WO2019031435A1 - Method for producing block polymer - Google Patents

Abstract

Provided is a method for producing a block polymer, the method including: a step of synthesizing a polymer by subjecting a styrene-based monomer as a first monomer to anionic polymerization in the presence of an initiator using a flow reactor comprising a two-liquid blending mixer provided with a flow path capable of blending a plurality of liquids; and a step of synthesizing a block polymer by block polymerizing an acrylic monomer as a second monomer with the polymer. The flow reactor comprises a two-liquid blending mixer which is provided therein with: a joint member having a double pipe; or a static mixer member.

Description

Method for producing block polymer

The present invention relates to a method of producing a block polymer.

BACKGROUND ART In recent years, flow chemistry in which chemical synthesis is continuously performed while flowing a solution using a reaction apparatus called a flow reactor or a microreactor attracts attention. Flow chemistry has the advantage that precise temperature control is possible and the mixing efficiency is good because reactions are carried out using a small reaction vessel, as compared with the batch method conventionally practiced.

In the two-liquid mixed flow synthesis, insoluble matter often precipitates in the mixing part (mixer), and the flow path is blocked, causing pressure fluctuation, and continuous operation can not be performed for a long time, or the quality of the obtained compound is It becomes a problem that it is not stable. In particular, in a reaction system using an organolithium reagent such as anionic polymerization of a polymer, this problem is remarkable, and it is not easy to achieve stable long-term continuous operation and highly efficient mixing at the same time.

JP, 2009-067999, A

The present invention has been made in view of the above circumstances, and an object thereof is to provide a method capable of stably producing a block polymer for a long time.

As a result of intensive studies to achieve the above object, the present inventors produced a block polymer containing a polymer block derived from a styrenic monomer and a polymer block derived from an acrylic monomer, By using a predetermined flow reactor, it has been found that a block polymer can be stably produced over a long time, and the present invention has been completed.

Accordingly, the present invention provides the following method for producing a block polymer.
1. A step of anionically polymerizing a styrenic monomer as a first monomer in the presence of an initiator to synthesize a polymer, using a flow reactor comprising a two-liquid mixing mixer having a flow path capable of mixing a plurality of liquids; A method for producing a block polymer, comprising block polymerizing an acrylic monomer as a second monomer to the polymer to synthesize a block polymer,
The method for producing a block polymer, wherein the flow reactor comprises a two-component mixing mixer including a joint member having a double pipe inside or a static mixer member.
2. A method for producing a block polymer according to 1, comprising the step of reacting a non-homopolymerizable monomer before anionically polymerizing a first monomer to synthesize a polymer and then block polymerizing a second monomer.
3. The method for producing the block polymer according to 1 or 2, wherein the non-homopolymerizable monomer is 1,1-diphenylethylene or a derivative thereof.
4. The method for producing a block polymer according to any one of 1 to 3, wherein the static mixer member comprises a cylindrical body and an element body inserted into the inside of the cylindrical body.
5. The method for producing a block polymer according to any one of 1 to 4, wherein the mixer for two-component mixing comprises a joint member having a double pipe inside and a static mixer member.
6. The two-component mixing mixer includes a joint member having a double pipe therein and a static mixer member,
The static mixer member comprises a tubular body and an element body inserted therein;
The block of 5, wherein the joint member and the static mixer member are connected such that the end face of the cylindrical body on the double pipe side abuts against the end face of the double pipe on the static mixer member side Method of producing a polymer
7. The manufacturing method of the block polymer of 6 whose end by the side of the static mixer member of the said double pipe | tube exists in the inside of the said joint member.
8. The joint member has an insertion hole for inserting an inner pipe through which an initiator solution flows, and in a state where the inner pipe is inserted, the inner pipe inner side and the inner pipe at least near the tip of the inner pipe. The method for producing a block polymer according to any one of 5 to 7, wherein the double pipe is formed by a pipe outer wall and a space constructed by the inner wall of the insertion hole.
9. The method for producing the block polymer according to claim 8, wherein the joint member has an introduction hole for introducing a monomer solution, and the introduction hole is connected to the insertion hole.
10. The insertion hole is formed to have a hole diameter substantially the same as the outer diameter of the inner pipe in the vicinity of the connection portion with the introduction hole, and from the connection portion to the tip of the inner pipe 9. A method for producing a block polymer of 9 formed to have a pore diameter larger than the outer diameter.
11. The method for producing a block polymer according to any one of 8 to 10, wherein the joint member has a static mixer member connecting hole, and the insertion hole is connected to the connecting hole.
12. The production of a block polymer according to any one of 4 to 11, wherein the element body is inserted into the tubular body such that one end thereof is substantially flush with the end face of the tubular body on the double tube side Method.
13. The method for producing a block polymer according to any one of 4 to 12, wherein the element body has a shape in which a right twist blade and a left twist blade are alternately and continuously connected in the twist axis direction.
14. The method for producing a block polymer according to any one of 1 to 13, wherein the initiator is a mono-organolithium compound.
15. The method for producing a block polymer according to any one of 1 to 14, wherein the styrenic monomer is a compound represented by the following formula (1):

(Wherein, 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 a carbon number which may be substituted with a halogen atom) an alkyl group having 1 to 10, -OSiR ⁷ ₃ or -SiR ⁷ _3, R ⁷ are independently an alkyl group having 1 to 10 carbon atoms, a phenyl group, an alkoxy group or a carbon number of 1 to 5 carbon atoms 1 to 5 alkylsilyl groups.)
16. The method for producing a block polymer according to any one of 1 to 15, wherein the acrylic monomer is a compound represented by the following formula (2):

(Wherein, R ¹¹ represents a hydrogen atom or a methyl group, and each R ¹² independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or 6 carbon atoms An aryl group of -20, or an aralkyl group having 7 to 20 carbon atoms.)

The two-liquid mixing mixer used in the flow reactor is difficult to be clogged and has a good mixing efficiency. Therefore, according to the method of producing a polymer of the present invention using the same, the polymer can be stably produced over a long time it can. In particular, the block polymer obtained by the production method of the present invention has a low degree of dispersion (Mw / Mn) (narrow molecular weight distribution), and the structure is controlled to a high order, and the semiconductor lithography technology by induced self-assembly and others The present invention can be applied to the application to nanopatterning technology or to the production of highly functional elastomers and the like.

It is a perspective view which concerns on the form of the mixer for 2 liquid mixing used by this invention. It is a disassembled perspective view of the mixer for two-component mixing of FIG. FIG. 3 is a cross-sectional view of the main body taken along line III-III of FIG. 2; FIG. 4 is a cross-sectional view taken along the line IV-IV of FIG. It is an expanded sectional view of the double tube | pipe part of FIG. It is a bottom view of the main body in the state where the inner pipe was inserted. It is the figure which looked at the element body of the static mixer member from the orthogonal direction to the twist axis direction. It is a perspective view which shows the form of the mixer for 2 liquid mixing used by this invention. It is a schematic diagram which shows the form of the flow reactor used by this invention. It is a schematic diagram which shows the structure of the flow reactor used in the Example. It is a schematic diagram which shows the structure of the flow reactor used in the comparative example. 5 is a graph showing the pressure trend during the reaction in Example 1. FIG. 1 is a ¹ H-NMR chart of a polymer obtained in Example 1. It is a graph which shows the pressure trend in reaction in the comparative example 1. FIG. It is a graph which shows the pressure trend during reaction in comparative example 2.

The method for producing a block polymer of the present invention uses a flow reactor equipped with a two-liquid mixing mixer provided with a flow path capable of mixing a plurality of liquids, and uses a styrenic monomer as the first monomer in the presence of an initiator. It comprises the steps of polymerizing to synthesize a homopolymer, and block polymerizing said homopolymer with an acrylic monomer as a second monomer to synthesize a block polymer.

[Flow reactor]
The flow reactor is not particularly limited as long as it is equipped with a two-component mixing mixer having a double pipe inside, but one having the following configuration is preferable. That is, the mixer for two-component mixing preferably has a joint member having a double pipe inside or a static mixer member. It is more preferable that the mixer for two-component mixing includes both a joint member having a double pipe inside and a static mixer member, and the static mixer member is a cylindrical body and an element body inserted into the inside thereof. And the joint member and the static mixer member are connected such that the end face of the cylindrical body on the double pipe side abuts on the end face of the double pipe on the static mixer member side. More preferred.

In this manner, the joint member and the static mixer member are connected such that the end surface of the cylindrical body on the double tube side abuts with the end surface of the double tube on the static mixer member side. The mixer, while maintaining the mixing efficiency, is not easily clogged, and stable long-term continuous operation is possible.

That is, the mixer has a configuration in which the double pipe and the static mixer (the cylindrical body of the mixer) are connected inside the joint, but the abutment of each end face is more reliably compared to the conventional microreactor structure As a result, since the two liquids flowing out of the double pipe will flow into the static mixer almost simultaneously when flowing out, more reliable mixing of the two liquids is performed at the start of the reaction.

In the mixer for two-component mixing, it is preferable that an end portion on the static mixer member side of the double pipe is inside the joint member. With such a configuration, the construction of the double pipe is simplified, so that the manufacture of the joint member is facilitated, and the contact between the joint member and the static mixer member is easily confirmed.

In the mixer for two-component mixing, the joint member has an insertion hole for inserting an inner pipe through which the first liquid flows, and in the state where the inner pipe is inserted, at least near the end of the inner pipe Preferably, the double pipe is formed by the inner side of the inner pipe and a space formed by the inner pipe outer wall and the inner wall of the insertion hole. With such a configuration, the construction of the double pipe is simplified, and as a result, the manufacture of the joint member is facilitated.

This insertion hole can be formed by cutting, using a mold provided with a mold corresponding to the insertion hole, or the like. At this time, the inner pipe is detachably fixed from the joint member main body even if the inner pipe is fixed to the joint member main body in a state inserted in the insertion hole formed in the joint member as long as liquid tight can be maintained. Although it may be fixed, it is preferable to be removably fixed from the joint member main body. By making the inner pipe removable in this way, it becomes easy to clean the double pipe after use, and it can be replaced if the inner pipe is broken, blocked or contaminated. It has the advantage of

The means for fixing and fixing the inner pipe is not particularly limited as long as it can maintain liquid tightness as described above, but fixing with an adhesive, fixing with welding, etc. or removable fixing means with screw fastening etc. may be mentioned. It is preferred to use removable fixing means, such as by fastening.

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

Further, although the formation position of the introduction hole in the joint member is not particularly limited, it is preferable to form in the direction orthogonal to the insertion hole, and in consideration of shortening the length of the double pipe, It is preferable to form in the position which can be connected with an insertion hole in the near end part rather than the center part of an end and an end part.

Further, the insertion hole is formed to have a hole diameter substantially the same as the outer diameter of the inner pipe in the vicinity of the connection portion with the introduction hole, and the inside from the connection portion to the tip of the inner pipe is The hole diameter is preferably larger than the outer diameter of the tube. By setting it as the hole structure which has such a different diameter, since a space is hardly formed between the inner pipe and the insertion hole in the connection portion, the proximal end portion of the insertion hole of the second liquid flowing from the introduction hole Leakage to the side can be prevented, and the two solutions can be efficiently mixed.

Preferably, the joint member has a static mixer member connecting hole, and the insertion hole is connected to the connecting hole. With such a configuration, since the joint member and the static mixer member can be designed separately, adjustment of the internal structure of the two-component mixing mixer is facilitated. Similar to the insertion holes, the connection holes can be formed by cutting or using a die.

Similar to the above-described inner pipe, the static mixer member is also fixed to the joint member main body in a state of being inserted in the connection hole formed in the joint member as long as liquid tightness can be maintained. It may be releasably fixed from the member body, but is preferably fixed releasably from the joint member body. By making it removable, it becomes easy to adjust the position of the element body inside the static mixer member and to clean the mixer after use, and it becomes possible to replace each part when it becomes contaminated or deteriorated. The fixing and fixing means of the static mixer member may be the same as the means described for the inner pipe, but also in this case, it is preferable to use a removable fixing means by screw fastening or the like.

Furthermore, it is preferable that the element body is inserted into the inside of the cylindrical body such that one end thereof is substantially flush with an end face of the cylindrical body on the side of the double pipe. As described above, when the end face of the cylindrical body substantially coincides with the end of the element body, the two liquids flowing out of the double pipe will flow into the element body and be mixed almost simultaneously as they flow out, From the start of the reaction, more efficient mixing and stirring will be performed.

The shape of the cylindrical body is not particularly limited, but is preferably cylindrical in consideration of the flowability and mixing property of the two liquids passing through the inside.

The structure of the element body is not particularly limited, and can be appropriately selected from those used as an element body of a static mixer. For example, the right and left torsion blades extend in the longitudinal direction (torsion axis direction And the like), those having a shape in which a plurality of alternating lines are formed, those having a spiral shape with a constant twisting direction, and those in which a plurality of plates provided with one or more holes are stacked, etc. It is preferable that the blade and the left twist blade have a shape in which plural blades are alternately connected in the twist axis direction. By using the element body of such a shape, it becomes possible to mix more efficiently, and blocking of the mixer at the time of reaction also becomes less likely to occur.

The element body may be a removable structure that is simply inserted into the tubular body, or may be a non-removable structure that is inserted and then fixed to the inside of the tubular body, but is only removable. It is preferable to set it as the following structure. The removable structure facilitates the adjustment of the position inside the cylindrical body of the element body and the 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 it is preferable that the diameter (maximum diameter) thereof is 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 inside the cylindrical body. The diameter of the element body is preferably about 1 to 10 mm, more preferably about 1.6 to 8 mm, and still more preferably about 2 to 5 mm, in consideration of the application of the mixer for mixing two liquids.

Further, the length of the element body is not particularly limited as long as it can be inserted into the inside of the cylindrical body, but it is preferable to make the length substantially the same as the length of the cylindrical body. In this way, the alignment between the end of the element body and the end face of the tubular body on the double tube side is facilitated.

The flow reactor used in the present invention is provided with the mixer for two-component mixing. The flow reactor may include one or two or more mixers for mixing the two liquids. When two or more mixers for two-component mixing are provided, multistage flow synthesis is possible. The two-component mixing mixer is less likely to be clogged, so there is less pressure loss when flow synthesis is performed using a flow reactor, stable long-term continuous operation is possible, and it is suitable for mass synthesis.

In the flow reactor used in the present invention, in addition to the mixer for two-component mixing, other components necessary for reactions such as a pump for liquid transfer, a tube for flow path formation, a temperature control device for temperature control, etc. The various members of may be provided.

The feed pump is not particularly limited, and commonly used pumps such as a plunger pump, a syringe pump, and a rotary pump can be used.

The material of the tube for forming the flow path is not particularly limited, and metals such as stainless steel, titanium, iron, copper, nickel, and aluminum, polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer It may be a resin such as (FEP), perfluoroalkoxy fluorine (PFA), polyetheretherketone (PEEK), polypropylene (PP) or the like.

The inner diameter of the tube for forming the flow path may be appropriately set according to the purpose within the range that does not impair the effects of the present invention, but generally, about 0.5 to 10 mm is preferable, and about 0.7 to 4 mm is more preferable. Preferably, about 1 to 2 mm is more preferable. The length of the tube for forming the flow path may be appropriately set according to the purpose as long as the effects of the present invention are not impaired. Usually, about 0.1 to 20 m is preferable, and about 0.2 to 10 m is more preferable. Preferably, about 0.3 to 5 m is more preferable.

Hereinafter, the mixer for two-component mixing and the flow reactor used in the present invention will be specifically described based on the drawings. As shown in FIG. 1, the two-component mixing mixer 1 includes a joint member 2 and a static mixer member 3. The joint member 2 includes a stainless steel main body 21 and a stainless steel inner pipe 22 (outside diameter: 1.6 mm, inside diameter: 1.0 mm) through which the first liquid flows.

As shown in FIGS. 2 and 3, the main body 21 is an insertion hole 211 for inserting the inner tube 22, and a second liquid orthogonal to the insertion hole 211 and connected to the insertion hole 211 inside the main body 21. And a static mixer member connecting hole 213. On the inner wall of the insertion hole 211, the introduction hole 212, and the connection hole 213, female screw parts 211a, 212a, 213a corresponding to the male screw parts formed in each connector described later are formed. The introduction tube through which the liquid flows and the static mixer member 3 can be fixed to the main body 21 by screw fastening.

The insertion hole 211 has a female screw portion 211a from the base end side to the terminal end side, and a liquid-tight portion 211b which is subsequently formed and has a trapezoidal cross-sectional diameter-reduced in accordance with a connector tip shape described later. It is comprised from the inner pipe | tube passage part 211c formed following this. Here, as shown in FIG. 5, the inner diameter b of the inner pipe passage portion 211 c of the insertion hole 211 has a hole diameter 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. The inner diameter c of the inner pipe passage portion 211 c 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 while being formed as described above. In this manner, a gap is hardly formed between the inner pipe 22 and the insertion hole 211 at the connection portion 214, and the second liquid flowing from the introduction hole 212 leaks to the proximal end side of the insertion hole 211. , And as shown in FIG. 6, the double pipe 25 is constructed by the space 24 formed by the inner pipe inner side 221 and the inner pipe outer wall 222 and the inner wall 211d of the insertion hole. .

Further, as shown in FIG. 3, the insertion hole 211 is connected to the connection hole 213 at its base end, whereby the hole formed by the insertion hole 211 and the connection hole 213 is a main body. 21 penetrates.

As shown in FIG. 2, the inner pipe 22 is formed with a hole (not shown) through which the inner pipe 22 passes, and is formed integrally with a substantially hexagonal columnar head 232 for screwing. Then, the connector 23 having the male screw portion 231 and the seal portion 233 having an inverted truncated cone shape for maintaining fluid tightness inside the joint body 21 is attached, and in this state, the insertion hole 211 having the above-mentioned female screw portion 211a. It is inserted and fixed to the main body 21 by screw fastening.

As shown in FIG. 3, the introduction hole 212 has a female screw portion 212a from the proximal end side to the terminal end side, and a liquid having a rectangular cross section according to the shape of a connector tip portion described later, which is subsequently formed. It comprises a dense portion 212 b and a connecting portion 212 c extending from there to a connecting portion 214 to the insertion hole 211. The insertion hole 211 and the introduction hole 212 are connected closer to the end than the center of the proximal end and the end of the insertion hole 211.

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

The static mixer member 3 is, as shown in FIGS. 1 and 2, a cylindrical tubular member 31 (inner diameter 3.0 mm) made of fluorine resin or stainless steel, and an element body 32 made of polyacetal inserted in the inside thereof. (3 mm diameter) and. As shown in FIGS. 2 and 4, the element body 32 is inserted into the tubular body 31 in a state where the base end thereof is flush with the end face of the tubular body 31 on the double tube 25 side. Here, as shown in FIG. 7, the element body 32 has a shape in which a plurality of right twist blades 321 and left twist blades 322 are alternately arranged in the direction of a twist axis (central axis in the longitudinal direction) 323. .

As shown in FIG. 2, at the upper end portion of the cylindrical body 31 in the drawing, a hole (not shown) through which the cylindrical body 31 passes is formed inside, and a fluorine resin connector 33 having a male screw portion 331 Is inserted into the connection hole 213 having the above-mentioned female screw portion 213a, and is fixed to the main body 21 by screw fastening.

Subsequently, the internal structure of the two-component mixing mixer 1 having the above-described configuration will be described with reference to FIGS. As described above, the hole diameter of the insertion hole 211, specifically, the inner diameter b of the inner pipe passage portion 211c in the vicinity of the connection portion 214 with the introduction hole 212 is substantially the same as the outer diameter a of the inner pipe 22. Further, the inner diameter c of the inner pipe passage portion 211c from the connection portion 214 between the insertion hole 211 and the introduction hole 212 to the end 223 of the inner pipe 22 on the static mixer member 3 side is formed larger than the outer diameter a of the inner pipe 22. It is done. Thus, the double pipe 25 is formed by the inner side 221 of the inner pipe 22 and the space 24 formed by the outer wall 222 of the inner pipe 22 and the inner wall 211 d of the insertion hole 211.

Further, the end face of the cylindrical body 31 of the static mixer member 3 on the double tube 25 side is in contact with the end face of the double tube 25 on the static mixer member 3 side, and in the present embodiment, as described above Since the base end of the element body 32 is flush with the end face of the cylindrical body 31 on the double pipe 25 side, the end face of the double pipe 25 on the static mixer member 3 side and the base end of the element body 32 (see FIG. 4) The middle upper end is also in contact.

The second liquid is introduced from the introduction hole 212. In this case, as shown in FIG. 8, the introduction tube 26 through which the second liquid flows is a hole through which the introduction tube 26 passes (not shown) And a connector 27 having a male screw 271 and a seal (not shown) for maintaining liquid tightness inside the joint main body 21 and fixedly connected to the introducing hole 212 by screw fastening.

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

A first liquid feed pump 41a is connected to the inner pipe 22a of the first two-liquid mixing mixer 1a via a PTFE tube 42a (inner diameter: 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, the second liquid feed pump 41b is provided with PTFE at the tip thereof through which the second liquid flows. It is connected via a tube 42b (inner diameter: 1.0 mm).

In the introduction hole of the two-liquid mixing mixer 1b, a third pump 41c for liquid transfer is provided via a PTFE tube 42c (inner diameter 1.0 mm) through which the third liquid provided with a connector at its tip flows. A PTFE tube 42e (inner diameter: 1.5 mm) is connected to the end of the static mixer member 3b of the two-component mixing mixer 1b.

In the flow reactor 4 having such a configuration, each liquid fed from the first liquid feed pump 41a and the second liquid feed pump 41b is a joint member of the first two-liquid mixing mixer 1a. After flowing into the main body 21a and passing through the double pipe built in the inside, it flows into the static mixer member 3a in contact with the end of the double pipe, and while being mixed and stirred by the element body inside The first reaction occurs. The first reaction liquid after reaction passes through the tube 42d, and then flows into the joint member main body 21b through the inner pipe 22b of the second two-liquid mixing mixer 1b. The first reaction liquid passes through the double pipe in the joint member main body 21b together with the third liquid sent from the third liquid delivery pump 41c and flowing 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.

In addition, the mixer and flow reactor for two-liquid mixing used by this invention are not limited to each embodiment mentioned above, You may perform the change and improvement in the range which can achieve the objective of this invention, and an effect.

That is, in the two-component mixing mixer 1 described above, the inner pipe 22 and the static mixer member 3 are removably screwed to the joint member main body 21, but these are configured to be removable by other fixing means. It may be connected and fixed in a non-removable manner.

Moreover, although the connectors 23 and 33 of another body were provided in the inner pipe 22 and the cylindrical body 31, even if it forms these fixing means suitable for the inner pipe and cylindrical body itself without providing these. Good.

Furthermore, although the introduction hole 212 is formed in the joint member main body 21 in a manner to be orthogonally connected to the insertion hole 211, it may be connected to the insertion hole at another angle, and the position of the introduction hole 212 is also arbitrary. It can be set in place of

The material of the main body 21, the inner pipe 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 etc., PTFE, FEP, PFA, PEEK, PP etc. It may be a resin.

The inner diameter of the inner pipe 22 may be appropriately set according to the purpose within the range that does not impair the effects of the present invention, but generally, about 0.1 to 3 mm is preferable, and about 0.5 to 2 mm is more preferable. About 5 to 1 mm is more preferable. The outer diameter of the inner pipe 22 may be appropriately set according to the purpose within the range that does not impair the effects of the present invention, but generally, about 0.8 to 4 mm is preferable, and about 0.8 to 3 mm is more preferable. It is more preferable that the distance be about 8 to 1.6 mm.

The hole diameter c of the insertion hole 211 may be appropriately set according to the purpose within the range that does not impair the effects of the present invention, but generally, about 0.1 to 5 mm is preferable and about 0.5 to 4 mm is more preferable. 8 to 2 mm is more preferable.

The material of the cylindrical body 31 is not limited to stainless steel, and may be another metal such as titanium, iron, copper, nickel, or aluminum, or a resin such as PTFE, FEP, PFA, PEEK, or 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.

In addition, the shape of the element body 32 may be a spiral shape having a constant twisting direction, a plurality of plates provided with one or more holes, or the like.

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

The inner diameter of the cylindrical body 31 may be appropriately set according to the purpose within the range that does not impair the effects of the present invention, but generally, about 1 to 10 mm is preferable, about 1.6 to 8 mm is more preferable, and 2 to 5 mm The degree is even more preferred. Also, the diameter of the element body 32 may be appropriately set according to the purpose within the range not impairing the effects of the present invention, and usually about 1 to 10 mm is preferable, about 1.6 to 8 mm is more preferable, and 2 to 5 mm The degree is even more preferred.

The flow reactor 4 is provided with two two-liquid mixing mixers, so two-stage flow synthesis is possible, but when performing one-step flow synthesis, one two-liquid mixing mixer may be used. When n-stage flow synthesis is performed, the flow reactor may be assembled as described above using n two-liquid mixing mixers.

Further, the inner diameters of the tubes 42a to 42e constituting the flow reactor 4 may be appropriately set according to the purpose within the range that does not impair the effects of the present invention, but in general 0.5 to 10 mm is preferable, 0.7 It is more preferably about 4 mm, and even more preferably about 1 to 2 mm. In addition, the length may be appropriately set according to the purpose as long as the effect of the present invention is not impaired, but generally, about 0.1 to 20 m is preferable, about 0.2 to 10 m is more preferable, and 0.3 to About 5 m is more preferable.

[First monomer]
The styrene-based monomer as the first monomer is not particularly limited as long as it is a styrene derivative, but those represented by the following formula (1) are preferable.

In the formula, R ¹ represents a hydrogen atom or a methyl group. 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 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 having 1 to 10 carbon atoms may be linear, branched or cyclic, and specifically, 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 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 Group, 1-isopropyl-cyclopropyl group, 2-isopropyl-cyclopropyl group, 1,2,2-trimethyl-cyclic Propyl 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 And 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 preferable, those having 1 to 6 carbon atoms are more preferable, and those having 1 to 3 carbon atoms are still more preferable.

Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, a cyclopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a cyclobutoxy group, 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- Kuropuropokishi group, 2,3-dimethyl - cyclopropoxy group, 1-ethyl - cyclopropoxy group, 2-ethyl - cyclopropoxy group, and the like. The structure of the alkoxy group is preferably linear or branched. Among these, those having 1 to 3 carbon atoms are preferable.

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.

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

Specific examples of the styrene derivative 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) silyloxystyrene, 2-methoxystyrene, 3- Methoxystyrene, 4-methoxystyrene, 4-ethoxystyrene, 3,4-dimethylstyrene, 2,6-dimethylstyrene, 2,4-dimethoxystyrene, 3,4-dimethoxystyrene, 3,4,5-trimethoxystyrene Etc.

Among them, styrene, 4-tert-butylstyrene, 4-methoxystyrene, 4-trimethylsilylstyrene and the like are preferable as the styrene-based monomer from the viewpoint that monodispersed polymers can be easily obtained even at relatively high temperatures.

[Second monomer]
The acrylic monomer as the second monomer is not particularly limited as long as it is a compound having a (meth) acryloyl group, but one having one (meth) acryloyl group is preferable. As such a compound, those represented by the following formula (2) are particularly preferable.

In the formula, R ¹¹ is a hydrogen atom or a methyl group. R ¹² each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms is there.

The alkyl group having 1 to 20 carbon atoms may be linear, branched or cyclic, and specifically, 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, 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 group -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, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, 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, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl -Cyclopropyl group, 1-isopropyl-cyclopropyl group, 2-isopropyl-cyclopropyl group, 1,2,2-trimethyl-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 Pill group, 2-ethyl-2-methyl-cyclopropyl group, 2-ethyl-3-methyl-cyclopropyl group, n-heptyl group, 1-methyl-n-hexyl group, 2-methyl-n-hexyl group, 3-methyl-n-hexyl group, 1,1-dimethyl-n-pentyl group, 1,2-dimethyl-n-pentyl group, 1,3-dimethyl-n-pentyl group, 2,2-dimethyl-n- group Pentyl group, 2,3-dimethyl-n-pentyl group, 3,3-dimethyl-n-pentyl group, 1-ethyl-n-pentyl group, 2-ethyl-n-pentyl group, 3-ethyl-n-pentyl group Group, 1-methyl-1-ethyl-n-butyl group, 1-methyl-2-ethyl-n-butyl group, 1-ethyl-2-methyl-n-butyl group, 2-methyl-2-ethyl-n group -Butyl, 2-ethyl-3-methyl-n-butyl, n- Kutyl group, 1-methyl-n-heptyl group, 2-methyl-n-heptyl group, 3-methyl-n-heptyl group, 1,1-dimethyl-n-hexyl group, 1,2-dimethyl-n-hexyl group Group, 1,3-dimethyl-n-hexyl group, 2,2-dimethyl-n-hexyl group, 2,3-dimethyl-n-hexyl group, 3,3-dimethyl-n-hexyl group, 1-ethyl- n-hexyl group, 2-ethyl-n-hexyl group, 3-ethyl-n-hexyl group, 1-methyl-1-ethyl-n-pentyl group, 1-methyl-2-ethyl-n-pentyl group, 1 -Methyl-3-ethyl-n-pentyl group, 2-methyl-2-ethyl-n-pentyl group, 2-methyl-3-ethyl-n-pentyl group, 3-methyl-3-ethyl-n-pentyl group , N-nonyl group, n-decyl group, isodecyl group, n-un group Silyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, 16-methyl-n-octadecyl group, n-nonadecyl Groups, icosyl groups, adamantyl groups, norbornyl groups, isobornyl groups, 2-methyl-2-adamantyl groups and the like.

Examples of the halogenated alkyl group having 1 to 20 carbon atoms include those in which part or all of the hydrogen atoms of the aforementioned alkyl group are substituted with a halogen atom such as fluorine, chlorine, bromine or iodine. Specific examples thereof include trifluoromethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2,2-pentafluoroethyl group, 3,3,3-trifluoropropyl group, 2, 2,3,3,3-pentafluoropropyl group, 1,1,2,2,3,3,3-heptafluoropropyl group, 4,4,4-trifluorobutyl group, 3,3,4,4 2,4-pentafluorobutyl, 2,2,3,3,4,4,4-heptafluorobutyl, 1,1,2,2,3,3,4,4,4-nonafluorobutyl and the like Can be mentioned.

Examples of the aryl group having 6 to 20 carbon atoms include phenyl group, naphthyl group, naphthyl group, anthryl group and phenanthryl group.

Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl group, 2-phenylethyl group and anthrylmethyl group.

Among them, as R ¹² , an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms are preferable, and an alkyl group having 1 to 10 carbon atoms and 6 carbon atoms An aryl group of -14 and an aralkyl group having 7 to 15 carbon atoms are more preferable.

As the (meth) acrylic compound, 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-octadecyl (meth) acrylate, 16-methyl-n-heptadecyl (meth) acrylate , Phenyl (meth) acrylic , Naphthyl (meth) acrylate, anthryl (meth) acrylate, benzyl (meth) acrylate, 2-phenylethyl (meth) acrylate, anthrylmethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy Propyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,2-trichloroethyl (meth) acrylate, 2,2,3,3,4,4,4-heptafluorobutyl (Meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, n-butoxyethyl (meth) acrylate, 3-chloro-2-hydroxy Propyl (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 the like.

Among these, tert-butyl (meth) acrylate and isopropyl (meth) acrylate are preferable as the acrylic monomer from the viewpoint that monodispersed polymer can be easily obtained even at relatively high temperature.

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

Examples of the organic lithium compound include methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, isobutyllithium, sec-butyllithium, tert-butyllithium, pentyllithium, hexyllithium, methoxymethyllithium, ethoxy Methyllithium, phenyllithium, naphthyllithium, benzyllithium, phenylethyllithium, α-methylstyryllithium, 1,1-diphenylhexyllithium, 1,1-diphenyl 3-methylpentryllithium, 3-methyl-1,1- Diphenyl pentyl lithium, vinyl lithium, allyl lithium, propenyl lithium, butenyl lithium, ethynyl lithium, butynyl lithium, pentynyl lithium, hexynyl lithium, 2 Monoorganic lithium compounds such as thienyllithium, 4-pyridyllithium, 2-quinolyllithium; 1,4-dilithiobutane, 1,5-dilithiopentane, 1,6-dilithiohexane, 1,10-dilithiodecane, 1,1- Dilithiodiphenylene, dilithiopolybutadiene, dilithiopolyisoprene, 1,4-dilithiobenzene, 1,2-dilithio-1,2-diphenylethane, 1,4-dilithio-2-ethylcyclohexane, 1,3, Polyfunctional organolithium compounds such as 5-trilithiobenzene and 1,3,5-trilithio-2,4,6-triethylbenzene can be mentioned. Among these, mono-organic lithium compounds such as n-butyllithium, sec-butyllithium and tert-butyllithium are preferable.

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

Hereinafter, the method for producing the block polymer of the present invention will be described by taking the synthesis of a binary block polymer as an example. First, the first monomer solution containing the above-mentioned monomer is introduced into the flow reactor through the introduction hole of the first mixer, and the solution containing the above-mentioned initiator is introduced into the flow reactor through the inner pipe of the first mixer By polymerization, a homopolymer consisting of the first monomer is synthesized. 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, the pressure loss is suppressed, and the polymer is stably produced for a long time. be able to.

After synthesizing a homopolymer consisting of the first monomer, in order to adjust its reactivity, a non-homopolymerizing monomer such as 1,1-diphenylethylene (DPE) or a derivative thereof is reacted to form an end of the polymer. You may modify Here, the term "non-homopolymerizable monomer" refers to a monomer which does not cause anionic polymerization with only that monomer.

The DPE is introduced into the flow reactor from the inlet of the second mixer. In this case, DPE may be introduced into the flow reactor as it is, or may be diluted with an appropriate solvent before being introduced into the flow reactor. Examples of the solvent used for dilution include tetrahydrofuran (THF), 2-methyl THF, diethyl ether, tetrahydropyran (THP), ether solvents such as oxepane and 1,4-dioxane, toluene, dichloromethane, diethoxyethane and the like. Be The concentration of DPE is preferably 0.1 to 5.7 mol / L.

After reacting a non-polymerizable monomer such as DPE, the second monomer solution is introduced into the flow reactor from the introduction hole of the third mixer to synthesize a block polymer.

The solvent for dissolving the first monomer and the second monomer is not particularly limited, and examples thereof include THF, 2-methyl THF, diethyl ether, THP, oxepan, ether solvents such as 1,4-dioxane, toluene, dichloromethane And diethoxy ethane are preferable.

The concentration of the first monomer is 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, 0.1 Particularly preferred is -2 mol / L. The concentration of the second monomer is also not particularly limited and may be appropriately set depending on the purpose, but is preferably 0.1 to 9.4 mol / L, and more preferably 1.0 to 9.4 mol / L. Preferably, 2.0 to 9.4 mol / L is particularly preferred. If the monomer concentration is in the above-mentioned range, clogging of the flow reactor is unlikely to occur, the pressure loss is suppressed, and the polymer can be stably produced over a long time.

The flow rate of the first monomer flowing in the flow channel of the flow reactor is not particularly limited and may be appropriately set according to the purpose, but it is preferably 1 to 50 mL / min, and preferably 5 to 30 mL / min. Is more preferable, and 10 to 30 mL / min is particularly preferable. The flow rate of the second monomer is also not particularly limited and may be appropriately set depending on the purpose, but is preferably 0.1 to 50 mL / min, more preferably 0.1 to 30 mL / min, 0.1 -20 mL / min is particularly preferred. If the flow rate of the monomer is in the above range, clogging of the flow reactor is unlikely to occur, the pressure loss is suppressed, and the polymer can be stably produced over a long time.

In particular, n-butyllithium can be suitably used as the initiator. The anionic polymerization is usually carried out at a low temperature because the polymerization rate is increased when it is carried out in a polar solvent (for example, THF). Therefore, there is a disadvantage that the initiation reaction is difficult to achieve unless sec-butyllithium is used as the initiator. On the other hand, when it is carried out in a nonpolar solvent (for example, toluene), the reaction rate is slow and heating is required. In this case, less reactive n-butyllithium may be used as an initiator. The method for producing a block polymer using the flow reactor of the present invention is characterized in that low reactivity n-butyllithium can be used as an initiator because it can be reacted in a polar solvent at around room temperature.

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

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

The flow rate of the initiator flowing through the flow channel of the flow reactor is not particularly limited and may be appropriately set according to the purpose, preferably 0.1 to 10 mL / min, and more preferably 0.5 to 8 mL. / Min is more preferable, and 1 to 6 mL / min is particularly preferable. If the flow rate of the initiator is in the above range, the flow reactor is unlikely to be clogged, the pressure loss can be suppressed, and the polymer can be stably produced over a long 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, but from the viewpoint of the reaction rate, -80 ° C or higher is preferable, -40 ° C or higher Is more preferable, and -20.degree. C. or more is even more preferable. The reaction temperature is preferably 100 ° C. or less, more preferably 50 ° C. or less, and still more preferably 30 ° C. or less from the viewpoint of side reaction suppression and suppression of inactivation of growth terminals.

As a method of terminating the reaction, a method of recovering the polymerization reaction solution coming out of the flow reactor with a container containing a reaction terminator such as an excess amount of methanol, or three mixers for mixing the two liquids in the flow reactor It is set as the structure which has the above, and the method of pouring reaction terminators, such as methanol, etc. from one side of the mixer for two last liquid mixing, etc. are mentioned.

According to the production method of the present invention, a polymer having a small degree of dispersion (Mw / Mn) (narrow 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 still 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 the polystyrene conversion measurement values by gel permeation chromatography (GPC). The Mw of the polymer obtained by the production method of the present invention is not particularly limited, but is preferably 1,000 to 100,000, and more preferably 1,000 to 50,000.

Hereinafter, the present invention will be specifically described by showing synthesis examples, examples and comparative examples, but the present invention is not limited to the following examples.

The schematic diagram of the flow reactor (reactor) used in the following Example is shown in FIG. In FIG. 10, arrows indicate the flow direction of the liquid. Plunger using a PTFE tube (inner diameter 1.0 mm, outer diameter 1.6 mm, length 2 m) using the plunger pump 1 (HP-12 manufactured by Fromm) for feeding the first monomer solution Connect pump 1 and mixer 1, and use syringe pump 1 (1000D Syringe pump made by TELEDYNE ISCO), PTFE tube (inner diameter 1.0 mm, outer diameter 1.6 mm, length 2 m) for initiator solution delivery. The syringe pump 1 and the mixer 1 were connected using this. The outlet of mixer 1 and the inlet of mixer 2 are connected by PFA tube 1 (internal diameter 2.0 mm, outer diameter 3 mm, length 1 m), and the other inlet of mixer 2 is a syringe for reaction modifier solution delivery The pump 2 (Keychem-L, manufactured by YMC Co., Ltd.) was connected with 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 are connected with a PFA tube 2 (inside diameter 2.0 mm, outer diameter 3 mm, length 1 m), and the other inlet of the mixer 3 is for feeding the second monomer solution The plunger pump 2 (KP-12 manufactured by Fromm) was connected by a PTFE tube (inner diameter 1.0 mm, outer diameter 1.6 mm, length 2 m). The outlet of the mixer 3 and the inlet of the mixer 4 are connected by a PFA tube 3 (internal diameter 2.0 mm, outer diameter 3 mm, length 5 m), and the other inlet of the mixer 4 is a syringe for reaction solution supply Pump 3 (Asia manufactured by Syrris) was connected by a PTFE tube (inner diameter 1.0 mm, outer diameter 1.6 mm, length 2 m). At the outlet of the mixer 4, a PFA tube 4 (inner diameter: 2.0 mm, outer diameter: 3 mm, length: 0.7 m) was connected. The flow path from each pump to the tip and 90% length of the tube 4 was immersed in a thermostat at 24 ° C. to adjust the temperature. Also, the pressure sensor log of the initiator solution delivery pump is shown as a pressure trend.

The schematic diagram of the flow reactor used by the following comparative example is shown in FIG. In FIG. 11, the arrow indicates the flow direction of the liquid. Plunger using a PTFE tube (inner diameter 1.0 mm, outer diameter 1.6 mm, length 2 m) using the plunger pump 1 (HP-12 manufactured by Fromm) for feeding the first monomer solution The pump 1 and the mixer 1 are connected, and a syringe pump 2 (Keychem-L manufactured by YMC Co., Ltd.) and a PTFE tube (inner diameter 1.0 mm, outer diameter 1.6 mm, length 2 m) are used for initiator solution delivery. The syringe pump 2 and the mixer 1 were connected using The outlet of mixer 1 and the inlet of mixer 2 are connected by PTFE tube 1 (inner diameter 1.5 mm, outer diameter 3 mm, length 1.3 m (comparative example 1), 0.7 m (comparative example 2)) The other inlet of 2 was connected with a syringe pump 3 for supplying a solution for stopping reaction (Syrris Asia) with a PTFE tube (inner diameter 1.0 mm, outer diameter 1.6 mm, length 2 m). At the outlet of the mixer 2, a PTFE tube 2 (inner diameter 1.5 mm, outer diameter 3 mm, length 1.3 m (comparative example 1), 0.7 m (comparative example 2)) was connected. The temperature was adjusted by immersing in the thermostatic baths of 5 ° C. (Comparative Example 1) and -20 ° C. (Comparative Example 2) for the flow paths from each pump to the tip and 90% length of the tube 2. Also, the pressure sensor log of the initiator solution delivery pump is shown as a pressure trend.

The measurement conditions of GPC are as follows.
Column: PLgel 3μm MIXED-E (manufactured by Agilent Technologies)
Mobile phase: tetrahydrofuran (THF)
Flow rate: 1.0 mL / min
Column oven: 40 ° C
Detector: UV detector Calibration curve: Standard polystyrene

The measurement conditions for ¹ H-NMR (300 MHz) are as follows.
Measurement solvent: Heavy chloroform Reference substance: Tetramethylsilane (TMS) (δ 0.0 ppm)

Example 1
The first monomer is mixed with a 0.25 mol / L styrene / THF solution and an initiator as a 0.05 mol / L n-butyllithium hexane solution at a flow rate of 30 mL / min and 6 mL / min, respectively, using a mixer 1 Were polymerized. The joint member of the mixer 1 was made of stainless steel, and the cylindrical body was made of stainless steel. Further, as the static mixer element body, one processed by DSP-MXA3-17 (element made of polyacetal, number of torsion blades: 17, 3 mm diameter) manufactured by Noritake Co., Limited is used. Subsequently, the reactivity with the second monomer was adjusted by mixing 1,1-diphenylethylene (DPE) with the mixer 2 at 56 μL / min. The mixer 2 used the same one as the mixer 1. Subsequently, tert-butyl methacrylate as a second monomer was mixed by a mixer 3 at 1.2 mL / min to perform block polymerization. The mixer 3 used was the same as the mixer 1. Subsequently, a 0.25 mol / L methanol / THF solution as a polymerization terminator was mixed with the mixer 4 at 10 mL / min to terminate the polymerization. In addition, the mixer 4 used the general simple double pipe mixer. The first monomer solution tube is connected to the inlet of the mixer 1, the initiator solution tube is connected to the inner tube inlet, the tube 1 is connected to the inlet of the mixer 2, and the DPE fluid tube is connected to the inner tube inlet. A tube 2 was connected to the inlet, a tert-butyl methacrylate liquid tube was connected to the inner tube inlet, a polymerization terminator solution tube was connected to the inlet of the mixer 4, and a tube 3 was connected to the inner tube inlet. The solution was sent for 10 minutes and the effluent was collected. The pressure trend during the reaction is shown in FIG. There was almost no pressure fluctuation for 10 minutes.
Furthermore, after the solvent was distilled off with an evaporator to make 130 g of the effluent, the solution was added dropwise to a mixed solution of 401 g of methanol and 101 g of water at room temperature. The resulting white suspension was filtered through a 0.5 μm membrane filter and then washed with 201 g of methanol. The obtained white solid was dried under reduced pressure (50 ° C., 2.5 hours) to obtain 17.51 g of PS-b-PtBuMA. It was Mn = 10,053 and Mw / Mn = 1.09 when it analyzed by GPC. The ¹ H-NMR chart of the obtained polymer is shown in FIG.

Comparative Example 1
The mixer 1 and the mixer 2 are T-shaped mixers (manufactured by Sanko Seiki Kogyo Co., Ltd., made of stainless steel, inner diameter 0.25 mm), and each pump and the first monomer solution collide with each other at 180 °. Connected. A 1.0 mol / L 4-methoxystyrene / THF solution as the first monomer and a 0.11 mol / L sec-butyl lithium hexane solution as the initiator are mixed with a mixer 1 at a flow rate of 5 mL / min and 1 mL / min, respectively. , And the first monomer was polymerized. Subsequently, 0.25 mol / L methanol / THF solution as a polymerization terminator was mixed at 6.3 mL / min with mixer 2 to terminate the polymerization.
The pressure trend when liquid is sent for 10 minutes is shown in FIG. The pressure fluctuation was rapidly observed from 5 minutes after the liquid transfer.

Comparative Example 2
As mixer 1 and mixer 2, Comet X-01 (made of stainless steel) manufactured by Techno Applications Inc. was used. The first monomer solution tube is connected to the inlet side of the outer tube portion of the mixer 1, the initiator solution tube is connected to the inlet side of the inner tube portion, the polymerization stopper solution tube is connected to the inlet side of the outer tube portion of the mixer 2, and the inlet side of the inner tube portion. The tube 1 was connected. As a first monomer, a 2.0 mol / L styrene / THF solution and an 0.1 mol / L sec-butyllithium hexane solution as an initiator are mixed by a mixer 1 at a flow rate of 5 mL / min and 1 mL / min, respectively. Were polymerized. Subsequently, 0.25 mol / L methanol / THF solution as a polymerization terminator was mixed with the mixer 2 at 6.1 mL / min to terminate the polymerization.
The pressure trend when liquid is sent for 35 minutes is shown in FIG. A slight pressure fluctuation and a pressure rise over time were observed.

As described above, according to the method for producing a polymer of the present invention, since clogging of the flow channel of the flow reactor is unlikely to occur, no pressure fluctuation is observed, and the polymer can be produced stably for a long time .

DESCRIPTION OF SYMBOLS 1 Two-liquid mixing mixer 2 joint member 21 main body 211 insertion hole 212 introduction hole 213 connection hole 22 inner pipe 221 inner pipe inner side 222 inner pipe outer wall 223 inner pipe outer end 24 space 25 double pipe 3 static mixer member 31 cylindrical body 32 element body 321 right twist blade 322 left twist blade 4 flow reactor

Claims (16)

1. A step of anionically polymerizing a styrenic monomer as a first monomer in the presence of an initiator to synthesize a polymer, using a flow reactor comprising a two-liquid mixing mixer having a flow path capable of mixing a plurality of liquids; A method for producing a block polymer, comprising block polymerizing an acrylic monomer as a second monomer to the polymer to synthesize a block polymer,
   The method for producing a block polymer, wherein the flow reactor comprises a two-component mixing mixer including a joint member having a double pipe inside or a static mixer member.
2. The method for producing a block polymer according to claim 1, comprising the step of reacting a non-homopolymerizable monomer before anionically polymerizing the first monomer to synthesize a polymer and then block polymerizing the second monomer.
3. The method for producing a block polymer according to claim 1 or 2, wherein the non-homopolymerizable monomer is 1,1-diphenylethylene or a derivative thereof.
4. The method for producing a block polymer according to any one of claims 1 to 3, wherein the static mixer member comprises a cylindrical body and an element body inserted into the inside of the cylindrical body.
5. The method for producing a block polymer according to any one of claims 1 to 4, wherein the two-component mixing mixer comprises a joint member having a double pipe inside and a static mixer member.
6. The two-component mixing mixer includes a joint member having a double pipe therein and a static mixer member,
   The static mixer member comprises a tubular body and an element body inserted therein;
   The joint member and the static mixer member are connected such that the end surface of the cylindrical body on the double tube side abuts on the end surface of the double tube on the static mixer member side. The manufacturing method of the described block polymer.
7. The method for producing a block polymer according to claim 6, wherein an end of the double pipe on the static mixer member side is inside the joint member.
8. The joint member has an insertion hole for inserting an inner pipe through which an initiator solution flows, and in a state where the inner pipe is inserted, the inner pipe inner side and the inner pipe at least near the tip of the inner pipe. The method for producing a block polymer according to any one of claims 5 to 7, wherein the double pipe is formed by a pipe outer wall and a space constructed by an inner wall of the insertion hole.
9. 9. The method for producing a block polymer according to claim 8, wherein the joint member has an introduction hole for introducing a monomer solution, and the introduction hole is connected to the insertion hole.
10. The insertion hole is formed to have a hole diameter substantially the same as the outer diameter of the inner pipe in the vicinity of the connection portion with the introduction hole, and from the connection portion to the tip of the inner pipe The method for producing a block polymer according to claim 9, wherein the pore size is larger than the outer diameter.
11. The method for producing a block polymer according to any one of claims 8 to 10, wherein the joint member has a static mixer member connecting hole, and the insertion hole is connected to the connecting hole.
12. The element according to any one of claims 4 to 11, wherein the element body is inserted into the cylindrical body such that one end thereof is substantially flush with the end face of the cylindrical body on the side of the double tube. Of producing block polymers.
13. The method for producing a block polymer according to any one of claims 4 to 12, wherein the element body has a shape in which a right twist blade and a left twist blade are alternately and continuously connected in the twist axis direction.
14. The method for producing a block polymer according to any one of claims 1 to 13, wherein the initiator is a mono-organolithium compound.
15. The method for producing a block polymer according to any one of claims 1 to 14, wherein the styrenic monomer is a compound represented by the following formula (1).
    

    

    (Wherein, 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 a carbon number which may be substituted with a halogen atom) an alkyl group having 1 to 10, -OSiR ⁷ ₃ or -SiR ⁷ _3, R ⁷ are independently an alkyl group having 1 to 10 carbon atoms, a phenyl group, an alkoxy group or a carbon number of 1 to 5 carbon atoms 1 to 5 alkylsilyl groups.)
16. The method for producing a block polymer according to any one of claims 1 to 15, wherein the acrylic monomer is a compound represented by the following formula (2).
    

    

    (Wherein, R ¹¹ represents a hydrogen atom or a methyl group, and each R ¹² independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or 6 carbon atoms An aryl group of -20, or an aralkyl group having 7 to 20 carbon atoms.)

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