Polymer manufacturing device and manufacturing method

Abstract

A polymer manufacturing device according to the present invention comprises a catalyst supply part having: a first flow path through which a ligand solution is fed; a second flow path which is filled with a powdery metal catalyst in the direction of gravity; and an introduction part which introduces the ligand solution from the first flow path to the second flow path. The second flow path is disposed so that the ligand solution introduced from the introduction part is fed downward in the direction of gravity.

Description

Polymer manufacturing apparatus and manufacturing method

[0001] The present disclosure relates to a polymer production method and apparatus.

[0002] In recent years, methods using flow-type microreactors have been attracting attention in chemical synthesis. Generally, microreactors are devices in which reactions occur within minute channels with internal structures measuring several micrometers to several millimeters. Such microreactors have advantages in chemical synthesis, such as high temperature controllability and good mixing efficiency, due to their large surface area per unit volume. In chemical synthesis, the large surface area and high heat transfer properties allow, for example, heat generated during a reaction to easily diffuse to the surroundings, enabling temperature control. This increases yields and reduces the molecular weight dispersity of polymeric materials. Furthermore, due to their fast mixing efficiency, they are used in reactions using unstable raw materials.

[0003] For example, in polymer synthesis, the molecular weight dispersity can be reduced in the case of polymer polymerization such as living cationic polymerization (see, for example, Patent Document 1) or living anionic polymerization (see, for example, Patent Document 2).

[0004] Japanese Patent No. 4417811 JP 2015-127425 A

[0005] The above-mentioned methods (Patent Documents 1 and 2) are all homogeneous synthesis methods, and in reaction systems using catalysts with low solubility in solvents, such as coupling reactions, there is a problem that the microreactor becomes clogged.

[0006] The present disclosure is intended to solve the above-mentioned conventional problems, and aims to provide a polymer production apparatus that can deliver a catalyst solution containing a ligand-exchanged metal catalyst to a microchannel for microflow synthesis without clogging in a reaction system that uses a catalyst with low solubility in a solvent, such as in a coupling reaction.

[0007] A polymer production apparatus according to one embodiment of the present disclosure comprises a first flow path for transporting a ligand solution, a second flow path filled with a powdered metal catalyst, and an inlet section for introducing the first flow path into the second flow path, and the second flow path is positioned so that the ligand solution introduced from the inlet section is transported in the direction of gravity.

[0008] Furthermore, a method for producing a polymer according to one embodiment of the present invention includes the steps of: sending a ligand solution to a first flow path; introducing the ligand solution into a second flow path filled with a powdered metal catalyst; sending the ligand solution introduced into the second flow path in the direction of gravity; and sending a solution containing the metal catalyst that has undergone ligand exchange in the second flow path from the second flow path.

[0009] According to the polymer production apparatus and method disclosed herein, even in the production of polymers using metal catalysts that have low solubility in solvents, stable liquid delivery can be achieved without clogging the metal catalyst.

[0010] Fig. 1 is a schematic diagram showing the configuration of a polymer production apparatus according to Embodiment 1. Fig. 2 is a flowchart of a polymer production method according to Embodiment 1. Fig. 3 is Table 1 showing the conditions and evaluation results of Examples 1 to 4 and Comparative Examples 1 and 2.

[0011] The polymer production apparatus according to the first aspect comprises a catalyst supply section having a first flow path for supplying a ligand solution, a second flow path filled with a powdered metal catalyst along the direction of gravity, and an introduction section for introducing the ligand solution from the first flow path into the second flow path, and the second flow path is arranged so that the ligand solution introduced from the introduction section is supplied downward in the direction of gravity.

[0012] A polymer production apparatus according to a second aspect is the above-mentioned first aspect, wherein the second flow path may further include a pressure applying mechanism that applies pressure to the inside of the second flow path.

[0013] A third aspect of the polymer production apparatus is the first or second aspect, wherein the introduction part is disposed below an upper end of the second flow path in the direction of gravity.

[0014] The polymer production apparatus according to a fourth aspect may be any of the first to third aspects, further comprising a detection unit downstream of the second flow path that detects the amount of the ligand-exchanged metal catalyst in the solution delivered from the second flow path.

[0015] The polymer production apparatus according to the fifth aspect may further include, in the above-mentioned fourth aspect, a control unit that controls the conditions for sending the ligand solution to the first flow path based on the results detected by the detection unit, and a ligand supply unit that supplies the ligand solution to the first flow path in accordance with the sending conditions from the control unit.

[0016] In the polymer production apparatus according to the sixth aspect, in the fourth or fifth aspect, the detection unit may include a mechanism for evaluating the intensity of an absorbance peak corresponding to the metal catalyst that has undergone ligand exchange in the second flow path.

[0017] A seventh aspect of the present invention is directed to the polymer production apparatus of the fifth aspect, wherein the liquid sending condition is at least one of the amount and temperature of the ligand solution introduced into the first flow path.

[0018] The polymer production apparatus according to an eighth aspect is the polymer production apparatus according to any one of the first to seventh aspects, wherein an angle formed between the longitudinal direction of the second flow path and the direction of gravity may be within a range of 45 degrees or less.

[0019] A polymer production apparatus according to a ninth aspect is the polymer production apparatus according to any one of the first to eighth aspects, wherein the second flow path may have a cylindrical shape.

[0020] The polymer production apparatus according to a tenth aspect may be the polymer production apparatus according to any one of the first to ninth aspects, further comprising: a raw material supply unit that supplies a solution containing at least one type of monomer; and a mixing unit that mixes the solution containing the ligand-exchanged metal catalyst supplied from the second flow path of the catalyst supply unit with the at least one type of monomer.

[0021] The polymer production apparatus according to an eleventh aspect may be the polymer production apparatus according to the tenth aspect, further comprising a synthesis section connected to the mixing section, which synthesizes a polymer using the ligand-exchanged metal catalyst and the monomer mixed in the mixing section.

[0022] The polymer production method according to the twelfth aspect includes the steps of: sending a ligand solution to a first flow path; introducing the ligand solution into a second flow path filled with a powdered metal catalyst along the direction of gravity; sending the ligand solution introduced into the second flow path downward in the direction of gravity within the second flow path; and sending a solution containing the metal catalyst that has undergone ligand exchange in the second flow path downstream from the second flow path.

[0023] A thirteenth aspect of the present invention relates to the polymer production method of the twelfth aspect, wherein the step of transporting the metal catalyst in the second flow path may include applying pressure to the second flow path.

[0024] The polymer production method according to the fourteenth aspect may be the method according to the twelfth or thirteenth aspect, further comprising the step of detecting the amount of the ligand-exchanged metal catalyst.

[0025] A fifteenth aspect of the present invention relates to the polymer production method of the fourteenth aspect, wherein the detecting step may include a step of evaluating the absorbance peak intensity corresponding to the ligand-exchanged metal catalyst.

[0026] The polymer production method according to the sixteenth aspect may be the same as the fourteenth or fifteenth aspect, and may include the steps of controlling the conditions for sending the ligand solution to the first flow path based on the results detected in the detection step, and supplying the ligand solution to the first flow path in accordance with the control step.

[0027] A seventeenth aspect of the present invention relates to the polymer production method of the sixteenth aspect, wherein the liquid sending condition is at least one of the amount and temperature of the ligand solution introduced into the first flow path.

[0028] A polymer production method according to an eighteenth aspect may be the method according to the thirteenth aspect, wherein the pressure is 0.001 MPa or more and 1.2 MPa or less.

[0029] A polymer production method according to a nineteenth aspect is the seventeenth aspect, wherein the temperature of the liquid transfer condition is −25° C. or higher and 250° C. or lower.

[0030] A polymer production method according to a twentieth aspect may be any of the twelfth to nineteenth aspects, further comprising a raw material supplying step of supplying at least one type of monomer, and a mixing step of mixing a solution containing the ligand-exchanged metal catalyst supplied from the second flow path in the catalyst supplying step with the at least one type of monomer supplied in the raw material supplying step.

[0031] A polymer production method according to a twenty-first aspect may be the same as that of the twentieth aspect, further comprising, following the mixing step, a synthesis step of synthesizing a polymer using the ligand-exchanged metal catalyst and a monomer.

[0032] Hereinafter, polymer production apparatuses and production methods according to embodiments will be described with reference to the accompanying drawings, in which substantially identical components are designated by the same reference numerals.

[0033] (Embodiment 1) <Polymer Production Apparatus> Fig. 1 is a schematic diagram showing the configuration of a polymer production apparatus according to Embodiment 1. Fig. 2 is a flowchart of a polymer production method according to Embodiment 1.

[0034] As shown in FIGS. 1 and 2 , the polymer production apparatus 10 according to the first embodiment includes a catalyst supply unit 20 for supplying a catalyst. The catalyst supply unit 20 includes a first flow path unit 100, a second flow path unit 200, and an inlet unit 141. The polymer production apparatus 10 further includes a raw material supply unit 40 for supplying monomers serving as raw materials for the polymer, a mixing unit 50, and a synthesis unit 60. The first flow path 100 delivers a ligand solution. The first flow path 100 includes a ligand solution tank 101, a ligand delivery pump 111, a reactor 121 for temperature adjustment, and a temperature regulator 131. The second flow path 200 contains a powdered metal catalyst filled along the direction of gravity. The inlet unit 141 introduces the ligand solution from the first flow path 100 into the second flow path 200. The second flow path 200 includes a flow path 201 for filling with a powdered metal catalyst and a pressure application device 211, and is arranged so that the ligand solution introduced from the inlet 141 is sent downward in the direction of gravity. The metal catalyst filled in the second flow path 200 undergoes ligand exchange with the ligand solution, and a catalyst solution containing the ligand-exchanged metal catalyst is sent downstream of the second flow path 200. The catalyst supply unit 20 may include an evaluation control unit 300. The evaluation control unit 300 includes a catalyst amount evaluation device 301 and a control device 311, and is arranged downstream of the second flow path 200 between the mixing unit 50 and the catalyst supply unit 200. The control device 311 controls the supply amount or temperature of the ligand in the first flow path based on the results detected by the catalyst amount evaluation device 301. The raw material supply unit 40 includes a raw material solution tank 401 and a raw material liquid delivery pump 411, and supplies a raw material solution containing at least one monomer. The mixing section 50 has a mixer 501 that mixes the raw material solution with a catalyst solution containing a ligand-exchanged metal catalyst. The synthesis section 60 is connected in series to the mixing section 50 and has a synthesis reactor 601 and a temperature regulator 611, and adjusts the temperature to the temperature required for synthesis. In the synthesis section 60, a polymer is synthesized from a monomer and the ligand-exchanged metal catalyst.

[0035] <Polymer Production Method> The polymer production method according to the first embodiment also includes a ligand solution preparation step P0 prior to feeding the ligand solution, a ligand solution feeding step P1, a ligand exchange step P2 of introducing the ligand solution into a second flow path filled with a powdered metal catalyst along the direction of gravity and feeding the ligand solution in the direction of gravity to perform ligand exchange, a detection step P3 of the amount of ligand-exchanged catalyst, a control step P4 of controlling the ligand supply amount or temperature based on the detection result, a raw material solution preparation step P5 of preparing a solution containing monomers that will be used as raw materials for the polymer, a raw material solution feeding step P6 of feeding the raw material solution, a mixing step P7 of mixing the ligand-exchanged metal catalyst solution and the raw material solution, and a synthesis step P8 of synthesizing the mixed reaction solution.

[0036] The polymer production method according to the first embodiment will be described in relation to the polymer production apparatus. The ligand liquid delivery process P1 includes a ligand solution tank 101, a ligand liquid delivery pump 111, a reactor 121 for adjusting the temperature, a temperature regulator 131, and an introduction section 141 for introducing the first flow path into the second flow path. The ligand exchange process P2 includes a flow path 201 for filling a powdered metal catalyst and a pressure application device 211. The detection process P3 includes a catalyst amount evaluation device 301. The control process P4 includes a control device 311.

[0037] Each step of this polymer production method will be described below.

[0038] <Ligand Solution Preparation Step P0> The ligand solution preparation step P0 is a step of mixing and dissolving the ligand of the metal catalyst in a solvent to prepare a ligand solution.

[0039] The ligand for the metal catalyst is not particularly limited and is selected depending on the type of reaction, substrate, and conditions. Examples include phosphines such as t-butyl isocyanide, norbornadiene, 2,2′-bipyridine, acrylonitrile, triphenylphosphine, and cyclopentadiene, amines, and dienes.

[0040] The solvent for the ligand solution is not particularly limited and is selected depending on the type of reaction, substrate, and conditions, and examples thereof include tetrahydrofuran, toluene, xylene, dimethyl ether, dioxane, dimethylformamide, dimethylacetamide, acetonitrile, dimethyl sulfoxide, N-methylpyrrolidone, benzene, hexane, diethyl ether, alcohols such as methanol, ethanol, isopropanol, and butanol, and ionic liquids.

[0041] <Ligand Solution Transfer Step P1> The ligand solution transfer step P1 is a step of transferring a ligand solution using a ligand transfer pump, adjusting the temperature to a desired value, and then introducing the resulting solution into the second flow path filled with a metal catalyst.

[0042] The temperature for adjusting the ligand in the ligand solution delivery step P1 is not particularly limited as long as it is a temperature that can adjust the amount of ligand exchange and does not affect the reaction temperature, but it can be, for example, −35° C. or higher and 260° C. or lower. It may also be −25° C. or higher and 250° C. or lower.

[0043] The temperature adjustment time is not particularly limited as long as the desired temperature is reached, but may be, for example, 0.01 minutes or more and 10 minutes or less.

[0044] The ligand solution tank 101 and the ligand solution pump 111 are not particularly limited, but must be selected according to the required synthesis amount, flow rate, pressure, and atmosphere.

[0045] <Ligand exchange process P2> The ligand exchange process P2 is a process in which the ligand solution is introduced into a second flow path filled with a powdered metal catalyst, and while the solution is being sent downward in the direction of gravity, the ligands of the ligand solution are coordinated to the metal catalyst filled in the second flow path, thereby forming a ligand-exchanged metal catalyst.

[0046] <Metal catalyst> The metal catalyst is not particularly limited, but is selected depending on the type of reaction, substrate, and conditions, and is a catalyst with low solubility in the solvent. For example, transition metal catalysts such as Ni, Cu, Pd, and Ru are used, and CuCl ２ , RuCl ２ , Ni(acac) ２ , Ni(COD) ２ , Pd(PPh３ ) ４ , Pd(dba) ２ , etc.

[0047] The inlet port for introducing the ligand solution into the second flow path, which is filled with the metal catalyst along the direction of gravity, is preferably positioned downward in the direction of gravity from the upper end of the second flow path. More preferably, it is positioned 0.1 x 1 below the upper end of the second flow path relative to the length 1 of the second flow path, and even more preferably, it is positioned 0.2 x 1 below the upper end of the second flow path. By positioning the inlet port downward in the direction of gravity from the upper end of the second flow path, the metal catalyst undergoes ligand exchange and flows out as a catalyst solution, resulting in a reduction in volume relative to the initial filling volume. Even in this case, as long as the reduction is from the upper end of the second flow path to the inlet port, the volume of the metal catalyst below the inlet port remains constant, thereby suppressing variation in the amount of ligand exchange.

[0048] The cross-sectional shape of the second flow path filled with the metal catalyst is preferably cylindrical or elliptical. By having a cylindrical or elliptical shape, the filled metal catalyst can easily flow and the volume below the introduction part tends to be constant.

[0049] The angle between the longitudinal direction of the second flow path (vertical direction from upper to lower side) and the downward direction of gravity is preferably in the range of 45 degrees or less. If the angle is greater than 45 degrees, the filled metal catalyst will have difficulty flowing downward, and the filled volume will be more likely to vary. In this case, the angle between the two directions will be either less than 90 degrees or more than 90 degrees, but here we will focus on angles less than 90 degrees.

[0050] The pressure application device is not particularly limited, but may be any device that prevents the ligand solution introduced from the introduction part from flowing downward in the direction opposite to the direction of gravity, and may be, for example, a compressor, a cylinder, or piping managed within a factory.

[0051] <Detection step P3, control step P4> The detection step P3 and the control step P4 are steps of detecting the amount of ligand-exchanged metal catalyst in the catalyst solution sent downstream of the second flow path, and controlling the amount of ligand supplied or the temperature based on the results of the detection.

[0052] The catalyst amount evaluation device 301 measures the peak intensity I of the absorption spectrum of the ligand-exchanged metal catalyst in the continuous flow channel. ｃａｔ For example, by checking a calibration curve of peak intensity and concentration in advance, the amount of metal catalyst that has undergone ligand exchange can be calculated. Based on the result, the control device 311 is fed back to control at least one of the amount of ligand supplied and the temperature.

[0053] <Raw Material Solution Preparation Step P5> The raw material solution preparation step P5 is a step of mixing and dissolving the raw materials of the polymer in a solvent to prepare a raw material solution.

[0054] <Raw Materials> The raw materials are not particularly limited, but are selected depending on the desired polymer and are at least one monomer having a reactive group according to the catalyst used. Examples include combinations of aryl or vinyl boronic acids such as phenylboronic acid and benzenediboronic acid bis(pinacol) ester with aryl or vinyl halogen compounds such as bromobenzene and iodothiophene, and aryl halogen compounds such as dibromobenzene and dibromothiophene.

[0055] The solvent for the raw material solution is not particularly limited and is selected depending on the type of reaction, substrate, and conditions. Examples include tetrahydrofuran, toluene, xylene, dimethyl ether, dioxane, dimethylformamide, dimethylacetamide, acetonitrile, dimethyl sulfoxide, N-methylpyrrolidone, benzene, hexane, diethyl ether, alcohols such as methanol, ethanol, isopropanol, and butanol, ionic liquids, and mixed solutions of the above solvents with water.

[0056] <Raw Material Liquid Transfer Step P6> The raw material liquid transfer step P6 is a step of transferring the raw material at a predetermined flow rate.

[0057] The raw material solution tank 401 and the ligand liquid delivery pump 411 are not particularly limited, but must be selected according to the required synthesis amount, flow rate, pressure, and atmosphere.

[0058] <Mixing Step P7> The mixing step P7 is a step of mixing the ligand-exchanged metal catalyst solution with the raw material solution.

[0059] The mixer 501 is not particularly limited as long as it can mix the raw material solution and the ligand-exchanged metal catalyst, and examples thereof include a T-shaped mixer, a Y-shaped mixer, a plate mixer processed into an arbitrary shape, a double-tube mixer, a triple-tube mixer, a static mixer, a mixer equipped with a mechanism for promoting stirring such as a Taylor reactor, or a mixer that combines two or more of these.

[0060] The inner diameter of the mixer is preferably in the range of 0.01 mm to 3.00 mm, more preferably in the range of 0.05 mm to 2.50 mm. If it is smaller than 0.01 mm, there is a high risk of clogging, and if it is larger than 3.00 mm, mixing performance tends to decrease. However, this does not apply to mixers equipped with a stirring mechanism such as static mixers or Taylor reactors.

[0061] <Synthesis Step P8> The synthesis step P8 is a step in which a polymer is synthesized by adjusting the temperature required for synthesis using a synthesis reactor 601 and a temperature regulator 611 connected in series to the mixing section.

[0062] The inner diameter of the synthesis reactor is preferably in the range of 0.01 mm to 5.00 mm, more preferably in the range of 0.05 mm to 4.00 mm. If it is smaller than 0.01 mm, the risk of clogging increases, and internal resistance increases, making it difficult to transport the liquid. If it is larger than 5.00 mm, the uniformity of the reaction field, which is an advantage of microflow, decreases, and variation increases.

[0063] The residence time in the synthesis reactor is not particularly limited, but may be selected depending on the type of reaction, substrate, and conditions, and may be, for example, 0.01 to 60 minutes.

[0064] The temperature regulator 611 is not particularly limited as long as it can regulate the temperature to a level required for polymer synthesis, and examples thereof include an oil bath, a mantle heater, an electric furnace, etc. when the temperature is to be raised above room temperature, and a cooler bath, an ice bath, etc. when the temperature is to be lowered below room temperature.

[0065] The controlled temperature is not particularly limited, but is selected depending on the type of reaction, substrate, and conditions, and is, for example, from -25°C to 250°C.

[0066] From the above, the polymer production apparatus according to the embodiment can stably transfer the liquid without clogging even when producing a polymer using a catalyst that has low solubility in a solvent.

[0067] It should be noted that the present disclosure includes appropriate combinations of any of the various embodiments and / or examples described above, and can achieve the effects of each embodiment and / or example.

[0068] It can also be carried out in the case where a base is added.

[0069] (Examples 1 to 4 and Comparative Examples 1 and 2) Examples and comparative examples carried out by the inventors will be described below.

[0070] [Regarding Evaluation] The presence or absence of blockage of the microflow was evaluated as "absent" when no blockage occurred for 15 minutes or more, and as "present" when blockage occurred for less than 15 minutes.

[0071] The amount of ligand exchange is determined by the peak intensity I of the absorption spectrum of the metal catalyst after the start of liquid transfer. ｃａｔ０ is set to 100, and the peak intensity I ｃａｔｔ The ratio of the above was taken as the change in the amount of ligand exchange, and a change in the amount of ligand exchange of less than 5% was rated as "low," a change in the amount of ligand exchange of less than 20% was rated as "medium," and a change in the amount of ligand exchange of 20% or more was rated as "high."

[0072] FIG. 3 is Table 1 showing the conditions and evaluation results of Examples 1 to 4 and Comparative Examples 1 and 2.

[0073] (Example 1) As a powder metal catalyst, nickel catalyst Ni(COD) ２ The pressure in the second flow path was 0.2 MPa.

[0074] A ligand solution containing 66.0 mmol of bipyridine dissolved in 55 mL of DMA was introduced into the upper end of the second flow path at a flow rate of 0.2 mL / min and heated to 40°C for 10 minutes.

[0075] The raw material monomer solution was prepared by dissolving 30 mmol of dichlorothiophene in 55 mL of dimethylacetamide (DMA) as an organic solvent. The flow rate of the raw material solution was set to 0.2 mL / min.

[0076] The catalyst solution containing the ligand-exchanged metal catalyst was mixed with the raw material solution to synthesize the compound. The synthesis temperature was 80° C. and the synthesis time was 10 minutes.

[0077] In Example 1, the microflow did not clog for 15 minutes or more, and was rated "None." The change in the amount of ligand exchange was 14%, which was less than 20%, and was rated "Medium."

[0078] Example 2 Example 2 was the same as Example 1, except that the location where the ligand solution was introduced into the second flow path was 0.05 l from the upper end of the second flow path with respect to the length l.

[0079] In Example 2, the microflow did not clog for 15 minutes or more, and was rated "None." The change in the amount of ligand exchange was 11%, which was less than 20%, and was rated "Medium."

[0080] Example 3 Example 3 was similar to Example 1, except that the point where the ligand solution was introduced into the second flow path was 0.1 liters from the upper end of the second flow path with respect to the length 1 of the second flow path.

[0081] In Example 3, the microflow did not clog for 15 minutes or more, and was rated as "none." The change in the amount of ligand exchange was 7%, which was less than 20%, and was rated as "medium."

[0082] Example 4 Example 4 was similar to Example 1, except that the location where the ligand solution was introduced into the second flow path was 0.2 l from the upper end of the second flow path with respect to the length l.

[0083] In Example 4, the microflow did not clog for 15 minutes or more, and was rated "None." The change in the amount of ligand exchange was 4%, which was less than 5%, and was rated "Low."

[0084] Comparative Example 1 In Comparative Example 1, unlike Example 1, the second flow path was not used, and the ligand solution and the metal catalyst were mixed in a tank.

[0085] In Comparative Example 1, the microflow was clogged in less than 15 minutes, and was rated as "Yes." The change in the amount of ligand exchanged was 6%, which was less than 20%, and was rated as "Medium."

[0086] Comparative Example 2 is different from Example 1 in that the longitudinal direction of the second flow path is horizontal and the direction in which the powder metal catalyst is filled into the second flow path is also horizontal.

[0087] In Comparative Example 2, the microflow did not clog for 15 minutes or more, and was rated "None." The change in the amount of ligand exchange was 31%, which was rated "High" since it was 20% or more.

[0088] According to Examples 1 to 4, the change in the amount of ligand exchange from the top end to 0.1 L, where the ligand solution was introduced into the second flow path filled with the metal catalyst along the gravity direction, was less than 20%, rated as "medium," but from the top end to 0.2 L, the change in the amount of ligand exchange was less than 5%, rated as "low." Therefore, the location where the ligand solution is introduced may be any location downward from the top end in the gravity direction, and the length l of the second flow path may be 0.2 L or less.

[0089] Comparing Examples 1 to 4 with Comparative Example 2, when the longitudinal direction of the second flow path is the direction of gravity, the microflow does not clog for 15 minutes or more, ie, "None," and the change in the amount of ligand exchange is less than 20%, ie, "Medium," or less than 5%, ie, "Low." In contrast, when the longitudinal direction of the second flow path is horizontal, the microflow does not clog for 15 minutes or more, ie, "None," but the change in the amount of ligand exchange is 20% or more, ie, "High." In other words, it is preferable that the longitudinal direction of the second flow path is the direction of gravity. The angle between the longitudinal direction of the second flow path and the downward direction of gravity may be within a range of 45 degrees or less.

[0090] According to the polymer production apparatus of the present disclosure, even in the production of polymers using catalysts that have low solubility in solvents, a catalyst solution containing a metal catalyst can be stably delivered without causing blockage, and a flow-type microreactor can be used even when raw materials are not soluble in solvents during chemical synthesis.

[0091] REFERENCE SIGNS LIST 10 Polymer production apparatus 20 Catalyst supply section 40 Raw material supply section 50 Mixing section 60 Synthesis section 100 First flow path section 101 Ligand solution tank 111 Ligand liquid delivery pump 121 Ligand reactor 131 Temperature regulator 141 Introduction section 200 Second flow path section 201 Catalyst filling flow path 211 Pressure application device 300 Evaluation control section 301 Catalyst amount evaluation device 311 Control device 400 Raw material supply section 401 Raw material solution tank 411 Raw material liquid delivery pump 501 Mixer 601 Synthesis reactor 611 Temperature regulator

Claims

1. A polymer production apparatus comprising: a catalyst supply unit having: a first flow path for supplying a ligand solution; a second flow path filled with a powdered metal catalyst along the direction of gravity; and an introduction unit for introducing the ligand solution from the first flow path into the second flow path, wherein the second flow path is positioned so that the ligand solution introduced from the introduction unit is supplied downward in the direction of gravity.

2. The polymer production apparatus according to claim 1, wherein the second flow path further comprises a pressure applying mechanism that applies pressure to the inside of the second flow path.

3. The manufacturing apparatus according to claim 1 or 2, wherein the introduction section is disposed below the upper end of the second flow path in the direction of gravity.

4. The polymer production apparatus according to claim 1 or 2, further comprising a detection unit downstream of the second flow path that detects the amount of the ligand-exchanged metal catalyst in the solution delivered from the second flow path.

5. The polymer manufacturing apparatus described in claim 4, further comprising: a control unit that controls the liquid supply conditions of the ligand solution to the first flow path based on the results detected by the detection unit; and a ligand supply unit that supplies the ligand solution to the first flow path in accordance with the liquid supply conditions from the control unit.

6. The polymer production apparatus according to claim 4, wherein the detection unit includes a mechanism for evaluating the intensity of an absorbance peak corresponding to the metal catalyst that has undergone ligand exchange in the second flow path.

7. The polymer production apparatus according to claim 5, wherein the liquid transfer condition is at least one of the amount and temperature of the ligand solution introduced into the first flow path.

8. The polymer production apparatus according to claim 1 or 2, wherein the angle formed between the longitudinal direction of the second flow path and the downward direction of gravity is within a range of 45 degrees or less.

9. The polymer production apparatus according to claim 1 or 2, wherein the second flow path has a cylindrical shape.

10. The polymer production apparatus according to claim 1 or 2, further comprising: a raw material supply unit that delivers a solution containing at least one type of monomer; and a mixing unit that mixes a solution containing the ligand-exchanged metal catalyst delivered from the second flow path of the catalyst supply unit with the at least one type of monomer delivered from the raw material supply unit.

11. The polymer production apparatus according to claim 10, further comprising a synthesis section connected to the mixing section for synthesizing a polymer from the ligand-exchanged metal catalyst and the monomer mixed in the mixing section.

12. A polymer production method comprising a catalyst supplying step, the steps being: sending a ligand solution to a first flow path; introducing the ligand solution into a second flow path filled with a powdered metal catalyst along the direction of gravity; sending the ligand solution introduced into the second flow path downward in the direction of gravity within the second flow path; and sending a solution containing the metal catalyst that has been ligand-exchanged in the second flow path downstream from the second flow path.

13. The method for producing a polymer according to claim 12, wherein the step of transporting the metal catalyst in the second flow path includes applying pressure to the inside of the second flow path.

14. The method for producing a polymer according to claim 12 or 13, further comprising the step of detecting the amount of the metal catalyst that has undergone the ligand exchange.

15. The method for producing a polymer according to claim 14, wherein the detecting step comprises the step of evaluating the absorbance peak intensity corresponding to the ligand-exchanged metal catalyst.

16. The polymer production method according to claim 14, further comprising: a step of controlling the conditions for sending the ligand solution to the first flow path based on the results detected in the detecting step; and a step of supplying the ligand solution to the first flow path in accordance with the controlling step.

17. The polymer production method according to claim 16, wherein the liquid transfer condition is at least one of the amount and temperature of the ligand solution introduced into the first flow path.

18. The method for producing a polymer according to claim 13, wherein the pressure is 0.001 MPa or more and 1.2 MPa or less.

19. The polymer production method according to claim 17, wherein the temperature of the liquid transfer conditions is -25°C or higher and 250°C or lower.

20. The polymer production method according to claim 12 or 13, further comprising a raw material supplying step of supplying at least one type of monomer, and a mixing step of mixing the solution containing the ligand-exchanged metal catalyst supplied from the second flow path in the catalyst supplying step with the at least one type of monomer supplied in the raw material supplying step.

21. The method for producing a polymer according to claim 20, further comprising, following the mixing step, a synthesis step of synthesizing a polymer using the ligand-exchanged metal catalyst and the monomer.

Images