Manufacturing method for polymer

Abstract

A method for manufacturing a polymer according to one embodiment of the present application comprises the steps of: manufacturing a nickel complex precursor in a first continuous reactor; supplying the nickel complex precursor to a second continuous reactor; supplying a ligand to the second continuous reactor and reacting the nickel complex precursor and the ligand to produce a nickel complex; supplying the nickel complex to a third reactor; and supplying a monomer to the third reactor and performing a polymerization reaction.

Description

Technology Field

[0001] This application relates to a method for manufacturing a polymer. Background Technology

[0002] There are several known methods for manufacturing conventional polymers, examples of which include Suzuki polymerization described in International Patent Application Publication No. WO 2000 / 053656 and Yamamoto polymerization described in the literature [T. Yamamoto, "Electrically Conducting And Thermally Stable ð-Conjugated Poly(arylene)s Prepared by Organometallic Processes", Progress in Polymer Science 1993, 17, 1153-1205]. All of these polymerization techniques operate through "metal insertion," in which a metal atom of a metal complex catalyst is inserted between the leaving group and the aryl group of the monomer. In the case of Yamamoto polymerization, a nickel complex catalyst is used, and in the case of Suzuki polymerization, a palladium complex catalyst is used.

[0003] The characteristics of a polymer are determined by the properties, characteristics, and composition of the monomers used in its manufacture. In addition, polymers are required to possess process characteristics, such as reproducibility, which enables the production of a consistent product regardless of the number of reactions or the scale of the reaction. However, achieving such reproducibility is practically difficult in conventional batch reaction manufacturing processes.

[0004] The properties of the polymer are affected by various reaction conditions such as the shape of the reactor, the monomer input rate, and the reaction temperature, but it is difficult to consistently control these reaction conditions for each reaction cycle. Prior art literature

[0005] J Org Chem (1990), 4229-4230 The problem to be solved

[0006] The present application aims to provide a method for manufacturing a polymer using a nickel complex. means of solving the problem

[0007] One embodiment of the present application is,

[0008] A step of producing a nickel complex precursor in a first continuous reactor;

[0009] A step of supplying the above nickel complex precursor to a second continuous reactor;

[0010] A step of supplying a ligand to the second continuous reactor and reacting the nickel complex precursor and the ligand to produce a nickel complex;

[0011] A step of supplying the nickel complex to a third reactor; and

[0012] The method includes the step of supplying a monomer to the third reactor and performing a polymerization reaction.

[0013] The first continuous reactor and the second continuous reactor are each a plug flow reactor (PFR), and

[0014] The present invention provides a method for manufacturing a polymer in which the third reactor is a Continuous Stirred Tank Reactor (CSTR) or a semi-batch reactor. Effects of the invention

[0015] A method for manufacturing a polymer according to one embodiment of the present application can secure high yield and reproducibility by using a continuous reaction process instead of a conventional batch method.

[0016] In particular, the method for manufacturing a polymer according to one embodiment of the present application applies a plug flow reactor (PFR) as the first continuous reactor and the second continuous reactor, respectively, and applies a continuous stirred tank reactor (CSTR) or a semi-batch reactor as the third reactor, thereby not only ensuring the activity and stability of the Ni complex catalyst produced by the continuous process but also improving the yield and quality stability of the polymer produced. Brief explanation of the drawing

[0017] FIG. 1 is a schematic diagram showing the process flow of a method for manufacturing a polymer according to one embodiment of the present application. Specific details for implementing the invention

[0018] The present specification will be described in more detail below.

[0019] The nickel complex catalyst used in the above Yamamoto polymerization is prepared by reacting a nickel compound such as Ni(COD)2 with a ligand, but since Ni(COD)2 is an unstable substance that reacts easily with air, water, or light and oxidizes, there was a problem of low reaction yield and poor reproducibility.

[0020] Furthermore, Ni(COD)2 is a highly sensitive reactant whose quality varies depending on the supplier, and even when manufactured by the same supplier, quality differences can occur depending on the production batch. Additionally, because Ni(COD)2 is highly sensitive to air and water and decomposes easily, it is recommended to store it at -20°C and use it in a glove box in principle. Moreover, Ni(COD)2 must be synthesized at cryogenic temperatures such as -78°C, and due to the difficulty of filtration and crystallization, the purification process is complex, resulting in a very high price. Thus, although Ni(COD)2 is an important raw material for manufacturing nickel complex catalysts, its commercial use has been limited due to the difficulty of mass production and high manufacturing costs.

[0021] Although a method for producing polymers using the Yamamoto reaction with Ni(COD)2 has been known in the past, it has been difficult to produce polymers with excellent stability due to differences in quality of Ni(COD)2, high instability, polymerization yield, and low reproducibility.

[0022] Furthermore, the batch method suffers from problems such as increased by-products during mass production leading to lower purity and reduced yield. Additionally, since product yield and characteristics vary from batch to batch, the performance of the final product is inconsistent, making it difficult to apply to commercial production.

[0023] Conventional batch reactors present challenges during commercial-scale production, including difficulties in operation and increased investment and operating costs. Furthermore, processes utilizing batch reactors typically require the repetition of a series of operations, such as heating, reactant injection, reaction, cooling, and product discharge. Consequently, due to low productivity per batch operation, there is a problem in that the reactor volume or the number of reactors must be increased to achieve mass production.

[0024] In addition, when reacting the manufactured Ni(COD)2 with a ligand, there is a problem in that a separate purification process of Ni(COD)2 is required.

[0025] Accordingly, the present application aims to provide a process for manufacturing various catalysts / coupling agents in large quantities by applying a continuous manufacturing process to continuously produce Ni(COD)2 and reacting it with other ligands without a purification process of Ni(COD)2. In addition, the present application aims to provide a method for manufacturing a polymer with improved yield and stable quality by reacting a catalyst produced from Ni(COD)2 with one or more monomers.

[0026] A method for manufacturing a polymer according to one embodiment of the present application comprises the steps of: manufacturing a nickel complex precursor in a first continuous reactor; supplying the nickel complex precursor to a second continuous reactor; supplying a ligand to the second continuous reactor and reacting the nickel complex precursor and the ligand to produce a nickel complex; supplying the nickel complex to a third reactor; and supplying a monomer to the third reactor and performing a polymerization reaction. In this case, the first continuous reactor and the second continuous reactor are each a plug flow reactor (PFR), and the third reactor is a continuous stirred tank reactor (CSTR) or a semi-batch reactor.

[0027] The method for manufacturing a polymer according to one embodiment of the present application has the advantage of being suitable for large-scale continuous processes by minimizing quality variations occurring between processes. More specifically, the quality evaluation items can be compared using methods generally used in the field to which this technology belongs. For example, a method can be used to calculate the conversion rate, molecular weight, etc., of the manufactured polymer and compare them by process.

[0028] In addition, when using conventional batch reactors, it is difficult to create an inert environment, which leads to an increased risk of accidents due to highly flammable reactants. However, the method for manufacturing a polymer according to one embodiment of the present application has the advantage of improved stability even when using highly flammable reactants, as it is easy to create an inert environment inside the reactor.

[0029] A method for manufacturing a polymer according to one embodiment of the present application is characterized by not using a commercial nickel complex precursor, but by manufacturing a nickel complex precursor in a first continuous reactor and using it immediately for the production of a nickel complex without a separate processing step. As with conventional commercial nickel complex precursors, they are prone to oxidation due to their easy reaction with air, water, light, etc., making it difficult to secure high yield and reproducibility. On the other hand, the method for manufacturing a polymer according to one embodiment of the present application prevents raw materials from being exposed to the atmosphere during the nickel complex production process by directly manufacturing the nickel complex precursor and using it immediately in a continuous process. Furthermore, the reactors facilitate the creation of an inert environment, which provides the advantage of improved stability when using highly flammable materials as raw materials.

[0030] In the present application, "nickel complex precursor" refers to a precursor material used to prepare a nickel complex and may be in the form of a complex. The nickel complex precursor refers to a nickel compound in which the oxidation number of nickel is controlled to 0, and more specifically, may be bis(1,5-cyclooctadiene) nickel {bis(1,5-cyclooctadiene) nickel: Ni(COD)2}.

[0031] In the present application, "nickel complex" means a compound in which nickel and a ligand are complexed. More specifically, it is represented as Ni(L)n, where n is an integer from 2 to 4 and L represents a ligand. When n is 2 or greater, L in parentheses may be the same or different.

[0032] The above L represents a ligand and may be a pyridine-based ligand, a phosphine-based ligand, a carboxylic acid-based ligand, a nitrile-based ligand, or a halide-based ligand.

[0033] More specifically, the nickel complex may be t-BuNC [Ni(t-BuNC)2], [Ni(nbd)2], [Ni(cod)(bpy)], [Ni(AN)2], [Ni(PPh3)4], [Ni(cod)(PPh3)2], [NiBr(C3H5)2], [NiBr(C3H5)2], or NiCl(C3H5)(PPh3). Here, nbd means bicycle[2.2.1]hepta-2,5-dien, bpy means 2,2'-biphyridyl, and AN means ancrylonitrile. In addition to the examples above, it may refer to various types of nickel complexes exemplified in prior papers [J Org Chem (1990), 4229-4230, Tetrahedron lettres 39, 3375-3378 (1975), Organometallics 2017, 36, 3508-3519, Chem.Soc.Rev., 1985, 14, 93-120, etc.].

[0034] In the present application, the "continuous reactor" is a reactor that carries out a reaction while continuously feeding the reactants used in the reaction, and the supply of reactants and the discharge of products can be performed simultaneously.

[0035] In this application, unless otherwise specified, the description of a "continuous reactor" may apply to both the first continuous reactor and the second continuous reactor.

[0036] In the present application, "first continuous reactor" refers to a reactor for producing a nickel complex precursor. In this case, the first continuous reactor may be connected in series with other continuous reactors. The means of connection are not particularly limited and may be connected through pipes used in chemical processes.

[0037] In the present application, "second continuous reactor" refers to a reactor for producing a nickel complex. In this case, the second continuous reactor may be connected in series with other continuous reactors. The means of connection are not particularly limited and may be connected through pipes used in chemical processes.

[0038] In the present application, "third reactor" refers to a reactor that produces a polymer using a nickel complex. In this case, the third reactor may be connected in series with other continuous reactors. The means of connection are not particularly limited and may be connected through pipes used in chemical processes.

[0039] In one embodiment of the present application, the first continuous reactor, the second continuous reactor, and the third reactor may be connected in series with each other. In this case, it is advantageous to create an inert environment inside the reactor, and there is an advantage that the product can be produced in each reactor and simultaneously supplied to another reactor. The connecting means is not particularly limited and may be connected through pipes used in chemical processes.

[0040] In one embodiment of the present application, the supply of raw materials and the discharge of products to each reactor may be performed simultaneously. More specifically, the steps of supplying the nickel complex precursor to a second continuous reactor; supplying a ligand to the second continuous reactor; and reacting the nickel complex precursor and the ligand to produce a nickel complex may be performed simultaneously. Additionally, the steps of supplying the nickel complex to a third reactor; supplying a monomer to the third reactor; and performing a polymerization reaction may be performed simultaneously. The meaning of "performed simultaneously" is that the supply of raw materials and the discharge of products are performed simultaneously without a separate storage time.

[0041] In this case, the product can be manufactured and discharged simultaneously from the reactor, and the input of raw materials, reaction, and product discharge can be performed continuously as a series of processes. By utilizing such a continuous process, the reactor capacity can be significantly reduced compared to conventional batch reactions, reaction conditions can be easily controlled, and a constant reaction environment can be maintained. Furthermore, by feeding reaction raw materials at a constant speed or ratio, nickel complexes with consistent composition and performance can be manufactured, thereby minimizing product variation even when producing large quantities.

[0042] In one embodiment of the present application, the step of manufacturing the nickel complex precursor in a first continuous reactor comprises the step of supplying and reacting a nickel (II) source, a diene compound, and a reducing agent in the first continuous reactor. When using a conventional batch reactor, it is difficult to create an inert environment, which increases the risk of accidents due to highly flammable reactants. However, when manufacturing the nickel complex precursor in the first continuous reactor, it is easy to create an inert environment inside the reactor, thus providing the advantage of improved stability even when using highly flammable reactants.

[0043] In one embodiment of the present application, the nickel complex precursor is characterized by being manufactured in a first continuous reactor. Conventionally, nickel complex precursors were manufactured in a batch reactor, which required dropping a reducing agent for at least 30 minutes and undergoing an additional aging time of at least 30 minutes. However, when using a first continuous reactor as in the present application, additional aging time is unnecessary, and thus, a yield equivalent to that of the batch process can be secured with a short process time. Furthermore, in the case of a conventional batch reactor, the reaction must be carried out under an ultra-low temperature environment of -78°C or lower, but when using a first continuous reactor as in the present application, heat removal is easy, so there is an advantage that an equivalent yield can be secured even in an environment higher than the ultra-low temperature (e.g., -20°C) without separate reaction heat control. Meanwhile, conventional batch reactors pose a risk of accidents due to the influx of moisture and oxygen during the manufacturing process; however, using a first continuous reactor as in the present application allows for operation under inert conditions, which has the advantage of minimizing the aforementioned risk of accidents.

[0044] In one embodiment of the present application, the nickel (II) source, the diene compound, and the reducing agent are materials that serve as raw materials for the production of the nickel complex precursor, and their types and characteristics are not particularly limited.

[0045] In one embodiment of the present application, the nickel (II) source may be a material commonly used in the field to which this technology belongs, as a material for supplying nickel atoms. However, from the standpoint of stability and economic feasibility, it is preferable to include nickel acetylacetonate {Ni(acac)2}.

[0046] In one embodiment of the present application, the diene compound may be one or more selected from the group consisting of 1,4-cyclohexadiene, picyclo[2.2.2]hept-2,5-diene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-vinyl-2-norbornene, bicyclo[2.2.2]oct-2,5-diene, 4-vinylcyclohex-1-ene, bicyclo[2.2.1]hept-2,5-diene, bicyclopentadiene, methyltetrahydroindene, 5-allylbicyclo[2.2.1]hept-2-ene and 1,5-cyclooctadiene, and 1,4-cyclohexadiene is more preferred.

[0047] In one embodiment of the present application, the reducing agent may be an organic reducing agent or an inorganic reducing agent. Examples include DIBAL (Diisobutylaluminium hydride), NaBH4, KBH4, Zn powder, magnesium, hydrogen, etc., but DIBAL is preferred.

[0048] In one embodiment of the present application, the method of supplying the nickel (II) source, the diene-based compound, and the reducing agent to the first continuous reactor is not particularly limited. For example, the first continuous reactor may include one or more reactant inlets, and the nickel (II) source, the diene-based compound, and the reducing agent may each be supplied to the reactant inlets.

[0049] In one embodiment of the present application, the first continuous reactor may include one or more reactant inlets, and more specifically, may include one to ten reactant inlets.

[0050] In one embodiment of the present application, the first continuous reactor comprises one or more reactant inlets, and the nickel (II) source, diene compound, and reducing agent may be supplied to the same or different reactant inlets.

[0051] In one embodiment of the present application, the first continuous reactor comprises three or more reactant inlets, and the nickel (II) source, the diene compound, and the reducing agent may all be supplied to different reactant inlets. For example, the first continuous reactor may comprise first to third reactant inlets, and the nickel (II) source may be supplied to the first reactant inlet, the diene compound may be supplied to the second reactant inlet, and the reducing agent may be supplied to the third reactant inlet.

[0052] In one embodiment of the present application, the first continuous reactor comprises two or more reactant inlets, and two of the nickel (II) source, diene compound, and reducing agent may be supplied to the same reactant inlet and the other to the other reactant inlet. For example, the first continuous reactor comprises first and second reactant inlets, and the nickel (II) source and the diene compound may be supplied to the first reactant inlet, and the reducing agent may be supplied to the second reactant inlet.

[0053] In one embodiment of the present application, the step of mixing the nickel (II) source and the diene-based compound may be further included. Through the mixing step, the mixing ratio of each material can be increased to reduce the occurrence of unreacted materials and improve the heat removal effect, and consequently, improve the conversion rate of the raw material.

[0054] In one embodiment of the present application, the step of mixing the nickel (II) source and the diene compound may be performed using a mixer, and the description of the mixer is as follows.

[0055] In one embodiment of the present application, the nickel (II) source, the diene compound, and the reducing agent may each be supplied in the form of a solution containing the same. The solvent included in the solution may be of the same type as described below.

[0056] In one embodiment of the present application, the supply rates of the nickel (II) source, the diene compound, and the reducing agent may be the same or different from each other, and may be 0.5 g / min to 500 g / min each. Within the range of supply rates, the supply of each raw material is carried out smoothly, thereby preventing side reactions and reducing the operating time.

[0057] In one embodiment of the present application, the reaction in the step of preparing the nickel complex precursor may be carried out under conditions of a temperature of -78°C to 10°C and a pressure of 1 bar to 10 bar. When controlled within these ranges, the exothermic reaction during preparation can be controlled, and the reaction rate can be easily controlled. The temperature can be achieved through a pre-temperature coil and a constant-temperature bath provided in the first continuous reactor. The pressure can be achieved by controlling the flow rate and supply rate of the reactants introduced into the first continuous reactor. More specifically, it can be controlled using a back pressure regulator (BPR).

[0058] In one embodiment of the present application, the molar ratio of the nickel (II) source to the diene compound may be 1:2 to 1:10 and 1:4 to 1:6. When within the above range, the reaction between the nickel (II) source and the diene compound can proceed smoothly.

[0059] In one embodiment of the present application, the molar ratio of the nickel (II) source to the reducing agent may be 1:2 to 1:5, 1:2.3 to 1:3, or 1:2.3 to 1:2.5. When within the above range, the phenomenon of color deterioration caused by the reducing agent is prevented, and a yield of at least a certain level can be secured.

[0060] In one embodiment of the present application, the reaction of the step of preparing the nickel complex precursor may be carried out under an inert environment. Methods for creating an inert environment include removing moisture and oxygen inside the first continuous reactor before supplying the reactant to the first continuous reactor, or supplying an inert gas inside the first continuous reactor before supplying the reactant. Examples of the inert gas include argon (Ar) or nitrogen (N2).

[0061] The nickel complex precursor manufactured above is continuously supplied to the second continuous reactor. At this time, the problem of having to separately store or process the nickel complex precursor, which is difficult to handle, was resolved. Since the nickel complex precursor is manufactured in the first continuous reactor and simultaneously supplied to the second continuous reactor, there is an advantage in reducing the cost and effort required to stabilize the nickel complex precursor.

[0062] In one embodiment of the present application, the step of mixing the nickel complex precursor and the ligand may be further included. In this case, the mixing ratio of the materials can be increased to reduce the occurrence of unreacted materials, improve the heat removal effect, and consequently improve the conversion rate. After mixing the nickel complex precursor and the ligand, the mixture can be supplied through a single reactant inlet.

[0063] In one embodiment of the present application, the step of mixing the nickel complex precursor and the ligand may be performed using a mixer.

[0064] In one embodiment of the present application, the mixer may include one or more of a static mixer, a T mixer, and a microreactor. The static mixer may be a plate mixer, a Kenics mixer, or a Sulzer mixer, but is not limited thereto.

[0065] In one embodiment of the present application, the microreactor may include a plurality of microchannels that repeatedly branch and merge. By including the microchannels, the mixing efficiency of the reactants can be further increased.

[0066] In one embodiment of the present application, the microchannel may have various hydrodynamic structures, for example, a single flow path may form a deep wave shape, or two or more flow paths may be connected by repeatedly branching and merging to form a plurality of branching points.

[0067] In one embodiment of the present application, the size of the microchannel may be 1 μm to 10 mm.

[0068] In one embodiment of the present application, the method of supplying the nickel complex precursor and ligand to the second continuous reactor is not particularly limited. For example, the second continuous reactor may include one or more reactant inlets, and the nickel complex precursor and ligand may be supplied to each of the reactant inlets. In this case, the supply power may be provided through a separately connected supply device or pump. Through the device, the raw materials can be supplied to the second continuous reactor at a constant rate, and the amount supplied can also be measured. The supply device may be used without limitation as long as it can prevent contact with air and uniformly control the flow rate, such as a mass flow controller (MFC), a syringe pump, or a peristaltic pump.

[0069] In one embodiment of the present application, the reactant inlet is configured to introduce a reactant into a reactor. The reactant inlet may refer to an input section (or injection section) for controlling the input amount of each raw material within a continuous reactor. At this time, the input amount of the raw material injected into each reactant inlet can be controlled, and the input amount can be controlled according to the reaction environment, thereby minimizing side reactions.

[0070] In one embodiment of the present application, the second continuous reactor may include 1 to 10 reactant inlets.

[0071] In one embodiment of the present application, the second continuous reactor comprises one or more reactant inlets, and the nickel complex precursor and ligand may be supplied through the same or different reactant inlets.

[0072] In one embodiment of the present application, the second continuous reactor comprises one or more reactant inlets, and the nickel complex precursor and the ligand can be supplied through the same reactant inlet.

[0073] In one embodiment of the present application, the nickel complex precursor and the ligand may each be supplied in the form of a solution containing the same.

[0074] In one embodiment of the present invention, the solvent may be a hydrocarbon solvent and may be one or more selected from linear hydrocarbon compounds such as pentane, hexane, and octane; derivatives thereof having side branches; cyclic hydrocarbon compounds such as cyclohexane and cycloheptane; aromatic hydrocarbon compounds such as benzene, toluene, and xylene; linear and cyclic ethers such as dimethyl ether, diethyl ether, anisole, and tetrahydrofuran; and amide solvents such as dimethylacetamide and dimethylformamide (hereinafter referred to as DMF). More specifically, the solvent may be cyclohexane, hexane, tetrahydrofuran diethyl ether, or dimethylformamide.

[0075] In one embodiment of the present application, the nickel complex precursor and the ligand may each be supplied in the form of a composition dissolved in a solvent, and the composition may each contain 0.1% to 35% by weight of the nickel complex precursor and the ligand.

[0076] In one embodiment of the present application, the feeding rates of the nickel complex precursor and the ligand may be the same or different from each other, and may be 0.1 g / min to 500 g / min, and preferably 0.2 g / min to 200 g / min. The feeding rates may be controlled via a mass flow controller (MFC) or a pump. Within the above-described range, there is an effect of minimizing side reactions without abrupt changes in the amount of material injected into each reactant inlet.

[0077] In one embodiment of the present application, the molar ratio of the nickel complex precursor to the ligand may be 1:10 to 10:1, preferably 1:5 to 5:1, and more preferably 1:0.9 to 0.9:1. Within this range, the reaction between the nickel complex precursor and the ligand can proceed smoothly, and the nickel complex precursor and the ligand can react in equal equivalent amounts. More specifically, when Ni(COD)2 is used as the nickel complex precursor and BPD is used as the ligand, a mixture of Ni(COD)2, Ni(BPD)2, Ni(COD)(BPD), etc., may be produced. Among these, since Ni(COD)(BPD) exhibits the best activity, it is desirable to adjust the molar ratio of the nickel complex precursor and the ligand to the above range in order to produce it.

[0078] In one embodiment of the present application, the second continuous reactor may be maintained at a temperature of 25°C to 200°C and a pressure of 1 bar to 20 bar. When controlled within this range, the exothermic reaction during the production of the nickel complex can be controlled, and the reaction rate can be easily controlled. The temperature can be achieved through a pre-temperature coil and a constant-temperature bath provided in the second continuous reactor. The pressure can be achieved by controlling the flow rate and supply rate of the reaction materials introduced into the second continuous reactor. Specifically, it can be controlled using a back pressure regulator (BPR).

[0079] In one embodiment of the present application, the second continuous reactor may include a pre-temperature coil. This allows the temperature of the reactants to be pre-controlled before being introduced into the second continuous reactor.

[0080] In one embodiment of the present application, the continuous reactor may include a constant-temperature bath. This allows the temperature to be controlled to a desired range while the reaction takes place within the continuous reactor.

[0081] In one embodiment of the present application, the second continuous reactor may be in an inert environment. Methods for creating an inert environment include removing moisture and oxygen inside the second continuous reactor before supplying reactants to the second continuous reactor, or supplying an inert gas inside the second continuous reactor before supplying reactants. Examples of the inert gas include argon (Ar) or nitrogen (N2).

[0082] In one embodiment of the present application, the second continuous reactor may contain an inert gas at a molar concentration of 99% or more. In this case, high yield and reproducibility can be ensured by minimizing the deactivation of the nickel complex precursor, which is sensitive to oxygen and moisture.

[0083] In one embodiment of the present application, the step of mixing the nickel complex and the monomer may be further included. In this case, the mixing ratio of the materials can be increased to reduce the occurrence of unreacted materials, temperature control can be facilitated, and consequently, the conversion rate can be improved. Additionally, after mixing the nickel complex and the monomer, the mixture can be supplied through a single reactant inlet.

[0084] In one embodiment of the present application, the step of mixing the nickel complex and the monomer may be performed for 1 minute to 300 minutes. At this time, since a polymerization reaction may be initiated simultaneously with the mixing of the nickel complex and the monomer, the time of 1 minute to 300 minutes may refer to the combined time for mixing and polymerization. To control the time, an Rt coil may be connected to each reactor.

[0085] In one embodiment of the present application, the feeding rate of the nickel complex; and the feeding rate of the monomer may be the same or different from each other and may be 0.5 g / min to 500 g / min each. The weight (g) of the feeding rate may be the total weight of the nickel complex or monomer composition itself; or a solution containing them.

[0086] The above-mentioned feed rate can be controlled via a separately connected mass flow controller (MFC) or pump. Within the aforementioned range, this has the effect of minimizing side reactions without abrupt changes in the amount of material injected into each reactant inlet.

[0087] In one embodiment of the present application, the third reactor may be maintained at a temperature of 25°C to 200°C and a pressure of 1 bar to 20 bar. When controlled within this range, the exothermic reaction during polymer production can be controlled, and the reaction rate can be easily controlled. The temperature can be achieved through a pre-temperature coil and a constant-temperature bath provided in the third reactor. The pressure can be achieved by controlling the flow rate and supply rate of the reaction materials introduced into the third reactor. Specifically, it can be controlled using a back pressure regulator (BPR).

[0088] In one embodiment of the present application, the polymerization reaction may be carried out under an inert environment. Specifically, the interior of the third reactor may be configured as an inert environment, which has the effect of preventing side reactions or explosions. Details regarding the inert gas are as described above.

[0089] In one embodiment of the present application, the first continuous reactor, the second continuous reactor, and the third reactor may each include a heat removal device, and said heat removal device may be pre-connected to each reactor. The reaction occurring in each reactor may be an exothermic reaction, and the reaction may be carried out in a constant temperature bath to rapidly control the reaction heat generated therein. More specifically, a pre-temperature coil may be installed at the front of each reactor, and its length may be adjusted to achieve thermal equilibrium according to the flow rate.

[0090] In one embodiment of the present application, each reactor may further include a holding coil (Rt coil). The residence time during which the reaction proceeds can be controlled through the holding coil. Specifically, the residence time can be controlled by controlling the time during which the material supplied to each reactor reacts and resides within the holding coil. The residence time can be controlled more finely by controlling the length of the holding coil and the supply speed of the supplied material.

[0091] In one embodiment of the present application, the monomer may comprise a base monomer; and an end-capper.

[0092] In one embodiment of the present application, the monomer may be supplied in the form of a solution containing it. The solvent is the same as that described above.

[0093] In one embodiment of the present application, the solution containing the monomer may contain the monomer in an amount of 0.1% to 35% by weight.

[0094] In one embodiment of the present application, the "polymerization reaction" is a reaction in which monomers polymerize with each other by the nickel complex acting as a catalyst. In this case, a reaction may occur in which the terminal groups of the monomers are replaced with the terminal-capping monomers.

[0095] In one embodiment of the present application, the polymerization reaction may be a Yamamoto polymerization reaction. The Yamamoto polymerization is carried out in such a manner that nickel atoms of the nickel complex catalyst are inserted between monomers, and the specific polymerization method is the same as that described in the literature [T. Yamamoto, "Electrically Conducting And Thermally Stable ð-Conjugated Poly(arylene)s Prepared by Organometallic Processes", Progress in Polymer Science 1993, 17, 1153-1205].

[0096] In the present application, a “monomer” is a raw material to be polymerized to form a polymer. A monomer is chemically bonded to another monomer to form a chain. By itself, each monomer can be considered to have two or more “functional groups” (i.e., the positions where the monomer is chemically bonded to another monomer). By chemically bonding each end of the monomer to another monomer, a chain of monomers is formed and a polymer is produced. A monomer may have more than two such positions, and in such case, this may result in a branched polymer.

[0097] When the above monomer is polymerized (regardless of whether other types of monomers are used), a polymer comprising repeating units is formed. The polymer preferably comprises repeating units selected from arylene repeating units as disclosed, for example, in the literature [Adv. Mater. 2000 12(23) 1737-1750] and its cited literature. Exemplary first repeating units include 1,4-phenylene repeating units as disclosed in the literature [J. Appl. Phys. 1996, 79, 934]; fluorene repeating units as disclosed in European Patent No. 0842208; indenofluorene repeating units as disclosed, for example, in the literature [Macromolecules 2000, 33(6), 2016-2020]; and spirofluorene repeating units as disclosed in European Patent No. 0707020. Each of these repeating units is optionally substituted. Examples of substituents are soluble groups, e.g., C 1-20 It includes alkyl or alkoxy; electron-withdrawing groups, such as fluorine, nitro, or cyano; and substituents that increase the glass transition temperature (Tg) of the polymer.

[0098] The above monomer type may include a leaving group, and the leaving group may be a halogen group such as F, Cl, Br, or I.

[0099] The above monomer may be a monomer represented by the chemical formula 1 below.

[0100] [Chemical Formula 1]

[0101]

[0102] In the above formula 1, R1 and R2 are independently selected from the group consisting of hydrogen; optionally substituted alkyl, alkoxy, aryl, arylalkyl, heteroaryl, and heteroarylalkyl in which one or more non-neighboring carbon atoms may be replaced with O, S, N, C=O, or -COO-. More preferably, one or more of R1 and R2 are optionally substituted C4-C20 alkyl groups or aryl groups.

[0103] In the above chemical formula 1, X1 and X2 are independently chlorine, bromine, and iodine, respectively, and most preferably bromine.

[0104] In one embodiment of the present application, the end-capper may be a single functional unit having one attachment site.

[0105] In one embodiment of the present application, the end-capper may include a crosslinker or a deuterated crosslinker.

[0106] In one embodiment of the present application, the end-capper may comprise a hydrocarbon aryl group or a deuterated hydrocarbon aryl group.

[0107] In one embodiment of the present application, the end-capper is selected from the group consisting of phenyl, biphenyl, diphenylamino, their substituted derivatives, and their deuterated analogs. In some embodiments, the substituent is C 1-10 It may be an alkyl group, a crosslinking group, or a deuterated derivative thereof.

[0108] In one embodiment of the present application, the end-capper may have the following structure.

[0109]

[0110]

[0111] A method for manufacturing a polymer according to one embodiment of the present application is characterized by having a small deviation in the physical properties of the polymer measured by varying process times within the same process cycle or process cycle. In this case, the process cycle may be divided into before and after the reactor start-up process. For example, after performing the first process, a process of removing all material inside the reactor may be performed, followed by the second process, and the physical properties of the polymer produced after the first and second processes can be measured and compared. Additionally, the physical properties of the polymer discharged from the reactor may be measured and compared as process time passes within the same process cycle.

[0112] In one embodiment of the present application, the coefficient of variation (CV) of one or more of the yield, number average molecular weight (Mn), and weight average molecular weight (Mw) of the polymer produced according to the method for producing the polymer may be 5.5% or less, 4% or less, or 3% or less. The coefficient of variation (CV) may be calculated by calculating the standard deviation and average values ​​of each physical property, and then dividing the standard deviation value by the average value.

[0113] The yield, number average molecular weight, and weight average molecular weight of the above polymer can be calculated by measuring the corresponding physical property values ​​in the following formula, and the physical property values ​​below can be calculated using methods commonly used in the field to which this technology belongs. For example, they can be calculated using gas chromatography (GC) or gel permeation chromatography (GPC) methods of the above polymer.

[0114] [Number Average Molecular Weight]

[0115]

[0116] [Weight Average Molecular Weight]

[0117]

[0118] (N i : Number of moles of polymer molecules, Mi : Polymer molecular weight, w i : Polymer weight)

[0119] A process flow diagram of a method for manufacturing a polymer according to one embodiment of the present application is schematically shown in Fig. 1 below.

[0120] If a conventional plug flow reactor (PFR) is applied as the third reactor, instead of applying a continuous stirred tank reactor (CSTR) or a semi-batch reactor as in one embodiment of the present application, mass production may be difficult due to clogging inside the tubes during long-term operation.

[0121] Furthermore, coupling polymerization is performed in the third reactor, which is a reaction in which Ni / halide-derived materials detach; as a result, Ni oxides and the like may gradually adhere to or coat the inner walls of the reactor. Therefore, as in one embodiment of the present application, when a Continuous Stirred Tank Reactor (CSTR) or a semi-batch reactor is applied as the third reactor, the aforementioned phenomenon of Ni oxides gradually adhering or coating is minimal relative to the size of the reactor and does not significantly affect the progress of the polymerization reaction. However, in the case of tubular reactors such as microchannels or plug flow reactors (PFRs), the internal channels of the reactor may become clogged, which can become a critical problem.

[0122] When using the above-mentioned plug flow reactor (PFR), the aforementioned problem may become clearly apparent as time passes. In particular, since the plug flow reactor (PFR) is structurally designed so that the reactants must pass directly through the back pressure regulator (BPR), clogging may occur within the regulator channel. However, in the case of a continuous stirred tank reactor (CSTR) or a semi-batch reactor such as in one embodiment of the present application, a back pressure regulator (BPR) can be used, but there is a difference in that it is used for depressurization / pressurization of an inert gas (N2) without the reactants passing through.

[0123] In one embodiment of the present application, the residence time of the reactants in the first continuous reactor may be 10 to 60 minutes and 15 to 55 minutes. Additionally, the residence time of the reactants in the second continuous reactor may be 0.01 seconds to 5 minutes, although not particularly limited as long as perfect mixing is achieved. Additionally, the residence time of the reactants in the third reactor may be 10 to 40 minutes and 15 to 35 minutes. When the residence times of the reactants in the first, second, and third reactors described above are satisfied, the activity and stability of the Ni complex catalyst and the yield of the polymer produced, which are the effects of the present application, can be more effectively improved.

[0124] Hereinafter, the present application will be described in detail with reference to examples to specifically explain the present application. However, the embodiments according to the present application may be modified in various different forms, and the scope of the present application is not to be interpreted as being limited to the embodiments described below. The embodiments of the present application are provided to more completely explain the present application to those with average knowledge in the art.

[0125] <Example>

[0126] <Example 1>

[0127] 1) First Continuous Reactor (PFR): Ni(COD) 2 manufacturing

[0128] Two vacuum-dried 2L stainless steel pressure vessels were prepared. Ni(acac)2 (100g), 532g of tetrahydrofuran, and 168g of 1,5-cyclooctadiene were added to the first pressure vessel to prepare the first reaction solution. 800g of Dibal (a 1M solution dissolved in toluene) solution was added to the second pressure vessel to prepare the second reaction solution. With the pressure in each pressure vessel maintained constant above atmospheric pressure, the first reaction solution and the second reaction solution were injected into the first continuous reactor (PFR) at an injection rate of 1.5 g / min and 1.5 g / min, respectively, using a mass flow meter. At this time, the temperature of the first continuous reactor was maintained at -5℃ and the residence time was maintained at 30 minutes. At this time, the molar ratio of Ni(acac)2: 1,5-cyclooctadiine : Dival was 1 : 4 : 2.5.

[0129] The manufactured Ni(COD)2 was continuously fed into the second continuous reactor (PFR).

[0130] 2) Second Continuous Reactor (PFR): Preparation of Ni complex

[0131] A vacuum-dried 2L stainless steel pressure vessel was prepared, and 13g of 2,2'-Bipyridyl (BPD) and 387g of DMF were added and stirred to prepare a 3.25 wt% BPD solution. With the pressure of the pressure vessel maintained at a constant level above atmospheric pressure, the BPD solution was injected into a second continuous reactor (PFR) at an injection rate of 2.5 g / min using a mass flow meter, and the solution was reacted continuously with Ni(COD)2 to produce a Ni complex.

[0132] The manufactured Ni complex was continuously injected into the third reactor (CSTR).

[0133] 3) Third Reactor (CSTR): Preparation of polymer

[0134] A vacuum-dried 2L stainless steel pressure vessel was prepared, and 12.4g of 9,9-Dioctyl-2,7-dibromofluorene, 0.4g of Bromobenzene, and 987.2g of TOL were added and stirred to prepare a monomer solution. While maintaining the pressure of the pressure vessel constant above atmospheric pressure, the monomer solution was injected into the third reactor (CSTR) at an injection rate of 10.0 g / min using a mass flow meter and reacted with the Ni complex. The polymer was prepared by allowing an additional polymerization time (residence time) of 20 min in the third reactor. The polymerization reaction of the prepared polymer was terminated continuously at room temperature.

[0135] <Example 2>

[0136] 1) First Continuous Reactor (PFR): Ni(COD) 2 manufacturing

[0137] Two vacuum-dried 2L stainless steel pressure vessels were prepared. 2100g of Ni(acac), 532g of tetrahydrofuran, and 168g of 1,5-cyclooctadiene were added to the first pressure vessel to prepare the first reaction solution. 800g of Dibal (a 1M solution dissolved in toluene) solution was added to the second pressure vessel to prepare the second reaction solution. With the pressure in each pressure vessel maintained constant above atmospheric pressure, the first reaction solution and the second reaction solution were injected into the first continuous reactor (PFR) at an injection rate of 1.5 g / min and 1.5 g / min, respectively, using a mass flow meter. At this time, the temperature of the first continuous reactor (PFR) was maintained at -5℃ and the residence time was maintained at 30 minutes. At this time, the molar ratio of Ni(acac)2: 1,5-cyclooctadiine : Dival was 1 : 4 : 2.5.

[0138] The manufactured Ni(COD)2 was continuously fed into the second continuous reactor (PFR).

[0139] 2) Second Continuous Reactor (PFR): Preparation of Ni complex

[0140] A vacuum-dried 2L stainless steel pressure vessel was prepared, and 13g of 2,2'-Bipyridyl (BPD) and 387g of DMF were added and stirred to prepare a 3.25 wt% BPD solution. With the pressure of the pressure vessel maintained at a constant level above atmospheric pressure, the BPD solution was injected into a second continuous reactor (PFR) at an injection rate of 2.5 g / min using a mass flow meter and reacted with Ni(COD)2 to produce a Ni complex.

[0141] The manufactured Ni complex was continuously injected into the third reactor (CSTR).

[0142] 3) Third Reactor (CSTR): Preparation of polymer

[0143] A vacuum-dried 2L stainless steel pressure vessel was prepared, and 4.6g of 4,4'-Dibromotriphenylamine, 4.6g of 1,4-dibromo-2,5-dihexylbenzene, 0.4g of bromobenzene, and 990.4g of TOL were added and stirred to prepare a monomer solution. With the pressure of the pressure vessel maintained constant above atmospheric pressure, the monomer solution was injected into the third reactor (CSTR) at an injection rate of 10.0 g / min using a mass flow meter and reacted with the Ni complex. The polymer was prepared by allowing an additional polymerization time (residence time) of 20 min in the third reactor (CSTR). The polymerization reaction of the prepared polymer was terminated continuously at room temperature.

[0144] <Example 3>

[0145] 1) First Continuous Reactor (PFR): Ni(COD) 2 manufacturing

[0146] Two vacuum-dried 2L stainless steel pressure vessels were prepared. Ni(acac)2 (100g), 532g of tetrahydrofuran, and 168g of 1,5-cyclooctadiene were added to the first pressure vessel to prepare the first reaction solution. 800g of Dibal (a 1M solution dissolved in toluene) solution was added to the second pressure vessel to prepare the second reaction solution. With the pressure in each pressure vessel maintained constant above atmospheric pressure, the first reaction solution and the second reaction solution were injected into the first continuous reactor (PFR) at an injection rate of 1.5 g / min and 1.5 g / min, respectively, using a mass flow meter. At this time, the temperature of the first continuous reactor was maintained at -5℃ and the residence time was maintained at 30 minutes. At this time, the molar ratio of Ni(acac)2: 1,5-cyclooctadiine : Dival was 1 : 4 : 2.5.

[0147] The manufactured Ni(COD)2 was continuously fed into the second continuous reactor (PFR).

[0148] 2) Second Continuous Reactor (PFR): Preparation of Ni complex

[0149] A vacuum-dried 2L stainless steel pressure vessel was prepared, and 13g of 2,2'-Bipyridyl (BPD) and 387g of DMF were added and stirred to prepare a 3.25 wt% BPD solution. With the pressure of the pressure vessel maintained at a constant level above atmospheric pressure, the BPD solution was injected into a second continuous reactor (PFR) at an injection rate of 2.5 g / min using a mass flow meter, and the solution was reacted continuously with Ni(COD)2 to produce a Ni complex.

[0150] The manufactured Ni complex was continuously injected into the third reactor (semi-batch).

[0151] 3) Third reactor (semi-batch): Preparation of polymer

[0152] A vacuum-dried 2L stainless steel pressure vessel was prepared, and 12.4g of 9,9-Dioctyl-2,7-dibromofluorene, 0.4g of Bromobenzene, and 987.2g of TOL were added and stirred to prepare a monomer solution. While maintaining the pressure of the pressure vessel constant above atmospheric pressure, the monomer solution was injected into the third reactor (semi-batch) at an injection rate of 10.0 g / min using a mass flow meter and reacted with the Ni complex. An additional polymerization time of 20 min was given in the third reactor to prepare the polymer. The reaction of the prepared polymer was terminated at room temperature.

[0153] <Example 4>

[0154] 1) First Continuous Reactor (PFR): Ni(COD) 2 manufacturing

[0155] Two vacuum-dried 2L stainless steel pressure vessels were prepared. 2100g of Ni(acac), 532g of tetrahydrofuran, and 168g of 1,5-cyclooctadiene were added to the first pressure vessel to prepare the first reaction solution. 800g of Dibal (a 1M solution dissolved in toluene) solution was added to the second pressure vessel to prepare the second reaction solution. With the pressure in each pressure vessel maintained constant above atmospheric pressure, the first reaction solution and the second reaction solution were injected into the first continuous reactor (PFR) at an injection rate of 1.5 g / min and 1.5 g / min, respectively, using a mass flow meter. At this time, the temperature of the first continuous reactor (PFR) was maintained at -5℃ and the residence time was maintained at 30 minutes. At this time, the molar ratio of Ni(acac)2: 1,5-cyclooctadiine : Dival was 1 : 4 : 2.5.

[0156] The manufactured Ni(COD)2 was continuously fed into the second continuous reactor (PFR).

[0157] 2) Second Continuous Reactor (PFR): Preparation of Ni complex

[0158] A vacuum-dried 2L stainless steel pressure vessel was prepared, and 13g of 2,2'-Bipyridyl (BPD) and 387g of DMF were added and stirred to prepare a 3.25 wt% BPD solution. With the pressure of the pressure vessel maintained at a constant level above atmospheric pressure, the BPD solution was injected into a second continuous reactor (PFR) at an injection rate of 2.5 g / min using a mass flow meter and reacted with Ni(COD)2 to produce a Ni complex.

[0159] The manufactured Ni complex was continuously injected into the third reactor (semi-batch).

[0160] 3) Third reactor (semi-batch): Preparation of polymer

[0161] A vacuum-dried 2L stainless steel pressure vessel was prepared, and 4.6g of 4,4'-Dibromotriphenylamine, 4.6g of 1,4-dibromo-2,5-dihexylbenzene, 0.4g of bromobenzene, and 990.4g of TOL were added and stirred to prepare a monomer solution. While maintaining the pressure of the pressure vessel constant above atmospheric pressure, the monomer solution was injected into the third reactor (semi-batch) at an injection rate of 10.0 g / min using a mass flow meter and reacted with the Ni complex. The polymer was prepared by allowing an additional polymerization time of 20 min in the third reactor (semi-batch). The reaction of the prepared polymer was terminated at room temperature.

[0162] <Comparative Example 1>

[0163] Ni(COD)21.4g and toluene 35g were added to a 200ml Schlenk flask, and 0.56g of 1,5-cyclooctadiene was added to prepare a Ni(COD)2 solution. Since Ni(COD)2 is unstable in air, the above steps were performed in a globe box.

[0164] 0.82g of BPD was placed in a 25ml Schlenk flask and vacuum dried, and then 10g of anhydrous DMF was added to prepare a BPD solution.

[0165] 1.3g of 9,9-Dioctyl-2,7-dibromofluorene and 0.04g of Bromobenzene were placed in a 25ml Schlenk flask, vacuum dried, and then 8g of anhydrous toluene was added to prepare a monomer solution.

[0166] After immersing the Ni(COD)2 solution flask in a 60℃ olive bath, stirring was started at 300 rpm, and the entire BPD solution was drawn with a syringe and added to the Ni(COD)2 solution.

[0167] Next, the entire monomer solution was also drawn up using a syringe and added to the reaction flask.

[0168] All reactants were added, and after a polymerization time of 60 minutes, the reaction was terminated by removing the product to room temperature.

[0169] <Comparative Example 2>

[0170] Ni(COD)21.4g and toluene 35g were added to a 200ml Schlenk flask, and 0.56g of 1,5-cyclooctadiene was added to prepare a Ni(COD)2 solution. Since Ni(COD)2 is unstable in air, the above steps were performed in a globe box.

[0171] 0.82g of BPD was placed in a 25ml Schlenk flask and vacuum dried, and then 10g of anhydrous DMF was added to prepare a BPD solution.

[0172] 0.48g of 4,4'-Dibromotriphenylamine, 0.48g of 1,4-dibromo-2,5-dihexylbenzene, and 0.042g of bromobenzene were placed in a 25ml Schlenk flask, vacuum dried, and then 8g of anhydrous toluene was added to prepare a monomer solution.

[0173] After immersing the Ni(COD)2 solution flask in a 60℃ olive bath, stirring was started at 300 rpm, and the entire BPD solution was drawn with a syringe and added to the Ni(COD)2 solution.

[0174] Next, the entire monomer solution was also drawn up using a syringe and added to the reaction flask.

[0175] All reactants were added, and after a polymerization time of 60 minutes, the reaction was terminated by removing the product to room temperature.

[0176] <Comparative Example 3>

[0177] The procedure was carried out in the same manner as Example 1 above, except that a PFR was used instead of a CSTR as the third reactor.

[0178] <Comparative Example 4>

[0179] The procedure was carried out in the same manner as Example 2 above, except that a PFR was used instead of a CSTR as the third reactor.

[0180] In the case of Comparative Examples 3 and 4 above, as time passed, clogging occurred inside the tube, making it impossible to operate for more than 30 minutes. More specifically, in the case of Comparative Examples 3 and 4 above, an attempt was made to maintain the process pressure at 1 bar using a back pressure regulator (BPR), but the pressure rose in a sticky manner, and a clogging occurred at the reactor outlet, preventing the reaction product from being discharged.

[0181] <Experimental Example>

[0182] Polymers were prepared by setting up a new start-up three times each using the methods of the above examples and comparative examples, and the yield, Mn, and Mw of the prepared polymers were recorded for each process and are shown in Table 1 below.

[0183] [Table 1]

[0184]

[0185] The above yield refers to the yield of the polymer obtained after polymer purification, Mn and Mw are numerical values ​​obtained through the PS calibration GPC method of the obtained polymer (equipment used: Agilent 1200 series), and the above CV is the coefficient of variation, which means the value obtained by dividing the average value by the standard deviation of the polymer yield, Mn and Mw formed per process recovery.

[0186] When the polymer was manufactured using the continuous process of the example, the yield was excellent and the coefficient of variation for each evaluation item was low. Through this, it was confirmed that the reproducibility of the polymer's physical properties is excellent when the polymer is manufactured using the continuous process of the example.

[0187] On the other hand, when the polymer was manufactured using the batch process of the comparative example, the yield was low and the coefficient of variation for each evaluation item was high. Through this, it was confirmed that the reproducibility of the polymer's physical properties is low when the polymer is manufactured using the batch process of the comparative example.

[0188] As shown in the above results, the method for manufacturing a polymer according to one embodiment of the present application can secure high yield and reproducibility by using a continuous reaction process instead of a conventional batch method.

[0189] In particular, the method for manufacturing a polymer according to one embodiment of the present application applies a plug flow reactor (PFR) as the first continuous reactor and the second continuous reactor, respectively, and applies a continuous stirred tank reactor (CSTR) or a semi-batch reactor as the third reactor, thereby not only ensuring the activity and stability of the Ni complex catalyst produced by the continuous process but also improving the yield and quality stability of the polymer produced.

Claims

Claim 1 A method for manufacturing a polymer comprising: a step of manufacturing a nickel complex precursor in a first continuous reactor; a step of supplying the nickel complex precursor to a second continuous reactor; a step of supplying a ligand to the second continuous reactor and reacting the nickel complex precursor and the ligand to manufacture a nickel complex; a step of supplying the nickel complex to a third reactor; and a step of supplying a monomer to the third reactor and performing a polymerization reaction, wherein the first continuous reactor and the second continuous reactor are each a plug flow reactor (PFR), the third reactor is a continuous stirred tank reactor (CSTR) or a semi-batch reactor, and the first continuous reactor, the second continuous reactor, and the third reactor are connected in series with each other. Claim 2 A method for manufacturing a polymer according to claim 1, wherein the step of manufacturing the nickel complex precursor in a first continuous reactor comprises the step of supplying and reacting a nickel (II) source, a diene-based compound, and a reducing agent to the first continuous reactor. Claim 3 delete Claim 4 A method for manufacturing a polymer according to claim 1, wherein the supply of raw materials and the discharge of products of the first continuous reactor, the second continuous reactor, and the third reactor are performed simultaneously. Claim 5 A method for producing a polymer according to claim 1, wherein the feeding rate of the nickel complex precursor and the ligand is 0.5 g / min to 500 g / min, respectively. Claim 6 A method for producing a polymer according to claim 1, wherein the feeding rate of the nickel complex and the monomer is 0.5 g / min to 500 g / min, respectively. Claim 7 A method for manufacturing a polymer according to claim 1, wherein the polymerization reaction utilizes Yamamoto polymerization. Claim 8 A method for producing a polymer according to claim 1, wherein the coefficient of variation (CV) of at least one of the yield, number average molecular weight (Mn), and weight average molecular weight (Mw) of the produced polymer is 5.5% or less.

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