Method for producing polymer and apparatus for producing polymer

Abstract

The present invention is a method for producing a polymer by a polymerization reaction occurring in a flow path through which a fluid flows, said fluid containing three types of raw materials, namely, at least one type of monomer, a ligand, and a metal catalyst. The method includes: a mixing step of separately feeding one fluid containing a part of the three types of raw materials and another fluid containing another part of the three types of raw materials to the flow path to form a mixed fluid containing the three types of raw materials in the flow path; and a slag flow formation step of introducing an insoluble fluid that is insoluble in the mixed fluid into the flow path and merging the mixed fluid and the insoluble fluid to form a slag flow. The slag flow formation step includes controlling the formation of the slag flow so as to merge the mixed fluid and the insoluble fluid within a predetermined amount of time after the mixed fluid is formed.

Description

Polymer manufacturing method and polymer manufacturing apparatus

[0001] The present disclosure relates to a polymer production method and a polymer production apparatus, and more particularly to a polymer production method and a polymer production apparatus for producing a polymer by a polymerization reaction.

[0002] Conventionally, polymerization reactions of monomers to produce polymers have been carried out in a batch process, which has the drawback of being difficult to control for uniform temperature and uniform mixing of reactants in a reaction vessel when synthesizing a polymer with a narrow molecular weight distribution, and is therefore unsuitable for mass production.

[0003] In recent years, chemical reactions using minute containers called microreactors have been studied in the field of chemical synthesis. A microreactor is a minute container equipped with a fluid flow channel and a supply channel that is connected to the channel and supplies the fluid to the channel. Fluids consisting of raw materials for multiple polymerization reactions are supplied through the supply channel, and are merged and mixed within the channel. As the fluids flow, the polymerization reaction progresses, synthesizing a polymer. The channel diameter of the channels that make up a microreactor is typically several tens of micrometers to several millimeters.

[0004] Reactions using microreactors enable more accurate flow control, temperature control, and rapid mixing of the reaction solution, and are therefore expected to improve conversion and selectivity compared to conventional batch reactions, and are attracting attention as an efficient production method. Patent Document 1 discloses, for example, a production method for synthesizing a polymer using a microreactor.

[0005] Japanese Patent Application Laid-Open No. 2015-127425

[0006] In a polymerization reaction of a monomer, particles that are insoluble in a solvent may be present. In such a case, for example, in the manufacturing method using a microreactor disclosed in Patent Document 1, the particles that are insoluble in the solvent may adhere to and accumulate on the inner wall surface of the flow channel. Therefore, there is a problem that the insoluble particles may adhere to the inner wall surface of the flow channel during the polymer manufacturing process.

[0007] An object of the present disclosure is to provide a polymer production method and production apparatus that can suppress adhesion of insoluble particles to the inner wall surface of a flow channel during the polymer production process.

[0008] A polymer production method according to one aspect of the present disclosure is a polymer production method in which a polymer is produced by a polymerization reaction occurring in a flow path through which a fluid containing three types of raw materials, namely, at least one type of monomer, a ligand, and a metal catalyst, flows. The method includes a mixing step in which one fluid containing some of the three types of raw materials and another fluid containing the other types of raw materials are separately fed into the flow path to form a mixed fluid containing the three types of raw materials in the flow path; and a slug flow formation step in which an insoluble fluid that is insoluble in the mixed fluid is introduced into the flow path to merge the mixed fluid and the insoluble fluid to form a slug flow. The slug flow formation step includes controlling the formation of the slug flow so that the mixed fluid and the insoluble fluid merge within a predetermined time after the mixed fluid is formed.

[0009] Furthermore, a polymer production apparatus according to one aspect of the present disclosure is a polymer production apparatus that produces a polymer by a polymerization reaction that occurs in a flow path through which a fluid containing three types of raw materials, i.e., at least one type of monomer, a ligand, and a metal catalyst, flows. The polymer production apparatus includes: a flow path; a liquid delivery section that separately delivers one fluid containing some of the three types of raw materials and another fluid containing the other types of raw materials into the flow path; a mixing section that is disposed upstream within the flow path and forms a mixed fluid containing the three types of raw materials delivered from the liquid delivery section; a slug flow former that is disposed downstream within the flow path and the mixing section; an insoluble fluid introduction section that introduces an insoluble fluid that is insoluble in the mixed fluid into the slug flow former; and a control section. The slug flow former merges the mixed fluid and the insoluble fluid to form a slug flow, and the control section controls the flow rate of the mixed fluid so that the mixed fluid reaches the slug flow former from the mixing section within a predetermined time.

[0010] The term "slug flow" as used herein refers to two fluids with no mutual affinity that flow alternately side by side along a flow path. For example, in the present disclosure, when a first fluid, a "mixed fluid," and a second fluid, an "immiscible fluid," flow simultaneously within a flow path, the mixed fluid and the immiscible fluid are separated from each other by a phase interface, forming alternating "mixed fluid cells" and "immiscible fluid cells." Within a slug flow, a circulating flow occurs within the mixed fluid cells, and this circulating flow causes local stirring. Note that the "mixed fluid cells" and "immiscible fluid cells" referred to here refer to columnar mixed fluid segments and immiscible fluid segments, respectively, that flow alternately side by side within the flow path.

[0011] According to the polymer production method or polymer production apparatus according to one aspect of the present disclosure, adhesion of insoluble particles to the inner wall surface of a flow channel can be suppressed during the polymer production process.

[0012] Schematic diagram showing an example of the configuration of a polymer production apparatus according to an embodiment of the present disclosure. Conceptual diagram showing slug flow in a flow channel of the polymer production apparatus of FIG. 1. Flowchart showing an example of a polymer production process using the polymer production apparatus according to an embodiment of the present disclosure. Table showing measurement results of flow channel blockage in the polymer production processes carried out in Examples 1-2 and Comparative Example 1.

[0013] According to a first aspect of the present disclosure, there is provided a polymer production method for producing a polymer by a polymerization reaction occurring in a flow channel through which fluids containing three types of raw materials, namely, at least one type of monomer, a ligand, and a metal catalyst, flow, the method including: a mixing step of separately feeding one fluid containing some of the three types of raw materials and another fluid containing the other types of raw materials into the flow channel to form a mixed fluid containing the three types of raw materials in the flow channel; and a slug flow formation step of introducing an insoluble fluid that is insoluble in the mixed fluid into the flow channel to merge the mixed fluid and the insoluble fluid to form a slug flow, wherein the slug flow formation step includes controlling the formation of the slug flow so that the mixed fluid and the insoluble fluid merge within a predetermined time after the mixed fluid is formed.

[0014] According to this embodiment, insoluble particles can be prevented from adhering to the inner wall of the flow channel during the polymer production process.

[0015] According to a second aspect of the present disclosure, there is provided the method for producing a polymer according to the first aspect, wherein controlling the formation of the slug flow comprises adjusting a flow rate of at least one of the one fluid or the other fluid fed into the flow channel.

[0016] According to a third aspect of the present disclosure, there is provided the polymer production method according to the first or second aspect, wherein the slug flow forming step includes adjusting a flow rate of the immiscible fluid introduced into the flow channel.

[0017] According to a fourth aspect of the present disclosure, there is provided a method for producing a polymer according to any one of the first to third aspects, further comprising a heating reaction step of heating the slug stream.

[0018] According to a fifth aspect of the present disclosure, the metal catalyst is M(cod) ２ wherein M is a metal comprising at least one of nickel, platinum, and palladium.

[0019] According to a sixth aspect of the present disclosure, there is provided the method for producing a polymer according to any one of the first to fifth aspects, wherein the inner wall of the flow channel is made of a material with low polarity.

[0020] According to a seventh aspect of the present disclosure, there is provided a method for producing a polymer according to the sixth aspect, wherein the three raw materials are dissolved or dispersed in a polar solvent.

[0021] According to an eighth aspect of the present disclosure, there is provided the method for producing a polymer according to the sixth aspect, wherein the immiscible fluid comprises a non-polar solvent.

[0022] According to a ninth aspect of the present disclosure, there is provided the method for producing a polymer according to any one of the first to seventh aspects, wherein the immiscible fluid comprises a gas.

[0023] According to a tenth aspect of the present disclosure, there is provided a polymer production apparatus for producing a polymer by a polymerization reaction occurring in a flow path through which fluids containing three types of raw materials, i.e., at least one type of monomer, a ligand, and a metal catalyst, flow, the polymer production apparatus comprising: a flow path; a liquid delivery section that separately delivers one fluid containing some of the three types of raw materials and another fluid containing the other types of raw materials into the flow path; a mixing section that is disposed upstream within the flow path and forms a mixed fluid containing the three types of raw materials delivered from the liquid delivery section; a slug flow former that is disposed downstream of the mixing section within the flow path; an insoluble fluid introduction section that introduces an insoluble fluid that is insoluble in the mixed fluid into the slug flow former; and a control section, wherein the slug flow former merges the mixed fluid and the insoluble fluid to form a slug flow, and the control section controls the flow rate of the mixed fluid so that the mixed fluid reaches the slug flow former from the mixing section within a predetermined time.

[0024] According to an eleventh aspect of the present disclosure, there is provided a polymer production apparatus according to the tenth aspect, wherein the control unit is configured to adjust the flow rate of at least one of the one fluid or the other fluid fed into the flow path.

[0025] According to a twelfth aspect of the present disclosure, there is provided the polymer production apparatus according to the tenth or eleventh aspect, wherein the control unit is configured to adjust a flow rate at which the immiscible fluid is introduced into the slug flow former.

[0026] According to a thirteenth aspect of the present disclosure, there is provided the polymer production apparatus according to any one of the tenth to twelfth aspects, further comprising a heating section disposed in the flow path downstream of the slug flow former.

[0027] According to a fourteenth aspect of the present disclosure, there is provided the polymer production apparatus according to any one of the tenth to thirteenth aspects, wherein the inner wall of the flow channel is made of a material with low polarity.

[0028] Any of the above-described various embodiments may be combined appropriately to achieve the effects of each of them.

[0029] Hereinafter, embodiments will be described in detail with reference to the accompanying drawings. However, more detailed explanation than necessary may be omitted. For example, detailed explanation of well-known matters or redundant explanation of substantially the same configuration may be omitted. This is to avoid unnecessary redundancy in the following explanation and to facilitate understanding by those skilled in the art.

[0030] A polymer production method and a polymer production apparatus according to an embodiment of the present disclosure will be described with reference to Figures 1 to 3. The accompanying drawings and the following description are provided to enable those skilled in the art to fully understand the present disclosure, and are not intended to limit the subject matter described in the claims. In addition, in each drawing, each element is exaggerated for ease of explanation. Note that substantially identical components in the drawings are designated by the same reference numerals.

[0031] (Polymer Polymerization Reaction and Raw Materials Thereof) The polymer production method and polymer production apparatus of the present disclosure are used to produce polymers by a polymerization reaction of monomers. Examples of polymers produced include, but are not limited to, conductive polymers such as polyphenylene and polythiophene, or polymers having functional groups at their terminals that are used in ion exchange resins, etc. In addition, in embodiments according to the present disclosure, three types of raw materials are used in the polymerization reaction to produce these polymers: at least one type of monomer, a ligand, and a metal catalyst.

[0032] The monomers used as raw materials for the polymerization reaction are not particularly limited, and can be appropriately selected depending on the purpose as long as they have a functional group such as a halogen group at the end group depending on the coupling reaction used. Examples include phenylene, thiophene, fluorene, etc., which have functional groups such as alkyl groups, allyl groups, acyl groups, benzoyl groups, nitro groups, sulfo groups, and amino groups depending on the purpose, and hydrocarbons and aromatic compounds containing alkyls, sulfones, ethers, fluorides, etc., which have functional groups. These monomers may be used alone or in combination of two or more.

[0033] The ligand used as a raw material for the polymerization reaction is not limited to, but may be, for example, bipyridine, triphenylphosphine, etc. These ligands can form complexes with metal ions of the metal catalyst in the polymerization reaction of the monomers, thereby accelerating the coupling reaction of the monomers.

[0034] The metal catalyst used as the raw material for the polymerization reaction is M(cod) ２ where M is a metal preferably comprising at least one of nickel (Ni), platinum (Pt), and palladium (Pd).

[0035] In a monomer polymerization reaction, three raw materials—a monomer, a ligand, and a metal catalyst—are dissolved or dispersed in a solvent and mixed. During this process, a complex formed between the ligand and the metal of the metal catalyst promotes the polymerization reaction while also producing by-products that are insoluble in the solvent, such as chlorides, bromides, and iodides of the metal. As the polymerization reaction progresses, the aforementioned by-products that are insoluble in the solvent are produced, which grow into particles and become insoluble particles. These insoluble particles adhere to and accumulate on the inner wall surfaces of the flow channels, resulting in flow channel blockage. The polymer production method and polymer production apparatus of the present disclosure can suppress adhesion of insoluble particles generated during the polymer production process to the inner wall surfaces of the flow channels, thereby improving polymer productivity. The configuration of a polymer production apparatus 100 according to an embodiment of the present disclosure will be described below with reference to FIG. 1 .

[0036] (Embodiment) <Configuration of Polymer Production Apparatus> Fig. 1 is a schematic diagram showing an example of the configuration of a polymer production apparatus 100 according to an embodiment of the present disclosure. The polymer production apparatus 100 shown in Fig. 1 includes a flow path 10, a liquid delivery section 20, an immiscible fluid introduction section 30, a control section 40, a mixing section 50, a slug flow former 60, a heating section 70, and a recovery section 80. The polymer production apparatus 100 can be used to produce a polymer by a polymerization reaction of a monomer that proceeds within the flow path 10.

[0037] The liquid delivery section 20 of the polymer production apparatus 100 shown in Figure 1 includes fluid supply sections 21 and 22 and is used to deliver raw materials for producing a polymer by a polymerization reaction of a monomer into the flow path 10. The fluid supply sections 21 and 22 are equipped with, for example, a storage section and a liquid delivery device (not shown), and a solution in which raw materials for producing a polymer are dissolved or dispersed in a solvent is stored in the storage section, and the solution in the storage section is delivered by the liquid delivery device. The liquid delivery device can be configured, for example, by a syringe pump, plunger pump, diaphragm pump, tube pump, mono pump, piezoelectric pump, etc. (not shown).

[0038] In the present embodiment, as shown in the figure, the liquid delivery unit 20 is configured to separate a fluid containing three raw materials for producing a polymer, namely, a monomer, a ligand, and a metal catalyst, into a first fluid 20A and a second fluid 20B, which are separately delivered into the flow path 10 via pipes 24A and 24B by fluid supply units 21 and 22, respectively. Here, the first fluid 20A contains some of the three raw materials, and in this embodiment, it can contain any two of the monomer, the ligand, and the metal catalyst. The second fluid 20B contains the other of the three raw materials, and in this embodiment, it can contain, for example, another one of the monomer, the ligand, and the metal catalyst, which is different from the first fluid 20A.

[0039] Although FIG. 1 illustrates the liquid delivery unit 20 dividing the solution of three types of raw materials for the polymerization reaction into two fluids 20A and 20B and delivering them separately to the flow channel 10, the present disclosure is not limited to this. The liquid delivery unit 20 may include any number of fluid supply units. For example, three fluid supply units may be provided, and the three types of raw materials may be divided into fluids each containing one type of raw material and delivered separately to the flow channel 10. Furthermore, the liquid delivery unit 20 is not limited to the type of fluid delivered to the flow channel. For example, depending on the application, the liquid delivery unit 20 may be configured to deliver another fluid to the flow channel 10 together with the three types of raw materials or from a different fluid supply unit.

[0040] In this way, by dividing the raw materials used in the polymer polymerization reaction into two or more fluids and sending them separately into the flow path, it is possible to suppress the generation of insoluble particles due to the progress of the polymerization reaction before the raw materials are sent into the flow path.

[0041] As shown in FIG. 1 , the polymer production apparatus 100 includes a control unit 40. In this embodiment, the control unit 40 may be configured, for example, with flow rate control devices 41, 42, and 43 disposed in the pipes 24A and 24B of the liquid delivery unit 20 and the pipe 34 of the insoluble fluid introduction unit 30 (described later). The flow rate control devices 41, 42, and 43 can adjust the flow rates of the first fluid 20A, the second fluid 20B, and the insoluble fluid 55, respectively, fed into the flow path 10. The control unit 40 can control the formation of a slug flow in the flow path 10 by adjusting the flow rates of the fluids fed into the flow path 10. The control unit 40 will be described in detail later.

[0042] The first fluid 20A and the second fluid 20B are fed into the flow path 10 through the pipes 24A and 24B in the directions A1 and B1, respectively.

[0043] The flow channel 10 extends between the mixing section 50 at the upstream end and the recovery section 80 at the downstream end and may be configured, for example, as a microgroove. Solutions of three raw materials—a monomer, a ligand, and a metal catalyst—mix and flow through the flow channel 10, whereby a polymerization reaction of the monomers progresses to produce a polymer. The flow channel 10 may have a diameter of, for example, 250 μm or more and 6 mm or less. The present disclosure is not limited to the cross-sectional shape of the flow channel 10. The flow channel 10 may have a cross-sectional shape and / or flow channel diameter that differs from, for example, the piping 24A, 24B of the liquid delivery section 20 or the piping 34 of the insoluble fluid introduction section 30 described later. Furthermore, the flow channel 10 may have a variable flow channel diameter between the mixing section 50 at the upstream end and the recovery section 80 at the downstream end.

[0044] The inner wall of the flow channel 10 can be made of a material with low polarity. Examples of materials that can be used to make the inner wall of the flow channel 10 include fluorine-based resins such as polytetrafluoroethylene (PTFE) and tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and olefin-based resins such as polyethylene (PE) and polypropylene (PP), and one or a combination of two or more of these can be used. Furthermore, not only the inner wall but also the entire flow channel 10 may be made primarily of a material with low polarity.

[0045] The mixing section 50 is disposed on the upstream side of the flow path 10 and can be configured as a part of the flow path 10, and can be configured, for example, by a flow path connecting member. The first fluid 20A and the second fluid 20B sent from the liquid sending section 20 are mixed in the mixing section 50 to form a mixed fluid 51. At this time, a polymerization reaction of the monomers starts and progresses.

[0046] The mixed fluid 51 formed in the mixing section 50 flows downstream along the flow path 10 and reaches the slug flow former 60. The slug flow former 60 is connected to the immiscible fluid inlet section 30.

[0047] The immiscible fluid introduction section 30 can introduce the immiscible fluid 55 for forming a slug flow into the slug flow former 60. In this specification, the immiscible fluid includes a liquid or gas that is insoluble in the mixed fluid formed in the mixing section. The immiscible fluid introduction section 30 includes, for example, a storage section and a liquid delivery device (not shown). The storage section stores the liquid or gas that is insoluble in the mixed fluid, and the delivery device supplies the immiscible fluid in the storage section. The delivery device can be, for example, a syringe pump, a plunger pump, a diaphragm pump, a tube pump, a mono pump, a piezoelectric pump, or the like (not shown).

[0048] The insoluble fluid 55 in the insoluble fluid inlet 30 can be pumped through the pipe 34 to the slug flow former 60 by, for example, the pressure of a pump 43 disposed in the pipe 34. The pump 43 can be used as a flow rate adjusting means when feeding the insoluble fluid, and can introduce the insoluble fluid into the slug flow former 60 at a desired flow rate (flow velocity).

[0049] The slug flow former 60 is configured to form a slug flow by combining the mixed fluid 51 sent from the mixing section 50 and the insoluble fluid 55 introduced by the insoluble fluid inlet section 30. The slug flow former 60 can be configured as a part of the flow path 10, and can be configured as, for example, a flow path connecting member.

[0050] The insoluble fluid inlet 30 introduces the insoluble fluid 55 into the slug flow former 60. The introduced insoluble fluid 55 merges with the mixed fluid 51 in the slug flow former 60 to form a slug flow in which mixed-fluid cells and insoluble fluid cells flow alternately. The insoluble fluid inlet 30 can be positioned to introduce the insoluble fluid 55 into the slug flow former 60 from a direction intersecting the flow direction C1 of the mixed fluid 51. In this embodiment, as shown in FIG. 1 , the insoluble fluid inlet 30 introduces the insoluble fluid 55 into the slug flow former 60 from a direction D substantially perpendicular to the flow direction C1 of the mixed fluid 51. By forming a slug flow, adhesion and deposition of insoluble particles generated as the polymerization reaction progresses on the inner wall surface of the flow channel 10 can be suppressed. This will be described in detail later.

[0051] The slug flow formed in the slug flow former 60 flows further downstream along the flow path 10 in the direction C2 from the slug flow former 60 and is sent into the heating section 70 on the downstream side.

[0052] The heating section 70 can be configured as a part of the flow path 10 and can have a length of, for example, 10 cm or more and 20 m or less. For example, a thermostatic bath or the like can be provided in the heating section 70 to heat the slug flow in the flow path. In this embodiment, as shown in FIG. 1 , the heating section 70 is configured with a flow path formed in a spiral shape, thereby improving heating efficiency. The heating temperature of the heating section 70 can be set depending on the raw materials used in the polymerization reaction in the flow path.

[0053] By heating the fluid in which the slug flow has formed in the flow path of the heating unit 70, the polymerization reaction of the monomers in the flow path can be accelerated, thereby improving the polymer production rate. In addition, by heating the fluid in which the slug flow has formed to accelerate the polymerization reaction, the grain growth of the by-products of the polymerization reaction can be suppressed, and the occurrence of flow path blockage due to the adhesion and accumulation of insoluble particles on the inner wall surface of the flow path can be prevented.

[0054] The fluid that has passed through the heating unit 70 flows further downstream along the flow path 10 in the direction C3 and is introduced into the recovery unit 80.

[0055] The recovery section 80 is disposed at the downstream end of the flow channel 10 and can be configured, for example, as shown in the figure, as a cylindrical container having a predetermined height. In the recovery section 80, for example, the fluid in the flow channel 10 can be separated based on the difference in specific gravity, and the polymer product can be recovered.

[0056] <Formation of Slug Flow> The formation of a slug flow in the flow channel 10 of the polymer production apparatus 100 will be described with reference to Fig. 2. Fig. 2 is a conceptual diagram showing a slug flow in the flow channel 10 of the polymer production apparatus 100 of Fig. 1 .

[0057] 2, the slug flow 61 formed in the slug flow former 60 and flowing in the flow path 10 includes fluid cells of the mixed fluid (hereinafter referred to as "mixed fluid cells") 51a, 51b and fluid cells of the immiscible fluid (hereinafter referred to as "immiscible fluid cells") 55a, 55b. The mixed fluid cells 51a, 51b and the immiscible fluid cells 55a, 55b are arranged alternately along the flow path 10 and flow in the downstream direction C.

[0058] In the slug flow 61, a circulating flow R1 is generated in the fluid mixing cells 51a and 51b, and the circulating flow R1 generates a local stirring action, thereby promoting liquid mixing in the fluid mixing cells 51a and 51b.

[0059] In this embodiment, three types of raw materials, namely, a monomer, a ligand, and a metal catalyst, are mixed in the mixing section 50, and a polymerization reaction of the monomer progresses and by-products are generated in the mixed fluid 51. The precipitated polymer particles aggregate on the surface of the by-products, generating insoluble particles 52 that are not dissolved in the solvent of the mixed fluid 51.

[0060] In the slug flow former 60, a slug flow 61 is generated, and the stirring action of the circulating flow R1 generated in the fluid mixture cells 51 a, 51 b can prevent the insoluble particles 52 in the fluid mixture 51 from adhering to the inner wall surface 10 a of the flow path 10 and from accumulating on the inner wall surface 10 a. This can prevent the flow path of the polymer production apparatus 100 from being blocked during the polymerization reaction.

[0061] In the present embodiment, the control unit 40 can perform control so that after the mixed fluid 51 is formed in the mixing unit 50, the mixed fluid 51 reaches the slug flow former 60 within a predetermined time, and the mixed fluid 51 and the immiscible fluid 55 are merged together. Preferably, the control is performed so that the mixed fluid 51 reaches the slug flow former 60 from the mixing unit 50 within a time longer than 0 seconds and shorter than 5 seconds.

[0062] The polymerization reaction of the monomers progresses as the mixed fluid 51 flows from the mixing section 50 to the slug flow former 60, causing grain growth of the by-products. By controlling the confluence of the mixed fluid 51 and the insoluble fluid 55 within a predetermined time, a slug flow can be formed before insoluble particles 52 resulting from grain growth of the by-products begin to adhere to and deposit on the inner wall surface 10a of the flow channel 10. In the formed slug flow, stirring by the circulating flow R1 in the mixed fluid cells 51a and 51b suppresses grain growth of the by-products and adhesion and deposition of the insoluble particles 52 on the inner wall surface 10a of the flow channel 10, thereby preventing the occurrence of flow channel clogging and allowing the polymerization reaction of the monomers to proceed.

[0063] In this embodiment, as shown in FIG. 1 , the control unit 40 includes flow rate control devices 41, 42, and 43. The flow rate control devices 41, 42, respectively, disposed in the pipes 24A and 24B of the liquid delivery unit 20, adjust the flow rates of the first fluid 20A and the second fluid 20B fed into the flow path 10. This allows the mixed fluid 51 to reach the slug flow former 60 and merge with the insoluble fluid 55 within a predetermined time after its formation. Furthermore, the flow rate control device 43, disposed in the pipe 34 of the insoluble fluid introduction unit 30, adjusts the flow rate of the insoluble fluid 55 fed into the flow path 10. This allows the flow rate ratio of the mixed fluid 51 to the insoluble fluid 55 in the flow path 10 to be set to a predetermined value. This allows a stable slug flow 61 to flow within the flow path 10, suppressing adhesion and deposition of insoluble particles 52 on the inner wall surface 10a and effectively preventing flow path blockage.

[0064] The present disclosure is not limited to the configuration of the control unit 40. The control unit 40 may have other configurations for controlling the formation of a slug flow. For example, the control unit 40 may be configured to adjust the configuration of the flow path between the mixing unit 50 and the slug flow former 60. The present disclosure is not limited to the configuration of the flow rate adjustment device. The flow rate adjustment device may be, for example, any one of a pump, a flow meter, a proportional control supply valve, etc. (not shown), or any combination thereof. The flow rate adjustment device is not limited to being disposed in a pipe connected to the flow path. For example, a flow rate adjustment device may be disposed in the flow path 10 to adjust the flow rate of the mixed fluid.

[0065] In this embodiment, the solvent for dissolving or dispersing the three raw materials for the monomer polymerization reaction is preferably a polar solvent, such as, but not limited to, dimethyl sulfoxide, N,N-dimethylacetamide, tetrahydrofuran, ethanol, water, etc., and among these, dimethyl sulfoxide, N,N-dimethylacetamide, and tetrahydrofuran are preferably used.

[0066] In this embodiment, the immiscible fluid 55 may be a liquid or a gas. If it is a liquid, it may contain a non-polar solvent. The non-polar solvent is not limited to these, but it is preferable to use, for example, a straight-chain saturated hydrocarbon, an aromatic hydrocarbon, or a silicone oil. If it is a gas, it is preferable to use, for example, argon gas or nitrogen gas.

[0067] In this embodiment, as described above, the inner wall of the flow channel 10 can be made of a material with low polarity. When the immiscible fluid 55 is made of a nonpolar solvent, as shown in FIG. 2 , the immiscible fluid cells 55a and 55b have a higher affinity for the inner wall surface 10a of the flow channel 10 than the mixed fluid cells 51a and 51b. Therefore, the contact area between the mixed fluid cells 51a and 51b and the inner wall surface 10a in the slug flow 61 is reduced. This further suppresses adhesion and deposition of the insoluble particles 52 on the inner wall surface 10a of the flow channel 10.

[0068] <Polymer Production Process> A polymer production process will be described with reference to Fig. 3. Fig. 3 is a flowchart showing an example of a polymer production process using the polymer production apparatus 100 according to an embodiment of the present disclosure.

[0069] As shown in Fig. 3, the polymer production process can include steps S101 to S105. Each step will be described below. The polymer production process by polymerization of two types of monomers, including Monomer 1 and Monomer 2, will be described below with reference to Fig. 1 as well.

[0070] In the storing step S101, for example, a first fluid in which monomer 1, monomer 2, and a ligand are dissolved in a solvent is stored in a storage portion of the fluid supply portion 21 of the liquid delivery portion 20, and a second fluid in which a metal catalyst is dissolved or dispersed in a solvent is stored in a storage portion of the fluid supply portion 22 of the liquid delivery portion 20. In addition, the insoluble fluid 55 is stored in a storage portion of the insoluble fluid introduction portion 30. Note that the configuration of the first fluid and the second fluid is not limited to this, and it is sufficient if one fluid contains some of the three types of raw materials, i.e., the monomer, the ligand, and the metal catalyst, and the other fluid contains the other types of raw materials.

[0071] In the raw material mixing step S102, the liquid delivery devices of the fluid supply units 21 and 22 of the liquid delivery unit 20 are operated to deliver the first fluid and the second fluid to the mixing unit 50. In the mixing unit 50, three types of raw materials dissolved or dispersed in a solvent are mixed to form a mixed fluid 51. At this time, the polymerization reaction of the monomers begins to proceed.

[0072] Next, in the slug flow formation step S103, the insoluble fluid 55 is introduced into the slug flow former 60 by operating the feeding device of the insoluble fluid inlet section 30. In the slug flow former 60, the mixed fluid 51 from the mixing section 50 and the insoluble fluid 55 introduced from the insoluble fluid inlet section 30 join together to form a slug flow 61.

[0073] Moreover, at this time, the control unit 40 can control the mixed fluid 51 to reach the slug flow former 60 within a predetermined time and merge with the insoluble fluid 55 by adjusting the flow rates of the first fluid and the second fluid fed into the flow channel 10. This allows the slug flow 61 to be formed before insoluble particles 52 produced by the polymerization reaction of the monomer begin to adhere and deposit on the inner wall surface 10a of the flow channel 10. Furthermore, the control unit 40 can set the flow rate ratio of the mixed fluid 51 to the insoluble fluid 55 in the flow channel 10 to a predetermined value by adjusting the flow rate of the insoluble fluid 55 fed into the flow channel 10. This allows a stable slug flow 61 to flow in the flow channel 10.

[0074] Next, in the heating reaction step S104, the slug flow 61 formed in the slug flow former 60 and flowing through the flow path 10 is passed through the heating unit 70 and heated to promote the polymerization reaction of the monomers. At this time, the stirring caused by the circulating flow within the mixed fluid cell suppresses the grain growth of by-products of the polymerization reaction and also suppresses the adhesion and deposition of insoluble particles on the inner wall surface of the flow path, thereby preventing the occurrence of flow path blockage.

[0075] Finally, in the recovery step S105, the fluid in the channel 10 is separated and the product polymer is recovered.

[0076] A polymer can be produced by the above steps. Note that the above polymer production process is merely an example, and the production of a polymer is not limited to the above process.

[0077] According to the polymer production apparatus and polymer production process of the present embodiment described above, adhesion of insoluble particles to the inner wall surface of the flow path can be suppressed during the polymer production process, thereby improving polymer productivity.

[0078] Examples and Comparative Examples In Examples 1 and 2 and Comparative Example 1, polymers were produced using raw materials consisting of one type of monomer, a ligand, and a metal catalyst. Examples 1 and 2 and Comparative Example 1 will be described below.

[0079] <Polymer Production Apparatus> The polymer production process shown in FIG. 3 was carried out using the polymer production apparatus 100 shown in FIG. 1. In the polymer production apparatus 100, the flow path diameters in the mixing section 50 and the slug flow former 60 were 1 mm, and the flow path diameters of the other flow paths were 2 mm. In Example 1-2, the slug flow former 60 was connected to a flow path position approximately 6.5 cm away from the mixing section 50. The flow rate adjuster of the control section 40 was set so that the mixed fluid reached the slug flow former 60 from the mixing section 50 in approximately 0.3 seconds. At this time, the flow rate of the mixed fluid from the mixing section was approximately 4.0 ml / min. The heating temperature of the heating section 70 was set to 80°C.

[0080] Example 1 In Example 1, 2,5-dichloropyridine was used as the raw material monomer, bipyridine was used as the ligand, and Ni(cod) was used as the metal catalyst. ２ The three raw materials were dissolved or dispersed in N,N-dimethylacetamide as a solvent, and Ar gas was used as the insoluble fluid.

[0081] Example 2 Example 2 was the same as Example 1 except that p-dichlorobenzene was used as the raw material monomer and triphenylphosphine was used as the ligand.

[0082] Comparative Example 1 Comparative Example 1 was the same as Example 1, except that in the polymer production apparatus 100 of Figure 1 , the insoluble fluid inlet section 30 and the slug flow former 60 were not connected to the flow path 10. In this case, the polymer production apparatus 100 was configured to include the flow path 10, the liquid delivery section 20, the control section 40, the mixing section 50, the heating section 70, and the recovery section 80.

[0083] (Evaluation of Channel Blockage in Examples and Comparative Examples) Measurement of channel blockage in the polymer production processes of Examples 1-2 and Comparative Example will be described with reference to Fig. 4. Fig. 4 is a table showing the measurement results of channel blockage in the polymer production processes carried out in Examples 1-2 and Comparative Example 1.

[0084] The occurrence of flow path blockage was evaluated in the polymer production processes of Examples 1-2 and Comparative Example. To evaluate flow path blockage, a pressure gauge (FC-PSU-1000, manufactured by DFC) was used to measure the pressure in the flow path at a flow path position upstream of the mixing section 50. If a pressure increase was observed, it was determined that flow path blockage had occurred due to adhesion and deposition of insoluble particles on the inner wall surface of the flow path, and if no pressure increase was observed, it was determined that flow path blockage had not occurred. In the table of FIG. 4, "no flow path blockage" is indicated by a circle, and "flow path blockage" is indicated by an x.

[0085] As shown in the table of Figure 4, in Examples 1 and 2, no increase in pressure was observed downstream of the slug flow former 60. In this case, the mixed fluid reached the slug flow former 60 from the mixing section 50 in approximately 0.3 seconds, and thus merged with the insoluble fluid 55 to form a slug flow before the insoluble particles produced by the polymerization reaction of the monomer began to adhere to and deposit on the inner wall surface of the flow channel. This indicates that, within the mixed fluid cell of the slug flow, the stirring caused by the circulating flow prevented the insoluble particles from adhering to and depositing on the inner wall surface of the flow channel, and the polymerization reaction of the monomer proceeded without causing flow channel blockage.

[0086] On the other hand, in Comparative Example 1, in the polymer production apparatus 100 to which the slug flow former 60 was not connected, a pressure increase was observed downstream of the mixing section 50. At this time, it was found that the polymerization reaction of the monomer started in the mixing section 5, and as the polymerization reaction progressed, insoluble particles generated by the grain growth of the by-products adhered to and accumulated on the inner wall surface of the flow path, causing blockage of the flow path.

[0087] As described above, the accompanying drawings and detailed description have been provided to explain exemplary embodiments of the technology disclosed herein. Therefore, the components described in the accompanying drawings and detailed description may include not only components essential for solving the problem, but also components that are not essential for solving the problem in order to illustrate the technology. Therefore, the fact that these non-essential components are described in the accompanying drawings or detailed description should not be interpreted as immediately indicating that these non-essential components are essential.

[0088] Although the present disclosure has been fully described in connection with the preferred embodiments with reference to the accompanying drawings, various modifications are possible within the scope of the claims, and such modifications and embodiments obtained by appropriately combining the technical means disclosed in the different embodiments are also included in the technical scope of the present disclosure.

[0089] The present disclosure is applicable to the production of polymers. For example, the present disclosure is applicable to the production of polymers using microreactors.

[0090] DESCRIPTION OF SYMBOLS 10 Flow path 20 Liquid delivery section 21, 22 Fluid supply section 30 Insoluble fluid introduction section 40 Control section 41, 42, 43 Flow rate control device 24A, 24B, 34 Piping 50 Mixing section 51 Mixed fluid 52 Insoluble particles 55 Insoluble fluid 60 Slug flow former 61 Slug flow 70 Heating section 80 Recovery section 100 Polymer production apparatus

Claims

1. A method for producing a polymer by a polymerization reaction that occurs in a flow path through which a fluid containing three types of raw materials, namely at least one type of monomer, a ligand, and a metal catalyst, flows, the method comprising: a mixing step of separately feeding one fluid containing a portion of the three types of raw materials and another fluid containing the other type of raw materials into the flow path to form a mixed fluid containing the three types of raw materials in the flow path; and a slug flow formation step of introducing an insoluble fluid that is insoluble in the mixed fluid into the flow path and merging the mixed fluid and the insoluble fluid to form a slug flow, the slug flow formation step including controlling the formation of the slug flow so that the mixed fluid and the insoluble fluid are merged within a predetermined time after the mixed fluid is formed.

2. The method for producing a polymer according to claim 1, wherein controlling the formation of the slug flow comprises adjusting a flow rate of at least one of the one fluid or the other fluid fed into the flow channel.

3. The method for producing a polymer according to claim 1 or 2, wherein the slug flow forming step includes adjusting a flow rate of the immiscible fluid introduced into the flow channel.

4. The method for producing a polymer according to claim 1 or 2, further comprising a heating reaction step of heating the slug stream.

5. The metal catalyst is M(cod) ２ 3. The method of claim 1 or 2, wherein M is a metal comprising at least one of nickel, platinum, and palladium.

6. The method for producing a polymer according to claim 1 or 2, wherein the inner wall of the flow channel is made of a material with low polarity.

7. The method for producing a polymer according to claim 6, wherein the three types of raw materials are dissolved or dispersed in a polar solvent.

8. The method for producing a polymer according to claim 6, wherein the immiscible fluid comprises a non-polar solvent.

9. The method for producing a polymer according to claim 1 or 2, wherein the immiscible fluid is a gas.

10. A polymer production apparatus for producing a polymer by a polymerization reaction occurring in a flow path through which a fluid containing three types of raw materials, namely at least one type of monomer, a ligand, and a metal catalyst, flows, the polymer production apparatus comprising: a flow path; a liquid delivery section which separately delivers one fluid containing a portion of the three types of raw materials and another fluid containing the other portion of the three types of raw materials into the flow path; a mixing section which is disposed upstream within the flow path and forms a mixed fluid containing the three types of raw materials delivered from the liquid delivery section; a slug flow former which is disposed downstream within the mixing section in the flow path; an insoluble fluid introduction section which introduces an insoluble fluid that is insoluble in the mixed fluid into the slug flow former; and a control section; the slug flow former forms a slug flow by merging the mixed fluid and the insoluble fluid, and the control section controls the flow rate of the mixed fluid so that the mixed fluid reaches the slug flow former from the mixing section within a predetermined time.

11. The polymer production apparatus according to claim 10, wherein the control unit is configured to adjust a flow rate of at least one of the one fluid or the other fluid fed into the flow channel.

12. The polymer production apparatus according to claim 10 or 11, wherein the control unit is configured to adjust a flow rate at which the immiscible fluid is introduced into the slug flow former.

13. The polymer production apparatus according to claim 10 or 11, further comprising a heating section disposed in the flow path downstream of the slug flow former.

14. The polymer production apparatus according to claim 10 or 11, wherein the inner wall of the flow channel is made of a material with low polarity.

Images