JP2022126566A - Polymer, and method for producing the same - Google Patents

Abstract

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

Description

The present invention relates to polymers and methods for their production.

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

Reactions using microreactors are thought to enable precise residence time control, precise temperature control, and high-speed mixing. It is expected to improve and is attracting attention as a highly efficient production method.

On the other hand, anionic polymerization has a fast reaction rate and is a powerful tool for synthesizing styrenic polymers. However, sufficient research has not been conducted because the polymerization of styrene modified with functional groups is greatly restricted by the reactivity of the functional groups.
So far, anionic polymerization of halogenated styrene using sec-BuLi as an initiator has been reported (see, for example, Non-Patent Document 3). have not been obtained, nor has a modified polymer derived from a narrowly dispersed halogenated styrene polymer been obtained.

Therefore, a method for efficiently producing a narrowly dispersed modified polymer derived from a halogenated styrene polymer has not yet been provided, and prompt provision thereof is strongly desired.

Chimia 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 conventional problems and to achieve the following objects. That is, an object of the present invention is to provide a method for efficiently producing a narrowly dispersed modified polymer derived from a halogenated styrene polymer.

As a result of intensive studies by the present inventors to achieve the above object, a halogenated styrene monomer is subjected to anionic polymerization using a microreactor in the presence of an initiator represented by the following general formula (1). and a modification step of modifying the polymer obtained in the anionic polymerization step (provided that in the general formula (1), one of R ¹ and R ² is an aryl group, The other is an aryl group or an alkyl group having 1 to 10 carbon atoms), it was found that a method for efficiently producing a modified polymer derived from a halogenated styrene polymer with narrow dispersion can be provided.

＜２＞ 下記一般式（３）又は（４）のいずれかで表され、分子量分布が１．４以下であるポリマーである。

ただし、前記一般式（３）中、ｍ及びｎは重合度を表し、ｍは０以上の整数であり、ｎは１以上の整数である。Ｒ^５及びＲ^６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；Ｙは、水素原子、重水素原子、アルデヒド基、ボリル基、ヒドロキシ基、アセトキシ基、トリメチルシリル基、又は下記構造式（４）から（６）のいずれかで表される基であり；ａは、１～５の整数である。Ｙ基を有しないスチレン構造単位とＹ基を有するスチレン構造単位の結合順序は順不同であり、前記ポリマーは、ランダムポリマーであってもブロックポリマーであってもよい。

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以上の整数である。Ｒ^５及びＲ^６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のアルキル基であり；Ｙは、水素原子、重水素原子、アルデヒド基、ボリル基、ヒドロキシ基、アセトキシ基、トリメチルシリル基、又は下記構造式（４）から（６）のいずれかで表される基である。ベンズアルデヒド基を有するスチレン構造単位とＹ基を有するスチレン構造単位の結合順序は順不同であり、前記ポリマーは、ランダムポリマーであってもブロックポリマーであってもよい。

The present invention is based on the findings of the present inventors, and means for solving the above problems are as follows. Namely
<1> An anionic polymerization step of anionically polymerizing a halogenated styrene monomer using a microreactor in the presence of an initiator represented by the following general formula (1), and the polymer obtained in the anionic polymerization step A method for producing a polymer including a modification step of modifying (provided that 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) ).

<2> A polymer represented by either the following general formula (3) or (4) and having a molecular weight distribution of 1.4 or less.

However, in said general formula (3), m and n represent the degree of polymerization, m is an integer of 0 or more, and n is an integer of 1 or more. one of R ⁵ and R ⁶ is an aryl group and the other is an aryl group or an alkyl group having 1 to 10 carbon atoms; X is any of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an astatine atom; Y is a hydrogen atom, a deuterium atom, an aldehyde group, a boryl group, a hydroxy group, an acetoxy group, a trimethylsilyl group, or a group represented by any of the following structural formulas (4) to (6) ; a is an integer of 1 to 5; The order of bonding of the styrene structural units not having a Y group and the styrene structural units having a Y group is random, and the polymer may be a random polymer or a block polymer.

However, in said general formula (4), m and n represent the degree of polymerization, and each is an integer of 1 or more. one of R ⁵ and R ⁶ is an aryl group and the other is an aryl group or an alkyl group having 1 to 10 carbon atoms; Y is a hydrogen atom, a deuterium atom, an aldehyde group, a boryl group, a hydroxy group, an acetoxy group; group, a trimethylsilyl group, or a group represented by any one of the following structural formulas (4) to (6). The order of bonding of the styrene structural unit having a benzaldehyde group and the styrene structural unit having a Y group may be random, and the polymer may be a random polymer or a block polymer.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a method for efficiently producing a narrowly dispersed modified polymer derived from a halogenated styrene polymer.

FIG. 1 is a schematic diagram of a flow microreactor used in one example of the manufacturing method of the present invention. FIG. 2 is a schematic diagram of a flow microreactor used in one example of the manufacturing method of the present invention. FIG. 3 is a schematic diagram of a flow microreactor used in one example of the manufacturing method of the present invention. FIG. 4 is a schematic diagram of a flow microreactor used in one example of the manufacturing method of the present invention. 5 is a schematic diagram of the microreactor system used in Production Example 1. FIG. 6 is a MALDI-TOFMS spectrum of poly-p-bromostyrene obtained in Production Example 1. FIG. 7 is a schematic diagram of the microreactor system used in Production Example 2. FIG. 8 is a MALDI-TOFMS spectrum of poly-p-chlorostyrene obtained in Production Example 2. FIG. 9 is a MALDI-TOFMS spectrum of the modified polymer obtained in Example 1. FIG. FIG. 10 is a MALDI-TOFMS spectrum of the modified polymer obtained in Example 2-1. FIG. 11 is a MALDI-TOFMS spectrum of the modified polymer obtained in Example 2-2. 12 is a MALDI-TOFMS spectrum of the modified polymer obtained in Example 3. FIG. 13 is a MALDI-TOFMS spectrum of the modified polymer obtained in Example 4. FIG. 14 is a MALDI-TOFMS spectrum of the modified polymer obtained in Example 5. FIG. 15 is a schematic diagram of the microreactor system used in Example 6. FIG. FIG. 16 is a MALDI-TOFMS spectrum of the modified polymer obtained in Example 6-1. FIG. 17 is a MALDI-TOFMS spectrum of the modified polymer obtained in Example 6-2. FIG. 18 is the ¹ H-NMR spectrum of the modified polymer obtained in Example 6-3. FIG. 19 is the ¹ H-NMR spectrum of the modified polymer obtained in Example 6-4. FIG. 20 is the ¹ H-NMR spectrum of the modified polymer obtained in Example 6-5. FIG. 21 is the ¹ H-NMR spectrum of the modified polymer obtained in Example 6-6. 22 is a schematic diagram of the microreactor system used in Example 7. FIG. 23 is the ¹ H-NMR spectrum of the modified polymer obtained in Example 7. FIG.

(Method for producing polymer)
The method for producing the polymer includes an anionic polymerization step and a modification step, and may further include other steps.

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

-Halogenated Styrene Monomer-
The halogenated styrene monomer is not particularly limited and can be appropriately selected depending ^on the intended purpose. R ⁴ is a hydrogen atom, a chlorine atom, an alkyl group having 1 to 4 carbon atoms, or a trimethylsilyl group; X is a halogen atom such as fluorine, chlorine, bromine, iodine, astatine; , which is an integer of 1 to 5).

Among the monomers represented by the general formula (2), those in which the X is a chlorine atom or a bromine atom are preferable. The monomer in which X is a chlorine atom or a bromine atom is not particularly limited and can be appropriately selected depending on the purpose. styrene), 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.

- 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 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, one of R ¹ and R ² in the general formula (1) has a carbon number of An alkyl group of 1 to 10 is preferred.

The alkyl group having 1 to 10 carbon atoms is not particularly limited and can be appropriately selected depending on the purpose. An alkyl group having 1 to 8 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, an alkyl group having 1 to 2 carbon atoms is particularly preferable, and a methyl group is most preferable. preferable.

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

Examples of the compound represented by the general formula (1) include the compound (DPHLi) represented by the following structural formula (1), the compound (2PHLi) represented by the following structural formula (2), and the following structural formula ( 3) and the like (3POLi).
Among these, the compound (2PHLi) represented by the following structural formula (2) is preferable from the viewpoint of efficiently achieving a high conversion rate and obtaining a narrowly dispersed polymer.

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

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

The alkylbenzene compound is not particularly limited and can be appropriately selected depending on the purpose. Examples include 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 (o-ethylstyrene), 3-ethylstyrene (m-ethylstyrene), 4-ethylstyrene (p-ethylstyrene), 1,5-diethylstyrene, 2,4-diethylstyrene and other ethylstyrene compounds, 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, 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 even more preferable, from the viewpoint that a high conversion rate can be efficiently obtained and a narrowly dispersed polymer can be obtained.

The lower limit of the reaction temperature between sec-BuLi and the alkylaryl compound is not particularly limited and can be appropriately selected depending on the purpose. is obtained, the temperature 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.

The upper limit of the reaction temperature between the sec-BuLi and the alkylaryl compound is not particularly limited and can be appropriately selected depending on the purpose. 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.

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 intended purpose. From the viewpoint of obtaining, it is preferably 1.0 molar equivalents or more, more preferably 1.1 molar equivalents or more, further preferably 1.2 molar equivalents or more, particularly preferably 1.3 molar equivalents or more, and 1.4 molar equivalents or more. is most preferred.

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 obtaining, it is preferably 2.0 molar equivalents or less, more preferably 1.9 molar equivalents or less, further preferably 1.8 molar equivalents or less, particularly preferably 1.7 molar equivalents or less, and 1.6 molar equivalents or less. is most preferred.

The lower limit of the reaction temperature between the halogenated styrene monomer and the initiator is not particularly limited and can be appropriately selected depending on the purpose. -60°C or higher is preferred, -55°C or higher is more preferred, -50°C or higher is even more preferred, and -45°C or higher is particularly preferred, in terms of obtaining a good polymer.

The upper limit of the reaction temperature between the halogenated styrene monomer and the initiator is not particularly limited and can be appropriately selected depending on the purpose. -20° C. or lower is preferable, -25° C. or lower is more preferable, -30° C. or lower is even more preferable, and -35° C. or lower is particularly preferable, in terms of obtaining a good polymer.

－Micro Reactor－
The microreactor is not particularly limited and can be appropriately selected depending on the purpose. (sometimes referred to as "flow microreactor").
The mixing means and the flow path may be integrated or separated.

The mixing means is a means capable of mixing two or more liquids.
The flow path is a tube through which liquid can flow. The flow passage is connected with at least one of the mixing means.

By using the flow microreactor, it is possible to shorten the residence time from the generation to the next reaction of a compound with low stability, thereby suppressing side reactions.
In addition, since the flow microreactor has excellent cooling efficiency, it is possible to suppress side reactions caused by 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.

The substrate-type micromixer is composed of a substrate having passages formed therein or on its surface, and is sometimes referred to as a microchannel.
The substrate-type micromixer is not particularly limited and can be appropriately selected according to the purpose. ; the mixer described in the document ““Microreactors” Chapter 3, W. Ehrfeld, V. Hessel, H. Lowe, published by Wiley-VCH Co.”, and the like.

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.

It is preferable that the substrate-type micromixer is formed with an introduction path, in addition to the flow path, which 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 channels is not particularly limited, and can be appropriately selected according to the purpose. is preferred. It should be noted that a configuration may be adopted in which one liquid is charged in advance into the flow path and another liquid is introduced through the introduction path.

--Separate flow microreactor--
In the separate flow microreactor, the mixing means and the flow path are connected.

The mixing means is not particularly limited as long as it can mix two or more liquids, and can be appropriately selected according to the purpose. Examples thereof include a pipe joint type micromixer.

The pipe joint type micromixer has a channel formed inside, and if necessary, a connection member for connecting the channel formed inside and the flow channel. The connection method of the connection member is not particularly limited, and can be appropriately selected from known connection methods according to the purpose. Welding type, flange type, bite type, flare type, mechanical type, and the like are included.

It is preferable that an introduction path communicating with the flow path and introducing a plurality of liquids into the flow path is formed inside the pipe joint type micromixer in addition to 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. When the number of the 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 the introduction paths is three, can use, for example, a cross shape. It should be noted that a configuration may be adopted in which one liquid is charged in advance into the flow path and another liquid is introduced through the introduction path.

The material of the pipe joint type micromixer is not particularly limited, and can be appropriately selected according to requirements such as heat resistance, pressure resistance, solvent resistance, and ease of processing. Titanium, copper, nickel, aluminum, silicon, fluorine resins such as Teflon (registered trademark), PFA (perfluoroalkoxy resin), TFAA (trifluoroacetamide), and the like.

As the pipe joint type micromixer, commercially available products can be used, for example, YM-1 type mixer and YM-2 type mixer manufactured by Yamatake Corporation; mixing tees and tees (T-shaped connector) manufactured by Shimadzu GLC; Micro High Mixer developed by Toray Engineering Co., Ltd. Union Tee manufactured by Swagelok, T-shaped Micro Mixer manufactured by Sanko Seiki Kogyo Co., Ltd.

The method of mixing two or more raw materials in the mixing means is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include mixing by laminar flow and mixing by turbulent flow. Among them, laminar flow mixing (static mixing) is preferable in terms of more efficient reaction control and heat removal.

Since the flow path in the mixing means is minute, the plurality of liquids introduced into the mixing means naturally tend to flow laminarly, and are diffused and mixed in the direction perpendicular to the flow. In mixing by laminar flow, a configuration may be adopted in which branch points and confluence points are further provided in the flow path to divide the laminar cross section of the flowing liquid, thereby increasing the mixing speed.
In addition, when performing mixing (dynamic mixing) by turbulent flow in the channel of the mixing means, the flow rate and the shape of the channel (three-dimensional shape of the wetted part, shape such as bending of the channel, wall surface roughness, etc.) can be changed from laminar to turbulent. The turbulent mixing has the advantage of high mixing efficiency and high mixing speed compared to the laminar mixing.

Here, the smaller the inner diameter of the flow path in the mixing means, the shorter the diffusion distance of molecules, so the time required for mixing can be shortened and the mixing efficiency can be improved. Furthermore, the smaller the inner diameter of the flow channel, the larger the ratio of the surface area to the volume, making it easier 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 increases when the liquid flows, and a pump with a special high pressure resistance is required for the liquid transfer, which increases the manufacturing cost. There is In addition, the structure of the micromixer may also be limited due to the limitation of the flow rate of liquid transfer.

The inner diameter of the channel in the mixing means is not particularly limited and can be appropriately selected according to the purpose, but is preferably 50 μm to 4 mm, more preferably 100 μm to 3 mm, further preferably 250 μm to 2 mm, 500 μm to 1 mm are particularly preferred.
If the inner diameter is less than 50 μm, 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 reaction heat may become difficult. On the other hand, when the inner diameter is within the particularly preferable 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 channel formed inside the mixing means is preferably 50 μm to 1,000 μm, more preferably 100 μm to 800 μm, and still more preferably 250 μm to 500 μm.

^The cross ^{- sectional} area of the flow channel is not particularly limited and can be appropriately selected ^according to the ^purpose . ~2.1 mm ² is more preferred, and 190,000 µm ² to 1 mm ² is particularly preferred.

The cross-sectional shape of the flow channel is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include circular, rectangular, semicircular, triangular and the like.

The flow path is not particularly limited as long as it is a tube that is connected to at least one of the mixing means and can circulate the liquid, and can be appropriately selected according to the purpose. The configuration such as the material can be appropriately selected according to the desired reaction.

The flow path is used, for example, when supplying raw materials to the mixing means.
Further, the flow path is used, for example, when supplying the 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 within the flow path.

Commercially available products can be used as the flow path. 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 path is not particularly limited, and those exemplified as the material of the mixing means can be preferably used.

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

The inner diameter of the flow path connected downstream of the mixing means is preferably 50 μm to 4 mm, more preferably 100 μm to 2 mm, even 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 can be appropriately selected according to the purpose. /min to 15 ml/min, or 3.0 ml/min to 10 ml/min.

The residence time of the reaction liquid in the flow path through which the reaction liquid flows is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include 0.001 sec to 10 sec.

The lower limit of the length between the micromixer for reacting the sec-BuLi and the alkylaryl compound and the micromixer for anionic polymerization is not particularly limited, and can be appropriately selected depending on the purpose. However, it is preferably 100 cm or more, more preferably 150 cm or more, still more preferably 170 cm or more, and particularly preferably 190 cm or more.
The upper limit of the length between the micromixer for reacting the sec-BuLi and the alkylaryl compound and the micromixer for anionic polymerization is not particularly limited, and can be appropriately selected depending on the purpose. However, it 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.

--other means--
The other means are not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include liquid feeding means, temperature control means and the like.

The liquid sending means is not particularly limited as long as it can supply various raw materials to the flow path of the flow microreactor, and can be appropriately selected according to the purpose. Examples thereof include a pump.

The pump is not particularly limited and can be appropriately selected from those that can be used industrially, but those that do not cause pulsation during liquid feeding are preferable, and examples include plunger pumps, gear pumps, rotary pumps, and diaphragm pumps. etc.

The temperature control means is not particularly limited as long as the temperature of the mixing means and the channel of the flow microreactor can be controlled, and can be appropriately selected according to the purpose.

<Modification process>
The modifying step is a step of modifying the polymer obtained in the anionic polymerization step.
The modification is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include substitution of halogen atoms in the polymer with the same or different functional groups.
The modification step may be performed using a flow microreactor.

The substitution method is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include substitution by Suzuki coupling reaction, substitution by Miyaura boronation reaction, and substitution by lithiation reaction.

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

The method of the Suzuki coupling reaction is not particularly limited and can be appropriately selected depending on the purpose. Method of dissolving methyl-1,3,2-dioxaborolan-2-yl)benzaldehyde, Pd(dppf)Cl ₂ and K ₂ CO ₃ in THF/H ₂ O (9:1) and refluxing under Ar atmosphere , the polymer obtained in the anionic polymerization step, 4,4,5,5-tetramethyl-2-(4-(oxiran-2-ylmethoxy)phenyl)-1,3,2-dioxaborolane, Pd(dppf)Cl ₂ , and K ₂ CO ₃ in THF/H ₂ O (9:1) and refluxing under Ar atmosphere, the polymer obtained in the anionic polymerization step, 4,4,5,5-tetramethyl -2-(4-vinylphenyl)-1,3,2-dioxaborolane, Pd(dppf)Cl ₂ and K ₂ CO ₃ were dissolved in THF/H ₂ O (9:1) and refluxed under Ar atmosphere. and methods to do so.

The reflux time is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include overnight reflux.
The reflux temperature is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include room temperature.

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

The Miyaura boronation reaction is a chemical reaction in which an aryl halide and bispinacolato diboron are coupled in the presence of a palladium catalyst.

The method of the Miyaura boronation reaction is not particularly limited and can be appropriately selected depending on the purpose. A method of dissolving Xphos, bis(pinacolato)diboron, and KOAc in 1,4-dioxane and refluxing them in an Ar atmosphere can be used.

The reflux time is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include overnight reflux.
The reflux temperature is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include room temperature.

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

The method of the lithiation reaction is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include a method of mixing the BuLi solution and the polymer solution obtained in the anionic polymerization step. The lithiation reaction may be performed using a flow microreactor.

The lower limit of the temperature at which the BuLi solution and the polymer solution obtained in the anionic polymerization step are mixed is not particularly limited and can be appropriately selected depending on the purpose. -60°C or higher is preferred, -55°C or higher is more preferred, -50°C or higher is even more preferred, and -45°C or higher is particularly preferred.

The upper limit of the temperature at which the BuLi solution and the polymer solution obtained in the anionic polymerization step are mixed is not particularly limited and can be appropriately selected depending on the purpose. -20°C or lower is preferred, -25°C or lower is more preferred, -30°C or lower is even more preferred, and -35°C or lower is particularly preferred.

The substitution with different functional groups is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include multistep modification (multistep substitution).
The multi-stage modification is not particularly limited and can be appropriately selected depending on the purpose. Examples include substitution by Suzuki coupling reaction after functionalization of the polymer after grouping and lithiation reaction.

The method for substituting the boryl groups of the polymer after the Miyaura _boronation reaction with hydroxy groups is not particularly limited and can be appropriately selected depending on the purpose. A method of dissolving _PO4 in THF, dropping an oxidizing agent such as an Oxone (registered trademark) aqueous solution, and stirring the mixture can be used.

The stirring time is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include 1 hour.
The reflux temperature is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include room temperature.

The method for functionalizing the polymer after the lithiation reaction is not particularly limited and can be appropriately selected according to the purpose. a method of introducing an electrophile solution into a mixture with the obtained polymer solution. Functionalization of the polymer after the lithiation reaction may be performed using a flow microreactor.

The electrophilic reagent is not particularly limited and can be appropriately selected depending _on the intended purpose. Boron compounds such as -1,3,2-dioxaborolane, carbonyl compounds such as DMF, ester compounds such as methyl chloroformate, silicon compounds such as TMSCl (chlorotrimethylsilane), alkyl halides, nitrile compounds, epoxy compounds, etc. be done.

The lower limit of the temperature when the BuLi solution and the polymer solution obtained in the anionic polymerization step are mixed and the electrophile solution is introduced into the mixture is not particularly limited, and may be appropriately selected according to the purpose. However, the temperature 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, from the viewpoint of obtaining a polymer efficiently.

The upper limit of the temperature when the BuLi solution and the polymer solution obtained in the anionic polymerization step are mixed and the electrophile solution is introduced into the mixture is not particularly limited, and may be appropriately selected according to the purpose. However, the temperature 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, from the viewpoint of obtaining a polymer efficiently.

The lower limit of the temperature of the microtube reactor through which the electrophilic reagent solution is passed after introduction is not particularly limited and can be appropriately selected depending on the purpose. is preferred, 5°C or higher is more preferred, 10°C or higher is even more preferred, and 15°C or higher is particularly preferred.

The upper limit of the temperature of the microtube reactor through which the electrophile solution is passed after introduction is not particularly limited and can be appropriately selected depending on the purpose. is preferred, 35°C or lower is more preferred, 30°C or lower is even more preferred, and 25°C or lower is particularly preferred.

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

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

-Monomer polymerization step after anionic polymerization step-
The monomer polymerization step after the anionic polymerization step is a step of polymerizing the monomer obtained by anionically polymerizing the halogenated styrene monomer in the anionic polymerization step.

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

(polymer)
The polymer can be produced by the method for producing a polymer described above.
Said polymer is a modified polymer derived from a narrowly dispersed halogenated styrene polymer.

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

ただし、前記一般式（３）中、ｍ及びｎは重合度を表し、ｍは０以上の整数であり、ｎは１以上の整数である。Ｒ^５及びＲ^６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。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る。Ｙは、鈴木カップリング反応により導入される基、宮浦ホウ素化反応により導入される基、又はブロモ基をリチオ化した後に反応させる求電子試薬によって導入される官能基であり、例えば、水素原子、重水素原子、アルデヒド基、ボリル基、ヒドロキシ基、アセトキシ基、トリメチルシリル基、又は下記構造式（４）から（６）のいずれかで表される基などが挙げられる。ａは、１～５の整数である。Ｙ基を有しないスチレン構造単位とＹ基を有するスチレン構造単位の結合順序は順不同であり、前記ポリマーは、ランダムポリマーであってもブロックポリマーであってもよい。

However, in said general formula (3), m and n represent the degree of polymerization, m is an integer of 0 or more, and n is an integer of 1 or more. One of R ⁵ and R ⁶ is an aryl group, and the other 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 astatine atom. Y is a group introduced by a Suzuki coupling reaction, a group introduced by a Miyaura boronation reaction, or a functional group introduced by an electrophilic reagent reacted after lithiating a bromo group, for example, a hydrogen atom, A deuterium atom, an aldehyde group, a boryl group, a hydroxy group, an acetoxy group, a trimethylsilyl group, or a group represented by any one of the following structural formulas (4) to (6). a is an integer from 1 to 5; The order of bonding of the styrene structural units not having a Y group and the styrene structural units having a Y group is random, and the polymer may be a random polymer or a block polymer.

m in the general formula (3) is not particularly limited as long as it is an integer of 0 or more and can be appropriately selected depending on the purpose. By increasing or decreasing the equivalent of boronic acid compounds such as boronic acids, boronic esters, and borate salts. When synthesized, it can be adjusted by the equivalent amount of the lithium reagent used in the lithiation reaction.

n in the general formula (3) is not particularly limited as long as it is an integer of 1 or more and can be appropriately selected according to the purpose, but is preferably 5 or more, more preferably 10 or more, and further 15 or more. 20 or more is particularly preferred, and 25 or more is most preferred.
m and n when synthesized by multi-step modification depend on the composition of the starting polymer (previous-step polymer).

R ⁵ and R ⁶ in the general formula (3) are not particularly limited as long as one is an aryl group and the other is an aryl group or an alkyl group having 1 to 10 carbon atoms, and is appropriately selected depending on the purpose. However, one of R ⁵ and R ⁶ is preferably an alkyl group having 1 to 10 carbon atoms.
The alkyl group having 1 to 10 carbon atoms is not particularly limited and can be appropriately selected depending on the intended purpose. An alkyl group having 1 to 4 carbon atoms is more preferred, an alkyl group having 1 to 2 carbon atoms is particularly preferred, and a methyl group is most preferred.
The aryl group is not particularly limited and can be appropriately selected depending on the intended purpose, but is preferably a phenyl group, a tolyl group, or an o-xylyl group, more preferably a phenyl group.

X in the general formula (3) is not particularly limited as long as it is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an astatine atom, and can be appropriately selected depending on the purpose. Atom, or bromine atom is preferred.

In the general formula (3), the order of bonding of the styrene structural units not having a Y group and the styrene structural units having a Y group is random, and the polymer may be a random polymer or a block polymer. When m is an integer of 0 or more and n is an integer of 1 or more, the polymer represented by the general formula (3) is a structural unit represented by the following general formula (5) of 1, A polymer having a structural unit represented by the following general formula (6), which is an integer of 0 or more, and a structural unit represented by the following general formula (7), which is an integer of 1 or more, and is represented by the general formula (6) The order of bonding of the structural unit represented by the general formula (7) and the structural unit represented by the general formula (7) is random, and the polymer represented by the general formula (3) may be a random polymer or a block polymer. means good. In addition, the polymer represented by the general formula (3) has a structural unit represented by the general formula (5) on one end side and a hydrogen atom on the other end side.

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以上の整数である。Ｒ^５及びＲ^６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。Ｙは、ブロモ基をリチオ化した後に反応させる求電子試薬によって導入される官能基であり、例えば、水素原子、重水素原子、アルデヒド基、ボリル基、ヒドロキシ基、アセトキシ基、トリメチルシリル基、又は下記構造式（４）から（６）のいずれかで表される基などが挙げられる。ベンズアルデヒド基を有するスチレン構造単位とＹ基を有するスチレン構造単位の結合順序は順不同であり、前記ポリマーは、ランダムポリマーであってもブロックポリマーであってもよい。

However, in said general formula (4), m and n represent the degree of polymerization, and each is an integer of 1 or more. One of R ⁵ and R ⁶ is an aryl group, and the other is an aryl group or an alkyl group having 1 to 10 carbon atoms. Y is a functional group introduced by an electrophilic reagent reacted after lithiating a bromo group, such as a hydrogen atom, a deuterium atom, an aldehyde group, a boryl group, a hydroxy group, an acetoxy group, a trimethylsilyl group, or Examples thereof include groups represented by any one of structural formulas (4) to (6). The order of bonding of the styrene structural unit having a benzaldehyde group and the styrene structural unit having a Y group may be random, and the polymer may be a random polymer or a block polymer.

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

n in the general formula (4) is not particularly limited as long as it is an integer of 1 or more and can be appropriately selected according to the purpose, but is preferably 5 or more, more preferably 10 or more, and further 15 or more. 20 or more is particularly preferred, and 25 or more is most preferred.

R ⁵ and R ⁶ in the general formula (4) are not particularly limited as long as one is an aryl group and the other is an aryl group or an alkyl group having 1 to 10 carbon atoms, and is appropriately selected depending on the purpose. However, one of R ⁵ and R ⁶ is preferably an alkyl group having 1 to 10 carbon atoms.
The alkyl group having 1 to 10 carbon atoms is not particularly limited and can be appropriately selected depending on the intended purpose. An alkyl group having 1 to 4 carbon atoms is more preferred, an alkyl group having 1 to 2 carbon atoms is particularly preferred, and a methyl group is most preferred.
The aryl group is not particularly limited and can be appropriately selected depending on the intended purpose, but is preferably a phenyl group, a tolyl group, or an o-xylyl group, more preferably a phenyl group.

In the general formula (4), the order of bonding of the styrene structural unit having a benzaldehyde group and the styrene structural unit having a Y group is random, and the polymer may be a random polymer or a block polymer. In the case where m and n are each an integer of 1 or more, the polymer represented by the general formula (4) is composed of a structural unit represented by the following general formula (5) of 1, and an integer of 1 or more of the following general A polymer having a structural unit represented by the formula (8) and a structural unit represented by the following general formula (9), which is an integer of 1 or more, wherein the structural unit represented by the general formula (8) and the general The order of bonding of the structural units represented by formula (9) is random, and the polymer represented by general formula (4) may be either a random polymer or a block polymer. In addition, the polymer represented by the general formula (4) has a structural unit represented by the general formula (5) on one end side and a hydrogen atom on the other end side.

The molecular weight distribution (polydispersity index (PDI): Mw/Mn) of the polymer is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 1.8 or less, and 1.5 or less. It is 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 preferably 1.2 or less.
The molecular weight distribution (polydispersity index (PDI): Mw/Mn) of the polymer is comparable to that of the narrowly dispersed halogenated styrene polymer (polydispersity index (PDI): Mw/Mn).
The molecular weight distribution is measured by the following GPC analysis.

-GPC analysis-
Using a SHIMADZU Prominence equipped with a Shodex LF-604 column, THF (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) at 40° C. is used. Reflection index (RI) is recorded on Shodex RI-504. The molecular weight distribution (polydispersity index (PDI): Mw/Mn) is determined by a calibration curve obtained from commercially available polystyrene. Prior to GPC analysis, solutions are filtered through Millex-HN (Merck, 0.45 μm).

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

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

Here, an example of a flow microreactor suitably used in the above polymer production method and a polymer production method using the flow microreactor will be described with reference to the drawings.

FIG. 1 is a schematic diagram showing an example of a flow microreactor.
The flow microreactor shown in FIG. 1 comprises two mixing means and five flow channels.
The flow path P1 is connected to the mixing means M1.
The flow path P2 is connected to the mixing means M1.
The flow path P3 is connected to the mixing means M2.
The flow path R1 is connected to the mixing means M1 and the mixing means M2. The flow path R1 is also a reaction section.
The flow path R2 is connected to the mixing means M2. The flow path R2 is also a reaction section.

The initiator represented by the general formula (1) is supplied from the flow path P1 to the mixing means M1. A halogenated styrene monomer is supplied from the flow path 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 resulting liquid, the initiator represented by the general formula (1) A living anionic polymerization of the halogenated styrenic monomer is initiated using the agent as an anionic polymerization initiator to form a living polymer.
The liquid during the polymerization reaction, for example, flows through the flow path R1, which is also the reaction section, while being polymerized. The resulting polymer is a living polymer. Therefore, in order to terminate the active terminal, a solution containing a terminating agent (e.g., methanol) is passed through the flow path P3 and mixed with the polymer solution by the mixing means M2 to carry out the termination reaction.

FIG. 2 is a schematic diagram showing an example of a flow microreactor.
The flow microreactor shown in FIG. 2 comprises three mixing means and seven flow channels.
The flow path P1 is connected to the mixing means M1.
The flow path P2 is connected to the mixing means M1.
The flow path P3 is connected to the mixing means M2.
The flow path P4 is connected to the mixing means M3.
The flow path R1 is connected to the mixing means M1 and the mixing means M2. The flow path R1 is also a reaction section.
The flow path R2 is connected to the mixing means M2 and the mixing means M3. The flow path R2 is also a reaction section.
The flow path R3 is connected to the mixing means M3. The flow path R3 is also a reaction section.

An alkylaryl compound is supplied from the flow path P1 to the mixing means M1. sec-BuLi is supplied from the flow path 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 initiated in the resulting 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 the reaction section, while reacting.
The liquid containing the initiator represented by the general formula (1) flowing through the flow path 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 path P3, and in the obtained liquid, the initiator represented by the general formula (1) is used as an anionic polymerization initiator. Living anionic polymerization of the halogenated styrene monomer used is initiated to produce a living polymer.
The liquid during the polymerization reaction, for example, flows through the flow path R2, which is also the reaction section, while being polymerized. The resulting polymer is a living polymer. Therefore, in order to terminate the active terminal, a solution containing a terminating agent (e.g., methanol) is passed through the flow path P4 and mixed with the polymer solution by the mixing means M3 to perform the termination reaction.

FIG. 3 is a schematic diagram showing an example of a flow microreactor.
The flow microreactor shown in FIG. 3 comprises four mixing means and nine flow channels.
The flow path P1 is connected to the mixing means M1.
The flow path P2 is connected to the mixing means M1.
The flow path P3 is connected to the mixing means M2.
The flow path P4 is connected to the mixing means M3.
The flow path P5 is connected to the mixing means M4.
The flow path R1 is connected to the mixing means M1 and the mixing means M2. The flow path R1 is also a reaction section.
The flow path R2 is connected to the mixing means M2 and the mixing means M3. The flow path R2 is also a reaction section.
The flow path R3 is connected to the mixing means M3 and the mixing means M4. The flow path R3 is also a reaction section.
The flow path R4 is connected to the mixing means M4. The flow path R4 is also a reaction section.

An alkylaryl compound is supplied from the flow path P1 to the mixing means M1. sec-BuLi is supplied from the flow path 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 initiated in the resulting 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 the reaction section, while reacting.
The liquid containing the initiator represented by the general formula (1) flowing through the flow path 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 path P3, and in the obtained liquid, the initiator represented by the general formula (1) is used as an anionic polymerization initiator. Living anionic polymerization of the halogenated styrene monomer used is initiated to produce a living polymer.
The liquid during the polymerization reaction, for example, flows through the flow path R2, which is also the reaction section, while being polymerized. The liquid containing the living polymer flowing through the flow path 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 path P4, and in the resulting liquid, living anionic polymerization of styrene or a styrene derivative occurs at the growth terminal of the living polymer. initiated to produce living polymer. The liquid during the polymerization reaction, for example, flows through the flow path R3, which is also the reaction section, while being polymerized. The resulting polymer is a living polymer. Therefore, in order to terminate the active terminal, a solution containing a terminating agent (e.g., methanol) is passed through the flow path P5 and mixed with the polymer solution by the mixing means M4 to perform the termination reaction.

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

A BuLi solution is supplied from the flow path P1 to the mixing means M1. A THF solution is supplied from the flow path P2 to the mixing means M1. Then, in the mixing means M1, the BuLi solution and the THF solution are mixed and flow through the flow path R1.
The BuLi solution flowing through the flow path R1 is introduced into the mixing means M2. In the mixing means M2, the BuLi solution and the halogenated styrene polymer solution supplied from the flow path P3 are mixed to lithiate the halogenated styrene polymer.
The liquid during the reaction flows through the flow path R2, which is also the reaction section. A solution containing an electrophilic reagent solution is passed through the flow path P4 and mixed with the polymer solution by the mixing means M3 to perform functionalization.

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

(Production Example 1 Production of bromostyrene polymer)
5, 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.), and microtube reactors (R1, R1″, R2) , and R3: from GL Sciences), one PTFE tube (R1′: from ISIS Co, Ltd.), 100 cm precooling unit (P1, P2, P3, and P4: from GL Sciences). A flow microreactor system was used.

The flow reactor composed of P1, P2, M1, 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 baths at different temperatures were connected with PTFE tubes (R1′).
α-Methylstyrene solution (0.12 M THF solution, flow rate: 5.625 mL/min; 1.5 molar equivalents to sec-BuLi) and sec-BuLi solution (0.2 M hexane solution, flow rate: 2.25 mL /min) was introduced into M1 (φ=250 μm) by means of a syringe pump and the mixture (initiator solution) was passed through R1 (internal diameter 1000 μm, 100 cm, t ^R1 =6.0 s).
The initiator solution was 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) and cooled to −40° C. cooled.

Next, the initiator solution and p-bromostyrene solution (0.75M THF solution, flow rate: 12.0 mL/min) were mixed in M2 (φ = 500 µm), and the mixture was R2 (inner diameter 1000 µm, 100 cm, t ^R2 = 2.1 s).
The resulting solution was introduced into M3 (φ = 500 µm), into which MeOH solution (0.15 M THF solution, flow rate: 4.5 mL/min) was introduced, and the mixture was transferred to R3 (inner diameter 1000 µm, 100 cm, t ^R3 = 1.7s).
After reaching steady state, an aliquot of the product solution was collected for 10 seconds and the aliquot was treated with saturated aqueous NH ₄ Cl 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. Table 1 shows the results.
FIG. 6 shows the MALDI-TOFMS spectrum of the obtained poly-p-bromostyrene.

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

-GPC analysis-
Using a SHIMADZU Prominence equipped with a Shodex LF-604 column, THF (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was used at 40°C. Reflection index (RI) was recorded with Shodex RI-504. Mn was determined by a calibration curve obtained from commercial polystyrene. Solutions were filtered through Millex-HN (Merck, 0.45 μm) prior to GPC analysis.

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

(Production Example 2 Production of chlorostyrene polymer)
7, 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.), and microtube reactors (R1, R1″, R2) , and R3: from GL Sciences), one PTFE tube (R1′: from ISIS Co, Ltd.), 100 cm precooling unit (P1, P2, P3, and P4: from GL Sciences). A flow microreactor system was used.

The flow reactor composed of P1, P2, M1, 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 baths at different temperatures were connected with PTFE tubes (R1′).
α-Methylstyrene solution (0.12 M THF solution, flow rate: 5.625 mL/min; 1.5 molar equivalents to sec-BuLi) and sec-BuLi solution (0.2 M hexane solution, flow rate: 2.25 mL /min) was introduced into M1 (φ=250 μm) by means of a syringe pump and the mixture (initiator solution) was passed through R1 (internal diameter 1000 μm, 100 cm, t ^R1 =6.0 s).
The initiator solution was 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) and cooled to −40° C. cooled.

Next, the initiator solution and p-chlorostyrene solution (0.75 M THF solution, flow rate: 12.0 mL/min) were mixed in M2 (φ = 500 µm), and the mixture was R2 (inner diameter 1000 µm, 100 cm, t ^R2 = 2.1 s).
The resulting solution was introduced into M3 (φ = 500 µm), into which MeOH solution (0.15 M THF solution, flow rate: 4.5 mL/min) was introduced, and the mixture was transferred to R3 (inner diameter 1000 µm, 100 cm, t ^R3 = 1.7s).
After reaching steady state, an aliquot of the product solution was collected for 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 were obtained.
FIG. 8 shows the MALDI-TOFMS spectrum of the obtained poly-p-chlorostyrene (Mn=3388 Da, PDI=1.12).

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

FIG. 9 shows the MALDI-TOFMS spectrum of the obtained modified polymer.
The peak interval of the MALDI-TOFMS spectrum of FIG. 6 is 183, and the peak interval of the MALDI-TOFMS spectrum of FIG.

(Example 2-1 Introduction of boryl group (Bpin) to poly-p-chlorostyrene by Miyaura boronation reaction)
As shown in the scheme below, the poly-p-chlorostyrene obtained in Production Example 2 (49 mg, Mn = 3388 Da, PDI = 1.12), tris(dibenzylideneacetone) dipalladium (0) (14 mg, 0.005 mol). 015 mmol), Xphos (33 mg, 0.070 mmol), bis(pinacolato)diboron (133 mg, 0.53 mmol), and KOAc (93 mg, 0.95 mmol) were dissolved in 1.7 mL of 1,4-dioxane and placed in an Ar atmosphere. Reflux overnight. The mixture was washed with brine and the organic phase was removed under reduced pressure. The modified polymer was then reprecipitated with THF and MeOH as good and poor solvents, respectively, to give 27 mg of modified polymer (Mn=7599 Da, PDI=1.15).

FIG. 10 shows the MALDI-TOFMS spectrum of the obtained modified polymer.
From the peak interval of 138 in the MALDI-TOFMS spectrum of FIG. 8 and the peak interval of 230 in the MALDI-TOFMS spectrum of FIG.

得られた修飾ポリマーのＭＡＬＤＩ－ＴＯＦＭＳスペクトルを図１１に示した。
図８のＭＡＬＤＩ－ＴＯＦＭＳスペクトルのピーク間隔が２３０であり、図１１のＭＡＬＤＩ－ＴＯＦＭＳスペクトルのピーク間隔が１２０であることより、ボリル基がヒドロキシ基に置換できたことが分かった。 (Example 2-2 Poly-p-hydroxystyrene synthesis multi-step modification)
As shown in the scheme below, the poly-p-Bpin styrene (19 mg, Mn=7599 Da, PDI=1.15) obtained in Example 2-1 and K ₃ PO ₄ (103 mg, 0.48 mmol) were combined with THF ( 4.2 mL) and Oxone® (84 mg, 0.14 mmol) in H ₂ O (2.5 ml) was added dropwise. The mixture was stirred at room temperature for 1 hour. The solution was then washed with brine and the organic phase removed under reduced pressure. The polymer was purified by GPC (THF) to give 16 mg of modified polymer (Mn=6961 Da, PDI=1.14).

FIG. 11 shows the MALDI-TOFMS spectrum of the obtained modified polymer.
The peak interval of the MALDI-TOFMS spectrum of FIG. 8 is 230, and the peak interval of the MALDI-TOFMS spectrum of FIG.

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

FIG. 12 shows the MALDI-TOFMS spectrum of the obtained modified polymer.
The peak interval of the MALDI-TOFMS spectrum of FIG. 6 is 183, and the peak interval of the MALDI-TOFMS spectrum of FIG. I found out.

(Example 4 Introduction of phenyl group having epoxy group to poly-p-bromostyrene by Suzuki coupling reaction)
As shown in the scheme below, the poly-p-bromostyrene obtained in Production Example 1 (49 mg, Mn = 4106 Da, PDI = 1.20), 4,4,5,5-tetramethyl-2-(4- (oxiran-2-ylmethoxy)phenyl)-1,3,2-dioxaborolane (147 mg, 0.53 mmol), Pd(dppf)Cl ₂ (18 mg, 0.025 mmol), and K ₂ CO ₃ (104 mg, 0.75 mmol) ) was dissolved in 2.6 mL of THF/H ₂ O (9:1) and refluxed overnight under Ar atmosphere. The mixture was washed with brine and the organic phase was removed under reduced pressure. The modified polymer was then reprecipitated with THF and MeOH as good and poor solvents, respectively, to give 75 mg of modified polymer (Mn=6029 Da, PDI=1.20).

FIG. 13 shows the MALDI-TOFMS spectrum of the obtained modified polymer.
The peak interval of the MALDI-TOFMS spectrum of FIG. 6 is 183, and the peak interval of the MALDI-TOFMS spectrum of FIG.

(Example 5 Introduction of a phenyl group having a vinyl group into poly-p-bromostyrene by Suzuki coupling reaction)
As shown in the scheme below, the poly-p-bromostyrene obtained in Production Example 1 (52 mg, Mn = 4106 Da, PDI = 1.20), 4,4,5,5-tetramethyl-2-(4- Vinylphenyl)-1,3,2-dioxaborolane (126 mg, 0.55 mmol), Pd(dppf)Cl ₂ (19 mg, 0.026 mmol), and K ₂ CO ₃ (107 mg, 0.77 mmol) in 2.6 mL. It was dissolved in THF/H ₂ O (9:1) and a small amount of 4-tert-butylpyrocatechol was added as a polymerization inhibitor for styrene derivatives. The solution was then refluxed overnight under Ar atmosphere. The mixture was washed with brine and the organic phase was removed under reduced pressure. The modified polymer was then reprecipitated with THF and MeOH as good and poor solvents, respectively, to give 92 mg of modified polymer (Mn=6102 Da, PDI=1.33).

FIG. 14 shows the MALDI-TOFMS spectrum of the obtained modified polymer.
The peak interval of the MALDI-TOFMS spectrum of FIG. 6 is 183, and the peak interval of the MALDI-TOFMS spectrum of FIG. I found out.

(Example 6 Lithiation and functionalization of poly-p-bromostyrene using a flow reactor)
15, two T-type micromixers (M1, M3: manufactured by Sanko Seiki Kogyo Co., Ltd.), one V-type micromixer (M2: manufactured by Sanko Seiki Kogyo Co., Ltd.), microtube reactors (R1, R2, and R3: from GL Sciences), and an integrated flow microreactor system consisting of a 100 cm pre-cooling unit (P1, P2, P3, and P4: from GL Sciences).

A flow reactor composed of P1, P2, P3, P4, M1, M2, M3, R1, and R2 was cooled in a −40° C. acetone-dry ice bath, and a flow reactor composed of R3 was cooled in 20° C. water. Cooled in a bath.
nBuLi solution (1.58 M hexane solution, commercially available, flow rate: 0.755 mL/min) and THF solution (flow rate: 0.745 mL/min) were introduced into M1 (φ = 250 µm) by a syringe pump, and the mixture was transferred to R1 ( 25 cm).
A BuLi solution and a poly-p-bromostyrene solution (0.01 M THF solution, flow rate: 12.0 mL/min based on the number of Br groups estimated from MALDI-TOFMS measurement) were mixed with M2 (φ = 500 µm). , the mixture was passed through R2 (100 cm).
The resulting solution was introduced into M3 (φ=500 μm), into which the electrophile solution described in Examples 6-1 to 6-6 below (1.2 M THF solution, flow rate: 2.0 mL /min) was introduced and the mixture was passed through R3 (100 cm).
After reaching steady state, the resulting solution was collected in a vial containing 2 mL of saturated aqueous NH ₄ Cl for 60 seconds. The mixture was washed with brine and the organic phase was removed under reduced pressure. The modified polymer was then reprecipitated.

(Example 6-1 Hydrogenation)
Using poly-p-bromostyrene (Mn=4106 Da, PDI=1.20) and MeOH as an electrophile, reprecipitation with THF and MeOH as good and poor solvents, respectively, yielded 12.7 mg of the modified polymer. (Mn=4255, PDI=1.15).

FIG. 16 shows the MALDI-TOFMS spectrum of the obtained modified polymer.
The peak interval of the MALDI-TOFMS spectrum of FIG. 6 is 183, and the peak interval of the MALDI-TOFMS spectrum of FIG. rice field.

(Example 6-2 D conversion)
Using poly-p-bromostyrene (Mn=4106 Da, PDI=1.20) and _CD3OD as electrophile, reprecipitation with THF and MeOH as good and poor solvents, respectively, yielded 13 mg of the modified polymer. (Mn=3764 Da, PDI=1.18).

FIG. 17 shows the MALDI-TOFMS spectrum of the obtained modified polymer.
The peak interval of the MALDI-TOFMS spectrum of FIG. 6 is 183, and the peak interval of the MALDI-TOFMS spectrum of FIG. rice field.

(Example 6-3 Borylation)
Using poly-p-bromostyrene (Mn = 4106 Da, PDI = 1.20) and 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane as an electrophile, Reprecipitation with THF and MeOH as good and poor solvents respectively gave 16 mg of modified polymer (Mn=6623 Da, PDI=1.15).

FIG. 18 shows the ¹ H-NMR spectrum of the obtained modified polymer.
In FIG. 18, a large peak around 1.5 ppm is the peak derived from the pinacolboryl group.
From the results of FIG. 18, it was found that pinacolboryl groups could be introduced into poly-p-bromostyrene.

(Example 6-4 formylation)
Using poly-p-bromostyrene (Mn = 4106 Da, PDI = 1.20) and DMF as an electrophile, reprecipitation was performed with THF and hexane as good and poor solvents, respectively, to obtain 18 mg of the modified polymer. (Mn=4534 Da, PD=1.20).

¹ H-NMR spectrum of the obtained modified polymer is shown in FIG.
In FIG. 19, the peak around 10 ppm is the peak derived from the aldehyde group.
From the results of FIG. 19, it was found that aldehyde groups could be introduced into poly-p-bromostyrene.
(Example 6-5 esterification)
Using poly-p-bromostyrene (Mn = 4106 Da, PDI = 1.20) and methyl chloroformate as electrophiles, THF and MeOH as good and poor solvents, respectively, were reprecipitated to yield 15 mg of the modified polymer. (Mn=6439 Da, PDI=1.39).

The ¹ H-NMR spectrum of the obtained modified polymer is shown in FIG.
In FIG. 20, the peak around 4 ppm is the peak derived from methyl ester.
From the results of FIG. 20, it was found that methyl ester could be introduced into poly-p-bromostyrene.

(Example 6-6 TMS conversion)
Reprecipitation using poly-p-bromostyrene (Mn=4106 Da, PDI=1.20) and TMSCl as electrophile with THF and MeOH as good and poor solvents, respectively, yielded 18 mg of modified polymer. (Mn=5597 Da, PDI=1.16).

¹ H-NMR spectrum of the obtained modified polymer is shown in FIG.
In FIG. 21, the peak around 0.3 ppm is the peak derived from the methyl group of TMS.
From the results of FIG. 21, it was found that trimethylsilyl groups could be introduced into poly-p-bromostyrene.

Example 7 Partial lithiation and functionalization of poly-p-bromostyrene using a flow reactor followed by Suzuki coupling to synthesize block copolymers.
22, two T-type micromixers (M1, M3: manufactured by Sanko Seiki Kogyo Co., Ltd.), one V-type micromixer (M2: manufactured by Sanko Seiki Kogyo Co., Ltd.), microtube reactors (R1, R2, and R3: from GL Sciences), and an integrated flow microreactor system consisting of a 100 cm pre-cooling unit (P1, P2, P3, and P4: from GL Sciences).

(Example 7-1 Partial lithiation and TMS conversion of poly-p-bromostyrene using a flow reactor)
A flow reactor composed of P1, P2, P3, P4, M1, M2, M3, R1, and R2 was cooled in a −40° C. acetone-dry ice bath, and a flow reactor composed of R3 was cooled in 20° C. water. Cooled in a bath.
nBuLi solution (1.58 M hexane solution, commercially available, flow rate: 0.151 mL/min) and THF solution (flow rate: 1.349 mL/min) were introduced into M1 (φ = 250 µm) by a syringe pump, and the mixture was transferred to R1 ( 25 cm).
BuLi solution and poly-p-bromostyrene solution (0.01 M THF solution, flow rate: 12.0 mL/min, Mn = 4106 Da, PDI = 1.20, based on the number of Br groups estimated from MALDI-TOFMS measurements) was mixed in M2 (φ=500 μm) and the mixture was passed through R2 (100 cm). The resulting solution was introduced into M3 (φ=500 μm) into which TMSCl solution (1.2 M THF solution, flow rate: 2 .0 mL/min) was introduced and the mixture was passed through R3 (100 cm).
After reaching steady state, the resulting solution was collected in a vial containing 2 mL of saturated aqueous NH ₄ Cl for 120 seconds. The mixture was washed with brine and the organic phase was removed under reduced pressure. The modified polymer was then reprecipitated.

(Example 7-2 Suzuki coupling)
As shown in the scheme below, the total amount of modified polymer obtained in Example 7-1, 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzaldehyde (121 mg , 0.52 mmol), Pd(dppf) _Cl2 (18 mg, 0.024 mmol), and _{K2CO3 (} 124 mg, 0.90 mmol) were dissolved in 2.6 mL of THF/ _H2O (9:1). , refluxed overnight under an Ar atmosphere. The mixture was washed with brine and the organic phase was removed under reduced pressure. The modified polymer was then reprecipitated with THF and MeOH as good and poor solvents, respectively, to give 39 mg of modified polymer (Mn=6383 Da, PDI=1.14).

¹ H-NMR spectrum of the obtained modified polymer is shown in FIG.
In FIG. 23, the peak around 10 ppm is the peak derived from the aldehyde group, and the peak around 0.3 ppm is the peak derived from the methyl group of TMS.
From the results of FIG. 23, it was found that a random copolymer could be synthesized from poly-p-bromostyrene.

Mass spectrometry is the most accurate method for identifying synthesized polymers. If the halogen conversion rate in polyhalostyrene is sufficiently high, such as about 100%, a group of peaks having a single distribution at the mass intervals of the units constituting the polymer can be obtained in mass spectrometry. For example, in the case of the introduction of benzaldehyde by Suzuki coupling, the MALDI-TOF MS of the resulting polymer has peaks distributed at intervals of 208 m/z.
In functionalization after lithiation, H- and D-conversions using methanol and heavy methanol were not complete, but relatively sharp peaks were observed, and identification by MALDI-TOFMS was possible. rice field.
In TMS conversion, borylation, formylation, and esterification after lithiation, although lithiation proceeded at a sufficient conversion rate, functionalization did not proceed sufficiently, so identification by mass spectrometry was impossible. I couldn't. On the other hand, characteristic peaks derived from TMS group, pinacolboryl group, aldehyde group, and methyl ester group were observed in the ¹ H-NMR spectrum. I was able to judge that the conversion was done.

＜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＞ さらに、前記アニオン重合工程において、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＜４＞のいずれかに記載のポリマーの製造方法である。
＜６＞ 前記修飾工程における修飾が、前記ポリマーにおけるハロゲン原子の少なくとも一部を、鈴木カップリング反応、宮浦ホウ素化反応、及びリチオ化反応の少なくともいずれかにより、同一の又は異なる官能基で置換することを含む、前記＜１＞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＞ 前記修飾工程における修飾が、前記ポリマーにおけるハロゲン原子の少なくとも一部を、ヒドロキシ基で置換することを含む、前記＜６＞に記載のポリマーの製造方法である。
＜８＞ 前記修飾工程における修飾が、前記ポリマーにおけるハロゲン原子の少なくとも一部を、宮浦ホウ素化反応によりホウ素含有基で置換し、置換した前記ホウ素含有基を酸化剤によりヒドロキシ基に置換することを含む、前記＜６＞に記載のポリマーの製造方法である。
＜９＞ 前記修飾工程における修飾が、前記ポリマーをマイクロリアクターを用いて修飾することを含む、前記＜１＞から＜８＞のいずれかに記載のポリマーの製造方法である。
＜１０＞ 下記一般式（３）又は（４）のいずれかで表され、分子量分布が１．４以下であるポリマーである。

ただし、前記一般式（３）中、ｍ及びｎは重合度を表し、ｍは０以上の整数であり、ｎは１以上の整数である。Ｒ^５及びＲ^６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；Ｙは、水素原子、重水素原子、アルデヒド基、ボリル基、ヒドロキシ基、アセトキシ基、トリメチルシリル基、又は下記構造式（４）から（６）のいずれかで表される基であり；ａは、１～５の整数である。Ｙ基を有しないスチレン構造単位とＹ基を有するスチレン構造単位の結合順序は順不同であり、前記ポリマーは、ランダムポリマーであってもブロックポリマーであってもよい。

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以上の整数である。Ｒ^５及びＲ^６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のアルキル基であり；Ｙは、水素原子、重水素原子、アルデヒド基、ボリル基、ヒドロキシ基、アセトキシ基、トリメチルシリル基、又は下記構造式（４）から（６）のいずれかで表される基である。ベンズアルデヒド基を有するスチレン構造単位とＹ基を有するスチレン構造単位の結合順序は順不同であり、前記ポリマーは、ランダムポリマーであってもブロックポリマーであってもよい。

Embodiments of the present invention include, for example, the following.
<1> An anionic polymerization step of anionically polymerizing a halogenated styrene monomer using a microreactor in the presence of an initiator represented by the following general formula (1), and the polymer obtained in the anionic polymerization step A method for producing a polymer including a modification step of modifying.
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.

<2> The method for producing the 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 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> Further, in the anion polymerization step, the polymer obtained by anionic polymerization of the halogenated styrene monomer is polymerized with a monomer, wherein the monomer is styrene or a styrene derivative. A method for producing the polymer according to any one of <1> to <4>.
<6> The modification in the modification step substitutes at least part of the halogen atoms in the polymer with the same or different functional groups by at least one of Suzuki coupling reaction, Miyaura boronation reaction, and lithiation reaction. A method for producing a polymer according to any one of <1> to <5>, comprising:
<7> The method for producing a polymer according to <6>, wherein the modification in the modifying step includes substituting at least part of the halogen atoms in the polymer with hydroxy groups.
<8> The modification in the modifying step includes substituting at least part of the halogen atoms in the polymer with boron-containing groups by Miyaura boronation reaction, and substituting the substituted boron-containing groups with hydroxy groups using an oxidizing agent. The method for producing the polymer according to <6> above.
<9> The method for producing a polymer according to any one of <1> to <8>, wherein the modification in the modifying step includes modifying the polymer using a microreactor.
<10> A polymer represented by the following general formula (3) or (4) and having a molecular weight distribution of 1.4 or less.

However, in said general formula (3), m and n represent the degree of polymerization, m is an integer of 0 or more, and n is an integer of 1 or more. one of R ⁵ and R ⁶ is an aryl group and the other is an aryl group or an alkyl group having 1 to 10 carbon atoms; X is any of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an astatine atom; Y is a hydrogen atom, a deuterium atom, an aldehyde group, a boryl group, a hydroxy group, an acetoxy group, a trimethylsilyl group, or a group represented by any of the following structural formulas (4) to (6) ; a is an integer of 1 to 5; The order of bonding of the styrene structural units not having a Y group and the styrene structural units having a Y group is random, and the polymer may be a random polymer or a block polymer.

However, in said general formula (4), m and n represent the degree of polymerization, and each is an integer of 1 or more. one of R ⁵ and R ⁶ is an aryl group and the other is an aryl group or an alkyl group having 1 to 10 carbon atoms; Y is a hydrogen atom, a deuterium atom, an aldehyde group, a boryl group, a hydroxy group, an acetoxy group; group, a trimethylsilyl group, or a group represented by any one of the following structural formulas (4) to (6). The order of bonding of the styrene structural unit having a benzaldehyde group and the styrene structural unit having a Y group may be random, and the polymer may be a random polymer or a block polymer.

Claims (10)

An anionic polymerization step of anionically polymerizing a halogenated styrene monomer using a microreactor in the presence of an initiator represented by the following general formula (1), and a modification of modifying the polymer obtained in the anionic polymerization step. A method of making a polymer comprising steps.

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. 2. The method for producing a polymer according to claim 1, wherein said aryl group is a phenyl group. 3. The method for producing a polymer according to claim 1, wherein one of R ¹ and R ² in the general formula (1) 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 general formula (1) is obtained by reacting sec-BuLi with an alkylaryl compound. Furthermore, in the anion polymerization step, the step of polymerizing a monomer with respect to the polymer obtained by anionically polymerizing the halogenated styrene monomer,
5. The method for producing a polymer according to any one of claims 1 to 4, wherein the monomer is styrene or a styrene derivative. The modification in the modification step includes substituting at least a portion of the halogen atoms in the polymer with the same or different functional groups by at least one of Suzuki coupling reaction, Miyaura boronation reaction, and lithiation reaction. A method for producing a polymer according to any one of claims 1 to 5. 7. The method for producing a polymer according to claim 6, wherein the modification in the modifying step includes substituting at least part of the halogen atoms in the polymer with hydroxy groups. wherein the modification in the modifying step comprises substituting at least a portion of the halogen atoms in the polymer with boron-containing groups through a Miyaura boronation reaction, and substituting the substituted boron-containing groups with hydroxy groups using an oxidizing agent. Item 7. A method for producing the polymer according to item 6. The method for producing a polymer according to any one of claims 1 to 8, wherein the modification in the modifying step includes modifying the polymer using a microreactor. A polymer represented by either the following general formula (3) or (4) and having a molecular weight distribution of 1.4 or less.

However, in said general formula (3), m and n represent the degree of polymerization, m is an integer of 0 or more, and n is an integer of 1 or more. one of R ⁵ and R ⁶ is an aryl group and the other is an aryl group or an alkyl group having 1 to 10 carbon atoms; X is any of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an astatine atom; Y is a hydrogen atom, a deuterium atom, an aldehyde group, a boryl group, a hydroxy group, an acetoxy group, a trimethylsilyl group, or a group represented by any of the following structural formulas (4) to (6) ; a is an integer of 1 to 5; The order of bonding of the styrene structural units not having a Y group and the styrene structural units having a Y group is random, and the polymer may be a random polymer or a block polymer.

However, in said general formula (4), m and n represent the degree of polymerization, and each is an integer of 1 or more. one of R ⁵ and R ⁶ is an aryl group and the other is an aryl group or an alkyl group having 1 to 10 carbon atoms; Y is a hydrogen atom, a deuterium atom, an aldehyde group, a boryl group, a hydroxy group, an acetoxy group; group, a trimethylsilyl group, or a group represented by any one of the following structural formulas (4) to (6). The order of bonding of the styrene structural unit having a benzaldehyde group and the styrene structural unit having a Y group may be random, and the polymer may be a random polymer or a block polymer.

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