Method for producing zerovalent nickel compound and method for producing polymer

Abstract

The present disclosure relates to methods of making zerovalent nickel compounds and methods of making polymers.

Description

Technical Field

[0001] This application claims priority to and the benefit of Korean Patent Application Nos. 10-2020-0101053 and 10-2020-0101128, filed on August 12, 2020, in the Korean Intellectual Property Office, the disclosures of which are incorporated herein by reference in their entirety.

[0002] The present disclosure relates to methods of making zerovalent nickel compounds and methods of making polymers. Background Art

[0003] Nickel complexes are produced by reacting zero-valent nickel compounds with ligands. This method has the disadvantages of being difficult to handle due to its sensitivity to oxygen and moisture, and of being expensive to produce. Furthermore, the reducing agents used in the manufacturing process, such as DIBAL, are highly flammable and carry a high risk of accidents.

[0004] Furthermore, batch processes generate many by-products during large-scale production, leading to problems of reduced purity and yield, and are difficult to use for commercial production because product yield and properties vary from batch to batch and the performance of the final product is not constant.

[0005] General batch reactors are difficult to operate in industrial-scale production and have the problem of increasing investment costs and running costs. In addition, the operation using a batch reactor usually requires repeating a series of operations such as heating, reactant injection, reaction, cooling and product release. Therefore, the productivity of each batch operation is low, which leads to the problem of increasing the reactor volume or the number of reactors for mass production.

[0006] In addition, regarding methods for producing polymers using nickel complexes, there are many known methods for producing polymers in the art, and examples thereof may include, for example, Suzuki polymerization described in International Patent Application Publication No. WO 00 / 53656, and, for example, the Yamamoto reaction 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 methods operate by "metal insertion," in which the metal atom of a metal complex catalyst is inserted between a leaving group and an aromatic group of a monomer. A nickel complex catalyst is used in polymerization using the Yamamoto reaction, and a palladium complex catalyst is used in polymerization using the Suzuki reaction.

[0007] The properties of polymers are determined by the characteristics, properties, and composition of the monomers used to make them. Furthermore, polymer production requires process characteristics such as reproducible production of consistent products regardless of the number of reactions or the scale. However, this reproducibility is practically difficult to achieve using existing batch reaction manufacturing processes.

[0008] This is because the properties of the polymer are affected by various reaction conditions, such as reactor shape, monomer feed rate, and reaction temperature, and it is difficult to uniformly control these reaction conditions for each reaction run.

[0009] Non-patent documents

[0010] J.Org.Chem.(1990),4229-4230 Summary of the Invention

[0011]

Technical Issues

[0012] The present disclosure aims to provide a method for producing a zero-valent nickel compound.

[0013] The present disclosure is directed to a method for producing a polymer using a nickel complex.

[0014]

Technical solution

[0015] One embodiment of the present disclosure provides a method for producing a zerovalent nickel compound, the method comprising 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, wherein supply rates of the nickel (II) source, the diene-based compound, and the reducing agent are the same as or different from each other and are each in a range of 0.5 g / min to 500 g / min.

[0016] One embodiment of the present disclosure provides a method for producing a polymer, the method comprising continuously supplying a zerovalent nickel compound to a second continuous reactor; supplying a ligand to the second continuous reactor; preparing a nickel complex by reacting the zerovalent nickel compound with the ligand; continuously supplying the nickel complex to a third continuous reactor; continuously supplying a monomer to the third continuous reactor; and performing a polymerization reaction, wherein a supply rate of the nickel complex and a supply rate of the monomer are the same as or different from each other and are each in a range of 0.5 g / min to 500 g / min.

[0017] Beneficial effects

[0018] By using a continuous reaction process instead of the existing batch method, the method for producing a zero-valent nickel compound according to one embodiment of the present disclosure can produce a zero-valent nickel compound with constant quality, and the deviation of the produced zero-valent nickel compound can be adjusted to be small even in mass production.

[0019] Furthermore, the method of manufacturing a zerovalent nickel compound according to one embodiment of the present disclosure has greater stability by rapidly controlling heat generation.

[0020] A method for producing a polymer according to one embodiment of the present disclosure can ensure high yield and reproducibility by using a continuous reaction process instead of an existing batch method. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 is a process diagram illustrating the method of producing a zerovalent nickel compound according to the present disclosure.

[0022] Figure 2 is a process diagram illustrating a method of manufacturing a polymer according to one embodiment of the present disclosure.

[0023] Figure 3 This is a process diagram schematically illustrating a process for producing a polymer corresponding to a conventional method. DETAILED DESCRIPTION

[0024] Hereinafter, this specification will be described in more detail.

[0025] As mentioned above, existing batch reactors have the problem that it is difficult to operate the reactors on a commercial scale, and the investment and operation costs increase. In addition, there is the problem of batch quality variation.

[0026] In view of this, one embodiment of the present disclosure provides a method for producing a zerovalent nickel compound, the method comprising 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.

[0027] The method for producing a zero-valent nickel compound has the advantage of being suitable for large-scale continuous production by minimizing quality deviations between processes. Specifically, methods commonly used in the art can be used to compare parameters used to evaluate the quality of zero-valent nickel compounds. For example, when using the produced zero-valent nickel compound to produce polymers, a method for calculating conversion rates and comparing the performance of each process can be used.

[0028] In addition, when using existing batch reactors, it is difficult to establish an inert environment, which leads to the problem of increased risk of accidents caused by highly flammable reactants. However, by using a continuous reactor in the method for producing a zero-valent nickel compound according to one embodiment of the present disclosure, the interior of the reactor is easily placed under an inert atmosphere, which has the advantage of improving stability even when using highly flammable reactants.

[0029] In this specification, a "zero-valent nickel compound" refers to a precursor material for producing a nickel complex, and may be in the form of a complex. Specifically, it refers to a nickel compound having the nickel oxidation number adjusted to 0, and specifically may be bis(1,5-cyclooctadiene)nickel (Ni(COD)2).

[0030] In this specification, the “zerovalent nickel compound” may also be expressed as a “nickel complex precursor”.

[0031] In this specification, "nickel complex" refers to a compound composed of nickel and a ligand. Specifically, it is represented by Ni(L)n, where n is an integer from 2 to 4 and L represents a ligand. When n is 2 or greater, the L's within the brackets may be the same or different.

[0032] 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] 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 represents bicyclo[2.2.1]hepta-2,5-diene, bpy represents 2,2'-bipyridine, and AN represents acrylonitrile. In addition to the above examples, various nickel complexes described in existing literature [J. Org. Chem. (1990), 4229-4230; Tetrahedron letters 39, 3375 to 3378 (1975); Organometallics 2017, 36, 3508-3519; Chem. Soc. Rev., 1985, 14, 93-120, etc.] can also be included.

[0034] In this specification, a "continuous reactor" is a reactor in which a reaction is carried out while continuously introducing a reactant used in the reaction, and the supply of the reactant and the release of the product can be carried out simultaneously. The type of reactor is not particularly limited, and examples thereof may 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).

[0035] In this specification, unless otherwise specified, the description about the "continuous reactor" may apply to all the first continuous reactors, the second continuous reactors or the third continuous reactors.

[0036] In this specification, the "first continuous reactor" refers to a reactor for producing a zerovalent nickel compound, and the "second continuous reactor" refers to a reactor for producing a nickel complex. The second continuous reactor and the first continuous reactor can be continuously connected to each other. The connection method is not particularly limited, and pipes used in chemical processes can be used.

[0037] In this specification, the "third continuous reactor" refers to a reactor for producing a polymer using a nickel complex. The third continuous reactor can be continuously connected to another continuous reactor. The connection method is not particularly limited, and a tube used in a chemical process can be used.

[0038] Figure 1 is a process diagram illustrating a method for producing the zerovalent nickel compound of the present disclosure, and Figure 1 A process for supplying a nickel (II) source, a diene-based compound, and a reducing agent to a first continuous reactor is described. Figure 1 As shown, a semi-batch reactor type, a PFR type or a CSTR type can be selected as the first continuous reactor.

[0039] In one embodiment of the present disclosure, a first continuous reactor and a second continuous reactor can be connected in series. This facilitates maintaining an inert environment within the reactors and has the advantage of producing a product in each reactor while simultaneously supplying the product to the other reactor. The connection method is not particularly limited, and pipes used in chemical processes can be used.

[0040] According to one embodiment of the present disclosure, a method for producing a zero-valent nickel compound is performed in a first continuous reactor. By continuously supplying the produced zero-valent nickel compound to a second continuous reactor connected in series with the first continuous reactor, the problem of storing or handling the difficult-to-handle zero-valent nickel compound separately can be resolved. Since the zero-valent nickel compound is produced in the first continuous reactor and simultaneously supplied to the second continuous reactor, the cost and effort required to stabilize the zero-valent nickel compound are reduced.

[0041] In one embodiment of the present disclosure, the method for producing a zero-valent nickel compound is carried out in a continuous process. In the prior art, the zero-valent nickel compound is produced in a batch reactor, and the reducing agent is added dropwise for at least 30 minutes, and an additional 30 minutes or longer aging time is required. However, in the continuous process, no additional aging time is required, and the same level of yield can be ensured even with a short process time compared to the above-mentioned batch process. In addition, in the existing batch reactor, the reaction needs to be carried out in an extremely low temperature environment below -78°C. However, in the continuous process, heat is easily controlled, and even in an environment above an extremely low temperature (e.g., -20°C), the same level of yield can be ensured without the need for separate reaction heat control. At the same time, the existing batch reactor has the risk of accidents due to the introduction of moisture and oxygen during production. However, the continuous process of the present disclosure has the advantage of minimizing the risk of accidents because the operation is carried out under inert conditions.

[0042] In one embodiment of the present disclosure, the nickel (II) source, the diene-based compound, and the reducing agent are materials used as raw materials for producing the zerovalent nickel compound, and their types and properties are not particularly limited.

[0043] In one embodiment of the present disclosure, the nickel (II) source is a material for providing nickel atoms, and materials commonly used in the art can be used. However, from the perspective of stability and economic feasibility, it is preferably nickel acetylacetonate {Ni(acac)2}.

[0044] In one embodiment of the present disclosure, the diene-based compound may be any one or more selected from the group consisting of 1,4-cyclohexadiene, bicyclo[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, dicyclopentadiene, methyltetrahydroindene, 5-allylbicyclo[2.2.1]hept-2-ene and 1,5-cyclooctadiene, and more preferably 1,4-cyclohexadiene.

[0045] In one embodiment of the present disclosure, the reducing agent may be an organic reducing agent or an inorganic reducing agent. Examples thereof may include DIBAL, NaBH4 or KBH4, Zn powder, magnesium or hydrogen, and preferably DIBAL.

[0046] In one embodiment of the present disclosure, 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, but for example, the first continuous reactor includes one or more continuous channels, and the nickel (II) source, the diene-based compound, and the reducing agent can each be supplied to the continuous channel.

[0047] In one embodiment of the present disclosure, continuous channel is a structure for introducing reaction materials into a reactor. Continuous channel may refer to an input unit (or injection unit) for adjusting the input amount of each raw material in a continuous reactor. Here, the input amount of the raw material injected into each continuous channel may be adjusted, and, by adjusting each input amount according to the reaction environment, side reactions may be minimized.

[0048] In one embodiment of the present disclosure, the first continuous reactor may include one or more continuous channels, and specifically, may include 1 to N (N is a positive integer from 1 to 10) continuous channels.

[0049] In one embodiment of the present disclosure, the first continuous reactor includes one or more continuous channels, and the nickel (II) source, the diene-based compound, and the reducing agent may be supplied to the same continuous channel or different continuous channels.

[0050] In one embodiment of the present disclosure, the first continuous reactor includes one or more continuous channels, and the nickel (II) source, the diene-based compound, and the reducing agent can all be supplied to different continuous channels. For example, the first continuous reactor includes first to third continuous channels, and the nickel (II) source can be supplied to the first continuous channel, the diene-based compound can be supplied to the second continuous channel, and the reducing agent can be supplied to the third continuous channel.

[0051] In one embodiment of the present disclosure, the first continuous reactor includes one or more continuous channels, and two types of nickel (II) sources, diene-based compounds and reducing agents can be supplied to the same continuous channel, and another can be supplied to another continuous channel. For example, the first continuous reactor includes a first and a second continuous channel, and the nickel (II) source and the diene-based compound can be supplied to the first continuous channel, and the reducing agent can be supplied to the second continuous channel.

[0052] In one embodiment of the present disclosure, the first continuous reactor includes one or more continuous channels, and the nickel (II) source, the diene-based compound, and the reducing agent may all be supplied to the same continuous channel.

[0053] In one embodiment of the present disclosure, supplying a nickel (II) source to a first continuous reactor, supplying a diene-based compound to the first continuous reactor, and supplying a reducing agent to the first continuous reactor can each be repeated two or more times, and the continuous channels for supplying each material can be the same or different. For example, the same diene-based compound can be supplied twice, or different diene-based compounds can be supplied continuously two or more times.

[0054] In one embodiment of the present disclosure, the step of mixing a nickel (II) source, a diene-based compound, and a reducing agent is further included. By this step, the generation of unreacted materials can be reduced by increasing the mixing ratio of each material, and the temperature can be easily controlled, so that the conversion rate can be improved.

[0055] In one embodiment of the present disclosure, the mixing of the nickel (II) source, the diene-based compound, and the reducing agent may be performed using a mixer.

[0056] like Figure 1 As shown, the nickel (II) source, the diene-based compound, and the reducing agent may be mixed using a mixer before being supplied to the first continuous reactor.

[0057] In one embodiment of the present disclosure, the mixer may include any one or more of a static mixer, a T-type mixer, and a microreactor. The static mixer may be a plate mixer, a Kenics mixer, or a Sulzer mixer, but is not limited thereto.

[0058] In one embodiment of the present disclosure, the microreactor may include a plurality of microchannels that are repeatedly branched and connected. The mixing efficiency of the reactants can be further increased by including microchannels.

[0059] In one embodiment of the present disclosure, the microchannel may have various fluid dynamic structures, for example, may have a structure in which one flow path forms a deep wavy shape, or a structure in which two or more flow paths are connected by forming multiple branch points while repeatedly branching and connecting.

[0060] In one embodiment of the present disclosure, the microchannel has a size of 1 μm to 10 mm.

[0061] In one embodiment of the present disclosure, the nickel (II) source, the diene-based compound, and the reducing agent may be provided in the form of a composition comprising the same.

[0062] In one embodiment of the present disclosure, the composition may include various materials and an organic solvent. The concentration of each material is not particularly limited and may be adjusted to have a molar ratio as described later.

[0063] In one embodiment of the present disclosure, the solvent can be a hydrocarbon solvent that does not react with anions, and examples thereof can include any one or more selected from the following: straight-chain hydrocarbon compounds such as pentane, hexane and octane; derivatives thereof with double branches; cyclic hydrocarbon compounds such as cyclohexane and cycloheptane; aromatic hydrocarbon compounds such as benzene, toluene and xylene; straight-chain and cyclic ethers such as dimethyl ether, diethyl ether, anisole and tetrahydrofuran; and amide-based solvents such as dimethylacetamide and dimethylformamide (hereinafter referred to as DMF). Specifically, the organic solvent can be toluene, cyclohexane, hexane, tetrahydrofuran, ether or dimethylformamide. More specifically, toluene can be the most preferred.

[0064] In one embodiment of the present disclosure, the supply rates of the nickel (II) source, the diene-based compound, and the reducing agent are the same or different from each other, and can be 0.5 g / min to 500 g / min, and 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 range, side reactions can be prevented from occurring by stably supplying each raw material, and the operating time can be reduced.

[0065] In one embodiment of the present disclosure, nickel (II) source, diene-based compound and reducing agent can be supplied by the pressure vessel comprising each material. Its flow velocity and supply rate can be controlled by a separately connected supply device or pump. By the device, raw material can be introduced into the reactor at a constant rate, and input amount can also be measured. Supply device can be used without restriction, as long as it can prevent contact with air and control flow rate uniformly, such as mass flow controller (MFC), syringe pump or peristaltic pump.

[0066] In one embodiment of the present disclosure, producing a zerovalent nickel compound in a first continuous reactor includes reacting a nickel (II) source, a diene-based compound, and a reducing agent in the first continuous reactor. The zerovalent nickel compound can be produced by the reaction, and the produced zerovalent nickel compound is released from the first continuous reactor.

[0067] In one embodiment of the present disclosure, the reaction can be carried out under the conditions of a temperature of -78 DEG C to 10 DEG C and a pressure of 1 bar to 10 bar. When the conditions are adjusted to the above range, the exothermic reaction can be controlled during manufacture and the reaction rate can be easily controlled. The temperature can be achieved by a pre-temperature maintenance device (pre-temperature coil) and a constant temperature maintenance device (constant temperature bath) arranged in the first continuous reactor. Pressure can be achieved by regulating the flow velocity and the supply rate of the reaction material introduced into the reactor.

[0068] In one embodiment of the present disclosure, a pre-temperature maintaining device (pre-temperature coil) may be further included at the front end of the first continuous reactor, thereby preliminarily adjusting the temperature of the reactants before being introduced into the first continuous reactor.

[0069] like Figure 1 As shown, the pre-temperature maintaining device (pre-temperature coil) can pre-adjust the temperature by a heat exchange coil, and more specifically, can also pre-adjust the temperature of a mixer for mixing a nickel (II) source, a diene-based compound, and a reducing agent before supply, however, the role is not limited thereto.

[0070] In one embodiment of the present disclosure, the first continuous reactor may include a constant temperature maintaining device (constant temperature bath), thereby adjusting the temperature to a target temperature range during the reaction in the first continuous reactor.

[0071] In one embodiment of the present disclosure, the molar ratio of the nickel (II) source to the diene-based compound may be 1:2 to 1:10, or 1:4 to 1:6. Within the above range, the reaction between the nickel source and the diene-based compound may proceed smoothly.

[0072] In one embodiment of the present disclosure, the molar ratio of the nickel (II) source to the reducing agent may be 1: 2 to 1: 5, 1: 2.3 to 1: 2.5, or 1: 2.3 to 1: 3. Within the above range, color degradation caused by the reducing agent can be prevented, and a yield above a certain level can be ensured.

[0073] In one embodiment of the present disclosure, the method for producing a zerovalent nickel compound can have a total process time of 0.01 seconds to 20 minutes, or 1 second to 10 minutes. The total process time is the sum of the total time during which the material resides in the reactor, from the moment the reactants are introduced into the input unit of the reactor to the moment the output as the reaction product of the reactants is obtained from the reactor.

[0074] In one embodiment of the present disclosure, the reaction for producing the zerovalent nickel compound may be performed in an inert atmosphere. Methods for establishing an inert atmosphere include removing moisture and oxygen from the reactor before the reactants are supplied to the reactor, supplying an inert gas to the reactor before the reactants are supplied, and the like. Examples of the inert gas may include argon (Ar) or nitrogen (N2).

[0075] In one embodiment of the present disclosure, as a method for supplying an inert gas to the first continuous reactor, a method of supplying a gas having an inert gas concentration of 99% or higher, preferably 99.9% or higher, can be used. In addition to the inert gas, the gas contains very small amounts of air and moisture. As described above, by increasing the inert gas concentration to 99% or higher, preferably 99.9% or higher, it is possible to ensure high yield and reproducibility by minimizing the deactivation of zerovalent nickel compounds that are sensitive to oxygen and moisture.

[0076] In one embodiment of the present disclosure, the step of continuously supplying the zerovalent nickel compound to a second continuous reactor continuously connected to the first continuous reactor may be further included. The type of the second continuous reactor is not particularly limited, and examples thereof may include a semi-batch reactor, in this case also including a PFR or a CSTR.

[0077] As described above, the method for producing a zerovalent nickel compound of the present disclosure is effective in improving the yield when producing the zerovalent nickel compound from a nickel (II) source.

[0078] Furthermore, one embodiment of the present disclosure provides a method of manufacturing a polymer.

[0079] Figure 2 is a process diagram illustrating a method for producing a polymer according to one embodiment of the present disclosure, and is a diagram schematically illustrating a second continuous reactor into which a zerovalent nickel compound and a ligand are supplied, and a third continuous reactor into which a nickel complex produced in the second continuous reactor and a monomer are supplied.

[0080] In the disclosed method for producing a polymer, the supply of raw materials and the release of products can be performed simultaneously in each reactor. Specifically, the continuous supply of a zerovalent nickel compound to the second continuous reactor, the supply of a ligand to the second continuous reactor, and the preparation of a nickel complex by reacting the zerovalent nickel compound with the ligand can be performed simultaneously. Furthermore, the continuous supply of a nickel complex to the third continuous reactor, the continuous supply of a monomer to the third continuous reactor, and the polymerization reaction can be performed simultaneously. Simultaneous operation means that the supply of raw materials and the release of products occur simultaneously, without separate storage time.

[0081] In one embodiment of the present disclosure, the third continuous reactor may be maintained under conditions of a temperature of 25° C. to 200° C. and a pressure of 1 bar to 20 bar.

[0082] In this case, the product can be released while it is being generated in the continuous reactor, and the introduction and reaction of the raw materials and the release of the product can be carried out continuously as a series of processes. Compared with existing batch reactions, the use of this continuous process can significantly reduce the reactor capacity, and 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 rate or ratio, nickel complexes with constant composition and performance can be prepared, and the deviation of the product can be minimized even when manufactured in large quantities.

[0083] In one embodiment of the present disclosure, a zero-valent nickel compound produced by the above-described method for producing a zero-valent nickel compound can be used as the zero-valent nickel compound. In other words, the zero-valent nickel compound produced in the above-described continuous manner can be used.

[0084] In one embodiment of the present disclosure, the process may further include mixing a zerovalent nickel compound with a ligand. This can reduce the generation of unreacted materials by increasing the mixing ratio of the materials, enhance heat control, and ultimately improve conversion. After mixing the zerovalent nickel compound and the ligand, the resulting mixture can be supplied to a reactant inlet.

[0085] In one embodiment of the present disclosure, the mixing of the zerovalent nickel compound and the ligand can be performed using a mixer. The description of the mixer for mixing the zerovalent nickel compound and the ligand can be the same as the description of the mixer for mixing the nickel (II) source, the diene-based compound, and the reducing agent.

[0086] Figure 2 of The mixer is schematically illustrated.

[0087] In one embodiment of the present disclosure, the method for supplying the zerovalent nickel compound and the ligand to the second continuous reactor is not particularly limited, but for example, the second continuous reactor includes one or more reactant inlets, and the zerovalent nickel compound and the ligand can be supplied to the reactant inlet separately. Here, the power for supply can be obtained by a separately connected supply device or pump. Through this device, the raw materials can be introduced into the reactor at a constant rate, and the input amount can also be measured. The supply device can be used without restriction as long as it can prevent contact with air and control the flow rate to be uniform, such as a mass flow controller (MFC), a syringe pump or a peristaltic pump.

[0088] In one embodiment of the present disclosure, the zerovalent nickel compound and the ligand can be supplied from a storage container containing each material. The flow ratio and supply rate thereof can be adjusted by a supply device or pump connected to the rear end of the storage container.

[0089] In one embodiment of the present disclosure, the reactant inlet is a structure for introducing reaction materials into the reactor. The reactant inlet may refer to an input unit (or injection unit) for adjusting the input amount of each raw material in the continuous reactor. Here, the input amount of the raw material injected into each reactant inlet can be adjusted, and, by adjusting each input amount according to the reaction environment, side reactions can be minimized.

[0090] In one embodiment of the present disclosure, the second continuous reactor may include 1 to N (N is a positive integer from 1 to 10) reactant inlets.

[0091] In one embodiment of the present disclosure, the second continuous reactor includes one or more reactant inlets, and the zerovalent nickel compound and the ligand can be supplied to the same reactant inlet or different reactant inlets.

[0092] In one embodiment of the present disclosure, the first continuous reactor comprises one or more reactant inlets, and the zerovalent nickel compound and the ligand may be supplied through the same reactant inlet.

[0093] In one embodiment of the present disclosure, the zerovalent nickel compound and the ligand may each be supplied in the form of a solution containing them.

[0094] In one embodiment of the present disclosure, the solvent may be a hydrocarbon solvent, and examples thereof may include one or more selected from the following: linear hydrocarbon compounds such as pentane, hexane, and octane; derivatives thereof having double 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-based solvents such as dimethylacetamide and dimethylformamide (hereinafter referred to as DMF). Specifically, the organic solvent may be cyclohexane, hexane, tetrahydrofuran, ether, or dimethylformamide.

[0095] In one embodiment of the present disclosure, the zerovalent nickel compound and the ligand may each be supplied in the form of a composition dissolved in a solvent, and the composition may contain 0.1 wt % to 35 wt % of each of the zerovalent nickel compound and the ligand.

[0096] In one embodiment of the present disclosure, the supply rates of the zerovalent nickel compound and the ligand are 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, 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 rate may be adjusted by a mass flow controller (MFC) or a pump. Within the above range, the effect of minimizing side reactions is achieved without abruptly changing the amount of material injected into each reactant inlet.

[0097] In one embodiment of the present disclosure, the zerovalent nickel compound and the ligand may have a molar ratio of 1:2, preferably 1:5, and more preferably 1:10, however, the molar ratio is not limited thereto, and the ligand may be added in excess. However, within the above range, the zerovalent nickel compound and the ligand can react smoothly, and the zerovalent nickel compound and the ligand can react in the same equivalent amount. Specifically, when Ni(COD)2 is used as the zerovalent nickel compound and BPD is used as the ligand, a mixture of Ni(COD)2, Ni(BPD)2, Ni(COD)(BPD), etc. is generated. Among them, Ni(COD)(BPD) has the most excellent activity, and in order to produce it, it is preferred to adjust the molar ratio of the zerovalent nickel compound and the ligand to the above range.

[0098] In one embodiment of the present disclosure, the second continuous reactor can be maintained at a temperature of -78°C to 70°C and a pressure of 1 bar to 10 bar. When the conditions are adjusted to the above range, the exothermic reaction can be controlled during the preparation of the nickel complex and the reaction rate can be easily controlled. The temperature can be achieved by a pre-temperature maintenance device (pre-temperature coil) and a constant temperature maintenance device (constant temperature bath) provided in the continuous reactor. Pressure can be achieved by regulating the flow rate and supply rate of the reaction material introduced into the reactor. Specifically, a BPR (back pressure regulator) can be used in the regulation.

[0099] In one embodiment of the present disclosure, the second continuous reactor may include a pre-temperature maintaining device (pre-temperature coil), thereby preliminarily adjusting the temperature of the reactants before being introduced into the continuous reactor.

[0100] In one embodiment of the present disclosure, the continuous reactor may include a constant temperature maintaining device (constant temperature bath), thereby adjusting the temperature to a target temperature range during the reaction in the continuous reactor.

[0101] In one embodiment of the present disclosure, the total process time may be 0.01 seconds to 20 minutes or 1 second to 10 minutes. The total process time is the sum of the total time during which the material resides in the reactor from the moment the reactants are introduced into the input unit of the reactor to the moment the output as the reaction product of the reactants from the reactor is obtained.

[0102] In one embodiment of the present disclosure, the reaction of the zerovalent nickel compound and the ligand to prepare the nickel complex can be carried out under an inert environment. In other words, the interior of the second continuous reactor can be in an inert environment. Here, the method for establishing the inert environment is the same as the method used for the reaction when producing the zerovalent nickel compound under an inert gas as described above, including a method of removing moisture and oxygen from the interior of the reactor before supplying the reactants to the reactor, a method of supplying an inert gas to the reactor before supplying the reactants, etc. Examples of the inert gas may include argon (Ar) or nitrogen (N2).

[0103] In one embodiment of the present disclosure, a gas having an inert gas concentration of 99% or greater, preferably 99.9% or greater, can be used as a method for supplying an inert gas to the second continuous reactor. In addition to the inert gas, the gas contains very small amounts of air and moisture. As described above, by increasing the inert gas concentration to 99% or greater, preferably 99.9% or greater, it is possible to ensure high yield and reproducibility by minimizing the deactivation of zerovalent nickel compounds that are sensitive to oxygen and moisture.

[0104] In one embodiment of the present disclosure, the step of mixing the nickel complex with the monomer may be further included. This can reduce the generation of unreacted materials by increasing the mixing ratio of the materials, enhance the heat control effect, and ultimately improve the conversion rate. In addition, after the nickel complex is mixed with the monomer, the resulting mixture can be supplied to a reactant inlet.

[0105] In one embodiment of the present disclosure, the mixing of nickel complex and monomer can be carried out from 1 minute to 300 minutes. Here, polyreaction sometimes starts when nickel complex and monomer are mixed, and therefore, the time from 1 minute to 300 minutes can refer to the sum of mixing time and the time of carrying out polyreaction. In order to adjust the time, a coil (RT coil) can be kept connected to each reactor.

[0106] Figure 2 of The holding coils present in the reactor are schematically illustrated.

[0107] In one embodiment of the present disclosure, the supply rate of the nickel complex and the supply rate of the monomer are the same or different from each other and can be 0.5 g / min to 500 g / min, and 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 amount can be the weight of the nickel complex or monomer composition itself; or the total weight of the solution containing these.

[0108] The supply rate can be adjusted by a separately connected mass flow controller (MFC).Within the above range, the effect of minimizing side reactions is obtained without abruptly changing the amount of material injected into each reactant inlet.

[0109] In one embodiment of the present disclosure, the polymerization reaction can be carried out under an inert environment. Specifically, the interior of the reactor is easily placed in an inert environment, and the effect of preventing side reactions or explosions can be obtained. The description of the inert gas is the same as that provided above.

[0110] In one embodiment of the present disclosure, each continuous reactor may include a heat control device, and the heat control device may be pre-connected to each continuous reactor. The reaction occurring in each continuous reactor is an exothermic reaction, and in order to quickly control the heat of reaction produced herein, the reaction may be carried out in a thermostat. Specifically, a pre-heating maintenance coil (pre-heating coil) is installed at the front end of each reactor, and its length may be adjusted to reach thermal equilibrium according to flow rate.

[0111] In one embodiment of the present disclosure, each continuous reactor may further include a retaining coil (Rt coil). By retaining the coil, the residence time for the reaction can be adjusted. Specifically, the residence time can be adjusted by adjusting the time during which the material supplied to each continuous reactor reacts and remains in the retaining coil. By adjusting the length of the retaining coil and adjusting the supply rate of the supplied material, the residence time can be adjusted more finely.

[0112] In one embodiment of the present disclosure, the monomer may include a base monomer; and a capping monomer (capping agent).

[0113] In one embodiment of the present disclosure, the monomer may be supplied in the form of a solution containing the monomer. The solvent is the same as described above.

[0114] In one embodiment of the present disclosure, the composition including the monomer may include 0.1 wt % to 35 wt % of the monomer.

[0115] In one embodiment of the present disclosure, a "polymerization reaction" is a reaction in which monomers are polymerized with each other using a nickel complex as a catalyst. In this case, a reaction may occur in which the end groups of the monomers are substituted with end-capping monomers.

[0116] In one embodiment of the present disclosure, the polymerization reaction may be a Yamamoto polymerization reaction. In the Yamamoto reaction, polymerization is achieved by inserting nickel atoms of a nickel complex catalyst between monomers. The specific polymerization method is 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].

[0117] In the present disclosure, "monomer" is a raw material that is polymerized to form a polymer. One monomer is chemically bonded to another monomer to form a chain. In itself, each monomer can be considered to have two or more "functional groups" (in other words, the position at which a monomer is chemically bonded to another monomer). By chemically bonding each end of a monomer to another monomer, a monomer chain is formed to produce a polymer. As described above, a monomer can have more than two positions, and in this case, a polymer with a branched chain can be formed.

[0118] When the monomer is polymerized (regardless of whether other types of monomers are used), a polymer comprising repeating units is formed. The polymer preferably comprises, for example, a repeating unit selected from the group consisting of arylene repeating units disclosed in [Adv. Mater. 2000 12 (23) 1737-1750] and references thereto. Exemplary first repeating units include 1,4-phenylene repeating units as disclosed in [J. Appl. Phys. 1996, 79, 934]; fluorene repeating units disclosed in European Patent No. 0842208; indenofluorene repeating units disclosed in [Macromolecules 2000, 33 (6), 2016-2020]; and spirofluorene repeating units disclosed in European Patent No. 0707020. Each of these repeating units is optionally substituted. Examples of the substituent may include a solubilizing group such as a C1-20 alkyl group or an alkoxy group; an electron withdrawing group such as a fluorine group, a nitro group, or a cyano group; and a substituent that increases the glass transition temperature of the polymer.

[0119] The type of monomer may contain a leaving group, and the leaving group may be a halogen group such as F, Cl, Br or I.

[0120] The monomer may be a monomer represented by the following Chemical Formula 1.

[0121] [Chemical Formula 1]

[0122]

[0123] In Formula 1, R1 and R2 are independently selected from the following: hydrogen; an optionally substituted alkyl group, wherein one or more non-adjacent carbon atoms may be replaced by O, S, N, C=O, or -COO-; an alkoxy group, an aryl group, an arylalkyl group, a heteroaryl group, and a heteroarylalkyl group. More preferably, one or more of R1 and R2 is an optionally substituted C4-C20 alkyl group or an aryl group.

[0124] In Chemical Formula 1, X1 and X2 are each independently chlorine, bromine and iodine, and most preferably bromine.

[0125] In one embodiment of the present disclosure, the end-capping monomer (end-capping agent) may be represented by the following structural formula.

[0126] In one embodiment of the present disclosure, the end-capping monomer (end-capping agent) may be a monofunctional unit having one attachment point.

[0127] In one embodiment of the present disclosure, the end-capping monomer (end-capping agent) may include a cross-linking group or a deuterated cross-linking group.

[0128] In one embodiment of the present disclosure, the end-capping monomer (end-capping agent) may include a hydrocarbon aryl group or a deuterated hydrocarbon aryl group.

[0129] In one embodiment of the present disclosure, the end-capping monomer (end-capping agent) comprises a group selected from phenyl, biphenyl, diphenylamino, substituted derivatives thereof, and deuterated analogs thereof. In some embodiments, the substituent may be a C1-10 alkyl, a cross-linking group, or a deuterated derivative thereof.

[0130] In one embodiment of the present disclosure, the end-capping monomer (end-capping agent) may have the following structure.

[0131]

[0132]

[0133] In one embodiment of the present disclosure, 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 polymer produced according to the method for producing a polymer may be 5% or less, 4% or less, or 3% or less. The coefficient of variation (CV) can be calculated by dividing the standard deviation value by the average value after calculating the standard deviation value and the average value of each property.

[0134] The yield, number average molecular weight and weight average molecular weight of the polymer can be calculated by measuring and calculating the values ​​of the properties corresponding to the following equations, and the values ​​of the following properties can be calculated using methods commonly used in the art. For example, the method of gas chromatography (GC) or gel permeation chromatography (GPC) of the polymer can be used for calculation.

[0135] [Number average molecular weight]

[0136]

[0137] [Weight average molecular weight]

[0138]

[0139] (N i : molar number of polymer molecules, M i : molecular weight of the polymer, w i : weight of polymer)

[0140] Hereinafter, the present disclosure will be described in more detail with reference to Examples and Comparative Examples. However, these are for illustrating the present disclosure and are not intended to limit the scope of the present disclosure.

[0141] Preparation Example 1

[0142] A first continuous reactor was formed comprising first and second continuous channels and two vacuum-dried 2 L stainless steel pressure vessels.

[0143] A first solution (first reaction solution) was prepared and introduced into the first pressure vessel, which was obtained by mixing nickel acetylacetonate {Ni(acac)2} (100 g) as a nickel (II) source, a diene-based compound (1,5-cyclooctadiene) (168 g) and an organic solvent (tetrahydrofuran) (532 g).

[0144] Into the second pressure vessel, a second solution (second reaction solution) obtained by dissolving a DIBAL reducing agent in toluene at a concentration of 1 M was prepared and introduced.

[0145] While maintaining the pressure of the first pressure vessel and the second pressure vessel at 3 bar respectively, the first reaction solution and the second reaction solution were injected into each of the continuous reactors by injecting the first reaction solution into the first continuous channel at an injection rate of 1.0 g / min and injecting the second reaction solution into the second continuous channel at an injection rate of 1.0 g / min.

[0146] Here, the molar ratio of nickel acetylacetonate {Ni(acac)2}:1,5-cyclooctadiene:DIBAL is 1:4:2.05.

[0147] Here, 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.

[0148] After the reaction is completed, a zero-valent nickel compound {Ni(COD)2} is obtained with a yield of 75%.

[0149] Preparation Example 2

[0150] The preparation 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 an injection rate of 5.0 g / min, and the second reaction solution was injected into the second continuous channel at an injection rate of 5.0 g / min, thereby injecting the first reaction solution and the second reaction solution into the second continuous channel at an injection rate of 5.0 g / min, respectively, into the continuous reactors. After completion of the reaction, a zerovalent nickel compound {Ni(COD)2} was obtained in a yield of 72%.

[0151] Preparation Example 3

[0152] The preparation 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 an injection rate of 10.0 g / min, and the second reaction solution was injected into the second continuous channel at an injection rate of 10.0 g / min, thereby injecting the first reaction solution and the second reaction solution into the second continuous channel at an injection rate of 10.0 g / min, respectively, into the continuous reactors. After completion of the reaction, a zerovalent nickel compound {Ni(COD)2} was obtained in a yield of 73%.

[0153] Preparation Example 4

[0154] Preparation Example 1 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 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 1.6 g / min, thereby injecting the first reaction solution and the second reaction solution into each of the continuous reactors, and the molar ratio of nickel acetylacetonate {Ni(acac)2}:1,5-cyclooctadiene:DIBAL was changed to 1:4:2.6. After completion of the reaction, a zerovalent nickel compound {Ni(COD)2} was obtained in a yield of 68%.

[0155] Preparation Example 5

[0156] Preparation Example 1 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 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 2.3 g / min, thereby injecting the first reaction solution and the second reaction solution into each of the continuous reactors, and the molar ratio of nickel acetylacetonate {Ni(acac)2}:1,5-cyclooctadiene:DIBAL was changed to 1:4:3. After completion of the reaction, a zerovalent nickel compound {Ni(COD)2} was obtained in a yield of 65%.

[0157] Preparation Example 6

[0158] The preparation was carried out in the same manner as in Preparation Example 1, except that the second solution was changed to a solution obtained by dissolving the DIBAL reducing agent in hexane at a concentration of 1 M. After the reaction was completed, a zerovalent nickel compound {Ni(COD)2} was obtained with a yield of 70%.

[0159] Preparation Example 7

[0160] Nickel acetylacetonate {Ni(acac)2} (4.67 g) as a nickel (II) source, a diene-based compound (1,5-cyclooctadiene) (7.93 g) and an organic solvent (tetrahydrofuran) (25 mL) were introduced into a Schlenk flask under nitrogen and cooled to -78°C to control heat.

[0161] A solution obtained by dissolving a DIBAH reducing agent (0.0454 mmol) in tetrahydrofuran (THF) at a molar concentration of 1.0 M was added thereto, and the resultant was stirred for 1 hour. Thereafter, the reaction was carried out while the temperature was raised to 0°C for 1 hour, and the resultant was further stirred at 0°C for 1 hour to obtain the final zerovalent nickel compound {Ni(COD)2} in a yield of 72%.

[0162] Example 1

[0163] Prepare 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. The second continuous reactor is connected to a pre-prepared pressure vessel 1, and the third continuous reactor is connected to a pre-prepared pressure vessel 2.

[0164] In pressure vessel 1, a ligand composition was prepared by introducing and dissolving 2,2'-bipyridine ligand at 5.2 wt% in DMF solvent.

[0165] In pressure vessel 2, a monomer composition was prepared by dissolving 2,7-dibromo-9,9-dioctylfluorene (6.93 wt%) and bromobenzene (0.22 wt%) in toluene solvent.

[0166] Then, the zerovalent nickel compound prepared in the first continuous reactor of Preparation Example 1 was supplied to the second continuous reactor, and the ligand composition was supplied from pressure vessel 1 to the second continuous reactor (PFR) to prepare a nickel complex. The prepared nickel complex was supplied to the third continuous reactor.

[0167] Then, after being held in the first holding coil (Rt coil) for 1 minute, the monomer composition was discharged from the pressure vessel 2 to initiate a coupling reaction in the third continuous reactor (PFR).

[0168] All process lines were maintained at 60 degrees Celsius using a thermostat, and after the pressure was adjusted to 3 bar by injecting nitrogen into each pressure vessel, the flow rates were adjusted to 1.06 g / min, 0.4 g / min, and 0.5 g / min, respectively, by connecting to a mass flow meter.

[0169] After the coupling reaction was completed, the resultant was aged in the second holding coil (Rt coil) for 60 minutes, and the final product was released from the reactor.

[0170] Afterwards, the solution containing the final product was cooled to room temperature, and the final product was added dropwise by stirring in the quenching solution. The obtained polymer sample was stirred for 2 hours to completely quench and filtered to obtain only a solid component, and the solid component was analyzed by GPC.

[0171] In other words, in Example 1, the polymer was prepared according to the following sequence.

[0172]

[0173] Example 2

[0174] The preparation was carried out in the same manner as in Example 1, except that a monomer composition obtained by dissolving 2,7-dibromo-9,9-dioctylfluorene (6.93 wt %), 1,3,5-tris(4-bromophenyl)benzene (2.56 wt %) and bromobenzene (1.17 wt %) in toluene solvent was prepared in pressure vessel 2, the monomer composition was discharged from pressure vessel 2 to induce a coupling reaction in a third continuous reactor (PFR), all process lines were maintained at 60 degrees Celsius using a thermostat, and after the pressure was adjusted to 3 bar by injecting nitrogen into each pressure vessel, the flow rate was adjusted to 1.86 g / min, 0.71 g / min and 0.5 g / min, respectively, by connecting to a mass flow meter.

[0175] In other words, in Example 2, the polymer was prepared according to the following sequence.

[0176]

[0177] Comparative Example 1

[0178] The polymer was prepared in the same sequence as in Example 1, and a batch process was used instead of a continuous process.

[0179] Specifically, the ligand composition was prepared by introducing and dissolving 2,2′-bipyridine ligand at 5.2 wt % in DMF solvent in a first pressure vessel.

[0180] In a second pressure vessel, a monomer composition was prepared by dissolving 2,7-dibromo-9,9-dioctylfluorene (6.93 wt %) and bromobenzene (0.22 wt %) in a toluene solvent.

[0181] Furthermore, nitrogen and vacuum were alternately injected into a Schlenk flask having a capacity of 100 mL to establish an inert atmosphere, and the flask was closed with a rubber septum, taken out, and immersed in a thermostat at 60 degrees Celsius.

[0182] Thereafter, the zerovalent nickel compound (21 ml) prepared in the first continuous reactor of Preparation Example 1 was extracted using a gastight syringe and injected into the Schlenk flask.

[0183] Similarly, the ligand composition (7.4 ml) was extracted using a gas-tight syringe and injected into the flask, and the resultant was held for 1 minute.

[0184] Finally, a monomer composition (9.95 ml) was extracted in the same manner and injected into the flask, and the resultant was reacted for 60 minutes.

[0185] Afterwards, the solution containing the final product was cooled to room temperature, and the final product was added dropwise by stirring in the quenching solution. The obtained polymer sample was stirred for 2 hours to completely quench and filtered to obtain only a solid component, and the solid component was analyzed by GPC.

[0186] Comparative Example 2

[0187] The polymer was prepared in the same sequence as in Example 2, and a batch process was used instead of a continuous process.

[0188] More specifically, the preparation was performed in the same manner as in Comparative Example 1, except that a monomer composition obtained by dissolving 2,7-dibromo-9,9-dioctylfluorene (6.93 wt %), 1,3,5-tris(4-bromophenyl)benzene (2.56 wt %) and bromobenzene (1.17 wt %) in a toluene solvent was prepared in a second pressure vessel.

[0189] Figure 3is a process diagram schematically illustrating a process for producing the polymers of Comparative Examples 1 and 2 corresponding to the existing method, and shows a preparation process by sequentially introducing a zerovalent nickel compound, a ligand, and a monomer.

[0190] Experimental Examples

[0191] The yields and Mn / Mw ratios of the polymers prepared in Examples and Comparative Examples were measured and shown in Tables 1 and 2 below.

[0192]

Table 1

[0193]

[0194]

[0195]

Table 2

[0196]

[0197] The yield represents the yield of the polymer obtained after purification of the polymer, Mn and Mw are the values ​​obtained by the PS-calibrated GPC method (equipment used: Agilent 1200 series) of the obtained polymer, and CV is the coefficient of variation, which represents the value obtained by dividing the standard deviation value by the average value for the yield, Mn and Mw of the polymer produced for each number of each process.

[0198] When the polymer was produced using the continuous process of the examples, the yield was excellent and the coefficient of variation of each evaluation item was low. Thus, it was confirmed that when the polymer was produced using the continuous process of the examples, the reproducibility of the properties of the polymer was excellent.

[0199] On the other hand, when the batch process of the comparative example was used to prepare the polymer, the yield was low and the coefficient of variation of each evaluation item was high. Thus, it was determined that when the batch process of the comparative example was used to prepare the polymer, the reproducibility of the polymer properties was low.

[0200] From the results, it was determined that when the continuous process of the present disclosure was used instead of the existing batch method, the yield of polymer increased and the reproducibility of properties was significantly improved.

[0201] Furthermore, from the fact that the reproducibility of properties of polymers prepared using the zero-valent nickel compound prepared according to the method for producing a zero-valent nickel compound of the present disclosure is significantly improved, it can be determined that when a zero-valent nickel compound is prepared according to the method for producing a zero-valent nickel compound of the present disclosure, a zero-valent nickel compound with stable quality and high yield can be prepared.

[0202] Furthermore, it was determined that the method for producing a zerovalent nickel compound according to one embodiment of the present disclosure had a shorter reaction time and higher stability compared to a batch method.

Claims

1. A method for producing a polymer, the method comprising: supplying a nickel(II) source to a first continuous reactor; supplying a diene-based compound to a first continuous reactor; supplying a reducing agent to the first continuous reactor; reacting the nickel(II) source, the diene-based compound, and the reducing agent in a first continuous reactor to produce a zerovalent nickel compound, continuously supplying a zerovalent nickel compound to a second continuous reactor continuously connected to the first continuous reactor; supplying a ligand to a second continuous reactor; preparing a nickel complex by reacting the zerovalent nickel compound with the ligand; continuously supplying the nickel complex to a third continuous reactor; continuously supplying monomer to the third continuous reactor; as well as Carry out polymerization reaction, wherein the supply rates of the nickel(II) source, the diene-based compound, and the reducing agent are the same as or different from each other and are each in the range of 0.5 g / min to 500 g / min, The supply rate of the nickel complex and the supply rate of the monomer are the same as or different from each other and are each in the range of 0.5 g / min to 500 g / min.

2. The method for producing a polymer according to claim 1, wherein The first continuous reactor includes one or more continuous channels, and the nickel (II) source, the diene-based compound, and the reducing agent are each supplied to the continuous channels.

3. The method for producing a polymer according to claim 1, wherein The reaction in the first continuous reactor is carried out under the conditions of a temperature of -78°C to 10°C and a pressure of 1 bar to 10 bar.

4. The method for producing a polymer according to claim 1, wherein The nickel (II) source comprises nickel acetylacetonate {Ni(acac)2}.

5. The method for producing a polymer according to claim 1, wherein The diene-based compound is any one or more selected from the group consisting of 1,4-cyclohexadiene, bicyclo[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, dicyclopentadiene, methyltetrahydroindene, 5-allylbicyclo[2.2.1]hept-2-ene, and 1,5-cyclooctadiene.

6. The method for producing a polymer according to claim 1, wherein The total process time until the zerovalent nickel compound is produced is 0.01 seconds to 20 minutes.

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

8. The method for producing a polymer according to claim 1, wherein The second continuous reactor and the third continuous reactor are continuously connected to each other.

9. The method for producing a polymer according to claim 1, wherein The second continuous reactor is maintained under conditions of a temperature of -78°C to 70°C and a pressure of 1 bar to 10 bar.

10. The method for producing a polymer according to claim 1, wherein The polymerization reaction used Yamamoto polymerization.

11. The method for producing a polymer according to claim 1, wherein The preparation of the nickel complex by reacting the zerovalent nickel compound and the ligand is performed under an inert environment.

12. The method for producing a polymer according to claim 1, wherein The third continuous reactor is maintained under conditions of a temperature of 25° C. to 200° C. and a pressure of 1 bar to 20 bar.

13. The method for producing a polymer according to claim 1, wherein The polymerization reaction is carried out under an inert environment.

14. The method for producing a polymer according to claim 1, wherein 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 produced polymer is 5% or less.

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