Polymer and its manufacturing method

Abstract

To provide a method for efficiently producing a modified polymer derived from a halogenated styrene polymer with narrow dispersion.SOLUTION: A method for producing a polymer includes an anion polymerization step for subjecting a halogenated styrene monomer, in the presence of an initiator represented by general formula (1), to anion polymerization using a micro reactor, and a modification step for modifying a polymer obtained in the anion polymerization step (in the general formula (1), one of R1 and R2 is an aryl group and the other is an aryl group, or a C1-10 alkyl group).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to polymers and methods for their production. [Background technology]

[0002] In recent years, in the field of chemical synthesis, chemical reactions using minute containers called microreactors have been studied (see, for example, Non-Patent Documents 1 and 2). A microreactor is a tiny container equipped with a flow path capable of mixing multiple liquids, and an inlet path that communicates with the flow path and introduces liquids into the flow path. The multiple liquids supplied through the inlet path of the microreactor join together in the flow path, where they are mixed and a reaction occurs.

[0003] Reactions using microreactors are thought to enable precise control of residence time, precise temperature control, and high-speed mixing, and are expected to improve conversion and selectivity compared to conventional batch-type reactions, making them a highly efficient production method.

[0004] On the other hand, anionic polymerization is a powerful tool for synthesizing styrene-based polymers because of its fast reaction rate. However, the polymerization of styrene modified with functional groups is largely limited by the reactivity of the functional groups, and therefore has not been thoroughly studied. Although anionic polymerization of halogenated styrenes using sec-BuLi as an initiator has been reported (e.g., see Non-Patent Document 3), a halogenated styrene polymer with high conversion and narrow dispersion has not been obtained, and no modified polymer derived from a narrow dispersion halogenated styrene polymer has been obtained.

[0005] Therefore, a method for efficiently producing a narrowly dispersed modified polymer derived from a halogenated styrene polymer has not yet been provided, and there is a strong demand for its prompt provision. [Prior art documents] [Non-patent literature]

[0006] [Non-Patent Document 1] Chimia 2002 56:636 [Non-Patent Document 2] Tetrahedron) 2002 58:4735-4757 [Non-Patent Document 3] Polymer Preprints 2018 67 1B17 Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention aims to solve the above-mentioned problems in the prior art and to achieve the following object: That is, the present invention aims to provide a method for efficiently producing a narrowly disperse halogenated styrene polymer-derived modified polymer. [Means for solving the problem]

[0008] As a result of intensive research conducted by the present inventors in order to achieve the above object, a method for producing a polymer comprising: an anionic polymerization step of anionically polymerizing a halogenated styrene monomer using a microreactor in the presence of an initiator represented by the following general formula (1); and a modification step of modifying the polymer obtained in the anionic polymerization step (wherein in the general formula (1), R 1 and R 2 wherein one of said monomers is an aryl group and the other is an aryl group or an alkyl group having 1 to 10 carbon atoms), it has been found that a method for efficiently producing a narrowly dispersed modified polymer derived from a halogenated styrene polymer can be provided. [ka]

[0009] The present invention is based on the above findings by the present inventors, and the means for solving the above problems are as follows. <1> A method for producing a polymer, comprising: an anionic polymerization step of anionically polymerizing a halogenated styrene monomer using a microreactor in the presence of an initiator represented by the following general formula (1); and a modification step of modifying the polymer obtained in the anionic polymerization step (wherein, in the general formula (1), R 1 and R 2 one of them is an aryl group, and the other is an aryl group or an alkyl group having 1 to 10 carbon atoms. [ka] <2> The polymer is represented by either of the following general formulas (3) or (4) and has a molecular weight distribution of 1.4 or less. [ka] In the general formula (3), m and n represent the degree of polymerization, m is an integer of 0 or more, and n is an integer of 1 or more. 5 and R 6 one of them is an aryl group and the other is an aryl group or an alkyl group having 1 to 10 carbon atoms; X is any one of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and an astatine atom; Y is a hydrogen atom, a deuterium atom, an aldehyde group, a boryl group, a hydroxy group, an acetoxy group, a trimethylsilyl group, or a group represented by any one of the following structural formulas (4) to (6); and a is an integer of 1 to 5. The bonding order of the styrene structural unit not having a Y group and the styrene structural unit having a Y group is in no particular order, and the polymer may be a random polymer or a block polymer. [ka] [ka] [ka] [ka] In the general formula (4), m and n each represent a degree of polymerization and are an integer of 1 or more.5 and R 6 one of them is an aryl group and the other is an aryl group or an alkyl group having 1 to 10 carbon atoms; and Y is a hydrogen atom, a deuterium atom, an aldehyde group, a boryl group, a hydroxy group, an acetoxy group, a trimethylsilyl group, or a group represented by any one of the following structural formulas (4) to (6). The styrene structural unit having a benzaldehyde group and the styrene structural unit having a Y group may be bonded in any order, and the polymer may be a random polymer or a block polymer. [ka] [ka] [ka] Effect of the Invention

[0010] According to the present invention, there can be provided a method for efficiently producing a narrowly disperse modified polymer derived from a halogenated styrene polymer. [Brief description of the drawings]

[0011] [Figure 1] FIG. 1 is a schematic diagram of a flow microreactor used in one example of the production method of the present invention. [Diagram 2] FIG. 2 is a schematic diagram of a flow microreactor used in one example of the production method of the present invention. [Diagram 3] FIG. 3 is a schematic diagram of a flow microreactor used in one example of the production method of the present invention. [Figure 4] FIG. 4 is a schematic diagram of a flow microreactor used in one example of the production method of the present invention. [Diagram 5] FIG. 5 is a schematic diagram of the microreactor system used in Production Example 1. [Figure 6] FIG. 6 is a MALDI-TOF MS spectrum of the poly-p-bromostyrene obtained in Production Example 1. [Figure 7] FIG. 7 is a schematic diagram of the microreactor system used in Production Example 2. [Figure 8] FIG. 8 is a MALDI-TOF MS spectrum of the poly-p-chlorostyrene obtained in Production Example 2. [Figure 9] FIG. 9 is a MALDI-TOF MS spectrum of the modified polymer obtained in Example 1. [Figure 10] FIG. 10 is a MALDI-TOFMS spectrum of the modified polymer obtained in Example 2-1. [Figure 11] FIG. 11 is a MALDI-TOF MS spectrum of the modified polymer obtained in Example 2-2. [Figure 12] FIG. 12 is a MALDI-TOF MS spectrum of the modified polymer obtained in Example 3. [Figure 13] FIG. 13 is a MALDI-TOF MS spectrum of the modified polymer obtained in Example 4. [Figure 14] FIG. 14 is a MALDI-TOF MS spectrum of the modified polymer obtained in Example 5. [Figure 15] FIG. 15 is a schematic diagram of the microreactor system used in Example 6. [Figure 16] FIG. 16 is a MALDI-TOF MS spectrum of the modified polymer obtained in Example 6-1. [Figure 17] FIG. 17 is a MALDI-TOF MS spectrum of the modified polymer obtained in Example 6-2. [Figure 18] FIG. 18 is the 1H-NMR spectrum of the modified polymer obtained in Example 6-3. [Figure 19] FIG. 19 is the 1H-NMR spectrum of the modified polymer obtained in Example 6-4. [Figure 20] FIG. 20 is the 1H-NMR spectrum of the modified polymer obtained in Example 6-5. [Figure 21] FIG. 21 is the 1H-NMR spectrum of the modified polymer obtained in Example 6-6. [Figure 22] FIG. 22 is a schematic diagram of the microreactor system used in Example 7. [Diagram 23] FIG. 23 is a 1H-NMR spectrum of the modified polymer obtained in Example 7. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] (Polymer manufacturing method) The method for producing the polymer includes an anionic polymerization step and a modification step, and may further include other steps.

[0013] <Anionic polymerization process> The anionic polymerization step is a step in which a halogenated styrene monomer is anionically polymerized in the presence of an initiator using a flow microreactor.

[0014] -Halogenated styrene monomers- The halogenated styrene monomer is not particularly limited and can be appropriately selected depending on the purpose. For example, a monomer represented by the following general formula (2) (wherein R 3 is a hydrogen atom or a methyl group; R 4 represents a hydrogen atom, a chlorine atom, an alkyl group having 1 to 4 carbon atoms, or a trimethylsilyl group; X represents a halogen atom such as fluorine, chlorine, bromine, iodine, or astatine; and a represents an integer of 1 to 5). [ka]

[0015] Among the monomers represented by the general formula (2), the monomers in which X is a chlorine atom or a bromine atom are preferred. The monomers in which X is a chlorine atom or a bromine atom are not particularly limited and can be appropriately selected according to the purpose, but 2-bromostyrene (o-bromostyrene), 3-bromostyrene (m-bromostyrene), 4-bromostyrene (p-bromostyrene), dibromostyrene, tribromostyrene, 2-chlorostyrene (o-chlorostyrene), 3-chlorostyrene (m-chlorostyrene), 4-chlorostyrene (p-chlorostyrene), dichlorostyrene, and trichlorostyrene are preferred, and 2-bromostyrene (o-bromostyrene), 3-bromostyrene (m-bromostyrene), 4-bromostyrene (p-bromostyrene), 2-chlorostyrene (o-chlorostyrene), 3-chlorostyrene (m-chlorostyrene), and 4-chlorostyrene (p-chlorostyrene) are more preferred.

[0016] -Initiator- The initiator is represented by the following general formula (1). [ka]

[0017] In the general formula (1), "s-Bu" represents a sec-butyl group, and "Li" represents a lithium group.

[0018] In the general formula (1), R 1 and R 2 One of them is an aryl group, and the other is an aryl group or an alkyl group having 1 to 10 carbon atoms. Among these, R in the general formula (1) is preferred because it suppresses the softening of reactivity and makes the initiation reaction uniform, thereby obtaining a narrowly dispersed polymer. 1 and R 2 It is preferable that one of them is an alkyl group having 1 to 10 carbon atoms.

[0019] The alkyl group having 1 to 10 carbon atoms is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoints of efficiently achieving a high conversion rate and obtaining a narrowly dispersed polymer, an alkyl group having 1 to 8 carbon atoms is preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, an alkyl group having 1 to 4 carbon atoms is even more preferred, an alkyl group having 1 to 2 carbon atoms is particularly preferred, and a methyl group is most preferred.

[0020] The aryl group is not particularly limited and can be appropriately selected depending on the purpose. Examples of the aryl group include a phenyl group, a tolyl group, and an o-xylyl group. Among these, a phenyl group is preferred since it provides an efficient high conversion rate and a narrowly dispersed polymer.

[0021] Examples of the compound represented by the general formula (1) include a compound represented by the following structural formula (1) (DPHLi), a compound represented by the following structural formula (2) (2PHLi), and a compound represented by the following structural formula (3) (3POLi). Among these, the compound (2PHLi) represented by the following structural formula (2) is preferred, since it can efficiently achieve a high conversion rate and can give a polymer with a narrow dispersion. [ka] [ka] [ka]

[0022] --Initiator manufacturing method-- The method for producing the initiator is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include a method of reacting sec-BuLi with an alkylaryl compound, etc. The initiator may be produced using a flow microreactor.

[0023] The alkylaryl compound is not particularly limited and can be appropriately selected depending on the purpose. Examples of the alkylaryl compound include alkylbenzene compounds.

[0024] The alkylbenzene compound is not particularly limited and can be appropriately selected depending on the purpose. For example, methylstyrene compounds such as α-methylstyrene, β-methylstyrene, 2-methylstyrene (o-methylstyrene), 3-methylstyrene (m-methylstyrene), 4-methylstyrene (p-methylstyrene), 1,5-dimethylstyrene, and 2,4-dimethylstyrene; ethylstyrene compounds such as α-ethylstyrene, β-ethylstyrene, 2-ethylstyrene (o-ethylstyrene), 3-ethylstyrene (m-ethylstyrene), 4-ethylstyrene (p-ethylstyrene), 1,5-diethylstyrene, and 2,4-diethylstyrene; Examples of such benzene derivatives include 1,2-divinylbenzene (o-divinylbenzene), 1,3-divinylbenzene (m-divinylbenzene), 1,4-divinylbenzene (p-divinylbenzene), 1,2-bis(1-methylethenyl)benzene (o-bis(1-methylethenyl)benzene), 1,3-bis(1-methylethenyl)benzene (m-bis(1-methylethenyl)benzene), 1,4-bis(1-methylethenyl)benzene (p-bis(1-methylethenyl)benzene), 1,2,3-tris(1-methylethenyl)benzene, 1,2,4-tris(1-methylethenyl)benzene, and 1,3,5-tris(1-methylethenyl)benzene.

[0025] Among these, from the viewpoints of efficiently achieving a high conversion rate and obtaining a narrowly dispersed polymer, a methylstyrene compound or an ethylstyrene compound is preferred, a methylstyrene compound is more preferred, and α-methylstyrene is even more preferred.

[0026] The lower limit of the reaction temperature between the sec-BuLi and the alkylaryl compound is not particularly limited and may be appropriately selected depending on the purpose. From the viewpoints of efficiently achieving a high conversion rate and obtaining a narrowly dispersed polymer, the lower limit is preferably 0° C. or higher, more preferably 5° C. or higher, even more preferably 10° C. or higher, and particularly preferably 15° C. or higher.

[0027] The upper limit of the reaction temperature between the sec-BuLi and the alkylaryl compound is not particularly limited and may be appropriately selected depending on the purpose. From the viewpoints of efficiently achieving a high conversion rate and obtaining a narrowly dispersed polymer, the upper limit is preferably 40° C. or lower, more preferably 35° C. or lower, even more preferably 30° C. or lower, and particularly preferably 25° C. or lower.

[0028] The lower limit of the amount of the alkylaryl compound relative to the sec-BuLi is not particularly limited and can be appropriately selected depending on the purpose. However, from the viewpoint of efficiently achieving a high conversion rate and obtaining a narrowly dispersed polymer, the amount is preferably 1.0 molar equivalent or more, more preferably 1.1 molar equivalent or more, even more preferably 1.2 molar equivalent or more, particularly preferably 1.3 molar equivalent or more, and most preferably 1.4 molar equivalent or more.

[0029] The upper limit of the amount of the alkylaryl compound relative to the sec-BuLi is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoint of efficiently achieving a high conversion rate and obtaining a narrowly dispersed polymer, the upper limit is preferably 2.0 molar equivalents or less, more preferably 1.9 molar equivalents or less, even more preferably 1.8 molar equivalents or less, particularly preferably 1.7 molar equivalents or less, and most preferably 1.6 molar equivalents or less.

[0030] The lower limit of the reaction temperature between the halogenated styrene monomer and the initiator is not particularly limited and may be appropriately selected depending on the purpose. However, from the viewpoints of efficiently obtaining a high conversion rate and a narrowly dispersed polymer, the lower limit is preferably -60°C or higher, more preferably -55°C or higher, even more preferably -50°C or higher, and particularly preferably -45°C or higher.

[0031] The upper limit of the reaction temperature between the halogenated styrene monomer and the initiator is not particularly limited and may be appropriately selected depending on the purpose. However, from the viewpoints of efficiently obtaining a high conversion rate and a narrowly dispersed polymer, the upper limit is preferably -20°C or lower, more preferably -25°C or lower, even more preferably -30°C or lower, and particularly preferably -35°C or lower.

[0032] -Microreactor- The microreactor is not particularly limited and can be appropriately selected depending on the purpose. Examples of the microreactor include a microreactor that includes a mixing means and a flow channel, and further includes other means as necessary (hereinafter, may be referred to as a "flow microreactor"). The mixing means and the flow passage may be of an integral type or of a separate type.

[0033] The mixing means is a means capable of mixing two or more kinds of liquids. The flow passage is a pipe through which a liquid can flow, and is connected to at least one of the mixing means.

[0034] By using the flow microreactor, it is possible to shorten the residence time from the production to the next reaction of a less stable compound, thereby suppressing side reactions. In addition, the flow microreactor has excellent cooling efficiency, and therefore can suppress side reactions caused by heat generated in an exothermic reaction.

[0035] --Integrated flow microreactor-- The mixing means and the flow passage of the integrated flow microreactor may be a substrate-type micromixer.

[0036] The substrate-type micromixer is made of a substrate having a passage formed therein or on its surface, and may be called a microchannel. The substrate-type micromixer is not particularly limited and may be appropriately selected depending on the purpose. Examples of the substrate-type micromixer include the mixer having fine flow paths for mixing described in International Publication No. 96 / 30113; and the mixer described in the literature "Microreactors, Chapter 3, by W. Ehrfeld, V. Hessel, and H. Lowe, published by Wiley-VCH."

[0037] In the substrate-type micromixer, the mixing means and the flow passage are formed of minute flow passages capable of mixing a plurality of liquids.

[0038] In addition to the flow paths, the substrate-type micromixer is preferably provided with inlet paths that communicate with the flow paths and introduce a plurality of liquids into the flow paths. That is, it is preferable that the flow paths are branched on the upstream side depending on the number of the inlet paths.

[0039] The number of the introduction paths is not particularly limited and can be appropriately selected depending on the purpose, but it is preferable to introduce multiple liquids to be mixed from separate introduction paths and merge them in the flow path to mix them. Note that a configuration in which one liquid is preliminarily charged in the flow path and the other liquids are introduced through the introduction paths may also be used.

[0040] --Separate flow microreactor-- The separate type flow microreactor is configured by connecting a mixing means and a flow passage.

[0041] The mixing means is not particularly limited as long as it can mix two or more liquids, and can be appropriately selected depending on the purpose. For example, a pipe joint type micromixer can be mentioned.

[0042] The pipe joint type micromixer includes a flow path formed therein, and if necessary, a connecting member that connects the flow path formed therein and the flow passage. The connection method of the connecting member is not particularly limited and can be appropriately selected from known connection methods depending on the purpose, and examples thereof include a screw type, a union type, a butt welding type, a plug welding type, a socket welding type, a flange type, a bite type, a flare type, and a mechanical type.

[0043] In addition to the flow paths, it is preferable that an inlet path is formed inside the pipe joint type micromixer, which is connected to the flow paths and introduces a plurality of liquids into the flow paths. That is, it is preferable that the upstream side of the flow paths is branched depending on the number of the inlet paths. When the number of the inlet paths is two, for example, a T-shape or Y-shape can be used as the pipe joint type micromixer, and when the number of the inlet paths is three, for example, a cross shape can be used. Note that it is also possible to use a configuration in which one liquid is charged in the flow paths in advance and the other liquids are introduced through the inlet paths.

[0044] The material of the pipe joint type micromixer is not particularly limited and can be appropriately selected depending on requirements such as heat resistance, pressure resistance, solvent resistance, and ease of processing. Examples of the material include stainless steel, titanium, copper, nickel, aluminum, silicon, Teflon (registered trademark), fluororesins such as PFA (perfluoroalkoxy resin), and TFAA (trifluoroacetamide).

[0045] As the pipe joint type micro mixer, commercially available products can be used, such as YM-1 type mixer and YM-2 type mixer manufactured by Yamatake Corporation; mixing tee and tee (T-shaped connector) manufactured by Shimadzu GLC Corporation; micro-high mixer developed by Toray Engineering; union tee manufactured by Swagelok Corporation, and T-shaped micro mixer manufactured by Sanko Seiki Kogyo Co., Ltd.

[0046] The method of mixing two or more raw materials in the mixing means is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include mixing by laminar flow, mixing by turbulent flow, etc. Among them, mixing by laminar flow (static mixing) is preferred in terms of more efficient reaction control and heat removal.

[0047] In addition, since the flow path in the mixing means is minute, the liquids introduced into the mixing means tend to naturally flow in a laminar manner, and are mixed by diffusing in a direction perpendicular to the flow. In the mixing by laminar flow, a branch point and a junction point may be provided in the flow path to divide the laminar cross section of the flowing liquid, thereby increasing the mixing speed. Furthermore, when turbulent mixing (dynamic mixing) is performed in the flow path of the mixing means, the laminar flow can be changed to a turbulent flow by adjusting the flow rate and the shape of the flow path (the three-dimensional shape of the liquid-contacting portion, the shape of the flow path such as bending, the roughness of the wall surface, etc.). The mixing by the turbulent flow has the advantages of better mixing efficiency and faster mixing speed than the mixing by the laminar flow.

[0048] Here, the smaller the inner diameter of the flow passage in the mixing means, the shorter the diffusion distance of the molecules, and therefore the shorter the time required for mixing and the higher the mixing efficiency.Furthermore, the smaller the inner diameter of the flow passage, the larger the ratio of the surface area to the volume, and therefore the easier it is to control the temperature of the liquid, for example, to remove the heat of reaction. On the other hand, if the inner diameter of the flow path is too small, the pressure loss during the flow of the liquid increases, and a special high-pressure pump is required for the liquid delivery, which may increase the manufacturing cost. In addition, the liquid delivery flow rate is limited, which may limit the structure of the micromixer.

[0049] The inner diameter of the flow channel in the mixing means is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 50 μm to 4 mm, more preferably 100 μm to 3 mm, even more preferably 250 μm to 2 mm, and particularly preferably 500 μm to 1 mm. If the inner diameter is less than 50 μm, the pressure loss may increase. If the inner diameter is more than 4 mm, the surface area per unit volume becomes small, which may result in difficulty in rapid mixing and removal of reaction heat. On the other hand, if the inner diameter is within the particularly preferred range, it is advantageous in that mixing can be performed more quickly and reaction heat can be removed more efficiently. More specifically, the inner diameter of the flow channel formed inside the mixing means is preferably 50 μm to 1,000 μm, more preferably 100 μm to 800 μm, and even more preferably 250 μm to 500 μm.

[0050] The cross-sectional area of ​​the flow channel is not particularly limited and can be appropriately selected depending on the purpose. 2 ~16mm 2 is preferable, and 1,000 μm 2 ~4.0mm 2 More preferably, 10,000 μm 2 ~2.1mm 2 More preferably, 190,000 μm 2 ~1mm 2 is particularly preferred.

[0051] The cross-sectional shape of the flow channel is not particularly limited and can be appropriately selected depending on the purpose. Examples of the cross-sectional shape include a circle, a rectangle, a semicircle, and a triangle.

[0052] The flow passage is not particularly limited as long as it is a tube that is connected to at least one of the mixing means and can flow a liquid, and can be appropriately selected depending on the purpose. The configuration of the flow passage, such as its inner diameter, outer diameter, length, material, etc., can be appropriately selected depending on the desired reaction.

[0053] The flow passage is used, for example, when supplying raw materials to the mixing means. The flow passage is used, for example, when supplying a reaction product of two or more kinds of substances mixed by the mixing means to a subsequent mixing means. Note that, at this time, the reaction may continue to occur in the flow passage.

[0054] The flow passage may be a commercially available product, such as a stainless steel tube manufactured by GL Sciences Inc. (outer diameter 1 / 16 inch (1.58 mm), inner diameter selectable from 250 μm, 500 μm, and 1,000 μm, tube length adjustable by the user).

[0055] The material of the flow passage is not particularly limited, and the materials exemplified as the materials of the mixing means can be suitably used.

[0056] The inner diameter of the flow passage is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 50 μm to 4 mm, more preferably 100 μm to 3 mm, further preferably 250 μm to 2 mm, and particularly preferably 500 μm to 1 mm. More specifically, the inner diameter of the flow passage is preferably from 50 μm to 1,000 μm, more preferably from 100 μm to 800 μm, and even more preferably from 250 μm to 500 μm.

[0057] The inner diameter of the flow passage connected downstream of the mixing means is preferably 50 μm to 4 mm, more preferably 100 μm to 2 mm, and even more preferably 500 μm to 1 mm.

[0058] The flow rate of the liquid in the flow passage for supplying the raw material is not particularly limited and can be appropriately selected depending on the purpose, and may be, for example, 1.0 ml / min to 20 ml / min, 2.0 ml / min to 15 ml / min, or 3.0 ml / min to 10 ml / min.

[0059] The residence time of the reaction liquid in the flow passage through which the reaction liquid flows is not particularly limited and can be appropriately selected depending on the purpose, and may be, for example, 0.001 sec to 10 sec.

[0060] The lower limit of the length between the micromixer in which the sec-BuLi and the alkylaryl compound are reacted and the micromixer in which the anionic polymerization is performed is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 100 cm or more, more preferably 150 cm or more, even more preferably 170 cm or more, and particularly preferably 190 cm or more. The upper limit of the length between the micromixer in which the sec-BuLi and the alkylaryl compound are reacted and the micromixer in which the anionic polymerization is performed is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 300 cm or less, more preferably 280 cm or less, even more preferably 250 cm or less, and particularly preferably 230 cm or less.

[0061] --Other methods-- The other means are not particularly limited and can be appropriately selected depending on the purpose. Examples of the other means include a liquid delivery means and a temperature adjustment means.

[0062] The liquid delivery means is not particularly limited as long as it can supply various raw materials to the flow passage of the flow microreactor, and can be appropriately selected depending on the purpose. For example, a pump can be used.

[0063] The pump is not particularly limited and can be appropriately selected from those that can be used industrially. Preferably, the pump does not generate pulsation during liquid transfer. Examples of the pump include a plunger pump, a gear pump, a rotary pump, and a diaphragm pump.

[0064] The temperature control means is not particularly limited as long as it can control the temperature of the mixing means and the flow path of the flow microreactor, and can be appropriately selected depending on the purpose.

[0065] <Modification process> The modification step is a step of modifying the polymer obtained in the anionic polymerization step. The modification is not particularly limited and can be appropriately selected depending on the purpose. For example, the modification may be substitution of halogen atoms in the polymer with the same or different functional groups. The modification step may be carried out using a flow microreactor.

[0066] The method of substitution is not particularly limited and may be appropriately selected depending on the purpose. Examples of the substitution include substitution by Suzuki coupling reaction, substitution by Miyaura boronation reaction, and substitution by lithiation reaction.

[0067] The Suzuki coupling reaction is a chemical reaction in which an aryl halide and an organoboron compound are cross-coupled by the action of a palladium catalyst and a nucleophilic species such as a base.

[0068] The method for the Suzuki coupling reaction is not particularly limited and can be appropriately selected depending on the purpose. For example, a method in which the polymer obtained in the anionic polymerization step, 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzaldehyde, Pd(dppf)Cl2, and K2CO3 are dissolved in THF / H2O (9:1) and refluxed under an Ar atmosphere; a method in which 4,4,5,5-tetramethyl-2-(4-vinylphenyl)-1,3,2-dioxaborolane, Pd(dppf)Cl2, and K2CO3 are dissolved in THF / H2O (9:1) and refluxed under an Ar atmosphere; and a method in which the polymer obtained in the anionic polymerization step, 4,4,5,5-tetramethyl-2-(4-vinylphenyl)-1,3,2-dioxaborolane, Pd(dppf)Cl2, and K2CO3 are dissolved in THF / H2O (9:1) and refluxed under an Ar atmosphere.

[0069] The reflux time is not particularly limited and can be appropriately selected depending on the purpose. For example, reflux for one night can be mentioned. The reflux temperature is not particularly limited and can be appropriately selected depending on the purpose. For example, room temperature can be mentioned.

[0070] In the Suzuki coupling reaction, a polymerization inhibitor for the styrene derivative can be added. The polymerization inhibitor is not particularly limited and can be appropriately selected depending on the purpose. Examples of the polymerization inhibitor include 4-tert-butylpyrocatechol.

[0071] The Miyaura boronation reaction is a chemical reaction in which an aryl halide is coupled with bis-pinacolatodiboron in the presence of a palladium catalyst.

[0072] The method for the Miyaura boronation reaction is not particularly limited and can be appropriately selected depending on the purpose. For example, a method in which the polymer obtained in the anionic polymerization step, tris(dibenzylideneacetone)dipalladium(0), Xphos, bis(pinacolato)diboron, and KOAc are dissolved in 1,4-dioxane and refluxed under an Ar atmosphere can be mentioned.

[0073] The reflux time is not particularly limited and can be appropriately selected depending on the purpose. For example, reflux for one night can be mentioned. The reflux temperature is not particularly limited and can be appropriately selected depending on the purpose. For example, room temperature can be mentioned.

[0074] The lithiation reaction is a halogen-metal exchange reaction between an aryl halide and an alkyllithium compound.

[0075] The method of the lithiation reaction is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include a method of mixing a BuLi solution with the polymer solution obtained in the anionic polymerization step. The lithiation reaction may be carried out using a flow microreactor.

[0076] The lower limit of the temperature at which the BuLi solution and the polymer solution obtained in the anionic polymerization step are mixed is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoint of efficiently obtaining a polymer, however, the lower limit is preferably -60°C or higher, more preferably -55°C or higher, even more preferably -50°C or higher, and particularly preferably -45°C or higher.

[0077] The upper limit of the temperature at which the BuLi solution and the polymer solution obtained in the anionic polymerization step are mixed is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoint of efficiently obtaining a polymer, however, the upper limit is preferably -20°C or lower, more preferably -25°C or lower, even more preferably -30°C or lower, and particularly preferably -35°C or lower.

[0078] The substitution with different functional groups is not particularly limited and can be appropriately selected depending on the purpose. For example, multi-step modification (multi-step substitution) and the like can be mentioned. The multi-step modification is not particularly limited and can be appropriately selected depending on the purpose. Examples of the multi-step modification include substitution of a boryl group of a polymer after a Miyaura boronation reaction with a hydroxyl group or the like, functionalization of a polymer after a lithiation reaction, and substitution by a Suzuki coupling reaction after functionalization of a polymer after a lithiation reaction.

[0079] The method for replacing the boryl group of the polymer after the Miyaura boronation reaction with a hydroxy group is not particularly limited and may be appropriately selected depending on the purpose. For example, a method in which the polymer after the Miyaura boronation reaction and KPO are dissolved in THF, an oxidizing agent such as an aqueous solution of Oxone (registered trademark) is added dropwise, and the mixture is stirred may be mentioned.

[0080] The stirring time is not particularly limited and can be appropriately selected depending on the purpose, and may be, for example, 1 hour. The reflux temperature is not particularly limited and can be appropriately selected depending on the purpose. For example, room temperature can be mentioned.

[0081] The method for functionalizing the polymer after the lithiation reaction is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include a method of introducing an electrophilic reagent solution into a mixture of the BuLi solution and the polymer solution obtained in the anionic polymerization step in the lithiation reaction. The functionalization of the polymer after the lithiation reaction may be performed using a flow microreactor.

[0082] The electrophilic reagent is not particularly limited and can be appropriately selected depending on the purpose. Examples of the electrophilic reagent include boron compounds such as water, heavy water, MeOH, CD3OD, and 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, carbonyl compounds such as DMF, ester compounds such as methyl chloroformate, silicon compounds such as TMSCl (chlorotrimethylsilane), alkyl halides, nitrile compounds, and epoxy compounds.

[0083] The lower limit of the temperature when the BuLi solution is mixed with the polymer solution obtained in the anionic polymerization step and the electrophilic reagent solution is introduced into this mixture is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoint of efficiently obtaining a polymer, however, the lower limit is preferably -60°C or higher, more preferably -55°C or higher, even more preferably -50°C or higher, and particularly preferably -45°C or higher.

[0084] The upper limit of the temperature when the BuLi solution is mixed with the polymer solution obtained in the anionic polymerization step and the electrophilic reagent solution is introduced into this mixture is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoint of efficiently obtaining a polymer, however, the upper limit is preferably -20°C or lower, more preferably -25°C or lower, even more preferably -30°C or lower, and particularly preferably -35°C or lower.

[0085] The lower limit of the temperature of the microtube reactor through which the electrophilic reagent solution is introduced and then passed is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoint of efficiently obtaining a polymer, however, the lower limit is preferably 0°C or higher, more preferably 5°C or higher, even more preferably 10°C or higher, and particularly preferably 15°C or higher.

[0086] The upper limit of the temperature of the microtube reactor through which the electrophilic reagent solution is introduced and then passed is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoint of efficiently obtaining a polymer, however, the upper limit is preferably 40° C. or less, more preferably 35° C. or less, even more preferably 30° C. or less, and particularly preferably 25° C. or less.

[0087] <Other processes> The other steps are not particularly limited and may be appropriately selected depending on the purpose. Examples of the other steps include a step of producing an initiator before the anionic polymerization step, and a monomer polymerization step after the anionic polymerization step.

[0088] -Initiator manufacturing process before anionic polymerization process- The step of preparing an initiator before the anionic polymerization step is a step of reacting the sec-BuLi with an alkylaryl compound before the anionic polymerization step. The step of reacting the sec-BuLi with the alkylaryl compound is as described in the above-mentioned method for producing the initiator.

[0089] -Monomer polymerization process after anionic polymerization process- The monomer polymerization step subsequent to the anionic polymerization step is a step of polymerizing a monomer with respect to the polymer obtained by anionically polymerizing the halogenated styrene monomer in the anionic polymerization step.

[0090] The monomer is not particularly limited and can be appropriately selected depending on the purpose. Examples of the monomer include styrene and styrene derivatives.

[0091] (polymer) The polymer can be produced by the above-mentioned method for producing a polymer. The polymer is a modified polymer derived from a narrow dispersity halogenated styrene polymer.

[0092] The polymer is not particularly limited and can be appropriately selected depending on the purpose. Examples of the polymer include polymers represented by the following general formula (3) or (4).

[0093] [ka] In the general formula (3), m and n represent the degree of polymerization, m is an integer of 0 or more, and n is an integer of 1 or more. 5 and R 6 one of the groups is an aryl group and the other is an aryl group or an alkyl group having 1 to 10 carbon atoms. X is any one of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and an astatine atom. Y is a group introduced by a Suzuki coupling reaction, a group introduced by a Miyaura boronation reaction, or a functional group introduced by an electrophilic reagent reacted after lithiation of a bromo group, and examples thereof include a hydrogen atom, a deuterium atom, an aldehyde group, a boryl group, a hydroxy group, an acetoxy group, a trimethylsilyl group, and a group represented by any one of the following structural formulas (4) to (6). a is an integer of 1 to 5. The bonding order of the styrene structural unit not having a Y group and the styrene structural unit having a Y group is not limited, and the polymer may be a random polymer or a block polymer. [ka] [ka] [ka]

[0094] In the general formula (3), m is not particularly limited as long as it is an integer of 0 or more, and can be appropriately selected depending on the purpose. When synthesis is performed by Suzuki coupling reaction, m can be adjusted by increasing or decreasing the equivalent of a boronic acid compound such as boronic acid, boronic acid ester, or borate salt used in the Suzuki coupling reaction. When synthesis is performed by Miyaura boration reaction, m can be adjusted by increasing or decreasing the equivalent of a diborane compound used in the Miyaura boration reaction. When synthesis is performed by lithiation reaction, m can be adjusted by the equivalent of a lithium reagent used in the lithiation reaction.

[0095] In the general formula (3), n is not particularly limited as long as it is an integer of 1 or more and can be appropriately selected depending on the purpose. It is preferably 5 or more, more preferably 10 or more, even more preferably 15 or more, particularly preferably 20 or more, and most preferably 25 or more. In the case of synthesis by multi-stage modification, m and n depend on the composition of the raw polymer (the polymer in the previous stage).

[0096] R in the general formula (3) 5 and R 6 is not particularly limited and can be appropriately selected depending on the purpose as long as one of them is an aryl group and the other is an aryl group or an alkyl group having 1 to 10 carbon atoms. 5 and R 6 It is preferable that one of them is an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms is not particularly limited and can be appropriately selected depending on the purpose, but is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably an alkyl group having 1 to 4 carbon atoms, particularly preferably an alkyl group having 1 to 2 carbon atoms, and most preferably a methyl group. The aryl group is not particularly limited and can be appropriately selected depending on the purpose, but is preferably a phenyl group, a tolyl group, or an o-xylyl group, and more preferably a phenyl group.

[0097] X in the general formula (3) is not particularly limited as long as it is any one of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an astatine atom, and can be appropriately selected depending on the purpose, but is preferably a chlorine atom or a bromine atom.

[0098] In the general formula (3), the bonding order of the styrene structural unit not having a Y group and the styrene structural unit having a Y group is in no particular order, and the polymer may be a random polymer or a block polymer, means that when m is an integer of 0 or more and n is an integer of 1 or more, the polymer represented by the general formula (3) is a polymer having a structural unit represented by the following general formula (5) of 1, a structural unit represented by the following general formula (6) of an integer of 0 or more, and a structural unit represented by the following general formula (7) of an integer of 1 or more, the bonding order of the structural unit represented by the general formula (6) and the structural unit represented by the general formula (7) is in no particular order, and the polymer represented by the general formula (3) may be a random polymer or a block polymer. The polymer represented by the general formula (3) has a structural unit represented by the general formula (5) on one end side and a hydrogen atom on the other end side.

[0099] [ka] [ka] [ka]

[0100] [ka] In the general formula (4), m and n each represent a degree of polymerization and are an integer of 1 or more. 5 and R 6one of them is an aryl group, and the other is an aryl group or an alkyl group having 1 to 10 carbon atoms. Y is a functional group introduced by an electrophilic reagent reacted after lithiation of the bromo group, and examples thereof include a hydrogen atom, a deuterium atom, an aldehyde group, a boryl group, a hydroxy group, an acetoxy group, a trimethylsilyl group, or a group represented by any one of the following structural formulas (4) to (6). The bonding order of the styrene structural unit having a benzaldehyde group and the styrene structural unit having a Y group is in no particular order, and the polymer may be a random polymer or a block polymer. [ka] [ka] [ka]

[0101] The polymer represented by the general formula (4) can be synthesized from a block copolymer obtained by partially lithiating and functionalizing polybromostyrene, among the compounds represented by the general formula (3), as a raw material. m and n in the general formula (4) depend on the composition (degree of polymerization) of the block copolymer used as a raw material.

[0102] In the general formula (4), n is not particularly limited as long as it is an integer of 1 or more and can be appropriately selected depending on the purpose. It is preferably 5 or more, more preferably 10 or more, even more preferably 15 or more, particularly preferably 20 or more, and most preferably 25 or more.

[0103] R in the general formula (4) 5 and R 6 is not particularly limited and can be appropriately selected depending on the purpose as long as one of them is an aryl group and the other is an aryl group or an alkyl group having 1 to 10 carbon atoms. 5 and R 6 It is preferable that one of them is an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms is not particularly limited and can be appropriately selected depending on the purpose, but is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably an alkyl group having 1 to 4 carbon atoms, particularly preferably an alkyl group having 1 to 2 carbon atoms, and most preferably a methyl group. The aryl group is not particularly limited and can be appropriately selected depending on the purpose, but is preferably a phenyl group, a tolyl group, or an o-xylyl group, and more preferably a phenyl group.

[0104] In the general formula (4), the bonding order of the styrene structural unit having a benzaldehyde group and the styrene structural unit having a Y group is random, and the polymer may be a random polymer or a block polymer, means that when m and n are each an integer of 1 or more, the polymer represented by the general formula (4) is a polymer having a structural unit represented by the following general formula (5) of 1, a structural unit represented by the following general formula (8) of an integer of 1 or more, and a structural unit represented by the following general formula (9) of an integer of 1 or more, the bonding order of the structural unit represented by the general formula (8) and the structural unit represented by the general formula (9) is random, and the polymer represented by the general formula (4) may be a random polymer or a block polymer. The polymer represented by the general formula (4) has a structural unit represented by the general formula (5) at one end and a hydrogen atom at the other end.

[0105] [ka] [ka] [ka]

[0106] The molecular weight distribution (polydispersity index (PDI): Mw / Mn) of the polymer is not particularly limited and may be appropriately selected depending on the purpose, but is preferably 1.8 or less, more preferably 1.5 or less, even more preferably 1.4 or less, even more preferably 1.35 or less, particularly preferably 1.3 or less, most preferably 1.25 or less, and most particularly preferably 1.2 or less. The molecular weight distribution (polydispersity index (PDI): Mw / Mn) of the polymer is similar to that of the narrowly disperse halogenated styrene polymer (polydispersity index (PDI): Mw / Mn). The molecular weight distribution is measured by the following GPC analysis.

[0107] -GPC analysis- The analysis is carried out in THF (FUJIFILM Wako Pure Chemicals) at 40° C. using a SHIMADZU Prominence equipped with a Shodex LF-604 column. The reflectance index (RI) is recorded on a Shodex RI-504. The molecular weight distribution (polydispersity index (PDI): Mw / Mn) is determined by a calibration curve obtained from commercial polystyrene. Before GPC analysis, the solution is filtered through Millex-HN (Merck, 0.45 μm).

[0108] (Initiator for polymerization of halogenated styrene monomers) The initiator for polymerization of the halogenated styrene monomer is the same as the initiator described above.

[0109] (Method of producing initiator for polymerization of halogenated styrene monomers) The method for producing the halogenated styrene monomer polymerization initiator is the same as the method for producing the initiator described above.

[0110] Here, an example of a flow microreactor that can be suitably used in the above-mentioned polymer production method and a polymer production method using the same will be described with reference to the drawings.

[0111] FIG. 1 is a schematic diagram showing an example of a flow microreactor. The flow microreactor shown in FIG. 1 includes two mixing means and five flow paths. The flow passage P1 is connected to a mixing means M1. The flow passage P2 is connected to the mixing means M1. The flow passage P3 is connected to the mixing means M2. The flow passage R1 is connected to the mixing means M1 and the mixing means M2. The flow passage R1 also serves as a reaction section. The flow passage R2 is connected to the mixing means M2. The flow passage R2 also serves as a reaction section.

[0112] An initiator represented by the general formula (1) is supplied to the mixing means M1 from a flow path P1. A halogenated styrene monomer is supplied to the mixing means M1 from a flow path P2. Then, in the mixing means M1, the initiator represented by the general formula (1) and the halogenated styrene monomer are mixed, and in the resulting liquid, living anionic polymerization of the halogenated styrene monomer is initiated using the initiator represented by the general formula (1) as an anionic polymerization initiator, to produce a living polymer. The liquid undergoing the polymerization reaction flows through the flow path R1, which is also a reaction section, while polymerizing. The resulting polymer is a living polymer. Therefore, in order to terminate the active ends, a solution containing a terminator (e.g., methanol) is circulated through the flow path P3 and mixed with the polymer solution by the mixing means M2 to carry out the termination reaction.

[0113] FIG. 2 is a schematic diagram showing an example of a flow microreactor. The flow microreactor shown in FIG. 2 includes three mixing means and seven flow paths. The flow passage P1 is connected to a mixing means M1. The flow passage P2 is connected to the mixing means M1. The flow passage P3 is connected to the mixing means M2. The flow passage P4 is connected to the mixing means M3. The flow passage R1 is connected to the mixing means M1 and the mixing means M2. The flow passage R1 also serves as a reaction section. The flow passage R2 is connected to the mixing means M2 and the mixing means M3. The flow passage R2 also serves as a reaction section. The flow passage R3 is connected to the mixing means M3. The flow passage R3 also serves as a reaction section.

[0114] An alkylaryl compound is supplied to the mixing means M1 from a flow path P1. Sec-BuLi is supplied to the mixing means M1 from a flow path P2. Then, the alkylaryl compound and sec-BuLi are mixed in the mixing means M1, and an addition reaction is started in the resulting liquid, and the initiator represented by the general formula (1) is produced. The liquid during the reaction flows through the flow path R1, which is also a reaction section, while reacting. The liquid containing the initiator represented by the general formula (1) flowing through the flow passage R1 is introduced into the mixing means M2. In the mixing means M2, the liquid is mixed with a halogenated styrene monomer supplied from the flow passage P3, and in the resulting liquid, living anionic polymerization of the halogenated styrene monomer is initiated using the initiator represented by the general formula (1) as an anionic polymerization initiator, to produce a living polymer. The liquid undergoing the polymerization reaction flows through the flow passage R2, which is also a reaction section, while polymerizing. The resulting polymer is a living polymer. Therefore, in order to terminate the active ends, a solution containing a terminator (e.g., methanol) is circulated through the flow passage P4 and mixed with the polymer solution by the mixing means M3 to carry out the termination reaction.

[0115] FIG. 3 is a schematic diagram showing an example of a flow microreactor. The flow microreactor shown in FIG. 3 includes four mixing means and nine flow passages. The flow passage P1 is connected to a mixing means M1. The flow passage P2 is connected to the mixing means M1. The flow passage P3 is connected to the mixing means M2. The flow passage P4 is connected to the mixing means M3. The flow passage P5 is connected to the mixing means M4. The flow passage R1 is connected to the mixing means M1 and the mixing means M2. The flow passage R1 also serves as a reaction section. The flow passage R2 is connected to the mixing means M2 and the mixing means M3. The flow passage R2 also serves as a reaction section. The flow passage R3 is connected to the mixing means M3 and the mixing means M4. The flow passage R3 also serves as a reaction section. The flow passage R4 is connected to the mixing means M4. The flow passage R4 also serves as a reaction section.

[0116] An alkylaryl compound is supplied to the mixing means M1 from a flow path P1. Sec-BuLi is supplied to the mixing means M1 from a flow path P2. Then, the alkylaryl compound and sec-BuLi are mixed in the mixing means M1, and an addition reaction is started in the resulting liquid, and the initiator represented by the general formula (1) is produced. The liquid during the reaction flows through the flow path R1, which is also a reaction section, while reacting. The liquid containing the initiator represented by the general formula (1) flowing through the flow passage R1 is introduced into the mixing means M2. In the mixing means M2, the liquid is mixed with a halogenated styrene monomer supplied from the flow passage P3, and in the resulting liquid, living anionic polymerization of the halogenated styrene monomer is initiated using the initiator represented by the general formula (1) as an anionic polymerization initiator, to produce a living polymer. The liquid undergoing the polymerization reaction flows, for example, through the flow channel R2, which is also a reaction section, while polymerizing. The liquid containing the living polymer flowing through the flow channel R2 is introduced into the mixing means M3. In the mixing means M3, the liquid is mixed with styrene or a styrene derivative supplied from the flow channel P4, and in the resulting liquid, living anionic polymerization of styrene or a styrene derivative is initiated at the growing end of the living polymer to produce a living polymer. The liquid undergoing the polymerization reaction flows, for example, through the flow channel R3, which is also a reaction section, while polymerizing. The resulting polymer is a living polymer. Therefore, in order to terminate the active ends, a solution containing a terminator (for example, methanol) is circulated through the flow channel P5 and mixed with the polymer solution in the mixing means M4 to carry out the termination reaction.

[0117] FIG. 4 is a schematic diagram showing an example of a flow microreactor. The flow microreactor shown in FIG. 4 includes three mixing means and seven flow paths. The flow passage P1 is connected to a mixing means M1. The flow passage P2 is connected to the mixing means M1. The flow passage P3 is connected to the mixing means M2. The flow passage P4 is connected to the mixing means M3. The flow passage R1 is connected to the mixing means M1 and the mixing means M2. The flow passage R1 also serves as a reaction section. The flow passage R2 is connected to the mixing means M2 and the mixing means M3. The flow passage R2 also serves as a reaction section. The flow passage R3 is connected to the mixing means M3. The flow passage R3 also serves as a reaction section.

[0118] A BuLi solution is supplied to the mixing means M1 through a flow path P1. A THF solution is supplied to the mixing means M1 through a flow path P2. Then, the BuLi solution and the THF solution are mixed in the mixing means M1 and flow through a flow path R1. The BuLi solution flowing through the flow passage R1 is introduced into the mixing means M2. In the mixing means M2, the BuLi solution is mixed with the halogenated styrene polymer solution supplied from the flow passage P3, and the halogenated styrene polymer is lithiated. The liquid undergoing the reaction flows through flow path R2, which also serves as the reaction section. A solution containing an electrophilic reagent is then circulated through flow path P4, and mixed with the polymer solution by mixing means M3 to perform functionalization. EXAMPLES

[0119] Examples of the present invention will be described below, but the present invention is not limited to these examples.

[0120] (Production Example 1: Production of bromostyrene polymer) An integrated flow microreactor system was used, which is shown in Figure 5 and consists of a V-type micromixer (M1: manufactured by Sanko Seiki Kogyo Co., Ltd.), two T-type micromixers (M2 and M3: manufactured by Sanko Seiki Kogyo Co., Ltd.), microtube reactors (R1, R1”, R2, and R3: manufactured by GL Sciences), one PTFE tube (R1’: manufactured by ISIS Co., Ltd.), and a 100 cm pre-cooling unit (P1, P2, P3, and P4: manufactured by GL Sciences).

[0121] The flow reactor consisting of P1, P2, M1, and R1 was cooled at 20°C, and the flow reactor consisting of P3, P4, M2, M3, R1″, R2, and R3 was cooled at −40°C. The stainless steel reactors in the cooling baths at different temperatures were connected with a PTFE tube (R1'). An α-methylstyrene solution (0.12 M in THF, flow rate: 5.625 mL / min; 1.5 molar equivalents relative to sec-BuLi) and a solution of sec-BuLi (0.2 M in hexane, flow rate: 2.25 mL / min) were introduced into M1 (φ = 250 μm) by a syringe pump, and the mixture (initiator solution) was poured into R1 (inner diameter 1000 μm, 100 cm, t R1 =6.0s). The initiator solution was placed in R1' (inner diameter 1000 μm, 12.5 cm, t R1’ =0.75s) and R1” (inner diameter 1000μm, 87.5cm, t R1’’ = 5.2 s) and cooled to -40 °C.

[0122] Next, the initiator solution and p-bromostyrene solution (0.75 M THF solution, flow rate: 12.0 mL / min) were mixed in M2 (φ=500 μm), and the mixture was transferred to R2 (inner diameter 1000 μm, 100 cm, t R2 =2.1s). The obtained solution was introduced into M3 (φ=500 μm), and a MeOH solution (0.15 M in THF, flow rate: 4.5 mL / min) was introduced thereinto, and the mixture was transferred to R3 (inner diameter 1000 μm, 100 cm, t R3 =1.7s). After reaching steady state, an aliquot of the product solution was collected for 10 seconds, and the aliquot was treated with saturated aqueous NH4Cl and brine. The solution was diluted with THF, and then n-tetradecane was added as an internal standard for GC. After filtration, the solution was analyzed by GC and GPC. The results are shown in Table 1. The MALDI-TOFMS spectrum of the obtained poly-p-bromostyrene is shown in FIG.

[0123] -GC analysis- The analysis was performed using a SHIMAZU GC-2014 equipped with a Restek Rtx-200 column, and each compound was detected by FID. The conversion rates of α-methylstyrene and p-bromostyrene were determined to be 100% since no peaks were detected in GC analysis. The amount of styrene present was calculated using a calibration curve prepared using a styrene solution containing n-tetradecane as an internal standard.

[0124] -GPC analysis- The analysis was carried out in THF (FUJIFILM Wako Pure Chemical Industries, Ltd.) at 40 °C using a SHIMADZU Prominence equipped with a Shodex LF-604 column. Reflectance indices (RI) were recorded on a Shodex RI-504. Mn was determined by a calibration curve obtained from commercial polystyrene. Before GPC analysis, the solution was filtered through Millex-HN (Merck, 0.45 μm).

[0125] -MALDI-TOFMS- Mass spectrometry was performed using a Bruker Daltonics ultrafleXtreme MALDI-TOF mass spectrometer. The polymers were dissolved in THF and applied to the plate, and DCTB was used as the matrix. Sodium or silver salts were used as additives as appropriate.

[0126] [Table 1]

[0127] (Production Example 2: Production of chlorostyrene polymer) An integrated flow microreactor system was used, which is shown in Figure 7 and consists of a V-type micromixer (M1: manufactured by Sanko Seiki Kogyo Co., Ltd.), two T-type micromixers (M2 and M3: manufactured by Sanko Seiki Kogyo Co., Ltd.), microtube reactors (R1, R1”, R2, and R3: manufactured by GL Sciences), one PTFE tube (R1’: manufactured by ISIS Co., Ltd.), and a 100 cm pre-cooling unit (P1, P2, P3, and P4: manufactured by GL Sciences).

[0128] The flow reactor consisting of P1, P2, M1, and R1 was cooled at 20°C, and the flow reactor consisting of P3, P4, M2, M3, R1″, R2, and R3 was cooled at −40°C. The stainless steel reactors in the cooling baths at different temperatures were connected with a PTFE tube (R1'). An α-methylstyrene solution (0.12 M in THF, flow rate: 5.625 mL / min; 1.5 molar equivalents relative to sec-BuLi) and a solution of sec-BuLi (0.2 M in hexane, flow rate: 2.25 mL / min) were introduced into M1 (φ = 250 μm) by a syringe pump, and the mixture (initiator solution) was poured into R1 (inner diameter 1000 μm, 100 cm, t R1 =6.0s). The initiator solution was placed in R1' (inner diameter 1000 μm, 12.5 cm, t R1’ =0.75s) and R1” (inner diameter 1000μm, 87.5cm, t R1’’ = 5.2 s) and cooled to -40 °C.

[0129] Next, the initiator solution and p-chlorostyrene solution (0.75 M THF solution, flow rate: 12.0 mL / min) were mixed in M2 (φ=500 μm), and the mixture was transferred to R2 (inner diameter 1000 μm, 100 cm, t R2 =2.1s). The obtained solution was introduced into M3 (φ=500 μm), and a MeOH solution (0.15 M in THF, flow rate: 4.5 mL / min) was introduced thereinto, and the mixture was transferred to R3 (inner diameter 1000 μm, 100 cm, t R3 =1.7s). After reaching a steady state, an aliquot of the product solution was collected for 2 minutes and 30 seconds. The mixture was washed with brine and the organic phase was removed under reduced pressure. The polymer was then reprecipitated with THF and MeOH as good and poor solvents, respectively. Finally, 3.3 g of poly-p-chlorostyrene was obtained. The MALDI-TOFMS spectrum of the obtained poly-p-chlorostyrene (Mn=3388 Da, PDI=1.12) is shown in FIG.

[0130] (Example 1 Introduction of boryl groups (Bpin) into poly-p-bromostyrene by Miyaura boronation reaction) As shown in the following scheme, poly-p-bromostyrene (71 mg, Mn=4106 Da, PDI=1.20) obtained by the same procedure as in Preparation Example 1, tris(dibenzylideneacetone)dipalladium(0) (18 mg, 0.020 mmol), Xphos (36 mg, 0.076 mmol), bis(pinacolato)diboron (141 mg, 0.55 mmol), and KOAc (106 mg, 1.1 mmol) were dissolved in 1.8 mL of 1,4-dioxane and refluxed overnight under Ar atmosphere. The mixture was washed with brine and the organic phase was removed under reduced pressure. The modified polymer was then reprecipitated with THF and MeOH as good and poor solvents, respectively, to obtain 60 mg of the modified polymer (Mn=7338 Da, PDI=1.20). [ka]

[0131] The MALDI-TOFMS spectrum of the resulting modified polymer is shown in FIG. The peak interval in the MALDI-TOFMS spectrum of FIG. 6 is 183, and the peak interval in the MALDI-TOFMS spectrum of FIG. 9 is 230, indicating that boryl groups were successfully introduced into poly-p-bromostyrene.

[0132] (Example 2-1 Introduction of boryl group (Bpin) into poly-p-chlorostyrene by Miyaura boronation reaction) As shown in the following scheme, poly-p-chlorostyrene (49 mg, Mn=3388 Da, PDI=1.12) obtained in Preparation Example 2, tris(dibenzylideneacetone)dipalladium(0) (14 mg, 0.015 mmol), Xphos (33 mg, 0.070 mmol), bis(pinacolato)diboron (133 mg, 0.53 mmol), and KOAc (93 mg, 0.95 mmol) were dissolved in 1.7 mL of 1,4-dioxane and refluxed overnight under Ar atmosphere. The mixture was washed with brine and the organic phase was removed under reduced pressure. The modified polymer was then reprecipitated with THF and MeOH as good and poor solvents, respectively, to obtain 27 mg of the modified polymer (Mn=7599 Da, PDI=1.15). [ka]

[0133] The MALDI-TOFMS spectrum of the resulting modified polymer is shown in FIG. The peak interval in the MALDI-TOFMS spectrum of FIG. 8 is 138, and the peak interval in the MALDI-TOFMS spectrum of FIG. 10 is 230, which indicates that the boryl group was successfully introduced into poly-p-chlorostyrene.

[0134] (Example 2-2 Synthesis of poly-p-hydroxystyrene: multi-step modification) As shown in the following scheme, poly-p-Bpinstyrene (19 mg, Mn=7599 Da, PDI=1.15) obtained in Example 2-1 and K3PO4 (103 mg, 0.48 mmol) were dissolved in THF (4.2 mL), and Oxone® (84 mg, 0.14 mmol) in H2O (2.5 ml) was added dropwise. The mixture was stirred at room temperature for 1 hour. The solution was then washed with brine, and the organic phase was removed under reduced pressure. The polymer was purified by GPC (THF) to obtain 16 mg of the modified polymer (Mn=6961 Da, PDI=1.14). [ka] The MALDI-TOFMS spectrum of the resulting modified polymer is shown in FIG. The peak interval in the MALDI-TOFMS spectrum of FIG. 8 is 230, and the peak interval in the MALDI-TOFMS spectrum of FIG. 11 is 120, which indicates that the boryl group was successfully substituted with a hydroxy group.

[0135] (Example 3) Introduction of a phenyl group having an aldehyde group into poly-p-bromostyrene by Suzuki coupling reaction) As shown in the following scheme, poly-p-bromostyrene (202 mg, Mn=3471 Da, PDI=1.15) obtained in Preparation Example 1, 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzaldehyde (491 mg, 2.1 mmol), Pd(dppf)Cl2 (80 mg, 0.11 mmol), and K2CO3 (443 mg, 3.2 mmol) were dissolved in 10 mL of THF / H2O (9:1) and refluxed overnight under Ar atmosphere. The mixture was washed with brine and the organic phase was removed under reduced pressure. The modified polymer was then reprecipitated with THF and MeOH as good and poor solvents, respectively, to obtain 238 mg of modified polymer (Mn=4304 Da, PDI=1.11). [ka]

[0136] The MALDI-TOFMS spectrum of the resulting modified polymer is shown in FIG. The peak interval in the MALDI-TOFMS spectrum of FIG. 6 is 183, and the peak interval in the MALDI-TOFMS spectrum of FIG. 12 is 208, which indicates that a phenyl group having an aldehyde group was successfully introduced into poly-p-bromostyrene.

[0137] (Example 4) Introduction of a phenyl group having an epoxy group into poly-p-bromostyrene by Suzuki coupling reaction) As shown in the following scheme, poly-p-bromostyrene (49 mg, Mn=4106 Da, PDI=1.20) obtained in Preparation Example 1, 4,4,5,5-tetramethyl-2-(4-(oxiran-2-ylmethoxy)phenyl)-1,3,2-dioxaborolane (147 mg, 0.53 mmol), Pd(dppf)Cl2 (18 mg, 0.025 mmol), and K2CO3 (104 mg, 0.75 mmol) were dissolved in 2.6 mL of THF / H2O (9:1) and refluxed overnight under Ar atmosphere. The mixture was washed with brine and the organic phase was removed under reduced pressure. The modified polymer was then reprecipitated with THF and MeOH as a good and poor solvent, respectively, to obtain 75 mg of the modified polymer (Mn=6029 Da, PDI=1.20). [ka]

[0138] The MALDI-TOFMS spectrum of the resulting modified polymer is shown in FIG. The peak interval in the MALDI-TOFMS spectrum of FIG. 6 is 183, and the peak interval in the MALDI-TOFMS spectrum of FIG. 13 is 252, which indicates that epoxy groups were successfully introduced into poly-p-bromostyrene.

[0139] (Example 5) Introduction of a phenyl group having a vinyl group into poly-p-bromostyrene by Suzuki coupling reaction) As shown in the following scheme, poly-p-bromostyrene (52 mg, Mn=4106 Da, PDI=1.20) obtained in Preparation Example 1, 4,4,5,5-tetramethyl-2-(4-vinylphenyl)-1,3,2-dioxaborolane (126 mg, 0.55 mmol), Pd(dppf)Cl2 (19 mg, 0.026 mmol), and K2CO3 (107 mg, 0.77 mmol) were dissolved in 2.6 mL of THF / H2O (9:1), and a small amount of 4-tert-butylpyrocatechol was added as a polymerization inhibitor for styrene derivatives. The solution was then refluxed overnight under an Ar atmosphere. The mixture was washed with brine, and the organic phase was removed under reduced pressure. The modified polymer was then reprecipitated with THF and MeOH as a good and poor solvent, respectively, to obtain 92 mg of the modified polymer (Mn=6102 Da, PDI=1.33). [ka]

[0140] The MALDI-TOFMS spectrum of the resulting modified polymer is shown in FIG. The peak interval in the MALDI-TOFMS spectrum of FIG. 6 is 183, and the peak interval in the MALDI-TOFMS spectrum of FIG. 14 is 206, which indicates that a phenyl group having a vinyl group was introduced into poly-p-bromostyrene.

[0141] Example 6 Lithiation and Functionalization of Poly-p-Bromostyrene Using a Flow Reactor An integrated flow microreactor system was used, which is shown in Figure 15 and consists of two T-type micromixers (M1, M3: manufactured by Sanko Seiki Kogyo Co., Ltd.), one V-type micromixer (M2: manufactured by Sanko Seiki Kogyo Co., Ltd.), microtube reactors (R1, R2, and R3: manufactured by GL Sciences), and a 100 cm pre-cooling unit (P1, P2, P3, and P4: manufactured by GL Sciences).

[0142] The flow reactor composed of P1, P2, P3, P4, M1, M2, M3, R1, and R2 was cooled in an acetone-dry ice bath at -40°C, and the flow reactor composed of R3 was cooled in a water bath at 20°C. A nBuLi solution (1.58 M in hexane, commercially available, flow rate: 0.755 mL / min) and a THF solution (flow rate: 0.745 mL / min) were introduced into M1 (φ=250 μm) by a syringe pump, and the mixture was passed through R1 (25 cm). The BuLi solution and poly-p-bromostyrene solution (based on the number of Br groups estimated from MALDI-TOFMS measurement, 0.01 M THF solution, flow rate: 12.0 mL / min) were mixed in M2 (φ = 500 μm), and the mixture was passed through R2 (100 cm). The obtained solution was introduced into M3 (φ=500 μm), and the electrophilic reagent solution (1.2 M THF solution, flow rate: 2.0 mL / min) described in the following Examples 6-1 to 6-6 was introduced thereinto, and the mixture was passed through R3 (100 cm). After reaching a steady state, the resulting solution was collected in a vial containing 2 mL of saturated aqueous NH4Cl for 60 s. The mixture was washed with brine and the organic phase was removed under reduced pressure. The modified polymer was then reprecipitated.

[0143] (Example 6-1: Hydrogenation) Poly-p-bromostyrene (Mn=4106 Da, PDI=1.20) was used as an electrophile and MeOH was used as a good and poor solvent for reprecipitation to obtain 12.7 mg of the modified polymer (Mn=4255, PDI=1.15).

[0144] The MALDI-TOFMS spectrum of the resulting modified polymer is shown in FIG. The peak interval in the MALDI-TOFMS spectrum of FIG. 6 is 183, and the peak interval in the MALDI-TOFMS spectrum of FIG. 16 is 104, which indicates that the bromine in poly-p-bromostyrene was successfully substituted with a hydrogen atom.

[0145] (Example 6-2 D) Poly-p-bromostyrene (Mn=4106 Da, PDI=1.20) was reprecipitated using CD3OD as an electrophile with THF and MeOH as good and poor solvents, respectively, to obtain 13 mg of the modified polymer (Mn=3764 Da, PDI=1.18).

[0146] The MALDI-TOFMS spectrum of the resulting modified polymer is shown in FIG. The peak interval in the MALDI-TOFMS spectrum of FIG. 6 is 183, and the peak interval in the MALDI-TOFMS spectrum of FIG. 17 is 105, which indicates that the bromine in poly-p-bromostyrene was successfully substituted with deuterium.

[0147] (Example 6-3 Borylation) Poly-p-bromostyrene (Mn=4106 Da, PDI=1.20) was used as the electrophile, and 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was used as the electrophile. THF and MeOH were used as the good and poor solvents, respectively, to reprecipitate the modified polymer (Mn=6623 Da, PDI=1.15), yielding 16 mg of the polymer.

[0148] The resulting modified polymer 1 The H-NMR spectrum is shown in Figure 18. In FIG. 18, the large peak near 1.5 ppm is a peak derived from the pinacolboryl group. The results in FIG. 18 show that the pinacolboryl group was successfully introduced into poly-p-bromostyrene.

[0149] (Example 6-4 Formylation) Poly-p-bromostyrene (Mn=4106 Da, PDI=1.20) was reprecipitated using DMF as an electrophile with THF and hexane as good and poor solvents, respectively, to obtain 18 mg of the modified polymer (Mn=4534 Da, PD=1.20).

[0150] The resulting modified polymer 1 The H-NMR spectrum is shown in Figure 19. In FIG. 19, the peak at about 10 ppm is a peak derived from an aldehyde group. The results in FIG. 19 show that aldehyde groups were successfully introduced into poly-p-bromostyrene. (Example 6-5 Esterification) Poly-p-bromostyrene (Mn=4106 Da, PDI=1.20) was reprecipitated using methyl chloroformate as an electrophile with THF and MeOH as good and poor solvents, respectively, to obtain 15 mg of the modified polymer (Mn=6439 Da, PDI=1.39).

[0151] The resulting modified polymer 1 The H-NMR spectrum is shown in Figure 20. In FIG. 20, the peak at about 4 ppm is a peak derived from the methyl ester. The results in FIG. 20 show that the methyl ester was successfully introduced into poly-p-bromostyrene.

[0152] (Example 6-6 TMS conversion) Poly-p-bromostyrene (Mn=4106 Da, PDI=1.20) was reprecipitated using TMSCl as an electrophile and THF and MeOH as good and poor solvents, respectively, to obtain 18 mg of the modified polymer (Mn=5597 Da, PDI=1.16).

[0153] The resulting modified polymer 1 The H-NMR spectrum is shown in Figure 21. In FIG. 21, the peak at about 0.3 ppm is a peak derived from the methyl group of TMS. The results in FIG. 21 show that trimethylsilyl groups were successfully introduced into poly-p-bromostyrene.

[0154] (Example 7) Partial lithiation and functionalization of poly-p-bromostyrene using a flow reactor and subsequent synthesis of block copolymers by Suzuki coupling) An integrated flow microreactor system was used, which is shown in FIG. 22 and consists of two T-type micromixers (M1, M3: manufactured by Sanko Seiki Kogyo Co., Ltd.), one V-type micromixer (M2: manufactured by Sanko Seiki Kogyo Co., Ltd.), microtube reactors (R1, R2, and R3: manufactured by GL Sciences), and a 100 cm pre-cooling unit (P1, P2, P3, and P4: manufactured by GL Sciences).

[0155] (Example 7-1 Partial lithiation and TMSification of poly-p-bromostyrene using a flow reactor) The flow reactor composed of P1, P2, P3, P4, M1, M2, M3, R1, and R2 was cooled in an acetone-dry ice bath at -40°C, and the flow reactor composed of R3 was cooled in a water bath at 20°C. A nBuLi solution (1.58 M in hexane, commercially available, flow rate: 0.151 mL / min) and a THF solution (flow rate: 1.349 mL / min) were introduced into M1 (φ=250 μm) by a syringe pump, and the mixture was passed through R1 (25 cm). The BuLi solution and poly-p-bromostyrene solution (based on the number of Br groups estimated from MALDI-TOFMS measurement, 0.01 M THF solution, flow rate: 12.0 mL / min, Mn = 4106 Da, PDI = 1.20) were mixed in M2 (φ = 500 μm), and the mixture was passed through R2 (100 cm). The obtained solution was introduced into M3 (φ=500 μm), and a TMSCl solution (1.2 M in THF, flow rate: 2.0 mL / min) was introduced therein, and the mixture was passed through R3 (100 cm). After reaching a steady state, the resulting solution was collected in a vial containing 2 mL of saturated aqueous NH4Cl for 120 s. The mixture was washed with brine and the organic phase was removed under reduced pressure. The modified polymer was then reprecipitated.

[0156] (Example 7-2 Suzuki Coupling) As shown in the following scheme, the total amount of modified polymer obtained in Example 7-1, 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzaldehyde (121 mg, 0.52 mmol), Pd(dppf)Cl2 (18 mg, 0.024 mmol), and K2CO3 (124 mg, 0.90 mmol) were dissolved in 2.6 mL of THF / H2O (9:1) and refluxed overnight under Ar atmosphere. The mixture was washed with brine, and the organic phase was removed under reduced pressure. The modified polymer was then reprecipitated with THF and MeOH as good and poor solvents, respectively, to obtain 39 mg of modified polymer (Mn=6383 Da, PDI=1.14). [ka]

[0157] The resulting modified polymer 1 The H-NMR spectrum is shown in Figure 23. In FIG. 23, the peak near 10 ppm is a peak derived from an aldehyde group, and the peak near 0.3 ppm is a peak derived from a methyl group of TMS. The results in FIG. 23 show that a random copolymer was synthesized from poly-p-bromostyrene.

[0158] Mass spectrometry is the most accurate method for identifying the synthesized polymer. If the conversion rate of the halogen in the polyhalostyrene is high enough, about 100%, mass spectrometry will give a distribution of peaks spaced by the masses of the units that make up the polymer. For example, in the case of the introduction of benzaldehyde by Suzuki coupling, the resulting polymer will have peaks spaced by 208 m / z in MALDI-TOFMS. In the functionalization after lithiation, the hydrogenation and deuterated functionalization using methanol and deuterated methanol were not complete, but the peaks were relatively sharp and could be identified by MALDI-TOFMS. In the TMS reaction, borylation, formylation, and esterification following lithiation, the lithiation proceeded with sufficient conversion, but the functionalization did not proceed sufficiently, so identification by mass spectrometry was not possible. 1 In the H-NMR spectrum, characteristic peaks derived from TMS groups, pinacolboryl groups, aldehyde groups, and methyl ester groups were observed, and it was determined that functionalization had been carried out based on the appearance of these peaks that were not observed in the raw material.

[0159] Examples of aspects of the present invention include the following. <1> The method for producing a polymer includes an anionic polymerization step of anionically polymerizing a halogenated styrene monomer in the presence of an initiator represented by the following general formula (1) using a microreactor, and a modification step of modifying the polymer obtained in the anionic polymerization step. In the above general formula (1), R 1 and R 2 One of them is an aryl group, and the other is an aryl group or an alkyl group having 1 to 10 carbon atoms. [ka] <2> The aryl group is a phenyl group. <1> The present invention relates to a method for producing a polymer according to the present invention. <3> In the general formula (1), R 1 and R 2 one of the groups is an alkyl group having 1 to 10 carbon atoms. <1> from <2> The present invention relates to a method for producing a polymer according to any one of the above. <4> The initiator represented by the general formula (1) is obtained by reacting sec-BuLi with an alkylaryl compound. <1> from <3> The present invention relates to a method for producing a polymer according to any one of the above. <5> The method further comprises a step of polymerizing a monomer with the polymer obtained by anionically polymerizing the halogenated styrene monomer in the anionic polymerization step, the monomer being styrene or a styrene derivative. <1> from <4> The present invention relates to a method for producing a polymer according to any one of the above. <6> The modification in the modification step includes substituting at least a part of the halogen atoms in the polymer with the same or different functional groups by at least one of Suzuki coupling reaction, Miyaura boronation reaction, and lithiation reaction. <1> from <5> The present invention relates to a method for producing a polymer according to any one of the above. <7> The modification in the modifying step includes substituting at least a portion of the halogen atoms in the polymer with hydroxy groups. <6> The present invention relates to a method for producing a polymer according to the present invention. <8> the modification in the modification step includes substituting at least a part of the halogen atoms in the polymer with boron-containing groups by a Miyaura boronation reaction, and substituting the substituted boron-containing groups with hydroxy groups by an oxidizing agent; <6> The present invention relates to a method for producing a polymer according to the present invention. <9> The modification in the modification step includes modifying the polymer using a microreactor. <1> from <8> The present invention relates to a method for producing a polymer according to any one of the above. <10> The polymer is represented by either of the following general formulas (3) or (4) and has a molecular weight distribution of 1.4 or less. [ka] In the general formula (3), m and n represent the degree of polymerization, m is an integer of 0 or more, and n is an integer of 1 or more. 5 and R 6 one of them is an aryl group and the other is an aryl group or an alkyl group having 1 to 10 carbon atoms; X is any one of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and an astatine atom; Y is a hydrogen atom, a deuterium atom, an aldehyde group, a boryl group, a hydroxy group, an acetoxy group, a trimethylsilyl group, or a group represented by any one of the following structural formulas (4) to (6); and a is an integer of 1 to 5. The bonding order of the styrene structural unit not having a Y group and the styrene structural unit having a Y group is in no particular order, and the polymer may be a random polymer or a block polymer. [ka] [ka] [ka] [ka] In the general formula (4), m and n each represent a degree of polymerization and are an integer of 1 or more. 5 and R 6 one of them is an aryl group and the other is an aryl group or an alkyl group having 1 to 10 carbon atoms; and Y is a hydrogen atom, a deuterium atom, an aldehyde group, a boryl group, a hydroxy group, an acetoxy group, a trimethylsilyl group, or a group represented by any one of the following structural formulas (4) to (6). The styrene structural unit having a benzaldehyde group and the styrene structural unit having a Y group may be bonded in any order, and the polymer may be a random polymer or a block polymer. [ka] [ka] [ka]

Claims

1. an anionic polymerization step of anionically polymerizing a halogenated styrene monomer using a microreactor in the presence of an initiator represented by the following general formula (1); A method for producing a polymer, comprising the step of modifying the polymer obtained in the anionic polymerization step. 【Chemistry 1】 In the above general formula (1), R １ and R ２ One of the groups is an aryl group, and the other is an aryl group or an alkyl group having 1 to 10 carbon atoms.

2. The method for producing a polymer according to claim 1 , wherein the aryl group is a phenyl group.

3. In the general formula (1), R １ and R ２ The method for producing a polymer according to claim 1 or 2, wherein one of the above is an alkyl group having 1 to 10 carbon atoms.

4. The method for producing a polymer according to any one of claims 1 to 3, wherein the initiator represented by the general formula (1) is obtained by reacting sec-BuLi with an alkylaryl compound.

5. The method further comprises a step of polymerizing a monomer with respect to the polymer obtained by anionically polymerizing the halogenated styrene monomer in the anionic polymerization step, The method for producing a polymer according to any one of claims 1 to 4, wherein the monomer is styrene or a styrene derivative.

6. 6. The method for producing a polymer according to claim 1 , wherein the modification in the modification step comprises substituting at least a portion of the halogen atoms in the polymer with the same or different functional groups by at least any one of Suzuki coupling reaction, Miyaura borylation reaction, and lithiation reaction.

7. The method for producing a polymer according to claim 6 , wherein the modification in the modifying step comprises substituting at least a portion of the halogen atoms in the polymer with hydroxy groups.

8. 7. The method for producing a polymer according to claim 6, wherein the modification in the modification step comprises substituting at least a portion of the halogen atoms in the polymer with boron-containing groups by a Miyaura boronation reaction, and substituting the substituted boron-containing groups with hydroxy groups using an oxidizing agent.

9. The method for producing a polymer according to claim 1 , wherein the modification in the modification step comprises modifying the polymer using a microreactor.

10. A polymer represented by the following general formula (3) or (4), having a molecular weight distribution of 1.4 or less: 【Chemistry 2】 In the general formula (3), m and n represent the degree of polymerization, m is an integer of 0 or more, and n is an integer of 1 or more. ５ and R ６ one of these is an aryl group and the other is an aryl group or an alkyl group having 1 to 10 carbon atoms; X is any one of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and an astatine atom; Y is a hydrogen atom, a deuterium atom, an aldehyde group, a boryl group, a hydroxy group, an acetoxy group, a trimethylsilyl group, or a group represented by any one of the following structural formulas (4) to (6); and a is an integer of 1 to 5. The bonding order of the styrene structural unit not having a Y group and the styrene structural unit having a Y group is in no particular order, and the polymer may be a random polymer or a block polymer. 【Chemistry 3】 【Chemistry 4】 【Chemistry 5】 【Chemistry 6】 In the general formula (4), m and n each represent a degree of polymerization and are an integer of 1 or more. ５ and R ６ one of the above is an aryl group and the other is an aryl group or an alkyl group having 1 to 10 carbon atoms; and Y is a hydrogen atom, a deuterium atom, an aldehyde group, a boryl group, a hydroxy group, an acetoxy group, a trimethylsilyl group, or a group represented by any one of the following structural formulas (4) to (6). The bonding order of the styrene structural unit having a benzaldehyde group and the styrene structural unit having a Y group is in any order, and the polymer may be a random polymer or a block polymer. 【Chemistry 7】 【Chemistry 8】 【Chemistry 9】

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