Method for producing zero-valent nickel compound and method for producing polymer

Abstract

The present invention relates to a method for producing a zero-valent nickel compound and a method for producing a polymer.

Description

[Technical field]

[0001] This application claims the benefit of the filing date of Korean Patent Applications Nos. 10-2020-0101053 and 10-2020-0101128, filed on August 12, 2020, respectively, in the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference.

[0002] The present invention relates to a method for producing a zero-valent nickel compound and a method for producing a polymer. [Background technology]

[0003] Nickel complexes are produced by reacting zero-valent nickel compounds with ligands, but the zero-valent nickel compounds are difficult to handle because they are sensitive to oxygen and moisture, and have the disadvantage of being expensive to produce. In addition, reducing agents such as DIBAL used in the production process are highly flammable, posing a high risk of accidents.

[0004] In addition, the batch method has problems in that during mass production, a large amount of by-products are produced, resulting in low purity and low yield. The yield and characteristics of the product vary from batch to batch, and the performance of the final product is not consistent, making it difficult to apply to commercial production.

[0005] A typical batch reactor has a problem that the operation of the reactor is difficult during commercial-scale production, leading to high investment and operating costs. Furthermore, operation using a batch reactor usually requires repeated operations such as heating, reactant injection, reaction, cooling, and product discharge. Therefore, the productivity per batch operation is low, and there is a problem that the volume of the reactor or the number of reactors must be increased in order to perform mass production.

[0006] Regarding the method for producing a polymer using the nickel complex, there are various known methods for producing conventional polymers, examples of which include Suzuki polymerization, as described in International Patent Application Publication No. WO00 / 53656, and Yamamoto reaction, as described in the literature [T. Yamamoto, "Electrically Conducting And Thermally Stable π-Conjugated Poly(arylene)s Prepared by Organometallic Processes", Progress in Polymer Science 1993,17,1153-1205]. Both of these polymerization techniques operate by "metal insertion", in which the metal atom of the metal complex catalyst is inserted between the leaving group and the aryl group of the monomer. In the case of polymerization using the Yamamoto reaction, a nickel complex catalyst is used, and in the case of polymerization using the Suzuki reaction, a palladium complex catalyst is used.

[0007] The properties of a polymer are determined by the properties, nature and composition of the monomers used in the production of the polymer. In addition, polymers are required to have process properties such as reproducibility, which allows a consistent product to be produced regardless of the number of reactions or the reaction scale. However, such reproducibility is practically difficult to realize in conventional batch reaction production processes.

[0008] This is because the properties of the polymer are affected by various reaction conditions such as the shape of the reactor, the monomer introduction rate, and the reaction temperature, and it is difficult to adjust such reaction conditions consistently for each reaction run. [Prior art documents] [Non-patent literature]

[0009] [Non-Patent Document 1] J Org Chem(1990),4229-4230 Summary of the Invention [Problem to be solved by the invention]

[0010] The present invention provides a method for producing a zero-valent nickel compound.

[0011] The present invention provides a method for producing a polymer using a nickel complex. [Means for solving the problem]

[0012] One embodiment of the present invention provides a method for producing a zero-valent nickel compound, comprising: supplying a nickel(II) source to a first continuous reactor; supplying a diene compound to the first continuous reactor; supplying a reducing agent to the first continuous reactor; and reacting the nickel(II) source, the diene compound, and the reducing agent in the first continuous reactor, wherein the supply rates of the nickel(II) source, the diene compound, and the reducing agent may be the same or different, and are each 0.5 g / min to 500 g / min.

[0013] One embodiment of the present invention provides a method for producing a polymer, comprising the steps of: continuously supplying a zero-valent nickel compound to a second continuous reactor; supplying a ligand to the second continuous reactor; reacting the zero-valent nickel compound and the ligand to produce a nickel complex; continuously supplying the nickel complex to a third continuous reactor; continuously supplying a monomer to the third continuous reactor; and conducting a polymerization reaction, wherein the supply rate of the nickel complex and the supply rate of the monomer may be the same or different and are each 0.5 g / min to 500 g / min. Effect of the Invention

[0014] According to an embodiment of the present invention, a method for producing a zero-valent nickel compound uses a continuous reaction process instead of a conventional batch process, thereby making it possible to produce a zero-valent nickel compound of consistent quality, and to reduce the variation in the zero-valent nickel compound produced even in mass production.

[0015] In addition, the method for producing a zero-valent nickel compound according to one embodiment of the present invention can quickly remove heat generated, thereby further improving stability.

[0016] The method for producing a polymer according to one embodiment of the present invention uses a continuous reaction process instead of the conventional batch method, thereby ensuring high yields and reproducibility. [Brief description of the drawings]

[0017] [Figure 1] FIG. 1 is an illustrative flow chart of a method for producing a zero-valent nickel compound of the present invention. [Diagram 2] FIG. 1 is an exemplary flow diagram of a method for producing a polymer according to one embodiment of the present invention. [Diagram 3] FIG. 1 is a process diagram illustrating a schematic diagram of a polymer production process according to a conventional method. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

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

[0019] As described above, conventional batch reactors have problems in that the reactor is difficult to operate on a commercial scale, leading to high investment and operating costs, and there is also a problem of variation in quality from batch to batch.

[0020] Thus, one embodiment of the present invention provides a method for producing a zero-valent nickel compound, comprising the steps of: supplying a nickel(II) source to a first continuous reactor; supplying a diene-based compound to the first continuous reactor; supplying a reducing agent to the first continuous reactor; and reacting the nickel(II) source, the diene-based compound, and the reducing agent in the first continuous reactor.

[0021] The method for producing a zero-valent nickel compound has the advantage of being suitable for large-scale continuous processing by minimizing the occurrence of quality variations in each process. Specifically, the items for evaluating the quality of the zero-valent nickel compound can be compared using a method commonly used in the field to which this technology belongs. For example, when a product such as a polymer is produced using the produced zero-valent nickel compound, a method of calculating a conversion rate and comparing the results for each process may be used.

[0022] In addition, when using a conventional batch reactor, it is difficult to form an inert environment, and there is a problem that the risk of accidents increases due to highly flammable reactants. However, the method for producing a zero-valent nickel compound according to one embodiment of the present invention has the advantage that the stability is improved even when a highly flammable reactant is used, since it is easy to create an inert environment inside the reactor by using a continuous reactor.

[0023] In this specification, the term "zero-valent nickel compound" refers to a precursor material used to produce a nickel complex, and may be in the form of a complex. Specifically, it refers to a nickel compound in which the oxidation number of nickel is controlled to 0, and may be bis(1,5-cyclooctadiene)nickel:Ni(COD2).

[0024] In this specification, the "zero-valent nickel compound" can also be expressed as a "nickel complex precursor".

[0025] In this specification, the term "nickel complex" refers to a compound in which nickel and a ligand are complexed. Specifically, it is represented by Ni(L)n, where n is an integer of 2 to 4, and L refers to a ligand. When n is 2 or more, the Ls in the parentheses may be the same or different.

[0026] The 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.

[0027] 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), where nbd means bicycle[2.2.1]hepta-2,5-diene, bpy means 2,2'-biphyridyl, and AN means ancrylonitrile. In addition to the above examples, it may refer to various types of nickel complexes exemplified in previous 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.].

[0028] In this specification, the term "continuous reactor" refers to a reactor in which the reaction proceeds while continuously feeding reactants used in the reaction, and the supply of the reactants and the discharge of the product may be performed simultaneously. The type of reactor is not particularly limited, and examples thereof include a semi-batch reactor, a plug flow reactor (hereinafter referred to as PFR), and a continuous stirred tank reactor (hereinafter referred to as CSTR).

[0029] In this specification, unless otherwise specified, the description of a "continuous reactor" can apply to any of the first continuous reactor, the second continuous reactor, and the third continuous reactor.

[0030] In the present specification, the "first continuous reactor" means a reactor for producing a zero-valent nickel compound, and the "second continuous reactor" means a reactor for producing a nickel complex. In this case, the second continuous reactor and the first continuous reactor may be connected to each other in series. The connecting means is not particularly limited, and they may be connected via a pipe used in a chemical process.

[0031] In the present specification, the term "third continuous reactor" refers to a reactor for producing a polymer using a nickel complex. In this case, the third continuous reactor may be connected to another continuous reactor in series. The connecting means is not particularly limited, and may be connected via a pipe used in a chemical process.

[0032] Fig. 1 is an exemplary process diagram of the method for producing a zero-valent nickel compound of the present invention, showing a process of supplying a nickel (II) source, a diene compound, and a reducing agent to a first continuous reactor. As shown in Fig. 1, the first continuous reactor may be a semi-batch reactor, a PFR, or a CSTR.

[0033] In one embodiment of the present invention, the first continuous reactor and the second continuous reactor may be connected to each other in series. In this case, it is advantageous to make the inside of the reactor an inert environment, and it is advantageous that the product can be produced from each reactor and simultaneously supplied to the other reactor. The connecting means is not particularly limited, and may be connected via a pipe used in a chemical process.

[0034] The method for producing a zero-valent nickel compound according to one embodiment of the present invention is carried out in the first continuous reactor. At this time, the produced zero-valent nickel compound is continuously supplied to another second continuous reactor connected in series like the first continuous reactor, thereby solving the problem of having to separately store or process the zero-valent nickel compound, which is difficult to handle. Since the zero-valent nickel compound is produced in the first continuous reactor and simultaneously supplied to the second continuous reactor, there is an advantage in that the cost and labor required to stabilize the zero-valent nickel compound are reduced.

[0035] In one embodiment of the present invention, the method for producing the zero-valent nickel compound is characterized in that it is carried out in a continuous process. In the past, zero-valent nickel compounds were produced in a batch reactor, but a reducing agent was added dropwise for at least 30 minutes and an additional aging time of at least 30 minutes was required. However, the continuous process does not require additional aging time, and a yield level equivalent to that of the batch process can be secured even in a short process time. In addition, in the case of a conventional batch reactor, the reaction must be carried out in an extremely low temperature environment of -78°C or less, but the continuous process has the advantage that heat removal is easy and a yield level equivalent to that of the batch process can be secured even in an environment higher than the extremely low temperature (ex. -20°C) without separate reaction heat control. Meanwhile, in the conventional batch reactor, moisture and oxygen flow in during production, which creates a risk of accidents, but the continuous process of the present invention has the advantage of minimizing the risk of accidents because it can be operated under inert conditions.

[0036] In one embodiment of the present invention, the nickel (II) source, diene compound and reducing agent are substances that serve as raw materials for producing the zero-valent nickel compound, and their types and properties are not particularly limited.

[0037] In one embodiment of the present invention, the nickel (II) source is a substance for supplying nickel atoms, and may be any substance commonly used in the field to which this technology pertains, although it is preferable to use nickel acetylacetonate {Ni(acac)2} from the viewpoints of stability and economy.

[0038] In one embodiment of the present invention, the diene compound may be any one or more selected from the group consisting of 1,4-cyclohexadiene, bicyclo[2.2.2]hepta-2,5-diene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-vinyl-2-norbornene, bicyclo[2.2.2]octa-2,5-diene, 4-vinylcyclohex-1-ene, bicyclo[2.2.1]hepta-2,5-diene, bicyclopentadiene, methyltetrahydroindene, 5-allylbicyclo[2.2.1]hepta-2-ene, and 1,5-cyclooctadiene, and 1,4-cyclohexadiene is more preferred.

[0039] In one embodiment of the present invention, the reducing agent may be an organic reducing agent or an inorganic reducing agent, such as DIBAL, NaBH4 or KBH4, Zn powder, magnesium or hydrogen, with DIBAL being preferred.

[0040] In one embodiment of the present invention, the method of supplying the nickel (II) source, the diene 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 continuous channels, and the nickel (II) source, the diene compound, and the reducing agent may be supplied to the continuous channels, respectively.

[0041] In one embodiment of the present invention, the continuous channel is configured to feed reactants into the reactor. The continuous channel may refer to an input (or injection) part for controlling the input amount of each raw material in the continuous reactor. In this case, the input amount of the raw material to be injected into each continuous channel may be controlled, and each input amount may be controlled according to the reaction environment to minimize side reactions.

[0042] In one embodiment of the present invention, the first continuous reactor may include one or more continuous channels, specifically, may include 1st to Nth continuous channels (N is a positive integer from 1 to 10).

[0043] In one embodiment of the present invention, the first continuous reactor comprises at least one continuous channel, and the nickel(II) source, diene-based compound and reducing agent may be fed to the same or different continuous channels.

[0044] In one embodiment of the present invention, the first continuous reactor may include one or more continuous channels, and the nickel (II) source, diene compound, and reducing agent may all be supplied to different continuous channels. For example, the first continuous reactor may include first to third continuous channels, and the nickel (II) source may be supplied to the first continuous channel, the diene compound may be supplied to the second continuous channel, and the reducing agent may be supplied to the third continuous channel.

[0045] In one embodiment of the present invention, the first continuous reactor may include one or more continuous channels, and two of the nickel (II) source, the diene-based compound, and the reducing agent may be supplied to the same continuous channel, and the other may be supplied to another continuous channel. For example, the first continuous reactor may include first and second continuous channels, and the nickel (II) source and the diene-based compound may be supplied to the first continuous channel, and the reducing agent may be supplied to the second continuous channel.

[0046] In one embodiment of the present invention, the first continuous reactor comprises one or more continuous channels, and the nickel(II) source, the diene-based compound and the reducing agent may all be fed into the same continuous channel.

[0047] In one embodiment of the present invention, the step of supplying a nickel (II) source to the first continuous reactor, the step of supplying a diene compound to the first continuous reactor, and the step of supplying a reducing agent to the first continuous reactor may each be repeated two or more times, and in this case, the continuous channels through which each substance is supplied may be the same or different. For example, the same diene compound may be supplied twice, and different diene compounds may be supplied in sequence two or more times.

[0048] In one embodiment of the present invention, the method may further include a step of mixing the nickel (II) source, the diene compound, and the reducing agent, which can increase the mixing ratio of each material to reduce the generation of unreacted materials, facilitate temperature control, and thereby improve the conversion rate.

[0049] In one embodiment of the present invention, the step of mixing the nickel (II) source, the diene compound and the reducing agent may be performed using a mixer.

[0050] As shown in FIG. 1, the nickel (II) source, diene compound and reducing agent may be mixed in a mixer before or after being fed to the first continuous reactor.

[0051] In one embodiment of the present invention, the mixer may include any one or more of a static mixer, a T-mixer, and a microreactor. The static mixer may be, but is not limited to, a plate mixer, a kenics mixer, or a Sulzer mixer.

[0052] In one embodiment of the present invention, the microreactor may include a plurality of microchannels that repeatedly branch and merge. By including the microchannels, the efficiency of mixing reactants can be further improved.

[0053] In one embodiment of the present invention, the microchannel may have various hydraulic structures, for example, a single flow path having a deep wavy shape, or two or more flow paths may be connected by repeatedly branching and merging to form multiple branching points.

[0054] In one embodiment of the present invention, the size of the microchannel may be from 1 μm to 10 mm.

[0055] In one embodiment of the present invention, the nickel (II) source, diene compound and reducing agent may be supplied in the form of a composition containing them.

[0056] In one embodiment of the present invention, the composition may contain each substance and an organic solvent, and the concentration of each substance is not particularly limited and may be adjusted to have the molar ratio described below.

[0057] In one embodiment of the present invention, the solvent may be a hydrocarbon solvent that does not react with anions, and may be any one or more selected from the following: chain hydrocarbon compounds such as pentane, hexane, and octane; their branched derivatives; cyclic hydrocarbon compounds such as cyclohexane and cycloheptane; aromatic hydrocarbon compounds such as benzene, toluene, and xylene; chain and cyclic ethers such as dimethyl ether, diethyl ether, anisole, and tetrahydrofuran; and amide solvents such as dimethylacetamide and dimethylformamide (hereinafter, DMF). Specifically, the organic solvent may be toluene, cyclohexane, hexane, tetrahydrofuran, or diethyl ether or dimethylformamide. More specifically, toluene may be the most preferred.

[0058] In one embodiment of the present invention, the supply rates of the nickel (II) source, diene compound and reducing agent may be the same or different, and may be 0.5 g / min to 500 g / min, preferably 0.5 g / min to 150 g / min, 0.5 g / min to 50 g / min, 0.5 g / min to 20 g / min, 0.5 g / min to 15 g / min, or 0.5 g / min to 1.5 g / min. Within the above numerical ranges, the supply of each raw material is smooth, thereby preventing side reactions from occurring and reducing the operation time.

[0059] In one embodiment of the present invention, the nickel (II) source, diene compound, and reducing agent may be supplied from pressure vessels containing the respective substances. The flow ratio and supply speed of the materials may be controlled through a separately connected supply device or pump. The raw materials can be fed to the reactor at a constant rate through the device, and the amount of the raw materials fed can also be measured. The supply device can be any device that can prevent contact with air and can uniformly adjust the flow rate, such as a mass flow controller (MFC), syringe pump, or peristaltic pump, and can be used without limitation.

[0060] In one embodiment of the present invention, the step of producing the zero-valent nickel compound in the first continuous reactor includes reacting the nickel (II) source, a diene compound and a reducing agent in the first continuous reactor. The reaction may produce a zero-valent nickel compound, and the produced zero-valent nickel compound is discharged from the first continuous reactor.

[0061] In one embodiment of the present invention, the reaction can be carried out under the conditions of a temperature of -78°C to 10°C and a pressure of 1 bar to 10 bar. When the temperature is adjusted to the above range, the exothermic reaction during the production can be controlled and the reaction rate can be easily controlled. The above temperature can be achieved by a pre-temperature coil and a constant-T bath installed in the first continuous reactor. The above pressure can be achieved by adjusting the flow rate and supply rate of the reactants flowing into the reactor.

[0062] In one embodiment of the present invention, the first continuous reactor may further include a pre-temperature coil at the front end thereof, thereby pre-adjusting the temperature of the reactants before they are introduced into the first continuous reactor.

[0063] As shown in FIG. 1, a pre-temperature coil can preliminarily adjust the temperature using a heat exchange coil. More specifically, the temperature of a mixer for mixing the nickel (II) source, the diene compound, and the reducing agent before supplying them can also be preliminarily adjusted, but is not limited thereto.

[0064] In one embodiment of the present invention, the first continuous reactor may include a constant-t bath, which allows the temperature to be controlled within a desired range during the reaction in the first continuous reactor.

[0065] In one embodiment of the present invention, the molar ratio of the diene compound to the nickel (II) source may be 1:2 to 1:10, or 1:4 to 1:6. When it is within the above range, the reaction between the nickel source and the diene compound can occur smoothly.

[0066] In one embodiment of the present invention, the molar ratio of the reducing agent to the nickel (II) source may be 1:2 to 1:5, 1:2.3 to 1:2.5, or 1:2.3 to 1:3. When it is within the above range, it is possible to prevent the phenomenon of color deterioration caused by the reducing agent and ensure a certain level or higher of yield.

[0067] In one embodiment of the present invention, the total process time of the method for producing a zero-valent nickel compound may be 0.01 seconds to 20 minutes or 1 second to 10 minutes. The total process time is a total time during which the materials reside in the reactor from the time when the reactants are introduced into the inlet of the reactor to the time when the resultant of the reaction of the reactants is discharged from the reactor.

[0068] In one embodiment of the present invention, the reaction in the step of preparing the zero-valent nickel compound may be carried out under an inert gas. The method of forming the inert environment includes a method of removing moisture and oxygen from the inside of the reactor before supplying the reactants to the reactor, and a method of supplying an inert gas to the inside of the reactor before supplying the reactants. Examples of the inert gas include argon (Ar) or nitrogen (N2).

[0069] In one embodiment of the present invention, the method of supplying the inert gas into the first continuous reactor may be a method of supplying a gas having an inert gas concentration of 99% or more, preferably 99.9% or more. The gas contains extremely small amounts of air and moisture excluding the inert gas, and as described above, by satisfying the inert gas concentration of 99% or more, preferably 99.9% or more in the gas, the inactivation of the zero-valent nickel compound, which is sensitive to oxygen and moisture, can be minimized, thereby ensuring high yield and reproducibility.

[0070] In one embodiment of the present invention, the method may further include continuously supplying the zero-valent nickel compound to a second continuous reactor continuously connected to the first continuous reactor. The type of the second continuous reactor is not particularly limited, and in this case, examples include a semi-batch reactor, a PFR, and a CSTR.

[0071] As described above, the method for producing a zero-valent nickel compound of the present invention has the effect of improving the yield when producing a zero-valent nickel compound from a nickel (II) supply source.

[0072] The present invention further provides a method for producing a polymer.

[0073] FIG. 2 is an exemplary process diagram of a method for producing a polymer according to an embodiment of the present invention, which is a schematic diagram showing a second continuous reactor to which a zero-valent nickel compound and a ligand are supplied, and a third continuous reactor to which a nickel complex produced in the second continuous reactor and a monomer are supplied.

[0074] In the method for producing a polymer of the present invention, the supply of raw materials and the discharge of products from each reactor may be performed simultaneously. Specifically, the step of continuously supplying the zero-valent nickel compound to the second continuous reactor, the step of supplying a ligand to the second continuous reactor, and the step of reacting the zero-valent nickel compound and the ligand to produce a nickel complex may be performed simultaneously. Furthermore, the step of continuously supplying the nickel complex to the third continuous reactor, the step of continuously supplying a monomer to the third continuous reactor, and the step of carrying out a polymerization reaction may be performed simultaneously. The term "simultaneously" means that the supply of raw materials and the discharge of products are performed simultaneously without a separate storage time.

[0075] In one embodiment of the present application, the third continuous reactor may be maintained at a temperature of 25° C. to 200° C. and a pressure of 1 bar to 20 bar.

[0076] In this case, the product can be produced in the continuous reactor and discharged at the same time, and the introduction of raw materials, reaction, and discharge of the product can be carried out continuously in a series of steps. By using such a continuous process, the volume of the reactor can be significantly reduced compared to conventional batch reactions, the reaction conditions can be easily controlled, and a constant reaction environment can be maintained. In addition, by introducing the reaction raw materials at a constant speed or ratio, a nickel complex with a constant composition and performance can be produced, and product variation can be minimized even when producing a large amount.

[0077] In one embodiment of the present invention, the zero-valent nickel compound may be a zero-valent nickel compound produced by the above-mentioned method for producing a zero-valent nickel compound. That is, the zero-valent nickel compound produced by the continuous method may be used.

[0078] In one embodiment of the present invention, the method may further include a step of mixing the zero-valent nickel compound and the ligand. In this case, the mixing ratio of the materials can be increased to reduce the generation of unreacted materials, and the heat removal effect can be improved, resulting in an improved conversion rate. After the zero-valent nickel compound and the ligand are mixed, they may be fed to one reactant inlet.

[0079] In one embodiment of the present invention, the step of mixing the zero-valent nickel compound and the ligand may be performed using a mixer. The description of the mixer used in the step of mixing the zero-valent nickel compound and the ligand may be applied in the same manner as the description of the mixer used in the step of mixing the nickel (II) source, the diene compound, and the reducing agent.

[0080] Figure 2 JPEG0007670805000001.jpg66 shows a schematic of the mixer.

[0081] In one embodiment of the present invention, the method of supplying the zero-valent nickel compound and the 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 zero-valent nickel compound and the ligand may be supplied to the reactant inlets, respectively. In this case, the supply power may be provided through a separately connected supply device or pump. The raw material can be fed to the reactor at a constant rate through the device, and the amount of the raw material fed can also be measured. The supply device may be a mass flow controller (MFC), a syringe pump, a peristaltic pump, or the like, without limitation, as long as it can prevent contact with air and adjust the flow rate uniformly.

[0082] In one embodiment of the present invention, the zero-valent nickel compound and the ligand may be supplied from a storage vessel containing each of the substances, and their flow ratio and supply rate may be adjusted via a supply device or pump connected to the rear end of the storage vessel.

[0083] In one embodiment of the present invention, the reactant inlet is configured to inject reactants into the reactor. The reactant inlet may refer to an inlet (or injection part) for controlling the amount of each raw material in the continuous reactor. In this case, the amount of raw material injected into each reactant inlet may be controlled, and each input amount may be controlled according to the reaction environment, thereby minimizing side reactions.

[0084] In one embodiment of the present invention, the second continuous reactor may include 1st to Nth reactant inlets (N is a positive integer of 1 to 10).

[0085] In one embodiment of the present invention, the second continuous reactor comprises one or more reactant inlets, and the zero-valent nickel compound and ligand may be supplied via the same or different reactant inlets.

[0086] In one embodiment of the present invention, the first continuous reactor includes one or more reactant inlets, and the zero-valent nickel compound and the ligand may be supplied through the same reactant inlet.

[0087] In one embodiment of the present invention, the zero-valent nickel compound and the ligand may be supplied in the form of a solution containing each of them.

[0088] In one embodiment of the present invention, the solvent may be a hydrocarbon solvent, for example, any one or more selected from chain hydrocarbon compounds such as pentane, hexane and octane; their branched derivatives; cyclic hydrocarbon compounds such as cyclohexane and cycloheptane; aromatic hydrocarbon compounds such as benzene, toluene and xylene; chain and cyclic ethers such as dimethyl ether, diethyl ether, anisole and tetrahydrofuran; and amide solvents such as dimethylacetamide and dimethylformamide (hereinafter, DMF).Specifically, the organic solvent may be cyclohexane, hexane, tetrahydrofuran, diethyl ether or dimethylformamide.

[0089] In one embodiment of the present invention, the zero-valent nickel compound and the ligand may be supplied in the form of a composition in which they are each dissolved in a solvent, and the composition may contain the zero-valent nickel compound and the ligand in an amount of 0.1% by weight to 35% by weight, respectively.

[0090] In one embodiment of the present invention, the supply rates of the zero-valent nickel compound and the ligand may be the same or different from each other, and may be 0.1 g / min to 500 g / min, preferably 0.2 g / min to 200 g / min, 0.2 g / min to 100 g / min, 0.2 g / min to 50 g / min, 0.2 g / min to 20 g / min, or 0.2 g / min to 2 g / min. The supply rates may be adjusted via a mass flow controller (MFC) or a pump. Within the above range, there is an effect of minimizing side reactions without a sudden change in the amount of material injected into each reactant inlet.

[0091] In one embodiment of the present invention, the molar ratio of the zero-valent nickel compound to the ligand may be 1:2, preferably 1:5, more preferably 1:10, but is not limited thereto, and the ligand may be added in excess. However, when it is within the above range, the reaction of the zero-valent nickel compound and the ligand can occur smoothly, and the zero-valent nickel compound and the ligand can react in the same equivalent amount. Specifically, when Ni(COD)2 is used as the zero-valent nickel compound and BPD is used as the ligand, a mixture of Ni(COD)2, Ni(BPD)2, Ni(COD)(BPD) and the like is produced. Among these, Ni(COD)(BPD) has the highest activity, so in order to produce it, it is preferable to adjust the molar ratio of the zero-valent nickel compound to the ligand to the above range.

[0092] In one embodiment of the present invention, the second continuous reactor may be maintained at a temperature of -78°C to 70°C and a pressure of 1 bar to 10 bar. When the temperature is adjusted to the above range, the exothermic reaction during the preparation of the nickel complex can be controlled, and the reaction rate can be easily controlled. The temperature can be controlled through a pre-temperature coil and a constant-T bath provided in the continuous reactor. The pressure can be controlled by adjusting the flow rate and supply rate of the reactants flowing into the reactor. Specifically, the pressure can be controlled using a back pressure regulator (BPR).

[0093] In one embodiment of the present invention, the second continuous reactor may include a pre-temperature coil, which allows the temperature of the reactants to be preliminarily adjusted before being introduced into the continuous reactor.

[0094] In one embodiment of the present invention, the continuous reactor may include a Constant-T bath, which allows the temperature to be controlled within the desired range during the reaction in the continuous reactor.

[0095] In one embodiment of the present invention, the total process time may be 0.01 seconds to 20 minutes or 1 second to 10 minutes. The total process time is the total time that the materials reside in the reactor from the time that the reactants are introduced into the inlet of the reactor to the time that the reaction product of the reactants is discharged from the reactor.

[0096] In one embodiment of the present invention, the step of preparing a nickel complex by reacting the zero-valent nickel compound with the ligand may be carried out in an inert environment. That is, the inside of the second continuous reactor may be an inert environment. In this case, the method of forming the inert environment may be a method of removing moisture and oxygen from the inside of the reactor before supplying reactants to the reactor, or a method of supplying an inert gas to the inside of the reactor before supplying reactants, as in the method used to carry out the reaction of the step of preparing a zero-valent nickel compound under an inert gas as described above. Examples of the inert gas include argon (Ar) or nitrogen (N2).

[0097] In one embodiment of the present invention, the method of supplying an inert gas into the second continuous reactor can use a gas having an inert gas concentration of 99% or more, preferably 99.9% or more. The gas contains a very small amount of air and moisture excluding the inert gas, and as described above, by satisfying the inert gas concentration of 99% or more, preferably 99.9% or more, in this case, it is possible to minimize the inactivation of the zero-valent nickel compound, which is sensitive to oxygen and moisture, and ensure high yield and reproducibility.

[0098] In one embodiment of the present invention, the method may further include a step of mixing the nickel complex and the monomer. In this case, the mixing ratio of the materials can be increased to reduce the generation of unreacted materials, and the heat removal effect can be improved, resulting in an improved conversion rate. After the nickel complex and the monomer are mixed, the mixture can be fed to one reactant inlet.

[0099] In one embodiment of the present invention, 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 started simultaneously with mixing the nickel complex and the monomer, the time of 1 minute to 300 minutes may mean a combined time during which the mixing and the polymerization reaction proceed. In order to adjust the time, a holding coil (RT coil) may be connected to each reactor.

[0100] Figure 2 JPEG0007670805000002.jpg910 is a schematic representation of the holding coils present in the reactor.

[0101] In one embodiment of the present invention, the supply rate of the nickel complex and the supply rate of the monomer may be the same or different, and may be 0.5 g / min to 500 g / min, preferably 0.5 g / min to 150 g / min, 0.5 g / min to 50 g / min, 0.5 g / min to 20 g / min, 0.5 g / min to 15 g / min, or 0.5 g / min to 1.5 g / min. The weight (g) of the supply rate may be the weight of the nickel complex or the monomer composition itself, or the total weight of the solution containing them.

[0102] The supply rate may be adjusted via a separately connected mass flow controller (MFC) within the above range, which has the effect of minimizing side reactions without abrupt changes in the amount of material injected into each reactant inlet.

[0103] In one embodiment of the present invention, the polymerization reaction may be carried out in an inert environment. Specifically, the inside of the reactor can be made into an inert environment, which has the effect of preventing side reactions or explosions. The details regarding the inert gas are as described above.

[0104] In one embodiment of the present invention, each continuous reactor may include a heat removal device, and the heat removal device may be pre-connected to each continuous reactor. The reaction occurring in each continuous reactor is an exothermic reaction, and the reaction may be carried out in a thermostatic bath in order to rapidly control the reaction heat generated at this time. Specifically, a pre-temperature coil may be installed at the front end of each reactor, and its length may be adjusted to achieve thermal equilibrium according to the flow rate.

[0105] In one embodiment of the present invention, each continuous reactor may further include a holding coil (Rt coil). The holding coil can adjust the residence time during which the reaction proceeds. Specifically, the residence time can be adjusted by adjusting the time during which the materials supplied to each continuous reactor react and reside in the holding coil. The residence time can be adjusted more precisely by adjusting the length of the holding coil and the supply rate of the supplied materials.

[0106] In one embodiment of the present invention, the monomers may include a base monomer; and an end-capping monomer.

[0107] In one embodiment of the present invention, the monomer may be supplied in the form of a solution containing the monomer, and the solvent may be the same as that described above.

[0108] In one embodiment of the present invention, the composition containing the monomer may contain the monomer in an amount of 0.1 to 35% by weight.

[0109] In one embodiment of the present invention, the "polymerization reaction" refers to a reaction in which monomers are polymerized with each other catalyzed by the nickel complex, and in this case, a reaction in which the end group of the monomer is replaced by the end-capping monomer may also occur.

[0110] In one embodiment of the present invention, the polymerization reaction may be a Yamamoto polymerization reaction, in which a nickel atom of a nickel complex catalyst is inserted between monomers, and the specific polymerization method is the same as that described in the literature [T. Yamamoto, "Electrically Conducting And Thermally Stable π-Conjugated Poly(arylene)s Prepared by Organometallic Processes", Progress in Polymer Science 1993,17,1153-1205].

[0111] In the present invention, a "monomer" is a raw material that is polymerized to form a polymer. The monomer is chemically bonded to other monomers to form a chain. As such, each monomer can be considered to have two or more "functional groups" (i.e., positions at which the monomer is chemically bonded to other monomers). By chemically bonding each end of a monomer with other monomers, a chain of monomers is formed to produce a polymer. A monomer can have more than two such positions, which can give rise to a branched polymer.

[0112] When the monomer is polymerized (regardless of the use of other types of monomers), a polymer containing repeat units is formed. The polymer preferably contains repeat units selected from arylene repeat units, such as those disclosed in Adv. Mater. 2000 12(23)1737-1750 and references cited therein. Exemplary first repeat units include 1,4-phenylene repeat units, such as those disclosed in J. Appl. Phys. 1996, 79, 934; fluorene repeat units, such as those disclosed in EP 0842208; indenofluorene repeat units, such as those disclosed in Macromolecules 2000, 33(6), 2016-2020; and spirofluorene repeat units, such as those disclosed in EP 0707020. Each of these repeat units is optionally substituted. Examples of substituents include solubilizing groups, such as C1-20 alkyl or alkoxy; electron withdrawing groups, such as fluoro, nitro or cyano; and substituents that increase the glass transition temperature (Tg) of the polymer.

[0113] The monomer species may include a leaving group, which may be a halogen group such as F, Cl, Br or I.

[0114] The monomer may be a monomer represented by the following formula 1:

[0115] [ka]

[0116] In the formula 1, R1 and R2 are independently selected from the group consisting of hydrogen, optionally substituted alkyl, in which one or more non-adjacent carbon atoms may be replaced with O, S, N, C=O, or -COO-, alkoxy, aryl, arylalkyl, heteroaryl, and heteroarylalkyl. More preferably, at least one of R1 and R2 is an optionally substituted C4-C20 alkyl or aryl group.

[0117] In the above Chemical Formula 1, X1 and X2 are each independently chlorine, bromine or iodine, and most preferably bromine.

[0118] In one embodiment of the invention, the end-capping monomer may be represented by the following structural formula:

[0119] In one embodiment of the invention, the end-capping monomer may be a monofunctional unit having one attachment point.

[0120] In one embodiment of the invention, the end-capping monomer may comprise a cross-linking group or a deuterated cross-linking group.

[0121] In one embodiment of the invention, the end-capping monomer may comprise a hydrocarbyl aryl group or a deuterated hydrocarbyl aryl group.

[0122] In one embodiment of the invention, the end-capping monomer is selected from the group consisting of phenyl, biphenyl, diphenylamino, substituted derivatives thereof, and deuterated analogs thereof. In some embodiments, the substituents may be C1-10 alkyl groups, bridging groups, or deuterated derivatives thereof.

[0123] In one embodiment of the invention, the end-capping monomer may have the following structure:

[0124] [ka]

[0125] [ka]

[0126] In one embodiment of the present invention, 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 by the method for producing a polymer may be 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 value of each physical property and then dividing the standard deviation value by the average value.

[0127] The yield, number average molecular weight and weight average molecular weight of the polymer may be calculated by measuring the corresponding physical property values ​​according to the following formulas, and the following physical property values ​​may be calculated by a method commonly used in the field of this technology. For example, the polymer may be calculated by gas chromatography (GC) or gel permeation chromatography (GPC).

[0128]

number

[0129] The present invention will be described in more detail below through examples and comparative examples, which are intended to aid in understanding the present invention and are not intended to limit the scope of the present invention.

[0130] (Production Example 1) A first continuous reactor was constructed containing first and second continuous channels and two vacuum dried 2 L stainless steel pressure vessels.

[0131] A first solution (first reaction solution) prepared by mixing 100 g of nickel acetylacetonate {Ni(acac)2}, which is the nickel (II) supply source, 168 g of a diene compound (1,5-cyclooctadiene), and 532 g of an organic solvent (tetrahydrofuran) was placed in the first pressure vessel.

[0132] A second solution (second reaction solution) prepared by dissolving a DIBAL reducing agent in toluene at a concentration of 1 M was introduced into a second pressure vessel.

[0133] While the pressures of the first pressure vessel and the second pressure vessel were each maintained at 3 bar, the first reaction solution was injected into the first continuous channel at an injection rate of 1.0 g / min, and the second reaction solution was injected into the second continuous channel at an injection rate of 1.0 g / min, respectively, into the continuous reactors.

[0134] At this time, the molar ratio of nickel acetylacetonate {Ni(acac)2}:1,5-cyclooctadiene:DIBAL was 1:4:2.05.

[0135] During this time, the temperature of the reactor was maintained at -5°C, the internal pressure was maintained at 2 bar using a back pressure regulator, and the total residence time was adjusted to 10 minutes.

[0136] After the reaction was completed, the zero-valent nickel compound {Ni(COD)2} was obtained in a yield of 75%.

[0137] (Production Example 2) The experiment was carried out in the same manner as in Preparation Example 1, except that the first reaction solution was injected into the first continuous channel at a rate of 5.0 g / min, and the second reaction solution was injected into the second continuous channel at a rate of 5.0 g / min. After the reaction was completed, a zero-valent nickel compound {Ni(COD)2} was obtained in a yield of 72%.

[0138] (Production Example 3) The experiment was conducted in the same manner as in Preparation Example 1, except that the first reaction solution was injected into the first continuous channel at a rate of 10.0 g / min, and the second reaction solution was injected into the second continuous channel at a rate of 10.0 g / min. After the reaction was completed, a zero-valent nickel compound {Ni(COD)2} was obtained in a yield of 73%.

[0139] (Production Example 4) The first reaction solution was injected into the first continuous channel at a rate of 1.0 g / min, and the second reaction solution was injected into the second continuous channel at a rate of 1.6 g / min. The experiment was carried out in the same manner as in Preparation Example 1, except that the molar ratio of nickel acetylacetonate {Ni(acac)2}:1,5-cyclooctadiene:DIBAL was changed to 1:4:2.6. After the reaction was completed, a zero-valent nickel compound {Ni(COD)2} was obtained in a yield of 68%.

[0140] (Production Example 5) The first reaction solution was injected into the first continuous channel at a rate of 1.0 g / min, and the second reaction solution was injected into the second continuous channel at a rate of 2.3 g / min. The experiment was carried out in the same manner as in Preparation Example 1, except that the molar ratio of nickel acetylacetonate {Ni(acac)2}:1,5-cyclooctadiene:DIBAL was changed to 1:4:3. After the reaction was completed, the zero-valent nickel compound {Ni(COD)2} was obtained in a yield of 65%.

[0141] (Production Example 6) The experiment was conducted in the same manner as in Preparation Example 1, except that the second solution was changed to one in which DIBAL reducing agent was dissolved in hexane at a concentration of 1M. After the reaction was completed, a zero-valent nickel compound {Ni(COD)2} was obtained in a yield of 70%.

[0142] (Production Example 7) A Schlenk flask was charged with 4.67 g of nickel acetylacetonate {Ni(acac)2} as a nickel(II) source, 7.93 g of a diene compound (1,5-cyclooctadiene), and 25 mL of organic solvent (tetrahydrofuran) under nitrogen and cooled to -78 °C for thermal control.

[0143] A solution of 0.0454 mmol of DIBAH reducing agent dissolved in tetrahydrofuran (THF) at a molar concentration of 1.0 M was added and stirred for 1 hour. The reaction was then carried out while raising the temperature to 0°C for 1 hour, and the final zero-valent nickel compound {Ni(COD)2} was obtained with a yield of 72% by stirring at 0°C for another 1 hour.

[0144] Example 1 A second continuous reactor continuously connected to the first continuous reactor of Preparation Example 1 and a third continuous reactor continuously connected to the second continuous reactor were prepared. The second continuous reactor was connected to a pressure vessel 1 prepared in advance, and the third continuous reactor was connected to a pressure vessel 2 prepared in advance.

[0145] The ligand 2,2'-bipyridyl was charged into the pressure vessel 1 and dissolved in the solvent DMF at 5.2 wt % to prepare a ligand composition.

[0146] A monomer composition in which 6.93 wt % of 2,7-dibromo-9,9-dioctylfluorene and 0.22 wt % of bromobenzene were dissolved in a toluene solvent was prepared in the pressure vessel 2 .

[0147] Thereafter, the zero-valent nickel compound produced in the first continuous reactor of Production Example 1 was supplied to the second continuous reactor, and the ligand composition was supplied from the pressure vessel 1 to the second continuous reactor (PFR) to produce a nickel complex. The produced nickel complex was supplied to the third continuous reactor.

[0148] Then, after holding for 1 minute in the first holding coil (Rt coil), the monomer composition was flowed from the pressure vessel 2 to induce a coupling reaction to occur in the third continuous reactor (PFR).

[0149] All process lines were maintained at 60 degrees Celsius using a thermostatic bath, and nitrogen was injected into each pressure vessel to adjust the pressure to 3 bar, and then the flow rates were adjusted to 1.06 g / min, 0.4 g / min, and 0.5 g / min by connecting them to a mass flow meter.

[0150] After the coupling reaction was completed, it was aged for 60 minutes in the second holding coil (Rt coil), and the final product was discharged out of the reactor.

[0151] Then, the solution containing the final product was cooled to room temperature and stirred and dropped into the quenching solution. The obtained polymer sample was stirred for 2 hours to completely quench, and then filtered to obtain only the solid component, which was analyzed by GPC.

[0152] That is, in Example 1, a polymer was produced according to the following procedure.

[0153] [ka]

[0154] Example 2 The monomer composition was prepared in the pressure vessel 2 by dissolving 6.93 wt% of 2,7-dibromo-9,9-dioctylfluorene, 2.56 wt% of 1,3,5-tris(4-bromophenyl)benzene, and 1.17 wt% of bromobenzene in a toluene solvent, and the monomer composition was fed from the pressure vessel 2 to induce a coupling reaction in the third continuous reactor (PFR). The process lines were all maintained at 60°C using a thermostatic bath, and nitrogen was injected into each pressure vessel to adjust the pressure to 3 bar, and then the flow rates were adjusted to 1.86 g / min, 0.71 g / min, and 0.5 g / min by connecting them to a mass flow meter, respectively. The same method as in Example 1 was used.

[0155] That is, in Example 2, a polymer was produced according to the following procedure.

[0156] [ka]

[0157] Comparative Example 1 A polymer was produced in the same manner as in Example 1, except that the polymer was produced in a batch manner instead of a continuous manner.

[0158] Specifically, the ligand 2,2'-bipyridyl was charged into a first pressure vessel and dissolved in a solvent DMF at 5.2 wt % to prepare a ligand composition.

[0159] A monomer composition in which 6.93 wt % of 2,7-dibromo-9,9-dioctylfluorene and 0.22 wt % of bromobenzene were dissolved in a toluene solvent was prepared in a second pressure vessel.

[0160] In addition, a 100 mL Schlenk flask was inflated with nitrogen and vacuum alternately, sealed with a rubber septum, removed from the flask, and immersed in a thermostatic bath at 60 degrees Celsius.

[0161] Then, 21 ml of the zero-valent nickel compound produced in the first continuous reactor of Production Example 1 was extracted using a gas-tight syringe and injected into the Schlenk flask.

[0162] Similarly, 7.4 ml of the ligand composition was extracted using a gas-tight syringe and injected into the flask and held for 1 minute.

[0163] Finally, 9.95 ml of the monomer composition was extracted in the same manner and injected into the flask, and allowed to react for 60 minutes.

[0164] Then, the solution containing the final product was cooled to room temperature and stirred and dropped into the quenching solution. The obtained polymer sample was stirred for 2 hours to completely quench, and then filtered to obtain only the solid component, which was analyzed by GPC.

[0165] Comparative Example 2 The polymer was produced in the same manner as in Example 2, except that the polymer was produced in a batch mode instead of a continuous mode.

[0166] More specifically, the same procedure as in Comparative Example 1 was carried out, except that a monomer composition in which 6.93 wt% of 2,7-dibromo-9,9-dioctylfluorene, 2.56 wt% of 1,3,5-tris(4-bromophenyl)benzene, and 1.17 wt% of bromobenzene were dissolved in a toluene solvent was prepared in a second pressure vessel.

[0167] FIG. 3 is a schematic flow chart showing the process for producing the polymers of Comparative Examples 1 and 2, which correspond to the conventional process, in which a zero-valent nickel compound, a ligand and a monomer are sequentially added to produce the polymers.

[0168] (Experimental Example) The yields and Mn / Mw ratios of the polymers prepared in the above examples and comparative examples were measured and are shown in Tables 1 and 2 below.

[0169] [Table 1]

[0170] [Table 2]

[0171] The yield means the yield of the polymer obtained after purification of the polymer, Mn and Mw are values ​​obtained by PS calibration GPC method of the obtained polymer (equipment used: Agilent 1200 series), and the CV means the value obtained by dividing the average value by the standard deviation of the yield, Mn and Mw of the polymer formed per each process by the coefficient of variation.

[0172] When the polymer was produced using the continuous process of the example, the yield was excellent and the coefficient of variation of each evaluation item was low. This confirmed that when the polymer was produced using the continuous process of the example, the reproducibility of the physical properties of the polymer was excellent.

[0173] On the other hand, when the polymer was produced by the batch process of the comparative example, the yield was low and the coefficient of variation of each evaluation item was high. This confirmed that when the polymer was produced by the batch process of the comparative example, the reproducibility of the physical properties of the polymer was low.

[0174] From the above results, it was confirmed that when the continuous process of the present invention is applied instead of the conventional batch method, the polymer yield is increased and the reproducibility of physical properties is significantly improved.

[0175] Furthermore, since the method for producing a zero-valent nickel compound of the present invention significantly improved the reproducibility of the physical properties of the polymer produced using the zero-valent nickel compound, it was confirmed that when a zero-valent nickel compound is produced by the method for producing a zero-valent nickel compound of the present invention, a zero-valent nickel compound of constant quality can be produced while having a high yield.

[0176] It was also confirmed that the method for producing a zero-valent nickel compound according to one embodiment of the present invention requires a shorter reaction time than the batch method, and has further improved stability.

Claims

1. providing a source of nickel(II) to a first continuous reactor; feeding a diene compound to the first continuous reactor; providing a reducing agent to said first continuous reactor; reacting the nickel (II) source, the diene compound, and the reducing agent in the first continuous reactor to produce a zero-valent nickel compound; continuously supplying the zero-valent nickel compound to a second continuous reactor continuously connected to the first continuous reactor; providing a ligand to the second continuous reactor; reacting the zero-valent nickel compound and the ligand to produce a nickel complex; continuously feeding said nickel complex to a third continuous reactor; continuously feeding monomer to a third continuous reactor; and Proceeding a polymerization reaction, The supply rates of the nickel (II) source, the diene compound, and the reducing agent are the same or different, and are each 0.5 g / min to 500 g / min; A method for producing a polymer, wherein the supply rate of the nickel complex and the supply rate of the monomer are the same or different and each is 0.5 g / min to 500 g / min.

2. The first continuous reactor comprises one or more continuous channels; The method for producing a polymer according to claim 1 , wherein the nickel (II) source, the diene compound and the reducing agent are each fed into the continuous channel.

3. The method for producing a polymer according to claim 1 or 2, wherein the reaction in the first continuous reactor is carried out at a temperature of -78°C to 10°C and a pressure of 0.1 MPa to 1 MPa (1 bar to 10 bar).

4. The nickel (II) source is nickel acetylacetonate (Ni(acac) 2 The method for producing a polymer according to any one of claims 1 to 3, wherein the polymer comprises a cyclic alkyl group.

5. The diene compound is at least one selected from the group consisting of 1,4-cyclohexadiene, bicyclo[2.2.2]hepta-2,5-diene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-vinyl-2-norbornene, bicyclo[2.2.2]octa-2,5-diene, 4-vinylcyclohexa-1-ene, bicyclo[2.2.1]hepta-2,5-diene, bicyclopentadiene, methyltetrahydroindene, 5-allylbicyclo[2.2.1]hepta-2-ene, and 1,5-cyclooctadiene. The method for producing a polymer according to any one of claims 1 to 4.

6. The method for producing a polymer according to any one of claims 1 to 5, wherein the total process time up to the step of producing the zero-valent nickel compound is 0.01 seconds to 20 minutes.

7. The method for producing a polymer according to any one of claims 1 to 6, wherein the reaction in the first continuous reactor is carried out under an inert gas.

8. The method for producing a polymer according to any one of claims 1 to 7, wherein the second continuous reactor and the third continuous reactor are connected in series to each other.

9. The method for producing a polymer according to any one of claims 1 to 8, wherein the second continuous reactor is maintained at a temperature of -78°C to 70°C and a pressure of 0.1 MPa to 1 MPa (1 bar to 10 bar).

10. The method for producing a polymer according to any one of claims 1 to 9, wherein the polymerization reaction utilizes Yamamoto polymerization.

11. The method for producing a polymer according to any one of claims 1 to 10, wherein the step of reacting the zero-valent nickel compound and the ligand to produce a nickel complex is carried out in an inert environment.

12. The method for producing a polymer according to any one of claims 1 to 11, wherein the third continuous reactor is maintained at a temperature of 25°C to 200°C and a pressure of 0.1 MPa to 2 MPa (1 bar to 20 bar).

13. The method for producing a polymer according to any one of claims 1 to 12, wherein the polymerization reaction is carried out in an inert environment.

14. The method for producing a polymer according to any one of claims 1 to 13, wherein the coefficient of variation (CV) of any one or more of the yield, number average molecular weight (Mn) and weight average molecular weight (Mw) of the produced polymer is 5% or less.

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