Manufacturing method for polymer

Abstract

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

Description

Technology Field

[0001] The present invention relates to a method for manufacturing a polymer. Background Technology

[0002] Polymers used as hole transport materials are core materials for organic light-emitting diodes, and the characteristics of hole transport materials are determined by the characteristics, properties, and composition of the monomers used in the manufacture of the polymers.

[0003] In addition, polymers are required to possess process characteristics such as reproducibility, which enables the production of a consistent product regardless of the number of reactions or the scale of the reaction. However, achieving such reproducibility is practically difficult in conventional batch reaction manufacturing processes.

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

[0005] KR 10-1244509 B1 The problem to be solved

[0006] The present invention relates to a method for manufacturing a polymer. means of solving the problem

[0007] One embodiment of the present invention comprises the step of supplying a monomer mixture comprising a monomer having one or more arylamine groups and a monomer linkage to a continuous reactor;

[0008] A step of carrying out a polymerization reaction in the above-mentioned continuous reactor; and

[0009] A method for manufacturing a polymer is provided, comprising the step of discharging a product from the continuous reactor while the polymerization reaction proceeds. Effects of the invention

[0010] By using the method for manufacturing a polymer according to one embodiment of the present invention, the yield can be improved under a stable process environment by using a continuous process, and product quality variation can be minimized, which has the advantage of being easy for mass production. Brief explanation of the drawing

[0011] Figure 1 shows the process diagrams of Examples 1 to 15. Figure 2 shows the process diagrams of Examples 16 and 17. Figure 3 shows the process diagrams of Comparative Examples 1 and 2. Specific details for implementing the invention

[0012] The present specification will be described in detail below.

[0013] Examples of substituents in this specification are described below, but are not limited thereto.

[0014] In this specification represents an attachment site within the polymer, and each can be independently substituted with a halogen group; boronic acid; or pinacol ester group.

[0015] The term "substitution" above means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the substitution site is not limited to the site where the hydrogen atom is substituted, that is, any site where a substituent can be substituted, and in the case of two or more substitutions, the two or more substituents may be the same or different from each other.

[0016] In this specification, the term “substituted or unsubstituted” means that it is substituted with one or more substituents selected from the group consisting of deuterium; halogen group; cyano group (-CN); nitro group; hydroxyl group; silyl group; boron group; alkyl group; alkenyl group; alkynyl group; alkoxy group; alkylthio group; aryloxy group; arylthio group; cycloalkyl group; aryl group; amine group; and heterocyclic group, or that two or more of the exemplified substituents are substituted with a connected substituent, or that it has no substituents.

[0017] In this specification, the connection of two or more substituents means that the hydrogen of one substituent is replaced by another substituent.

[0018] In the present specification, the connection of three substituents includes not only the connection of (substituent 1)-(substituent 2)-(substituent 3) in succession, but also the connection of (substituent 2) and (substituent 3) to (substituent 1).

[0019] In this specification, "substituted with A or B" includes not only cases where it is substituted with A or B alone, but also cases where it is substituted with both A and B.

[0020] In this specification, “substituted or unsubstituted” means being substituted with one or more substituents selected from the group consisting of deuterium; halogen group; cyano group (-CN); nitro group; hydroxyl group; silyl group; boron group; alkyl group having 1 to 10 carbon atoms; alkenyl group having 2 to 10 carbon atoms; alkynyl group having 2 to 10 carbon atoms; alkoxy group having 1 to 10 carbon atoms; alkylthio group having 1 to 10 carbon atoms; aryloxy group having 6 to 30 carbon atoms; arylthio group having 6 to 30 carbon atoms; cycloalkyl group having 3 to 30 carbon atoms; aryl group having 6 to 30 carbon atoms; amine group; and heterocyclic group having 2 to 30 carbon atoms, being substituted with a substituent connected with two or more groups selected from said group, or having no substituents.

[0021] In this specification, “substituted or unsubstituted” means being substituted with one or more substituents selected from the group consisting of deuterium; halogen group; cyano group (-CN); nitro group; hydroxyl group; silyl group; boron group; alkyl group having 1 to 6 carbon atoms; alkenyl group having 2 to 6 carbon atoms; alkynyl group having 2 to 6 carbon atoms; alkoxy group having 1 to 6 carbon atoms; alkylthio group having 1 to 6 carbon atoms; aryloxy group having 6 to 20 carbon atoms; arylthio group having 6 to 20 carbon atoms; cycloalkyl group having 3 to 20 carbon atoms; aryl group having 6 to 20 carbon atoms; amine group; and heterocyclic group having 2 to 20 carbon atoms, being substituted with a substituent connected with two or more groups selected from said group, or having no substituents.

[0022] Examples of the above substituents are described below, but are not limited thereto.

[0023] In this specification, examples of halogen groups include fluorine (-F), chlorine (-Cl), bromine (-Br), or iodine (-I).

[0024] In this specification, the alkyl group comprises a straight chain or a branched chain, and the number of carbon atoms is not particularly limited but is 1 to 60, 1 to 30, or 1 to 20. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, etc. The alkyl group may be a straight chain or a branched chain, and according to one example, the propyl group comprises an n-propyl group and an isopropyl group, and the butyl group comprises an n-butyl group, an isobutyl group, and a tert-butyl group.

[0025] In this specification, the number of carbon atoms in the cycloalkyl group is not particularly limited, but is 3 to 60, 3 to 30, 3 to 20, or 3 to 10. The cycloalkyl group includes not only a single ring but also a double ring such as a bridgehead, a fused ring, or a spiro ring. Specifically, it includes, but is not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and adamantyl groups.

[0026] In this specification, a cycloalkene is a non-aromatic ring group having a double bond within a hydrocarbon ring, and the number of carbon atoms is not particularly limited but is 3 to 60, 3 to 30, 3 to 20, or 3 to 10. A cycloalkene includes not only a single ring but also double rings such as a bridgehead, a fused ring, and a spiro ring. Examples of the cycloalkene include, but are not limited to, cyclopropene, cyclobutene, cyclopentene, and cyclohexene.

[0027] In this specification, the alkoxy group is one in which an aryl group is connected to an oxygen atom, and the alkylthio group is one in which an alkyl group is connected to a sulfur atom; the description of the alkyl group described above may be applied to the alkyl group of the alkoxy group and the alkylthio group.

[0028] In the present specification, the aryl group may be a monocyclic aryl group or a polycyclic aryl group, and the number of carbon atoms is not particularly limited but is 6 to 60, 6 to 30, or 6 to 20. The monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, a quadrphenyl group, etc., but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, triphenyl group, chrysenyl group, fluorenyl group, fluoranthenyl group, triphenylenyl group, etc., but is not limited thereto.

[0029] In the present specification, the 9th carbon atom (C) of the fluorenyl group can be substituted with an alkyl group, an aryl group, etc., and two substituents can bond together to form a spiro structure such as cyclopentane, fluorene, etc.

[0030] In this specification, the substituted aryl group may also include a form in which an aliphatic ring is condensed to the aryl group. For example, a tetrahydronaphthalene group is included in the substituted aryl group.

[0031] In this specification, an aryloxy group is one in which an aryl group is connected to an oxygen atom, and an arylthio group is one in which an aryl group is connected to a sulfur atom; the description of the aryl group described above may be applied to the aryl group of the aryloxy group and the arylthio group. The aryl group of the aryloxy group is the same as the example of the aryl group described above. Specifically, aryloxy groups include phenoxy groups, p-thoryloxy groups, m-thoryloxy groups, 3,5-dimethyl-phenoxy groups, 2,4,6-trimethylphenoxy groups, p-tert-butylphenoxy groups, 3-biphenyloxy groups, 4-biphenyloxy groups, 1-naphthyloxy groups, 2-naphthyloxy groups, 4-methyl-1-naphthyloxy groups, 5-methyl-2-naphthyloxy groups, 1-anthryloxy groups, 2-anthryloxy groups, 9-anthryloxy groups, 1-phenanthryloxy groups, 3-phenanthryloxy groups, 9-phenanthryloxy groups, etc., and arylthioxy groups include phenylthioxy groups, 2-methylphenylthioxy groups, 4-tert-butylphenylthioxy groups, etc., but are not limited thereto.

[0032] In the present specification, the silyl group may be represented by the chemical formula -SiYaYbYc, and Ya, Yb, and Yc may each be hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; or a substituted or unsubstituted aryl group. Specifically, the silyl group may be a trimethylsilyl group, a triethylsilyl group, a tert-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a dimethylphenylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, etc., but is not limited thereto.

[0033] In the present specification, the boron group may be represented by the chemical formula -BYdYe, and Yd and Ye may each be hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; or a substituted or unsubstituted aryl group. Specifically, the silyl group may be a dimethylboron group, a diethylboron group, a tert-butylmethylboron group, a vinylmethylboron group, a propylmethylboron group, a methylphenylboron group, a diphenylboron group, a phenylboron group, etc., but is not limited thereto.

[0034] In this specification, the amine group may be represented as -NRaRb, wherein Ra and Rb may each be hydrogen; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, but are not limited thereto. Depending on the type of substituent (Ra, Rb) to which the amine group is bonded, the amine group may be selected from the group consisting of an alkylamine group, an alkylarylamine group, an arylamine group, a heteroarylamine group, an alkylheteroarylamine group, and an arylheteroarylamine group.

[0035] In this specification, an alkylamine group refers to an amine group substituted with an alkyl group, and the number of carbon atoms is not particularly limited but may be 1 to 40 or 1 to 20. Specific examples of the alkylamine group include, but are not limited to, methylamine, dimethylamine, ethylamine, and diethylamine groups.

[0036] In this specification, examples of arylamine groups include substituted or unsubstituted monoarylamine groups, substituted or unsubstituted diarylamine groups, or substituted or unsubstituted arylheteroarylamine groups. The aryl group among the arylamine groups may be a monocyclic or polycyclic aryl group. Specific examples of the arylamine groups include, but are not limited to, phenylamine groups, naphthylamine groups, biphenylamine groups, anthracenylamine groups, diphenylamine groups, phenylnaphthylamine groups, bis(tert-butylphenyl)amine groups, etc.

[0037] In this specification, examples of heteroarylamine groups include substituted or unsubstituted monoheteroarylamine groups, substituted or unsubstituted diheteroarylamine groups, or substituted or unsubstituted arylheteroarylamine groups.

[0038] In this specification, an aryl heteroarylamine group refers to an amine group substituted with an aryl group and a heteroaryl group, and the descriptions regarding the aryl group described above and the heteroaryl group described below may be applied.

[0039] In this specification, the heterocyclic group is a ring group comprising one or more of the heteroatoms N, O, S, and Si, and the number of carbon atoms is not particularly limited but is 2 to 60 or 2 to 30. Examples of the heterocyclic group include, but are not limited to, a pyridyl group; a quinoline group; a thiophene group; a dibenzothiophen group; a furan group; a dibenzofuran group; a naphthobenzofuran group; a carbazole group; a benzocarbazole group; a naphthobenzothiophen group; a hexahydrocarbazole group; a diacridine group; a dihydrodibenzoazacilline group; a phenoxazine group; a phenothiazine group; a dihydrodibenzoazacilline group; a spiro(dibenzosilol-dibenzoazacilline) group; a spiro(acridine-fluorene) group.

[0040] In this specification, the description of the aforementioned heterocyclic group may apply, except that the heteroaryl group is aromatic.

[0041] In this specification, "adjacent" may mean a substituent substituted on an atom directly connected to the atom on which the substituent is substituted, a substituent located stereostructively close to the substituent, or another substituent substituted on the atom on which the substituent is substituted.

[0042] In this specification, "a ring formed by the combination of adjacent groups" means a hydrocarbon ring; or a hetero ring.

[0043] In this specification, "a five- or six-membered ring formed by combining adjacent groups" means that the ring containing the substituents participating in the ring formation is five- or six-membered. It may include the condensation of an additional ring to the ring containing the substituents participating in the ring formation.

[0044] In this specification, the hydrocarbon ring may be an aromatic, aliphatic, or an aromatic-aliphatic condensation ring, and the description of the aryl group described above may apply to the aromatic hydrocarbon ring except that it is not monovalent, and the description of the cycloalkyl group described above may apply to the aliphatic hydrocarbon ring except that it is not monovalent. Examples of aromatic-aliphatic condensation rings include, but are not limited to, 1,2,3,4-tetrahydronaphthalene groups, 2,3-dihydro-1H-indene groups, etc.

[0045] In this specification, the description of the heterocycle may apply except that the heterocycle is not monovalent.

[0046] In this specification, an aromatic hydrocarbon ring refers to a ring in which pi electrons are completely conjugated and it is planar, and the description of the aryl group described above may apply except that it is a divalent group.

[0047] In this specification, an aliphatic hydrocarbon ring refers to any hydrocarbon ring excluding an aromatic hydrocarbon ring, and may include a cycloalkyl ring. Except for the cycloalkyl ring being a divalent group, the description of the cycloalkyl group described above may apply. Substituted aliphatic hydrocarbon rings also include aliphatic hydrocarbon rings to which an aromatic ring is condensed.

[0048] In this specification, the description of the aryl group described above may apply except that the arylene group is a divalent group.

[0049] In this specification, the description of the cycloalkyl group described above may apply except that the cycloalkylene group is a divalent group.

[0050] In this specification, the term "polymer" is intended to mean a material having at least one repeating monomer unit. This term includes homopolymers having only one type of monomer unit, and copolymers having two or more different monomer units. A copolymer is a subset of polymers.

[0051] In this specification, a "continuous reactor" is a reactor that carries out a reaction while continuously feeding the reactants used in the reaction, wherein the supply of reactants and the discharge of products can be performed simultaneously. The type of reactor is not particularly limited, and examples include a Fed-batch reactor, a PFR reactor, and a CSTR reactor. The meaning of "performed simultaneously" is that the supply of raw materials and the discharge of products are performed simultaneously without any separate storage time.

[0052] When using conventional batch reactors, it is difficult to establish an inert environment, which poses a problem of increased risk of accidents due to highly flammable reactants. However, when the nickel complex precursor is manufactured in a continuous reactor, it is easy to establish an inert environment inside the reactor, thus offering the advantage of improved stability even when using highly flammable reactants.

[0053] In one embodiment of the present invention, the method for manufacturing the polymer may be carried out under an inert gas. Methods for creating an inert environment include removing moisture and oxygen from inside the reactor before supplying the reactants to the reactor, and supplying an inert gas to the reactor before supplying the reactants. Examples of the inert gas include argon (Ar) or nitrogen (N2).

[0054] One embodiment of the present invention provides a method for producing a polymer comprising the steps of: supplying a monomer comprising one or more arylamine groups; a monomer linker; and an end-capper to a continuous reactor; carrying out a polymerization reaction in the continuous reactor; and discharging a product from the continuous reactor while the polymerization reaction is carried out.

[0055] A method for manufacturing a polymer according to one embodiment of the present invention relates to a method for manufacturing a polymer by polymerizing a monomer containing one or more arylamine groups with a monomer linker and / or an end-capper. The monomer containing the arylamine groups is a material used as a raw material for polymerizing a hole transfer material for an organic light-emitting diode (OLED) and contains one or more arylamine groups.

[0056] According to a method for manufacturing a polymer according to one embodiment of the present invention, the reaction time can be determined by the size of the reactor and the time for the input of raw materials and the transfer of the product, and the reaction rate and the molecular weight of the final polymer can be controlled by adjusting the concentration of raw materials, the input rate, and the temperature or pressure inside the reactor. In the present invention, a series of processes leading from the input of raw materials to the polymerization reaction and the discharge of the product is performed continuously. By utilizing such a continuous process, the capacity of the reactor can be significantly reduced compared to conventional one-time reactions, reaction conditions can be easily controlled, and a constant reaction environment can be maintained. Furthermore, by inputting reaction raw materials at a constant ratio, a product with a constant composition can always be synthesized, thereby eliminating product variation even when producing large quantities.

[0057] In one embodiment of the present invention, the method may include a step of discharging a product from the continuous reactor while the polymerization reaction is in progress. That is, the polymerization reaction and the discharge of the product may be performed continuously as a series of processes.

[0058] In one embodiment of the present invention, the monomer mixture is supplied to a continuous reactor in the form of a monomer comprising one or more arylamine groups and a monomer linkage.

[0059] In one embodiment of the present invention, the monomer mixture may be fed into a continuous reactor at a constant rate, and a certain amount of monomers may be supplied to the reactor first and then the reaction may proceed.

[0060] In one embodiment of the present invention, the continuous reactor comprises a first continuous channel and a second continuous channel, and the monomer mixture may be continuously supplied to one or more of the first continuous channel and the second continuous channel. The continuous channel is configured to introduce reaction materials into the continuous reactor. The continuous channel may refer to an input section (or injection section) for controlling the input amount of each raw material within the continuous reactor. At this time, the input amount of the raw material injected into each reactant inlet may be controlled, and the input amount may be controlled according to the reaction environment, thereby minimizing side reactions.

[0061] In one embodiment of the present invention, the monomer mixture may be supplied to the first continuous channel, and an additive may be supplied to the second continuous channel.

[0062] In one embodiment of the present invention, the monomer mixture may be supplied to the first continuous channel, and the ligand composition may be supplied to the second continuous channel.

[0063] In one embodiment of the present invention, the monomer mixture may be supplied to the first continuous channel, and the catalyst composition may be supplied to the second continuous channel.

[0064] In one embodiment of the present invention, the monomer may be supplied in the form of a solution dissolved in a solvent. The solution may be a solution in which the monomer and a separate solvent are mixed together, and a method may be used to prepare a solution containing each monomer and supply the solution to a continuous reactor. Specifically, the monomer and the solvent may be stored in a pressure vessel connected to a continuous reactor, and then the solution may be supplied from the pressure vessel. At this time, the solution may be supplied using a mass flow controller (MFC) or a pump connected to the pressure vessel.

[0065] In one embodiment of the present invention, the monomer is supplied in the form of a solution dissolved in a solvent, and the monomer may be dissolved at a concentration of 1 to 10 parts by weight or 1 to 8 parts by weight relative to 100 parts by weight of the solvent. By controlling to the above range, the reaction rate can be maintained constant.

[0066] In one embodiment of the present invention, the feed rate of the monomer may be 0.1 g / min to 1,000 g / min, 0.1 g / min to 700 g / min, or 0.1 g / min to 400 g / min. Within the above-described range, side reactions can be minimized without abrupt changes in the amount of material injected into each continuous channel, and mass production is possible. The feed rate can be controlled via a mass flow controller (MFC) or a pump. Within the above-described range, there is an effect of minimizing side reactions without abrupt changes in the amount of material injected into each reactant inlet.

[0067] In one embodiment of the present invention, the solvent comprises: polar solvents such as DMF (N,N-dimethylformamide), DMSO (dimethyl sulfoxide), DMAc (N,N-dimethylacetamide), and NMP (N-methyl-2-pyrrolidone); ethers such as Et2O (diethyl ether), i-Pr2O (diisopropyl ether), TBME (methyl tert-butyl ether), CPME (cyclopentylmethyl ether), THF (tetrahydrofuran), and dioxane; aliphatic hydrocarbons such as pentane, hexane, heptane, and petroleum ether; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, and nitrobenzene; and halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, and dichloroethane. Lower fatty acid esters such as methyl acetate, ethyl acetate, butyl acetate, and methyl propionate; nitrile-based solvents such as acetonitrile, propionitrile, and butyronitrile may be used, and these solvents may be used alone or in a mixture of two or more. Preferably, the solvents are polar solvents such as DMF (N,N-dimethylformamide), DMSO (dimethyl sulfoxide), DMAc (N,N-dimethylacetamide), and NMP (N-methyl-2-pyrrolidone); ethers such as Et2O (diethyl ether), i-Pr2O (diisopropyl ether), TBME (methyl tert-butyl ether), CPME (cyclopentylmethyl ether), THF (tetrahydrofuran), and dioxane; It is an aliphatic hydrocarbon such as pentane, hexane, heptane, petroleum ether, and more preferably DMAc(N,N-dimethylacetamide) or THF(tetrahydrofuran).

[0068] In one embodiment of the present invention, the reaction may be carried out under temperature conditions of 25°C to 200°C, 25°C to 130°C, or 30°C to 120°C and pressure conditions of 1 bar to 20 bar, 1 bar to 10 bar, or 1 bar to 7 bar, within which the reaction rate is excellent and side reactions are minimized. The above temperature can be achieved through a pre-temperature coil and a constant-temperature bath provided in a continuous reactor. The above pressure can be achieved by controlling the flow rate and supply rate of the reaction materials introduced into the reactor. Specifically, it can be controlled using a back pressure regulator (BPR).

[0069] In one embodiment of the present invention, each continuous reactor may include a heat removal device, and the heat removal device may be pre-connected to each continuous reactor. The reaction occurring in each continuous reactor may be an exothermic reaction, and the reaction may be carried out in a constant temperature bath to rapidly control the reaction heat generated. Specifically, a pre-temperature coil may be installed at the front of each reactor, and its length may be adjusted to achieve thermal equilibrium according to the flow rate.

[0070] In one embodiment of the present invention, one or more reactors may be provided and connected to each other so that a product discharged from one reactor is transferred as a raw material to the next reactor to carry out a continuous reaction. That is, the reaction may be further carried out by continuously feeding the product discharged from the reactor into an additional continuous reactor connected in series with said reactor. For example, when synthesizing a polymer that requires a multi-stage reaction, reactors designed for the corresponding reaction stages may be connected in series. The means of connection are not particularly limited and may be connected through pipes used in chemical processes.

[0071] In one embodiment of the present invention, it may be configured to perform the same polymerization reaction simultaneously by including one or more reactors connected in parallel. For example, if the number of reactors produced for the same synthesis is increased by a factor of n and connected in parallel, the amount of product per unit time increases by a factor of n, and the manufacturing time required to produce the same amount decreases to 1 / n. That is, production volume can be increased without other peripheral equipment simply by increasing the number of reactor modules. In addition, since the raw materials are multi-injected, there is an advantage of preventing localized heating that occurs during the reaction in a batch reactor.

[0072] In one embodiment of the present invention, a retention coil may be further provided at the downstream end of the continuous reactor to control the residence time within the continuous reactor. At this time, the residence time may be controlled by adjusting the inner diameter and length of the retention coil.

[0073] In one embodiment of the present invention, the polymerization reaction may be a Suzuki, Yamamoto, Stille, or metal-catalyzed CN coupling reaction. Through this, CC or CN bonds of the polymer are induced.

[0074] In one embodiment of the present invention, the step of controlling the molecular weight of the product discharged from the continuous reactor may be included. The molecular weight of the product may be controlled by adjusting the molar ratio of the monomers, but may also be controlled by using an additional quenching reaction.

[0075] In the following, monomers for manufacturing polymers and polymers manufactured therefrom are described.

[0076] In one embodiment of the present invention, the monomer comprising one or more arylamine groups may be a monomer unit comprising at least one arylamine group.

[0077] In one embodiment of the present invention, the monomer comprising one or more arylamine groups may be represented by the following chemical formula A.

[0078] [Chemical Formula A]

[0079]

[0080] In chemical formula A,

[0081] Ar1 to Ar5 are identical or different from one another and are substituted or unsubstituted aryl groups; or are substituted or unsubstituted heterocyclic groups and combine with adjacent substituents to form substituted or unsubstituted rings, and

[0082] At least one of Ar1 to Ar5 is a substituted or unsubstituted aryl group, and

[0083] represents an attachment site within the polymer, and each can be independently substituted with a halogen group; boronic acid; or pinacol ester group, and

[0084] n1 is an integer from 0 to 10, and if n1 is 2 or greater, Ar3 are identical or different from each other, and

[0085] n2 is an integer greater than or equal to 0, and if n2 is greater than or equal to 2, the substituents within the parentheses are either identical or different.

[0086] In one embodiment of the present invention, Ar1 to Ar5 may be identical or different from each other and may each be a substituted or unsubstituted aryl group.

[0087] In one embodiment of the present invention, Ar1 to Ar5 may be identical or different from each other and may each be a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.

[0088] In one embodiment of the present invention, Ar1 to Ar5 may be identical or different from one another and may each be substituted or unsubstituted phenyl; substituted or unsubstituted biphenyl; or substituted or unsubstituted naphthylene.

[0089] In one embodiment of the present invention, the substituents of Ar1 to Ar5 may be deuterium; a halogen group; or a substituted or unsubstituted alkyl group.

[0090] In one embodiment of the present invention, the substituents of Ar1 to Ar5 may be substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms.

[0091] In one embodiment of the present invention, the substituents of Ar1 to Ar5 may be methyl, ethyl, propyl, isopropyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, or isohexyl.

[0092] In one embodiment of the present invention, the monomer comprising one or more arylamine groups may be represented by the following structural formula.

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099] In one embodiment of the present invention, the monomer linkage may be represented by the following chemical formula B.

[0100] [Chemical Formula B]

[0101]

[0102] In chemical formula B,

[0103] Z is C, Si, Ge, N, or an aromatic ring, and

[0104] Y is a direct bond; a substituted or unsubstituted alkylene group; or a substituted or unsubstituted arylene group, and

[0105] represents an attachment site within the polymer, and each can be independently substituted with a halogen group; boronic acid; or pinacol ester group, and

[0106] s is an integer from 2 to 5, and if it is 2 or greater, Y inside the parentheses are the same or different.

[0107] In one embodiment of the present invention, Y is a direct coupling.

[0108] In one embodiment of the present invention, Y is a substituted or unsubstituted arylene group having 6 to 20 carbon atoms.

[0109] In one embodiment of the present invention, Y is a substituted or unsubstituted phenylene group.

[0110] In one embodiment of the present invention, the monomer linkage can be represented by the following structural formula.

[0111]

[0112]

[0113]

[0114]

[0115]

[0116]

[0117]

[0118]

[0119] In one embodiment of the present invention, the step of supplying an end-capper monomer to the continuous reactor may be further included.

[0120] In one embodiment of the present invention, the end-capper is a monofunctional unit having one bonding site.

[0121] In one embodiment of the present invention, the end-capper is a monofunctional monomer unit.

[0122] In one embodiment of the present invention, the end-capper is a curable group or a deuterated curable group.

[0123] In one embodiment of the present invention, the end-capper monomer is an aryl group or a deuterated aryl group.

[0124] In one embodiment of the present invention, the end-capper is selected from an aryl group; an arylamino group; a curable group; and deuterated analogs thereof.

[0125] In one embodiment of the present invention, the end-capper is selected from the group consisting of a phenyl group; a biphenyl group; a diphenylamino group; substituted derivatives thereof and deuterated analogs thereof. In this case, the substituent is C 1-10 It is an alkyl group, a curing group, or a deuterated analogue thereof.

[0126] In one embodiment of the present invention, the end-capper may be represented by the following structural formula.

[0127]

[0128]

[0129]

[0130]

[0131]

[0132] The above represents an attachment site within the polymer, and each can be independently substituted with a halogen group; boronic acid; or pinacol ester group.

[0133] In one embodiment of the present invention, the step of supplying the transition metal catalyst to the continuous reactor may be further included.

[0134] In one embodiment of the present invention, the transition metal catalyst may be selected from palladium or a palladium compound, nickel or a nickel compound, cobalt or a cobalt compound, and iron or an iron compound.

[0135] In one embodiment of the present invention, the transition metal catalyst may include the transition metal catalyst precursor and the ligand. That is, the transition metal catalyst precursor and the ligand may be supplied together.

[0136] In one embodiment of the present invention, the transition metal catalyst may be one or more compounds comprising palladium in an oxidation state of 0. Here, tetrakis(triarylphosphine)palladium (0), in particular tetrakis(triphenylphosphine)palladium (0) and tetrakis(tri-o-tolylphosphine)palladium (O) and also tris(dibenzylideneacetone)dipalladium (0) (Pd2dba3) or bis(tri-tert-butylphosphine)palladium (O) are preferred.

[0137] In one embodiment of the present invention, the transition metal catalyst may be a compound containing palladium in an oxidation state of +2. Palladium(II) halide, in particular palladium(II) chloride, palladium(II) carboxylate, in particular palladium(II) acetate, dichloro-bis(triphenylphosphine)palladium(II), palladium(II)-β-ketoketonate, in particular palladium(II) acetylacetonate, nitrile palladium(II) halide, in particular dichloro-bis(benzonitrile)palladium(II), allyl palladium halide, olefin palladium halide, in particular dichloro(1,5-cyclooctadiene)palladium(II), or a mixture of two or more of these compounds is preferred. It is also possible for palladium(II) to be reduced to palladium(O) during the reaction.

[0138] In one embodiment of the present invention, the transition metal catalyst may be a nickel compound. Herein, elemental nickel or dispersed or colloidal metallic nickel (supported or unsupported), e.g., nickel sponge, nickel on Kiesselgur, nickel on aluminum oxide, nickel on silica, nickel on carbon, nickel(II)carboxylates, in particular nickel(II)acetate, nickel(II)formate and nickel(II)oxalate, nickel(II)ketoketonates, in particular nickel(II)acetylacetonate, nickel(II)halides, in particular nickel(II)chloride, bromide and iodide, nickel(II)carbonate, nickel(II)nitrate, nickel(II)sulfate or complexes derived therefrom, e.g., olefinic nickel(II)halides, allyl nickel(II)halides, addition compounds of the NiL2(Hal)2 type (wherein Hal is chlorine, bromine, or iodine and L is a non-charged ligand, e.g., ammonia, acetonitrile, propionitrile, or benzonitrile), It is a bis(cyclooctadiene)nickel(O), tetrakis(triphenylphosphine)nickel(O) or additional nickel(O) compound.

[0139] In one embodiment of the present invention, the ligand is a phosphine ligand from the group consisting of triarylphosphine, triheteroarylphosphine, diarylalkylphosphine, diheteroarylalkylphosphine, aryldialkylphosphine, heteroaryldialkylphosphine, or trialkylphosphine, and the substituents on the phosphorus phase may be the same or different and may be chiral or achiral, and one or more substituents may link the phosphorus groups of a plurality of phosphines, and such linkage may also be possible through one or more metal atoms. Additionally, halophosphine, dihalophorpine, alkoxyphosphine, aryloxyphosphine, heteroaryloxyphosphine, diallkoxyphosphine, diaryloxyphosphine, or diheteroaryloxyphosphine may be used. Particularly preferred phosphine ligands are tris(o- or m- or p-tolyl)phosphine, tris(o- or m- or p-anisyl)phosphine, tris(o- or m- or fluorophenyl)phosphine, tris(o- or m- or p-chlorophenyl)phosphine, tris(2,6-dimethylphenyl)phosphine, tris(2,6-dimethoxyphenyl)phosphine, tris(methityl)phosphine, tris(2,4,6-trimethoxyphenyl)phosphine, tris(pentafluorophenyl)phosphine, tert-butyldi-o-tolylphosphine, di-tert-butyl-o-tolylphosphine, dicyclohexyl-2-biphenylphosphine, di-tert-butyl-2-biphenylphosphine, triethylphosphine, triisopropylphosphine, tricyclohexylphosphine, tri-tert-butylphosphine, tri-tert-pentylphosphine, These are bis(di-tert-butylphosphino)methane and 1,1'-bis(di-tert-butylphosphino)ferrocene.

[0140] In one embodiment of the present invention, the step of supplying an additive to the continuous reactor may be further included. For example, a basic substance may be supplied to the continuous reactor to create an environment within the reactor.

[0141] The above basic substance may vary depending on the type of reaction to be induced, and any base known to those skilled in the art suitable for coupling reactions of organic compounds may be used as a base. Preferred bases are organic hydroxides, alkali metal and alkaline earth metal hydroxides, oxides, carboxylates, carbonates, hydrocarbonates, phosphates, hydrophosphates and fluorides, in particular sodium and potassium hydroxides, acetates, carbonates, hydrocarbonates, phosphates and fluorides, or metal alkoxides; while phosphates or carbonates are preferred, organic hydroxides, for example, tetraalkylammonium hydroxides, are also preferred. For anhydrous reactions, heavy alkali metals, particularly preferably cesium, are preferred as counterions due to the better solubility of the corresponding salt in organic solvents. Additional bases that may be used are organic amines, preferably triethylamine, diethylamine, or tri-n-butylamine, or nitrogen-containing, aromatic or non-aromatic heterocyclic bases, preferably pyridine or N-methylpyrrolidone. It is also possible to use a mixture of bases.

[0142] In one embodiment of the present invention, the coefficient of variation (CV) of one or more of the weight-average molecular weight, number-average molecular weight, and yield of the polymer produced according to the method for producing the polymer may be 5% or less, 4% or less, or 3% or less. The coefficient of variation (CV) may be calculated by calculating the standard deviation and average values ​​of the yield of the dimer, and then dividing the standard deviation value by the average value.

[0143] The above weight-average molecular weight (Mw) and number-average molecular weight (Mn) refer to the converted molecular weights for standard polystyrene measured using Gel Permeation Chromatography (GPC).

[0144] The above weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be measured using Gel Permeation Chromatography (GPC) as follows. First, the sample to be analyzed is placed in a 5 mL vial and diluted in Tetrahydrofuran (THF) to a concentration of approximately 1 mg / mL. Then, the standard sample for calibration and the sample to be analyzed are filtered through a syringe filter (pore size = 0.45 μm), and GPC is performed. The analysis program ChemStation from Agilent Technologies can be used, and the weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined by comparing the elution time of the sample with the calibration curve. The measurement conditions for the above GPC may be as follows.

[0145] Device: Agilent Technologies 1200 series

[0146] Column: Used 2 PL gel mixed B units from Polymer Laboratories

[0147] Solvent: THF

[0148] Column temperature: 40℃

[0149] Sample concentration: 1 mg / mL, 100 L injection

[0150] Standard Sample: Polystyrene (Mp: 3900000, 723000, 316500, 52200, 31400, 7200, 3940, 485)

[0151] The above yield refers to the total weight of the monomers polymerized to form a polymer relative to the total weight of the monomers introduced into the reactor, and represents the weight ratio of the produced polymer relative to the total weight of the introduced monomers. For example, when producing a polymer by polymerizing introduced monomer A, a monomer linker, and a terminal-capping monomer, the above yield can be calculated as [{Total weight of polymer) / {Weight of monomer A (g) + Weight of monomer linker (g) + Weight of terminal-capping monomer (g)}} * 100 (%).

[0152] The present invention will be described in more detail below through examples and comparative examples. However, this is intended to aid in understanding the invention and is not intended to limit its scope.

[0154] <Examples 1 to 15 and Comparative Example 1>

[0155] In Examples 1 to 15, polymers were prepared using the Suzuki coupling method. Monomer A and monomer linkages were converted into a polymer in the manner shown in FIG. 1, and then a terminal-capping monomer was added at the end. The terminal-capping monomer is added to remove residual functional groups remaining on the polymer.

[0157] Example 1

[0158]

[0159] Three vacuum-dried 2L stainless steel pressure vessels were prepared. In the first pressure vessel, a monomer solution was prepared by mixing and stirring 0.047 mol of monomer A containing an arylamine group (monomer A1: substituted with Br), 0.021 mol of a monomer linker (monomer B1: substituted with a pinacol ester group), 0.002 mol of catalyst Pd(amphos)Cl2, 0.008 mol of Aliquat 336, and 1L of toluene solvent. The pressure vessel was maintained at a pressure above atmospheric pressure to isolate it from external air.

[0160] A 2.04 wt% Tetramehylammonium Hydroxide solution was injected into the second pressure vessel and maintained at a pressure above atmospheric pressure to isolate it from external air.

[0161] A terminal-capping monomer solution was prepared by mixing and stirring 0.015 mol of terminal-capping monomer (End-capper E1: substituted with pinacol ester groups), 0.01 mol of iodobenzene, and 1 L of toluene solvent in a third pressure vessel. The pressure vessel was maintained at a pressure above atmospheric pressure to isolate it from external air.

[0162] The first pressure vessel was connected to the first continuous channel of the first continuous reactor, the second pressure vessel was connected to the second continuous channel of the first continuous reactor, the outlet of the first continuous channel was connected to the first continuous channel of the second continuous reactor, and the third pressure vessel was connected to the second continuous channel of the second continuous reactor.

[0163] A monomer solution was injected into the first continuous reactor at a rate of 1 g / min, and a tetramehylammonium hydroxide solution was injected at a rate of 1.111 g / min. The reaction was carried out with a residence time of 20 minutes, and the product was supplied to the second continuous reactor.

[0164] The terminal-capping monomer solution was injected into the second continuous reactor at a rate of 1.55 g / min and reacted.

[0165] The entire reactor and reaction line were maintained at 120°C, and the internal pressure was maintained at 8 bar using a backpressure regulator.

[0166] The product discharged after passing through all process lines was dropped into a quenching solution and cooled to room temperature to produce polymer P1.

[0168] Example 2

[0169]

[0170] Polymer P2 was prepared in the same manner as in Example 1, except that Monomer B2 (substituted with pinacol ester groups) was used instead of Monomer B1 as the monomer linker.

[0172] Example 3

[0173]

[0174] Polymer P3 was prepared in the same manner as in Example 1, except that Monomer B3 was used instead of Monomer B1 as the monomer linker. The above PE refers to a pinacol ester group.

[0176] Example 4

[0177]

[0178] Polymer P4 was prepared in the same manner as in Example 1, except that Monomer B4 was used instead of Monomer B1 as the monomer linker. The above PE refers to a pinacol ester group.

[0180] Example 5

[0181]

[0182] Polymer P5 was prepared in the same manner as in Example 1, except that Monomer B5 was used instead of Monomer B1 as the monomer linker. The above PE refers to a pinacol ester group.

[0184] Example 6

[0185]

[0186] Polymer P6 was prepared in the same manner as in Example 1, except that End-capper E2 was used instead of End-capper E1 as the end-capping monomer.

[0188] Example 7

[0189]

[0190] Polymer P7 was prepared in the same manner as in Example 1, except that End-capper E3 was used instead of End-capper E1 as the end-capping monomer.

[0192] Example 8

[0193]

[0194] Polymer P8 was prepared in the same manner as in Example 1, except that End-capper E4 was used instead of End-capper E1 as the end-capping monomer.

[0196] Example 9

[0197]

[0198] Polymer P9 was prepared in the same manner as in Example 1, except that End-capper E5 was used instead of End-capper E1 as the end-capping monomer.

[0200] Example 10

[0201] Polymer P10 was prepared in the same manner as in Example 1, except that monomer A2, in which the terminal group is substituted with bromine, was used instead of monomer A1, which contains an arylamine group.

[0203] Example 11

[0204] Polymer P11 was prepared in the same manner as in Example 1, except that monomer A3, in which the terminal group is substituted with bromine, was used instead of monomer A1, which contains an arylamine group.

[0206] Example 12

[0207] Polymer P12 was prepared in the same manner as in Example 1, except that monomer A4, in which the terminal group is substituted with bromine, was used instead of monomer A1, which contains an arylamine group.

[0209] Example 13

[0210] Polymer P13 was prepared in the same manner as in Example 1, except that monomer A5, in which the terminal group is substituted with bromine, was used instead of monomer A1, which contains an arylamine group.

[0212] Example 14

[0213] Polymer P14 was prepared in the same manner as in Example 1, except that monomer A6 was used instead of monomer A1 as the monomer containing an arylamine group.

[0215] Example 15

[0216]

[0218] Polymer P15 was prepared in the same manner as in Example 1, except that a monomer in which pinacol ester is substituted for Br in monomer A1 containing an arylamine group, and bromine is substituted for pinacol ester groups in the monomer linker and terminal-capping monomer, respectively. The PE above refers to a pinacol ester group.

[0220] Comparative Example 1

[0221] A monomer solution was prepared by adding 0.047 mmol of monomer A containing an arylamine group (monomer A1: substituted with Br), 0.021 mmol of monomer linker (Monomer B1), 0.02 mmol of catalyst Pd(amphos)Cl2, 0.08 mmol of Aliquat 336, and 10 mL of toluene solvent to a pressure reactor and stirring, and internal oxygen was removed through nitrogen bubbling.

[0222] With 120℃ oil circulated in the outer jacket of the pressure reactor, 11g of a 2.04 wt% Tetramehylammonium Hydroxide solution was drawn into the prepared solution using a syringe and the polymerization reaction was carried out for 1 hour.

[0223] A terminal-capping monomer solution was prepared by mixing and stirring 0.6 mmol of terminal-capping monomer (End-capper E1), 0.4 mmol of iodobenzene, and 10 mL of toluene solvent. Internal oxygen was removed through nitrogen bubbling. 3.875 g of the terminal-capping monomer solution was drawn with a syringe and placed into the pressure reactor, after which the polymerization reaction was carried out for 1 hour.

[0224] Polymer A was prepared by dropping the product, upon completion of polymerization, into a quenching solution and cooling it to room temperature.

[0226] <Examples 16, 17 and Comparative Example 2>

[0227] Examples 16 and 17 prepared polymers by the Yamamoto polymerization method as schematically illustrated in FIG. 2, and Comparative Example 2 prepared polymers by the method schematically illustrated in FIG. 3.

[0229] Example 16

[0230]

[0232] Three vacuum-dried 2L stainless steel pressure vessels were prepared. In the first pressure vessel, a monomer composition was prepared by dissolving 6.5 wt% of monomer A containing an arylamine group (monomer A1: substituted with Br), 1.006 wt% of a monomer linker (monomer B1: substituted with Br), and 0.805 wt% of a terminal-capping monomer (end-capper E1: substituted with Br) in toluene solvent.

[0233] A ligand composition was prepared by adding and dissolving ligand 2,2'-Bipyridyl at 5.2 wt% in the solvent DMF in a second pressure vessel.

[0234] A catalyst composition was prepared by introducing and dissolving the nickel compound Ni(COD)2{Bis(1,5-cyclooctadiene)nickel(0)} and the catalyst stabilizer COD into a first pressure vessel at concentrations of 3.5 wt% and 1.37 wt%, respectively, in a toluene solvent.

[0235] The above ligand composition was supplied to the first continuous channel of the first continuous reactor at a rate of 2 g / min, and the above catalyst composition was supplied to the second continuous channel of the first continuous reactor at a rate of 2.9 g / min to react.

[0236] The product discharged from the first continuous reactor was retained in a 1 / 8" Rt coil for 1 minute, and then supplied to the first continuous channel of the second continuous reactor.

[0237] The above monomer composition was supplied to the second continuous channel of the second continuous reactor at a feed rate of 1.12 g / min.

[0238] The product discharged from the second continuous reactor was retained in a 1 / 8" Rt coil for 30 minutes.

[0239] The entire reactor and Rt coil were maintained at 60°C using a constant temperature bath.

[0240] The product discharged after passing through all process lines was dropped into a quenching solution and cooled to room temperature to produce polymer P16.

[0242] Example 17

[0243]

[0245] Polymer P17 was prepared in the same manner as in Example 16, except that monomer B3 was used instead of monomer B1.

[0247] Comparative Example 2

[0248] Weighed nickel compound Ni(COD)2{Bis(1,5-cyclooctadiene)nickel(0)}, catalyst stabilizer, and toluene solvent were placed in a Schlenk flask, and the catalyst was packed so that the concentrations of the nickel compound and catalyst stabilizer were 3.5 wt% and 1.377 wt%, respectively. At this time, since the nickel compound is unstable in air, the process was carried out in a glove box.

[0249] A ligand composition of 3.35 g was prepared by dissolving ligand 2,2'-Bipyridyl in anhydrous DMF at 5.2 wt% in a separate Schlenk flask.

[0250] A monomer composition was prepared by dissolving 6.5 wt% of monomer A (monomer A1) containing an arylamine group, 1.006 wt% of a monomer linker (Monomer B1), and 0.805 wt% of an end-capping monomer (End-capper E1) in toluene. At this time, each monomer was vacuum dried before dissolving in toluene.

[0251] After immersing the Schlenk flask filled with the catalyst in a 60℃ oil bath, stirring was started at 300 rpm, and the ligand composition was drawn with a syringe and added to the Schlenk flask filled with the catalyst. Subsequently, the monomer composition was also added to the Schlenk flask filled with the catalyst.

[0252] Polymer B was prepared by allowing a polymerization time of 60 minutes, removing it to room temperature, dropping it into a quenching solution, and cooling it to room temperature.

[0254] Experimental example

[0255] The yield, Mn, and Mw of the polymers prepared in the above examples and comparative examples were measured and are shown in Tables 1 and 2 below.

[0257] Example 1 Comparative Example 1 Process time (h) Mn (g / mol) Mw (g / mol) transference number(%) Repeated experiment Mn (g / mol) Mw (g / mol) transference number(%) 1.5~2 32,165 151,351 90.1 A 35,897 161,578 83.8 2~2.5 31,787 150,412 89.7 B 28,167 144,021 85 2.5~3 32,215 161,789 91 C 30,191 151,400 82.1 3~3.5 31,10 149,927 91.2 D 25,221 140,657 88 3.5~4 31,652 153,212 90.1 E 32,481 156,784 85.4 CV (%) 1.63 2.86 0.64 CV (%) 8.05 5.14 2.91

[0258] Example 16 Comparative Example 2 Process time (h) Mn (g / mol) Mw (g / mol) transference number(%) Repeated experiment Mn (g / mol) Mw (g / mol) transference number(%) 1.5~2 15,643 58,286 92.8 A 14,876 53,218 88.5 2~2.5 15,872 59,728 90.9 B 16,287 61,347 84.1 2.5~3 14,936 58,019 91.1 C 13,210 55,121 81.7 3~3.5 15,218 57,937 92 D 17,335 68,155 85 3.5~4 15,600 58,443 93 E 14,092 59,110 83.6 CV (%) 2.16 1.11 0.93 CV (%) 9.79 8.81 2.65

[0260] The above yield refers to the ratio (%) of the weight of the produced polymer to the total weight of the monomer introduced into the reactor before polymer purification, and was calculated using the method described in the specification.

[0261] The above Mn and Mw are numerical values ​​obtained through the PS calibration GPC method of the obtained polymer (equipment used: Agilent 1200 series), and the above CV is the coefficient of variation, which represents the value obtained by dividing the mean value by the standard deviation of the polymer yield, Mn, and Mw formed per process recovery. The above molecular weight was measured using Agilent Technologies' 1200 series and the method described in the specification.

[0262] When the polymer was manufactured using the continuous process of the example, the yield was excellent and the coefficient of variation for each evaluation item was low. Through this, it was confirmed that the reproducibility of the polymer's physical properties is excellent when the polymer is manufactured using the continuous process of the example.

[0263] On the other hand, when the polymer was manufactured using the batch process of the comparative example, the yield was low and the coefficient of variation for each evaluation item was high. Through this, it was confirmed that the reproducibility of the polymer's physical properties is low when the polymer is manufactured using the batch process of the comparative example.

[0264] Through the above results, it was confirmed that applying the continuous process of the present invention instead of the conventional batch method increases the polymer yield and significantly improves the reproducibility of physical properties.

Claims

Claim 1 A method for preparing a polymer comprising: a step of supplying a monomer mixture including a monomer containing one or more arylamines and a monomer linker to a continuous reactor; a step of carrying out a polymerization reaction in the continuous reactor; and a step of discharging a product from the continuous reactor while the polymerization reaction is carried out, wherein the continuous reactor is composed of a first continuous reactor and a second continuous reactor, the continuous reactor includes a first continuous channel and a second continuous channel, a ligand composition is supplied to the first continuous channel of the first continuous reactor, a catalyst composition is supplied to the second continuous channel of the first continuous reactor, a product discharged from the first continuous reactor is supplied to the first continuous channel of the second continuous reactor, and the monomer mixture is supplied to the second continuous channel of the second continuous reactor, and the monomer linker is represented by the following chemical formula B: [Chemical Formula B] In chemical formula B, Z is C, Si, Ge, N, or an aromatic ring, and Y is a direct bond; a substituted or unsubstituted alkylene group; or a substituted or unsubstituted arylene group, and represents an attachment site within the polymer, each of which can be independently substituted with a halogen group; a boronic acid; or a pinacol ester group, and s is an integer from 2 to 5, and if s is 2 or more, Y in parentheses is the same or different from each other. Claim 2 delete Claim 3 A method for manufacturing a polymer according to claim 1, wherein the monomer is supplied in the form of a solution dissolved in a solvent. Claim 4 A method for producing a polymer according to claim 3, wherein the monomer is dissolved at a concentration of 1 to 10 parts by weight per 100 parts by weight of the solvent. Claim 5 A method for manufacturing a polymer according to claim 3, wherein the supply rate of the monomer is 0.1 g / min to 1,000 g / min. Claim 6 A method for manufacturing a polymer according to claim 1, wherein the reaction is carried out under conditions of a temperature of 25°C to 200°C and a pressure of 1 bar to 20 bar. Claim 7 A method for manufacturing a polymer according to claim 1, further comprising the step of feeding the product discharged from the continuous reactor into an additional continuous reactor connected in series with the continuous reactor. Claim 8 A method for manufacturing a polymer according to claim 1, wherein the step of carrying out a polymerization reaction in the continuous reactor further comprises controlling the residence time in the continuous reactor by providing a retention coil at the rear end of the continuous reactor. Claim 9 A method for producing a polymer according to claim 1, further comprising the step of supplying an end-capper monomer to the continuous reactor. Claim 10 A method for manufacturing a polymer according to claim 1, further comprising the step of supplying a transition metal catalyst to the continuous reactor. Claim 11 A method for manufacturing a polymer according to claim 1, further comprising the step of supplying an additive to the continuous reactor. Claim 12 A method for preparing a polymer according to claim 1, wherein the monomer comprising one or more arylamine groups is represented by the following chemical formula A: [Chemical Formula A] In chemical formula A, Ar1 and Ar4 are identical or different from each other and are substituted or unsubstituted aryl groups; or are substituted or unsubstituted heterocyclic groups, or form a substituted or unsubstituted ring by combining with an adjacent substituent, and Ar2, Ar3 and Ar5 are identical or different from each other and are substituted or unsubstituted divalent aryl groups; or are substituted or unsubstituted divalent heterocyclic groups, or form a substituted or unsubstituted divalent ring by combining with an adjacent substituent, and at least one of Ar1 to Ar5 is a substituted or unsubstituted aryl group or a substituted or unsubstituted divalent aryl group, and represents an attachment site within the polymer, which can be independently substituted with a halogen group; a boronic acid; or a pinacol ester group, n1 is an integer from 0 to 10, and if n1 is 2 or more, Ar3 are identical or different from each other, n2 is an integer of 0 or more, and if n2 is 2 or more, the substituents in parentheses are identical or different from each other. Claim 13 delete

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