JP2021138946A - Polymer production method, halogenated styrenic monomer polymerization initiator, and production method thereof - Google Patents

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

The present invention relates to a polymer production method, an initiator for halogenated styrene monomer polymerization, and a method for producing the same.

In recent years, in the field of chemical synthesis, chemical reactions using microreactors called microreactors have been studied (see, for example, Non-Patent Documents 1 and 2).
The microreactor is a microcontainer including a flow path capable of mixing a plurality of liquids and an introduction path that communicates with the flow path and introduces the liquid into the flow path, and is supplied through the introduction path of the microreactor. The plurality of liquids are mixed by merging in the flow path, and a reaction occurs.

Reactions using a microreactor are thought to enable precise residence time control, precise temperature control, and high-speed mixing, and have a higher conversion rate and selectivity than conventional batch-type reactions. Expected to improve, it is attracting attention as a highly efficient production method.

On the other hand, anionic polymerization has a high reaction rate and is a powerful tool for synthesizing styrene-based polymers. However, the polymerization of styrene modified with a functional group is largely limited by the reactivity of the functional group, and therefore sufficient research has not been conducted.
So far, anionic polymerization of halogenated styrene using sec-BuLi as an initiator has been reported (see, for example, Non-Patent Document 3), but a halogenated styrene polymer having a high conversion rate and a narrow dispersion. Has not been obtained.

Therefore, a method for efficiently producing a halogenated styrene polymer having a high conversion rate and a narrow dispersion has not yet been provided, and prompt provision thereof is strongly required.

Chemia 2002 56: 636 Tetrahedron) 2002 58: 4735-4757 Polymer Preprints 2018 67 1B17

An object of the present invention is to solve the above-mentioned problems in the past and to achieve the following object. That is, an object of the present invention is to provide a method for efficiently producing a halogenated styrene polymer having a high conversion rate and a narrow dispersion.

As a result of intensive studies to achieve the above object, the present inventors anionicly polymerized a halogenated styrene monomer using a microreactor in the presence of an initiator represented by the following general formula (1). According to the method for producing a polymer including the step of subjecting the polymer (however, in the general formula (1), ^one of R ^{1 and R 2} 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 producing a halogenated styrene polymer having a high conversion rate and a narrow dispersion can be provided efficiently.

＜２＞ 下記一般式（１）で表されるハロゲン化スチレン類モノマー重合用開始剤（ただし、前記一般式（１）中、Ｒ^１及びＲ^２の一方がアリール基であり、他方がアリール基、又は炭素数１〜１０のアルキル基である）である。

＜３＞ ｓｅｃ−ＢｕＬｉと、アルキルアリール化合物とを反応する工程を含む、下記一般式（１）で表されるハロゲン化スチレン類モノマー重合用開始剤の製造方法（ただし、前記一般式（１）中、Ｒ^１及びＲ^２の一方がアリール基であり、他方がアリール基、又は炭素数１〜１０のアルキル基である）である。

＜４＞ 下記一般式（３）又は（４）のいずれかで表されるポリマーである（ただし、前記一般式（３）中、ｍは、重合度を表し、１以上の整数であり；Ｒ^５は、アリール基、又は炭素数１〜１０のアルキル基であり；Ｘは、フッ素原子、塩素原子、臭素原子、ヨウ素原子、又はアスタチン原子のいずれかであり；ａは、１〜５の整数である。前記一般式（４）中、ｍ及びｎは重合度を表し、それぞれ１以上の整数であり；Ｒ^５は、アリール基、又は炭素数１〜１０のアルキル基であり；Ｒ^６は、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、アスタチン原子、炭素数１〜４のアルキル基、又はトリメチルシリル基のいずれかであり；Ｘは、フッ素原子、塩素原子、臭素原子、ヨウ素原子、又はアスタチン原子のいずれかであり；ａ及びｂは、それぞれ１〜５の整数である。）。

The present invention is based on the above-mentioned findings by the present inventors, and the means for solving the above-mentioned problems are as follows. That is,
<1> A method for producing a polymer, which comprises a step of anionic polymerization of a halogenated styrene monomer using a microreactor in the presence of an initiator represented by the following general formula (1) (however, the above general formula (1). ), One of R ¹ and R ² is an aryl group, and the other is an aryl group or an alkyl group having 1 to 10 carbon atoms).

<2> Initiator for polymerization of halogenated styrenes monomer represented by the following general formula (1) (However, in the general formula (1), ^one of R ^{1 and R 2} is an aryl group, and the other is an aryl group. , Or an alkyl group having 1 to 10 carbon atoms).

<3> A method for producing a halogenated styrene monomer polymerization initiator represented by the following general formula (1), which comprises a step of reacting sec-BuLi with an alkylaryl compound (however, the general formula (1)). Among them, ^one of R 1 and R ² is an aryl group, and the other is an aryl group or an alkyl group having 1 to 10 carbon atoms).

<4> A polymer represented by any of the following general formulas (3) or (4) (however, in the general formula (3), m represents the degree of polymerization and is an integer of 1 or more; R. ⁵ is an aryl group or an alkyl group having 1 to 10 carbon atoms; X is either a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an astatin atom; a is an integer of 1 to 5. In the general formula (4), m and n represent the degree of polymerization and are integers of 1 or more, respectively; R ⁵ is an aryl group or an alkyl group having 1 to 10 carbon atoms; R ⁶ is. , Hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, astatin atom, alkyl group having 1 to 4 carbon atoms, or trimethylsilyl group; X is fluorine atom, chlorine atom, bromine atom, iodine. It is either an atom or an statatin atom; a and b are integers 1-5, respectively).

According to the present invention, it is possible to provide a method for efficiently producing a halogenated styrene polymer having a high conversion rate and a narrow dispersion.

FIG. 1 is a schematic view of a flow microreactor used as an example of the manufacturing method of the present invention. FIG. 2 is a schematic view of a flow microreactor used as an example of the manufacturing method of the present invention. FIG. 3 is a schematic view of a flow microreactor used as an example of the manufacturing method of the present invention. FIG. 4 is a schematic view of the microreactor system used in Examples 1 and 2 and Comparative Examples 1 to 4. FIG. 5 is a schematic diagram of the microreactor system used in Examples 3-7 and 17-32. FIG. 6 is a schematic diagram of the microreactor system used in Examples 8-9. FIG. 7 is a schematic diagram of the microreactor system used in Examples 10-12. FIG. 8 is a chart diagram of GPCs of Examples 10 to 12. FIG. 9 is a schematic view of the microreactor system used in Examples 13-16. FIG. 10 is a schematic diagram of the microreactor system used in Examples 33-48. FIG. 11 is a schematic diagram of the microreactor system used in Examples 49-51. FIG. 12 is a schematic diagram of the microreactor system used in Examples 52-57. FIG. 13 is a schematic view of the microreactor system used in Example 58. FIG. 14 is a MALDI-TOFMS spectrum of the poly-p-chlorostyrene obtained in Example 58.

(Polymer manufacturing method)
The polymer production method includes an anionic polymerization step and may further include other steps.

<Anionic polymerization process>
The anionic polymerization step is a step of anionic polymerization of a halogenated styrene monomer using a flow microreactor in the presence of an initiator.

-Halogenated styrene monomer-
The halogenated styrenes monomers are not particularly limited and may be appropriately selected depending on the purpose, for example, monomers (however represented by the following general formula (2), R ³ is a hydrogen atom, or methyl a group; R ⁴ is a hydrogen atom, a chlorine atom, an alkyl group, or a trimethylsilyl group having from 1 to 4 carbon atoms; X is fluorine, chlorine, bromine, iodine, halogen atom such as astatine; a is , An integer of 1 to 5) and the like.

Among the monomers represented by the general formula (2), a monomer in which X is a chlorine atom or a bromine atom is preferable. The monomer in which X is a chlorine atom or a bromine atom is not particularly limited and may be appropriately selected depending on the intended purpose, but 2-bromostyrene (o-bromostyrene) and 3-bromostyrene (m-bromo). Styrene), 4-bromostyrene (p-bromostyrene), dibromostyrene, tribromostyrene, 2-chlorostyrene (o-chlorostyrene), 3-chlorostyrene (m-chlorostyrene), 4-chlorostyrene (p-) Chlorostyrene), dichlorostyrene, trichlorostyrene are preferable, 2-bromostyrene (o-bromostyrene), 3-bromostyrene (m-bromostyrene), 4-bromostyrene (p-bromostyrene), 2-chlorostyrene ( o-chlorostyrene), 3-chlorostyrene (m-chlorostyrene), 4-chlorostyrene (p-chlorostyrene) are more preferable.

-Initiator-
The initiator is represented by the following general formula (1).

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

In the general formula (1), ^one of R 1 and R ² is an aryl group, and the other is an aryl group or an alkyl group having 1 to 10 carbon atoms.
^{Among these, in the general formula (1), one} of R ^{1 and R 2} has the number of carbon atoms in that a narrowly dispersed polymer can be obtained by suppressing the softening of the reactivity and making the starting reaction uniform. It is preferably an alkyl group of 1-10.

The alkyl group having 1 to 10 carbon atoms is not particularly limited and may be appropriately selected depending on the intended purpose. However, carbon has a high conversion rate and a narrowly dispersed polymer can be obtained. Alkyl groups having 1 to 8 carbon atoms are preferable, alkyl groups having 1 to 6 carbon atoms are more preferable, alkyl groups having 1 to 4 carbon atoms are further preferable, alkyl groups having 1 to 2 carbon atoms are particularly preferable, and methyl groups are most preferable. preferable.

The aryl is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a phenyl group, a tolyl group and an o-xylyl group.
Among these, a phenyl group is preferable from the viewpoint of efficiently obtaining a high conversion rate and obtaining a narrowly dispersed polymer.

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 (2PHLi). Examples thereof include the compound (3POLi) represented by 3).
Among these, the compound (2PHLi) represented by the following structural formula (2) is preferable from the viewpoint that a polymer having a high conversion rate and a narrow dispersion can be obtained efficiently.

--Manufacturing method of initiator ---
The method for producing the initiator is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a method of reacting sec-BuLi with an alkylaryl compound.

The alkylaryl compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alkylbenzene compounds.

The alkylbenzene compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, α-methylstyrene, β-methylstyrene, 2-methylstyrene (o-methylstyrene), 3-methylstyrene ( m-Methylstyrene), 4-methylstyrene (p-methylstyrene), 1,5-dimethylstyrene, 2,4-dimethylstyrene and other methylstyrene compounds, α-ethylstyrene, β-ethylstyrene, 2-ethylstyrene Ethylstyrene compounds such as (o-ethylstyrene), 3-ethylstyrene (m-ethylstyrene), 4-ethylstyrene (p-ethylstyrene), 1,5-diethylstyrene, 2,4-diethylstyrene, 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) -Methyl ethenyl) benzene), 1,2,3-tris (1-methylethenyl) benzene, 1,2,4-tris (1-methylethenyl) benzene, 1,3,5-tris (1-methylethenyl) benzene, etc. Be done.
Among these, a methylstyrene compound or an ethylstyrene compound is preferable, a methylstyrene compound is more preferable, and α-methylstyrene is further preferable, from the viewpoint of efficiently obtaining a high conversion rate and obtaining a narrowly dispersed polymer.

The lower limit of the reaction temperature between sec-BuLi and the alkylaryl compound is not particularly limited and may be appropriately selected depending on the intended purpose, but it is a polymer having an efficient high conversion rate and a narrow dispersion. 0 ° C. or higher is preferable, 5 ° C. or higher is more preferable, 10 ° C. or higher is further preferable, and 15 ° C. or higher is particularly preferable.

The upper limit of the reaction temperature between sec-BuLi and the alkylaryl compound is not particularly limited and may be appropriately selected depending on the intended purpose, but it is a polymer having an efficient high conversion rate and a narrow dispersion. 40 ° C. or lower is preferable, 35 ° C. or lower is more preferable, 30 ° C. or lower is further preferable, and 25 ° C. or lower is particularly preferable.

The lower limit of the amount of the alkylaryl compound with respect to sec-BuLi is not particularly limited and may be appropriately selected depending on the intended purpose. From the point of view, 1.0 molar equivalent or more is preferable, 1.1 molar equivalent or more is more preferable, 1.2 molar equivalent or more is further preferable, 1.3 molar equivalent or more is particularly preferable, and 1.4 molar equivalent or more. Is the most preferable.
The upper limit of the amount of the alkylaryl compound with respect to sec-BuLi is not particularly limited and may be appropriately selected depending on the intended purpose. From the point of view, 2.0 molar equivalents or less is preferable, 1.9 molar equivalents or less is more preferable, 1.8 molar equivalents or less is further preferable, 1.7 molar equivalents or less is particularly preferable, and 1.6 molar equivalents or less. Is the most preferable.

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 intended purpose, but the conversion rate is efficiently high and the dispersion is narrow. From the viewpoint of obtaining a polymer, −60 ° C. or higher is preferable, −55 ° C. or higher is more preferable, −50 ° C. or higher is further preferable, and −45 ° C. or higher is particularly preferable.

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 intended purpose, but the conversion rate is efficiently high and the dispersion is narrow. From the viewpoint of obtaining a polymer, −20 ° C. or lower is preferable, −25 ° C. or lower is more preferable, −30 ° C. or lower is further preferable, and −35 ° C. or lower is particularly preferable.

-Microreactor-
The microreactor is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a microreactor including a mixing means, a flow passage, and other means as needed (hereinafter, "" (Sometimes referred to as "flow microreactor").
The mixing means and the flow path may be an integrated type or a separate type.

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. The flow path is connected to at least one of the mixing means.

By using the flow microreactor, it is possible to shorten the residence time from production to the next reaction and suppress side reactions for compounds with low stability.
Further, since the flow microreactor has excellent cooling efficiency, it is possible to suppress side reactions due to heat generation in the exothermic reaction.

--Integrated flow microreactor ---
Examples of the mixing means and the flow path of the integrated flow microreactor include a substrate-type micromixer and the like.

The substrate-type micromixer is composed of a substrate having a passage formed inside or on the surface, and is sometimes referred to as a microchannel.
The substrate-type micromixer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a mixer having a fine flow path for mixing described in International Publication No. 96/30113 pamphlet. Examples thereof include mixers described in the document "Chapter 3 of" Microreactors ", by W. Ehrfeld, V. Hessel, H. Lowe, published by Wiley-VCH".

In the substrate-type micromixer, the mixing means and the flow path are composed of minute flow paths capable of mixing a plurality of liquids.

In addition to the flow path, the substrate-type micromixer preferably has an introduction path that communicates with the flow path and introduces a plurality of liquids into the flow path. That is, it is preferable that the upstream side of the flow path is branched according to the number of the introduction paths.

The number of the introduction paths is not particularly limited and may be appropriately selected depending on the intended purpose. However, a plurality of liquids desired to be mixed are introduced from separate introduction paths, merged in the flow path, and mixed. Is preferable. In addition, one liquid may be charged in the flow path in advance, and the other liquid may be introduced through the introduction path.

--Separate type flow microreactor ---
The separate type flow microreactor is formed by connecting the mixing means and the flow passage.

The mixing means is not particularly limited as long as two or more kinds of liquids can be mixed, and can be appropriately selected depending on the intended purpose. Examples thereof include a pipe joint type micromixer.

The pipe joint type micromixer includes a flow path formed inside, and if necessary, includes a connecting member for connecting the flow path formed inside and the flow path. The connection method for the connection member is not particularly limited and may be appropriately selected from known connection methods according to the purpose. For example, a screw type, a union type, a butt welding type, a plug-in welding type, and a socket. Welding type, flange type, bite type, flare type, mechanical type and the like can be mentioned.

In addition to the flow path, it is preferable that an introduction path that communicates with the flow path and introduces a plurality of liquids into the flow path is formed inside the pipe joint type micromixer. That is, it is preferable that the upstream side of the flow path is branched according to the number of the introduction paths. When the number of introduction paths is two, for example, a T-shape or a Y-shape can be used as the pipe joint type micromixer, and when the number of introduction paths is three. Can use, for example, a cross shape. In addition, one liquid may be charged in the flow path in advance, and the other liquid may be introduced through the introduction path.

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

Commercially available products can be used as the pipe joint type micro mixer, for example, a YM-1 type mixer manufactured by Yamatake Co., Ltd., a YM-2 type mixer; a mixing tee and a tee (T-shaped connector) manufactured by Shimadzu GLC Co., Ltd .; Micro high mixer developed by Toray Engineering Co., Ltd .; Union tea manufactured by Swagelok Co., Ltd., T-shaped micro mixer manufactured by Sanko Seiki Kogyo Co., Ltd., etc. can be mentioned.

The method for mixing the two or more raw material substances in the mixing means is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include mixing by laminar flow and mixing by turbulent flow. Above all, mixing by laminar flow (static mixing) is preferable because reaction control and heat removal can be performed more efficiently.

Since the flow path in the mixing means is very small, the plurality of liquids introduced into the mixing means tend to be laminar-controlled flows, and are diffused and mixed in a direction orthogonal to the flow. In the laminar flow mixing, a branch point and a merging point may be further provided in the flow path to divide the laminar flow cross section of the flowing liquid and increase the mixing speed.
Further, when mixing by turbulent flow (dynamic mixing) in the flow path of the mixing means, the flow rate, the shape of the flow path (three-dimensional shape of the wetted portion, the shape such as bending of the flow path, and the wall surface) By adjusting the roughness, etc.), it is possible to change from laminar flow to turbulent flow. The mixing by the turbulent flow has an advantage that the mixing efficiency is high and the mixing speed is high as compared with the mixing by the laminar flow.

Here, when the inner diameter of the flow path in the mixing means is small, the diffusion distance of the molecules can be shortened, so that the time required for mixing can be shortened and the mixing efficiency can be improved. Further, the smaller the inner diameter of the flow path, the larger the ratio of the surface area to the volume, and it is possible to easily control the temperature of the liquid, for example, removing the heat of reaction.
On the other hand, if the inner diameter of the flow path is too small, the pressure loss when flowing the liquid increases, and a special high withstand voltage pump is required as the pump used for the liquid feeding, so that the manufacturing cost increases. There is. Further, the structure of the micromixer may be limited due to the limitation of the liquid feed flow rate.

The inner diameter of the flow path in the mixing means is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 50 μm to 4 mm, more preferably 100 μm to 3 mm, still more preferably 250 μm to 2 mm. 500 μm to 1 mm is particularly preferable.
If the inner diameter is less than 50 μm, the pressure loss may increase. If the inner diameter exceeds 4 mm, the surface area per unit volume becomes small, and as a result, rapid mixing and removal of heat of reaction may become difficult. On the other hand, when the inner diameter is in the particularly preferable range, it is advantageous in that the mixture can be mixed more quickly and the reaction heat can be removed more efficiently.
More specifically, the inner diameter of the flow path 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.

The cross-sectional area of the flow path is not particularly limited and may be appropriately selected depending on the intended purpose. 100 μm ^{2 to} 16 mm ² is preferable, 1,000 μm ^{2 to} 4.0 mm ² is more preferable, and 10,000 μm ^{2 is more preferable.} ~ 2.1 mm ² is more preferable, and 190,000 μm ^{2 to 1} mm ² is particularly preferable.

The cross-sectional shape of the flow path is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a circle, a rectangle, a semicircle, and a triangle.

The flow passage is not particularly limited as long as it is a pipe that is connected to at least one of the mixing means and can flow a liquid, and can be appropriately selected depending on the intended purpose. The composition such as the material can be appropriately selected according to the desired reaction.

The flow path is used, for example, when supplying the raw material to the mixing means.
Further, the flow passage is used, for example, when supplying a reaction product of two or more substances mixed by the mixing means to the next mixing means. At this time, the reaction may continue to occur in the flow path.

As the flow passage, a commercially available product can be used. For example, a stainless steel tube manufactured by GL Sciences Co., Ltd. (outer diameter 1/16 inch (1.58 mm), inner diameter 250 μm, 500 μm and 1,000 μm can be selected. The tube length can be adjusted by the user).

The material of the flow passage is not particularly limited, and those exemplified as the material of the mixing means can be preferably used.

The inner diameter of the flow passage is not particularly limited and may be appropriately selected depending on the intended 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. preferable.
More specifically, the inner diameter of the flow passage is preferably 50 μm to 1,000 μm, more preferably 100 μm to 800 μm, and even more preferably 250 μm to 500 μm.

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

The flow rate of the liquid in the flow path for supplying the raw material is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it may be 1.0 ml / min to 20 ml / min or 2.0 ml. It may be / min to 15 ml / min, or may be 3.0 ml / min to 10 ml / min.

The residence time of the reaction solution in the flow path through which the reaction solution flows is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 0.001 sec to 10 sec.

The lower limit of the length between the micromixer for reacting sec-BuLi with the alkylaryl compound and the micromixer for anionic polymerization is not particularly limited and may be appropriately selected depending on the intended purpose. However, 100 cm or more is preferable, 150 cm or more is more preferable, 170 cm or more is further preferable, and 190 cm or more is particularly preferable.
The upper limit of the length between the micromixer for reacting sec-BuLi with the alkylaryl compound and the micromixer for anionic polymerization is not particularly limited and may be appropriately selected depending on the intended purpose. However, 300 cm or less is preferable, 280 cm or less is more preferable, 250 cm or less is further preferable, and 230 cm or less is particularly preferable.

--Other means ---
The other means are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a liquid feeding means and a temperature controlling means.

The liquid feeding means is not particularly limited as long as various raw material substances can be supplied to the flow passage of the flow microreactor, and can be appropriately selected depending on the intended purpose. Examples thereof include a pump.

The pump is not particularly limited and may be appropriately selected from those that can be used industrially, but those that do not cause pulsation during liquid feeding are preferable, and for example, a plunger pump, a gear pump, a rotary pump, and a diaphragm pump are used. And so on.

The temperature adjusting means is not particularly limited as long as the temperatures of the mixing means of the flow microreactor and the flow path can be adjusted, and can be appropriately selected depending on the intended purpose.

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

-Manufacturing process of initiator before anionic polymerization process-
The step of producing the initiator before the anionic polymerization step is a step of reacting the sec-BuLi with the 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.

− Monomer polymerization step after anionic polymerization step −
The monomer polymerization step after the anionic polymerization step is a step of polymerizing the monomer with the polymer obtained by anionic polymerization of the halogenated styrenes monomer in the anionic polymerization step.

The monomer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include styrene and styrene derivatives.

(Initiator for Halogenated Styrene Monomer Polymerization)
The initiator for halogenated styrene monomer polymerization is as described above.

(Method for Producing Initiator for Halogenated Styrene Monomer Polymerization)
The method for producing the halogenated styrene monomer polymerization initiator is the same as the above-mentioned method for producing the initiator.

(polymer)
The polymer can be produced by the above-mentioned polymer production method.

The polymer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a polymer represented by any of the following general formulas (3) and (4).

ただし、前記一般式（３）中、ｍは、重合度を表し、１以上の整数であり；Ｒ^５は、アリール基、又は炭素数１〜１０のアルキル基であり；Ｘは、フッ素原子、塩素原子、臭素原子、ヨウ素原子、又はアスタチン原子のいずれかであり；ａは、１〜５の整数である。

However, in the general formula (3), m represents the degree of polymerization and is an integer of 1 or more; R ⁵ is an aryl group or an alkyl group having 1 to 10 carbon atoms; X is a fluorine atom. It is either a chlorine atom, a bromine atom, an iodine atom, or an astatine atom; a is an integer of 1 to 5.

As long as m in the general formula (3) is an integer of 1 or more, there is no particular limitation and it can be appropriately selected depending on the intended purpose, but 5 or more is preferable, 10 or more is more preferable, and 15 or more is further preferable. Preferably, 20 or more is particularly preferable, and 25 or more is most preferable.

Wherein R ⁵ in the general formula (3), an aryl group, or as long as an alkyl group having 1 to 10 carbon atoms is not particularly limited and may be appropriately selected depending on the purpose, having 1 to 10 carbon atoms Alkyl groups are preferred, and methyl groups are more preferred.

As long as X in the general formula (3) is a halogen atom, there is no particular limitation and it can be appropriately selected depending on the intended purpose, but a chlorine atom or a bromine atom is preferable.

ただし、前記一般式（４）中、ｍ及びｎは重合度を表し、それぞれ１以上の整数であり；Ｒ^５は、アリール基、又は炭素数１〜１０のアルキル基であり；Ｒ^６は、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、アスタチン原子、炭素数１〜４のアルキル基、又はトリメチルシリル基のいずれかであり；Ｘは、フッ素原子、塩素原子、臭素原子、ヨウ素原子、又はアスタチン原子のいずれかであり；ａ及びｂは、それぞれ１〜５の整数である。

However, in the general formula (4), m and n represent the degree of polymerization and are integers of 1 or more, respectively; R ⁵ is an aryl group or an alkyl group having 1 to 10 carbon atoms; R ⁶ is It is either a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an astatin atom, an alkyl group having 1 to 4 carbon atoms, or a trimethylsilyl group; X is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. , Or either of the astatin atoms; a and b are integers 1-5, respectively.

As long as m in the general formula (4) is an integer of 1 or more, there is no particular limitation and it can be appropriately selected depending on the intended purpose, but 5 or more is preferable, 10 or more is more preferable, and 15 or more is further preferable. Preferably, 20 or more is particularly preferable, and 25 or more is most preferable.

As long as n in the general formula (4) is an integer of 1 or more, there is no particular limitation and it can be appropriately selected depending on the intended purpose, but 5 or more is preferable, 10 or more is more preferable, and 15 or more is further preferable. Preferably, 20 or more is particularly preferable, and 25 or more is most preferable.

Wherein R ⁵ in the general formula (4), aryl group, or as long as an alkyl group having 1 to 10 carbon atoms is not particularly limited and may be appropriately selected depending on the purpose, having 1 to 10 carbon atoms Alkyl groups are preferred, and methyl groups are more preferred.

^{R 6} in the general formula (4) is particularly limited as long as it is any one of a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an astatin atom, an alkyl group having 1 to 4 carbon atoms, or a trimethylsilyl group. However, it can be appropriately selected depending on the intended purpose, but any one of a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group having 1 to 4 carbon atoms, or a trimethylsilyl group is preferable.

As long as X in the general formula (4) is a halogen atom, there is no particular limitation and it can be appropriately selected depending on the intended purpose, but a chlorine atom or a bromine atom is preferable.

The molecular weight distribution (multidispersity index (PDI): Mw / Mn) of the polymer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1.8 or less, preferably 1.5 or less. More preferably, 1.4 or less is further preferable, 1.35 or less is further preferable, 1.3 or less is particularly preferable, 1.25 or less is most preferable, and 1.2 or less is particularly preferable.
The molecular weight distribution is measured by the following GPC analysis.

-GPC analysis-
It is carried out in THF (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) at 40 ° C. using SHIMADZU Prominence equipped with a Shodex LF-604 column. The reflection index (RI) is recorded with Shodex RI-504. The molecular weight distribution (multidispersity index (PDI): Mw / Mn) is determined by a calibration curve obtained from commercially available polystyrene. Prior to GPC analysis, the solution is filtered through Millex-HN (Merck, 0.45 μm).

Here, an example of a flow microreactor preferably used in the method for producing a polymer and a method for producing a polymer using the same will be described with reference to the drawings.

FIG. 1 is a schematic view showing an example of a flow microreactor.
The flow microreactor shown in FIG. 1 includes two mixing means and five flow passages.
The flow passage P1 is connected to the 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 is also a reaction part.
The flow passage R2 is connected to the mixing means M2. The flow passage R2 is also a reaction part.

The initiator represented by the general formula (1) is supplied from the flow passage P1 to the mixing means M1. A halogenated styrene monomer is supplied from the flow passage P2 to the mixing means M1. Then, in the mixing means M1, the initiator represented by the general formula (1) and the halogenated styrene monomer are mixed, and in the obtained liquid, the initiator represented by the general formula (1) is started. Living anionic polymerization of the halogenated styrene monomer using the agent as an anionic polymerization initiator is initiated to produce a living polymer.
The liquid during the polymerization reaction flows through the flow passage R1 which is also a reaction part while polymerizing, for example. The obtained polymer is a living polymer. Therefore, in order to stop the active end, a solution containing a stop agent (for example, methanol) is circulated in the flow passage P3 and mixed with the polymer solution by the mixing means M2 to carry out a stop reaction.

FIG. 2 is a schematic view showing an example of a flow microreactor.
The flow microreactor shown in FIG. 2 includes three mixing means and seven flow passages.
The flow passage P1 is connected to the 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 is also a reaction part.
The flow passage R2 is connected to the mixing means M2 and the mixing means M3. The flow passage R2 is also a reaction part.
The flow passage R3 is connected to the mixing means M3. The flow passage R3 is also a reaction part.

The alkylaryl compound is supplied from the flow passage P1 to the mixing means M1. Sec-BuLi is supplied from the flow passage P2 to the mixing means M1. Then, in the mixing means M1, the alkylaryl compound and sec-BuLi are mixed, and the addition reaction is started in the obtained liquid to produce the initiator represented by the general formula (1). The liquid during the reaction flows through the flow path R1 which is also a reaction part 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 the halogenated styrene monomer supplied from the flow passage P3, and in the obtained liquid, the initiator represented by the general formula (1) is used as an anionic polymerization initiator. The living anionic polymerization of the halogenated styrene monomer used is started to produce a living polymer.
The liquid during the polymerization reaction flows through the flow passage R2, which is also a reaction part, while being polymerized, for example. The obtained polymer is a living polymer. Therefore, in order to stop the active end, a solution containing a stop agent (for example, methanol) is circulated in the flow passage P4 and mixed with the polymer solution by the mixing means M3 to carry out a stop reaction.

FIG. 3 is a schematic view 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 the 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 is also a reaction part.
The flow passage R2 is connected to the mixing means M2 and the mixing means M3. The flow passage R2 is also a reaction part.
The flow passage R3 is connected to the mixing means M3 and the mixing means M4. The flow passage R3 is also a reaction part.
The flow passage R4 is connected to the mixing means M4. The flow passage R4 is also a reaction part.

The alkylaryl compound is supplied from the flow passage P1 to the mixing means M1. Sec-BuLi is supplied from the flow passage P2 to the mixing means M1. Then, in the mixing means M1, the alkylaryl compound and sec-BuLi are mixed, and the addition reaction is started in the obtained liquid to produce the initiator represented by the general formula (1). The liquid during the reaction flows through the flow path R1 which is also a reaction part 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 the halogenated styrene monomer supplied from the flow passage P3, and in the obtained liquid, the initiator represented by the general formula (1) is used as an anionic polymerization initiator. The living anionic polymerization of the halogenated styrene monomer used is started to produce a living polymer.
The liquid during the polymerization reaction flows through the flow passage R2, which is also a reaction part, while being polymerized, for example. The liquid containing the living polymer flowing through the flow passage R2 is introduced into the mixing means M3. In the mixing means M3, the liquid is mixed with the styrene or the styrene derivative supplied from the flow passage P4, and in the obtained liquid, the living anionic polymerization of the styrene or the styrene derivative is carried out at the growth end of the living polymer. Started to produce living polymer. The liquid during the polymerization reaction flows through the flow passage R3, which is also a reaction part, while being polymerized, for example. The obtained polymer is a living polymer. Therefore, in order to stop the active end, a solution containing a stop agent (for example, methanol) is circulated in the flow passage P5 and mixed with the polymer solution by the mixing means M4 to carry out a stop reaction.

Hereinafter, examples of the present invention will be described, but the present invention is not limited to these examples.

<Manufacturing of bromostyrene polymer 1>
(Example 1)
Two T-type micromixers (M1 and M2: manufactured by Sanko Seiki Kogyo Co., Ltd.), a microtube reactor (R1 and R2: manufactured by GL Sciences), a 100 cm precooling unit (P1, P2, and) shown in FIG. A flow microreactor system composed of P3: manufactured by GL Sciences) was used.

The flow microreactor system was placed in a tank at 20 ° C., and a diphenylhexyl lithium (DPHLi) solution (flow rate: 6.0 mL / min) and a 4-bromostyrene solution (0.75 M THF solution: 0.75 M THF solution: prepared by the following method: A 0.75M solution was prepared by adding THF (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) to 4-bromostyrene (manufactured by Tokyo Chemical Industry Co., Ltd.), and a flow velocity: 12 mL / min) was mixed at M1 (φ = 500 μm). Then, the mixture was passed through R1 (inner diameter 1000 μm, 100 cm, t ^R1 = 2.6 s).
The obtained solution was introduced into M2 (φ = 500 μm), a MeOH solution (0.15 M THF solution, flow rate: 4.5 mL / min) was introduced therein, and the mixture was mixed with R2 (inner diameter 1000 μm, 100 cm, t ^R2 =). It passed through 2.1s).
After reaching a steady state, an aliquot of the product solution was collected for 10 seconds, an aliquot was treated with saturated aqueous NH 4 _Cl solution and brine. The solution was diluted with THF, filtered and then analyzed by gel permeation chromatography (GPC) as described below. The results are shown in Table 1.

-DPHLi manufacturing method-
DPHLi was prepared by adding THF (manufactured by Fujifilm Wako Pure Chemical Co., Ltd.) to 1,2-diphenylethylene THF solution (prepared by adding THF (manufactured by Fujifilm Wako Pure Chemical Co., Ltd.) to 1,2-diphenylethylene (manufactured by Tokyo Chemical Industry Co., Ltd.)) at 0 ° C. , 1.0 equivalent of sec-BuLi (manufactured by Kanto Chemical Co., Inc.) was added dropwise.

-GPC analysis-
It was carried out in THF (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) at 40 ° C. using SHIMADZU Prominence equipped with a Shodex LF-604 column. The reflection index (RI) was recorded with Shodex RI-504. Mn was determined by a calibration curve obtained from commercially available polystyrene. Prior to GPC analysis, the solution was filtered through Millex-HN (Merck, 0.45 μm).

(Example 2)
The same procedure as in Example 1 was carried out except that the flow microreactor system was placed in a tank at −40 ° C. The results are shown in Table 1.

(Comparative Example 1)
The procedure was the same as in Example 1 except that n-BuLi was used instead of DPHLi. The results are shown in Table 1.

(Comparative Example 2)
The procedure was the same as in Example 2 except that n-BuLi was used instead of DPHLi. The results are shown in Table 1.

(Comparative Example 3)
The procedure was the same as in Example 1 except that sec-BuLi was used instead of DPHLi. The results are shown in Table 1.

(Comparative Example 4)
The procedure was the same as in Example 2 except that sec-BuLi was used instead of DPHLi. The results are shown in Table 1.

From the results in Table 1, when DPHLi was used as the initiator, the conversion rate of bromostyrene was higher than that of n-BuLi or sec-BuLi, and the yield of non-target styrene was kept low. It was found that the desired bromostyrene polymer can be produced (that is, the lithiolysis reaction does not proceed).

<Manufacturing of bromostyrene polymer 2>
(Example 3)
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 shown in FIG. , And R3: GL Sciences), one PTFE tube (R1': ISIS Co, Ltd.), 100 cm precooling unit (P1, P2, P3, and P4: GL Sciences) A flow microreactor system was used.

The flow reactor composed of P1, P2, M1 and R1 was cooled at 20 ° C., and the flow reactor composed of P3, P4, M2, M3, R1 ”, R2, and R3 was cooled at −40 ° C.
Stainless steel reactors in cooling tanks at different temperatures were connected with PTFE tubes (R1').
α-Methylstyrene solution (0.12M THF solution, flow velocity: 3.75 mL / min; 1.0 molar equivalent relative to sec-BuLi) and sec-BuLi solution (0.2M hexane solution, flow velocity: 2.25 mL) / Min) was 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.

Next, the initiator solution and 4-bromostyrene solution (0.75 M THF solution, flow rate: 12.0 mL / min) are mixed with M2 (φ = 500 μm), and the mixture is passed through R2 (inner diameter 1000 μm, 100 cm). bottom.
The obtained solution was introduced into M3 (φ = 500 μm), a MeOH solution (0.15 M THF solution, 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, an aliquot of the product solution was collected for 10 seconds, an aliquot was treated with saturated aqueous NH 4 _Cl solution and brine. After diluting the solution with THF, 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.

(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.

(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 at −40 ° C. The results are shown in Table 2.

(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 with respect to sec-BuLi). The results are shown in Table 2.

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

From the results in Table 2, it was found that when the initiator obtained by reacting sec-BuLi with an alkylaryl compound was used, a bromostyrene polymer having a narrow molecular weight distribution could be produced.
Further, when the alkylaryl compound is 1.5 molar equivalents or more with respect to sec-BuLi, the target product is further maintained at a low yield of styrene, which is not the target product, as compared with 1.0 molar equivalent. It was found that the bromostyrene polymer of the above can be produced.

<Manufacturing of bromostyrene polymer 3>
(Example 8)
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 shown in FIG. , And R3: GL Sciences), one PTFE tube (R1'), 100 cm precooling unit (P1, P2, P3, and P4: GL Sciences) integrated flow microreactor system was used. ..
The flow reactor composed of P1, P2, M1 and R1 was heated at 35 ° C. and the flow reactor composed of P3, P4, M2, M3, R1 ”, R2 and R3 was cooled at −40 ° C.
Stainless steel reactors in cooling tanks at different temperatures were connected with PTFE tubes (R1').
Add α-methylstyrene solution (0.12 M THF solution, flow velocity: 5.625 mL / min) and sec-BuLi solution (0.2 M hexane solution, flow velocity: 2.25 mL / min) to M1 (φ = 250 μm). It was introduced by a syringe pump and the mixture (initiator solution ^{) was passed through R1 (inner diameter 1000 μm, 100 cm, t R1} = 6.0 s).
The initiator solution R1 '(inner diameter ^{1000μm, 12.5cm, t R1' =} 0.75s) and R1 "(inner diameter ^{1000μm, 87.5cm, t R1" =} 5.2s) on through, cooled to -40 ℃ bottom.

Next, the initiator solution and 2-bromostyrene solution (0.75 M THF solution, flow rate: 12.0 mL / min) are mixed with M2 (φ = 500 μm), and the mixture is R2 (inner diameter 1000 μm, 100 cm, t ^R2). = 2.1s).
The obtained solution was introduced into M3 (φ = 500 μm), a MeOH solution (0.15 M THF solution, flow rate: 4.5 mL / min) was introduced therein, and the mixture was mixed with R3 (inner diameter 1000 μm, 100 cm, t ^R3 =). It passed through 1.7s).
After reaching a steady state, an aliquot of the product solution was collected for 10 seconds, an aliquot was treated with saturated aqueous NH 4 _Cl solution and brine. The solution was diluted with THF, filtered and then analyzed by GPC. The results are shown in Table 3.

(Example 9)
The procedure was the same as in Example 8 except that 3-bromostyrene was used instead of 2-bromostyrene. The results are shown in Table 3.

From the results in Table 3, it was found that when 2-bromostyrene or 3-bromostyrene was used, a bromostyrene polymer having a narrow molecular weight distribution could be produced, similar to 4-bromostyrene.

<Manufacturing of bromostyrene polymer 4>
(Example 10)
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) shown in FIG. , R2, R3, and R4: GL Sciences), one PTFE tube (R1'), 100 cm precooling unit (P1, P2, P3, P4, and P5: GL Sciences) integrated flow A microreactor system was used.
The flow reactor composed of P1, P2, M1 and R1 is heated at 35 ° C., and the flow reactor composed of P3, P4, P5, M2, M3, M4, R1 ", R2, R3 and R4 is -40. Cooled at ° C.
Stainless steel reactors in cooling tanks at different temperatures were connected with PTFE tubes (R1').
Add α-methylstyrene solution (0.12 M THF solution, flow velocity: 5.625 mL / min) and sec-BuLi solution (0.2 M hexane solution, flow velocity: 2.25 mL / min) to M1 (φ = 250 μm). It was introduced by a syringe pump and the mixture (initiator solution ^{) was passed through R1 (inner diameter 1000 μm, 100 cm, t R1} = 6.0 s).
The initiator solution R1 '(inner diameter ^{1000μm, 12.5cm, t R1' =} 0.75s) and R1 "(inner diameter ^{1000μm, 87.5cm, t R1" =} 5.2s) on through, cooled to -4 ° C. bottom.

Next, the initiator solution and 2-bromostyrene solution (0.75 M THF solution, flow rate: 12.0 mL / min) are mixed with M2 (φ = 500 μm), and the mixture is 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 THF solution, flow rate: 6.0 mL / min) was introduced therein.
The mixed solution is passed through R3 (inner diameter 1000 μm, 200 cm, t ^R3 = 3.6 s), mixed with MeOH (0.60 M THF solution, flow rate: 1.5 mL / min) of M4, and the obtained solution is R4 (inner diameter). It was passed through 1000 μm, 100 cm, t ^R4 = 3.4 s).
After reaching steady state, the resulting aliquot of the solution was collected for 10 seconds, an aliquot was treated with saturated aqueous NH 4 _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 side of FIG.

(Example 11)
The procedure was the same as in Example 10 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.

(Example 12)
The procedure was the same as in Example 10 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.

From the results in Table 4, it was found that when a bromostyrene polymer produced by reacting the initiator of the present application with bromostyrenes was further reacted with a styrene monomer, a block copolymer of bromostyrenes and styrene could be produced. The reaction between the initiator of the present application and bromostyrenes was found to be living polymerization.
Furthermore, from the result of FIG. 8, it was found that it was a complete living polymerization.

<Manufacturing of bromostyrene polymer 5>
(Example 13)
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) shown in FIG. , R2, R3, and R4: GL Sciences), one PTFE tube (R1'), 100 cm precooling unit (P1, P2, P3, P4, and P5: GL Sciences) integrated flow A microreactor system was used.
The flow reactor composed of P1, P2, M1 and R1 is heated at 35 ° C., and the flow reactor composed of P3, P4, P5, M2, M3, M4, R1 ", R2, R3 and R4 is -40. Cooled at ° C.
Stainless steel reactors in cooling tanks at different temperatures were connected by PTFE tubes (R1').
Add α-methylstyrene solution (0.12 M THF solution, flow velocity: 5.625 mL / min) and sec-BuLi solution (0.2 M hexane solution, flow velocity: 2.25 mL / min) to M1 (φ = 250 μm). It was introduced by a syringe pump and the mixture (initiator solution ^{) was passed through R1 (inner diameter 1000 μm, 100 cm, t R1} = 6.0 s).
The initiator solution R1 '(inner diameter ^{1000μm, 12.5cm, t R1' =} 0.75s) and R1 "(inner diameter ^{1000μm, 87.5cm, t R1" =} 5.2s) on through, cooled to -40 ℃ bottom.

Next, the initiator solution and 4-bromostyrene solution (0.75 M THF solution, flow rate: 12.0 mL / min) are mixed with M2 (φ = 500 μm), and the mixture is 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 THF solution, flow rate: 3.0 mL / min) was introduced therein.
The mixed solution was passed through R3 (inner diameter 1000 μm, 200 cm), mixed with M4 MeOH (0.60 M THF solution, flow rate: 1.5 mL / min), and the obtained solution was passed through R4 (inner diameter 1000 μm, 100 cm). ..
After reaching steady state, the resulting aliquot of the solution was collected for 10 seconds, an aliquot was treated with saturated aqueous NH 4 _Cl solution and brine. The solution was diluted with THF, n-tetradecane was added, filtered, and then the solution was analyzed by GC and GPC. The results are shown in Table 5.

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

(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.

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

From the results in Table 5, it was found that the Mn value was proportional to the styrene equivalent, further demonstrating the living property.

<Production of bromostyrene polymer 6: Examination of reaction temperature>
(Example 17)
The same procedure as in Example 6 was carried out except that the flow reactor composed of P3, P4, M2, M3, R1 ”, R2, and R3 was cooled at 20 ° C. The results are shown in Table 6.

(Example 18)
The same procedure as in Example 6 was carried out except that the flow reactor composed of P3, P4, M2, M3, R1 ”, R2, and R3 was cooled at 0 ° C. The results are shown in Table 6.

(Example 19)
The flow reactor composed of P3, P4, M2, M3, R1 ”, R2, and R3 was cooled at −20 ° C. in the same manner as in Example 6. The results are shown in Table 6.

(Example 20)
The flow reactor composed of P3, P4, M2, M3, R1 ”, R2, and R3 was cooled at −78 ° C. in the same manner as in Example 6. The results are shown in Table 6.

(Example 21)
Except that the flow reactor composed of P1, P2, M1 and R1 was cooled at 20 ° C. and the flow reactor composed of P3, P4, M2, M3, R1 ”, R2 and R3 was cooled at 20 ° C. The same procedure as in Example 6 was carried out. The results are shown in Table 6.

(Example 22)
Except that the flow reactor composed of P1, P2, M1 and R1 was cooled at 20 ° C. and the flow reactor composed of P3, P4, M2, M3, R1 ”, R2 and R3 was cooled at 0 ° C. The same procedure as in Example 6 was carried out. The results are shown in Table 6.

(Example 23)
Except that the flow reactor composed of P1, P2, M1 and R1 was cooled at 20 ° C. and the flow reactor composed of P3, P4, M2, M3, R1 ”, R2 and R3 was cooled at −20 ° C. , The same procedure as in Example 6 was performed. The results are shown in Table 6.

(Example 24)
Except that the flow reactor composed of P1, P2, M1 and R1 was cooled at 20 ° C. and the flow reactor composed of P3, P4, M2, M3, R1 ”, R2 and R3 was cooled at −40 ° C. , The same procedure as in Example 6 was performed. The results are shown in Table 6.

(Example 25)
Except that the flow reactor composed of P1, P2, M1 and R1 was cooled at 20 ° C. and the flow reactor composed of P3, P4, M2, M3, R1 ”, R2 and R3 was cooled at −78 ° C. , The same procedure as in Example 6 was performed. The results are shown in Table 6.

(Example 26)
Except that the flow reactor composed of P1, P2, M1 and R1 was cooled at −40 ° C. and the flow reactor composed of P3, P4, M2, M3, R1 ”, R2 and R3 was cooled at 20 ° C. , The same procedure as in Example 6 was performed. The results are shown in Table 6.

(Example 27)
Except that the flow reactor composed of P1, P2, M1 and R1 was cooled at −40 ° C. and the flow reactor composed of P3, P4, M2, M3, R1 ”, R2 and R3 was cooled at 0 ° C. , The same procedure as in Example 6 was performed. The results are shown in Table 6.

(Example 28)
Except that the flow reactor composed of P1, P2, M1 and R1 was cooled at −40 ° C. and the flow reactor composed of P3, P4, M2, M3, R1 ”, R2 and R3 was cooled at −20 ° C. Was carried out in the same manner as in Example 6. The results are shown in Table 6.

(Example 29)
Except that the flow reactor composed of P1, P2, M1 and R1 was cooled at −40 ° C. and the flow reactor composed of P3, P4, M2, M3, R1 ”, R2 and R3 was cooled at −40 ° C. Was carried out in the same manner as in Example 6. The results are shown in Table 6.

(Example 30)
Except that the flow reactor composed of P1, P2, M1 and R1 was cooled at −40 ° C. and the flow reactor composed of P3, P4, M2, M3, R1 ”, R2 and R3 was cooled at −78 ° C. Was carried out in the same manner as in Example 6. The results are shown in Table 6.

<Manufacturing of bromostyrene polymer 7: Examination of reactor length>
(Example 31)
The same procedure as in Example 6 was carried out 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. Indicated.

(Example 32)
The same procedure as in Example 6 was carried out 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. Indicated.

<Production of bromostyrene polymer 8: Effect of mixing efficiency>
(Example 33)
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 shown in FIG. , And R3: GL Sciences), one PTFE tube (R1'), 100 cm precooling unit (P1, P2, P3, and P4: GL Sciences) integrated flow microreactor system was used. ..
The flow reactor composed of P1, P2, M1 and R1 was cooled at 20 ° C., and the flow reactor composed of P3, P4, M2, M3, R1 ”, R2, and R3 was cooled at −40 ° C.
Stainless steel reactors in cooling tanks at different temperatures were connected with PTFE tubes (R1').
Add α-methylstyrene solution (0.12 M THF solution, flow velocity: 1.406 mL / min) and sec-BuLi solution (0.2 M hexane solution, flow velocity: 0.5625 mL / min) to M1 (φ = 250 μm). It was introduced by a syringe pump and the mixture (initiator solution ^{) was passed through R1 (inner diameter 1000 μm, 100 cm, t R1} = 6.0 s).
The initiator solution R1 '(inner diameter ^{1000μm, 12.5cm, t R1' =} 0.75s) and R1 "(inner diameter ^{1000μm, 87.5cm, t R1" =} 5.2s) on through, cooled to -40 ℃ bottom.

Next, the initiator solution and 4-bromostyrene solution (0.75 M THF solution, flow rate: 3 mL / min) are mixed with M2 (φ = 1000 μm), and the mixture is mixed with R2 (inner diameter 1000 μm, 100 cm, t ^R2 = 2). .1s).
The obtained solution was introduced into M3 (φ = 500 μm), a MeOH solution (0.15 M THF solution, flow rate: 4.5 mL / min) was introduced therein, and the mixture was mixed with R3 (inner diameter 1000 μm, 100 cm, t ^R3 =). It passed through 1.7s).
After reaching a steady state, an aliquot of the product solution was collected for 10 seconds, an aliquot was treated with saturated aqueous NH 4 _Cl solution and brine. The solution was diluted with THF, filtered and then analyzed by GPC. The results are shown in Table 8.

(Example 34)
Performed 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. This was done in the same manner as in Example 33. The results are shown in Table 8.

(Example 35)
Performed 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. This was done in the same manner as in Example 33. The results are shown in Table 8.

(Example 36)
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. Was replaced with 5.625 mL / min, and the same procedure as in Example 33 was carried out. The results are shown in Table 8.

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

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

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

(Example 40)
M2 was replaced with a T-type micromixer (φ = 500 μm), the flow rate of the α-methylstyrene solution was replaced with 7.031 mL / min, the flow rate of the sec-BuLi solution was replaced with 2.813 mL / min, and 4-bromostyrene was used. The same procedure as in Example 33 was carried out except that the flow rate of the 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.

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

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

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

(Example 44)
M2 was replaced with a V-type micromixer (φ = 500 μm), the flow rate of the α-methylstyrene solution was replaced with 7.031 mL / min, the flow rate of the sec-BuLi solution was replaced with 2.813 mL / min, and 4-bromostyrene was used. The same procedure as in Example 33 was carried out except that the flow rate of the 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.

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

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

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

(Example 48)
M2 was replaced with a V-type micromixer (φ = 250 μm), the flow rate of the α-methylstyrene solution was replaced with 7.031 mL / min, the flow rate of the sec-BuLi solution was replaced with 2.813 mL / min, and 4-bromostyrene was used. The same procedure as in Example 33 was carried out except that the flow rate of the 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.

<Manufacturing of bromostyrene polymer 9: Examination of living property>
(Example 49)
Two V-type micromixers (M1 and M2: manufactured by Sanko Seiki Kogyo Co., Ltd.), T-type micromixers (M3: manufactured by Sanko Seiki Kogyo Co., Ltd.), microtube reactors (R1, R1 ", R2 shown in FIG. , And R3: GL Sciences), one PTFE tube (R1'), 100 cm precooling unit (P1, P2, P3, and P4: GL Sciences) integrated flow microreactor system was used. ..
The flow reactor composed of P1, P2, M1 and R1 was cooled at 20 ° C., and the flow reactor composed of P3, P4, M2, M3, R1 ”, R2, and R3 was cooled at −40 ° C.
Stainless steel reactors in cooling tanks at different temperatures were connected with PTFE tubes (R1').
Add α-methylstyrene solution (0.12 M THF solution, flow velocity: 5.625 mL / min) and sec-BuLi solution (0.2 M hexane solution, flow velocity: 2.25 mL / min) to M1 (φ = 250 μm). It was introduced by a syringe pump and the mixture (initiator solution ^{) was passed through R1 (inner diameter 1000 μm, 100 cm, t R1} = 6.0 s).
The initiator solution R1 '(inner diameter ^{1000μm, 12.5cm, t R1' =} 0.75s) and R1 "(inner diameter ^{1000μm, 87.5cm, t R1" =} 5.2s) on through, cooled to -40 ℃ bottom.

Next, the initiator solution and 4-bromostyrene solution (0.375 M THF solution, flow rate: 12 mL / min) are mixed with M2 (φ = 500 μm), and the mixture is mixed with R2 (inner diameter 1000 μm, 100 cm, t ^R2 = 2). .1s).
The obtained solution was introduced into M3 (φ = 500 μm), a MeOH solution (0.15 M THF solution, flow rate: 4.5 mL / min) was introduced therein, and the mixture was mixed with R3 (inner diameter 1000 μm, 100 cm, t ^R3 =). It passed through 1.7s).
After reaching a steady state, an aliquot of the product solution was collected for 10 seconds, an aliquot was treated with saturated aqueous NH 4 _Cl solution and brine. The solution was diluted with THF, filtered and then analyzed by GPC. The results are shown in Table 9.

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

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

<Manufacturing of bromostyrene polymer 10: Examination of block copolymer>
(Example 52)
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 Co., Ltd.) and one PTFE shown in FIG. An integrated flow microreactor system consisting of a tube (R1') and a 100 cm precooling unit (P1, P2, P3, and P4: manufactured by GL Sciences) was used.
The flow reactor composed of P1, P2, M1 and R1 was cooled at 20 ° C., and the flow reactor composed of P3, P4, M2, M3, R1 ”, R2, and R3 was cooled at −40 ° C.
Stainless steel reactors in cooling tanks at different temperatures were connected with PTFE tubes (R1').
Add α-methylstyrene solution (0.12 M THF solution, flow velocity: 5.625 mL / min) and sec-BuLi solution (0.2 M hexane solution, flow velocity: 2.25 mL / min) to M1 (φ = 250 μm). It was introduced by a syringe pump and the mixture (initiator solution ^{) was passed through R1 (inner diameter 1000 μm, 100 cm, t R1} = 6.0 s).
The initiator solution R1 '(inner diameter ^{1000μm, 12.5cm, t R1' =} 0.75s) and R1 "(inner diameter ^{1000μm, 87.5cm, t R1" =} 5.2s) on through, cooled to -40 ℃ bottom.

Next, the initiator solution and 4-bromostyrene solution (0.375 M THF solution, flow rate: 12 mL / min) are mixed with M2 (φ = 500 μm), and the mixture is mixed with R2 (inner diameter 1000 μm, 100 cm, t ^R2 = 2). .1s).
The obtained solution was introduced into M3 (φ = 500 μm), a 4-bromostyrene solution (2.0 M THF solution, flow rate: 4.5 mL / min) was introduced therein, and the mixture was mixed with R3 (inner diameter 1000 μm, 100 cm, 100 cm). It ^{was passed through t R3} = 1.7s).
After reaching a steady state, an aliquot of the resulting solution was collected for 10 seconds vessel containing methanol 100μL and 2 mL of THF, an aliquot was treated with saturated aqueous _NH 4 Cl solution and brine. The solution was diluted with THF, filtered and then analyzed by GPC. The results are shown in Table 10.

(Example 53)
Similar to Example 52, except that the concentration of bromostyrene introduced into M2 was replaced with 0.75M, the concentration of monomer B introduced into M3 was replaced with styrene, and the concentration of monomer B introduced into M3 was replaced with 3.0M. went. The results are shown in Table 10.

(Example 54)
The concentration of bromostyrene introduced into M2 is replaced with 3-bromostyrene, the concentration of bromostyrene introduced into M2 is replaced with 0.75M, the concentration of monomer B introduced into M3 is replaced with styrene, and the concentration of monomer B introduced into M3 is 3. The procedure was the same as in Example 52, except that the mixture was replaced with 0.0M. The results are shown in Table 10.

(Example 55)
The concentration of bromostyrene introduced into M2 is replaced with 2-bromostyrene, the concentration of bromostyrene introduced into M2 is replaced with 0.75M, the concentration of monomer B introduced into M3 is replaced with styrene, and the concentration of monomer B introduced into M3 is 3. The procedure was the same as in Example 52, except that the mixture was replaced with 0.0M. The results are shown in Table 10.

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

(Example 57)
The same procedure as in Example 52 was carried out except that the bromostyrene introduced into M2 was replaced with 2-bromostyrene and the monomer B introduced into M3 was replaced with 3-bromostyrene. The results are shown in Table 10.

<Manufacturing of chlorostyrene polymer 1>
(Example 58)
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 shown in FIG. , And R3: GL Sciences), one PTFE tube (R1': ISIS Co, Ltd.), 100 cm precooling unit (P1, P2, P3, and P4: GL Sciences) A flow microreactor system was used.

The flow reactor composed of P1, P2, M1 and R1 was cooled at 20 ° C., and the flow reactor composed of P3, P4, M2, M3, R1 ”, R2, and R3 was cooled at −40 ° C.
Stainless steel reactors in cooling tanks at different temperatures were connected by PTFE tubes (R1').
α-Methylstyrene solution (0.12M THF solution, flow velocity: 5.625 mL / min; 1.5 molar equivalents relative to sec-BuLi) and sec-BuLi solution (0.2M hexane solution, flow velocity: 2.25 mL) / Min) was 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, t R1} = 6.0 s).
The initiator solution is passed through R1'(inner diameter 1000 μm, 12.5 cm, t ^R1' = 0.75 s) and R1'(inner diameter 1000 μm, 87.5 cm, t ^R1'' = 5.2 s) to −40 ° C. Cooled.

Next, the initiator solution and p-chlorostyrene solution (0.75 M THF solution, 12.0 mL / min) are mixed with M2 (φ = 500 μm), and the mixture is mixed with R2 (inner diameter 1000 μm, 100 cm, t ^R2 = 2). .1s).
The obtained solution was introduced into M3 (φ = 500 μm), a MeOH solution (0.15 M THF solution, flow rate: 4.5 mL / min) was introduced therein, and the mixture was mixed with R3 (inner diameter 1000 μm, 100 cm, t ^R3 =). It passed through 1.7s).
After reaching steady state, an aliquot of 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 = 3388Da, PDI = 1.12) is shown in FIG.

-MALDI-TOFMS-
Mass spectrometry was performed using an ultrafreXtreme MALDI-TOF mass spectrometer from Bruker Daltonics. The polymer was dissolved in THF and applied to the plate and DCTB was used as the matrix. In addition, sodium salt or silver salt was appropriately used as an additive.

＜２＞ 前記アリール基がフェニル基である、前記＜１＞に記載のポリマーの製造方法である。
＜３＞ 前記一般式（１）中、Ｒ^１及びＲ^２の一方が、炭素数１〜１０のアルキル基である、前記＜１＞から＜２＞のいずれかに記載のポリマーの製造方法である。
＜４＞ 前記一般式（１）で表される開始剤が、ｓｅｃ−ＢｕＬｉと、アルキルアリール化合物とを反応させて得られる、前記＜１＞から＜３＞のいずれかに記載のポリマーの製造方法である。
＜５＞ 前記ｓｅｃ−ＢｕＬｉと、アルキルアリール化合物との反応温度が、０℃以上４０℃以下である、前記＜４＞に記載のポリマーの製造方法である。
＜６＞ 前記ｓｅｃ−ＢｕＬｉに対する、前記アルキルアリール化合物が、１．０モル当量以上２．０モル当量以下である、前記＜４＞から＜５＞のいずれかに記載のポリマーの製造方法である。
＜７＞ さらに、前記工程において、前記ハロゲン化スチレン類モノマーをアニオン重合させて得られたポリマーに対し、モノマーを重合させる工程を含み、前記モノマーが、スチレン、又はスチレン誘導体である、前記＜１＞から＜６＞のいずれかに記載のポリマーの製造方法である。
＜８＞ 下記一般式（１）で表されるハロゲン化スチレン類モノマー重合用開始剤（ただし、前記一般式（１）中、Ｒ^１及びＲ^２の一方がアリール基であり、他方がアリール基、又は炭素数１〜１０のアルキル基である）である。

＜９＞ 前記アリール基がフェニル基である、前記＜８＞に記載のハロゲン化スチレン類モノマー重合用開始剤である。
＜１０＞ 前記一般式（１）中、Ｒ^１及びＲ^２の一方が、炭素数１〜１０のアルキル基である、前記＜８＞から＜９＞のいずれかに記載のハロゲン化スチレン類モノマー重合用開始剤である。
＜１１＞ ｓｅｃ−ＢｕＬｉと、アルキルアリール化合物とを反応する工程を含む、
下記一般式（１）で表されるハロゲン化スチレン類モノマー重合用開始剤の製造方法である（ただし、前記一般式（１）中、Ｒ^１及びＲ^２の一方がアリール基であり、他方がアリール基、又は炭素数１〜１０のアルキル基である）。

＜１２＞ 前記ｓｅｃ−ＢｕＬｉと、アルキルアリール化合物との反応温度が、０℃以上４０℃以下である、前記＜１１＞に記載のハロゲン化スチレン類モノマー重合用開始剤の製造方法である。
＜１３＞ 前記ｓｅｃ−ＢｕＬｉに対する、前記アルキルアリール化合物が、１．０モル当量以上２．０モル当量以下である、前記＜１１＞から＜１２＞のいずれかに記載のハロゲン化スチレン類モノマー重合用開始剤の製造方法である。
＜１４＞ 下記一般式（３）又は（４）のいずれかで表されるポリマーである（ただし、前記一般式（３）中、ｍは、重合度を表し、１以上の整数であり；Ｒ^５は、アリール基、又は炭素数１〜１０のアルキル基であり；Ｘは、フッ素原子、塩素原子、臭素原子、ヨウ素原子、又はアスタチン原子のいずれかであり；ａは、１〜５の整数である。前記一般式（４）中、ｍ及びｎは重合度を表し、それぞれ１以上の整数であり；Ｒ^５は、アリール基、又は炭素数１〜１０のアルキル基であり；Ｒ^６は、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、アスタチン原子、炭素数１〜４のアルキル基、又はトリメチルシリル基のいずれかであり；Ｘは、フッ素原子、塩素原子、臭素原子、ヨウ素原子、又はアスタチン原子のいずれかであり；ａ及びｂは、それぞれ１〜５の整数である。）。

Examples of aspects of the present invention include the following.
<1> A method for producing a polymer, which comprises a step of anionic polymerization of a halogenated styrene monomer using a microreactor in the presence of an initiator represented by the following general formula (1) (however, the above general formula (1). ), One of R ¹ and R ² 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 <1>, wherein the aryl group is a phenyl group.
<3> The method for producing a polymer according to any one of <1> to <2>, wherein one of ^{R 1} and R ^{2 in} the general formula (1) is an alkyl group having 1 to 10 carbon atoms. be.
<4> Production of the polymer according to any one of <1> to <3>, wherein the initiator represented by the general formula (1) is obtained by reacting sec-BuLi with an alkylaryl compound. The method.
<5> The method for producing a polymer according to <4>, wherein the reaction temperature between 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 <4> to <5>, wherein the alkylaryl compound is 1.0 molar equivalent or more and 2.0 molar equivalent or less with respect to sec-BuLi. ..
<7> Further, in the above step, the step of polymerizing the monomer with respect to the polymer obtained by anionic polymerization of the halogenated styrene monomer is included, and the monomer is styrene or a styrene derivative. > To <6>. The method for producing a polymer.
<8> Initiator for polymerization of halogenated styrenes monomer represented by the following general formula (1) (However, in the general formula (1), ^one of R ^{1 and R 2} is an aryl group, and the other is an aryl group. , Or an alkyl group having 1 to 10 carbon atoms).

<9> The initiator for polymerizing a halogenated styrene monomer according to <8>, wherein the aryl group is a phenyl group.
<10> The halogenated styrene monomer according to any one of <8> to <9>, wherein ^one of R 1 and R ² is an alkyl group having 1 to 10 carbon atoms in the general formula (1). It is a polymerization initiator.
<11> A step of reacting sec-BuLi with an alkylaryl compound is included.
This is a method for producing a halogenated styrene monomer polymerization initiator represented by the following general formula (1) (however, in the general formula (1), ^one of R ^{1 and R 2} is an aryl group, and the other is an aryl group. Aryl group or alkyl group having 1 to 10 carbon atoms).

<12> The method for producing a halogenated styrene monomer polymerization initiator according to <11>, wherein the reaction temperature of the sec-BuLi and the alkylaryl compound is 0 ° C. or higher and 40 ° C. or lower.
<13> The halogenated styrene monomer polymerization according to any one of <11> to <12>, wherein the alkylaryl compound has 1.0 molar equivalent or more and 2.0 molar equivalent or less with respect to sec-BuLi. This is a method for producing an initiator.
<14> A polymer represented by any of the following general formulas (3) or (4) (however, in the general formula (3), m represents the degree of polymerization and is an integer of 1 or more; R. ⁵ is an aryl group or an alkyl group having 1 to 10 carbon atoms; X is either a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an astatin atom; a is an integer of 1 to 5. In the general formula (4), m and n represent the degree of polymerization and are integers of 1 or more, respectively; R ⁵ is an aryl group or an alkyl group having 1 to 10 carbon atoms; R ⁶ is. , Hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, astatin atom, alkyl group having 1 to 4 carbon atoms, or trimethylsilyl group; X is fluorine atom, chlorine atom, bromine atom, iodine. It is either an atom or an statatin atom; a and b are integers 1-5, respectively).

Claims (14)

A method for producing a polymer, which comprises a step of anionic polymerization of a halogenated styrene monomer using a microreactor in the presence of an initiator represented by the following general formula (1).

However, in the general formula (1), ^one of R 1 and R ² is an aryl group, and the other is an aryl group or an alkyl group having 1 to 10 carbon atoms. The method for producing a polymer according to claim 1, wherein the aryl group is a phenyl group. The method for producing a polymer according to any one of claims 1 to 2, wherein in the general formula (1), ^one of R 1 and R ^{2 is an alkyl group having 1 to 10 carbon atoms.} 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. The method for producing a polymer according to claim 4, wherein the reaction temperature of sec-BuLi and the alkylaryl compound is 0 ° C. or higher and 40 ° C. or lower. The method for producing a polymer according to any one of claims 4 to 5, wherein the alkylaryl compound is 1.0 molar equivalent or more and 2.0 molar equivalent or less with respect to sec-BuLi. Further, the step includes a step of polymerizing the monomer with respect to the polymer obtained by anionic polymerization of the halogenated styrene monomer.
The method for producing a polymer according to any one of claims 1 to 6, wherein the monomer is styrene or a styrene derivative. Initiator for polymerization of halogenated styrenes monomer represented by the following general formula (1).

However, in the general formula (1), ^one of R 1 and R ² is an aryl group, and the other is an aryl group or an alkyl group having 1 to 10 carbon atoms. The initiator for polymerizing a halogenated styrenes monomer according to claim 8, wherein the aryl group is a phenyl group. The initiator for halogenated styrene monomer polymerization according to any one of claims 8 to 9, wherein in the general formula (1), ^one of R 1 and R ^{2 is an alkyl group having 1 to 10 carbon atoms.} Includes a step of reacting sec-BuLi with an alkylaryl compound.
A method for producing a halogenated styrene monomer polymerization initiator represented by the following general formula (1).

However, in the general formula (1), ^one of R 1 and R ² is an aryl group, and the other is an aryl group or an alkyl group having 1 to 10 carbon atoms. The method for producing a halogenated styrene monomer polymerization initiator according to claim 11, wherein the reaction temperature of the sec-BuLi and the alkylaryl compound is 0 ° C. or higher and 40 ° C. or lower. The method for producing a halogenated styrene monomer polymerization initiator according to any one of claims 11 to 12, wherein the alkylaryl compound has 1.0 molar equivalent or more and 2.0 molar equivalent or less with respect to sec-BuLi. .. A polymer represented by either the following general formula (3) or (4).

However, in the general formula (3), m represents the degree of polymerization and is an integer of 1 or more; R ⁵ is an aryl group or an alkyl group having 1 to 10 carbon atoms; X is a fluorine atom. It is either a chlorine atom, a bromine atom, an iodine atom, or an astatine atom; a is an integer of 1 to 5.

However, in the general formula (4), m and n represent the degree of polymerization and are integers of 1 or more, respectively; R ⁵ is an aryl group or an alkyl group having 1 to 10 carbon atoms; R ⁶ is It is either a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an astatin atom, an alkyl group having 1 to 4 carbon atoms, or a trimethylsilyl group; X is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. , Or either of the astatin atoms; a and b are integers 1-5, respectively.

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