JP7176515B2 - Method for producing block polymer - Google Patents

Description

The present invention relates to a method for producing block polymers.

In the field of semiconductors, microfabrication technology (DSA lithography) using directed self-assembly (DSA) of block polymers has attracted attention. DSA lithography requires polymers with lower dispersity (Mw/Mn).

JP 2009-067999 A

An object of the present invention is to provide a method capable of producing a block polymer having a smaller degree of dispersion.

Unlike the case of synthesizing a block polymer by conventional batch type anionic polymerization, when synthesizing a block polymer by anionic polymerization using a flow reactor, the second monomer solution is mixed together by a mixer. It is susceptible to moisture, and the formation of low-molecular-weight polymers often results in increased dispersity. Therefore, the present inventors have made intensive studies to achieve the above object, and as a result, the block polymer obtained using a flow reactor is washed with a predetermined solvent to increase the degree of dispersion of the block polymer. The present invention was completed by finding improvement.

（式中、Ｒ¹は、水素原子又はメチル基を表し、Ｒ²～Ｒ⁶は、それぞれ独立に、水素原子、炭素数１～５のアルコキシ基、ハロゲン原子で置換されていてもよい炭素数１～１０のアルキル基、－ＯＳｉＲ⁷ ₃又は－ＳｉＲ⁷ ₃を表し、Ｒ⁷は、それぞれ独立に、炭素数１～１０のアルキル基、フェニル基、炭素数１～５のアルコキシ基又は炭素数１～５のアルキルシリル基を表す。）
１６．前記第１のモノマーが、下記式（２）で表される化合物であり、前記第２のモノマーが、下記式（３）で表される化合物である１５のブロックポリマーの製造方法。

（式中、Ｒ¹¹及びＲ²¹は、それぞれ独立に、水素原子又はメチル基であり、Ｒ¹²～Ｒ¹⁶は、それぞれ独立に、水素原子、炭素数１～５のアルコキシ基、又はハロゲン原子で置換されていてもよい炭素数１～１０のアルキル基であるが、少なくとも１つは炭素数１～５のアルコキシ基であり、Ｒ²²～Ｒ²⁶は、それぞれ独立に、水素原子、－ＯＳｉＲ²⁷ ₃又は－ＳｉＲ²⁷ ₃であるが、少なくとも１つは－ＯＳｉＲ²⁷ ₃又は－ＳｉＲ²⁷ ₃であり、Ｒ²⁷は、それぞれ独立に、炭素数１～１０のアルキル基、フェニル基、炭素数１～５のアルコキシ基又は炭素数１～５のアルキルシリル基である。）
１７．Ｒ¹⁴が炭素数１～５のアルコキシ基であり、Ｒ²⁴が－ＳｉＲ²⁷ ₃である１６のブロックポリマーの製造方法。
１８．Ｒ¹⁴がメトキシ基であり、Ｒ²⁴が－Ｓｉ(ＣＨ₃)₃である１７のブロックポリマーの製造方法。
１９．前記第１のモノマーのみから得られるホモポリマーは溶解するが、前記第２のモノマーのみから得られるホモポリマー及び前記ブロックポリマーは溶解しない溶媒が、ジメチルスルホキシドである１６～１８のいずれかのブロックポリマーの製造方法。
２０．前記第１のモノマーが、下記式（３）で表される化合物であり、前記第２のモノマーが、下記式（２）で表される化合物である１５のブロックポリマーの製造方法。

（式中、Ｒ¹¹～Ｒ¹⁶及びＲ²¹～Ｒ²⁶は、前記と同じ。）
２１．Ｒ¹⁴が炭素数１～５のアルコキシ基であり、Ｒ²⁴が－ＳｉＲ²⁷ ₃である２０のブロックポリマーの製造方法。
２２．Ｒ¹⁴がメトキシ基であり、Ｒ²⁴が－Ｓｉ(ＣＨ₃)₃である２１のブロックポリマーの製造方法。
２３．前記第１のモノマーのみから得られるホモポリマーは溶解するが、前記第２のモノマーのみから得られるホモポリマー及び前記ブロックポリマーは溶解しない溶媒が、炭素数４～７のアルコールである２０～２２のいずれかのブロックポリマーの製造方法。
２４．複数の液体を混合可能な流路を備える２液混合用ミキサーを備えるフローリアクターを用いて、第１のモノマーを開始剤の存在下でアニオン重合させ、ポリマーを合成し、前記ポリマーに第２のモノマーをブロック重合させて得られるブロックポリマーを、前記第１のモノマーのみから得られるホモポリマーは溶解するが、前記第２のモノマーのみから得られるホモポリマー及び前記ブロックポリマーは溶解しない溶媒で洗浄する、ブロックポリマーの精製方法。
２５．前記フローリアクターが、複数の液体を混合可能な流路、及び内部に二重管を有するジョイント部材又はスタティックミキサー部材を備える２液混合用ミキサーを備えるフローリアクターである２４のブロックポリマーの精製方法。Accordingly, the present invention provides a method for producing the following block polymer.
1. A step of anionically polymerizing a first monomer in the presence of an initiator to synthesize a homopolymer using a flow reactor equipped with a two-liquid mixing mixer equipped with a channel capable of mixing a plurality of liquids, and the homopolymer A step of block polymerizing a second monomer different from the first monomer to synthesize a block polymer, and a homopolymer obtained only from the first monomer is dissolved, but the first A method for producing a block polymer, comprising the step of washing with a solvent in which the homopolymer obtained only from the monomers of 2 and the block polymer are not dissolved.
2. 1. A method for producing a block polymer, wherein the flow reactor is a flow reactor provided with a flow reactor capable of mixing a plurality of liquids and a two-liquid mixing mixer provided with a joint member or a static mixer member having a double tube therein.
3. 2. The method for producing a block polymer according to 2, wherein the static mixer member comprises a cylindrical body and an element body inserted therein.
4. 2. A method for producing a block polymer of 2 or 3, wherein the mixer for mixing two liquids is provided with a joint member having a double tube inside and a static mixer member.
5. The two-liquid mixing mixer comprises a joint member and a static mixer member having a double pipe inside,
The static mixer member comprises a tubular body and an element body inserted therein,
Block 4, wherein the joint member and the static mixer member are connected so that the end face of the cylindrical body on the double pipe side contacts the end face of the static mixer member side of the double pipe. A method of making a polymer.
6. 5. The method for producing a block polymer according to 5, wherein the end of the double pipe on the side of the static mixer member is inside the joint member.
7. The joint member has an insertion hole for inserting an inner tube through which the initiator solution flows, and in a state in which the inner tube is inserted, at least near the tip of the inner tube, the inside of the inner tube and the inner tube 7. The method for producing a block polymer according to any one of 2 to 6, wherein the double tube is formed by the outer wall of the tube and the space formed by the inner wall of the insertion hole.
8. 7. The method for producing a block polymer according to 7, wherein the joint member has an introduction hole for introducing a monomer solution, and the introduction hole is connected to the insertion hole.
9. The insertion hole is formed to have substantially the same diameter as the outer diameter of the inner pipe in the vicinity of the connecting portion with the introduction hole, and the inner pipe extends from the connecting portion to the tip of the inner pipe. 8. A method for producing a block polymer formed so as to have a pore diameter larger than its outer diameter.
10. 10. The method for producing a block polymer according to any one of 7 to 9, wherein the joint member has a static mixer member connection hole, and the insertion hole is connected to the connection hole.
11. Production of the block polymer according to any one of 3 to 10, wherein the element body is inserted into the cylindrical body so that one end of the element body is substantially flush with the end surface of the double tube side of the cylindrical body. Method.
12. 12. The method for producing a block polymer according to any one of 3 to 11, wherein the element body has a shape in which a plurality of right-handed twisted blades and left-handedly twisted blades are alternately connected in the torsion axis direction.
13. 12. The method for producing a block polymer according to any one of 1 to 12, wherein the initiator is a monoorganolithium compound.
14. 14. The method for producing a block polymer according to any one of 1 to 13, wherein the first monomer and the second monomer are aromatic vinyl compounds.
15. 14. A method for producing a block polymer, wherein the aromatic vinyl compound is a styrene derivative represented by the following formula (1).

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² to R ⁶ each independently represent a hydrogen atom, an alkoxy group having 1 to 5 carbon atoms, or the number of carbon atoms optionally substituted with a halogen atom. represents an alkyl group having ₁ to 10 carbon atoms, _—OSiR ⁷³ or —SiR ^{73 , and each R 7 is} independently an alkyl group having 1 to 10 carbon atoms, a phenyl group, an alkoxy group having 1 to 5 carbon atoms, or represents an alkylsilyl group of 1 to 5.)
16. 15. The method for producing a block polymer according to 15, wherein the first monomer is a compound represented by the following formula (2), and the second monomer is a compound represented by the following formula (3).

(In the formula, R ¹¹ and R ²¹ are each independently a hydrogen atom or a methyl group, and R ¹² to R ¹⁶ are each independently a hydrogen atom, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom. an alkyl group having ¹ to 10 carbon atoms which may be substituted, at least one of which is an ^alkoxy group having ¹ to 5 carbon atoms; ₃ or -SiR ²⁷ ₃ , but at least one is -OSiR ²⁷ ₃ or -SiR ²⁷ ₃ , and each R ²⁷ is independently an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a 5 alkoxy group or an alkylsilyl group having 1 to 5 carbon atoms.)
17. A method for producing a block polymer of 16 wherein R ¹⁴ is an alkoxy group having ¹ to ₅ carbon atoms and R ²⁴ is -SiR 273 .
18. 17. A method for preparing a block polymer wherein R ¹⁴ is a methoxy group and R ²⁴ is --Si(CH ₃ ) ₃ .
19. 18. The block polymer according to any one of 16 to 18, wherein the homopolymer obtained only from the first monomer is soluble, but the homopolymer obtained only from the second monomer and the block polymer are not dissolved, and the solvent is dimethylsulfoxide. manufacturing method.
20. 15. The method for producing a block polymer according to 15, wherein the first monomer is a compound represented by the following formula (3), and the second monomer is a compound represented by the following formula (2).

(In the formula, R ¹¹ to R ¹⁶ and R ²¹ to R ²⁶ are the same as above.)
21. A method for producing a block polymer of ²⁰ _, wherein R ¹⁴ is an alkoxy group having 1 to 5 carbon atoms and R ²⁴ is —SiR 273 .
22. A method for preparing block polymers of 21 wherein R ¹⁴ is a methoxy group and R ²⁴ is --Si(CH ₃ ) ₃ .
23. the homopolymer obtained only from the first monomer is soluble, but the homopolymer obtained only from the second monomer and the block polymer are not dissolved; the solvent is an alcohol having 4 to 7 carbon atoms; Any method of making a block polymer.
24. A first monomer is anionically polymerized in the presence of an initiator to synthesize a polymer using a flow reactor equipped with a two-liquid mixing mixer having a channel capable of mixing a plurality of liquids, and the second polymer is added to the polymer. The block polymer obtained by block-polymerizing the monomers is washed with a solvent that dissolves the homopolymer obtained only from the first monomer but does not dissolve the homopolymer obtained only from the second monomer and the block polymer. , a method for purifying block polymers.
25. 24. A method for purifying a block polymer according to 24, wherein the flow reactor is a flow reactor provided with a flow reactor capable of mixing a plurality of liquids and a two-liquid mixing mixer provided with a joint member or a static mixer member having a double tube therein.

The two-liquid mixing mixer used in the flow reactor is less likely to clog and has good mixing efficiency. Therefore, according to the method for producing a block polymer of the present invention using this mixer, a polymer can be stably produced over a long period of time. can be done. In particular, the block polymer obtained by the production method of the present invention has a small degree of dispersion (Mw/Mn) (narrow molecular weight distribution), a highly controlled structure, and is suitable as a polymer for DSA lithography. can also be applied to other nanopatterning techniques. Moreover, the method for producing a block polymer of the present invention can be applied to the production of high-performance elastomers and the like.

1 is a perspective view showing the configuration of a two-liquid mixing mixer used in the present invention; FIG. 2 is an exploded perspective view of the two-liquid mixing mixer of FIG. 1. FIG. 3 is a cross-sectional view of the main body taken along line III-III of FIG. 2; FIG. FIG. 2 is a cross-sectional view taken along line IV-IV of FIG. 1; FIG. 5 is an enlarged cross-sectional view of the double tube portion of FIG. 4; It is a bottom view of the main body in a state in which the inner tube is inserted. FIG. 4 is a view of the element body of the static mixer member viewed from a direction orthogonal to the torsion axis direction; 1 is a perspective view showing the form of a two-liquid mixing mixer used in the present invention; FIG. 1 is a schematic diagram showing the form of a flow reactor used in the present invention; FIG. 1 is a schematic diagram showing the configuration of a flow reactor used in Examples. FIG. 1 is a ¹ H-NMR chart of the polymer synthesized in Synthesis Example 1. FIG. 1 is a ¹ H-NMR chart of a polymer synthesized in Synthesis Example 2. FIG.

In the method for producing a block polymer of the present invention, a first monomer is anionically polymerized in the presence of an initiator using a flow reactor equipped with a two-liquid mixing mixer equipped with channels capable of mixing a plurality of liquids, and homogenized a step of synthesizing a polymer, and a step of block-polymerizing the homopolymer with a second monomer different from the first monomer to synthesize a block polymer, and obtaining the obtained block polymer only from the first monomer. washing with a solvent that dissolves the homopolymer obtained but does not dissolve the homopolymer obtained only from the second monomer and the block polymer.

[Flow reactor]
The flow reactor is not particularly limited as long as it is provided with a two-liquid mixing mixer having channels capable of mixing a plurality of liquids, and conventionally known structures can be used.

The flow reactor preferably has the following configuration. That is, it is preferable that the two-liquid mixing mixer includes a joint member or a static mixer member having a channel capable of mixing a plurality of liquids and a double pipe inside. The two-liquid mixing mixer is more preferably provided with both a joint member having a double pipe inside and a static mixer member, and the static mixer member comprises a cylindrical body and an element body inserted therein. wherein the joint member and the static mixer member are connected such that the end face of the tubular body on the side of the double pipe abuts the end face of the static mixer member on the side of the double pipe More preferred.

In this way, the joint member and the static mixer member are connected so that the end surface of the cylindrical body on the side of the double tube contacts the end surface of the static mixer member on the side of the double tube. While maintaining mixing efficiency, the mixer for liquids is less likely to clog and can be stably operated continuously for a long period of time.

That is, the mixer has a structure in which the double pipe and (the cylindrical body of) the static mixer are connected inside the joint, so that the contact between the end surfaces is more reliable than in the conventional microreactor structure. As a result, the two liquids flowing out from the double tube flow into the static mixer at almost the same time as they flow out, so that the two liquids are mixed more reliably at the start of the reaction.

In the two-liquid mixing mixer, it is preferable that the end portion of the double tube on the side of the static mixer member is inside the joint member. By adopting such a configuration, the construction of the double pipe is simplified, and as a result, the joint member can be manufactured easily, and the points of contact between the joint member and the static mixer member can be easily confirmed.

In the two-liquid mixing mixer, the joint member has an insertion hole for inserting an inner tube through which the first liquid flows, and in a state in which the inner tube is inserted, at least near the terminal end of the inner tube In the above, it is preferable that the inner side of the inner tube and the space formed by the outer wall of the inner tube and the inner wall of the insertion hole form the double tube. By adopting such a configuration, construction of the double pipe is simplified, and as a result, manufacturing of the joint member is facilitated.

This insertion hole can be formed by cutting, using a mold having a mold corresponding to the insertion hole, or the like. At this time, as long as the inner pipe can be kept liquid-tight, even if it is fixed to the joint member main body while being inserted into the insertion hole formed in the joint member, the inner pipe is fixed removably from the joint member main body. Although it may be attached, it is preferably fixed so as to be detachable from the joint member main body. By making the inner tube removable in this way, it is easy to clean the double tube part after use, and it is possible to replace the inner tube if it is damaged, clogged, or contaminated. There is an advantage that

As described above, the means for fixing and fixing the inner tube is not particularly limited as long as it can maintain liquid tightness. It is preferable to use removable fixing means such as fastening.

Moreover, it is preferable that the joint member has an introduction hole for introducing the second liquid, and that the introduction hole is connected to the insertion hole. With such a configuration, the double pipe can be constructed inside the joint member main body, and as a result, the length of the double pipe can be shortened, which facilitates the manufacture of the joint member. This introduction hole can also be formed by cutting or a method using a mold, like the insertion hole.

In addition, the position of the introduction hole in the joint member is not particularly limited, but it is preferable to form it in a direction orthogonal to the insertion hole. It is preferable to form it at a position closer to the terminal end than the central part of the end and the terminal end so that it can be connected to the insertion hole.

Further, the insertion hole is formed in the vicinity of the connection portion with the introduction hole so as to have a hole diameter substantially equal to the outer diameter of the inner pipe, and the inner pipe extends from the connection portion to the tip of the inner pipe. It is preferably formed so as to have a hole diameter larger than the outer diameter of the tube. With such a hole structure having different diameters, almost no gap is formed between the inner tube and the insertion hole in the connecting portion, so that the second liquid flowing in from the introduction hole The leakage to the side can be prevented, and the two liquids can be efficiently mixed.

Moreover, it is preferable that the joint member has a static mixer member connection hole, and the insertion hole is connected to the connection hole. With such a configuration, the joint member and the static mixer member can be individually designed, which facilitates adjustment of the internal structure of the two-liquid mixing mixer. This connection hole can also be formed by a technique using cutting or a mold, like the insertion hole.

As with the inner tube described above, this static mixer member may also be fixed to the joint member main body in a state of being inserted into a connection hole formed in the joint member, as long as the liquid tightness can be maintained. Although it may be fixed removably from the member main body, it is preferably fixed removably from the joint member main body. By making it removable, it becomes easy to adjust the position of the element body inside the static mixer member and to wash the mixer after use, and also it becomes possible to replace each part when it is contaminated or deteriorated. The means for fixing and fixing the static mixer member may be the same as the means described for the inner tube, but in this case as well, it is preferable to use removable fixing means such as screw fastening.

Further, it is preferable that the element body is inserted into the cylindrical body so that one end thereof is substantially flush with the end face of the cylindrical body on the double tube side. Since the end face of the cylindrical body and the end of the element body are substantially aligned in this manner, the two liquids flowing out from the double tube flow into the element body almost simultaneously and are mixed. From the start of the reaction, more efficient mixing and stirring can be performed.

The shape of the tubular body is not particularly limited, but a cylindrical shape is preferable in consideration of the fluidity and mixing properties of the two liquids passing through the inside thereof.

The structure of the element body is not particularly limited, and can be appropriately selected from those used as element bodies of static mixers. ), those having a spiral shape with a constant twist direction, those having multiple layers of plates provided with one or more holes, etc., but right twist It is preferable to have a shape in which a plurality of blades and left-handed torsion blades are alternately connected in the torsion axis direction. By using the element body having such a shape, it becomes possible to perform mixing more efficiently, and clogging of the mixer during the reaction is less likely to occur.

The element body may have a removable structure that is simply inserted into the cylindrical body, or a non-removable structure that is fixed inside the cylindrical body after being inserted. structure. The detachable structure facilitates adjustment of the position of the element body inside the cylindrical body and replacement of the element body.

The diameter of the element body is not particularly limited as long as it can be inserted into the cylindrical body, but the diameter (maximum diameter) is preferably substantially the same as the inner diameter of the cylindrical body. By doing so, even when the element body is simply inserted into the cylindrical body, it is possible to prevent the position of the element body from fluctuating in the longitudinal direction and the lateral direction of the cylindrical body. Considering the use of the two-liquid mixing mixer, the diameter of the element body is preferably about 1 to 10 mm, more preferably about 1.6 to 8 mm, and even more preferably about 2 to 5 mm.

Also, the length of the element body is not particularly limited as long as it can be inserted into the cylindrical body, but it is preferable that the element body has substantially the same length as the cylindrical body. By doing so, it becomes easy to align the end of the element body with the end face of the tubular body on the side of the double tube.

The flow reactor used in the present invention is equipped with the two-liquid mixing mixer. The flow reactor may be provided with one mixer for mixing the two liquids, or may be provided with two or more. When two or more of the two-liquid mixing mixers are provided, multistage flow synthesis becomes possible. Since the two-liquid mixing mixer is less likely to clog, there is little pressure loss when performing flow synthesis using a flow reactor, and stable long-term continuous operation is possible, making it suitable for large-scale synthesis.

The flow reactor used in the present invention includes, in addition to the mixer for mixing the two liquids, other components necessary for the reaction, such as a pump for liquid transfer, a tube for forming a flow path, and a temperature control device for temperature control, if necessary. It may be provided with various members of.

The liquid-sending pump is not particularly limited, and commonly-used pumps such as plunger pumps, syringe pumps, and rotary pumps can be used.

The material of the tube for forming the flow path is not particularly limited, and includes metals such as stainless steel, titanium, iron, copper, nickel, and aluminum, polytetrafluoroethylene (PTFE), ethylene tetrafluoride/propylene hexafluoride copolymer. (FEP), perfluoroalkoxy fluorine (PFA), polyetheretherketone (PEEK), polypropylene (PP) and the like.

The inner diameter of the channel-forming tube may be appropriately set according to the purpose within a range that does not impair the effects of the present invention. It is preferably about 1 to 2 mm, and more preferably about 1 to 2 mm. The length of the tube for forming the flow path may be appropriately set according to the purpose within a range that does not impair the effects of the present invention. Preferably, about 0.3 to 5 m is more preferable.

The two-liquid mixing mixer and flow reactor used in the present invention will be specifically described below with reference to the drawings. A two-liquid mixing mixer 1 comprises a joint member 2 and a static mixer member 3, as shown in FIG. The joint member 2 includes a main body 21 made of stainless steel and an inner tube 22 made of stainless steel (outer diameter 1.6 mm, inner diameter 1.0 mm) through which the first liquid flows.

As shown in FIGS. 2 and 3, the main body 21 has an insertion hole 211 for inserting the inner tube 22, and a second liquid which is perpendicular to this and connected to the insertion hole 211 inside the main body 21. It has an introduction hole 212 for introducing the static mixer member connection hole 213 . The inner walls of the insertion hole 211, the introduction hole 212, and the connection hole 213 are formed with female threaded portions 211a, 212a, and 213a corresponding to male threaded portions formed in each connector described later. The introduction tube through which the liquid flows and the static mixer member 3 can be fixed to the main body 21 by screwing.

The insertion hole 211 has a female screw portion 211a, a liquid-tight portion 211b formed subsequently to the female screw portion 211a, and a trapezoidal cross-sectional liquid-tight portion 211b whose diameter is reduced according to the shape of the connector tip portion described later, from the base end side to the terminal end side. It is composed of an inner tube passing portion 211c that is subsequently formed. Here, as shown in FIG. 5, the inner diameter b of the inner pipe passage portion 211c of the insertion hole 211 is substantially the same as the outer diameter a of the inner pipe 22 in the vicinity of the connection portion 214 with the introduction hole 212. In addition, the inner diameter c of the inner pipe passage portion 211c from the connection portion 214 to the connection hole 213 is formed to be larger than the outer diameter a of the inner pipe 22 . In this way, a structure in which almost no space is formed between the inner pipe 22 and the insertion hole 211 in the connecting portion 214 is provided, and the second liquid flowing from the introduction hole 212 leaks to the proximal end side of the insertion hole 211. As shown in FIG. 6, a double tube 25 is constructed by a space 24 formed by an inner tube inner side 221, the inner tube outer wall 222, and the inner wall 211d of the insertion hole. .

Further, as shown in FIG. 3, the insertion hole 211 is connected at its proximal end to the connection hole 213, so that the hole formed by the insertion hole 211 and the connection hole 213 is connected to the main body. 21 passes through.

As shown in FIG. 2, the inner tube 22 is formed with a hole (not shown) through which the inner tube 22 passes. A connector 23 having a male threaded portion 231 and a sealing portion 233 having an inverted truncated cone shape for maintaining liquid tightness inside the joint main body 21 is attached. and is fixed to the main body 21 by screwing.

As shown in FIG. 3, the introduction hole 212 has a female screw portion 212a from the base end side to the terminal end side, followed by a female screw portion 212a, which is formed so as to have a rectangular cross section corresponding to the shape of the tip portion of the connector, which will be described later. It is composed of a dense portion 212 b and a connecting portion 212 c extending from there to a connection portion 214 with the insertion hole 211 . The insertion hole 211 and the introduction hole 212 are connected on the terminal side of the center of the base end and the terminal end of the insertion hole 211 .

As shown in FIG. 3, the static mixer connection hole 213 has a female screw portion 213a and a rectangular cross-sectional shape corresponding to the shape of the connector tip portion, which is formed subsequently to the female screw portion 213a, from the base end side to the terminal end side. and a liquid-tight portion 213b.

The static mixer member 3, as shown in FIGS. 1 and 2, comprises a cylindrical body 31 (inner diameter: 3.0 mm) made of fluororesin or stainless steel, and an element body 32 made of polyacetal inserted therein. (3 mm diameter). As shown in FIGS. 2 and 4, the element body 32 is inserted into the cylindrical body 31 so that its proximal end is flush with the end face of the cylindrical body 31 on the side of the double tube 25 . Here, as shown in FIG. 7, the element body 32 has a shape in which a plurality of right twisted blades 321 and left twisted blades 322 are alternately connected in the direction of the torsion axis (central axis in the longitudinal direction) 323. .

As shown in FIG. 2, a hole (not shown) through which the cylindrical body 31 passes is formed at the upper end of the cylindrical body 31, and a fluororesin connector having a male screw portion 331 is provided. 33 is attached, and in this state, it is inserted into the connection hole 213 having the female screw portion 213a and is fixed to the main body 21 by screwing.

Next, with reference to FIGS. 4 to 6, the internal structure of the two-liquid mixing mixer 1 having the configuration described above will be described. As described above, the hole diameter of the insertion hole 211 , specifically, the inner diameter b of the inner pipe passing portion 211 c near the connection portion 214 with the introduction hole 212 is substantially the same as the outer diameter a of the inner pipe 22 . The inner diameter c of the inner pipe passing portion 211c from the connecting portion 214 between the insertion hole 211 and the introduction hole 212 to the tip 223 of the inner pipe 22 on the side of the static mixer member 3 is formed larger than the outer diameter a of the inner pipe 22. It is As a result, the inner side 221 of the inner tube 22 and the space 24 formed by the outer wall 222 of the inner tube 22 and the inner wall 211 d of the insertion hole 211 form the double tube 25 .

Further, the end face of the tubular body 31 of the static mixer member 3 on the side of the double pipe 25 and the end face of the double pipe 25 on the side of the static mixer member 3 are in contact with each other. Since the base end of the element body 32 is flush with the end face of the tubular body 31 on the side of the double pipe 25, the end face of the double pipe 25 on the side of the static mixer member 3 and the base end of the element body 32 (Fig. 4 middle upper end) are also in contact with each other.

The second liquid is introduced through the introduction hole 212. In this case, as shown in FIG. ) is formed, and is fixedly connected to the introduction hole 212 by screwing using a connector 27 having a seal portion (not shown) for maintaining liquid-tightness inside the joint body 21 and a male screw portion 271 .

Next, an embodiment of a flow reactor using a two-liquid mixing mixer configured as described above will be described with reference to FIG.
In the flow reactor 4, a first two-liquid mixing mixer 1a and a second two-liquid mixing mixer 1b arranged inside a constant temperature layer 43 are connected in series by a PTFE tube 42d (inner diameter: 1.5 mm). are configured.

A pump 41a for feeding the first liquid is connected to the inner tube 22a of the first two-liquid mixing mixer 1a via a PTFE tube 42a (with an inner diameter of 1.0 mm). On the other hand, in the introduction hole provided in the main body 21a of the joint member of the two-liquid mixing mixer 1a, a pump 41b for feeding the second liquid is provided, and a connector is provided at the tip of the pump 41b, through which the second liquid flows. It is connected via a manufacturing tube 42b (inner diameter 1.0 mm).

A pump 41c for feeding a third liquid is connected to the introduction hole of the two-liquid mixing mixer 1b via a PTFE tube 42c (inside diameter 1.0 mm) through which the third liquid flows and which has a connector at its tip. A PTFE tube 42e (with an inner diameter of 1.5 mm) is connected to the terminal end of the static mixer member 3b of the two-liquid mixing mixer 1b.

In the flow reactor 4 having such a configuration, the liquids sent from the first liquid-feeding pump 41a and the second liquid-feeding pump 41b are transferred to the joint member of the first two-liquid mixing mixer 1a. After flowing into the main body 21a and passing through the double pipe built inside it, it flows into the static mixer member 3a in contact with the end of this double pipe, where it is mixed and stirred by the element body inside. A first reaction occurs. After the reaction, the first reaction liquid passes through the tube 42d and then flows through the inner tube 22b of the second two-liquid mixing mixer 1b into the joint member main body 21b. This first reaction liquid passes through the double pipe inside the joint member main body 21b together with the third liquid that is sent from the third liquid transfer pump 41c and flows into the joint member main body 21b, As in the case of the first two-liquid mixing mixer 1a, it flows into the static mixer member 3b, where the second reaction proceeds.

The two-liquid mixing mixer and flow reactor used in the present invention are not limited to the above-described embodiments, and may be modified or improved within the scope of achieving the objects and effects of the present invention.

That is, in the two-liquid mixing mixer 1 described above, the inner tube 22 and the static mixer member 3 are detachably screwed to the joint member main body 21, but they are configured to be detachable by other fixing means. It may also be permanently connected and affixed.

In addition, the inner tube 22 and the cylindrical body 31 are provided with the separate connectors 23 and 33, but the inner tube and the cylindrical body themselves may be provided with appropriate fixing means without providing them. good.

Furthermore, the introduction hole 212 is formed in the joint member main body 21 so as to be connected perpendicularly to the insertion hole 211, but it may be connected to the insertion hole at another angle, and the position of the introduction hole 212 is also arbitrary. can be set to the location of

The material of the main body 21, the inner tube 22 and the connector 23 is stainless steel, but it is not limited to this, and other metals such as titanium, iron, copper, nickel, aluminum, PTFE, FEP, PFA, PEEK, PP, etc. Resin may be used.

The inner diameter of the inner tube 22 may be appropriately set according to the purpose within a range that does not impair the effects of the present invention. About 5 to 1 mm is more preferable. The outer diameter of the inner tube 22 may be appropriately set according to the purpose within a range that does not impair the effects of the present invention. About 0.8 to 1.6 mm is even more preferable.

The hole diameter c of the insertion hole 211 may be appropriately set according to the purpose within a range that does not impair the effects of the present invention. About 0.8 to 2 mm is more preferable.

The material of the cylindrical body 31 is not limited to stainless steel, and may be other metals such as titanium, iron, copper, nickel, and aluminum, resins such as PTFE, FEP, PFA, PEEK, and PP.

The material of the element body 32 is not limited to polyacetal, and may be other resins such as PTFE, FEP, PFA, PEEK and PP, metals such as stainless steel, titanium, iron, copper, nickel and aluminum, and ceramics.

Further, the shape of the element body 32 may also be a helical shape with a constant twist direction, or a stack of a plurality of plates provided with one or two or more holes.

The material of the connector 33 is not limited to fluorine-based resin, and may be other resins such as PEEK and PP, and metals such as stainless steel, titanium, iron, copper, nickel, and aluminum.

The inner diameter of the cylindrical body 31 may be appropriately set according to the purpose within a range that does not impair the effects of the present invention. degree is even more preferred. Also, the diameter of the element body 32 may be appropriately set according to the purpose within a range that does not impair the effects of the present invention. degree is even more preferred.

Since the flow reactor 4 is equipped with two two-liquid mixing mixers, two-stage flow synthesis is possible. When n-step flow synthesis is to be performed, a flow reactor may be assembled as described above using n two-liquid mixing mixers.

In addition, the inner diameter of the tubes 42a to 42e constituting the flow reactor 4 may be appropriately set according to the purpose within a range that does not impair the effects of the present invention. About 4 mm is more preferable, and about 1 to 2 mm is even more preferable. In addition, the length may be appropriately set according to the purpose within a range that does not impair the effects of the present invention. About 5 m is even more preferable.

[monomer]
Monomers used in the method for producing a block polymer of the present invention are not particularly limited as long as they are capable of anionic polymerization. Examples of such monomers include aromatic vinyl compounds, conjugated dienes, (meth)acrylic compounds, and the like.

Examples of the aromatic vinyl compound include those represented by the following formula (1).

In the formula, R ¹ represents a hydrogen atom or a methyl group. R ² to R ⁶ each independently represents a hydrogen atom, an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, —OSiR ⁷ ₃ or —SiR ⁷ ₃ represents Each R ⁷ independently represents an alkyl group having 1 to 10 carbon atoms, a phenyl group, an alkoxy group having 1 to 5 carbon atoms or an alkylsilyl group having 1 to 5 carbon atoms.

The alkyl group may be linear, branched, or cyclic. Specific examples include methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n -nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n- propyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl -cyclopropyl group, 2-ethyl-cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n -pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2, 3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group , 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl- cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2 -n-propyl-cyclopropyl group, 1-isopropyl-cyclopropyl group, 2-isopropyl-cyclopropyl group, 1,2,2-tri methyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl- Cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group, 2-ethyl-3-methyl-cyclopropyl group and the like. Among these, those having 1 to 8 carbon atoms are preferred, those having 1 to 6 carbon atoms are more preferred, and those having 1 to 3 carbon atoms are even more preferred.

Examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, cyclopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, cyclobutoxy, and 1-methyl. -cyclopropoxy group, 2-methyl-cyclopropoxy group, n-pentyloxy group, 1-methyl-n-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1,1- dimethyl-n-propoxy group, 1,2-dimethyl-n-propoxy group, 2,2-dimethyl-n-propoxy group, 1-ethyl-n-propoxy group, 1,1-diethyl-n-propoxy group, cyclo pentoxy group, 1-methyl-cyclobutoxy group, 2-methyl-cyclobutoxy group, 3-methyl-cyclobutoxy group, 1,2-dimethyl-cyclopropoxy group, 2,3-dimethyl-cyclopropoxy group, 1- Ethyl-cyclopropoxy group, 2-ethyl-cyclopropoxy group and the like can be mentioned. The structure of the alkoxy group is preferably linear or branched. Among these, those having 1 to 3 carbon atoms are preferred.

As the halogen atom, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom are preferable, and a fluorine atom and a chlorine atom are more preferable.

R ⁴ is preferably an alkoxy group having 1 to 5 carbon atoms or -SiR ⁷ ₃ , more preferably a methoxy group or -Si(CH ₃ ) ₃ . R ² , R ³ , R ⁵ and R ⁶ are preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or —SiR ⁷ ₃ , and a hydrogen atom, a methoxy group or -Si(CH ₃ ) ₃ is more preferred.

Specific examples of the aromatic vinyl compound represented by formula (1) include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-tert-butylstyrene, 4-dimethylsilylstyrene, 4-trimethylsilylstyrene, 4-trimethylsilyloxystyrene, 4-dimethyl(tert-butyl)silylstyrene, 4-dimethyl(tert-butyl)silyloxy styrene, 2-methoxystyrene, 3-methoxystyrene, 4-methoxystyrene, 4-ethoxystyrene, 3,4-dimethylstyrene, 2,6-dimethylstyrene, 2,4-dimethoxystyrene, 3,4-dimethoxystyrene, Styrene derivatives such as 3,4,5-trimethoxystyrene are included.

As the aromatic vinyl compound, vinylnaphthalene, vinylanthracene, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine and the like can also be suitably used.

Examples of the conjugated dienes include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-heptadiene, 1,3-hexadiene, and 1,3-cyclohexadiene. etc.

Examples of the (meth)acrylic compound include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec -butyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, isopentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate , 2-ethylhexyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, n-dodecyl (meth)acrylate, n-stearyl (meth)acrylate, isostearyl (meth)acrylate, phenyl (meth)acrylate Acrylates, benzyl (meth)acrylate, naphthyl (meth)acrylate, anthryl (meth)acrylate, anthrylmethyl (meth)acrylate, 2-phenylethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (Meth)acrylates, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,2-trichloroethyl (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, tetrahydrofurfuryl (Meth)acrylate, isobornyl (meth)acrylate, n-butoxyethyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2 -adamantyl (meth)acrylate, 2-propyl-2-adamantyl (meth)acrylate, 2-methoxybutyl-2-adamantyl (meth)acrylate, 8-methyl-8-tricyclodecyl (meth)acrylate, 8-ethyl- 8-tricyclodecyl (meth)acrylate, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, and 2,2,3,3,4,4,4-heptafluorobutyl (meth) acrylates and the like.

Among these, aromatic vinyl compounds are preferred as the monomers used in the production method of the present invention, since side reactions can be suppressed even at relatively high temperatures and a monodisperse polymer can be easily obtained. In particular, both the first monomer and the second monomer are preferably aromatic vinyl compounds.

[Initiator]
The initiator used in the method for producing a block polymer of the present invention is not particularly limited as long as it is commonly used in anionic polymerization, and examples thereof include organic lithium compounds.

Examples of the organic lithium compound include alkyllithium such as methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, isobutyllithium, sec-butyllithium, tert-butyllithium, pentyllithium, and hexyllithium, methoxymethyllithium, ethoxymethyllithium, phenyllithium, naphthyllithium, benzyllithium, phenylethyllithium, α-methylstyryllithium, 1,1-diphenylhexyllithium, 1,1-diphenyl-3-methylpentryllithium, 3- methyl-1,1-diphenylpentyllithium, vinyllithium, allyllithium, propenyllithium, butenyllithium, ethynyllithium, butynyllithium, pentynyllithium, hexynyllithium, 2-thienyllithium, 4-pyridyllithium, 2- Monoorganolithium compounds such as quinolyllithium; Thiopolyisoprene, 1,4-dilithiobenzene, 1,2-dilithio-1,2-diphenylethane, 1,4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene, 1,3, Examples include polyfunctional organolithium compounds such as 5-trilithio-2,4,6-triethylbenzene. Among these, monoorganolithium compounds are preferred, and alkyllithiums such as n-butyllithium, sec-butyllithium and tert-butyllithium are preferred.

[Method for producing block polymer]
A block polymer having two monomer units can be synthesized by using a flow reactor having two mixers for mixing two liquids, such as the flow reactor 4 described above.

Hereinafter, the method for producing the block polymer of the present invention will be described by taking synthesis of a diblock polymer as an example. First, the first monomer solution containing the monomer described above is introduced into the flow reactor through the introduction hole of the first mixer, the solution containing the initiator described above is introduced into the flow reactor through the inner tube of the first mixer, and the reaction is carried out. to synthesize a homopolymer composed of the first monomer. At this time, by introducing the first monomer solution and the initiator solution as described above, clogging of the flow reactor is unlikely to occur, pressure loss is suppressed, and the polymer is stably produced over a long period of time. be able to.

Next, a second monomer solution containing the monomers described above is introduced into the flow reactor through the introduction hole of the second mixer to synthesize a block polymer.

The solvent for dissolving the first monomer and the second monomer is not particularly limited, but tetrahydrofuran (THF), 2-methylTHF, diethyl ether, tetrahydropyran (THP), oxepane, 1,4-dioxane, etc. Ether solvents, toluene, dichloromethane, diethoxyethane and the like are preferred.

The concentrations of the first monomer and the second monomer are not particularly limited and can be appropriately set according to the purpose, but is preferably 0.1 to 5 mol/L, more preferably 0.1 to 3 mol/L. 0.5 to 2 mol/L is particularly preferred. When the monomer concentration is within the above range, clogging of the flow reactor is less likely to occur, pressure loss is suppressed, and a polymer can be stably produced over a long period of time.

Further, the flow rate of the first monomer and the second monomer flowing through the channel of the flow reactor is not particularly limited, and can be appropriately set according to the purpose. Preferably, 0.5 to 20 mL/min is more preferable, and 10 to 20 mL/min is particularly preferable. When the flow rate of the monomer is within the above range, clogging of the flow reactor is less likely to occur, pressure loss is suppressed, and a polymer can be stably produced over a long period of time.

As the initiator, particularly n-butyllithium can be preferably used. The anionic polymerization is usually carried out at a low temperature because the polymerization speed increases when it is carried out in a polar solvent (for example, THF). Therefore, there is a drawback that the initiation reaction is difficult to complete unless sec-butyllithium is used as the initiator. On the other hand, if it is carried out in a non-polar solvent (for example, toluene), the reaction rate is slow and heating is required. In this case, n-butyllithium, which has low reactivity, may be used as an initiator. The method for producing a block polymer using the flow reactor of the present invention has the advantage that the reaction can be carried out in a polar solvent at around room temperature, so that n-butyllithium with low reactivity can be used as an initiator.

The solvent for dissolving the initiator is not particularly limited, but ether solvents such as hexane, THF, 2-methylTHF, diethyl ether, THP, oxepane, 1,4-dioxane, toluene, dichloromethane, diethoxyethane, Toluene, diethyl ether and the like are preferred.

The concentration of the initiator is not particularly limited and can be appropriately set according to the type of monomer, but is preferably 0.01 to 0.5 mol/L, more preferably 0.03 to 0.3 mol/L. , 0.05 to 0.1 mol/L are particularly preferred. When the concentration of the initiator is within the above range, clogging of the flow reactor is less likely to occur, pressure loss is suppressed, and a polymer can be stably produced over a long period of time.

Further, the flow rate of the initiator flowing through the flow reactor is not particularly limited, and can be appropriately set according to the purpose. /min is more preferred, and 1 to 3 mL/min is particularly preferred. When the flow rate of the initiator is within the above range, clogging of the flow reactor is less likely to occur, pressure loss is suppressed, and a polymer can be stably produced over a long period of time.

The reaction temperature (the temperature of the flow reactor) in the production method of the present invention is not particularly limited, and can be appropriately set according to the purpose. is more preferable, and −20° C. or higher is even more preferable. The reaction temperature is preferably 100° C. or lower, more preferably 50° C. or lower, and still more preferably 30° C. or lower, from the viewpoint of suppressing side reactions and suppressing deactivation of growing ends.

As a method for terminating the reaction, there is a method in which the polymerization reaction solution coming out of the flow reactor is collected in a container containing an excess amount of a reaction terminator such as methanol, and in the flow reactor, three mixers for mixing the two liquids are used. In the configuration having the above, a method of pouring a reaction terminator such as methanol from one side of the final two-liquid mixing mixer can be mentioned.

The collected block polymer is washed with a solvent that dissolves the homopolymer obtained only from the first monomer but does not dissolve the homopolymer obtained only from the second monomer and the block polymer. As a result, the residual homopolymer obtained only from the first monomer is removed, and the degree of dispersion of the block polymer can be further improved.

The washing method is not particularly limited, and includes, for example, a method of adding the solvent to the recovered block polymer, suspending and stirring, and then recovering the block polymer. In this case, the amount of the solvent is not particularly limited as long as it can sufficiently dissolve the homopolymer, but the mass ratio of the solvent to the block polymer is preferably about 1 to 50, more preferably about 10 to 30. The stirring time is not particularly limited as long as the homopolymer can be sufficiently dissolved, but it is preferably about 0.1 to 5 hours, more preferably about 1 to 2 hours. The method for recovering the block polymer is not particularly limited, and it can be recovered by a known method such as filtration.

The method for producing a block polymer of the present invention uses a monomer represented by the following formula (2) as a first monomer and a monomer represented by the following formula (3) as a second monomer to produce a block polymer. Alternatively, a block polymer obtained by using a monomer represented by the following formula (3) as the first monomer and a monomer represented by the following formula (2) as the second monomer is suitable for production.

In the formula, R ¹¹ and R ²¹ are each independently a hydrogen atom or a methyl group. R ¹² to R ¹⁶ are each independently a hydrogen atom, an alkoxy group having 1 to 5 carbon atoms, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, and at least one is a carbon It is an alkoxy group of numbers 1-5. R ²² to R ²⁶ are each independently a hydrogen atom, ^—OSiR 273 or —SiR ²⁷³ _, but at _least one is _—OSiR ²⁷³ or —SiR ²⁷³ and R ²⁷ is _each independently , an alkyl group having 1 to 10 carbon atoms, a phenyl group, an alkoxy group having 1 to 5 carbon atoms or an alkylsilyl group having 1 to 5 carbon atoms. Examples of the alkyl group, alkoxy group, and halogen atom include the same groups as those described above.

R ¹⁴ is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group. R ²⁴ is preferably -SiR ²⁷ ₃ , more preferably -Si(CH ₃ ) ₃ . R ¹² , R ¹³ , R ¹⁵ , R ¹⁶ , R ²² , R ²³ , R ²⁵ and R ²⁶ each represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or —SiR ⁷ ₃ is preferred, a hydrogen atom, a methoxy group or --Si(CH ₃ ) ₃ is more preferred, and a hydrogen atom is even more preferred.

When the monomer represented by formula (2) is used as the first monomer and the monomer represented by formula (3) is used as the second monomer, the homopolymer obtained only from the above-mentioned first monomer dissolves. However, dimethyl sulfoxide (DMSO) is preferable as a solvent in which the homopolymer and the block polymer obtained only from the second monomer are not dissolved.

When the monomer represented by formula (3) is used as the first monomer and the monomer represented by formula (2) is used as the second monomer, the homopolymer obtained only from the above-mentioned first monomer dissolves. However, an alcohol having 4 to 7 carbon atoms is preferable as the solvent in which the homopolymer and the block polymer obtained only from the second monomer are not dissolved.

Examples of the alcohol having 4 to 7 carbon atoms include 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-2-butanol, 2,2-dimethyl-1-propanol, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, 4-methyl-1-pentanol, 2-methyl-2-pentanol, 3-methyl-2-pentanol, 4 -methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-3-pentanol, 2,2-dimethyl-1-butanol, 2,3-dimethyl-1-butanol, 3,3- Dimethyl-1-butanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-2-butanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, etc. linear or branched fatty alcohols.

In the block polymer, the first polymer block preferably contains only structural units represented by formula (2), and the second polymer block contains only structural units represented by formula (3). preferably containing. Moreover, the block polymer preferably contains only the first polymer block and the second polymer block.

In the block polymer, the content of the polymer block composed of the monomer unit represented by formula (2) and the polymer block composed of the monomer unit represented by formula (3) is 1:1 to 1 in terms of molar ratio. :10 is preferred, and 1:1 to 1:3 is more preferred.

According to the production method of the present invention, a polymer with a smaller degree of dispersion (Mw/Mn) (narrower molecular weight distribution) can be synthesized. The degree of dispersion is preferably 1.5 or less, more preferably 1.3 or less, still more preferably 1.2 or less, and even more preferably 1.15 or less. In addition, Mw and Mn represent a weight average molecular weight and a number average molecular weight, respectively, and these are polystyrene conversion measured values by gel permeation chromatography (GPC). Although Mw of the polymer obtained by the production method of the present invention is not particularly limited, 1,000 to 100,000 is preferable, and 1,000 to 50,000 is more preferable.

EXAMPLES The present invention will be specifically described below with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples.

FIG. 10 shows a schematic diagram of a flow reactor (reaction device) used in the synthesis examples below. In addition, the arrow in FIG. 10 indicates the direction in which the liquid flows. A plunger pump (KP-12 or HP-12 manufactured by From Co., Ltd.) was used to send the first monomer liquid, and a PTFE tube (inner diameter: 1.0 mm, outer diameter: 1.6 mm, length: 2 m) was used. A plunger pump and a mixer 1 are connected, and a syringe pump 1 (YMC Co., Ltd. Keychem-L, Synthesis Example 1) and a syringe pump 2 (TELEDYNE ISCO Co., Ltd. 1000D Syringe Pump, Synthesis Example 1) are used to feed the initiator solution. 2), the syringe pump 1 and the mixer 1 were connected using a PTFE tube (inner diameter: 1.0 mm, outer diameter: 1.6 mm, length: 2 m). The outlet of mixer 1 and the inlet of mixer 2 are PTFE tubes 1 (inner diameter 1.5 mm, outer diameter 3 mm, length 5 m (synthesis example 1), 2 m (synthesis example 2)), and the other inlet of mixer 2 is , Second monomer liquid feeding syringe pump 3 (Keychem-L manufactured by YMC, Synthesis Examples 1 and 2) and a PTFE tube (inner diameter 1.0 mm, outer diameter 1.6 mm, length 2 m). . The outlet of the mixer 2 and the inlet of the mixer 3 were connected with a PTFE tube 2 (inner diameter 1.5 mm, outer diameter 3 mm, length 2 m (synthesis example 1), 5 m (synthesis example 2)). The other inlet of the mixer 3 was connected to a syringe pump for feeding a polymerization terminator solution (Syrris Asia) with a PTFE tube (inner diameter 1.0 mm, outer diameter 1.6 mm, length 2 m). A PTFE tube 3 (inner diameter: 1.5 mm, outer diameter: 3 mm, length: 0.7 m) was connected to the outlet of the mixer 3 . The flow path from each pump to 90% of the length of the tube 3 was immersed in a constant temperature bath at 5° C. to adjust the temperature.

The number average molecular weight (Mn) and weight average molecular weight (Mw) of the resulting polymer were measured by gel permeation chromatography (GPC). The measurement conditions of GPC are as follows.
Column: PLgel 5 μm MIXED-D (manufactured by Agilent Technologies)
Mobile phase: Tetrahydrofuran (THF)
Flow rate: 1.0mL/min
Column oven: 40°C
Detector: RI detector Calibration curve: standard polystyrene

[Synthesis Example 1] Synthesis of polymethoxystyrene-b-polytrimethylsilylstyrene block polymer (PMOST-b-PTMSS) 0.5 mol/L 4-methoxystyrene THF solution as first monomer and 0.05 mol/L as initiator The n-butyllithium hexane solutions were mixed in mixer 1 at flow rates of 10 mL/min and 1.2 mL/min, respectively, to polymerize the first monomer. The joint member 2 of the mixer 1 was made of stainless steel, and the cylindrical body 31 was made of stainless steel. As the static mixer element body, DSP-MXA3-17 manufactured by Noritake Co., Ltd. (polyacetal element, number of twisted blades: 17, diameter: 3 mm) was processed, and six elements were connected to make the number of twisted blades 102. Using. Subsequently, a 4-trimethylsilylstyrene liquid was mixed as a second monomer at a mixer 2 at 0.67 mL/min for block polymerization. As the mixer 2, Comet X-01 (made of stainless steel) manufactured by Techno Applications Co., Ltd. was used. Subsequently, a 0.25 mol/L methanol/THF solution as a polymerization terminator was mixed with mixer 3 at 10 mL/min to terminate the polymerization. In addition, the mixer 3 used the general simple double tube mixer. The first monomer solution tube is connected to the inlet of the inlet of the mixer 1, the initiator solution tube is connected to the inlet of the inner tube, the tube 1 is connected to the inlet of the inlet of the mixer 2, the second monomer liquid tube is connected to the inlet of the inner tube, A polymerization terminator solution was connected to the introduction hole inlet of the mixer 3, and the tube 2 was connected to the inner tube inlet. After feeding for 15 minutes, the effluent was collected.
Further, the solvent was removed from 258 g of the effluent by an evaporator to make 103 g, and the residue was added dropwise to 403 g of methanol at room temperature. The resulting white suspension was filtered through filter paper (No. 5B, manufactured by Kiriyama Seisakusho Co., Ltd.) and then washed with 202 g of methanol. Subsequently, the resulting white solid was dried under reduced pressure (50° C., 2.5 hours) to obtain 16 g of PMOST-b-PTMSS. GPC analysis of the resulting polymer revealed Mn=34,792 and Mw/Mn=1.13. Also, FIG. 11 shows the ¹ H-NMR chart of the polymer. From this result, the composition ratio of methoxystyrene units and trimethylsilylstyrene units was methoxystyrene units:trimethylsilylstyrene units=58:42.

[Synthesis Example 2] Synthesis of polytrimethylsilylstyrene-b-polymethoxystyrene block polymer (PTMSS-b-PMOST) 0.35 mol/L 4-trimethylsilylstyrene THF solution as first monomer and 0.05 mol/L as initiator The n-butyllithium hexane solutions were mixed in mixer 1 at flow rates of 10 mL/min and 1.5 mL/min, respectively, to polymerize the first monomer. Comet X-01 (made of stainless steel) manufactured by Techno Applications Co., Ltd. was used. Subsequently, a 4-methoxystyrene liquid as a second monomer was mixed with mixer 2 at 0.72 mL/min for block polymerization. As the mixer 2, Comet X-01 (made of stainless steel) manufactured by Techno Applications Co., Ltd. was used. Subsequently, a 0.25 mol/L methanol/THF solution as a polymerization terminator was mixed with mixer 3 at 10 mL/min to terminate the polymerization. As the mixer 3, a general and simple double-tube mixer was used. The first monomer solution tube is connected to the inlet of the inlet of the mixer 1, the initiator solution tube is connected to the inlet of the inner tube, the tube 1 is connected to the inlet of the inlet of the mixer 2, the second monomer liquid tube is connected to the inlet of the inner tube, A polymerization terminator solution was connected to the introduction hole inlet of the mixer 3, and the tube 2 was connected to the inner tube inlet. The solution was fed for 9 minutes, and the effluent was collected.
Further, the effluent was added dropwise to 396 g of methanol at room temperature. The resulting white suspension was filtered through filter paper (No. 5B, manufactured by Kiriyama Seisakusho Co., Ltd.), and then washed with 200 g of methanol. Subsequently, the obtained white solid was dried under reduced pressure (50° C., 2.5 hours) to obtain 10 g of PMOST-b-PTMSS. GPC analysis of the obtained polymer revealed Mn=33,734 and Mw/Mn=1.16. Also, FIG. 12 shows the ¹ H-NMR chart of the polymer. From this result, the composition ratio of methoxystyrene units and trimethylsilylstyrene units was methoxystyrene units:trimethylsilylstyrene units=60:40.

[Reference Synthesis Example 1] Synthesis of polymethoxystyrene (PMOST) A 0.5 mol/L 4-methoxystyrene THF solution as a monomer and a 0.06 mol/L n-butyllithium hexane solution as an initiator were mixed in mixer 1 at flow rates. Mixing was performed at 10 mL/min and 2.0 mL/min to polymerize the first monomer. The joint member 2 of the mixer 1 was made of stainless steel, and the cylindrical body 31 was made of fluororesin. As the static mixer element body, DSP-MXA3-17 manufactured by Noritake Co., Ltd. (polyacetal element, number of twisted blades: 17, diameter: 3 mm) was processed and seven elements were connected to make the number of twisted blades 119. Using. Subsequently, a 0.25 mol/L methanol/THF solution as a polymerization terminator was mixed with mixer 2 at 10 mL/min to terminate the polymerization. The joint member 2 of the mixer 2 was made of stainless steel, and the cylindrical body 31 was made of stainless steel. As the static mixer element body, processed DSP-MXA3-17 manufactured by Noritake Co., Ltd. (element made of polyacetal, number of twisted blades: 17, diameter: 3 mm) was used. A first monomer solution tube and an initiator solution tube were connected to the introduction hole inlet of the mixer 1 and the initiator solution tube to the inner tube inlet. After feeding for 15 minutes, the effluent was collected for 1 minute.
Further, the effluent was added dropwise to 87 g of methanol at room temperature. The resulting white suspension was filtered through filter paper (No. 5B, manufactured by Kiriyama Seisakusho Co., Ltd.), and then washed with 8 g of methanol. Subsequently, the obtained white solid was dried under reduced pressure (50° C., 0.5 hours) to obtain 537 mg of PMOST. GPC analysis of the resulting polymer revealed Mn=6,828 and Mw/Mn=1.09.

[Reference Synthesis Example 2] Synthesis of polytrimethylsilylstyrene (PTMSS) A 0.65 mol/L 4-trimethylsilylstyrene THF solution as a monomer and a 0.05 mol/L n-butyllithium hexane solution as an initiator were mixed in mixer 1 at respective flow rates. Mixing was performed at 10 mL/min and 2.0 mL/min to polymerize the first monomer. As the mixer 1, Comet X-01 (made of stainless steel) manufactured by Techno Applications Co., Ltd. was used. Subsequently, a 0.25 mol/L methanol/THF solution as a polymerization terminator was mixed with mixer 2 at 10 mL/min to terminate the polymerization. As the mixer 2, Comet X-01 (made of stainless steel) manufactured by Techno Applications Co., Ltd. was used. A first monomer solution tube and an initiator solution tube were connected to the introduction hole inlet of the mixer 1 and the initiator solution tube to the inner tube inlet. After feeding the liquid for 4 minutes, the effluent was collected for 1 minute.
Further, the effluent was added dropwise to 87 g of methanol at room temperature. The resulting white suspension was filtered through filter paper (No. 5B, manufactured by Kiriyama Seisakusho Co., Ltd.), and then washed with 8 g of methanol. Subsequently, the obtained white solid was dried under reduced pressure (50° C., 0.5 hours) to obtain 1 g of PTMSS. GPC analysis of the resulting polymer revealed Mn=12,199 and Mw/Mn=1.11.

[Examples, Comparative Examples]
Table 2 below shows the solubility of each polymer synthesized in the Synthesis Example and the Reference Synthesis Example in solvents. The solubility was evaluated by adding 500 μL of various solvents to 10 mg of the polymer, and "+" indicates dissolution and "-" indicates no dissolution. Dissolution was visually judged by the presence or absence of insoluble matter or cloudiness. Moreover, the solvents in Table 2 are as follows.
DMSO: dimethyl sulfoxide NMP: N-methyl-2-pyrrolidone 1-PrOH: 1-propanol 2-PrOH: 2-propanol 1-BuOH: 1-butanol 2-BuOH: 2-butanol 1-HexOH: 1-hexanol

[Example 1]
596.2 mg of PMOST-b-PTMSS obtained in Synthesis Example 1 was suspended in 6 mL of DMSO and stirred at room temperature for 1 hour. After that, after filtration with filter paper (manufactured by Kiriyama Seisakusho, No. 5B), it was washed with 4 mL of DMSO. The resulting white solid was dissolved in 5 mL of THF and reprecipitated with 100 mL of methanol. This suspension was filtered through a 0.5 μm membrane filter and then washed with 10 mL of methanol. The obtained white solid was dried under reduced pressure (50° C., 1.5 hours) to obtain 483.0 mg of PMOST-b-PTMSS. Analysis by GPC revealed that Mn=35,865 and Mw/Mn=1.10, indicating an improved degree of dispersion.

[Example 2]
610.0 mg of PTMSS-b-PMOST obtained in Synthesis Example 2 was suspended in 6 mL of 2-butanol and stirred at room temperature for 1 hour. Then, it was filtered through a 0.5 μm membrane filter and washed with 10 mL of 2-butanol. The resulting white solid was dissolved in 5 mL of THF and reprecipitated with 100 mL of methanol. This suspension was filtered through a 0.5 μm membrane filter and then washed with 10 mL of methanol. The obtained white solid was dried under reduced pressure (50° C., 1.5 hours) to obtain 500.0 mg of PTMSS-b-PMOST. Analysis by GPC revealed that Mn=34,886 and Mw/Mn=1.12, indicating an improved degree of dispersion.

[Example 3]
605.0 mg of PTMSS-b-PMOST obtained in Synthesis Example 2 was suspended in 6 mL of 1-hexanol and stirred at room temperature for 1 hour. Then, it was filtered through a 1.0 μm membrane filter and washed with 8 mL of 1-hexanol. The resulting white solid was dissolved in 5 mL of THF and reprecipitated with 100 mL of methanol. This suspension was filtered through a 0.5 μm membrane filter and then washed with 10 mL of methanol. The obtained white solid was dried under reduced pressure (50° C., 1.5 hours) to obtain 478.4 mg of PTMSS-b-PMOST. Analysis by GPC revealed that Mn=34,933 and Mw/Mn=1.12, indicating an improved degree of dispersion.

[Example 4]
605.0 mg of PTMSS-b-PMOST obtained in Synthesis Example 2 was suspended in 6 mL of tert-butanol and stirred at room temperature for 1 hour. Then, it was filtered through a 1.0 μm membrane filter and washed with 8 mL of tert-butanol. The resulting white solid was dissolved in 5 mL of THF and reprecipitated with 100 mL of methanol. This suspension was filtered through a 0.5 μm membrane filter and then washed with 10 mL of methanol. The obtained white solid was dried under reduced pressure (50° C., 1.5 hours) to obtain 478.4 mg of PTMSS-b-PMOST. Analysis by GPC revealed that Mn=33,152 and Mw/Mn=1.14, indicating an improved degree of dispersion.

[Comparative Example 1]
When 10 mg of PMOST-b-PTMSS obtained in Synthesis Example 1 was added to 0.5 mL of NMP, it dissolved and no suspension was obtained.

As described above, according to the method for producing a block polymer of the present invention, it was possible to obtain a block polymer with an improved degree of dispersion.

1 Two-liquid mixing mixer 2 Joint member 21 Main body 211 Insertion hole 212 Introduction hole 213 Connection hole 22 Inner tube 221 Inner tube inner side 222 Inner tube outer wall 223 Inner tube tip 24 Space 25 Double tube 3 Static mixer member 31 Cylindrical body 32 element body 321 right twisted blade 322 left twisted blade 4 flow reactor

Claims (25)

Using a flow reactor equipped with a flow reactor capable of mixing a plurality of liquids and a two-liquid mixing mixer equipped with a joint member having a double pipe inside and a static mixer member , the first monomer is added in the presence of an initiator. a step of anionically polymerizing to synthesize a homopolymer; a step of block-polymerizing the homopolymer with a second monomer different from the first monomer to synthesize a block polymer; washing with a solvent that dissolves the homopolymer obtained only from the monomer but does not dissolve the homopolymer obtained only from the second monomer and the block polymer. 2. The method for producing a block polymer according to claim 1, wherein said static mixer member comprises a cylindrical body and an element body inserted therein. 2. The joint member and the static mixer member are connected so that the end face of the cylindrical body on the side of the double pipe abuts the end face of the double pipe on the side of the static mixer member. A method for producing the described block polymer. 4. The method for producing a block polymer according to claim 3, wherein the end of the double pipe on the side of the static mixer member is inside the joint member. The joint member has an insertion hole for inserting an inner tube through which the initiator solution flows, and in a state in which the inner tube is inserted, at least near the tip of the inner tube, the inside of the inner tube and the inner tube 5. The method for producing a block polymer according to any one of claims 1 to 4, wherein the space constructed by the outer wall of the pipe and the inner wall of the insertion hole forms the double pipe. 6. The method for producing a block polymer according to claim 5, wherein the joint member has an introduction hole for introducing the monomer solution, and the introduction hole is connected to the insertion hole. The insertion hole is formed to have substantially the same diameter as the outer diameter of the inner pipe in the vicinity of the connecting portion with the introduction hole, and the inner pipe extends from the connecting portion to the tip of the inner pipe. 7. The method for producing a block polymer according to claim 6, wherein the pore diameter is larger than the outer diameter. 8. The method for producing a block polymer according to any one of claims 5 to 7, wherein the joint member has a static mixer member connection hole, and the insertion hole is connected to the connection hole. 9. The element body according to any one of claims 2 to 8, wherein the element body is inserted into the cylindrical body so that one end thereof is substantially flush with the end face of the cylindrical body on the double tube side. A method for producing a block polymer of 10. The method for producing a block polymer according to any one of claims 2 to 9, wherein the element body has a shape in which a plurality of right-handed twisted blades and left-handedly twisted blades are alternately connected in the torsion axis direction. The method for producing a block polymer according to any one of claims 1 to 10, wherein the initiator is a monoorganolithium compound. The method for producing a block polymer according to any one of claims 1 to 11, wherein the first monomer and the second monomer are aromatic vinyl compounds. 13. The method for producing a block polymer according to claim 12, wherein the aromatic vinyl compound is a styrene derivative represented by the following formula (1).

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² ～R ⁶ are each independently a hydrogen atom, an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 10 carbon atoms optionally substituted by a halogen atom, —OSiR ⁷ ₃ or -SiR ⁷ ₃ and R ⁷ each independently represents an alkyl group having 1 to 10 carbon atoms, a phenyl group, an alkoxy group having 1 to 5 carbon atoms or an alkylsilyl group having 1 to 5 carbon atoms. ) 14. The method for producing a block polymer according to claim 13, wherein the first monomer is a compound represented by the following formula (2), and the second monomer is a compound represented by the following formula (3).

(In the formula, R ¹¹ and R ^{twenty one} are each independently a hydrogen atom or a methyl group, and R ¹² ～R ¹⁶ are each independently a hydrogen atom, an alkoxy group having 1 to 5 carbon atoms, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, but at least one an alkoxy group and R ^{twenty two} ～R ²⁶ are each independently a hydrogen atom, —OSiR ²⁷ ₃ or -SiR ²⁷ ₃ but at least one -OSiR ²⁷ ₃ or -SiR ²⁷ ₃ and R ²⁷ each independently represents an alkyl group having 1 to 10 carbon atoms, a phenyl group, an alkoxy group having 1 to 5 carbon atoms or an alkylsilyl group having 1 to 5 carbon atoms. ) R. ¹⁴ is an alkoxy group having 1 to 5 carbon atoms, and R ^{twenty four} is-SiR ²⁷ ₃ 15. The method for producing a block polymer according to claim 14. R. ¹⁴ is a methoxy group, and R ^{twenty four} is-Si(CH ₃ ) ₃ 16. The method for producing a block polymer according to claim 15. 17. Any one of claims 14 to 16, wherein the solvent that dissolves the homopolymer obtained only from the first monomer but does not dissolve the homopolymer obtained only from the second monomer and the block polymer is dimethyl sulfoxide. A method for producing the block polymer according to the paragraph. 14. The method for producing a block polymer according to claim 13, wherein the first monomer is a compound represented by the following formula (3), and the second monomer is a compound represented by the following formula (2).

(In the formula, R ¹¹ and R ^{twenty one} are each independently a hydrogen atom or a methyl group, and R ¹² ～R ¹⁶ are each independently a hydrogen atom, an alkoxy group having 1 to 5 carbon atoms, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, but at least one an alkoxy group and R ^{twenty two} ～R ²⁶ are each independently a hydrogen atom, —OSiR ²⁷ ₃ or -SiR ²⁷ ₃ but at least one -OSiR ²⁷ ₃ or -SiR ²⁷ ₃ and R ²⁷ each independently represents an alkyl group having 1 to 10 carbon atoms, a phenyl group, an alkoxy group having 1 to 5 carbon atoms or an alkylsilyl group having 1 to 5 carbon atoms. ) R. ¹⁴ is an alkoxy group having 1 to 5 carbon atoms, and R ^{twenty four} is-SiR ²⁷ ₃ 19. The method for producing a block polymer according to claim 18. R. ¹⁴ is a methoxy group, and R ^{twenty four} is-Si(CH ₃ ) ₃ The method for producing a block polymer according to claim 19. Claims 18 to 18, wherein the solvent dissolves the homopolymer obtained only from the first monomer but does not dissolve the homopolymer obtained only from the second monomer and the block polymer is an alcohol having 4 to 7 carbon atoms. 21. A method for producing a block polymer according to any one of 20. A step of anionically polymerizing a first monomer in the presence of an initiator to synthesize a homopolymer using a flow reactor equipped with a two-liquid mixing mixer equipped with a channel capable of mixing a plurality of liquids, and the homopolymer A step of block polymerizing a second monomer different from the first monomer to synthesize a block polymer, and a homopolymer obtained only from the first monomer is dissolved, but the first a step of washing with a solvent in which the homopolymer and the block polymer obtained only from the monomers of 2 are not dissolved, wherein the first monomer is a compound represented by the following formula (2), and the second monomer is , a compound represented by the following formula (3),
A method for producing a block polymer.

(In the formula, R ¹¹ and R ^{twenty one} are each independently a hydrogen atom or a methyl group, and R ¹² , R ¹³ , R ¹⁵ , and R ¹⁶ are each independently a hydrogen atom, an alkoxy group having 1 to 5 carbon atoms, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom; ¹⁴ is an alkoxy group having 1 to 5 carbon atoms, and R ^{twenty two} , R ^{twenty three} , R ^{twenty five} , and R ²⁶ are each independently a hydrogen atom, —OSiR ²⁷ ₃ or -SiR ²⁷ ₃ and R ^{twenty four} Ha-SiR ²⁷ ₃ and R ²⁷ each independently represents an alkyl group having 1 to 10 carbon atoms, a phenyl group, an alkoxy group having 1 to 5 carbon atoms or an alkylsilyl group having 1 to 5 carbon atoms. ) A step of anionically polymerizing a first monomer in the presence of an initiator to synthesize a homopolymer using a flow reactor equipped with a two-liquid mixing mixer equipped with a channel capable of mixing a plurality of liquids, and the homopolymer A step of block polymerizing a second monomer different from the first monomer to synthesize a block polymer, and a homopolymer obtained only from the first monomer is dissolved, but the first The homopolymer and the block polymer obtained only from the monomers of 2 include a step of washing with a solvent that does not dissolve, the first monomer is a compound represented by the following formula (3), and the second monomer is , a compound represented by the following formula (2),
A method for producing a block polymer.

(In the formula, R ¹¹ and R ^{twenty one} are each independently a hydrogen atom or a methyl group, and R ¹² , R ¹³ , R ¹⁵ , and R ¹⁶ are each independently a hydrogen atom, an alkoxy group having 1 to 5 carbon atoms, or an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom; ¹⁴ is an alkoxy group having 1 to 5 carbon atoms, and R ^{twenty two} , R ^{twenty three} , R ^{twenty five} , and R ²⁶ are each independently a hydrogen atom, —OSiR ²⁷ ₃ or -SiR ²⁷ ₃ and R ^{twenty four} Ha-SiR ²⁷ ₃ and R ²⁷ each independently represents an alkyl group having 1 to 10 carbon atoms, a phenyl group, an alkoxy group having 1 to 5 carbon atoms or an alkylsilyl group having 1 to 5 carbon atoms. ) Using a flow reactor equipped with a flow reactor capable of mixing a plurality of liquids and a two-liquid mixing mixer equipped with a joint member having a double pipe inside and a static mixer member , the first monomer is added in the presence of an initiator. Anion polymerization is performed to synthesize a homopolymer , and a block polymer obtained by block-polymerizing a second monomer to the homopolymer is obtained by dissolving the homopolymer obtained only from the first monomer, but dissolving the second monomer. A method for purifying a block polymer, wherein the homopolymer obtained from chisel and the block polymer are washed with a solvent in which the block polymer is not dissolved. 25. The block polymer according to claim 24, wherein the flow reactor is a flow reactor comprising a two-liquid mixing mixer comprising a flow path capable of mixing a plurality of liquids and a joint member or a static mixer member having a double pipe inside. purification method.

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