A - Manufacturing system and manufacturing method of polymer - Google Patents

Abstract

To provide a manufacturing system and a manufacturing method of polymers, capable of continuously and stably manufacturing polymers, and capable of suppressing the occurrence of air bubbles in manufacturing.SOLUTION: A manufacturing system 1 of polymers, in which at least one of a first liquid A1 containing a first polyaddition-type polymerizable compound and a second liquid A2 containing a second polyaddition-type polymerizable compound is in a slurry state comprises: a first liquid supply part 112 for supplying the first liquid A1; a second liquid supply part 122 for supplying the second liquid A2; a first joining part J1 for joining the first liquid A1 and the second liquid A2 to generate a first joint mixed liquid B; and a first tubular mixing part 20 arranged at a downstream side of the first joining part J1, and generating a first tubular mixed liquid C by stirring the first joint mixed liquid B in a state of not contacting gas and progressing a polymerization reaction.SELECTED DRAWING: Figure 1

Description

The present invention relates to a polymer production system and a production method. In particular, 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 method for producing a polymer using a stirring tank has been known. In the batch method, the raw material liquid injected into the stirring tank is stirred to proceed with the polymerization reaction, but in this case, the gas phase at the upper part of the stirring tank is caught in the liquid phase by the stirring. Bubbles are contained in the polymerization solution. Then, when cast for producing a polyimide film using a polyamic acid, if air bubbles remain in the polymerization solution, a film defect occurs. The presence of air bubbles in the polymer solution poses a major quality problem.

On the other hand, for example, an efficient degassing method for a polymer solution has been proposed (see, for example, Patent Document 1). However, since the method disclosed in Patent Document 1 requires decompression equipment, there are cases where a high equipment cost is required for implementation. In addition, this method requires a long degassing time, which may reduce productivity.

Further, as a continuous method for producing a polyamic acid, for example, a method for producing fine particles of a polyamic acid (polyamic acid) using a tubular reactor or the like is known (see, for example, Patent Document 2). ..

Japanese Patent No. 2741208 JP-A-2006-249380

As described above, the batch manufacturing method using the stirring tank has a problem of generating bubbles. On the other hand, when a tubular reactor such as a tube is used as in the method disclosed in Patent Document 2, there are few problems related to the generation of bubbles.

However, although the method disclosed in Patent Document 2 is suitable for producing fine particles of polyamic acid, when polyamic acid is produced in a state of being dissolved in a liquid, the desired polyamic acid can be stably produced. There was a problem that it was difficult to obtain.

An object of the present invention is to provide a polymer production system and a production method capable of continuously and stably producing a polymer and suppressing the generation of bubbles during production.

Specific means for solving the above problems include the following embodiments.
<1> 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.
At least one of the first liquid and the second liquid is in the form of a slurry.
The first liquid supply unit that supplies the first liquid and
The second liquid supply unit that supplies the second liquid and
A first merging portion that merges the first liquid and the second liquid to generate a first merging mixed liquid.
With the first tube type mixing section which is arranged on the downstream side of the first merging section and produces the first tube mixed solution by stirring the first merging mixed solution in a state where it does not come into contact with the gas and advancing the polymerization reaction. A polymer production system comprising.

<2> Arranged on the downstream side of the first tube type mixing portion, the first tube mixed solution is stirred in a state of being in contact with a gas to generate a first stirring tank mixed solution, and the first tube mixed solution is prepared. The polymer production system according to <1>, further comprising a first flow type stirring tank type mixing unit that continuously receives and takes out the first stirring tank mixed liquid.

<3> A third liquid supply unit that supplies a slurry-like or solution-like third liquid containing a polyadditive third polymerizable compound, and a third liquid supply unit.
A second merging section that merges the first tube mixed liquid and the third liquid to generate a second merging mixed liquid, and
A second tube type mixing section which is arranged on the downstream side of the second merging section and produces a second tube mixed solution by stirring the second merging mixed solution in a state where it does not come into contact with a gas and advancing the polymerization reaction. The polymer production system according to <1>, further comprising.

<4> The first tube type mixing section is arranged between the first tube type mixing section and the second merging section, and the first tube mixed solution is stirred in contact with a gas to generate a first stirring tank mixed solution. Further provided with a first flow type stirring tank type mixing unit that continuously receives the first pipe mixed liquid and takes out the first stirring tank mixed liquid.
The polymer production system according to <3>, wherein the second merging section merges the first stirring tank mixture and the third solution to generate the second merging mixture.

<5> Arranged on the downstream side of the second tube type mixing portion, the second tube mixed solution is stirred in a state of being in contact with a gas to generate a second stirring tank mixed solution, and the second tube mixed solution is produced. The polymer production system according to <3> or <4>, further comprising a second flow-type stirring tank type mixing unit that continuously receives and takes out the second stirring tank mixed liquid.

<6> The first polymerizable compound or the first polymerizable compound is arranged on the upstream side of the first liquid supply unit that supplies the first liquid in the form of a slurry or the second liquid supply part that supplies the second liquid in the form of a slurry. A slurry preparation unit that prepares the first liquid in the form of a slurry or the second liquid in the form of a slurry by stirring the second polymerizable compound together with a dispersion medium.
Any one of <1> to <5>, which is arranged on the downstream side of the slurry preparation unit and further includes a defoaming unit for defoaming the slurry-like first liquid or the slurry-like second liquid. The polymer production system according to.

<7> The method according to <1> or <2>, wherein the first polymerizable compound and the second polymerizable compound satisfy any of the following (a) and (b) to produce a polyamic acid as the polymer. Polymer production system.
(A) Of the first polymerizable compound and the second polymerizable compound, one is a tetracarboxylic dianhydride and the other is a diamine.
(B) Of the first polymerizable compound and the second polymerizable compound, one is an acid anhydride group-terminated or amino group-terminated polyamic acid, and the other is a diamine or tetracarboxylic dianhydride.

<8> The first polymerizable compound and the second polymerizable compound satisfy any of the following (a) and (b), and the third polymerizable compound is tetracarboxylic acid dianhydride or diamine. The polymer production system according to any one of <3> to <5>, which produces a polyamic acid as a polymer.
(A) Of the first polymerizable compound and the second polymerizable compound, one is a tetracarboxylic dianhydride and the other is a diamine.
(B) Of the first polymerizable compound and the second polymerizable compound, one is an acid anhydride group-terminated or amino group-terminated polyamic acid, and the other is a diamine or tetracarboxylic dianhydride.

<9> The first polymerizable compound and the second polymerizable compound satisfy any of the following (a) and (b), and the third polymerizable compound is an acid anhydride group-terminated or amino group-terminated polyamic acid. The polymer production system according to any one of <3> to <5>, wherein the polyamic acid is produced as the polymer.
(A) Of the first polymerizable compound and the second polymerizable compound, one is a tetracarboxylic dianhydride and the other is a diamine.
(B) Of the first polymerizable compound and the second polymerizable compound, one is an acid anhydride group-terminated or amino group-terminated polyamic acid, and the other is a diamine or tetracarboxylic dianhydride.

<10> The polymer production system according to any one of <7> to <9>, further comprising an imidizing portion for imidizing the produced polyamic acid, and producing polyimide as the polymer.

<11> A method for producing a polymer, wherein a polymer is produced using a first liquid containing a polyadditive first polymerizable compound and a second liquid containing a polyadditive second polymerizable compound as raw materials. ,
At least one of the first liquid and the second liquid is in the form of a slurry.
The first liquid supply step of supplying the first liquid and
In the second liquid supply step of supplying the second liquid and the first merging portion, the first merging step of merging the first liquid and the second liquid to generate a first merging mixed liquid, and
A polymer comprising a first tube mixing step of producing a first tube mixed solution by stirring the first merging mixed solution in a first tube type mixing section without contacting a gas to advance a polymerization reaction. Manufacturing method.

<12> In the first flow type stirring tank type mixing unit, the first pipe mixed liquid is stirred in a state of being in contact with a gas to generate a first stirring tank mixed liquid, and the first pipe mixed liquid is received and described above. The method for producing a polymer according to <11>, further comprising a first stirring tank mixing step of continuously taking out the first stirring tank mixture.

<13> A third liquid supply step of supplying a slurry-like or solution-like third liquid containing a polyadditive third polymerizable compound, and a third liquid supply step.
In the second merging section, a second merging step of merging the first tube mixed liquid and the third liquid to generate a second merging mixed liquid, and
In the second tube type mixing section, the second tube mixing step of producing the second tube mixed solution by stirring the second merging mixed solution in a state where it does not come into contact with the gas and advancing the polymerization reaction is further included. 11> The method for producing a polymer.

<14> In the first flow type stirring tank type mixing unit, the first pipe mixed liquid is stirred in a state of being in contact with a gas to generate a first stirring tank mixed liquid, and the first pipe mixed liquid is received and described above. The first stirring tank mixing step of continuously taking out the first stirring tank mixture is further included.
The method for producing a polymer according to <13>, wherein the second merging step is a method for producing the second merging mixed solution by merging the first stirring tank mixed solution and the third liquid.

<15> In the second flow type stirring tank type mixing unit, the second pipe mixed liquid is stirred in a state of being in contact with a gas to generate a second stirring tank mixed liquid, and the second pipe mixed liquid is received and described above. The method for producing a polymer according to <13> or <14>, further comprising a second stirring tank mixing step of continuously taking out the second stirring tank mixture.

<16> In the slurry preparation unit, the slurry preparation step of preparing the slurry-like first liquid or the slurry-like second liquid by stirring the first polymerizable compound or the second polymerizable compound together with a dispersion medium. When,
Item 2. The polymer according to any one of <11> to <15>, further comprising a defoaming step of defoaming the slurry-like first liquid or the slurry-like second liquid in the defoaming portion. Production method.

<17> The method according to <11> or <12>, wherein the first polymerizable compound and the second polymerizable compound satisfy any of the following (a) and (b) to produce a polyamic acid as the polymer. Method for producing polymer.
(A) Of the first polymerizable compound and the second polymerizable compound, one is a tetracarboxylic dianhydride and the other is a diamine.
(B) Of the first polymerizable compound and the second polymerizable compound, one is an acid anhydride group-terminated or amino group-terminated polyamic acid, and the other is a diamine or tetracarboxylic dianhydride.

<18> The first polymerizable compound and the second polymerizable compound satisfy any of the following (a) and (b), and the third polymerizable compound is tetracarboxylic acid dianhydride or diamine. The method for producing a polymer according to any one of <13> to <15>, which produces a polyamic acid as a polymer.
(A) Of the first polymerizable compound and the second polymerizable compound, one is a tetracarboxylic dianhydride and the other is a diamine.
(B) Of the first polymerizable compound and the second polymerizable compound, one is an acid anhydride group-terminated or amino group-terminated polyamic acid, and the other is a diamine or tetracarboxylic dianhydride.

<19> The first polymerizable compound and the second polymerizable compound satisfy any of the following (a) and (b), and the third polymerizable compound is an acid anhydride group-terminated or amino group-terminated polyamic acid. The method for producing a polymer according to any one of <13> to <15>, wherein the polyamic acid is produced as the polymer.
(A) Of the first polymerizable compound and the second polymerizable compound, one is a tetracarboxylic dianhydride and the other is a diamine.
(B) Of the first polymerizable compound and the second polymerizable compound, one is an acid anhydride group-terminated or amino group-terminated polyamic acid, and the other is a diamine or tetracarboxylic dianhydride.

<20> The method for producing a polymer according to any one of <17> to <19>, further comprising an imidization step of imidizing the produced polyamic acid, and producing 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 production system in 1st Embodiment. It is a figure which shows the polymer production system in 2nd Embodiment. It is a figure which shows the polymer production system in 3rd Embodiment. It is a figure which shows the polymer production system in 4th 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 tube type mixing unit. The second embodiment is an example of a polymer production system in which a first tube type mixing unit and a first flow type stirring tank type mixing unit are provided. The third embodiment includes a first tube type mixing part and a second tube type mixing part, and is a polymer manufacturing system in which a liquid is added between the first tube type mixing part and the second tube type mixing part. This is an example. In the fourth embodiment, the second tube type mixing section and the second flow type stirring tank type mixing section are further provided on the downstream side of the first tube type mixing section and the first flow type stirring tank type mixing section, and the first flow This is an example of a polymer production system in which a liquid is added between the stirring tank type mixing section and the second tube type mixing section.

Here, in the following embodiments, the "first tube type mixing section" or "second tube type mixing section" means a mixing section having a tubular reactor that mixes while flowing the liquid. Further, the "first flow type stirring tank type mixing unit" or "second flow type stirring tank type mixing unit" is a stirring tank type reaction in which mixing is performed while continuously receiving and taking out the liquid. It means a mixing part having a vessel.

<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 first embodiment is an example of a polymer production system in which a first tube type mixing unit is provided.
The polymer production system 1 is a production system for producing a polymer using a first liquid A1 containing a polyadditive first polymerizable compound and a second liquid A2 containing a polyadditive second polymerizable compound as raw materials. Is. In the present embodiment, as an example, a case where the first liquid A1 containing the first polymerizable compound is in the form of a slurry and the second liquid A2 containing the second polymerizable compound is in the form of a solution will be described.

In the present embodiment, the slurry-like first liquid A1 is a suspension in which the first polymerizable compound is dispersed in a dispersion medium. The second liquid A2 in the form of a solution is a solution in which the second polymerizable compound is dissolved in a solvent.

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

The tetracarboxylic dianhydride is not particularly limited, and the same tetracarboxylic dianhydride used in the conventional polyimide synthesis can be used. Specific examples of the tetracarboxylic dianhydride include 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2, 3,3', 4'-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 1,3-bis (2,3-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (2, 3-Dicarboxyphenoxy) benzene dianhydride, 2,3,3', 4'-benzophenonetetracarboxylic dianhydride, 2,2', 3,3'-benzophenonetetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,2', 6,6'-biphenyltetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, Anthracene-2,3,6,7-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, 2,2-bis (4-hydroxyphenyl) propanibenzoate-3 , 3', 4,4'-Arophilic tetracarboxylic dianhydride such as tetracarboxylic dianhydride; aliphatic tetracarboxylic dianhydride such as butane-1,2,3,4-tetracarboxylic dianhydride Dihydride; alicyclic tetracarboxylic dianhydride such as cyclobutane-1,2,3,4-tetracarboxylic dianhydride; thiophene-2,3,4,5-tetracarboxylic dianhydride, pyridine Examples thereof include heterocyclic tetracarboxylic dianhydrides such as −2,3,5,6-tetracarboxylic dianhydrides; and the like. As the tetracarboxylic dianhydride, one type may be used alone, or two or more types may be used in combination.

As the dispersion medium of the first solution A1, a medium having low solubility of tetracarboxylic dianhydride and high solubility of polyamic acid is used. Specific examples of the dispersion medium include amide-based dispersion media such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and acetanilide; Cyclic ester-based dispersion medium such as γ-butyrolactone; Chain ester-based dispersion medium such as ethyl acetate; Ketone-based dispersion medium such as 2-propanone, 3-pentanone, acetone, and methyl ethyl ketone; Ether-based dispersion medium such as tetrahydrofuran and dioxolane; Examples thereof include alcohol-based dispersion media such as methanol, ethanol and isopropanol; and aromatic hydrocarbon-based dispersion media such as toluene and xylene. Among these, an amide-based dispersion medium, a cyclic ester-based dispersion medium, and an ether-based dispersion medium having high solubility of polyamic acid are preferable. As the dispersion medium, one type may be used alone, or two or more types may be mixed. For example, the solubility of polyamic acids is improved by mixing a highly polar alcohol-based dispersion medium with a dispersion medium having relatively low solubility of polyamic acids such as acetone, ethyl acetate, methyl ethyl ketone, toluene, and xylene. It is also possible to let it.

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

The diamine is not particularly limited, and a diamine similar to that 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, and 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 sulphon, 3,4'-diaminodiphenyl sulphon, 3,3'-diaminodiphenyl sulphon, 4,4'-methylene-bis (2-chloroaniline), 3, 3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminodiphenylsulfide, 2,6-diaminotoluene, 2,4-diaminochlorobenzene, 1,2-diaminoanthraquinone, 1,4-diaminoanthraquinone, Aromatic diamines such as 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 4,4'-diaminobibenzyl; 1,2-diaminoethane, 1,4-diamino Aliphatic diamines such as butane, tetramethylenediamine and 1,10-diaminododecane; 1,4-diaminocyclohexane, 1,2-diaminocyclohexane, bis (4-aminocyclohexyl) methane, 4,4'-diaminodicyclohexylmethane and the like. Alicyclic diamines; heterocyclic diamines such as 3,4-diaminopyridine; and the like. One type of diamine may be used alone, or two or more types may be used in combination.

As the solvent of the second liquid A2, a solvent in which diamine and polyamic acid are dissolved is used. Specific examples of the solvent include amide-based solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and acetoanilide; γ- Cyclic ester solvents such as butyrolactone; Chain ester solvents such as ethyl acetate; Ketone solvents such as 2-propanone, 3-pentanone, acetone and methyl ethyl ketone; Ether solvents such as tetrahydrofuran and dioxolane; Methanol, ethanol, isopropanol and the like Alcohol-based solvent; aromatic hydrocarbon-based solvent such as toluene and xylene; and the like. Among these, amide-based solvents, cyclic ester-based solvents, and ether-based solvents, which have high solubility of polyamic acids, are preferable. As the solvent, one type may be used alone, or two or more types may be mixed. For example, improving the solubility of polyamic acid by mixing a highly polar alcohol solvent with a solvent having relatively low solubility of polyamic acid such as acetone, ethyl acetate, methyl ethyl ketone, toluene, and xylene. Is also possible.

As shown in FIG. 1, in the polymer production system 1, the first liquid A1 and the second liquid A2, which are raw materials, are merged and mixed at the first merging portion J1 to generate the first merging mixed liquid B, and the first merging mixed liquid B is produced. The 1-tube mixed solution B is stirred in the 1-tube type mixing section 20 to proceed with the polymerization reaction to produce the 1-tube mixed solution C to produce a polyamic acid (polymer).

In addition, the polymer production system 1 has a liquid feeding line L that connects the first tank 11 and the second tank 12 to the cushion tank CT, which will be described later.

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 slurry liquid preparation tank 10 (slurry preparation section), an on-off valve 101 for the preparation tank, a defoaming pump 102 (defoaming section), and a first tank 11. , 1st tank on-off valve 111, 2nd tank 12, 2nd tank on-off valve 121, 1st supply pump 112 (1st liquid supply unit), 2nd supply pump 122 (2nd liquid supply unit) ), The first confluence unit J1, the first tube type mixing unit 20, the cushion tank CT, the liquid feeding line L, and the control unit 200. The above-mentioned liquid feeding line L includes a slurry liquid feeding unit Ls, a first liquid feeding unit L1, a second liquid feeding unit L2, a third liquid feeding unit L3, and a fourth liquid feeding unit L4. .. In addition, the polymer production system 1 includes a first flow rate measuring unit 113, a second flow rate measuring unit 123, and a first viscosity measuring unit 222.

The slurry liquid preparation tank 10 is arranged on the upstream side of the first tank 11 described later. In the slurry liquid preparation tank 10, the powdery solid of the first polymerizable compound is stirred together with the dispersion medium, and the powdery solid is dispersed in the dispersion medium while being pulverized under high shear conditions, for example, in the tank. A first liquid A1 in the form of a slurry is prepared. The first liquid A1 prepared in the slurry liquid preparation tank 10 is supplied to the first tank 11 via the slurry liquid feeding unit Ls.

The defoaming pump 102 is arranged on the downstream side of the slurry liquid preparation tank 10 to defoam the first liquid A1 containing air bubbles to be fed to the slurry liquid feeding unit Ls, and also to defoam the first liquid A1 in the form of a slurry. It is sent out toward the first tank 11. The slurry-like first liquid A1 sent out by the defoaming pump 102 is supplied to the first tank 11. The defoaming pump 102 has both a defoaming function for defoaming the first liquid A1 mixed with bubbles and a liquid feeding function for feeding the first liquid A1.

The first tank 11 contains a slurry-like first liquid A1 containing the first polymerizable compound. In the present embodiment, the first tank 11 contains a slurry-like first liquid A1 containing a tetracarboxylic dianhydride. The first liquid A1 contained in the first tank 11 is supplied to the first merging portion J1 via the first liquid feeding portion L1.

Although not clearly shown in the figure, it is preferable that the first tank 11 is devised so as not to entrap air bubbles. For example, the first liquid A1 may flow in from the lower part of the first tank 11, the intubation may be inserted from the upper part of the first tank 11 to transmit the first liquid A1 to the wall surface, or the outlet may be in the liquid. By arranging it, it is preferable to prevent air bubbles from being caught.

The first liquid feeding unit L1 is a line connecting the first tank 11 and the first merging unit J1. A first tank on-off valve 111, a first supply pump 112, and a first flow rate measuring unit 113 are located between the first tank 11 and the first merging unit J1 in the first liquid feeding unit L1 from the upstream side to the downstream side. They are arranged in this order toward the side.

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

The first supply pump 112 (first liquid supply unit) supplies the first liquid A1 contained in the first tank 11 to the first confluence unit J1. The first supply pump 112 discharges the first liquid A1 at a predetermined flow rate. For example, the first supply pump 112 is adjusted to supply the first liquid A1 under the condition that a polyamic acid having desired properties can be obtained.

In the present embodiment, the first supply pump 112 is composed of a metering pump.
In the present embodiment, the supply of the first liquid A1 supplied by the first supply pump 112 and the second liquid A2 supplied by the second supply pump 122, which will be described later, is controlled to obtain desired properties. Obtain a polyamic acid. Therefore, it is preferable that the supply accuracy of the first liquid A1 and the second liquid A2 is high. In the present embodiment, the first supply pump 112 is composed of a metering pump, and the second supply pump 122, which will be described later, is also a metering pump. It is composed.

The metering pump is a positive displacement pump, which repeatedly delivers a fixed amount of liquid with high accuracy. In the first supply pump 112, the first liquid A1 in the form of a slurry is sent out. Therefore, as the metering pump used for the first supply pump 112, a pump capable of sending the first liquid A1 in a slurry form without clogging the pump is used, and for example, a diaphragm pump; a mono pump; a piston type pump; etc. Can be mentioned.

The first flow rate measuring unit 113 measures the flow rate of the first liquid A1 on the downstream side of the first supply pump 112 in the first liquid feeding unit L1. In the present embodiment, the first flow rate measuring unit 113 is arranged between the first supply pump 112 and the first merging unit J1. The first flow rate measuring unit 113 outputs the measured flow rate of the first liquid A1 to the control unit 200 described later.

The second tank 12 contains the second liquid A2 in the form of a solution in which the second polymerizable compound is dissolved. In the present embodiment, the second tank 12 contains the second liquid A2 in the form of a solution in which the diamine is dissolved. The second liquid A2 contained in the second tank 12 is supplied to the first merging portion J1 via the second liquid feeding portion L2.

The second liquid feeding unit L2 is a line connecting the second tank 12 and the first confluence unit J1. A second tank on-off valve 121, a second supply pump 122, and a second flow rate measuring unit 123 are located between the second tank 12 and the first merging unit J1 in the second liquid feeding unit L2 from the upstream side to the downstream side. They are arranged in this order toward the side.

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

The second supply pump 122 (second liquid supply unit) supplies the second liquid A2 contained in the second tank 12 to the first confluence unit J1. The second supply pump 122 discharges the second liquid A2 at a predetermined flow rate. For example, the second supply pump 122 is adjusted to supply the second liquid A2 under the condition that a polyamic acid having desired properties can be obtained.

In the present embodiment, the second supply pump 122 is composed of a metering pump for the same reason as the first supply pump 112 described above. Since the second liquid A2 is a solution, the second supply pump 122 does not have to be capable of sending a slurry-like liquid.

The metering pump is a positive displacement pump, which repeatedly delivers a fixed amount of solution with high accuracy. In the second supply pump 122, the second liquid A2 in the form of a solution is sent out. Therefore, as the metering pump used for the second supply pump 122, for example, an extrusion type reciprocating pump such as a plunger pump; a rotary pump such as a gear pump provided with gears; and the like can be mentioned.

The second flow rate measuring unit 123 measures the flow rate of the second liquid A2 on the downstream side of the second supply pump 122 in the second liquid feeding unit L2. In the present embodiment, the second flow rate measuring unit 123 is arranged between the second supply pump 122 and the first merging unit J1. The second flow rate measuring unit 123 outputs the measured flow rate of the second liquid A2 to the control unit 200 described later.

The first confluence J1 is arranged on the downstream side of the first supply pump 112 and the second supply pump 122. The first merging portion J1 merges and mixes the first liquid A1 and the second liquid A2 to generate the first merging mixed liquid B. In the first merging portion J1, the first liquid A1 and the second liquid A2 are merged in a state where they do not come into contact with the gas. The first merging portion J1 is composed of a merging valve that joins the first liquid A1 supplied by the first supply pump 15 and the second liquid A2 supplied by the second supply pump 16.

The first tube type mixing section 20 is arranged on the downstream side of the first merging section J1. The first tube type mixing unit 20 produces the first tube mixed solution C by stirring the first merging mixed solution B in a state where it is not in contact with the gas and proceeding the polymerization reaction.

The first tube-type mixing unit 20 includes a tube-type reactor composed of a double tube extending in a predetermined direction. The first tube type mixing unit 20 has a first tube type mixing and stirring unit 21 arranged inside in the radial direction and a first temperature adjusting unit 22 arranged outside in the radial direction. The first tube type mixing unit 20 is formed so that the first merging mixed liquid B flows with a desired residence time.

The first tube type mixing / stirring unit 21 stirs the first merging mixture B. In the present embodiment, the first tube type mixing / stirring unit 21 stirs the first merging mixture B adjusted to a temperature suitable for the polymerization reaction by the first temperature adjusting unit 22.

The first tube type mixing / stirring unit 21 includes, for example, a static mixer such as a static mixer, a nozzle, and an orifice, and a drive type mixer such as a centrifugal pump, a swirl pump, and an in-line mixer having stirring blades. It is preferably configured to include a stationary mixer, and more preferably it is configured to include a static mixer. A tube in which a twist tape is inserted (see [Fig. 19] and the like in Japanese Patent Application Laid-Open No. 2003-314982) can also obtain a stirring promoting effect in the same manner as the static mixer, but the static mixer has a more stirring promoting effect. Is preferable because

The static mixer is not particularly limited, and for example, a Kenics mixer type, a Sulzer SMV type, a Sulzer SMX type, a Ray Hi-mixer type, a Komax mixer type, a Lightnin mixer type, a Ross ISG type, a Ross ISG type, a Ross ISG type, a Bran & Love mixer, etc. Can be mentioned. Among these, the Kenics mixer type static mixer is more preferable because it has a simple structure and therefore has no dead space.

The first temperature adjusting unit 22 is a piping unit arranged on the outer side in the radial direction of the first pipe type mixing / stirring unit 21. The first temperature adjusting unit 22 adjusts the temperature (for example, cooling) of the first merging mixture B flowing through the first tube type mixing and stirring unit 21 to a desired temperature condition. In the first temperature adjusting unit 22, the first merging mixture B is adjusted to a temperature suitable for the polymerization reaction, and is circulated through the first tube type mixing and stirring unit 21.

The generated first tube mixed liquid C is supplied to the cushion tank CT via the fourth liquid feeding unit L4.

The first viscosity measuring unit 222 acquires the viscosity information of the first tube mixed liquid C between the first tube type mixing unit 20 and the cushion tank CT in the fourth liquid feeding unit L4. Since the viscosity increases as the polymerization reaction proceeds, the viscosity information is effective information as reaction information. The first viscosity measuring unit 222 outputs the acquired viscosity information of the first tube mixed solution C to the control unit 200 described later.

The first viscosity measuring unit 222 of the present embodiment is an example of a measuring unit that acquires reaction information regarding the physical quantity and / or composition of the first tube mixed solution C.

The measuring unit is not limited to the first viscosity measuring unit 222 (type of physical quantity and / or composition, measuring method) of the present embodiment. The measuring unit includes, for example, a viscometer, a pressure gauge, a pump pressure gauge, an absorbance meter, an infrared spectroscope, a near-infrared spectroscope, a densitometer, a color difference meter, a refractive index meter, a spectrophotometer, a conductivity meter, and a turbidity meter. , And one or more selected from the group consisting of fluorescent X-ray analyzers. The measuring unit acquires one or more reaction information regarding the physical quantity and / or composition of the measurement target, and outputs the acquired reaction information to the control unit 200 described later.

The cushion tank CT accommodates the first tube mixed liquid C from the first tube type mixing unit 20. The cushion tank CT is, for example, a tank for accommodating a raw material liquid when imidizing a polyamic acid which is a polymer to produce a polyimide.

Although not clearly shown in the figure, it is preferable that the cushion tank CT is devised so as not to entrap air bubbles. For example, the structure is such that the first stirring tank mixture D flows in from the lower part of the cushion tank CT, the intubation tube is inserted from the upper part of the cushion tank CT, and the first tube mixture C is transmitted to the wall surface, or the outlet is set. By arranging it in the liquid, it is preferable to prevent air bubbles from being entrained.

When the polymer production system 1 in the present embodiment produces polyimide, the polymer production system 1 further includes an imidization unit for imidizing the polyamic acid. The imidization section (not shown) imidizes the polyamic acid by, for example, a thermal imidization method that thermally dehydrates and closes the ring, a chemical imidization method that uses a dehydrating agent and an imidization accelerator, and the like.

When the polymer manufacturing system 1 manufactures polyimide, the cushion tank CT may be omitted so that the liquid is sent from the first tube type mixing section 20 to the imidization section.

The control unit 200 will be described. A first supply pump 112, a second supply pump 122, a first flow rate measurement unit 113, a second flow rate measurement unit 123, and a first viscosity measurement unit 222 are electrically connected to the control unit 200. In this specification, the 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 each of the supply pumps 112 and 122 based on the flow rate values measured by the flow rate measuring units 113 and 123.
By controlling the first supply pump 112 and / or the second supply pump 122, for example, the control unit 200 controls the first polymerizable compound contained in the first liquid A1 and the second polymerizable compound contained in the second liquid A2. The molar ratio with the compound is controlled to be within a predetermined range. The above molar ratio is set so that, for example, a polyamic acid having desired properties can be obtained.

The control unit 200 controls the supply in the first supply pump 112 and / or the second supply pump 122 based on the first viscosity information (first reaction information) acquired by the first viscosity measurement unit 222 (measurement unit). To do.

Next, the operation of the polymer production system 1 (polyamic acid production system) in the first embodiment will be described.
First, by starting the operation in the polymer production system 1, in the slurry liquid preparation tank 10, the powdered solid of the charged first polymerizable compound is stirred together with the dispersion medium to form a powdered solid. Is crushed and stirred to prepare a slurry-like first liquid A1 (slurry preparation step). Then, the defoaming pump 102 supplies the first liquid A1 prepared by the slurry liquid preparation tank 10 to the first tank 11 while defoaming (defoaming step).

Next, the first supply pump 112 supplies the slurry-like first liquid A1 (first supply step), and the second supply pump 122 supplies the solution-like second liquid A2 (second supply step). Here, the discharge flow rates of the first supply pump 112 and the second supply pump 122 are controlled by the control unit 200 so as to supply the first liquid A1 and the second liquid A2 at a desired ratio. As a result, the first liquid A1 and the second liquid A2 are supplied to the first confluence portion J1. In the first merging section J1, the slurry-like first liquid A1 supplied by the first supply pump 112 and the solution-like second liquid A2 supplied by the second supply pump 122 are merged and mixed. The first merging mixture B is produced (first merging step).

The first merging mixture B generated in the first merging section J1 is fed to the third feeding section L3 by the supply operation of the first supply pump 112 and the second supply pump 122, and the first tube type mixing section It is supplied to 20.

In the first tube type mixing unit 20, the first tube mixing solution C is generated by stirring the first merging mixture B without contacting the gas and proceeding the polymerization reaction of the first merging mixture B. (First tube mixing step). In the first tube type mixing section 20, the first merging mixture B is stirred to allow the polymerization reaction to proceed. When the first tube type mixing unit 20 is a static mixer such as a static mixer, the first merging mixture B is simply passed through and stirred.

The first pipe mixed liquid C generated in the first pipe type mixing unit 20 is fed to the fourth liquid feeding unit L4 and supplied to the cushion tank CT.

Here, in the middle of the operation of the polymer manufacturing system 1 described above, the first viscosity measuring unit 222 acquires the viscosity information (measurement step).
The control unit 200 controls the supply in the first supply pump 112 and / or the second supply pump 122 based on the first viscosity information (first reaction information) acquired by the first viscosity measurement unit 222 (measurement unit). (Control process). Thereby, a polyamic acid having a desired property (viscosity) can be obtained.

Here, for example, the method for producing a polyamic acid in the present embodiment may be a part of the method for producing a polyimide. In this case, the polyimide production method further comprises an imidization step of imidizing the polyamic acid.
When the polymer manufacturing system 1 manufactures polyimide, the cushion tank CT may be omitted so that the liquid is sent from the first tube type mixing section 20 to the imidization section.

According to the polymer production system 1 of the present embodiment, the following effects are obtained.
The polymer production system 1 includes a first supply pump 112 for supplying a slurry-like first liquid A1 containing the polyadditive first polymerizable compound, and a solution-like first supply pump 112 containing the polyadditive second polymerizable compound. The second supply pump 122 that supplies the two liquids A2, the first merging portion J1 that merges the first liquid A1 and the second liquid A2 to generate the first merging mixed liquid B, and the downstream of the first merging portion J1. It is provided with a first tube type mixing unit 20 which is arranged on the side and produces a first tube mixed solution C by stirring the first confluent mixed solution B in a state where it does not come into contact with a gas and advancing the polymerization reaction. According to the polymer production system 1, it is possible to continuously and stably produce a polymer, and it is possible to suppress the generation of bubbles during production. Specifically, according to the polymer production system 1, a desired polymerization solution can be continuously and stably produced, and the generation of bubbles in the polymerization solution can be suppressed.

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

In this embodiment, a case where one of the first polymerizable compound and the second polymerizable compound is a tetracarboxylic dianhydride and the other is a diamine to produce a polyamic acid as a polymer has been described. It is not limited to this.
For example, of the first polymerizable compound and the second polymerizable compound, one 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 as a polymer. Polyamic acids may be produced. In this case, one of the first polymerizable compound and the second polymerizable compound is an acid anhydride group-terminated polyamic acid, and the other is a diamine. Further, of the first polymerizable compound and the second polymerizable compound, one is an amino group-terminated polyamic acid and the other is a tetracarboxylic dianhydride.

Further, in the present embodiment, the case where the first tube type mixing unit 20 is composed of a double tube of the first tube type mixing and stirring unit 21 and the first temperature adjusting unit 22 has been described, but the present invention is limited to this. It's not a thing. For example, the first tube type mixing section 20 may be composed of a single tube having only the first tube type mixing and stirring section 21, and the first tube type mixing and stirring section 21 may be immersed in a liquid for temperature control.

<Second Embodiment>
Next, the polymer production system according to the second embodiment will be described with reference to FIG. FIG. 2 is a diagram showing a polymer production system according to the second embodiment. In the second embodiment, in addition to the configuration of the first embodiment (see FIG. 1), the first flow type stirring tank type mixing section 30 is provided on the downstream side of the first tube type mixing section 20 of the first embodiment. In that respect, it differs mainly from the first embodiment. In the second embodiment, detailed description of the same configuration as that of the first embodiment will be omitted.

The 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 first flow type stirring tank type mixing section 30 is provided at the downstream end of the fourth liquid feeding section L4 of the first embodiment without providing the cushion tank CT. Deploy.

In the polymer production system 1A of the second embodiment, in addition to the polymer production system 1 of the first embodiment, the first flow type stirring tank type mixing unit 30, the on-off valve 31 for the first stirring tank, and the third The supply pump 32, the cushion tank CT, and the control unit 200A are further provided. The liquid feeding line L further includes a fifth liquid feeding unit L5. In addition, the polymer production system 1 further includes a third flow rate measuring unit 321 and a second viscosity measuring unit 322.

In the first tube type mixing section 20 of the second embodiment, the first merging mixture B is stirred in a state where it does not come into contact with the gas to allow the polymerization reaction of the first merging mixture B to proceed, so that the first tube mixture B is mixed. Generate C. In the present embodiment, since the first flow type stirring tank type mixing section 30 is provided on the downstream side of the first tube type mixing section 20, in the first tube type mixing section 20, the first merging mixture B It is preferable to generate the first tube mixed solution C in a state where the polymerization reaction has proceeded more than a predetermined amount. For example, when the first tube mixed solution C is produced from the first combined mixed solution B in the first tube type mixing section 20, the reaction rate is preferably 50% or more, more preferably 70% or more. , 90% or more is more preferable.

The first flow type stirring tank type mixing section 30 is arranged on the downstream side of the first tube type mixing section 20. The first flow type stirring tank type mixing unit 30 stirs the first pipe mixed liquid C in contact with the gas to generate the first stirring tank mixed liquid D. The first flow type stirring tank type mixing unit 30 continuously receives the first pipe mixed liquid C and takes out the first stirring tank mixed liquid D.

The first flow type stirring tank type mixing unit 30 includes a stirring tank type reactor 301 and a plurality of first stirring blades 302 (first stirring members). The reactor 301 is composed of a stirring tank provided with a jacket for temperature control. The first stirring blade 302 stirs the first tube mixture C introduced into the reactor 301 to generate the first stirring tank mixture D. In the present embodiment, the first flow type stirring tank type mixing section 30 is arranged in the latter stage of the first tube type mixing section 20 and the first flow type stirring tank type mixing section 30 which are continuously provided. Since the liquid is in a high viscosity state, a stirring member for high viscosity is used as the first stirring blade 302. Here, examples of the stirring member for high viscosity include an anchor blade; a helical ribbon blade; a screw blade; a wide paddle blade; and a log bone blade. However, these stirring members are examples and are not limited thereto.

Although not clearly shown in the figure, it is preferable that the first flow type stirring tank type mixing unit 30 is devised so as not to entrap air bubbles. For example, the first tube mixture C may flow in from the lower part of the reactor 301, the intubation tube may be inserted from the upper part of the reactor 301 to transmit the first tube mixture C to the wall surface, or the outlet may be a liquid. By arranging it inside, it is preferable to prevent air bubbles from being caught.

The first stirring blade 302 is preferably stirred under conditions where no air bubbles are involved. For example, the first stirring blade 302 is preferably rotated at a low speed so that air bubbles are not caught. Further, it is preferable that the Froude number of stirring of the first stirring blade 302 is, for example, 0.02 to 200. Here, the Froude number (Fr = n ² · d / g, n: rotation speed, d: blade diameter, g: gravitational acceleration) is the ratio of inertial force and gravity. For example, n = 20 rpm, in the case of d = 0.5 m becomes ^{Fr = 20 2 × 0.5 / 9.8} = 32.

In the above-mentioned first flow type stirring tank type mixing unit 30, the reactor 301 is in an open state while continuously accepting the first tube mixed liquid C and taking out the first stirring tank mixed liquid D. The supplied first tube mixture C is stirred by the first stirring blade 302.

In the above first tube type mixing section 20 and the first flow type stirring tank type mixing section 30, the first tube type mixing section 20 is arranged in the front stage, and the first flow type stirring tank type mixing section 30 is arranged in the rear stage. By doing so, when the viscosity unevenness in the axial direction of the pipe is found in the first pipe type mixing portion 20 in the previous stage, the viscosity unevenness in the axial direction of the pipe can be eliminated in the first flow type stirring tank type mixing portion 30 in the latter stage. ..

For example, when the viscosity of the mixed liquid becomes uneven due to the fluctuation of the ratio of the first liquid A1 and the second liquid A2, the mixed liquid is moved in the axial direction of the pipe in the first tube type mixing unit 20. , It is not possible to eliminate the uneven viscosity of the mixed solution in the axial direction of the pipe. On the other hand, by arranging the first tube type mixing section 20 in the front stage and arranging the first flow type stirring tank type mixing section 30 in the rear stage, the mixing liquid is polymerized in the first tube type mixing section 20 in the front stage. After advancing the reaction, by stirring the mixed solution in the first flow type stirring tank type mixing section 30 in the subsequent stage, the first tube mixed solution that could not be eliminated in the first tube type mixing section 20 in the previous stage could not be solved. The uneven viscosity of the C pipe in the axial direction can be eliminated in the first flow type stirring tank type mixing unit 30 in the subsequent stage.

The first stirring tank mixture D generated by stirring the first tube mixture C is supplied to the cushion tank CT via the fifth liquid feeding unit L5.
The fifth liquid feeding unit L5 is a line connecting the first flow type stirring tank type mixing unit 30 and the cushion tank CT. An on-off valve 31 for the first stirring tank, a third supply pump 32, and a third flow rate measuring unit 321 are located between the first flow type stirring tank type mixing section 30 and the cushion tank CT in the fifth liquid feeding section L5. , Arranged in this order from the upstream side to the downstream side.

The on-off valve 31 for the first stirring tank is arranged near the lower side of the first flow type stirring tank type mixing section 30 in the fifth liquid feeding section L5, and on the upstream side of the third supply pump 32, the fifth liquid feeding section L5. Opens and closes. The control unit 200A, which will be described later, controls the opening / closing operation of the opening / closing valve 31 for the first stirring tank and the discharge flow rate of the third supply pump 32 to allow the liquid to stay in the first flow type stirring tank type mixing unit 30. To control.

The third supply pump 32 supplies the first stirring tank mixture D housed in the first flow type stirring tank type mixing unit 30 to the cushion tank CT. The third supply pump 32 discharges the first stirring tank mixture D at a predetermined flow rate. If necessary, an in-line defoaming device may be installed upstream of the third supply pump 32.

In the present embodiment, the third supply pump 32 does not have to be a metering pump. It is not excluded that the third supply pump 32 is a metering pump, and the third supply pump 32 may be a metering pump. Further, as will be described in detail later, in the fourth embodiment, the third supply pump 32 (first stirring tank mixture supply unit) is composed of a metering pump.

The third flow rate measuring unit 321 measures the flow rate of the first stirring tank mixture D on the downstream side of the third supply pump 32 in the fifth liquid feeding unit L5. In the present embodiment, the third flow rate measuring unit 321 is arranged between the third supply pump 32 and the cushion tank CT. The third flow rate measuring unit 321 outputs the measured flow rate of the first stirring tank mixture D to the control unit 200A described later.

The second viscosity measuring unit 322 acquires the viscosity information of the first stirring tank mixed liquid D between the third flow rate measuring unit 321 and the cushion tank CT in the fifth liquid feeding unit L5. Since the viscosity increases as the polymerization reaction proceeds, the viscosity information is effective information as reaction information. The second viscosity measuring unit 322 outputs the acquired viscosity information of the first stirring tank mixture D to the control unit 200A described later.

The second viscosity measuring unit 322 of the present embodiment is an example of a measuring unit that acquires reaction information regarding the physical quantity and / or composition of any one or more of the first tube mixture C and the first stirring tank mixture D. is there.

The measuring unit is not limited to the second viscosity measuring unit 322 (physical quantity and / or composition type, measuring method) of the present embodiment, similarly to the first viscosity measuring unit 222 of the first embodiment described above. The measuring unit acquires one or more reaction information regarding the physical quantity and / or composition of the measurement target, and outputs the acquired reaction information to the control unit 200A described later.

The cushion tank CT accommodates the first stirring tank mixture D from the first flow type stirring tank type mixing unit 30. The cushion tank CT is, for example, a tank for accommodating a raw material liquid when imidizing a polyamic acid which is a polymer to produce a polyimide.

The control unit 200A will be described. In the control unit 200A, in addition to the configuration connected to the control unit 200 of the first embodiment, the on-off valve 31 for the first stirring tank, the third supply pump 32, the third flow rate measuring unit 321 and the second viscosity measuring unit The 322 is electrically connected. In this specification, the illustration of control lines from the control unit 200A to each pump, each measurement unit, and each valve is omitted.

The control unit 200A controls the supply pumps 112, 122, 32 based on the flow rate values measured by the flow rate measuring units 113, 123, 321.
By controlling the first supply pump 112 and / or the second supply pump 122, for example, the control unit 200A controls the first polymerizable compound contained in the first liquid A1 and the second polymerizable compound contained in the second liquid A2. The molar ratio with the compound is controlled to be within a predetermined range. The above molar ratio is set so that, for example, a polyamic acid having desired properties can be obtained.

The control unit 200A has the first viscosity information (first reaction information) acquired by the first viscosity measuring unit 222 (measuring unit) and / or the second viscosity information acquired by the second viscosity measuring unit 322 (measuring unit). Based on (second reaction information), the supply in the first supply pump 112 and / or the second supply pump 122 is controlled. Thereby, a polyamic acid having a desired property (viscosity) can be obtained.
The control unit 200A also has the function of the control unit 200 in the first embodiment, but detailed description of the parts common to the control unit 200 will be omitted.

Next, the operation of the polymer production system 1A in the second embodiment will be described. The same operation as that of the polymer production system 1 in the first embodiment will not be described.
In the operation of the polymer production system 1 in the first embodiment described above, in the first tube type mixing unit 20, when there is uneven viscosity of the first merging mixture B in the axial direction of the tube, the first merging mixture is mixed. Since the liquid B is moved in the axial direction of the pipe, it is not possible to eliminate the uneven viscosity of the first merging mixed liquid B in the pipe direction. Therefore, in the polymer production system 1A of the second embodiment, the first flow type stirring tank type mixing unit 30 is arranged on the downstream side of the first tube type mixing unit 20.

The first pipe mixed liquid C generated in the first pipe type mixing unit 20 is fed to the fourth liquid feeding unit L4 and supplied to the first flow type stirring tank type mixing unit 30.

In the first flow type stirring tank type mixing unit 30, the first tube mixed liquid C is stirred by the first stirring blade 302 in a state of being in contact with the gas to generate the first stirring tank mixed liquid D (first stirring). Tank mixing process). The first stirring blade 302 is a stirring member for high viscosity. In the first flow type stirring tank type mixing unit 30, the reception of the first pipe mixed liquid C and the removal of the first stirring tank mixed liquid D are continuously performed. As a result, when there is uneven viscosity of the first merging mixture B in the axial direction of the pipe of the first pipe type mixing unit 20, the first pipe mixing cannot be eliminated by the first pipe type mixing part 20 in the previous stage. The uneven viscosity of the liquid C in the axial direction can be eliminated in the first flow type stirring tank type mixing section 30 in the subsequent stage. Therefore, the desired polymer can be continuously and stably obtained.

The first stirring tank mixture D generated in the first flow type stirring tank type mixing section 30 is fed to the fifth liquid feeding section L5 and supplied to the cushion tank CT.

Here, during the operation of the polymer manufacturing system 1A described above, the first viscosity measuring unit 222 and the second viscosity measuring unit 322 acquire viscosity information (measurement step).
The control unit 200A has the first viscosity information (first reaction information) acquired by the first viscosity measuring unit 222 (measuring unit) and / or the second viscosity information acquired by the second viscosity measuring unit 322 (measuring unit). Based on (second reaction information), the supply in the first supply pump 112 and / or the second supply pump 122 is controlled (control step). Thereby, a polyamic acid having a desired property (viscosity) can be obtained.

According to the polymer production system 1A of the second embodiment, in addition to the above-mentioned effects of the first embodiment, the following effects are exhibited.
The polymer production system 1A is arranged on the downstream side of the first tube type mixing section 20 for generating the first tube type mixing solution C and the first tube type mixing section 20, and the first tube type mixing solution C is brought into contact with the gas. First flow type stirring tank type mixing unit 30 that stirs in this state to generate a first stirring tank mixed liquid D, and continuously receives the first tube mixed liquid C and takes out the first stirring tank mixed liquid D. And. In order to stir and mix the first tube mixed liquid C mixed in the first tube type mixing unit 20 arranged in the front stage in the first flow type stirring tank type mixing unit 30 arranged in the rear stage in this way. , If there is uneven viscosity of the first confluent mixed solution B in the axial direction of the tube of the first tube type mixing section 20, the first tube mixed solution C that cannot be eliminated by the first tube type mixing section 20 in the previous stage. The uneven viscosity of the pipe in the axial direction can be eliminated in the first flow type stirring tank type mixing unit 30 in the subsequent stage. Therefore, the desired polymer can be continuously and stably obtained.

Further, in the polymer production system 1, the first viscosity information (first reaction information) and / or the second viscosity measurement unit 322 (measurement unit) acquired by the first viscosity measurement unit 222 (measurement unit) 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). As a result, a polymer having desired properties (viscosity) can be obtained.

<Third Embodiment>
Next, the polymer production system according to the third embodiment will be described with reference to FIG. FIG. 3 is a diagram showing a polymer production system according to the third embodiment. In the polymer production system 1B of the third embodiment, in addition to the configuration of the first embodiment (see FIG. 1), the second tube type mixing unit 40 is located downstream of the first tube type mixing unit 20 of the first embodiment. It is mainly different from the first embodiment in that the third liquid A3 is additionally supplied between the first tube type mixing unit 20 and the second tube type mixing unit 40. In the third embodiment, detailed description of the same configuration as that of the first embodiment will be omitted.

The polymer production system 1B according to the third embodiment will be described with reference to FIG.
In the polymer production system 1B of the third embodiment, the first tube mixed liquid C produced in the polymer production system 1 of the first embodiment and the third liquid A3 which is a raw material are merged at the second merging portion J2. To produce a second merging mixture E, and agitate in the second tube type mixing unit 40 to proceed with the polymerization reaction to produce a second tube mixture F to produce a polyamic acid (polymer). It is configured to do.

In the polymer production system 1B of the third embodiment, the second confluence portion J2 is provided without providing the cushion tank CT at the downstream end of the fourth liquid feeding portion L4 of the polymer production system 1 of the first embodiment. Is arranged, and the third liquid A3 is additionally supplied at the second merging portion J2. In the third embodiment, the polyamic acid having desired properties is obtained by controlling the supply of the third liquid A3 additionally supplied from the additional liquid supply pump 132. Therefore, it is preferable that the supply accuracy of the third liquid A3 is high, and in the third embodiment, the additional liquid supply pump 132 described later is composed of a metering pump.

In the polymer production system 1B of the third embodiment, in addition to the polymer production system 1 of the first embodiment, the third tank 13, the on-off valve 131 for the third tank, and the supply pump 132 for additional liquid (third). A liquid supply unit), a second tube type mixing unit 40, a cushion tank CT, and a control unit 200B are further provided. Further, the liquid feeding line L further includes a sixth liquid feeding unit L6, a seventh liquid feeding unit L7, and an eighth liquid feeding unit L8. Further, the polymer production system 1B of the third embodiment further includes a flow rate measuring unit 133 for an additional liquid and a third viscosity measuring unit 422.

The third tank 13 contains the third liquid A3 containing the third polymerizable compound. In the present embodiment, the acid anhydride group-terminated polyamic acid is contained in the first tube mixed solution C, and the solution-like third liquid A3 containing a diamine or an amino group-terminated polyamic acid third polymerizable compound is contained. Will be described.

An on-off valve 131 for the third tank, a supply pump 132 for the additional liquid, and a flow rate measuring unit 133 for the additional liquid are located on the upstream side between the third tank 13 and the second confluence J2 in the sixth liquid feeding unit L6. It is arranged in this order from to the downstream side.

The third tank on-off valve 131 is arranged in the vicinity of the lower side of the third tank 13 in the sixth liquid feeding section L6, and opens and closes the sixth liquid feeding section L6 on the upstream side of the additional liquid supply pump 132.

The additional liquid supply pump 132 (third liquid supply unit) supplies the third liquid A3 contained in the third tank 13 to the second confluence J2. The additional liquid supply pump 132 discharges the third liquid A3 at a predetermined flow rate. For example, the additional liquid supply pump 132 is adjusted to supply the third liquid A3 under the condition that a polyamic acid having desired properties can be obtained. The supply amount of the additional liquid supply pump 132 can be set according to the properties and composition of the second pipe mixed liquid F.

In the third embodiment, the additional liquid supply pump 132 is composed of a metering pump for the reason described above.
When supplying the slurry-like third liquid A3, the additional liquid supply pump 132 can supply the slurry-like third liquid A3 without clogging the pump, similarly to the above-mentioned first supply pump 112. Things are used.
Further, when the additional liquid supply pump 132 supplies the solution-like third liquid A3, the additional liquid supply pump 132 does not send the slurry-like liquid, but sends the solution as in the case of the above-mentioned second supply pump 122. It consists of a metering pump that can liquid.

The additional liquid flow rate measuring unit 133 measures the flow rate of the third liquid A3 on the downstream side of the additional liquid supply pump 132 in the sixth liquid feeding unit L6. In the present embodiment, the additional liquid flow rate measuring unit 133 is arranged between the third tank 13 and the second merging unit J2. The flow rate measuring unit 133 for the additional liquid outputs the measured flow rate of the third liquid A3 to the control unit 200B described later.
A second merging section J2 is arranged on the downstream side of the flow rate measuring section 133 for additional liquid.

The second merging portion J2 is arranged on the downstream side of the first pipe type mixing portion 20 and the third supply pump 32. In the second merging portion J2, the first pipe mixed liquid C from the first pipe type mixing unit 20 and the third liquid A3 from the additional liquid supply pump 132 are merged and mixed, and the second merging mixed liquid E To generate. In the second merging portion J2, the first pipe mixed liquid C and the third liquid A3 are merged in a state where they do not come into contact with the gas. The second merging portion J2 is composed of a merging valve for merging the first pipe mixed liquid C from the first pipe type mixing unit 20 and the third liquid A3 from the additional liquid supply pump 132.

The second pipe type mixing portion 40 is arranged on the downstream side of the second merging portion J2. The second tube type mixing unit 40 produces the second tube mixed solution F by stirring the second merging mixture E in a state where it does not come into contact with the gas and proceeding the polymerization reaction.

The second tube-type mixing unit 40 includes a tube-type reactor composed of a double tube extending in a predetermined direction. The second tube type mixing unit 40 has a second tube type mixing and stirring unit 41 arranged inside in the radial direction and a second temperature adjusting unit 42 arranged outside in the radial direction. The second tube type mixing unit 40 is formed so that the second merging mixed liquid E flows with a desired residence time.

The second tube type mixing / stirring unit 41 stirs the second merging mixture E. In the present embodiment, the second tube type mixing / stirring unit 41 stirs the second merging mixture E adjusted to a temperature suitable for the polymerization reaction by the second temperature adjusting unit 42.
As a specific example of the configuration and configuration of the second tube type mixing and stirring unit 41, a specific example of the same configuration and configuration as the above-mentioned first tube type mixing and stirring unit 21 can be applied.

The second temperature adjusting unit 42 is a piping unit arranged outside in the radial direction of the second pipe type mixing / stirring unit 41. The second temperature adjusting unit 42 adjusts the temperature (for example, cooling) of the second merging mixture E flowing through the second tube type mixing / stirring unit 41 to a desired temperature condition. In the second temperature adjusting unit 42, the second merging mixture E is adjusted to a temperature suitable for the polymerization reaction, and is circulated through the second tube type mixing and stirring unit 41.

The generated second tube mixed liquid F is supplied to the cushion tank CT via the eighth liquid feeding unit L8.

The third viscosity measuring unit 422 acquires the viscosity information of the second tube mixed liquid F in the eighth liquid feeding unit L8. Since the viscosity increases as the polymerization reaction proceeds, the viscosity information is effective information as reaction information. The third viscosity measuring unit 422 outputs the acquired viscosity information of the second tube mixed solution F to the control unit 200B described later.

The third viscosity measuring unit 422 of the present embodiment has the same physical quantity and / or composition in any one or more of the second tube mixed liquid F as in the above-mentioned first viscosity measuring unit 222 and the second viscosity measuring unit 322. This is an example of a measuring unit that acquires reaction information related to.

The control unit 200B will be described. In addition to the configuration connected to the control unit 200 of the first embodiment, the control unit 200B includes an additional liquid supply pump 132 (third liquid supply unit), an additional liquid flow rate measuring unit 133, and a third viscosity measurement. The unit 422 is electrically connected. In this specification, the illustration of control lines from the control unit 200B to each pump, each measurement unit, and each valve is omitted.

The control unit 200B has a first viscosity information (first reaction information) acquired by the first viscosity measuring unit 222 (measuring unit) and / or a third viscosity acquired by the third viscosity measuring unit 422 (measuring unit). Based on the information (third reaction information), the supply in the first supply pump 112, the second supply pump 122 and / or the additional liquid supply pump 132 is controlled. Thereby, a polyamic acid having a desired property (viscosity) can be obtained.
The control unit 200B also has the function of the control unit 200 in the first embodiment, but detailed description of the parts common to the control unit 200 will be omitted.

Next, the operation of the polymer production system 1B in the third embodiment will be described. The same operation as that of the polymer production system 1 in the first embodiment will not be described.
In the polymer production system 1B, the first tube mixed solution C produced in the first tube type mixing section 20 described in the first embodiment is supplied to the second merging section J2 (first tube mixing step).
Further, the additional liquid supply pump 132 supplies the third liquid A3 to the second merging portion J2 (third liquid supply step).

Here, the additional liquid supply pump 132 is provided by the first viscosity information (first reaction information) acquired by the first viscosity measuring unit 222 (measuring unit) and / or by the third viscosity measuring unit 422 (measuring unit). Based on the acquired third viscosity information (third reaction information), the discharge flow rate is controlled by the control unit 200B so as to supply the first tube mixed liquid C and the third liquid A3 at a desired ratio. The discharge flow rate of the additional liquid supply pump 132 is controlled by the control unit 200B so as to supply the third liquid A3 at a desired ratio.

As a result, the first tube mixed liquid C and the third liquid A3 are supplied to the second merging portion J2. In the second merging portion J2, the first pipe mixed liquid C and the third liquid A3 supplied by the additional liquid supply pump 132 are merged and mixed to generate the second merging mixed liquid E (the second merging mixed liquid E). 2 merging process).

The second merging mixed liquid E generated in the second merging part J2 is fed to the seventh liquid feeding part L7 and supplied to the second tube type mixing part 40.

In the second tube type mixing section 40, the second tube mixed solution F is produced by advancing the polymerization reaction of the second combined mixed solution E (second tube mixing step). In the second tube type mixing unit 40, the second merging mixture E is stirred to allow the polymerization reaction to proceed. When the second tube type mixing unit 40 is a static mixer such as a static mixer, the second merging mixture E is stirred only by being passed through.

The second pipe mixed liquid F generated in the second pipe type mixing unit 40 is fed to the eighth liquid feeding unit L8 and supplied to the cushion tank CT.

According to the polymer production system 1B of the third embodiment, in addition to the above-mentioned effects of the first embodiment, the following effects are exhibited.
The polymer production system 1B includes a first tube type mixing unit 20 that performs the first stage treatment, and a second tube type mixing unit 40 that performs the second stage treatment on the downstream side thereof. Therefore, the polymer production system 1B is configured to carry out the polymerization reaction in two stages. As a result, according to the polymer production system 1B, it becomes easier to achieve the target reaction rate and the like, and the quality and yield of the produced polyamic acid can be further improved.

Further, in the polymer production system 1B, the first viscosity information (first reaction information) acquired by the first viscosity measuring unit 222 (measuring unit) and / or acquired by the third viscosity measuring unit 422 (measuring unit). The supply in the first supply pump 112, the second supply pump 122 and / or the additional liquid supply pump 132 is controlled based on the third viscosity information (third reaction information). As a result, a polymer having desired properties (viscosity) can be obtained.

<Fourth Embodiment>
Next, the polymer production system according to the fourth embodiment will be described with reference to FIG. FIG. 4 is a diagram showing a polymer production system according to the fourth embodiment. In addition to the configuration of the third embodiment (see FIG. 3), the polymer production system 1C of the fourth embodiment includes a first flow type stirring tank type mixing unit 30 on the downstream side of the first tube type mixing unit 20. At the same time, it is mainly different from the third embodiment in that the second flow type stirring tank type mixing section 50 is provided on the downstream side of the second tube type mixing section 40. The configuration in which the first flow type stirring tank type mixing unit 30 is arranged on the downstream side of the first tube type mixing unit 20 is the same as that of the polymer production system 1A of the second embodiment. In the fourth embodiment, detailed description of the same configurations as those of the second embodiment and the third embodiment will be omitted.

The polymer manufacturing system 1C according to the fourth embodiment will be described with reference to FIG.
In the polymer production system 1C of the fourth embodiment, the first tube mixed solution C is generated by stirring in the first tube type mixing section 20 to advance the polymerization reaction, and in the first flow type stirring tank type mixing section 30. The first stirring tank mixed liquid D is generated by stirring in contact with the gas, and the first stirring tank mixed liquid D and the third liquid A3 which is a raw material are merged and mixed at the second merging portion J2. 2 Combined mixture E is generated. Then, the second tube type mixing unit 40 is stirred to proceed with the polymerization reaction to generate the second tube mixed liquid F, and then the second flow type stirring tank type mixing unit 50 is stirred in contact with the gas. Then, the second stirring tank mixed solution G is produced to produce a polyamic acid (polymer).

The polymer production system 1C of the fourth embodiment is, in addition to the polymer production system 1B of the third embodiment, a first flow type stirring tank type between the first tube type mixing unit 20 and the second merging unit J2. The mixing section 30 and the third supply pump 32 are arranged, and on the downstream side of the second tube type mixing section 40, the second flow type stirring tank type mixing section 50, the on-off valve 51 for the second stirring tank, and the fourth supply The pump 52 and the pump 52 are arranged. The first flow type stirring tank type mixing unit 30 and the third supply pump 32 have the same configuration as the polymer production system 1A of the second embodiment. Further, the liquid feeding line L further includes a ninth liquid feeding unit L9. Further, the polymer production system 1C of the fourth embodiment further includes a fourth flow rate measuring unit 521 and a fourth viscosity measuring unit 522.

The first flow type stirring tank type mixing section 30 and the third supply pump 32 are arranged between the first tube type mixing section 20 and the second merging section J2. As for the configuration related to the first flow type stirring tank type mixing unit 30, the description of the first flow type stirring tank type mixing unit 30 of the second embodiment can be referred to. The first stirring tank mixture D generated in the first flow type stirring tank type mixing section 30 is fed to the fifth liquid feeding section L5 by the supply operation of the third supply pump 32, and is sent to the second merging section J2. Be supplied.

In the polymer production system 1C of the fourth embodiment, the third supply pump 32 (first stirring tank mixture supply unit) is composed of a metering pump. In the fourth embodiment, the supply of the first stirring tank mixture D supplied by the third supply pump 32 and the third liquid A3 additionally supplied by the additional liquid supply pump 132 is controlled. Obtain a polyamic acid with the desired properties. Therefore, it is preferable that the supply accuracy of the first stirring tank mixture D and the third liquid A3 is high. In the fourth embodiment, the third supply pump 32 is composed of the metering pump, and the additional liquid supply pump 132 is also included. It consists of a metering pump.

In the second tube type mixing section 40 of the fourth embodiment, the second merging mixture E is stirred in a state where it does not come into contact with the gas, and the polymerization reaction of the second merging mixture E is allowed to proceed, so that the second tube mixture E is allowed to proceed. Generate F. In the present embodiment, since the second flow type stirring tank type mixing section 50 is provided on the downstream side of the second tube type mixing section 40, in the second tube type mixing section 40, the second merging mixture E It is preferable to generate the second tube mixed solution F in a state where the polymerization reaction has proceeded more than a predetermined value. For example, the reaction rate when the second tube mixed solution F is produced from the second combined mixed solution E in the second tube type mixing unit 40 is preferably 50% or more, more preferably 70% or more. , 90% or more is more preferable.

The second flow type stirring tank type mixing section 50 is arranged on the downstream side of the second tube type mixing section 40. The second flow type stirring tank type mixing unit 50 stirs the second pipe mixed liquid F in contact with the gas to generate the second stirring tank mixed liquid G. The second flow type stirring tank type mixing unit 50 continuously receives the second pipe mixed liquid F and takes out the second stirring tank mixed liquid G.

The second flow 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 jacket for temperature control. The second stirring blade 502 stirs the second tube mixed liquid F introduced into the reactor 501 to generate the second stirring tank mixed liquid G. In the present embodiment, the second flow type stirring tank type mixing section 50 is arranged on the downstream side of the second tube type mixing section 40, and the liquid has a high viscosity. Therefore, as the second stirring blade 502, Use a stirring member for high viscosity. As an example of the stirring member for high viscosity, the same one as shown in the second embodiment can be mentioned. Further, it is preferable that the second stirring blade 502 is stirred under the condition that no air bubbles are entrained, like the first stirring blade 302 of the second embodiment.

Although not clearly shown in the figure, the second flow type stirring tank type mixing unit 50 is devised so as not to entrap air bubbles, similarly to the above-mentioned first flow type stirring tank type mixing unit 30. Is preferable. For example, the second tube mixture F may flow in from the lower part of the reactor 501, the intubation tube may be inserted from the upper part of the reactor 501 to transmit the second tube mixture F to the wall surface, or the outlet may be a liquid. By arranging it inside, it is preferable to prevent air bubbles from being caught.

In the above-mentioned second flow-type stirring tank type mixing section 50, the reactor 501 is continuously receiving the second tube mixed liquid F and taking out the second stirring tank mixed liquid G in an open state. The supplied second tube mixture F is stirred by the second stirring blade 502.

In the above-mentioned second tube type mixing section 40 and second flow type stirring tank type mixing section 50, the second tube type mixing section 40 is arranged in the front stage, and the second flow type stirring tank type mixing section 50 is arranged in the rear stage. By doing so, when the viscosity unevenness in the axial direction of the pipe is found in the second pipe type mixing portion 40 in the previous stage, the viscosity unevenness in the axial direction of the pipe can be eliminated in the second flow type stirring tank type mixing portion 50 in the latter stage. ..

For example, when the viscosity of the mixed solution becomes uneven due to the fluctuation of the ratio of the first stirring tank mixture D and the third solution A3, the mixed solution moves in the axial direction of the tube in the second tube type mixing section 40. Therefore, it is not possible to eliminate the uneven viscosity of the mixed solution in the axial direction of the tube. On the other hand, by arranging the second tube type mixing section 40 in the front stage and arranging the second flow type stirring tank type mixing section 50 in the rear stage, the mixing liquid is polymerized in the second tube type mixing section 40 in the front stage. After advancing the reaction, by stirring the mixed solution in the second flow type stirring tank type mixing section 50 in the subsequent stage, the second tube mixed solution that could not be eliminated in the second tube type mixing section 40 in the previous stage could not be solved. The uneven viscosity of the F pipe in the axial direction can be eliminated in the second flow type stirring tank type mixing unit 50 in the subsequent stage.

The second stirring tank mixture G produced by stirring the second tube mixture F to advance the polymerization reaction is supplied to the cushion tank CT via the ninth liquid feeding unit L9.
The ninth liquid feeding unit L9 is a line connecting the second flow type stirring tank type mixing unit 50 and the cushion tank CT. An on-off valve 51 for the second stirring tank, a fourth supply pump 52, and a fourth flow rate measuring unit 521 are located between the second flow type stirring tank type mixing section 50 and the cushion tank CT in the ninth liquid feeding section L9. , Arranged in this order from the upstream side to the downstream side.

The on-off valve 51 for the second stirring tank is arranged in the vicinity of the lower side of the second flow type stirring tank type mixing section 50 in the ninth liquid feeding section L9, and on the upstream side of the fourth supply pump 52, the ninth liquid feeding section L9 Opens and closes. The control unit 200C, which will be described later, controls the opening / closing operation of the on-off valve 51 for the second stirring tank and the discharge flow rate of the fourth supply pump 52, so that the residence time at which the liquid stays in the second flow type stirring tank type mixing unit 50 To control.

The fourth supply pump 52 supplies the second stirring tank mixture G housed in the second flow type stirring tank type mixing unit 50 to the cushion tank CT. The fourth supply pump 52 discharges the second stirring tank mixture G at a predetermined flow rate. If necessary, an in-line defoaming device may be installed upstream of the fourth supply pump 52.

In the present embodiment, the fourth supply pump 52 does not have to be a metering pump. It is not excluded that the fourth supply pump 52 is a metering pump, and the fourth supply pump 52 may be a metering pump.

The fourth flow rate measuring unit 521 measures the flow rate of the second stirring tank mixture G on the downstream side of the fourth supply pump 52 in the ninth liquid feeding unit L9. In the present embodiment, the fourth flow rate measuring unit 521 is arranged between the fourth supply pump 52 and the cushion tank CT. The fourth flow rate measuring unit 521 outputs the measured flow rate of the second stirring tank mixture G to the control unit 200C described later.

The fourth viscosity measuring unit 522 acquires the viscosity information of the second stirring tank mixed liquid G between the fourth flow rate measuring unit 521 and the cushion tank CT in the ninth liquid feeding unit L9. Since the viscosity increases as the polymerization reaction proceeds, the viscosity information is effective information as reaction information. The fourth viscosity measuring unit 522 outputs the acquired viscosity information of the second stirring tank mixture G to the control unit 200C described later.

The fourth viscosity measuring unit 522 of the present embodiment is any of the second stirring tank mixed liquid G, similarly to the first viscosity measuring unit 222, the second viscosity measuring unit 322, and the third viscosity measuring unit 422 described above. This is an example of a measuring unit that acquires reaction information regarding a physical quantity and / or composition in one or more.

The control unit 200C will be described. In addition to the configuration connected to the control unit 200A of the second embodiment and the control unit 200B of the third embodiment, the control unit 200C includes a fourth supply pump 52, a fourth flow rate measurement unit 521, and a fourth viscosity measurement. The unit 522 is electrically connected. In this specification, the illustration of control lines from the control unit 200C to each pump, each measurement unit, and each valve is omitted.

The control unit 200C has a first viscosity information (first reaction information) acquired by the first viscosity measuring unit 222 (measuring unit) and a second viscosity information (second viscosity information) acquired by the second viscosity measuring unit 322 (measuring unit). 2 Reaction Information), 3rd Viscosity Information (3rd Reaction Information) Acquired by 3rd Viscosity Measuring Unit 422 (Measuring Unit), and / or 4th Viscosity Acquired by 4th Viscosity Measuring Unit 522 (Measuring Unit) Based on the information (third reaction information), the supply in the third supply pump 32 and / or the additional liquid supply pump 132 is controlled. Thereby, a polyamic acid having a desired property (viscosity) can be obtained.
The control unit 200C also has the function of the control unit 200B in the third embodiment, but detailed description of the parts common to the control unit 200B will be omitted.

Next, the operation of the polymer production system 1C in the fourth embodiment will be described. The same operation as that of the polymer production systems 1 to 1B in the first to third embodiments will be omitted.
In the polymer production system 1C, the first stirring tank mixture D generated in the first flow type stirring tank type mixing unit 30 described in the second embodiment is fed by the supply operation of the third supply pump 32 to the fifth liquid. Part L5 is pumped and supplied to the second merging part J2 (first stirring tank mixing step).
Further, the additional liquid supply pump 132 supplies the third liquid A3 to the second merging portion J2 (third liquid supply step).

Here, the third supply pump 32 and the additional liquid supply pump 132 are 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). 2nd viscosity information (2nd reaction information), 3rd viscosity information (3rd reaction information) acquired by 3rd viscosity measuring unit 422 (measuring unit) and / or 4th viscosity measuring unit 522 Based on the 4th viscosity information (4th reaction information) acquired by (Measuring unit), the discharge flow rates of the 1st stirring tank mixed liquid D and the 3rd liquid A3 are controlled so as to be supplied at a desired ratio. It is controlled by unit 200C. The discharge flow rate of the additional liquid supply pump 132 is controlled by the control unit 200C so as to supply the third liquid A3 at a desired ratio.

As a result, the first stirring tank mixture D and the third liquid A3 are supplied to the second merging portion J2. In the second merging section J2, the first stirring tank mixture D supplied by the third supply pump 32 and the third liquid A3 supplied by the additional liquid supply pump 132 are merged and mixed, and the second The merging mixture E is generated (second merging step).

The second confluence mixture E generated in the second confluence J2 is fed to the seventh liquid supply unit L7 by the supply operation of the third supply pump 32 and the additional liquid supply pump 132, and is mixed in the second tube type. It is supplied to the unit 40.

In the second tube type mixing section 40, the second tube mixed solution F is produced by advancing the polymerization reaction of the second combined mixed solution E (second tube mixing step). In the second tube type mixing section 40, the second merging mixture E is stirred to allow the polymerization reaction to proceed. When the second tube type mixing unit 40 is a static mixer such as a static mixer, the second merging mixture E is stirred only by being passed through. Here, in the second tube type mixing unit 40, when the viscosity of the second merging mixture E is uneven in the axial direction of the tube, the second merging mixture E is moved in the axial direction of the tube. It is not possible to eliminate the viscosity unevenness in the axial direction of the pipe of the second merging mixture E.

The second pipe mixed liquid F generated in the second pipe type mixing unit 40 is fed to the eighth liquid feeding unit L8 and supplied to the second flow type stirring tank type mixing unit 50.

In the second flow type stirring tank type mixing unit 50, the second pipe mixed liquid F is stirred by the second stirring blade 502 in a state of being in contact with the gas to generate the second stirring tank mixed liquid G (second stirring). Tank mixing process). The second stirring blade 502 is a stirring member for high viscosity. In the second flow type stirring tank type mixing unit 50, the reception of the second pipe mixed liquid F and the removal of the second stirring tank mixed liquid G are continuously performed. As a result, the uneven viscosity of the second tube mixed liquid F in the axial direction, which cannot be eliminated by the second tube type mixing section 40 in the previous stage, is eliminated in the second flow type stirring tank type mixing section 50 in the latter stage. Can be done. Therefore, the desired polymer can be continuously and stably obtained.

The second stirring tank mixture G generated in the second flow type stirring tank type mixing section 50 is fed to the ninth liquid feeding section L9 and supplied to the cushion tank CT.

According to the polymer production system 1C of the fourth embodiment, in addition to the effects of the third embodiment described above, the following effects are exhibited.
The polymer production system 1C includes a first tube type mixing unit 20 for performing the first stage treatment and a first flow type stirring tank type mixing unit 30, and a second stage processing is performed on the downstream side thereof. It includes a tube type mixing unit 40 and a second flow type stirring tank type mixing unit 50. Therefore, in the first stage processing, the viscosity unevenness in the axial direction of the pipe of the first pipe mixed liquid C, which cannot be eliminated by the first pipe type mixing unit 20 in the previous stage, is eliminated by the first flow type stirring tank type mixing in the second stage. In the second stage treatment, the viscosity unevenness of the second tube mixed liquid F in the axial direction, which can be eliminated by the portion 30, and which cannot be eliminated by the second tube type mixing portion 40 in the previous stage, is eliminated in the latter stage. This can be solved in the second flow type stirring tank type mixing unit 50. Therefore, the desired polymer can be continuously and stably obtained.

Further, in the polymer production system 1C, the first viscosity information (first reaction information) acquired by the first viscosity measuring unit 222 (measuring unit) and the second viscosity acquired by the second viscosity measuring unit 322 (measuring unit). Information (second reaction information), third viscosity information (third reaction information) acquired by the third viscosity measuring unit 422 (measurement unit), and / or the third viscosity information acquired by the fourth viscosity measuring unit 522 (measuring unit). 4 The supply in the third supply pump 32 and / or the additional liquid supply pump 132 is controlled based on the viscosity information (third reaction information). As a result, a polymer having desired properties (viscosity) can be obtained.

<Modification example>
Although the four embodiments have been described above, the present invention is not limited to the above embodiments, and modifications, improvements, and the like within a range in which the object of the present invention can be achieved are included in the present invention.

For example, in the polymer production system of the above-described embodiment, in the first embodiment, the liquid is agitated and mixed in the first tubular mixing section, and in the second embodiment, the first tubular mixing section and The liquid is stirred and mixed in the first flow type stirring tank type mixing section, and in the third embodiment, the liquid is stirred and mixed in the first tube type mixing section and the second tube type mixing section. In the fourth embodiment, the liquids in the first tube type mixing section and the first flow type stirring tank type mixing section are stirred and mixed, and then the second tube type mixing section and the second flow type stirring tank type are mixed. The solution was configured to be agitated and mixed in the mixing section. However, it is not limited to this. A one-stage or a plurality of stages of a tube-type mixing unit or a flow-type stirring tank-type mixing unit may be provided on the downstream side of the configuration of any of the first to fourth embodiments. Further, a one-stage or a plurality of stages of a tube-type mixing section or a flow-type stirring tank-type mixing section may be provided between the first tube-type mixing section and the second tube-type mixing section of the third embodiment. Between the 1st tube type mixing section and the 1st flow type stirring tank type mixing section of the 4th embodiment and the 2nd tube type mixing section and the 2nd flow type stirring tank type mixing section of the 4th embodiment, 1 A tube-type mixing section or a flow-type stirring tank-type mixing section may be provided with one or more stages.

Further, in the above-described embodiment, the polymer production system for producing polyamic acid or polyimide has been described, but the polymer to be produced is not limited thereto. For example, the polymer production system may produce a polymer using a polyadditive monomer such as a urethane monomer or an epoxy monomer.

Further, in the above-described embodiment, the viscosity measuring unit provides viscosity information regarding the viscosities of the first tube mixed solution C, the first stirring tank mixed solution D, the second tube mixed solution F, and / or the second stirring tank mixed solution G. It was acquired, and based on the acquired viscosity information, the residence time was controlled and the supply amounts of the liquids A1, A2, and A3 were controlled, but the present invention is not limited to this. For example, the absorbance information regarding the absorbance of the first tube mixture C, the first stirring tank mixture D, the second tube mixture F, and / or the second stirring tank mixture G is acquired, and based on the acquired absorbance information. Therefore, the residence time may be controlled and the supply amounts of the liquids A1, A2 and A3 may be controlled.

Further, in the above-described embodiment, the case where the first liquid A1 is in the form of a slurry and the second liquid A2 is in the form of a solution has been described, but the present invention is not limited to this. For example, the first liquid A1 may be in the form of a solution and the second liquid may be in the form of a slurry, or both the first liquid A1 and the second liquid A2 may be in the form of a slurry.

1, 1A, 1B, 1C Polymer Production System 10 Slurry Liquid Preparation Tank (Slurry Preparation Department)
20 1st tube type mixing part 30 1st flow type stirring tank type mixing part 32 3rd supply pump (1st stirring tank mixed liquid supply part)
40 2nd tube type mixing part 50 2nd flow type stirring tank type mixing part 102 Defoaming pump (defoaming part)
112 1st supply pump (1st liquid supply unit)
122 Second supply pump (second liquid supply unit)
132 Additional liquid supply pump (3rd liquid supply unit)
200, 200A, 200B, 200C Control unit 222 1st viscosity measuring unit 322 2nd viscosity measuring unit A1 1st liquid A2 2nd liquid A3 3rd liquid B 1st confluence mixed liquid C 1st pipe mixed liquid D 1st stirring tank Mixing liquid E 2nd merging mixed liquid F 2nd pipe mixed liquid G 2nd stirring tank mixed liquid J1 1st merging part J2 2nd merging part L liquid feeding line

Claims (20)

A polymer production system for producing a polymer using a first liquid containing a polyadditive first polymerizable compound and a second liquid containing a polyadditive second polymerizable compound as raw materials.
At least one of the first liquid and the second liquid is in the form of a slurry.
The first liquid supply unit that supplies the first liquid and
The second liquid supply unit that supplies the second liquid and
A first merging portion that merges the first liquid and the second liquid to generate a first merging mixed liquid.
With the first tube type mixing section which is arranged on the downstream side of the first merging section and produces the first tube mixed solution by stirring the first merging mixed solution in a state where it does not come into contact with the gas and advancing the polymerization reaction. A polymer production system comprising. It is arranged on the downstream side of the first tube type mixing section, and the first tube mixed solution is stirred in contact with a gas to generate a first stirring tank mixed solution, and the first tube mixed solution is received and described above. The polymer production system according to claim 1, further comprising a first flow-type stirring tank type mixing unit that continuously takes out the first stirring tank mixed liquid. A third liquid supply unit that supplies a slurry-like or solution-like third liquid containing a multi-additive third polymerizable compound, and a third liquid supply unit.
A second merging section that merges the first tube mixed liquid and the third liquid to generate a second merging mixed liquid, and
A second tube type mixing section which is arranged on the downstream side of the second merging section and produces a second tube mixed solution by stirring the second merging mixed solution in a state where it does not come into contact with a gas and advancing the polymerization reaction. The polymer production system according to claim 1, further comprising. It is arranged between the first tube type mixing section and the second merging section, and the first tube mixed solution is stirred in a state of being in contact with a gas to generate a first stirring tank mixed solution, and the first tube is described. Further provided with a first flow type stirring tank type mixing unit that continuously receives the mixed liquid and takes out the first stirring tank mixed liquid.
The polymer production system according to claim 3, wherein the second merging section merges the first stirring tank mixture and the third solution to generate the second merging mixture. It is arranged on the downstream side of the second tube type mixing section, and the second tube mixed solution is stirred in a state of being in contact with a gas to generate a second agitated tank mixed solution, and the second tube mixed solution is received and described. The polymer production system according to claim 3 or 4, further comprising a second flow-type stirring tank type mixing unit that continuously takes out the second stirring tank mixed liquid. The first polymerizable compound or the second polymer is arranged on the upstream side of the first liquid supply unit that supplies the first liquid in the form of a slurry or the second liquid supply part that supplies the second liquid in the form of a slurry. A slurry preparation unit that prepares the first liquid in the form of a slurry or the second liquid in the form of a slurry by stirring the polymerizable compound together with a dispersion medium.
The item according to any one of claims 1 to 5, further comprising a defoaming unit that is arranged on the downstream side of the slurry preparation unit and defoams the slurry-like first liquid or the slurry-like second liquid. Polymer production system. 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) and (b), and a polyamic acid is produced as the polymer.
(A) Of the first polymerizable compound and the second polymerizable compound, one is a tetracarboxylic dianhydride and the other is a diamine.
(B) Of the first polymerizable compound and the second polymerizable compound, one is an acid anhydride group-terminated or amino group-terminated polyamic acid, and the other is a diamine or tetracarboxylic dianhydride. The first polymerizable compound and the second polymerizable compound satisfy any of the following (a) and (b), and the third polymerizable compound is tetracarboxylic acid dianhydride or diamine, as the polymer. The polymer production system according to any one of claims 3 to 5, which produces a polyamic acid.
(A) Of the first polymerizable compound and the second polymerizable compound, one is a tetracarboxylic dianhydride and the other is a diamine.
(B) Of the first polymerizable compound and the second polymerizable compound, one is an acid anhydride group-terminated or amino group-terminated polyamic acid, and the other is a diamine or tetracarboxylic dianhydride. The first polymerizable compound and the second polymerizable compound satisfy any of the following (a) and (b), and the third polymerizable compound is an acid anhydride group-terminated or amino group-terminated polyamic acid. The polymer production system according to any one of claims 3 to 5, wherein a polyamic acid is produced as the polymer.
(A) Of the first polymerizable compound and the second polymerizable compound, one is a tetracarboxylic dianhydride and the other is a diamine.
(B) Of the first polymerizable compound and the second polymerizable compound, one is an acid anhydride group-terminated or amino group-terminated polyamic acid, and the other is a diamine or tetracarboxylic dianhydride. The polymer production system according to any one of claims 7 to 9, further comprising an imidization unit for imidizing the produced polyamic acid, and producing polyimide as the polymer. A method for producing a polymer, which comprises producing a polymer from a first liquid containing a polyadditive first polymerizable compound and a second liquid containing a polyadditive second polymerizable compound as raw materials.
At least one of the first liquid and the second liquid is in the form of a slurry.
The first liquid supply step of supplying the first liquid and
In the second liquid supply step of supplying the second liquid and the first merging portion, the first merging step of merging the first liquid and the second liquid to generate a first merging mixed liquid, and
A polymer comprising a first tube mixing step of producing a first tube mixed solution by stirring the first merging mixed solution in a first tube type mixing section without contacting a gas to advance a polymerization reaction. Manufacturing method. In the first flow type stirring tank type mixing unit, the first pipe mixed liquid is stirred in a state of being in contact with a gas to generate a first stirring tank mixed liquid, and the first pipe mixed liquid is received and the first stirring is performed. The method for producing a polymer according to claim 11, further comprising a first stirring tank mixing step of continuously taking out the tank mixture. A third liquid supply step of supplying a slurry-like or solution-like third liquid containing a polyadditive third polymerizable compound, and a third liquid supply step.
In the second merging section, a second merging step of merging the first tube mixed liquid and the third liquid to generate a second merging mixed liquid, and
A claim further comprising a second tube mixing step of producing a second tube mixed solution by stirring the second merging mixed solution in a second tube type mixing section without contacting the gas and advancing the polymerization reaction. Item 8. The method for producing a polymer according to Item 11. In the first flow type stirring tank type mixing unit, the first pipe mixed liquid is stirred in a state of being in contact with a gas to generate a first stirring tank mixed liquid, and the first pipe mixed liquid is received and the first stirring is performed. Further including a first stirring tank mixing step in which the tank mixture is continuously taken out,
The method for producing a polymer according to claim 13, wherein the second merging step is the method for producing the second merging mixture by merging the first stirring tank mixture and the third solution to produce the second merging mixture. In the second flow type stirring tank type mixing section, the second pipe mixed liquid is stirred in a state of being in contact with the gas to generate a second stirring tank mixed liquid, and the second pipe mixed liquid is received and the second stirring is performed. The method for producing a polymer according to claim 13 or 14, further comprising a second stirring tank mixing step of continuously taking out the tank mixture. In the slurry preparation unit, a slurry preparation step of stirring the first polymerizable compound or the second polymerizable compound together with a dispersion medium to prepare the slurry-like first liquid or the slurry-like second liquid.
The method for producing a polymer according to any one of claims 11 to 15, further comprising a defoaming step of defoaming the slurry-like first liquid or the slurry-like second liquid in the defoaming portion. .. 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) and (b), and a polyamic acid is produced as the polymer. ..
(A) Of the first polymerizable compound and the second polymerizable compound, one is a tetracarboxylic dianhydride and the other is a diamine.
(B) Of the first polymerizable compound and the second polymerizable compound, one is an acid anhydride group-terminated or amino group-terminated polyamic acid, and the other is a diamine or tetracarboxylic dianhydride. The first polymerizable compound and the second polymerizable compound satisfy any of the following (a) and (b), and the third polymerizable compound is tetracarboxylic acid dianhydride or diamine, as the polymer. The method for producing a polymer according to any one of claims 13 to 15, wherein the polyamic acid is produced.
(A) Of the first polymerizable compound and the second polymerizable compound, one is a tetracarboxylic dianhydride and the other is a diamine.
(B) Of the first polymerizable compound and the second polymerizable compound, one is an acid anhydride group-terminated or amino group-terminated polyamic acid, and the other is a diamine or tetracarboxylic dianhydride. The first polymerizable compound and the second polymerizable compound satisfy any of the following (a) and (b), and the third polymerizable compound is an acid anhydride group-terminated or amino group-terminated polyamic acid. The method for producing a polymer according to any one of claims 13 to 15, wherein a polyamic acid is produced as the polymer.
(A) Of the first polymerizable compound and the second polymerizable compound, one is a tetracarboxylic dianhydride and the other is a diamine.
(B) Of the first polymerizable compound and the second polymerizable compound, one is an acid anhydride group-terminated or amino group-terminated polyamic acid, and the other is a diamine or tetracarboxylic dianhydride. The method for producing a polymer according to any one of claims 17 to 19, further comprising an imidization step of imidizing the produced polyamic acid, and producing polyimide as the polymer.

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