JP7249803B2 - Polymer production system and production method - Google Patents

Description

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

As a method for continuously synthesizing polyamic acid, for example, the method described in Patent Document 1 is known. Patent Literature 1 describes a method for producing polyamic acid (polyamic acid) and polyimide using a tube reactor. In Patent Document 1, by mixing two kinds of raw material solutions at a ratio within a predetermined narrow range, it is possible to suppress a decrease in the yield of the resulting polyamic acid fine particles and polyimide fine particles, and that the two raw material solutions are mixed in a predetermined range. It is stated that it is preferable to use a positive displacement pump with low pulsation to achieve the ratio. In addition, it is described that agitation by ultrasonic irradiation is performed in order to advance the reaction of the mixed solution.

Japanese Patent Application Laid-Open No. 2006-249380

However, when using a pump with small pulsation as in Patent Document 1, there is a problem that expensive equipment is required. Moreover, in order to perform ultrasonic irradiation, it is necessary to construct a reactor with a special device shape.

An object of the present invention is to provide a polymer production system and a production method capable of continuously and stably obtaining a desired polymer without using expensive equipment.

Specific means for solving the above problems include the following embodiments.
<1> A polymer is prepared from a first solution containing a first polyaddition polymerizable compound and a second solution containing a second polyaddition polymerizable compound that polyadditions with the first polymerizable compound as raw materials. A polymer manufacturing system for manufacturing,
a first supply unit that supplies the first solution;
a second supply unit that supplies the second solution;
a first mixing unit that mixes the first solution and the second solution to generate a first mixed solution;
a first flow rate measurement unit that measures the flow rate of the first solution;
a first flow rate adjusting unit capable of adjusting the flow rate of the first solution;
a second flow rate measurement unit that measures the flow rate of the second solution;
a second flow rate adjusting unit capable of adjusting the flow rate of the second solution;
It is arranged continuously downstream of the first mixing section, and includes a first polymer by advancing a polymerization reaction between the first polymerizable compound and the second polymerizable compound contained in the first mixed solution. a first reaction section that produces a first polymerization solution;
The flow rate fluctuations of the first solution and the second solution are controlled so as to be synchronized, and the difference between the flow rate fluctuation rate of the first solution and the flow rate fluctuation rate of the second solution is 3% or less. , a first control unit that adjusts the flow rate by the first flow rate adjustment unit and / or the second flow rate adjustment unit ,
Among the first polymerizable compound and the second polymerizable compound, one is a tetracarboxylic dianhydride and the other is a diamine, or one is an acid anhydride group-terminated or amino group-terminated polyamic acid, and the other is A diamine or a tetracarboxylic dianhydride,
A polymer production system for producing polyamic acid as the first polymer .

<2> The polymer production system according to <1>, wherein the first reaction section includes a first reaction stirring section that stirs the first mixed solution without contacting gas.

<3> The first polymer is a polyaddition polymer,
a third supply unit that supplies a third solution containing a polyadditive third polymerizable compound that polyadditions to the first polymer;
a second mixing unit that mixes the first polymerization solution and the third solution to generate a second mixed solution;
a polymerization solution flow rate measuring unit that measures the flow rate of the first polymerization solution;
a third flow rate measuring unit that measures the flow rate of the third solution;
a third flow rate adjusting unit capable of adjusting the flow rate of the third solution;
The first polymer from the first polymerization solution and the third polymerizable compound from the third solution, which are arranged continuously downstream of the second mixing section and are contained in the second mixed solution a second reaction part that advances the polymerization reaction of to generate a second polymerization solution containing the second polymer;
The flow rate fluctuations of the first polymerization solution and the third solution are controlled to be synchronized, and the difference between the flow rate fluctuation rate of the first polymerization solution and the flow rate fluctuation rate of the third solution is 3% or less. and a second control unit that adjusts the flow rate by the third flow rate adjustment unit ,
The first polymer is an acid anhydride group-terminated or amino group-terminated polyamic acid,
the third polymerizable compound is a diamine or a tetracarboxylic dianhydride,
The polymer production system according to <1> or <2>, which produces polyamic acid as the second polymer .

<4> The polymer production system according to <3> , wherein the second reaction section includes a second reaction stirring section that stirs the second mixed solution without contacting gas.

<5> The polymer production system according to any one of <1> to <4> , further comprising an imidization unit that imidizes the produced polyamic acid.

<6> A polymer is prepared from a first solution containing a first polyaddition polymerizable compound and a second solution containing a second polyaddition polymerizable compound that polyadditions with the first polymerizable compound as raw materials. A method for producing a polymer to be produced,
a first supply step of supplying the first solution;
a second supply step of supplying the second solution;
a first mixing step of mixing the first solution and the second solution to generate a first mixed solution;
a first measuring step of measuring the flow rate of the first solution;
a first flow rate adjustment step capable of adjusting the flow rate of the first solution;
a second measuring step of measuring the flow rate of the second solution;
a second flow rate adjustment step capable of adjusting the flow rate of the second solution;
a first reaction step of allowing a polymerization reaction between the first polymerizable compound and the second polymerizable compound contained in the first mixed solution to generate a first polymerization solution containing the first polymer;
The flow rate fluctuations of the first solution and the second solution are controlled so as to be synchronized, and the difference between the flow rate fluctuation rate of the first solution and the flow rate fluctuation rate of the second solution is 3% or less. , a first control step of adjusting the flow rate by the first flow rate adjustment step and / or the second flow rate adjustment step ,
Among the first polymerizable compound and the second polymerizable compound, one is a tetracarboxylic dianhydride and the other is a diamine, or one is an acid anhydride group-terminated or amino group-terminated polyamic acid, and the other is A diamine or a tetracarboxylic dianhydride,
A method for producing a polymer in which polyamic acid is produced as the first polymer .

<7> The method for producing a polymer according to <6> , wherein the first reaction step includes a first reaction-stirring step of stirring the first mixed solution without coming into contact with gas.

<8> The first polymer is a polyaddition polymer,
a third supplying step of supplying a third solution containing a polyadditional third polymerizable compound that polyadditions to the first polymer;
a second mixing step of mixing the first polymerization solution and the third solution to generate a second mixed solution;
a polymerization solution flow rate measuring step of measuring the flow rate of the first polymerization solution;
a third flow rate measuring step of measuring the flow rate of the third solution;
a third flow rate adjusting step capable of adjusting the flow rate of the third solution;
The polymerization reaction between the first polymer from the first polymerization solution contained in the second mixed solution and the third polymerizable compound from the third solution is allowed to proceed to produce a second polymer containing the second polymer. a second reaction step of producing a polymerization solution;
The flow rate fluctuations of the first polymerization solution and the third solution are controlled to be synchronized, and the difference between the flow rate fluctuation rate of the first polymerization solution and the flow rate fluctuation rate of the third solution is 3% or less. and a second control step of adjusting the flow rate by the third flow rate adjustment step ,
The first polymer is an acid anhydride group-terminated or amino group-terminated polyamic acid,
the third polymerizable compound is a diamine or a tetracarboxylic dianhydride,
The method for producing a polymer according to <6> or <7>, wherein a polyamic acid is produced as the second polymer .

<9> The method for producing a polymer according to <8> , wherein the second reaction step includes a second reaction-stirring step of stirring the second mixed solution without coming into contact with gas.

<10> The method for producing the polymer according to any one of <6> to <9> , further comprising imidizing the produced polyamic acid.

ADVANTAGE OF THE INVENTION According to this invention, the polymer manufacturing system and manufacturing method which can obtain a desired polymer continuously and stably can be provided.

It is a figure which shows the polymer manufacturing system in 1st Embodiment. It is a figure which shows the flow waveform which controlled the 1st flow rate of change and the 2nd flow rate of change. It is a flowchart explaining operation|movement of the polymer manufacturing system in 1st Embodiment. It is a figure which shows the polymer manufacturing system in 2nd Embodiment. It is a flowchart explaining operation|movement of the polymer manufacturing system in 2nd Embodiment.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
The first embodiment is an example of a polymer production system having a single reaction section. The second embodiment is an example of a polymer production system having a two-stage reaction section.

<First Embodiment>
A polymer manufacturing system according to the first embodiment will be described with reference to FIGS. 1 to 3. FIG. FIG. 1 is a diagram showing a polymer production system according to the first embodiment. FIG. 2 is a diagram showing a flow rate waveform in which the first flow rate fluctuation rate and the second flow rate fluctuation rate are controlled. FIG. 3 is a flowchart explaining the operation of the polymer production system in the first embodiment.

First, an overview of the polymer production system 1 in the first embodiment will be described.
The polymer production system 1 comprises a first solution A1 in which a first polyaddition polymerizable compound is dissolved, and a second solution A2 in which a second polyaddition polymerizable compound that polyadditions with the first polymerizable compound is dissolved. It is a production system for producing the first polymer using as a raw material. The first embodiment is an example of a polymer production system having a single reaction section.

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

The tetracarboxylic dianhydride is not particularly limited, and those similar to those used in conventional polyimide synthesis can be used. Specific examples of tetracarboxylic dianhydrides include 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 2, 3,3′,4′-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 1,3-bis(2,3-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(2, 3-dicarboxyphenoxy)benzene dianhydride, 2,3,3′,4′-benzophenonetetracarboxylic dianhydride, 2,2′,3,3′-benzophenonetetracarboxylic dianhydride, 2,2 ',3,3'-biphenyltetracarboxylic dianhydride, 2,2',6,6'-biphenyltetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, anthracene-2,3,6,7-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, 2,2-bis(4-hydroxyphenyl)propane dibenzoate-3 ,3′,4,4′-tetracarboxylic dianhydride and other aromatic tetracarboxylic dianhydrides; butane-1,2,3,4-tetracarboxylic dianhydride and other aliphatic tetracarboxylic dianhydrides; anhydride; alicyclic tetracarboxylic dianhydride such as cyclobutane-1,2,3,4-tetracarboxylic dianhydride; thiophene-2,3,4,5-tetracarboxylic dianhydride, pyridine- heterocyclic tetracarboxylic dianhydrides such as 2,3,5,6-tetracarboxylic dianhydride; Tetracarboxylic dianhydrides may be used alone or in combination of two or more.

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

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

The diamine is not particularly limited, and the same diamines as those used in conventional polyimide synthesis can be used. Specific examples of diamines include 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 4,4′-bis(4- aminophenoxy)biphenyl, 1,4'-bis(4-aminophenoxy)benzene, 1,3'-bis(4-aminophenoxy)benzene, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3, 4'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-methylene-bis(2-chloroaniline), 3, 3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl sulfide, 2,6-diaminotoluene, 2,4-diaminochlorobenzene, 1,2-diaminoanthraquinone, 1,4-diaminoanthraquinone, Aromatic diamines such as 3,3′-diaminobenzophenone, 3,4′-diaminobenzophenone, 4,4′-diaminobenzophenone, 4,4′-diaminobibenzyl; 1,2-diaminoethane, 1,4-diamino Aliphatic diamines such as butane, tetramethylenediamine, and 1,10-diaminododecane; heterocyclic diamines such as 3,4-diaminopyridine; and the like. A diamine may be used individually by 1 type, and may use 2 or more types together.

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

As shown in FIG. 1, the polymer production system 1 mixes a first solution A1 and a second solution A2, which are raw materials, in a first mixing section 20 to generate a first mixed solution B, and a first reaction section 30 , the polymerization reaction proceeds to generate the first polymerization solution C, thereby producing a polyamic acid (first polymer).

Here, the polymer production system 1 has a tubular liquid-feeding line L that connects the first and second tanks 11 and 12 described later to the first cushion tank 40 in a sealed state. As a result, the polymer production system 1 can continuously produce a polymer without generating air bubbles in the first mixed solution B or the first polymerization solution C.

Next, a specific configuration of the polymer production system 1 will be described.
As shown in FIG. 1, the polymer production system 1 includes a first tank 11, a second tank 12, a first supply pump 15 (first supply section), and a second supply pump 16 (second supply section). , a first mixing section 20 , a first reaction section 30 , a first cushion tank 40 , a liquid feeding line L, and a first control section 200 . The liquid feeding line L described above has a first liquid feeding section L1, a second liquid feeding section L2, and a third liquid feeding section L3. The polymer production system 1 also has a first flow rate adjusting section 151 , a first flow rate measuring section 152 , a second flow rate adjusting section 161 and a second flow rate measuring section 162 .

The first tank 11 contains a first solution A1 containing a first polyaddition polymerizable compound. In this embodiment, the first tank 11 contains a first solution A1 containing tetracarboxylic dianhydride. The first solution A1 stored in the first tank 11 is supplied to the first mixing section 20 via the first liquid feeding section L1.

Between the first tank 11 and the first mixing section 20 in the first liquid feeding section L1, the first supply pump 15 and the first flow rate measuring section 152 are arranged in this order from the upstream side to the downstream side. be.

The first supply pump 15 (first supply section) supplies the first solution A1 contained in the first tank 11 to the first mixing section 20 . The first supply pump 15 discharges the first solution A1 so as to supply the first solution A1 at a predetermined amount. For example, the first supply pump 15 is adjusted so as to supply the first solution A1 under the conditions under which polyamic acid (first polymer) having desired properties is obtained.

In this embodiment, the first supply pump 15 is configured by a positive displacement pump. Positive displacement pumps include, for example, push-type reciprocating pumps such as plunger pumps; rotary pumps such as gear pumps provided with gears; and the like.

As the first supply pump 15, it is preferable to select a pump having a small intrinsic pulsation rate (flow rate fluctuation rate). Instead of selecting the first supply pump 15 with a small pulsation rate (flow rate fluctuation rate), or selecting a first supply pump 15 with a small pulsation rate (flow rate fluctuation rate). In addition, it is also preferable to arrange a flow rate fluctuation damping device (for example, an accumulator) in the liquid feeding line L. By arranging a shock absorber such as an accumulator, the flow rate fluctuation rate can be further reduced.

The first flow rate adjusting section 151 is electrically connected to the first supply pump 15 and adjusts the flow rate of the first solution A1. The first flow rate adjusting section 151 is controlled by a first control section 200 which will be described later.

The first flow rate measuring unit 152 measures the flow rate of the first solution A1 on the downstream side of the first supply pump 15 in the first liquid feeding unit L1. In this embodiment, the first flow rate measuring section 152 is arranged between the first supply pump 15 and the first mixing section 20 . The first flow rate measurement unit 152 outputs the measured flow rate of the first solution A1 to the first control unit 200, which will be described later.

The second tank 12 contains a second solution A2 containing a second polyaddition polymerizable compound that polyadditions with the first polymerizable compound. In this embodiment, the second tank 12 contains a second solution A2 containing diamine. The second solution A2 stored in the second tank 12 is supplied to the first mixing section 20 via the second liquid feeding section L2.

Between the second tank 12 and the first mixing section 20 in the second liquid feeding section L2, the second supply pump 16 and the second flow rate measuring section 162 are arranged in this order from the upstream side to the downstream side. be.

The second supply pump 16 (second supply section) supplies the second solution A2 contained in the second tank 12 to the first mixing section 20 . The second supply pump 16 discharges the second solution A2 so as to supply the second solution A2 at a predetermined amount. For example, the second supply pump 16 is adjusted so as to supply the second solution A2 under conditions under which polyamic acid (first polymer) having desired properties is obtained.
In this embodiment, the second supply pump 16 is configured by a positive displacement pump, like the first supply pump 15 described above.

As the second supply pump 16, it is preferable to select a pump having a small intrinsic pulsation rate (flow rate fluctuation rate). Instead of selecting the second supply pump 16 having a small characteristic pulsation rate (flow rate fluctuation rate), or selecting a second supply pump 16 having a small characteristic pulsation rate (flow rate fluctuation rate). In addition, it is also preferable to arrange a flow rate fluctuation damping device (for example, an accumulator) in the liquid feeding line L. By arranging a shock absorber such as an accumulator, the flow rate fluctuation rate can be further reduced.

The second flow rate adjusting section 161 is electrically connected to the second supply pump 16 and adjusts the flow rate of the second solution A2. The second flow rate adjusting section 161 is controlled by the first control section 200, which will be described later.

The second flow rate measuring section 162 measures the flow rate of the second solution A2 on the downstream side of the second supply pump 16 in the second liquid feeding section L2. In this embodiment, the second flow rate measuring section 162 is arranged between the second supply pump 16 and the first mixing section 20 . The second flow rate measurement unit 162 outputs the measured flow rate of the second solution A2 to the first control unit 200, which will be described later.

The first mixing section 20 is arranged downstream of the first supply pump 15 and the second supply pump 16 . The first mixing section 20 generates a first mixed solution B by mixing the first solution A1 and the second solution A2. The first mixing section 20 is composed of a confluence valve that joins the first solution A1 supplied by the first supply pump 15 and the second solution A2 supplied by the second supply pump 16 .

In the present embodiment, the first solution A1 and the second solution A2 are controlled by the first control unit 200, the first flow rate adjustment unit 151, and the second flow rate adjustment unit 161 so that the peak value of the flow rate fluctuates synchronously. Liquid is sent (see FIG. 2). Here, the synchronous fluctuation of the peak value of the flow rate means that the cycle of the flow rate fluctuation is substantially the same, and a slight difference in phase is allowed. For example, let the distance between adjacent peaks (mountains) of the flow rate value of the first solution A1 be _L1 , and the distance between adjacent peaks (mountains) of the flow rate values of the first solution A1 and the flow rate value of the second solution A2 ( That is, it is preferable that _{L 1 and} M 1 satisfy the following equation (1), where M ₁ is the phase shift).
0≦(M ₁ /L ₁ )≦0.1 (1)

Although FIG. 2 illustrates a case where the period of fluctuation in the flow rate of the first solution A1 is constant, the period of fluctuation in the flow rate of the first solution A1 may not necessarily be constant. That is, the distance between adjacent peaks (mountains) of the flow rate value of the first solution A1 may not necessarily be constant. Similarly, although FIG. 2 illustrates the case where the period of fluctuation in the flow rate of the second solution A2 is constant, the period of fluctuation in the flow rate of the second solution A2 may not necessarily be constant. That is, the distance between adjacent peaks (mountains) of the flow rate value of the second solution A2 may not necessarily be constant.

The first reaction section 30 is arranged continuously downstream of the first mixing section 20 . The first reaction section 30 is a section where the polymerization reaction between the first polymerizable compound and the second polymerizable compound contained in the first mixed solution B proceeds. In the first reaction section 30, the polymerization reaction between the first polymerizable compound and the second polymerizable compound contained in the first mixed solution B progresses gradually, and the first polymerized solution C is obtained.

The first reaction section 30 is composed of a double pipe extending in a predetermined direction, and includes a first reaction stirring section 31 arranged radially inward and a first reaction temperature adjusting section 32 arranged radially outward. , has The first reaction section 30 is formed so that the first mixed solution B flows for a desired residence time.

The first reaction-stirring unit 31 stirs the first mixed solution B in which the first solution A1 and the second solution A2 are mixed without coming into contact with gas. In this embodiment, the first reaction-stirring unit 31 stirs the first mixed solution B, which has been adjusted to a temperature suitable for the polymerization reaction by the first reaction temperature adjusting unit 32, without coming into contact with gas.

The first reaction-stirring unit 31 includes, for example, static mixers, nozzles, orifices, and other stationary mixers, centrifugal pumps, volute pumps, and driven mixers, such as in-line mixers having stirring blades, preferably It comprises a static mixer, more preferably a static mixer. In addition, a pipe with a twist tape inserted (see [Fig. 19] of Japanese Patent Application Laid-Open No. 2003-314982, etc.) can also provide the same agitation promotion effect as a static mixer, but the static mixer has a better agitation promotion effect. is obtained.

The static mixer is not particularly limited, and examples thereof include static mixers such as Kenics mixer type, Sulzer SMV type, Sulzer SMX type, Tray Hi-mixer type, Komax mixer type, Lightnin mixer type, Ross ISG type, and Bran & Lube mixer type. mentioned. Among these, the Kenics mixer type static mixer is more preferable since it has a simple structure and has no dead space.

The first reaction temperature adjusting section 32 is a piping section arranged radially outside the first reaction stirring section 31 . The first reaction temperature adjusting section 32 adjusts (for example, cools) the first mixed solution B flowing through the first reaction stirring section 31 to a desired temperature condition. In the first reaction temperature adjustment section 32 , the first mixed solution B is adjusted to a temperature suitable for the polymerization reaction, and is passed through the first reaction stirring section 31 .

The first cushion tank 40 accommodates the first polymerization solution C from the first reaction section 30 . The first cushion tank 40 serves as a tank for containing a raw material solution, for example, when polyimide is produced by imidating polyamic acid, which is the first polymer.

When the polymer production system 1 according to the present embodiment produces polyimide, the polymer production system 1 further includes an imidization unit that imidizes the polyamic acid. The imidization unit (not shown) imidizes the polyamic acid by, for example, a thermal imidization method of thermal dehydration ring closure, a chemical imidization method using a dehydrating agent and an imidization accelerator, or the like.

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

The first control unit 200 will be explained. A first flow rate adjusting section 151 , a first flow rate measuring section 152 , a second flow rate adjusting section 161 and a second flow rate measuring section 162 are electrically connected to the first control section 200 .

The first control unit 200 controls the flow rate fluctuation rate of the first solution A1 (hereinafter also referred to as “first flow rate fluctuation rate”) and the flow rate fluctuation rate of the second solution A2 (hereinafter also referred to as “second flow rate fluctuation rate”). ), the first flow rate fluctuation rate and/or the second flow rate fluctuation rate is controlled. In the present embodiment, the difference between the first flow rate fluctuation rate and the second flow rate fluctuation rate is, for example, preferably 3% or less, more preferably 1% or less. Although the lower limit of the difference between the first flow rate fluctuation rate and the second flow rate fluctuation rate may be 0%, it is preferably 0.001% or more. By setting the difference between the first flow rate fluctuation rate and the second flow rate fluctuation rate to 0.001% or more and slightly shifting the mixing ratio of the first solution A1 and the second solution A2, the first solution A1 and the second solution A1 It tends to be well mixed with the solution A2.

In this embodiment, for example, as shown in the flow rate waveform before control in FIG. It is defined as a ratio (Ha=(Sa/Ka)×100[%]). Further, for example, the second flow rate fluctuation rate Hb is defined as the ratio of the flow rate Sb half the amplitude of the flow rate fluctuation to the flow rate value Kb at the center of the amplitude of the flow rate fluctuation (Hb=(Sb/Kb)×100 [%] ).
As the difference x between the first flow rate fluctuation rate Ha and the second flow rate fluctuation rate Hb, the absolute value of the difference between the first flow rate fluctuation rate Ha and the second flow rate fluctuation rate Hb is used (x=|Ha−Hb| ).
In the flow rate waveform before control in FIG. 2, the first solution A1 and the second solution A2 are not synchronized in flow rate variation. Further, for example, in the flow rate waveform before control in FIG. 2, the first flow rate fluctuation rate Ha is larger than the second flow rate fluctuation rate Hb of the second solution A2 (Ha>Hb).

For example, the first control unit 200 controls the first supply pump 15 via the first flow rate adjusting unit 151 and/or the second flow rate adjusting unit 161 so that the flow rate fluctuations of the first solution A1 and the second solution A2 are synchronized. and/or adjust the operation of the second feed pump 16 . Further, for example, when the difference between the first flow rate fluctuation rate Ha and the second flow rate fluctuation rate Hb is outside the predetermined range, the first control unit 200 sets the first flow rate fluctuation rate Ha and the second flow rate fluctuation rate Hb to The flow rate is adjusted by the first flow rate adjusting section 151 and/or the second flow rate adjusting section 161 so that the difference between is small. In this embodiment, the predetermined range of the difference between the first flow rate fluctuation rate Ha and the second flow rate fluctuation rate Hb is set to 3% or less, for example.

When performing control so that the difference between the first flow rate fluctuation rate Ha and the second flow rate fluctuation rate Hb becomes small, the first control unit 200 may perform control so that the first flow rate fluctuation rate Ha becomes small. , may be controlled to be large. Also, the second flow rate variation rate Hb may be controlled to decrease or may be controlled to increase.

This is because when the peak values of the flow rate value of the first solution A1 and the flow rate value of the second solution A2 fluctuate synchronously, the difference between the first flow rate fluctuation rate Ha and the second flow rate fluctuation rate Hb is If it is smaller, the peaks and troughs of the flow rate values overlap with each other in the peaks and valleys of the flow rate fluctuations of the first solution A1 and the second solution A2 regardless of the magnitude of the first flow rate fluctuation rate Ha and the second flow rate fluctuation rate Hb. is. That is, when the first solution A1 and the second solution A2 are mixed, the peaks of the flow rate values are mixed and the troughs of the flow rate values are mixed. Therefore, by executing control to reduce the difference between the first flow rate fluctuation rate Ha and the second flow rate fluctuation rate Hb, regardless of the magnitude of the first flow rate fluctuation rate Ha and the second flow rate fluctuation rate Hb, the first flow rate fluctuation rate The mixing ratio of the solution A1 and the second solution A2 can be made close to the same ratio.

For example, as shown in FIG. 2, when reducing the difference between the first flow rate fluctuation rate Ha and the second flow rate fluctuation rate Hb, the first control unit 200 reduces the second flow rate fluctuation rate with a small flow rate fluctuation rate before control. Control is performed so that the first flow rate fluctuation rate Ha is reduced in accordance with the rate Hb. If the first flow rate fluctuation rate Ha and the second flow rate fluctuation rate Hb are out of sync for some reason by reducing the first flow rate fluctuation rate Ha in accordance with the second flow rate fluctuation rate Hb having a small flow rate fluctuation rate, In this case as well, fluctuations in the mixing ratio of the first solution A1 and the second solution A2 can be minimized, and the mixing ratio of the first solution A1 and the second solution A2 can be stabilized.

Specifically, in the flow rate waveform before control in FIG. 2, the first flow rate fluctuation rate Ha is larger than the second flow rate fluctuation rate Hb (Ha>Hb). Therefore, the first control unit 200 controls the first flow rate adjusting unit 151 to reduce the first flow rate fluctuation rate Ha. As a result, the difference x (=|Ha−Hb|) between the first flow rate fluctuation rate Ha and the second flow rate fluctuation rate Hb becomes smaller.

Note that the first control unit 200 is not limited to controlling the first flow rate fluctuation rate Ha to be small in accordance with the second flow rate fluctuation rate Hb having a small flow rate fluctuation rate. Control may be performed to increase the second flow rate fluctuation rate Hb in accordance with the fluctuation rate Ha.

Next, operation of the polymer manufacturing system 1 in the first embodiment will be described with reference to FIG.
First, in the polymer production system 1, by starting the operation, the first supply pump 15 supplies the first solution A1 under the control of the first flow rate adjusting unit 151 (first supply step), and the second flow rate adjusting unit The second supply pump 16 supplies the second solution A2 under the control of 161 (second supply step). Here, the first flow rate adjusting section 151 and the second flow rate adjusting section 161 are controlled by the first control section 200 so as to supply the first solution A1 and the second solution A2 at a desired ratio.

Next, as shown in FIG. 3, in step ST11, the first flow rate measurement unit 152 measures and acquires the flow rate of the first solution A1 (first measurement step). Also, the second flow rate measuring unit 162 measures and acquires the flow rate of the second solution A2 (second measurement step). In the present embodiment, the peak values of the flow rate value of the first solution A1 and the flow rate value of the second solution A2 are synchronized by the first flow rate adjusting section 151 and the second flow rate adjusting section 161 controlled by the first control section 200. controlled to

Next, in step ST12, the first control section 200 determines whether or not the difference between the first flow rate fluctuation rate and the second flow rate fluctuation rate is outside the predetermined range.
As shown in FIG. 2, in the flow rate waveform before control, the first solution A1 and the second solution A2 are not synchronized in flow rate variation. Also, the difference x between the first flow rate fluctuation rate Ha and the second flow rate fluctuation rate Hb is |Ha-Hb| (>0). In this embodiment, the predetermined range of the difference x between the first flow rate fluctuation rate Ha and the second flow rate fluctuation rate Hb is set to, for example, 3% or less. This is because the desired polymer can be stably obtained when the difference between the first flow rate fluctuation rate Ha and the second flow rate fluctuation rate Hb is, for example, 3% or less.

If the first control unit 200 determines that the difference between the first flow rate fluctuation rate and the second flow rate fluctuation rate is outside the predetermined range (YES), the process proceeds to step ST13. If the first control unit 200 determines that the difference between the first flow rate fluctuation rate and the second flow rate fluctuation rate is not outside the predetermined range (NO), the process returns to step ST11.

Next, in step ST13, for example, when the difference between the first flow rate fluctuation rate and the second flow rate fluctuation rate is outside the predetermined range, the first control unit 200 sets the first flow rate fluctuation rate and the second flow rate fluctuation rate to A command is issued to the first flow rate adjusting section 151 and/or the second flow rate adjusting section 161 so as to reduce the difference in (first control step).
As a result, as shown in FIG. 2, after the control, the first flow rate fluctuation rate Ha is adjusted to be small, and the difference x (=|Ha- Hb|) is reduced so that it falls within a predetermined range.

Here, for the first solution A1 and the second solution A2, since the peak value of the flow rate of the first solution A1 and the peak value of the flow rate of the second solution A2 fluctuate synchronously, the first solution A1 and the second solution A2 are mixed in a state in which the peaks and valleys of the flow rate fluctuations coincide. Therefore, by controlling the difference between the first flow rate fluctuation rate and the second flow rate fluctuation rate to be small, the first solution A1 and the second solution A2 can be mixed at a ratio close to the same, and the desired A polymer can be stably obtained. In addition, when the polymer production system 1 produces polyimide, if the viscosity of the first polymerization solution C becomes stable, the desired quality of the imidized film product can be easily achieved.

Next, the control for reducing the difference between the first flow rate fluctuation rate and the second flow rate fluctuation rate in the first control section 200 enters a standby state (step ST14). After that, the process is returned to step ST11.

According to the polymer production system 1 of this embodiment, the following effects are obtained.
The polymer production system 1 includes a first mixing section 20 that mixes a first solution A1 and a second solution A2 with fluctuating peak flow rate values to generate a first mixed solution B, in which the first solution Synchronize the flow rate fluctuations of A1 and second solution A2, and control the first flow rate fluctuation rate and/or the second flow rate fluctuation rate so that the difference between the first flow rate fluctuation rate and the second flow rate fluctuation rate becomes small. A first control unit 200 is provided. According to such a polymer production system 1, the difference between the first flow rate fluctuation rate and the second flow rate fluctuation rate can be reduced, so it is possible to continuously and stably obtain a desired polymer.

Further, in the polymer production system 1, the first control unit 200 controls the first flow rate adjusting unit 151 and/or the second flow rate adjusting unit so that the difference between the first flow rate fluctuation rate and the second flow rate fluctuation rate becomes small. 161 adjusts the flow rate. As a result, the polymer production system 1 can reduce the difference between the first flow rate fluctuation rate and the second flow rate fluctuation rate and circulate the first solution A1 and the second solution A2 without changing the flow rate. , it is possible to obtain the desired polymer continuously and more stably.

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

In addition, in the present embodiment, the case where the first reaction section 30 is composed of a double pipe of the first reaction stirring section 31 and the first reaction temperature adjustment section 32 has been described, but the present invention is not limited to this. . For example, the first reaction section 30 may be composed of only the first reaction-stirring section 31 with a single tube, and the first reaction-stirring section 31 may be immersed in the temperature control liquid.

<Second embodiment>
Next, a polymer manufacturing system according to a second embodiment will be described with reference to FIGS. 4 and 5. FIG. FIG. 4 is a diagram showing a polymer production system in the second embodiment. FIG. 5 is a flowchart explaining the operation of the polymer production system in the second embodiment. The second embodiment is an example of a polymer production system having two stages of processing sections (reaction sections).

First, a polymer production system 1A in the second embodiment will be described with reference to FIG.
As shown in FIG. 4, the polymer production system 1A has a first processing section K1 and a second processing section K2.

Since the first processing unit K1 has the same configuration as the polymer production system 1 in the first embodiment, detailed description in this embodiment is omitted. The description in the first embodiment can be used for the configuration requirements, operation, and the like in the first processing unit K1. However, the first polymerization solution C produced in the first processing section K1 contains an acid anhydride group-terminated or amino group-terminated polyamic acid (prepolymer) as the first polymer.

The second processing section K2 uses the first polymerization solution C produced by the first processing section K1 (the polymer production system 1 in the first embodiment) and the third solution A3 as raw materials to further progress the polymerization reaction, A polyamic acid (second polymer) is produced. The second processing section K2 has the same basic configuration as the first processing section K1, but uses the first polymerization solution C produced by the first processing section K1 as a raw material to produce polyamic acid (second polymer). It is different from the first processing unit K1 in that

The second processing section K2 includes a third tank 13, a third supply pump 17 (third supply section), a second mixing section 50, a second reaction section 60, a second cushion tank 70, and a liquid feeding line. and a portion of L. A part of the liquid feeding line L described above has a fourth liquid feeding section L4 and a fifth liquid feeding section L5. The second processing unit K2 also has a third flow rate adjusting unit 171, a third flow rate measuring unit 172, and a fourth flow rate measuring unit 182 (polymerization solution flow rate measuring unit).

The fourth flow rate measuring section 182 measures the flow rate of the first polymerization solution C on the downstream side of the first reaction section 30 in the third liquid feeding section L3. The fourth flow rate measurement unit 182 outputs the measured flow rate of the first polymerization solution C to the second control unit 200A, which will be described later.

The third tank 13 contains a third solution A3 containing a polyaddition third polymerizable compound that polyadditions to the first polymer contained in the first polymerization solution C. As shown in FIG. In the case of the present embodiment, the third tank 13 is a third solution in which a diamine or a tetracarboxylic dianhydride that polyadds to an acid anhydride group-terminated or amino group-terminated polyamic acid contained in the first polymerization solution C is dissolved. Accommodates A3. The third solution A3 stored in the third tank 13 is supplied to the second mixing section 50 via the fourth liquid feeding section L4.

As an example, the case where the first polymerization solution C contains an acid anhydride group-terminated polyamic acid and the third solution A3 contains a diamine will be described below.

Between the third tank 13 and the second mixing section 50 in the fourth liquid feeding section L4, the third supply pump 17 and the third flow rate measuring section 172 are arranged in this order from the upstream side to the downstream side. be.

The third supply pump 17 (third supply section) supplies the third solution A3 contained in the third tank 13 to the second mixing section 50 . The third supply pump 17 discharges the third solution A3 so as to supply the third solution A3 at a predetermined amount. For example, the third supply pump 17 is adjusted so as to supply the third solution A3 under conditions under which polyamic acid (second polymer) with desired properties is obtained. The amount supplied by the third supply pump 17 can be set according to the properties and composition of the first polymerization solution C. Further, the supply amount of the third supply pump 17 can be set according to the reaction rate of the first polymerization solution C and the like. In other words, the supply amount of the third supply pump 17 can be adjusted to a supply amount that achieves the target properties, composition and reaction rate.
In this embodiment, the third supply pump 17 is a positive displacement pump, like the first supply pump 15 described above.

As the third supply pump 17, it is preferable to select a pump having a small intrinsic pulsation rate (flow rate fluctuation rate). Instead of selecting the third supply pump 17 having a small characteristic pulsation rate (flow rate fluctuation rate), or selecting a third supply pump 17 having a small characteristic pulsation rate (flow rate fluctuation rate). In addition, it is also preferable to arrange a flow rate fluctuation damping device (for example, an accumulator) in the liquid feeding line L. By arranging a shock absorber such as an accumulator, the flow rate fluctuation rate can be further reduced.

The third flow rate adjusting section 171 is electrically connected to the third supply pump 17 and adjusts the flow rate of the third solution A3. The third flow rate adjusting section 171 is controlled by a second control section 200A, which will be described later.

The third flow rate measuring section 172 measures the flow rate of the third solution A3 on the downstream side of the third supply pump 17 in the fourth liquid feeding section L4. In this embodiment, the third flow rate measuring section 172 is arranged between the third supply pump 17 and the second mixing section 50 . The third flow rate measurement unit 172 outputs the measured flow rate of the third solution A3 to the second control unit 200A, which will be described later.

The second mixing section 50 is arranged downstream of the first reaction section 30 and the third supply pump 17 of the first processing section K1. The second mixing section 50 mixes the first polymerization solution C from the first reaction section 30 and the third solution A3 from the third supply pump 17 to generate the second mixed solution D. The second mixing section 50 is composed of a confluence valve for combining the first polymerization solution C from the first reaction section 30 and the third solution A3 from the third supply pump 17 .

In the present embodiment, the first polymerization solution C and the third solution A3 are adjusted so that the peak values of the flow rate values are synchronized in the same manner as the first solution A1 and the second solution A2 of the first embodiment (see FIG. 2). Liquid is sent. Here, the synchronous fluctuation of the peak value of the flow rate means that the cycle of the flow rate fluctuation is substantially the same, and a slight difference in phase is allowed. For example, let _L2 be the distance between adjacent peaks (mountains) of the flow rate value of the first polymerization solution C, and When the distance (that is, the phase shift) is _M2 , it is preferable that _L2 and _M2 satisfy the following formula (2).
0≦(M ₂ /L ₂ )≦0.1 (2)

As in the first embodiment, the period of flow rate fluctuation of the first polymerization solution C and the period of flow rate fluctuation of the third solution A3 may not necessarily be constant.

The second reaction section 60 is arranged continuously downstream of the second mixing section 50 . In the present embodiment, the second reaction section 60 comprises an acid anhydride group-terminated polyamic acid (first polymer) from the first polymerization solution C contained in the second mixed solution D, and a diamine from the third solution A3. It is a portion that advances the polymerization reaction with (the third polymerizable compound). In the second reaction section 60, the acid anhydride group-terminated polyamic acid (first polymer) from the first polymerization solution C contained in the second mixed solution D and the diamine (third polymerizable compound) proceeds gradually, and a second polymerization solution E is obtained.

The second reaction section 60 is composed of a double tube extending in a predetermined direction, and includes a second reaction stirring section 61 arranged radially inward and a second reaction temperature adjusting section 62 arranged radially outward. , has The second reaction section 60 is formed so that the second mixed solution D flows for a desired residence time.

The second reaction stirring part 61 stirs the second mixed solution D in which the first polymerization solution C and the third solution A3 are mixed without coming into contact with gas. In the present embodiment, the second reaction stirring section 61 stirs the second mixed solution D adjusted to a temperature suitable for the polymerization reaction by the second reaction temperature adjusting section 62 without contacting gas.

The second reaction-stirring unit 61 includes, for example, static mixers, nozzles, orifices, and other stationary mixers, centrifugal pumps, volute pumps, and drive-type mixers, such as in-line mixers having stirring blades. It comprises a static mixer, more preferably a static mixer. As described above, a pipe with a twist tape inserted therein can also provide a stirring promotion effect in the same manner as a static mixer.

The static mixer is not particularly limited, and examples thereof include static mixers such as Kenics mixer type, Sulzer SMV type, Sulzer SMX type, Tray Hi-mixer type, Komax mixer type, Lightnin mixer type, Ross ISG type, and Bran & Lube mixer type. mentioned. Among these, the Kenics mixer type static mixer is more preferable since it has a simple structure and has no dead space.

The second reaction temperature adjusting section 62 is a piping section arranged radially outside the second reaction stirring section 61 . The second reaction temperature adjusting section 62 adjusts (for example, cools) the second mixed solution D flowing through the second reaction stirring section 61 to a desired temperature condition. In the second reaction temperature adjusting section 62 , the second mixed solution D is adjusted to a temperature suitable for the polymerization reaction, and is passed through the second reaction stirring section 61 .

The second cushion tank 70 accommodates the second polymerization solution E from the second reaction section 60 . The second cushion tank 70 serves as a tank for containing a raw material solution, for example, when polyimide is produced by imidating polyamic acid, which is the second polymer.

When the polymer manufacturing system 1A according to the present embodiment manufactures polyimide, the polymer manufacturing system 1A further includes an imidization unit that imidizes the polyamic acid. The imidization unit (not shown) imidizes the polyamic acid by, for example, a thermal imidization method of thermal dehydration ring closure, a chemical imidization method using a dehydrating agent and an imidization accelerator, or the like.

When the polymer manufacturing system 1A manufactures polyimide, the second cushion tank 70 may be omitted and the liquid may be fed from the second reaction section 60 to the imidization section. However, as described above, it is preferable to temporarily store the polyamic acid in the second cushion tank 70 .

The second control section 200A will be described. The second control unit 200A includes a first flow rate adjusting unit 151, a first flow measuring unit 152, a second flow adjusting unit 161, a second flow measuring unit 162, a third flow adjusting unit 171, a third flow measuring unit 172, and the fourth flow rate measurement unit 182 are electrically connected.

Although the second control unit 200A also has the functions of the first control unit 200 in the first embodiment, detailed descriptions of the parts common to the first control unit 200 will be omitted below.

The second control unit 200A controls the flow rate fluctuation rate of the first polymerization solution C (hereinafter also referred to as "polymerization solution flow rate fluctuation rate") and the flow rate fluctuation rate of the third solution A3 (hereinafter, "third flow rate fluctuation rate"). The flow rate fluctuation rate of the third solution A3 is controlled so that the difference between the third solution A3 and the In the present embodiment, the difference between the polymerization solution flow rate fluctuation rate and the third flow rate fluctuation rate is, for example, preferably 3% or less, more preferably 1% or less. The lower limit of the difference between the polymerization solution flow rate fluctuation rate and the third flow rate fluctuation rate may be 0%, but is preferably 0.001% or more. The difference between the polymerization solution flow rate fluctuation rate and the third flow rate fluctuation rate is set to 0.001% or more, and by slightly shifting the mixing ratio of the first polymerization solution C and the third solution A3, the first polymerization solution C and the third solution A3 are mixed. It tends to be well mixed with the third solution A3.

In this embodiment, based on the same concept as the first flow rate fluctuation rate Ha and the second flow rate fluctuation rate Hb of the first embodiment, for example, the polymerization solution flow rate fluctuation rate Hc is set to the flow rate value Kc at the center of the amplitude of the flow rate fluctuation. It is defined as the ratio of the flow rate Sc that is half the amplitude of the flow rate fluctuation to the (Hc=(Sc/Kc)×100[%]). Further, for example, the third flow rate fluctuation rate Hd is defined as the ratio of the flow rate Sd half the amplitude of the flow rate fluctuation to the flow rate value Kd at the center of the amplitude of the flow rate fluctuation (Hd=(Sd/Kd)×100 [%] ).
In addition, the difference y between the polymerization solution flow rate fluctuation rate Hc and the third flow rate fluctuation rate Hd is based on the same concept as the difference x between the first flow rate fluctuation rate Ha and the second flow rate fluctuation rate Hb in the first embodiment. The absolute value of the difference between the polymerization solution flow rate fluctuation rate Hc and the third flow rate fluctuation rate Hd is used (y=|Hc−Hd|).
Before the control of this embodiment, the first polymerization solution C and the third solution A3 are not synchronized in flow rate variation.

The second control unit 200A adjusts the operation of the third supply pump 17 via the third flow rate adjusting unit 171, for example, so that the flow rate fluctuations of the first polymerization solution C and the third solution A3 are synchronized. Further, for example, when the difference between the polymerization solution flow rate fluctuation rate Hc and the third flow rate fluctuation rate Hd is outside the predetermined range, the second control unit 200A changes the polymerization solution flow rate fluctuation rate Hc and the third flow rate fluctuation rate Hd The flow rate of the third solution A3 is adjusted by the third flow rate adjusting section 171 so that the difference between . In this embodiment, the predetermined range of the difference between the polymerization solution flow rate fluctuation rate Hc and the third flow rate fluctuation rate Hd is set to, for example, 3% or less.

When performing control so that the difference between the polymerization solution flow rate fluctuation rate Hc and the third flow rate fluctuation rate Hd becomes small, the second control unit 200A may perform control so that the third flow rate fluctuation rate Hd becomes small. , may be controlled to be large.

This is because when the peak values of the flow rates of the polymerization solution flow rate fluctuation rate Hc and the third flow rate fluctuation rate Hd fluctuate synchronously, the difference between the polymerization solution flow rate fluctuation rate Hc and the third flow rate fluctuation rate Hd is is small, irrespective of the magnitude of the polymerization solution flow rate fluctuation rate Hc and the third flow rate fluctuation rate Hd, the peaks and troughs of the flow rate values of the first polymerization solution C and the third solution A3 are This is because they overlap. That is, when the first polymerization solution C and the third solution A3 are mixed, the peaks of the flow rate values are mixed and the troughs of the flow rate values are mixed. Therefore, by executing control to reduce the difference between the polymerization solution flow rate fluctuation rate Hc and the third flow rate fluctuation rate Hd, regardless of the magnitudes of the polymerization solution flow rate fluctuation rate Hc and the third flow rate fluctuation rate Hd, the first The mixing ratio of the polymerization solution C and the third solution A3 can be brought close to the same ratio.

Next, operation of the polymer production system 1A in the second embodiment will be described with reference to FIG.
First, in the polymer production system 1A, by starting the operation, the first supply pump 15 supplies the first solution A1 under the control of the first flow rate adjusting unit 151 (first supply step), and the second flow rate adjusting unit 161 controls the second supply pump 16 to supply the second solution A2 (second supply step), and the third flow rate adjustment unit 171 controls the third supply pump 17 to supply the third solution A3 (third supply step). process). Here, the first flow rate adjusting section 151 and the second flow rate adjusting section 161 are controlled by the second control section 200A so as to supply the first solution A1 and the second solution A2 at a desired ratio. The third flow rate adjusting section 171 is controlled by the second control section 200A so as to supply the third solution A3 at a desired rate.

Next, as shown in FIG. 5, in step ST21, the fourth flow rate measurement unit 182 measures and acquires the flow rate of the first polymerization solution C (polymerization solution flow rate measurement step). Also, the third flow rate measuring unit 172 measures and acquires the flow rate of the third solution A3 (third measuring step). In the present embodiment, the peak value of the flow rate value of the first polymerization solution C and the flow rate value of the third solution A3 are controlled to be synchronized by the third flow rate adjusting section 171 controlled by the second control section 200A. .

Next, in step ST22, the second control section 200A determines whether or not the difference between the polymerization solution flow rate fluctuation rate and the third flow rate fluctuation rate is outside the predetermined range. In this embodiment, the predetermined range of the difference between the polymerization solution flow rate fluctuation rate and the third flow rate fluctuation rate is set to, for example, 3% or less. This is because a desired polymer can be stably obtained when the difference between the polymerization solution flow rate fluctuation rate and the third flow rate fluctuation rate is, for example, 3% or less.

Then, when the second control section 200A determines that the difference between the polymerization solution flow rate fluctuation rate and the third flow rate fluctuation rate is outside the predetermined range (YES), the process proceeds to step ST23. If the second control unit 200A determines that the difference between the polymerization solution flow rate fluctuation rate and the third flow rate fluctuation rate is not outside the predetermined range (NO), the process returns to step ST21.

Next, in step ST23, the second control unit 200A, for example, when the difference between the polymerization solution flow rate fluctuation rate and the third flow rate fluctuation rate is outside the predetermined range, the polymerization solution flow rate fluctuation rate and the third flow rate fluctuation rate (second control step).
As a result, after the control, the third flow rate fluctuation rate is adjusted to be smaller or larger, and the difference y between the polymerization solution flow rate fluctuation rate and the third flow rate fluctuation rate is reduced so as to be within a predetermined range. .

Here, for the first polymerization solution C and the third solution A3, since the peak value of the flow rate of the first polymerization solution C and the peak value of the flow rate of the third solution A3 fluctuate synchronously, the first The polymerization solution C and the third solution A3 are mixed in a state in which peaks and valleys of flow rate fluctuations are aligned. Therefore, by controlling the difference between the polymerization solution flow rate fluctuation rate and the third flow rate fluctuation rate to be small, the first polymerization solution C and the third solution A3 can be mixed at a ratio close to the same, and the desired can be stably obtained.

Next, the control for reducing the difference between the polymerization solution flow rate fluctuation rate and the third flow rate fluctuation rate in the second control section 200A enters a standby state (step ST24). After that, the process is returned to step ST21.

According to the polymer production system 1A of the present embodiment, the following effects are obtained in addition to the effects of the above-described first embodiment.
The polymer production system 1A is a system including a second mixing section 50 that mixes a first polymerization solution C and a third solution A3 in which the peak value of the flow rate fluctuates to generate a second mixed solution D, in which the first A second control unit 200A that controls the third flow rate fluctuation rate such that the flow rate fluctuations of the polymerization solution C and the third solution A3 are synchronized and the difference between the polymerization solution flow rate fluctuation rate and the third flow rate fluctuation rate becomes small. Prepare. According to such a polymer production system 1A, the difference between the polymerization solution flow rate fluctuation rate and the third flow rate fluctuation rate can be reduced, so it is possible to continuously and stably obtain a desired polymer.

In addition, in the polymer production system 1A, the second control section 200A adjusts the flow rate by the third flow rate adjusting section 171 so that the difference between the polymerization solution flow rate fluctuation rate and the third flow rate fluctuation rate becomes small. Thereby, the polymer production system 1A can reduce the difference between the polymerization solution flow rate fluctuation rate and the third flow rate fluctuation rate, and can circulate the first polymerization solution C and the third solution A3 without changing the flow rate. Therefore, a desired polymer can be obtained continuously and more stably.

In the present embodiment, the case where the second reaction section 60 is composed of a double pipe of the second reaction stirring section 61 and the second reaction temperature adjustment section 62 has been described, but it is not limited to this. . For example, the second reaction section 60 may be composed of only the second reaction-stirring section 61 with a single tube, and the second reaction-stirring section 61 may be immersed in the temperature control liquid.

<Specific example of control>
Specific examples of control in the polymer production system 1 and the polymer production system 1A will be described below. However, it is not limited to the following specific examples.

(1) Example 1
Plunger pumps are used as the first supply pump 15 and the second supply pump 16 . Coriolis mass flowmeters are used as the first flow rate measuring section 152 and the second flow rate measuring section 162 to measure the flow rates of the first solution A1 and the second solution A2. Based on the obtained flow rate information, the first control unit 200 causes the first flow rate adjusting unit 151 to control the first supply pump so that the flow rate fluctuation of the first solution A1 and the flow rate fluctuation of the second solution A2 are synchronized. Indicate 15 new stroke and rpm setting information. Then, the first flow rate adjusting section 151 changes the stroke and rotation speed of the first supply pump 15 . By doing so, it is possible to control the flow rate fluctuation of the first solution A1 and the flow rate fluctuation of the second solution A2 to be synchronized.

Based on the obtained flow rate information, the first control unit 200 issues an instruction to the second flow rate adjustment unit 161 so that the flow rate fluctuation of the second solution A2 is synchronized with the flow rate fluctuation of the first solution A1. may

(2) Example 2
Plunger pumps are used as the first supply pump 15 , the second supply pump 16 and the third supply pump 17 . Control of the flow rates of the first solution A1 and the second solution A2 is performed as shown in Example 1. Coriolis mass flowmeters are used as the fourth flow rate measuring section 182 and the third flow rate measuring section 172 to measure the flow rates of the first polymerization solution C and the third solution A3. The second control unit 200A controls the third flow rate adjusting unit 171 based on the obtained flow rate information so that the flow rate fluctuation of the third solution A3 and the flow rate fluctuation of the first polymerization solution C are synchronized. A new stroke and rotation speed setting information for the pump 17 is instructed. Then, the third flow rate adjusting section 171 changes the stroke and rotation speed of the third supply pump 17 . By doing so, it is possible to control the fluctuation of the flow rate of the third solution A3 and the fluctuation of the flow rate of the first polymerization solution C so as to synchronize with each other.

In addition, based on the obtained flow rate information, the second control unit 200A controls the first flow rate adjusting unit 151 and/or An instruction may be issued to the second flow rate adjustment unit 161 . However, in the case of Example 2, it is preferable to issue an instruction to the third flow rate adjusting section 171 in order to adjust the flow rate variation of the third solution A3 from the viewpoint of facilitating the instruction and adjustment.

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

For example, in the above-described embodiments, the polymer production system is configured to have one or two reaction units (treatment units), but is not limited to this, and may include three or more reaction units (treatment units). part). That is, the polymer production system is not limited to one that performs one-stage or two-stage reactions, and may be one that performs three or more stages of reactions. For example, the polymer production system may be configured to have three or more sets of mixing sections and reaction sections. The polymer production system can adjust the amount of supply and the like in a multi-step manner so as to approach the target reaction rate and quality each time it passes through each reaction section (treatment section).

Also, in the above-described embodiments, the polymer production system for producing polyamic acid or polyimide was described, but the polymer to be produced is not limited to these. For example, the polymer production system may produce polymers using polyaddition monomers such as urethane monomers and epoxy monomers.

Further, in the polymer production system, the first solution A1 and/or the second solution A2 may contain a filler. By adding a filler to the first solution A1 and/or the second solution A2, it is possible to easily introduce the filler into the produced polymer.

1, 1A polymer production system 15 first supply pump (first supply unit)
16 second supply pump (second supply unit)
17 Third supply pump (third supply unit)
20 first mixing section 30 first reaction section 50 second mixing section 60 second reaction section 151 first flow rate adjusting section 152 first flow rate measuring section 161 second flow rate adjusting section 162 second flow rate measuring section 171 third flow rate adjusting section 172 third flow rate measuring section 182 fourth flow rate measuring section (polymerization solution flow rate measuring section)
200 First control unit 200A Second control unit A1 First solution A2 Second solution A3 Third solution B First mixed solution C First polymerization solution D Second mixed solution E Second polymerization solution L Liquid sending line

Claims (10)

a first solution containing a first polyaddition polymerizable compound and a second solution containing a second polyaddition polymerizable compound that polyadditions with the first polymerizable compound as raw materials to produce a polymer; A combined manufacturing system,
a first supply unit that supplies the first solution;
a second supply unit that supplies the second solution;
a first mixing unit that mixes the first solution and the second solution to generate a first mixed solution;
a first flow rate measurement unit that measures the flow rate of the first solution;
a first flow rate adjusting unit capable of adjusting the flow rate of the first solution;
a second flow rate measurement unit that measures the flow rate of the second solution;
a second flow rate adjusting unit capable of adjusting the flow rate of the second solution;
It is arranged continuously downstream of the first mixing section, and includes a first polymer by advancing a polymerization reaction between the first polymerizable compound and the second polymerizable compound contained in the first mixed solution. a first reaction section that produces a first polymerization solution;
The flow rate fluctuations of the first solution and the second solution are controlled so as to be synchronized, and the difference between the flow rate fluctuation rate of the first solution and the flow rate fluctuation rate of the second solution is 3% or less. , a first control unit that adjusts the flow rate by the first flow rate adjustment unit and / or the second flow rate adjustment unit ,
Among the first polymerizable compound and the second polymerizable compound, one is a tetracarboxylic dianhydride and the other is a diamine, or one is an acid anhydride group-terminated or amino group-terminated polyamic acid, and the other is A diamine or a tetracarboxylic dianhydride,
A polymer production system for producing polyamic acid as the first polymer . 2. The polymer production system according to claim 1 , wherein the first reaction section has a first reaction/stirring section that stirs the first mixed solution without coming into contact with gas. The first polymer is a polyaddition polymer,
a third supply unit that supplies a third solution containing a polyadditive third polymerizable compound that polyadditions to the first polymer;
a second mixing unit that mixes the first polymerization solution and the third solution to generate a second mixed solution;
a polymerization solution flow rate measuring unit that measures the flow rate of the first polymerization solution;
a third flow rate measuring unit that measures the flow rate of the third solution;
a third flow rate adjusting unit capable of adjusting the flow rate of the third solution;
The first polymer from the first polymerization solution and the third polymerizable compound from the third solution, which are arranged continuously downstream of the second mixing section and are contained in the second mixed solution a second reaction part that advances the polymerization reaction of to generate a second polymerization solution containing the second polymer;
The flow rate fluctuations of the first polymerization solution and the third solution are controlled to be synchronized, and the difference between the flow rate fluctuation rate of the first polymerization solution and the flow rate fluctuation rate of the third solution is 3% or less. and a second control unit that adjusts the flow rate by the third flow rate adjustment unit ,
The first polymer is an acid anhydride group-terminated or amino group-terminated polyamic acid,
the third polymerizable compound is a diamine or a tetracarboxylic dianhydride,
3. The polymer production system according to claim 1, wherein polyamic acid is produced as the second polymer . 4. The polymer production system according to claim 3 , wherein the second reaction section has a second reaction/stirring section that stirs the second mixed solution without coming into contact with gas. The polymer production system according to any one of claims 1 to 4, further comprising an imidization unit that imidizes the produced polyamic acid. a first solution containing a first polyaddition polymerizable compound and a second solution containing a second polyaddition polymerizable compound that polyadditions with the first polymerizable compound as raw materials to produce a polymer; A method of manufacturing a coalescence,
a first supply step of supplying the first solution;
a second supply step of supplying the second solution;
a first mixing step of mixing the first solution and the second solution to generate a first mixed solution;
a first measuring step of measuring the flow rate of the first solution;
a first flow rate adjustment step capable of adjusting the flow rate of the first solution;
a second measuring step of measuring the flow rate of the second solution;
a second flow rate adjustment step capable of adjusting the flow rate of the second solution;
a first reaction step of allowing a polymerization reaction between the first polymerizable compound and the second polymerizable compound contained in the first mixed solution to generate a first polymerization solution containing the first polymer;
The flow rate fluctuations of the first solution and the second solution are controlled so as to be synchronized, and the difference between the flow rate fluctuation rate of the first solution and the flow rate fluctuation rate of the second solution is 3% or less. , a first control step of adjusting the flow rate by the first flow rate adjustment step and / or the second flow rate adjustment step ,
Among the first polymerizable compound and the second polymerizable compound, one is a tetracarboxylic dianhydride and the other is a diamine, or one is an acid anhydride group-terminated or amino group-terminated polyamic acid, and the other is A diamine or a tetracarboxylic dianhydride,
A method for producing a polymer in which polyamic acid is produced as the first polymer . 7. The method for producing a polymer according to claim 6 , wherein the first reaction step includes a first reaction-stirring step of stirring the first mixed solution without contacting gas. The first polymer is a polyaddition polymer,
a third supplying step of supplying a third solution containing a polyadditional third polymerizable compound that polyadditions to the first polymer;
a second mixing step of mixing the first polymerization solution and the third solution to generate a second mixed solution;
a polymerization solution flow rate measuring step of measuring the flow rate of the first polymerization solution;
a third flow rate measuring step of measuring the flow rate of the third solution;
a third flow rate adjusting step capable of adjusting the flow rate of the third solution;
The polymerization reaction between the first polymer from the first polymerization solution contained in the second mixed solution and the third polymerizable compound from the third solution is allowed to proceed to produce a second polymer containing the second polymer. a second reaction step of producing a polymerization solution;
The flow rate fluctuations of the first polymerization solution and the third solution are controlled to be synchronized, and the difference between the flow rate fluctuation rate of the first polymerization solution and the flow rate fluctuation rate of the third solution is 3% or less. and a second control step of adjusting the flow rate by the third flow rate adjustment step ,
The first polymer is an acid anhydride group-terminated or amino group-terminated polyamic acid,
the third polymerizable compound is a diamine or a tetracarboxylic dianhydride,
8. The method for producing a polymer according to claim 6, wherein polyamic acid is produced as the second polymer . 9. The method for producing a polymer according to claim 8 , wherein the second reaction step includes a second reaction-stirring step of stirring the second mixed solution without coming into contact with gas. 10. The method for producing the polymer according to any one of claims 6 to 9, further comprising an imidization step of imidizing the produced polyamic acid.

Images