KR20220088104A - Manufacturing method for polymer - Google Patents

Abstract

The present specification includes the steps of continuously supplying a nickel complex precursor to a first continuous reactor; supplying a ligand to the first continuous reactor; preparing a nickel complex by reacting the nickel complex precursor and a ligand; continuously feeding the nickel complex to a second continuous reactor; continuously supplying monomers to the second continuous reactor; and conducting a polymerization reaction, wherein at least one of the first continuous reactor and the second continuous reactor is a continuous stirred tank reactor or a semi-batch reactor It relates to a method for producing a polymer.

Description

Polymer manufacturing method {MANUFACTURING METHOD FOR POLYMER}

The present invention relates to a method for preparing a polymer.

There are several known methods for preparing polymers in the prior art, examples of which include, for example, Suzuki polymerization described in WO 00/53656 and, for example, T. Yamamoto, "Electrically Conducting And Thermally Stable ð-Conjugated Poly(arylene)s Prepared by Organometallic Processes", Progress in Polymer Science 1993, 17, 1153-1205]. Both of these polymerization techniques operate via "metal insertion" in which a metal atom of the metal complex catalyst is inserted between the leaving group of the monomer and the aryl group. 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.

The properties of a polymer are determined by the properties, properties and composition of the monomers used to make the polymer. In addition, the polymer also requires process characteristics such as reproducibility to produce a constant product regardless of the number of reaction cycles or reaction scale. However, such reproducibility is practically difficult to implement in a conventional batch reaction manufacturing process.

The properties of the polymer are affected by various reaction conditions such as the shape of the reactor, the monomer input rate, and the reaction temperature, because it is difficult to uniformly control these reaction conditions for each reaction cycle.

J Org Chem (1990), 4229-4230

The present invention relates to a method for preparing a polymer using a nickel complex.

The nickel complex catalyst used in the Yamamoto reaction is prepared in the form of a nickel complex by reacting a nickel compound such as Ni(COD) ₂ with a ligand, and Ni(COD) ₂ reacts easily with air, water or light. Corresponding to an unstable substance that is oxidized, there was a problem in that the reaction yield was low and the reproducibility was low.

In addition, in the batch method, there are many by-products during mass production, which lowers the purity and lowers the yield, and since the product yield and characteristics are different for each batch, the performance of the final product is not constant, so it is difficult to apply it to commercial production.

A typical batch reactor has problems in that it is difficult to operate the reactor during commercial-scale production, and investment and operating costs increase. In addition, operation using a batch reactor usually requires repeating a series of operations such as temperature increase, reactant injection, reaction, cooling, and product discharge. Therefore, since productivity per batch operation is low, there is a problem in that the volume of the reactor or the number of reactors must be increased for mass production.

In addition, when the prepared complex precursor is reacted with a ligand, there is a problem in that a separate purification process is required.

On the other hand, in a plug flow reactor used in a general continuous process, it was difficult to control the properties of a polymer when polymerizing a monomer, but a continuous stirred tank reactor and a semi-batch reactor Since the monomer input ratio and space time can be easily controlled, there is an advantage in that it is easy to control physical properties such as molecular weight and dispersion degree (PDI) of the prepared polymer.

An exemplary embodiment of the present invention comprises the steps of continuously supplying a nickel complex precursor to a first continuous reactor;

supplying a ligand to the first continuous reactor;

preparing a nickel complex by reacting the nickel complex precursor and a ligand;

continuously supplying the nickel complex to a second continuous reactor;

continuously supplying monomers to the second continuous reactor; and

Including the step of proceeding the polymerization reaction,

It provides a method for producing a polymer that at least one of the first continuous reactor and the second continuous reactor is a continuous stirred tank reactor (Continuous Stirred Tank Reactor) or a semi-batch reactor.

The method for producing a polymer according to an exemplary embodiment of the present invention can secure high yield and excellent reproducibility by using a continuous reaction process rather than a conventional batch method.

1 is an exemplary process diagram of a method for producing a polymer according to an embodiment of the present invention.

Hereinafter, the present specification will be described in more detail.

As described above, the conventional batch reactor has problems in that it is difficult to operate the reactor during commercial scale production, and investment and operating costs increase. In addition, since it is difficult to handle a nickel complex precursor used for preparing a nickel complex corresponding to a catalyst for preparing a polymer, there is a problem in that a separate purification process is required when applied to the process.

An exemplary embodiment of the present invention comprises the steps of continuously supplying a nickel complex precursor to a first continuous reactor;

supplying a ligand to the first continuous reactor;

preparing a nickel complex by reacting the nickel complex precursor and a ligand;

continuously supplying the nickel complex to a second continuous reactor;

continuously supplying monomers to the second continuous reactor; and

Including the step of proceeding the polymerization reaction,

It provides a method for producing a polymer that at least one of the first continuous reactor and the second continuous reactor is a continuous stirred tank reactor (Continuous Stirred Tank Reactor) or a semi-batch reactor.

An example of a method for preparing the polymer is shown in FIG. 1 . Specifically, one embodiment of the present invention comprises the steps of continuously supplying the nickel complex precursor (1) to the first continuous reactor (4); supplying a ligand (2) to the first continuous reactor (4); reacting the nickel complex precursor (1) and the ligand (2) to prepare a nickel complex; continuously supplying the nickel complex to a second continuous reactor (5); continuously feeding the monomer (3) to the second continuous reactor (5); and conducting a polymerization reaction. In this case, at least one of the first continuous reactor 4 and the second continuous reactor 5 may be a continuous stirred tank reactor or a semi-batch reactor. The polymer (6) prepared through the above manufacturing method is discharged and recovered to the outside of the reactor.

According to the manufacturing method of the polymer, there is an advantage suitable for a large-scale continuous process by minimizing the occurrence of quality deviation for each process. Specifically, the item for evaluating the quality may include a method of comparing and calculating a deviation by a method generally used in the field to which this technology belongs. For example, a method of calculating the yield and molecular weight of the prepared polymer and comparing them for each process may be used.

In addition, when using a conventional batch reactor, it is difficult to create an inert environment inside the reactor, and there is a problem in that the risk of an accident is increased due to a highly flammable reactant. However, in the method for producing a polymer according to an exemplary embodiment of the present invention, by using a continuous reactor such as a continuous stirred tank reactor or a semi-batch reactor, the inside of the reactor is turned into an inert environment. Since the composition is easy, even if a highly flammable reactant is used, stability is improved.

As used herein, the term “nickel complex precursor” refers to a precursor material used to prepare a nickel complex, and may be in the form of a complex. Also, it may be in the form of a zero-valent nickel compound. The zero-valent nickel compound refers to a nickel compound in which the oxidation number of nickel is adjusted to 0, and specifically, bis (1,5-cyclooctadiene) nickel {bis (1, 5-cyclooctadiene) nickel: Ni(COD) ₂ } can be

As used herein, the term “nickel complex” refers to a compound in which nickel and a ligand are complexed. Specifically, it is represented by Ni(L)n, n is an integer of 2 to 4, and L means a ligand. When n is 2 or more, L in parentheses may be the same or different.

L means 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.

Specifically, the nickel complex is t-BuNC [Ni(t-BuNC) ₂ ], [Ni(nbd) ₂ ], [Ni(cod)(bpy)], [Ni(AN) ₂ ], [Ni(PPh) ₃ ) ₄ ], [Ni(cod)(PPh ₃ ) ₂ ], [NiBr(C ₃ H ₅ ) ₂ ], [NiBr(C ₃ H ₅ ) ₂ ] or NiCl(C ₃ H ₅ )(PPh ₃ ) can be Here, nbd means bicycle[2.2.1]hepta-2,5-dien, bpy means 2,2'-biphyridyl, and AN means ancrylonitrile. In addition to the above examples, conventional 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.] may refer to various types of nickel complexes.

In the present specification, a "continuous reactor" is a reactor in which the reaction proceeds while continuously inputting the reactants used for the reaction, and the supply of the reactants and the discharge of the product may be performed simultaneously.

In the present specification, unless otherwise specified, the description of "continuous reactor" may be applied to both the first continuous reactor and the second continuous reactor.

In the present specification, the "first continuous reactor" means a reactor for producing a nickel complex (complex). In this case, the first continuous reactor may be continuously connected to another continuous reactor. The connecting means is not particularly limited, and may be connected through a tube used in a chemical process.

As used herein, the "second continuous reactor" refers to a reactor for producing a polymer using a nickel complex. In this case, the second continuous reactor may be continuously connected to another continuous reactor. The connecting means is not particularly limited, and may be connected through a tube used in a chemical process.

In the present specification, "continuous supply" refers to supplying the reactants to the reactor by a flow, and the supply of the reactants and the discharge of the products converted from the reactants may occur at the same time.

In an exemplary embodiment of the present invention, the first continuous reactor and the second continuous reactor may be continuously connected to each other. This means that only members capable of continuous flow of reactants and products exist between the first continuous reactor and the second continuous reactor. In this case, it is advantageous to create an inert environment inside the reactor, and there is an advantage that a product can be produced in each reactor and supplied to another reactor at the same time. The connection means is not particularly limited, and the first continuous reactor and the second continuous reactor may be directly connected or may be connected through a pipe used in a chemical process.

In an exemplary embodiment of the present invention, at least one of the first continuous reactor and the second continuous reactor is a continuous stirred tank reactor or a semi-batch reactor. have The continuous stirred tank reactor (Continuous Stirred Tank Reactor) and the semi-batch reactor (semi-batch) can easily control the monomer input ratio and space time (space time), so that the molecular weight of the prepared polymer, dispersion (PDI), etc. There is an advantage in that it is easy to control the physical properties.

In one embodiment of the present invention, the first continuous reactor is a PFR reactor,

The second continuous reactor may be a continuous stirred tank reactor (CSTR) or a semi-batch reactor. When the reactor combination is used, the process can be performed stably, polymerization time can be easily controlled, and physical properties such as molecular weight and PDI of the prepared polymer can be easily controlled.

Specifically, the nickel complex is prepared in the first continuous reactor, and the nickel complex precursor corresponds to an unstable material that is easily oxidized by reacting with air, water or light, so it is preferable to prepare the nickel complex under an inert environment. The PFR reactor has the advantage that it is easy to implement a completely closed space (Closed System), and it is easy to create an inert environment inside the reactor.

The polymer is polymerized in the second continuous reactor, and a by-product may be generated during the polymerization process. When a plug flow reactor is used as the second continuous reactor, the produced polymer or the by-product is deposited inside the reactor to block the reactor flow, which may cause clogging. On the other hand, when a continuous stirred tank reactor (CSTR) or a semi-batch reactor is used as the second continuous reactor, the aging time in the reactor tank can be controlled relatively easily, so that the countercurrent phenomenon is prevented while There is an advantage in that the physical properties of the polymer can be easily controlled.

In an exemplary embodiment of the present invention, raw material supply and product discharge of each reactor may be performed simultaneously. Specifically, continuously supplying the nickel complex precursor to a first continuous reactor; supplying a ligand to the first continuous reactor; and reacting the nickel complex precursor and the ligand to prepare a nickel complex may be simultaneously performed. In addition, continuously supplying the nickel complex to a second continuous reactor; continuously supplying monomers to the second continuous reactor; And the step of proceeding the polymerization reaction may be carried out at the same time. The meaning of being performed at the same time means that the supply of raw materials and discharge of the product are performed simultaneously without a separate storage time.

In this case, the product may be produced and discharged at the same time as the product is produced in the continuous reactor, and the input of the raw material, the reaction, and the discharge of the product may be continuously performed as a series of processes. By using such a continuous process, it is possible to significantly reduce the capacity of the reactor required for the process compared to when using a conventional batch reactor, it is possible to easily control the reaction conditions, and it is possible to maintain a constant reaction environment. In addition, by introducing the reaction raw material at a constant rate or ratio, it is possible to manufacture a nickel complex and a polymer having a constant composition, so that even if a large amount is produced, product deviation can be minimized.

In an exemplary embodiment of the present invention, the method may further include mixing the nickel complex precursor and the ligand. In this case, it is possible to reduce the generation of unreacted substances by increasing the mixing rate of the materials, to improve the heat removal effect, and consequently to improve the conversion rate. On the other hand, after mixing the nickel complex precursor and the ligand, it may be supplied to one reactant inlet provided in the first continuous reactor.

In one embodiment of the present invention, mixing the nickel complex precursor and the ligand may be performed using a mixer. The mixer may be mounted inside the first continuous reactor.

In one embodiment of the present invention, the mixer may include any one or more of a static mixer, a T mixer, and a micro-reactor. The static mixer may be a plate mixer, a kenics mixer, or a Sulzer mixer, but is not limited thereto.

In one embodiment of the present invention, the microreactor may include a plurality of microchannels that repeat branching and confluence. By including the microchannel, the mixing efficiency of the reactants may be further increased.

In one embodiment of the present invention, the microchannel may have various hydrodynamic structures, for example, one flow path may form a deep wave shape, and two or more flow paths may branch and merge. It may be in a form connected by repeating and forming a plurality of branch points.

In one embodiment of the present invention, the method of supplying the nickel complex precursor or ligand to the first continuous reactor is not particularly limited, but, for example, the first continuous reactor includes one or more reactant inlets and , the nickel complex precursor and the ligand may be supplied to the reactant inlet, respectively. In this case, the supply power may be performed through a separately connected supply device or a pump. The raw materials may be introduced into the reactor at a constant rate through the device, and the input amount may be measured. The supply device is a mass flow controller (MFC), a syringe pump (Syringe Pump), a peristaltic pump (Peristaltic Pump), etc. It can be used without limitation as long as it can prevent contact with air and control the flow rate uniformly.

In one embodiment of the present invention, the nickel complex precursor and the ligand may be supplied from a storage container containing each material. Their flow rate and supply rate can be adjusted through a pump or a supply device connected to the rear end of the storage container. At this time, the description of the supply device is the same as described above.

In an exemplary embodiment of the present invention, the reactant inlet is configured to introduce the reactant into the reactor. The reactant inlet may mean an input part (or an 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 injected into each reactant inlet may be adjusted, and each input amount may be adjusted according to the reaction environment, thereby minimizing side reactions.

In an exemplary embodiment of the present invention, the first continuous reactor may include first to Nth reactant inlets (N is a positive integer of 1 to 10).

In an exemplary embodiment of the present invention, the first continuous reactor includes one or more reactant inlets, and the nickel complex precursor and ligand may be supplied through the same or different reactant inlets.

In an exemplary embodiment of the present invention, the first continuous reactor may include one or more reactant inlets, and the nickel complex precursor and the ligand may be supplied through the same reactant inlet.

In one embodiment of the present invention, the nickel complex precursor and the ligand may be supplied in the form of a solution containing them, respectively.

In one embodiment of the present invention, the solvent may be a hydrocarbon solvent, for example, linear hydrocarbon compounds such as pentane, hexane and octane; its derivatives having double branches; cyclic hydrocarbon compounds such as cyclohexane and cycloheptane; aromatic hydrocarbon compounds such as benzene, toluene and xylene; and linear and cyclic ethers such as dimethyl ether, diethyl ether, anisole and tetrahydrofuran; It may be at least one selected from amide solvents of dimethylacetamide and dimethylformamide (hereinafter, DMF). Specifically, the organic solvent may be cyclohexane, hexane, tetrahydrofuran diethyl ether or dimethylformamide.

In one embodiment of the present invention, the nickel complex precursor and the ligand may be supplied in the form of a composition dissolved in a solvent, respectively, and the composition may include 0.1 to 35 wt% of the nickel complex precursor and the ligand, respectively .

In one embodiment of the present invention, the supply rates of the nickel complex precursor and the ligand are the same or different from each other, and each is 0.1 g/min to 500 g/min, preferably 0.2 g/min to 200 g/min. can The feed rate may be regulated via a mass flow controller (MFC) or a pump. Within the above-described range, there is an effect of minimizing side reactions without a sudden change in the amount of material injected into each reactant inlet. The weight (g) of the feed rate is the nickel complex precursor and the ligand itself; Or it may be the total weight of the solution containing them.

In an exemplary embodiment of the present invention, the molar ratio of the nickel complex precursor and the ligand may be 1:10 to 10:1, preferably 1:5 to 5:1, more preferably 1:0.9 to 0.9 It can be :1. In the above range, the reaction of the nickel complex precursor and the ligand may occur smoothly, and the nickel complex precursor and the ligand may react with the same equivalent. Specifically, when Ni(COD)2 is used as the nickel complex precursor and BPD is used as a ligand, a mixture of Ni(COD) ₂ , Ni(BPD) ₂ , Ni(COD)(BPD), etc. is produced. Among them, since Ni(COD)(BPD) has the best activity, it is preferable to adjust the molar ratio of the nickel complex precursor and the ligand to the above range in order to prepare it.

In an exemplary embodiment of the present invention, the first continuous reactor may be maintained at a temperature of -78 °C to 70 °C and a pressure of 1 bar to 10 bar. When adjusted to the above range, it is possible to control the exothermic reaction during the preparation of the nickel complex, and to easily control the reaction rate. The temperature may be achieved through a pre-temperature coil and a constant-T bath provided in the continuous reactor. The pressure may be achieved by controlling the flow rate and feed rate of the reactants introduced into the reactor. Specifically, it can be controlled using a back pressure regulator (BPR).

In one embodiment of the present invention, the continuous reactor may include a constant-temperature maintenance device (Constant-T bath). Through this, it is possible to control the desired temperature range during the reaction in the continuous reactor.

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 sum of the total time the materials stay in the reactor from the time the reactants are introduced into the introduction part of the first continuous reactor until the polymer prepared in the second continuous reactor is derived.

In one embodiment of the present invention, the first continuous reactor may be an inert environment. Methods of creating an inert environment include a method of removing moisture and oxygen inside the reactor before supplying the reactants to the reactor, and a method of supplying an inert gas into the reactor before supplying the reactants. Examples of the inert gas include argon (Ar) or nitrogen (N ₂ ).

In an exemplary embodiment of the present invention, the first continuous reactor may include an inert gas in a molar concentration of 99% or more. In this case, it is possible to secure high yield and reproducibility by minimizing the inactivation of the nickel complex precursor, which is sensitive to oxygen and moisture.

In an exemplary embodiment of the present invention, the method may further include mixing the nickel complex and the monomer. In this case, it is possible to reduce the generation of unreacted substances by increasing the mixing rate of the materials, to improve the heat removal effect, and consequently to improve the conversion rate. In addition, after mixing the nickel complex and the monomer, it may be supplied to one reactant inlet.

In an exemplary embodiment of the present invention, mixing the nickel complex and the monomer may be performed for 1 minute to 300 minutes. At this time, since the polymerization reaction may be started at the same time as the nickel complex and the monomer are mixed, the time period of 1 minute to 300 minutes may mean the total time for mixing and polymerization reaction.

In one embodiment of the present invention, the supply rate of the nickel complex; and feed rates of the monomers may be the same or different from each other and may be 0.5 g/min to 500 g/min, respectively. The weight (g) of the feed rate is the nickel complex or the monomer composition itself; Or it may be the total weight of the solution containing them.

The feed rate may be regulated via a separately connected mass flow controller (MFC). Within the above-described range, there is an effect of minimizing side reactions without a sudden change in the amount of material injected into each reactant inlet.

In one embodiment of the present invention, the polymerization may be carried out under an inert environment. Specifically, it is possible to create an inert environment inside the reactor, and there is an effect of preventing side reactions or explosions from occurring. The content of the inert gas is the same as described above.

In one embodiment of the present invention, each continuous reactor may include a heat removal device, and the heat removal device may be connected in advance to each continuous reactor. The reaction occurring in each continuous reactor is an exothermic reaction, and the reaction may proceed in a thermostat to quickly control the reaction heat generated at this time. Specifically, a pre-temperature coil may be installed at the front end of each reactor, and the length may be adjusted to achieve thermal equilibrium according to the flow rate.

In one embodiment of the present invention, the monomer is a base monomer; and an end-capping monomer.

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

In an exemplary embodiment of the present invention, the composition including the monomer may include 0.1 to 35% by weight of the monomer.

In an exemplary embodiment of the present invention, the "polymerization reaction" is a reaction in which the nickel complex acts as a catalyst and the monomers are polymerized with each other. In this case, a reaction may occur in which the terminal group of the monomer is replaced by the end-capping monomer.

In an exemplary embodiment of the present invention, the polymerization reaction may be a Yamamoto polymerization reaction. In the Yamamoto reaction, polymerization is performed in such a way that nickel atoms of the nickel complex catalyst are inserted between monomers, and a specific polymerization method is described in [T. Yamamoto, "Electrically Conducting And Thermally Stable π-Conjugated Poly(arylene)s Prepared by Organometallic Processes", Progress in Polymer Science 1993, 17, 1153-1205].

In the present invention, the "base monomer" is a raw material for polymerization to form a polymer. Monomers are chemically bound to other monomers to form chains. As such, each monomer can be considered as having two or more "functional groups" (ie, positions at which the monomer is chemically bonded to the other monomer). By chemically bonding each end of a monomer to another monomer, a chain of monomers is formed to form a polymer. The monomer may have two or more positions as described above, and in this case, a polymer having a branched chain may be prepared.

When the monomer is polymerized, a polymer comprising repeating units is formed. The polymer is preferably described, for example, in Adv. Mater. 2000 12(23) 1737-1750] and its citations. Exemplary first repeating units include those described in J. Appl. Phys. 1996, 79, 934; fluorene repeat units as disclosed in European Patent No. 0842208; indenofluorene repeat units as disclosed, for example, in Macromolecules 2000, 33(6), 2016-2020; and spirofluorene repeat units as disclosed in European Patent No. 0707020. Each of these repeating units is optionally substituted. Examples of substituents include soluble groups such as C1-20 alkyl or alkoxy; electron withdrawing groups such as fluorine, nitro or cyano; and substituents that increase the glass transition temperature (Tg) of the polymer.

The base monomer may include a leaving group, and the leaving group may be a halogen group such as F, Cl, Br or I.

The base monomer may be a monomer represented by Formula 1 below.

[Formula 1]

In Formula 1, R 1 　 and R 2 are hydrogen; optionally substituted alkyl wherein one or more non-neighboring carbon atoms may be replaced by O, S, N, C=O or -COO-; independently selected from the group consisting of alkoxy, aryl, arylalkyl, heteroaryl and heteroarylalkyl. More preferably, at least one of R1 and R2 is an optionally substituted C4-C20alkyl or aryl group.

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

In an exemplary embodiment of the present invention, the end-capper may be a monofunctional unit having one attachment point.

In one embodiment of the present invention, the end-capping monomer (end-capper) may include a crosslinking group or a deuterated crosslinking group.

In one embodiment of the present invention, the end-capping monomer (end-capper) may include a hydrocarbon aryl group or a deuterated hydrocarbon aryl group.

In one embodiment of the present invention, the end-capper is selected from the group consisting of phenyl, biphenyl, diphenylamino, substituted derivatives thereof, and deuterated analogs thereof. In some embodiments, the substituent can be a C 1-10 alkyl group, a crosslinking group, or a deuterated derivative thereof.

In one embodiment of the present invention, the end-capping monomer (end-capper) may have the following structure.

In one embodiment of the present invention, the coefficient of variation (CV) of at least one of the yield, number average molecular weight (Mn) and weight average molecular weight (Mw) of the polymer prepared by the polymerization reaction of the method for preparing the polymer is 5% Hereinafter, it may be 4% or less. The coefficient of variation (CV) may be calculated by calculating the standard deviation value and the average value of each property, and then dividing the standard deviation value by the average value.

Specifically, the coefficient of variation (CV) of the yield of the polymer may be 5% or less, 4% or less, or 3% or less.

The coefficient of variation (CV) of the number average molecular weight (Mn) of the polymer may be 5% or less or 4% or less.

The coefficient of variation (CV) of the weight average molecular weight (Mw) of the polymer may be 5% or less.

The yield, number average molecular weight and weight average molecular weight of the polymer can be calculated by measuring and calculating the corresponding physical property values of the formula below, and the following physical property values can be calculated by a method generally used in the field to which this technology belongs. . For example, it can be calculated using a gas chromatography (GC) or gel permeation chromatography (GPC) method of the polymer.

[Number average molecular weight]

[Weight Average Molecular Weight]

(N _i : number of moles of polymer molecules, M _i : molecular weight of polymer, w _i : polymer weight)

Hereinafter, the present invention will be described in more detail through Examples and Comparative Examples. However, this is intended to help the understanding of the present invention and is not intended to limit the scope.

Example 1

A polymer was prepared according to the procedure below.

In the first pressure vessel, a toluene solvent was added so that the concentrations of the nickel complex precursor Ni(COD) ₂ {Bis(1,5-cyclooctadiene)nickel(0)} and the catalyst stabilizer COD (cyclooctadiene) were 3.5 wt% and 1.37 wt%, respectively. And dissolved to prepare a nickel complex precursor solution.

Ligand composition was prepared by adding and dissolving ligand 2,2'-bipyridyl in a solvent dimethylformamide (DMF) to a concentration of 3.25 wt% in a second pressure vessel.

In the third pressure vessel, 12.4 g of 9,9-dioctyl-2,7-dibromofluorene and 0.4 g of bromobenzene as monomers were mixed with 987.2 g of toluene. A monomer composition was prepared by inputting and stirring to the .

All process lines were maintained at 60 degrees Celsius using a thermostat, and the pressure of each pressure vessel was adjusted to normal pressure.

The nickel complex precursor solution in the first pressure vessel and the ligand composition in the second pressure vessel were each flowed into the first continuous reactor (Plug Flow Reactor: PFR) at a feed rate of 2.5 g/min to prepare a nickel complex, It was fed to a second continuous stirred tank reactor (CSTR). At this time, the first continuous reactor and the second continuous reactor were continuously connected with a process line so that the raw material supply and product discharge of each reactor were performed simultaneously, and the first continuous reactor maintained an inert environment.

Then, the monomer composition was flowed from the third pressure vessel to the second continuous reactor at a feed rate of 10 g/min, and the nickel complex supplied from the first continuous reactor reacted with the monomer to induce a Yamamoto coupling reaction.

After completion of the coupling reaction, it was aged in a second continuous stirred tank reactor (CSTR) for 60 minutes, and the final polymer was discharged out of the reactor.

Then, the solution containing the final polymer was cooled to room temperature, and dropped into a quenching solution with stirring. The obtained polymer sample was completely quenched by stirring for 2 hours, and then filtered to obtain only the solid component and analyzed by GPC.

Example 2

In a third pressure vessel, 4.6 g of 4,4'-Dibromotriphenylamine, 1,4-dibromo-2,5-dihexylbenzene (1,4-Dibromo-2, A polymer was prepared in the same manner as in Example 1, except that 4.6 g of 5-dihexylbenzene) and 0.4 g of bromobenzene were added to 990.4 g of toluene and stirred to prepare a monomer composition.

Example 3

A polymer was prepared in the same manner as in Example 1, except that the type of the second continuous reactor was changed to a semi-batch reactor.

Example 4

In a third pressure vessel, 4.6 g of 4,4'-dibromotriphenylamine as a monomer, 1,4-dibromo-2,5-dihexylbenzene (1,4-Dibromo- 2,5-dihexylbenzene) 4.6 g and bromobenzene 0.4 g were added to 990.4 g of toluene and stirred to prepare a monomer composition, and the type of the second continuous reactor was changed to a semi-batch reactor A polymer was prepared in the same manner as in Example 1 except for the above.

Comparative Example 1

1.4 g of nickel complex precursor Ni(COD) ₂ was dissolved in 35 g of toluene and added to a 200 ml Schlenk flask, and 0.56 g of cyclooctadiene was additionally added to prepare a nickel complex precursor composition. At this time, the preparation was performed in a glove box.

0.82 g of ligand 2,2'-bipyridyl (2,2'-Bipyridyl) was placed in a 25 ml Schlenk flask, dried under vacuum, and then 10 g of anhydrous DMF was additionally added to prepare a ligand composition.

1.3 g of 9,9-dioctyl-2,7-dibromobenzene (9,9-Dioctyl-2,7-dibromofluorene) and 0.04 g of bromobenzene were placed in a 25 ml Schlenk flask, dried under vacuum, and 8 g of anhydrous toluene was additionally added. A monomer composition was prepared.

After immersing the flask containing the nickel complex precursor composition in an oil bath at 60° C., stirring was started at 300 rpm, and the ligand composition was extracted with a syringe and put into the flask.

The monomer composition was extracted with a syringe and put into the flask. After adding all the reactants, polymerization was performed for 60 minutes to prepare a polymer.

Comparative Example 2

1.4 g of nickel complex precursor Ni(COD) ₂ was dissolved in 35 g of toluene and added to a 200 ml Schlenk flask, and 0.56 g of cyclooctadiene was additionally added to prepare a nickel complex precursor composition. At this time, the preparation was performed in a glove box.

0.82 g of ligand 2,2'-bipyridyl (2,2'-Bipyridyl) was placed in a 25 ml Schlenk flask, dried under vacuum, and then 10 g of anhydrous DMF was additionally added to prepare a ligand composition.

4,4'-dibromotriphenylamine (4,4'-Dibromotriphenylamine) 0.48g, 1,4-dibromo-2,5-dihexylbenzene (1,4-Dibromo-2,5-dihexylbenzene) 0.48 g and 0.042 g of bromobenzene were placed in a 25 ml Schlenk flask, dried under vacuum, and 8 g of anhydrous toluene was further added to prepare a monomer composition.

After immersing the flask containing the nickel complex precursor composition in an oil bath at 60° C., stirring was started at 300 rpm, and the ligand composition was extracted with a syringe and put into the flask.

The monomer composition was extracted with a syringe and put into the oil bath. After adding all the reactants, polymerization was performed for 60 minutes to prepare a polymer.

Experimental example

The number average molecular weight (Mn), weight average molecular weight (Mw), dispersion (PDI: value obtained by dividing Mw by Mn) and yield of the polymers prepared in Examples and Comparative Examples were measured and shown in Table 1 below. In each Example and Comparative Example, the experiment was repeated 3 times (A to C) under the same conditions, and the number average molecular weight (Mn) of the prepared polymer using the PS calibration GPC method (equipment used: Agilent's 1200 series) , weight average molecular weight (Mw), and dispersion (PDI: the value obtained by dividing Mw by Mn) were measured, and the yield was calculated using the formula below.

[formula]

Polymer Yield (%) = Total weight of the prepared polymer (g) / Total weight of monomers added to the reactor (g)

A coefficient of variation (CV) was calculated for the calculated Mn, Mw, PDI and yield, respectively, and is shown in Tables 1 and 2 below. The coefficient of variation means a value obtained by dividing the standard deviation by the average value after calculating the standard deviation and the average value for the values derived in each process.

Mn (g/mol) Mw (g/mol) PDI Polymer Yield (%) measurement process Example 1 Example 3 Comparative Example 1 Example 1 Example 3 Comparative Example 1 Example 1 Example 3 Comparative Example 1 Example 1 Example 3 Comparative Example 1 A 8,552 24,031 11,672 24,031 28,522 35,320 2.81 2.85 3.02 95 93 70 B 8,816 24,420 7,657 24,420 28,715 24,355 2.77 2.84 3.18 96 96 81 C 8,147 22,974 8,321 22,974 29,213 29,123 2.82 2.87 3.50 92 95 75 Average 8,505 23,808 9,217 23,808 28,817 29,599 2.8 2.85 3.23 94 95 75 CV (%) 3.9 3.1 23.3 3.1 1.2 18.5 0.9 0.5 7.5 2.2 1.6 7.3

Mn (g/mol) Mw (g/mol) PDI Polymer Yield (%) Measurement process (h) Example 2 Example 4 Comparative Example 2 Example 2 Example 4 Comparative Example 2 Example 2 Example 4 Comparative Example 2 Example 2 Example 4 Comparative Example 2 A 3,597 4,012 3,683 8,849 10,311 11,260 2.46 2.57 3.06 88 89 72 B 3,431 4,277 3,376 8,406 10,778 8,361 2.45 2.52 2.48 90 86 70 C 3,356 4,348 4,416 8,021 11,305 9,505 2.39 2.6 2.29 89 87 75 Average 3,461 4,212 3,825 8,425 10,798 9,709 2.43 2.56 2.61 89 87 72 CV (%) 3.56 4.2 13.9 4.9 4.6 15.0 1.5 1.5 15.3 1.1 1.7 3.4

When the polymer was prepared using the continuous process of Examples, the yield was excellent and the coefficient of variation of each evaluation item was low. Through this, it was confirmed that when the polymer was prepared using the continuous process of the example, the reproducibility of the physical properties of the polymer was excellent.

On the other hand, when the polymer was prepared through the batch process of Comparative Example, the yield was low and the coefficient of variation of each evaluation item was high. Through this, it was confirmed that when the polymer was prepared using the batch process of the comparative example, the reproducibility of the physical properties of the polymer was low.

Through the above results, when the continuous process of the present invention is applied instead of the conventional batch method, it can be confirmed that the polymer yield is increased and the reproducibility of physical properties is greatly improved.

Claims (12)

continuously supplying the nickel complex precursor to the first continuous reactor;
supplying a ligand to the first continuous reactor;
preparing a nickel complex by reacting the nickel complex precursor and a ligand;
continuously supplying the nickel complex to a second continuous reactor;
continuously supplying monomers to the second continuous reactor; and
Including the step of proceeding the polymerization reaction,
Any one or more of the first continuous reactor and the second continuous reactor is a continuous stirred tank reactor (Continuous Stirred Tank Reactor) or a semi-batch reactor. The method according to claim 1,
The method for producing a polymer in which the first continuous reactor and the second continuous reactor are continuously connected to each other. The method according to claim 1,
the first continuous reactor is a plug flow reactor,
The method for producing a polymer wherein the second continuous reactor is a continuous stirred tank reactor (Continuous Stirred Tank Reactor) or a semi-batch reactor. The method according to claim 1,
A method for producing a polymer in which raw material supply and product discharge of each reactor are performed simultaneously. The method according to claim 1,
The step of preparing a nickel complex by reacting the nickel complex precursor and a ligand
Method for producing a polymer further comprising the step of mixing the nickel complex precursor and the ligand. The method according to claim 1,
wherein the first continuous reactor comprises one or more reactant inlets;
The method for producing a polymer wherein the nickel complex precursor and the ligand are respectively supplied to the reactant inlet. The method according to claim 1,
The method for producing a polymer wherein the nickel complex precursor and the ligand are each supplied in the form of a solution containing the same. The method according to claim 1,
The supply rate of the nickel complex precursor and the ligand is the same or different from each other, each of 0.1 g / min to 500 g / min Method of producing a polymer. The method according to claim 1,
Wherein the first continuous reactor is an inert environment. The method according to claim 1,
the feed rate of the nickel complex; and
The feed rate of the monomers is the same as or different from each other and each is 0.5 g/min to 500 g/min. The method according to claim 1,
The polymerization reaction is a method for producing a polymer using Yamamoto polymerization. The method according to claim 1,
A method for producing a polymer 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 polymer prepared by the polymerization reaction is 5% or less.

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