Polymer manufacturing method

Abstract

To provide a method of producing a halogenated styrene polymer with high efficiency, high conversion and narrow dispersity.SOLUTION: The polymer production method comprises using a microreactor for subjecting a halogenated styrenic monomer to anionic polymerization in the presence of an initiator represented by the general formula (1) in the figure. (In the general formula (1), one of R1 and R2 is an aryl group and the other is an aryl group or C1-10 alkyl group.)SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a method for producing a polymer. By law Regarding. [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-based 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 styrene using sec-BuLi as an initiator has been reported (for example, see Non-Patent Document 3), halogenated styrene polymers with high conversion and narrow dispersion have not been obtained.

[0005] Therefore, a method for efficiently producing a halogenated styrene polymer with a high conversion rate and a narrow dispersion has not yet been provided, and there is a strong demand for the prompt provision of such a method. [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 halogenated styrene polymer with a high conversion rate and a narrow polydispersity. [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 the step of anionically polymerizing a halogenated styrene monomer using a microreactor in the presence of an initiator represented by the following general formula (1) (wherein, in the general formula (1), R 1 and R 2 It has been found that by using a halogenated styrene polymer having a high conversion rate and a narrow polydispersity, a method for producing a halogenated styrene polymer having a high conversion rate and a narrow polydispersity 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 the step of anionically polymerizing a halogenated styrene monomer using a microreactor in the presence of an initiator represented by the following general formula (1), 1and 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> A halogenated styrene monomer polymerization initiator represented by the following general formula (1) (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] <3> A method for producing a halogenated styrene monomer polymerization initiator represented by the following general formula (1), comprising a step of reacting sec-BuLi with an alkylaryl compound. 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] <4> The polymer is represented by either of the following general formulas (3) or (4). (In the general formula (3), m represents the degree of polymerization and is an integer of 1 or more.) 5 represents an aryl group or an alkyl group having 1 to 10 carbon atoms; X represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an astatine atom; and a represents an integer of 1 to 5. In the general formula (4), m and n represent the degree of polymerization, each of which is an integer of 1 or more; R 5 is an aryl group or an alkyl group having 1 to 10 carbon atoms; R 6 represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an astatine atom, an alkyl group having 1 to 4 carbon atoms, or a trimethylsilyl group; X represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an astatine atom; and a and b each represent an integer of 1 to 5. [ka] [ka] Effect of the Invention

[0010] According to the present invention, there can be provided a method for efficiently producing a halogenated styrene polymer with a high conversion and a narrow polydispersity. [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 the microreactor system used in Examples 1 and 2 and Comparative Examples 1 to 4. [Diagram 5] FIG. 5 is a schematic diagram of the microreactor system used in Examples 3 to 7 and 17 to 32. [Figure 6] FIG. 6 is a schematic diagram of the microreactor system used in Examples 8 to 9. [Figure 7] FIG. 7 is a schematic diagram of the microreactor system used in Examples 10 to 12. [Figure 8] FIG. 8 is a GPC chart of Examples 10 to 12. [Figure 9] FIG. 9 is a schematic diagram of the microreactor system used in Examples 13 to 16. [Figure 10] FIG. 10 is a schematic diagram of the microreactor system used in Examples 33 to 48. [Figure 11] FIG. 11 is a schematic diagram of the microreactor system used in Examples 49 to 51. [Figure 12] FIG. 12 is a schematic diagram of the microreactor system used in Examples 52 to 57. [Figure 13] FIG. 13 is a schematic diagram of the microreactor system used in Example 58. [Figure 14] FIG. 14 is a MALDI-TOF MS spectrum of the poly-p-chlorostyrene obtained in Example 58. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] (Polymer manufacturing method) The method for producing the polymer includes an anionic polymerization 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. For example, there is a method in which sec-BuLi is reacted with an alkylaryl compound.

[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. 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.

[0025] 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.

[0026] 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.

[0027] 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. 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.

[0028] 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.

[0029] 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.

[0030] -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.

[0031] 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.

[0032] 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.

[0033] --Integrated flow microreactor-- The mixing means and the flow passage of the integrated flow microreactor may be a substrate-type micromixer.

[0034] 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."

[0035] 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.

[0036] 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.

[0037] 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.

[0038] --Separate flow microreactor-- The separate type flow microreactor is configured by connecting a mixing means and a flow passage.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] 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).

[0043] 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.

[0044] 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.

[0045] In addition, since the flow path in the mixing means is minute, the liquids introduced into the mixing means naturally tend to 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] 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).

[0053] 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.

[0054] 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.

[0055] 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.

[0056] 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.

[0057] 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.

[0058] 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.

[0059] --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.

[0060] 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.

[0061] 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.

[0062] 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.

[0063] <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.

[0064] -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.

[0065] -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.

[0066] The monomer is not particularly limited and can be appropriately selected depending on the purpose. Examples of the monomer include styrene and styrene derivatives.

[0067] (Initiator for polymerization of halogenated styrene monomers) The initiator for polymerization of the halogenated styrene monomer is the same as the initiator described above.

[0068] (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.

[0069] (polymer) The polymer can be produced by the above-mentioned method for producing a polymer.

[0070] 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).

[0071] [ka] In the general formula (3), m represents the degree of polymerization and is an integer of 1 or more; 5 represents an aryl group or an alkyl group having 1 to 10 carbon atoms; X represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an astatine atom; and a represents an integer of 1 to 5.

[0072] In the general formula (3), m 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.

[0073] R in the general formula (3) 5 is not particularly limited as long as it is an aryl group or an alkyl group having 1 to 10 carbon atoms and can be appropriately selected depending on the purpose, but is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably a methyl group.

[0074] X in the general formula (3) is not particularly limited as long as it is a halogen atom and can be appropriately selected depending on the purpose, but is preferably a chlorine atom or a bromine atom.

[0075] [ka] In the general formula (4), m and n each represent a degree of polymerization and are an integer of 1 or more; 5 is an aryl group or an alkyl group having 1 to 10 carbon atoms; R 6 represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an astatine atom, an alkyl group having 1 to 4 carbon atoms, or a trimethylsilyl group; X represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an astatine atom; and a and b each represent an integer of 1 to 5.

[0076] In the general formula (4), m 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.

[0077] 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.

[0078] R in the general formula (4) 5 is not particularly limited as long as it is an aryl group or an alkyl group having 1 to 10 carbon atoms and can be appropriately selected depending on the purpose, but is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably a methyl group.

[0079] R in the general formula (4) 6 is not particularly limited as long as it is any of a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an astatine atom, an alkyl group having 1 to 4 carbon atoms, or a trimethylsilyl group, and can be appropriately selected depending on the purpose, but is preferably any of a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, or a trimethylsilyl group.

[0080] X in the general formula (4) is not particularly limited as long as it is a halogen atom and can be appropriately selected depending on the purpose, but is preferably a chlorine atom or a bromine atom.

[0081] 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 is measured by the following GPC analysis.

[0082] -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).

[0083] 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.

[0084] 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.

[0085] 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.

[0086] 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.

[0087] 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.

[0088] 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.

[0089] 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. EXAMPLES

[0090] Examples of the present invention will be described below, but the present invention is not limited to these examples.

[0091] <Production of bromostyrene polymer 1> Example 1 A flow microreactor system was used, which is shown in Figure 4 and consists of two T-type micromixers (M1 and M2: manufactured by Sanko Seiki Kogyo Co., Ltd.), microtube reactors (R1 and R2: manufactured by GL Sciences), and a 100 cm pre-cooling unit (P1, P2, and P3: manufactured by GL Sciences).

[0092] The flow microreactor system was placed in a tank at 20°C, and a diphenylhexyllithium (DPHLi) solution (flow rate: 6.0 mL / min) and a 4-bromostyrene solution (0.75 M THF solution: 4-bromostyrene (Tokyo Chemical Industry Co., Ltd.) was added to THF (Fujifilm Wako Pure Chemical Industries Co., Ltd.) to prepare a 0.75 M solution, flow rate: 12 mL / min) prepared by the following method were mixed in M1 (φ = 500 μm), and the mixture was mixed in R1 (inner diameter 1000 μm, 100 cm, t R1 =2.6s). The obtained solution was introduced into M2 (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 R2 (inner diameter 1000 μm, 100 cm, t R2 =2.1s). After reaching a steady state, collect an aliquot of the product solution for 10 s and immerse the aliquot in saturated NH 4 The solution was treated with aqueous Cl and brine. After dilution with THF and filtration, the solution was analyzed by gel permeation chromatography (GPC) as described below. The results are shown in Table 1.

[0093] -DPHLi manufacturing method- DPHLi was prepared by adding 1.0 equivalent of sec-BuLi (Kanto Chemical Co., Ltd.) dropwise to a 1,2-diphenylethylene THF solution (prepared by adding THF (FUJIFILM Wako Pure Chemical Industries, Ltd.) to 1,2-diphenylethylene (Tokyo Chemical Industry Co., Ltd.)) at 0°C.

[0094] -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).

[0095] [Table 1]

[0096] Example 2 The same procedure as in Example 1 was carried out, except that the flow microreactor system was placed in a bath at −40° C. The results are shown in Table 1.

[0097] Comparative Example 1 Except for using n-BuLi instead of DPHLi, the same procedure as in Example 1 was carried out. The results are shown in Table 1.

[0098] Comparative Example 2 The same procedure as in Example 2 was carried out except that n-BuLi was used instead of DPHLi. The results are shown in Table 1.

[0099] Comparative Example 3 Except for using sec-BuLi instead of DPHLi, the same procedure as in Example 1 was carried out. The results are shown in Table 1.

[0100] Comparative Example 4 The same procedure as in Example 2 was carried out except that sec-BuLi was used instead of DPHLi. The results are shown in Table 1.

[0101] The results in Table 1 show that when DPHLi was used as an initiator, the conversion rate of bromostyrene was higher than that when n-BuLi or sec-BuLi was used, and the target bromostyrene polymer could be produced while keeping the yield of styrene, which is not the target product, low (i.e., the lithiation reaction did not proceed).

[0102] <Production of bromostyrene polymer 2> Example 3 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).

[0103] 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: 3.75 mL / min; 1.0 molar equivalent 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 passed through R1 (inner diameter 1000 μm, 100 cm). The initiator solution was passed through R1' (inner diameter 1000 μm, 12.5 cm) and R1'' (inner diameter 1000 μm, 87.5 cm) and cooled to -40°C.

[0104] Next, the initiator solution and 4-bromostyrene solution (0.75 M in THF, flow rate: 12.0 mL / min) were mixed in M2 (φ=500 μm), and the mixture was passed through R2 (inner diameter 1000 μm, 100 cm). 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 therein, and the mixture was passed through R3 (inner diameter 1000 μm, 100 cm). After reaching a steady state, collect an aliquot of the product solution for 10 s and immerse the aliquot in saturated NH 4The solution was treated with aqueous Cl and brine. The solution was diluted with THF, and 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 2.

[0105] [Table 2]

[0106] Example 4 The same procedure as in Example 3 was carried out, except that the flow reactor composed of P1, P2, M1, and R1 was heated at 35° C. The results are shown in Table 2.

[0107] Example 5 The same procedure as in Example 3 was carried out, except that the flow reactor composed of P1, P2, M1, and R1 was cooled to −40° C. The results are shown in Table 2.

[0108] Example 6 The same procedure as in Example 3 was carried out except that the flow rate of the α-methylstyrene solution was set to 5.625 mL / min (1.5 molar equivalents relative to sec-BuLi). The results are shown in Table 2.

[0109] Example 7 The same procedure as in Example 3 was carried out except that the flow rate of the α-methylstyrene solution was set to 7.5 mL / min (2.0 molar equivalents relative to sec-BuLi). The results are shown in Table 2.

[0110] The results in Table 2 show that when an initiator obtained by reacting sec-BuLi with an alkylaryl compound is used, a bromostyrene polymer having a narrow molecular weight distribution can be produced. In addition, it was found that when the alkylaryl compound was used in an amount of 1.5 molar equivalents or more relative to sec-BuLi, the desired bromostyrene polymer could be produced while maintaining a lower yield of styrene, which is not the desired product, compared to when the amount was 1.0 molar equivalent.

[0111] <Production of bromostyrene polymer 3> Example 8 An integrated flow microreactor system was used, which is shown in Figure 6 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'), and a 100 cm pre-cooling unit (P1, P2, P3, and P4: manufactured by GL Sciences). The flow reactor consisting of P1, P2, M1, and R1 was heated at 35°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) 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.

[0112] Next, the initiator solution and the 2-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 a steady state, collect an aliquot of the product solution for 10 s and immerse the aliquot in saturated NH 4 The solution was treated with aqueous Cl and brine. After dilution with THF and filtration, the solution was analyzed by GPC. The results are shown in Table 3.

[0113] [Table 3]

[0114] Example 9 The same procedure as in Example 8 was repeated except that 3-bromostyrene was used instead of 2-bromostyrene. The results are shown in Table 3.

[0115] The results in Table 3 show that when 2-bromostyrene or 3-bromostyrene was used, a bromostyrene polymer having a narrow molecular weight distribution could be produced, similar to the case of 4-bromostyrene.

[0116] <Production of bromostyrene polymer 4> Example 10 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.), three T-type micromixers (M2, M3, and M4: manufactured by Sanko Seiki Kogyo Co., Ltd.), microtube reactors (R1, R1'', R2, R3, and R4: manufactured by GL Sciences), one PTFE tube (R1'), and a 100 cm pre-cooling unit (P1, P2, P3, P4, and P5: manufactured by GL Sciences). The flow reactor consisting of P1, P2, M1, and R1 was heated at 35°C, and the flow reactor consisting of P3, P4, P5, M2, M3, M4, R1″, R2, R3, and R4 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) 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 -4°C.

[0117] Next, the initiator solution and the 2-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 styrene solution (3.0 M in THF, flow rate: 6.0 mL / min) was introduced therein. Pour the mixed solution into R3 (inner diameter 1000μm, 200cm, t R3 =3.6 s), mixed with MeOH (0.60 M in THF, flow rate: 1.5 mL / min), and the resulting solution was poured into R4 (inner diameter 1000 μm, 100 cm, t R4 =3.4s). After reaching a steady state, collect an aliquot of the resulting solution for 10 s and immerse the aliquot in saturated NH 4 The solution was treated with an aqueous Cl solution and brine. The solution was diluted with THF, filtered, and then analyzed by GPC. The results are shown in Table 4. The GPC chart is shown on the left in Figure 8.

[0118] [Table 4]

[0119] Example 11 The same procedure as in Example 10 was repeated except that 3-bromostyrene was used instead of 2-bromostyrene. The results are shown in Table 4. The GPC chart is shown in the center of FIG.

[0120] Example 12 The same procedure as in Example 10 was repeated except that 4-bromostyrene was used instead of 2-bromostyrene. The results are shown in Table 4. The GPC chart is shown on the right side of FIG.

[0121] From the results in Table 4, it was found that when a bromostyrene polymer produced by reacting the initiator of the present invention with a bromostyrene compound is further reacted with a styrene monomer, a block copolymer of a bromostyrene compound and styrene can be produced, and it was found that the reaction of the initiator of the present invention with a bromostyrene compound is living polymerization. Furthermore, the results in FIG. 8 demonstrate that this is a completely living polymerization.

[0122] <Production of bromostyrene polymer 5> (Example 13) An integrated flow microreactor system was used, which is shown in Figure 9 and consists of a V-type micromixer (M1: manufactured by Sanko Seiki Kogyo Co., Ltd.), three T-type micromixers (M2, M3, and M4: manufactured by Sanko Seiki Kogyo Co., Ltd.), microtube reactors (R1, R1'', R2, R3, and R4: manufactured by GL Sciences), one PTFE tube (R1'), and a 100 cm pre-cooling unit (P1, P2, P3, P4, and P5: manufactured by GL Sciences). The flow reactor consisting of P1, P2, M1, and R1 was heated at 35°C, and the flow reactor consisting of P3, P4, P5, M2, M3, M4, R1″, R2, R3, and R4 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) 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.

[0123] Next, the initiator solution and the 4-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 styrene solution (1.5 M in THF, flow rate: 3.0 mL / min) was introduced therein. The mixed solution was passed through R3 (inner diameter 1000 μm, 200 cm) and mixed with M4 in MeOH (0.60 M in THF, flow rate: 1.5 mL / min), and the resulting solution was passed through R4 (inner diameter 1000 μm, 100 cm). After reaching a steady state, collect an aliquot of the resulting solution for 10 s and immerse the aliquot in saturated NH 4 The solution was treated with aqueous Cl and brine. The solution was diluted with THF, n-tetradecane was added, and after filtration, the solution was analyzed by GC and GPC. The results are shown in Table 5.

[0124] [Table 5]

[0125] Example 14 The same procedure as in Example 13 was carried out except that the flow rate of the styrene solution was changed to 6.0 mL / min. The results are shown in Table 5.

[0126] Example 15 The same procedure as in Example 13 was carried out except that the flow rate of the styrene solution was changed to 9.0 mL / min. The results are shown in Table 5.

[0127] (Example 16) The same procedure as in Example 13 was carried out except that the flow rate of the styrene solution was changed to 12.0 mL / min. The results are shown in Table 5.

[0128] From the results in Table 5, it was found that the Mn value was proportional to the styrene equivalent, further proving the living nature.

[0129] <Production of bromostyrene polymer 6: Examination of reaction temperature> (Example 17) The same procedure as in Example 6 was repeated, except that the flow reactor consisting of P3, P4, M2, M3, R1", R2, and R3 was cooled to 20° C. The results are shown in Table 6.

[0130] [Table 6]

[0131] (Example 18) The same procedure as in Example 6 was repeated, except that the flow reactor consisting of P3, P4, M2, M3, R1", R2, and R3 was cooled to 0° C. The results are shown in Table 6.

[0132] (Example 19) The same procedure as in Example 6 was repeated, except that the flow reactor consisting of P3, P4, M2, M3, R1", R2, and R3 was cooled to -20°C. The results are shown in Table 6.

[0133] (Example 20) The same procedure as in Example 6 was repeated, except that the flow reactor consisting of P3, P4, M2, M3, R1", R2, and R3 was cooled to -78°C. The results are shown in Table 6.

[0134] Example 21 The same procedure as in Example 6 was repeated, except that 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 20° C. The results are shown in Table 6.

[0135] Example 22 The same procedure as in Example 6 was repeated, except that 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 0° C. The results are shown in Table 6.

[0136] (Example 23) The same procedure as in Example 6 was repeated, except that 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 −20° C. The results are shown in Table 6.

[0137] Example 24 The same procedure as in Example 6 was repeated, except that 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 results are shown in Table 6.

[0138] (Example 25) The same procedure as in Example 6 was repeated, except that 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 −78° C. The results are shown in Table 6.

[0139] (Example 26) The same procedure as in Example 6 was repeated, except that the flow reactor consisting of P1, P2, M1, and R1 was cooled at −40° C., and the flow reactor consisting of P3, P4, M2, M3, R1″, R2, and R3 was cooled at 20° C. The results are shown in Table 6.

[0140] Example 27 The same procedure as in Example 6 was repeated, except that the flow reactor consisting of P1, P2, M1, and R1 was cooled at −40° C., and the flow reactor consisting of P3, P4, M2, M3, R1″, R2, and R3 was cooled at 0° C. The results are shown in Table 6.

[0141] (Example 28) The same procedure as in Example 6 was repeated, except that the flow reactor consisting of P1, P2, M1, and R1 was cooled at −40° C., and the flow reactor consisting of P3, P4, M2, M3, R1″, R2, and R3 was cooled at −20° C. The results are shown in Table 6.

[0142] (Example 29) The same procedure as in Example 6 was repeated, except that the flow reactor consisting of P1, P2, M1, and R1 was cooled at −40° C., and the flow reactor consisting of P3, P4, M2, M3, R1″, R2, and R3 was cooled at −40° C. The results are shown in Table 6.

[0143] (Example 30) The same procedure as in Example 6 was repeated, except that the flow reactor consisting of P1, P2, M1, and R1 was cooled at −40° C., and the flow reactor consisting of P3, P4, M2, M3, R1″, R2, and R3 was cooled at −78° C. The results are shown in Table 6.

[0144] <Production of bromostyrene polymer 7: Consideration of reactor length> (Example 31) The same procedure as in Example 6 was repeated, except that the total length of the microtube reactor (R1), the microtube reactor (R1"), and the TFE tube (R1') was changed from 200 cm to 110 cm. The results are shown in Table 7.

[0145] Example 32 The same procedure as in Example 6 was repeated, except that the total length of the microtube reactor (R1), the microtube reactor (R1"), and the TFE tube (R1') was changed from 200 cm to 150 cm. The results are shown in Table 7.

[0146] [Table 7]

[0147] <Production of bromostyrene polymers 8: Effect of mixing efficiency> (Example 33) An integrated flow microreactor system was used, which is shown in Figure 10 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'), and a 100 cm pre-cooling unit (P1, P2, P3, and P4: manufactured by GL Sciences). 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: 1.406 mL / min) and a solution of sec-BuLi (0.2 M in hexane, flow rate: 0.5625 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.

[0148] Next, the initiator solution and the 4-bromostyrene solution (0.75 M THF solution, flow rate: 3 mL / min) were mixed in M2 (φ=1000 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, collect an aliquot of the product solution for 10 s and immerse the aliquot in saturated NH 4 The solution was treated with aqueous Cl and brine. The solution was diluted with THF and filtered, after which the solution was analyzed by GPC. The results are shown in Table 8.

[0149] [Table 8]

[0150] (Example 34) The same procedure as in Example 33 was repeated, except that the flow rate of the α-methylstyrene solution was changed to 2.8125 mL / min, the flow rate of the sec-BuLi solution was changed to 1.125 mL / min, and the flow rate of the 4-bromostyrene solution was changed to 6 mL / min. The results are shown in Table 8.

[0151] Example 35 The same procedure as in Example 33 was repeated, except that the flow rate of the α-methylstyrene solution was changed to 5.625 mL / min, the flow rate of the sec-BuLi solution was changed to 2.25 mL / min, and the flow rate of the 4-bromostyrene solution was changed to 9 mL / min. The results are shown in Table 8.

[0152] (Example 36) The same procedure was followed as in Example 33, except that the flow rate of the α-methylstyrene solution was changed to 7.031 mL / min, the flow rate of the sec-BuLi solution was changed to 2.813 mL / min, the flow rate of the 4-bromostyrene solution was changed to 15 mL / min, and the flow rate of the MeOH solution was changed to 5.625 mL / min. The results are shown in Table 8.

[0153] (Example 37) The same procedure as in Example 33 was carried out except that M2 was replaced with a T-type micromixer (φ=500 μm). The results are shown in Table 8.

[0154] (Example 38) The same procedure as in Example 33 was carried out except that M2 was replaced with a T-type micromixer (φ=500 μm), the flow rate of the α-methylstyrene solution was changed to 2.8125 mL / min, the flow rate of the sec-BuLi solution was changed to 1.125 mL / min, and the flow rate of the 4-bromostyrene solution was changed to 6 mL / min. The results are shown in Table 8.

[0155] (Example 39) The same procedure as in Example 33 was carried out except that M2 was replaced with a T-type micromixer (φ=500 μm), the flow rate of the α-methylstyrene solution was changed to 5.625 mL / min, the flow rate of the sec-BuLi solution was changed to 2.25 mL / min, and the flow rate of the 4-bromostyrene solution was changed to 9 mL / min. The results are shown in Table 8.

[0156] (Example 40) The same procedure as in Example 33 was carried out except that M2 was replaced with a T-type micromixer (φ=500 μm), the flow rate of the α-methylstyrene solution was changed to 7.031 mL / min, the flow rate of the sec-BuLi solution was changed to 2.813 mL / min, the flow rate of the 4-bromostyrene solution was changed to 15 mL / min, and the flow rate of the MeOH solution was changed to 5.625 mL / min. The results are shown in Table 8.

[0157] (Example 41) The same procedure as in Example 33 was carried out except that M2 was replaced with a V-type micromixer (φ=500 μm). The results are shown in Table 8.

[0158] (Example 42) The same procedure as in Example 33 was carried out except that M2 was replaced with a V-type micromixer (φ=500 μm), the flow rate of the α-methylstyrene solution was changed to 2.8125 mL / min, the flow rate of the sec-BuLi solution was changed to 1.125 mL / min, and the flow rate of the 4-bromostyrene solution was changed to 6 mL / min. The results are shown in Table 8.

[0159] (Example 43) The same procedure as in Example 33 was carried out except that M2 was replaced with a V-type micromixer (φ=500 μm), the flow rate of the α-methylstyrene solution was changed to 5.625 mL / min, the flow rate of the sec-BuLi solution was changed to 2.25 mL / min, and the flow rate of the 4-bromostyrene solution was changed to 9 mL / min. The results are shown in Table 8.

[0160] (Example 44) The same procedure as in Example 33 was carried out except that M2 was replaced with a V-type micromixer (φ=500 μm), the flow rate of the α-methylstyrene solution was changed to 7.031 mL / min, the flow rate of the sec-BuLi solution was changed to 2.813 mL / min, the flow rate of the 4-bromostyrene solution was changed to 15 mL / min, and the flow rate of the MeOH solution was changed to 5.625 mL / min. The results are shown in Table 8.

[0161] (Example 45) The same procedure as in Example 33 was carried out except that M2 was replaced with a V-type micromixer (φ=250 μm). The results are shown in Table 8.

[0162] (Example 46) The same procedure as in Example 33 was carried out except that M2 was replaced with a V-type micromixer (φ=250 μm), the flow rate of the α-methylstyrene solution was changed to 2.8125 mL / min, the flow rate of the sec-BuLi solution was changed to 1.125 mL / min, and the flow rate of the 4-bromostyrene solution was changed to 6 mL / min. The results are shown in Table 8.

[0163] (Example 47) The same procedure as in Example 33 was carried out except that M2 was replaced with a V-type micromixer (φ=250 μm), the flow rate of the α-methylstyrene solution was changed to 5.625 mL / min, the flow rate of the sec-BuLi solution was changed to 2.25 mL / min, and the flow rate of the 4-bromostyrene solution was changed to 9 mL / min. The results are shown in Table 8.

[0164] (Example 48) The same procedure as in Example 33 was carried out except that M2 was replaced with a V-type micromixer (φ=250 μm), the flow rate of the α-methylstyrene solution was changed to 7.031 mL / min, the flow rate of the sec-BuLi solution was changed to 2.813 mL / min, the flow rate of the 4-bromostyrene solution was changed to 15 mL / min, and the flow rate of the MeOH solution was changed to 5.625 mL / min. The results are shown in Table 8.

[0165] <Production of bromostyrene polymers 9: Study of living properties> (Example 49) An integrated flow microreactor system was used, which is shown in FIG. 11 and is composed of two V-type micromixers (M1 and M2: manufactured by Sanko Seiki Kogyo Co., Ltd.), a T-type micromixer (M3: manufactured by Sanko Seiki Kogyo Co., Ltd.), microtube reactors (R1, R1”, R2, and R3: manufactured by GL Sciences), one PTFE tube (R1′), and a 100 cm pre-cooling unit (P1, P2, P3, and P4: manufactured by GL Sciences). 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) 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.

[0166] Next, the initiator solution and the 4-bromostyrene solution (0.375 M in THF, flow rate: 12 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, collect an aliquot of the product solution for 10 s and immerse the aliquot in saturated NH 4 The solution was treated with aqueous Cl and brine. The solution was diluted with THF and filtered, and then the solution was analyzed by GPC. The results are shown in Table 9.

[0167] [Table 9]

[0168] (Example 50) The same procedure as in Example 49 was carried out, except that the concentration of the 4-bromostyrene solution was changed to 0.75 M. The results are shown in Table 9.

[0169] (Example 51) The same procedure as in Example 49 was carried out, except that the concentration of the 4-bromostyrene solution was changed to 1.125 M. The results are shown in Table 9.

[0170] <Production of bromostyrene polymers 10: Study of block copolymers> (Example 52) An integrated flow microreactor system was used, which is shown in Figure 12 and consists of three V-type micromixers (M1, 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'), and a 100 cm pre-cooling unit (P1, P2, P3, and P4: manufactured by GL Sciences). 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) 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.

[0171] Next, the initiator solution and the 4-bromostyrene solution (0.375 M in THF, flow rate: 12 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 4-bromostyrene solution (2.0 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 resulting solution was collected in a container containing 100 μL of methanol and 2 mL of THF for 10 s, and the aliquot was then rinsed with saturated NH 4 The solution was treated with aqueous Cl and brine. The solution was diluted with THF and filtered, after which the solution was analyzed by GPC. The results are shown in Table 10.

[0172] [Table 10]

[0173] (Example 53) The same procedure as in Example 52 was repeated, except that the concentration of bromostyrene introduced into M2 was changed to 0.75 M, the monomer B introduced into M3 was changed to styrene, and the concentration of monomer B introduced into M3 was changed to 3.0 M. The results are shown in Table 10.

[0174] (Example 54) The same procedure as in Example 52 was repeated, except that the bromostyrene introduced into M2 was changed to 3-bromostyrene, the concentration of bromostyrene introduced into M2 was changed to 0.75 M, the monomer B introduced into M3 was changed to styrene, and the concentration of monomer B introduced into M3 was changed to 3.0 M. The results are shown in Table 10.

[0175] (Example 55) The same procedure as in Example 52 was repeated, except that the bromostyrene introduced into M2 was changed to 2-bromostyrene, the concentration of bromostyrene introduced into M2 was changed to 0.75 M, the monomer B introduced into M3 was changed to styrene, and the concentration of monomer B introduced into M3 was changed to 3.0 M. The results are shown in Table 10.

[0176] (Example 56) The procedure was the same as in Example 52, except that the monomer B introduced into M3 was changed to 2-bromostyrene. The results are shown in Table 10.

[0177] (Example 57) The same procedure as in Example 52 was repeated, except that the bromostyrene introduced into M2 was changed to 2-bromostyrene, and the monomer B introduced into M3 was changed to 3-bromostyrene. The results are shown in Table 10.

[0178] <Production of chlorostyrene polymer 1> (Example 58) An integrated flow microreactor system was used, which is shown in FIG. 13 and is composed 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).

[0179] 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.

[0180] Next, the initiator solution and p-chlorostyrene solution (0.75 M THF solution, 12.0 mL / min) were mixed into 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.

[0181] -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.

[0182] The aspects of the present invention include, for example, the following. <1> A method for producing a polymer, comprising the step of anionically polymerizing a halogenated styrene monomer using a microreactor in the presence of an initiator represented by the following general formula (1), 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 reaction temperature between the sec-BuLi and the alkylaryl compound is 0° C. or higher and 40° C. or lower. <4> The present invention relates to a method for producing a polymer according to the present invention. <6> The amount of the alkylaryl compound relative to the sec-BuLi is 1.0 molar equivalent or more and 2.0 molar equivalents or less. <4> from <5> The present invention relates to a method for producing a polymer according to any one of the above. <7> The method further comprises a step of polymerizing a monomer with the polymer obtained by anionically polymerizing the halogenated styrene monomer, the monomer being styrene or a styrene derivative. <1> from <6> The present invention relates to a method for producing a polymer according to any one of the above. <8> A halogenated styrene monomer polymerization initiator represented by the following general formula (1) (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] <9> The aryl group is a phenyl group. <8> 1. The halogenated styrene monomer polymerization initiator according to claim 1. <10> In the general formula (1), R 1 and R 2 one of the groups is an alkyl group having 1 to 10 carbon atoms. <8> from <9> 10. The halogenated styrene monomer polymerization initiator according to claim 9, <11> The method includes reacting sec-BuLi with an alkylaryl compound. The present invention relates to a method for producing a halogenated styrene monomer polymerization initiator represented by the following general formula (1): 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] <12> The reaction temperature between the sec-BuLi and the alkylaryl compound is 0° C. or higher and 40° C. or lower. <11> 2. A method for producing the halogenated styrene monomer polymerization initiator according to claim 1. <13> The amount of the alkylaryl compound relative to the sec-BuLi is 1.0 molar equivalent or more and 2.0 molar equivalents or less. <11> from <12> 10. The method for producing the halogenated styrene monomer polymerization initiator according to claim 9, <14> The polymer is represented by either of the following general formulas (3) or (4). (In the general formula (3), m represents the degree of polymerization and is an integer of 1 or more.) 5 represents an aryl group or an alkyl group having 1 to 10 carbon atoms; X represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an astatine atom; and a represents an integer of 1 to 5. In the general formula (4), m and n represent the degree of polymerization, each of which is an integer of 1 or more; R 5 is an aryl group or an alkyl group having 1 to 10 carbon atoms; R 6 represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an astatine atom, an alkyl group having 1 to 4 carbon atoms, or a trimethylsilyl group; X represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an astatine atom; and a and b each represent an integer of 1 to 5. [ka] [ka]

Claims

1. A method for producing a polymer, comprising a step of anionically polymerizing a halogenated styrene monomer using a microreactor in the presence of an initiator represented by the following general formula (1): 【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 for producing a polymer according to claim 4, wherein the reaction temperature between the sec-BuLi and the alkylaryl compound is 0° C. or higher and 40° C. or lower.

6. The method for producing a polymer according to any one of claims 4 and 5, wherein the amount of the alkylaryl compound relative to the sec-BuLi is 1.0 molar equivalent or more and 2.0 molar equivalents or less.

7. The method further includes a step of polymerizing a monomer with respect to the polymer obtained by anionically polymerizing the halogenated styrene monomer in the above step, The method for producing a polymer according to any one of claims 1 to 6, wherein the monomer is styrene or a styrene derivative.

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