JP6573812B2 - Polymer production method and flow reaction system for producing polymer - Google Patents

Description

  The present invention relates to a method for producing a polymer. The present invention also relates to a flow reaction system used for production of a polymer.

Semiconductor elements used for logic circuits such as thin film transistors (TFTs), RF tags (Radio Frequency Identifiers) and memories used in liquid crystal displays and organic electroluminescent displays because they can be reduced in weight, cost and flexibility. Organic semiconductor materials are widely used.
Until now, miniaturization of integrated circuits of semiconductor devices has been promoted in order to increase the processing capability of the semiconductor devices. The miniaturization of the integrated circuit has been mainly performed by photolithography, but the pitch of the circuit pattern to be formed is limited by the optical wavelength, and the resolution is limited. In recent years, an optical lithography technique using extreme ultraviolet light (EUV) has been proposed, and a finer circuit pattern can be formed. However, there are many technical problems for practical use.

Under such circumstances, a guided self-assembly (DSA) lithography technique has attracted attention as a next-generation lithography technique. This technique uses a block copolymer as a DSA resist. This block copolymer is applied onto a substrate, and after the phase separation of the block copolymer by annealing (heat treatment), a specific block is removed by etching to form a fine pattern. For example, Non-Patent Document 1 describes that a pattern is formed with a resolution of several nm by using a block copolymer having polyhedral oligomeric silsesquioxane (POSS) as a DSA resist.
In order to form a high-precision fine pattern by DSA lithography, it is necessary to use a block copolymer with a highly monodispersed molecular weight distribution (a block copolymer having an extremely narrow molecular weight distribution) as a DSA resist. In this regard, Non-Patent Document 1 adopts a living anionic polymerization using sec-butyllithium as an initiator, and further optimizes the polymerization conditions to obtain a molecular weight distribution of 1.08 or less, a molecular weight of 13,400 to 47, It is described that 700 block copolymers were obtained.

  As described in Non-Patent Document 1, the living anionic polymerization is usually performed in a batch system. However, in the batch method, it is necessary to carry out living anionic polymerization at a very low temperature in order to remove heat generated during polymerization and suppress chain transfer reaction and termination reaction, which are side reactions, for example, monomers and initiators. Mix while cooling below -78 ° C. Therefore, there has been a problem that an ultra-low temperature cooling facility is required and is not suitable for mass production. In addition, since the polymerization reaction in a batch system is carried out under mechanical stirring, local unevenness of monomers and polymerization initiators is likely to occur in the reaction system, and there are restrictions on improving the degree of dispersion of the resulting polymer. .

  On the other hand, a method is also known in which a polymer having a narrow molecular weight distribution is continuously obtained by living anionic polymerization using a flow reactor such as a microreactor. For example, Patent Document 1 uses a microreactor equipped with a flow channel capable of mixing a plurality of liquids, and a monomer is living polymerized in the presence of an initiator, and the dispersity (Mw / Mn) is 1.25 or less. A method for producing certain polymers is described.

JP2015-127425A

“Polymer Papers”, August 2009, vol. 66, no. 8, p. 321-330

However, the technique described in Patent Document 1 has not yet achieved a stable polymer that is highly monodispersed in molecular weight distribution, that is, excellent in monodispersibility, which is required for DSA resists. Moreover, in the technique of the said patent document 1, in order to obtain a polymer with a dispersion degree of 1.25 or less, it describes that the internal diameter of an introduction flow path shall be 500 micrometers or less. When such an introduction channel is used, the introduction flow rate must be suppressed in order to suppress an excessive increase in the system pressure. As a result, the improvement in productivity is restricted, and there remains a problem in application of the polymer to industrial production.
The present invention provides a method for producing a polymer, in which a polymer having a highly monodispersed molecular weight distribution and excellent monodispersibility can be obtained continuously and stably with high productivity. This is the issue. Moreover, this invention makes it a subject to provide the flow type reaction system suitable for implementing the said manufacturing method.

As a result of intensive studies in view of the above problems, the present inventors have determined that the equivalent diameter of the introduction flow path used in the flow type reaction system is within a specific range and the anion polymerization reaction is performed in the flow type reaction system. It has been found that the above problem can be solved by setting the flow rate for introducing the polymerization initiator within a specific range.
More specifically, a liquid containing an anion polymerizable monomer (hereinafter also simply referred to as “monomer solution”), a liquid containing an anionic polymerization initiator (hereinafter also simply referred to as “initiator solution”), and polymerization termination The monomer solution and the initiator solution are joined while introducing each agent into a different flow channel, and each solution is allowed to flow through each flow channel. When the monomer is anionically polymerized, and further downstream, the polymerization terminator is joined to terminate the anion polymerization reaction to obtain a polymer solution, and a channel for introducing the monomer solution and a channel for introducing the initiator are provided. By introducing an equivalent diameter within a specific range and introducing an initiator solution at a flow rate within the specific range, a polymer having a highly monodispersed molecular weight can be obtained efficiently and continuously. Be able to I began to have. The present invention has been further studied based on these findings and has been completed.

That is, the subject of this invention was solved by the following means.
[1]
A method for producing a polymer that performs an anionic polymerization reaction by a flow-type reaction,
Liquid A containing an anionic polymerizable monomer, liquid B containing an anionic polymerization initiator, and a polymerization terminator are introduced into different flow paths, and the liquids are circulated in the flow paths. The anionic polymerizable monomer is anionically polymerized while the combined liquid flows downstream in the reaction flow path, and the polymerization reaction liquid flowing in the reaction flow path and the polymerization terminator are merged to form a polymerization reaction. Including stopping the
The equivalent diameter of the flow path into which the liquid A is introduced and the flow path into which the liquid B is introduced is 1 to 10 mm,
The equivalent diameter of the flow path at the junction of the liquid A and the liquid B is 0.2 to 10 mm,
The flow rate for introducing the liquid A is 10 to 2000 mL / min,
The flow rate for introducing the liquid B is more than 10 mL / min and 500 mL / min or less,
A method for producing a polymer, wherein the anionic polymerization initiator is alkyl lithium.
However, when the anionic polymerization initiator is butyllithium, the butyllithium is n-butyllithium.
[2]
The production method according to [1], wherein the length of the reaction channel is 3 to 50 m.
[3]
The total of the number of flow paths through which the liquid A flows and the number of flow paths through which the liquid B flows, which are connected to the junction of the liquid A and the liquid B, is 3 to 10, [1] [2] The production method according to [2].
[4]
The manufacturing method according to any one of [1] to [3], wherein the number of flow paths through which the liquid A flows is greater than the number of flow paths through which the liquid B flows.
[5]
The production method according to any one of [1] to [4], wherein an equivalent diameter of a flow path at a junction of the liquid A and the liquid B is 1 to 10 mm .
[6 ]
The production method according to any one of [1] to [ 5 ], wherein n-butyllithium is used as the anionic polymerization initiator.
[ 7 ]
The production method according to any one of [1] to [ 6 ], wherein the liquid B contains an aromatic hydrocarbon.
[ 8 ]
A method for producing a block copolymer that performs an anionic polymerization reaction by a flow-type reaction,
The liquid A1 containing the first anionic polymerizable monomer, the liquid B containing the anionic polymerization initiator, the liquid A2 containing the second anionic polymerizable monomer, and the polymerization terminator are introduced into different flow paths, respectively. The liquid A1 and the liquid B are circulated in the flow path, and the combined liquid anionically polymerizes the first anionic polymerizable monomer while flowing downstream in the first reaction flow path,
The polymerization reaction liquid flowing in the first reaction channel and the liquid A2 are merged, and the combined liquid anionically polymerizes the second anionic polymerizable monomer while flowing downstream in the second reaction channel, 2 merging a polymerization reaction liquid and a polymerization terminator flowing in the reaction flow path to stop the polymerization reaction,
The equivalent diameter of the flow path into which the liquid A1 is introduced and the flow path into which the liquid B is introduced is 1 to 10 mm,
The equivalent diameter of the flow path at the junction of the liquid A1 and the liquid B is 0.2 to 10 mm,
The flow rate for introducing the liquid A1 is 10 to 2000 mL / min,
The flow rate for introducing the liquid B is more than 10 mL / min and 500 mL / min or less,
A method for producing a block copolymer, wherein the anionic polymerization initiator is alkyl lithium.
However, when the anionic polymerization initiator is butyllithium, the butyllithium is n-butyllithium.
[ 9 ]
[ 8 ] The production method according to [ 8 ], wherein the length of the first reaction channel is 3 m or more and 50 m or less.
[ 10 ]
[ 8 ] or [ 9 ] The production method according to [ 9 ].
[ 11 ]
The manufacturing method according to any one of [ 8 ] to [ 10 ], wherein the number of flow paths through which the liquid A1 flows is greater than the number of flow paths through which the liquid B flows .
[12 ]
The production method according to any one of [ 8 ] to [ 11 ], wherein n-butyllithium is used as the anionic polymerization initiator.
[ 13 ]
The production method according to any one of [ 8 ] to [ 12 ], wherein the liquid B contains an aromatic hydrocarbon.
[ 14 ]
After the liquid A1 and the liquid B are merged, and the merged liquid is anionically polymerized with the first anionic polymerizable monomer while flowing downstream in the first reaction channel, the first reaction channel before merging the polymerization reaction solution and the solution A2 that flows comprises merging the polymerization liquid flowing through the first reaction channel, and a liquid C containing polymerization control agent, [8] - [ 13 ] The production method according to any one of [ 13 ].
[ 15 ]
A flow reaction system for producing a polymer by an anionic polymerization reaction,
The first flow path through which the anionic polymerizable monomer flows, the second flow path through which the anionic polymerization initiator flows, the third flow path through which the polymerization terminator flows, and the first flow path and the second flow path merge. A first merging portion, a reaction tube connected downstream of the first merging portion, a second merging portion where the reaction tube and the third flow path merge, and a pipe connected downstream of the second merging portion; Have
The equivalent diameters of the first channel and the second channel are both 1 to 10 mm,
The total of the number of the first flow paths and the number of the second flow paths connected to the first merge portion is 3 to 10,
A flow reaction system, wherein the anionic polymerization initiator is alkyllithium.
However, when the anionic polymerization initiator is butyllithium, the butyllithium is n-butyllithium.
[ 16 ]
The flow reaction system according to [ 15 ], wherein the number of the first flow paths connected to the first merge part is larger than the number of the second flow paths connected to the first merge part.
[ 17 ]
A flow reaction system for producing a block copolymer by an anionic polymerization reaction,
A first flow path through which the first anionic polymerizable monomer flows, a second flow path through which the anionic polymerization initiator flows, a third flow path through which the second anionic polymerizable monomer flows, and a polymerization stopper flow. A fourth flow path, a first merge section where the first flow path and the second flow path merge, a first reaction tube connected downstream of the first merge section, a first reaction tube, and a third flow path Of the second merging portion, the second reaction tube connected downstream of the second merging portion, the third merging portion where the second reaction tube and the fourth flow path merge, and the third merging portion A pipe connected downstream,
The equivalent diameters of the first channel and the second channel are both 1 to 10 mm,
The total of the number of the first flow paths and the number of the second flow paths connected to the first merge portion is 3 to 10,
A flow reaction system, wherein the anionic polymerization initiator is alkyllithium.
However, when the anionic polymerization initiator is butyllithium, the butyllithium is n-butyllithium.
[ 18 ]
The flow reaction system according to [ 17 ], wherein the number of the first flow paths connected to the first merge part is larger than the number of the second flow paths connected to the first merge part.
[ 19 ]
A flow reaction system for producing a block copolymer by an anionic polymerization reaction,
A first flow path through which the first anionic polymerizable monomer flows, a second flow path through which the anionic polymerization initiator flows, a third flow path through which the polymerization control agent flows, and a second anionic polymerizable monomer flow through. A fourth flow path, a fifth flow path through which the polymerization terminator circulates, a first merge section where the first flow path and the second flow path merge, and a first reaction connected downstream of the first merge section. A pipe, a second merging portion where the first reaction tube and the third flow path merge, a second reaction pipe connected downstream of the second merging section, and the second reaction pipe and the fourth flow path merge. Connected to the third merging portion, the third reaction tube connected downstream of the third merging portion, the fourth merging portion where the third reaction tube and the fifth flow path merge, and the downstream of the fourth merging portion. Pipes, and
The equivalent diameters of the first channel and the second channel are both 1 to 10 mm,
The total of the number of the first flow paths and the number of the second flow paths connected to the first merge portion is 3 to 10,
A flow reaction system, wherein the anionic polymerization initiator is alkyllithium.
However, when the anionic polymerization initiator is butyllithium, the butyllithium is n-butyllithium.
[ 20 ]
The flow reaction system according to [ 19 ], wherein the number of the first flow paths connected to the first merge part is larger than the number of the second flow paths connected to the first merge part.

  In this specification, about the display of a compound (a polymer is included), it uses for the meaning containing its salt and its ion besides the compound itself. In addition, it means that a part of the structure is changed as long as the desired effect is achieved.

  In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

  According to the production method of the present invention, a polymer having a highly monodispersed molecular weight can be obtained continuously and stably with high productivity. In addition, the flow reaction system of the present invention is used to carry out the above-described production method, thereby obtaining a polymer having a highly monodispersed molecular weight continuously with high productivity. Make it possible.

It is explanatory drawing which shows the outline of one Embodiment of the flow type reaction system of this invention. It is explanatory drawing which shows the outline of another embodiment of the flow type reaction system of this invention. It is explanatory drawing which shows the outline of another embodiment of the flow type reaction system of this invention. It is explanatory drawing which shows the outline of another embodiment of the flow type reaction system of this invention. It is explanatory drawing which shows the outline of another embodiment of the flow type reaction system of this invention.

[Flow reaction system]
One embodiment of a flow reaction system used in a method for producing a polymer of the present invention (hereinafter also referred to as “production method of the present invention”) will be described with reference to the drawings. In addition, this invention is not limited to the form shown by drawing except the matter prescribed | regulated by this invention.
FIG. 1 is a schematic view showing an example of a flow reaction system used in the production method of the present invention. The flow reaction system (100) shown in FIG. 1 has an anionic polymerizable monomer supply channel (I) having an inlet (I) for introducing a liquid containing an anionic polymerizable monomer (hereinafter also referred to as “liquid A”). 1) An anionic polymerization initiator supply channel (2) having an inlet (II) for introducing a liquid containing an anionic polymerization initiator (hereinafter also referred to as “liquid B”), an introduction for introducing a polymerization terminator A polymerization terminator supply channel (3) provided with a port (III), a junction (C1) where the anion polymerizable monomer supply channel (1) and the anion polymerization initiator supply channel (2) merge, A reaction tube (4) connected to the downstream end of the merging portion (C1), a merging portion (C2) where the reaction tube (4) and the polymerization terminator supply channel (3) merge, and this merging portion A pipe (5) connected to the downstream end of (C2) is provided.

In the embodiment of FIG. 1, at least the merging portion (C1), a portion from the merging portion (C1) to the merging portion (C2), a part of the pipe (5) following the merging portion (C2) and the merging portion (C2). Is arranged in a thermostat (R1), and the liquid temperature in the anionic polymerization reaction and the polymerization termination reaction is -100 ° C to 40 ° C (preferably -80 ° C to 20 ° C, more preferably -50 ° C to 10 ° C). It is preferable to be controlled so that
In addition, a liquid feed pump (not shown) such as a syringe pump is usually connected to each of the inlets (I), (II), and (III). By operating this pump, liquid A, liquid B and the polymerization terminator can be circulated in each flow path.

In this specification, “upstream” and “downstream” are used in the direction in which the liquid flows, and the side where the liquid is introduced (inlet (I), (II), (III) side in FIG. 1). Is upstream and the opposite side is downstream.
Each configuration of the embodiment of FIG. 1 will be described in more detail.

<Anion polymerizable monomer supply channel (1)>
The anionic polymerizable monomer supply channel (1) is a channel for supplying the liquid A introduced from the inlet (I) to the junction (C1). The anionic polymerizable monomer supply channel (1) has an equivalent diameter of 1 to 10 mm. By setting the equivalent diameter of the anionic polymerizable monomer supply channel (1) to 1 mm or more, an excessive increase in the internal pressure can be suppressed even if the flow rate is increased to some extent, and the productivity of the polymer can be further increased. it can. Further, by setting the equivalent diameter of the anionic polymerizable monomer supply channel (1) to 10 mm or less, the liquid temperature at the time of introducing the junction (C1) can be accurately controlled. The equivalent diameter of the anionic polymerizable monomer supply channel (1) is more preferably 1 to 8 mm, further preferably 1 to 6 mm, and further preferably 1 to 4 mm.
The “equivalent diameter” is also called an equivalent diameter and is a term used in the field of mechanical engineering. When an equivalent circular pipe is assumed for a pipe or flow passage having an arbitrary cross-sectional shape in the pipe, the diameter of the cross-section in the pipe of the equivalent circular pipe is called an equivalent diameter. The equivalent diameter (deq) is defined as deq = 4 A / p, using A: cross-sectional area of the pipe in the pipe and p: wetted length (inner circumference) of the pipe. When applied to a circular pipe, this equivalent diameter corresponds to the diameter of the cross-section of the circular pipe. The equivalent diameter is used to estimate the flow or heat transfer characteristics of the pipe based on the data of the equivalent circular pipe, and represents the spatial scale (typical length) of the phenomenon. The equivalent diameter is deq = 4a ² / 4a = a for a regular square tube with one side a in the tube cross section, deq = a / 3 ^{1/2 for} a regular triangle tube with one side a, and flow between parallel flat plates with a channel height h. Then, deq = 2h (for example, see “Mechanical Engineering Encyclopedia” edited by Japan Society of Mechanical Engineers, 1997, Maruzen Co., Ltd.).

There is no restriction | limiting in particular in the length of an anion polymerizable monomer supply flow path (1), For example, it can comprise with a tube about 10 cm-10 m in length (preferably 30 cm-5 m).
The material of the tube is not particularly limited. For example, perfluoroalkoxyalkane (PFA), Teflon (registered trademark), aromatic polyether ketone resin, stainless steel, copper (or an alloy thereof), nickel (or an alloy thereof), titanium (Or an alloy thereof), quartz glass, lime soda glass, and the like. From the viewpoint of flexibility and chemical resistance, the material of the tube is preferably PFA, Teflon (registered trademark), stainless steel, nickel alloy (Hastelloy), or titanium.

  The flow rate at which the liquid A is introduced from the introduction port (I) is not particularly limited, and can be appropriately selected according to the purpose in consideration of the equivalent diameter of the flow path, the concentration of the liquid B, the introduction flow rate of the liquid B, and the like. . For example, 1 to 2000 mL / min is preferable, 5 to 500 mL / min is more preferable, 10 to 200 mL / min is further preferable, and 10 to 100 mL / min is further preferable. By setting the introduction flow rate of the liquid A within the above range, the polymer that can increase the mixing efficiency in the joining portion can be more monodispersed, and the risk of pressure loss is also reduced.

-Liquid A containing an anionic polymerizable monomer-
The liquid A flowing through the anion polymerizable monomer supply flow path (1) may be the anion polymerizable monomer itself. However, from the viewpoint of removal of melting point, viscosity, and heat of reaction, the anion is usually contained in the solvent. It is a solution obtained by dissolving a polymerizable monomer. The solvent contained in the liquid A may be appropriately selected according to the type of monomer used, and examples thereof include linear, branched, and cyclic ether solvents, hydrocarbon solvents, and the like. More specifically, as the ether solvent, tetrahydrofuran, dioxane, trioxane, methyl tertiary butyl ether, cyclopentyl methyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, and derivatives thereof can be used. . As the hydrocarbon solvent, hexane, heptane, octane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, decalin, tetralin, and derivatives thereof can be used. Of these, tetrahydrofuran is preferably used from the viewpoints of monomer solubility and polymerization rate.

  There is no restriction | limiting in particular in the anion polymerizable monomer in the liquid A, According to the objective, it can select suitably. For example, vinyl aromatic hydrocarbons, acrylic monomers, methacrylic monomers, conjugated dienes and the like can be mentioned.

  Examples of the vinyl aromatic hydrocarbon include styrene, styrene derivatives (p-dimethylsilylstyrene, (p-vinylphenyl) methyl sulfide, p-hexynylstyrene, p-methoxystyrene, p-tert-butyldimethylsiloxystyrene. , O-methylstyrene, p-methylstyrene, p-tert-butylstyrene, α-methylstyrene, etc.), vinylnaphthalene, vinylanthracene, 1,1-diphenylethylene, and the like.

Examples of the acrylic monomer include methyl acrylate, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, epoxy acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, trimethylolpropane triacrylate, tetramethylene glycol tetraacrylate, 2-hydroxy-1, 3-Diacryloxypropane, 2,2-bis [4- (acryloxymethoxy) phenyl] propane, 2,2-bis [4- (acryloxyethoxy) phenyl] propane, dicyclopentenyl acrylate tricyclodecanyl acrylate , Tris (acryloxyethyl) isocyanurate, urethane acrylate and the like.
Moreover, as said methacryl monomer, the monomer of the form which made the acryloyl group of the monomer illustrated as said acrylic monomer into the methacryloyl group can be mentioned.

Examples of the conjugated diene include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1, Examples include 3-cyclohexadiene.
The said monomer may be used individually by 1 type, and may use 2 or more types together.

There is no restriction | limiting in particular in content of the anion polymerizable monomer in the liquid A, In consideration of the initiator density | concentration in the liquid B, the introduction | transduction flow rate of the liquid B, etc., it adjusts suitably according to the objective. The content of the anionic polymerizable monomer in the liquid A is preferably 1 to 100% by mass, more preferably 3 to 70% by mass, further preferably 5 to 50% by mass, and further preferably 10 to 40% by mass. .
Further, from the viewpoint of removing the viscosity and heat of reaction, the molar concentration of the anionic polymerizable monomer in the liquid A is preferably 0.5 to 10M, and more preferably 0.5 to 5M.

<Anionic polymerization initiator supply channel (2)>
The anionic polymerization initiator supply channel (2) is a channel for supplying the liquid B introduced from the inlet (II) to the junction (C1). The anionic polymerization initiator supply channel (2) has an equivalent diameter of 1 to 10 mm. By setting the equivalent diameter of the anionic polymerization initiator supply channel (2) to 1 mm or more, an excessive increase in the system pressure can be suppressed even if the flow rate is increased to some extent, and the productivity of the polymer can be further increased. it can. Further, by setting the equivalent diameter of the anionic polymerization initiator supply channel (2) to 10 mm or less, the liquid temperature at the time of introducing the junction (C1) can be appropriately controlled. The equivalent diameter of the anionic polymerization initiator supply channel (2) is more preferably 1 to 8 mm, further preferably 1 to 6 mm, and further preferably 1 to 4 mm.

There is no restriction | limiting in particular in the length of an anionic polymerization initiator supply flow path (2), For example, it can comprise with a tube about 10 cm-10 m in length (preferably 30 cm-5 m).
There is no restriction | limiting in particular in the material of a tube, The tube of the material illustrated by the said anion polymerizable monomer supply flow path (1) can be used.

The flow rate at which the liquid B is introduced from the introduction port (II) is faster than 10 mL / min and 500 mL / min or less (that is, more than 10 mL / min and 500 mL / min or less). By setting the flow rate of the liquid B within the above range, the polymer that can increase the mixing efficiency in the joining portion can be monodispersed, and the concern about pressure loss is also reduced. The introduction flow rate of the liquid B is preferably 11 to 200 mL / min, more preferably 12 to 100 mL / min, and further preferably 12 to 50 mL / min.
The flow rate B for introducing the liquid B from the inlet (II) is preferably slower than the flow rate A for introducing the liquid A from the inlet (I) from the viewpoint of controlling the molecular weight of the polymer. The ratio between the flow velocity A and the flow velocity B is preferably [flow velocity A] / [flow velocity B] = 20/1 to 1.2 / 1, and [flow velocity A] / [flow velocity B] = 10/1 to 1.3 / 1. Is more preferable. In this specification, the unit of the flow rate is mL / min.

-Liquid B containing an anionic polymerization initiator-
The liquid B flowing through the anionic polymerization initiator supply channel (2) may be the anionic polymerization initiator itself, but from the viewpoint of viscosity and safety, the anionic polymerization initiator is usually dissolved in a solvent. This is a solution. The solvent contained in the liquid B may be appropriately selected according to the type of initiator used, and examples thereof include linear, branched, and cyclic hydrocarbon solvents. More specifically, hexane, heptane, octane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, decalin, tetralin, derivatives thereof, and the like can be given.
Especially, it is preferable that the solvent used for the liquid B contains an aromatic hydrocarbon. Preferable examples of the aromatic hydrocarbon include toluene and xylene. Among them, it is preferable to use toluene. By using an aromatic hydrocarbon as the solvent, the monomer conversion rate increases and the polymerization rate can be further increased. Among these, by using toluene, the monomer conversion rate can be increased to a high degree, which is particularly advantageous when a high molecular weight polymer is produced.

-Anionic polymerization initiator-
There is no restriction | limiting in particular in the anion polymerization initiator used for the liquid B, The initiator used for normal anion polymerization can be widely used, and it selects suitably according to the kind of monomer to be used.
Examples of the polymerization initiator when the polymerization method is an anionic polymerization of a living polymerization method include an organic lithium compound or an organic magnesium compound.

  The organolithium compound is not particularly limited and can be appropriately selected from conventionally known organolithium compounds. For example, methyllithium, ethyllithium, propyllithium, butyllithium (n-butyllithium, sec-butyllithium, iso-butyllithium, tert-butyllithium, etc.), alkyllithium such as pentyllithium, hexyllithium, methoxymethyllithium, ethoxymethyllithium; α-methylstyryllithium, 1,1-diphenyl-3-methylpentryllithium, 3- Benzyl lithium such as methyl-1,1-diphenylpentyl lithium; alkenyl lithium such as vinyl lithium, allyl lithium, propenyl lithium, butenyl lithium; ethynyl lithium, butynyl lithium, pentynyl lithium Alkynyl lithium such as um lithium and hexynyl lithium; Aralkyl lithium such as benzyl lithium and phenylethyl lithium; Aryl lithium such as phenyl lithium and naphthyl lithium; Heterocycle such as 2-thienyl lithium, 4-pyridyl lithium and 2-quinolyl lithium Examples of the lithium include alkyl lithium magnesium complexes such as tri (n-butyl) magnesium lithium and trimethyl magnesium lithium. Among these, alkyllithium is more preferable, and n-butyllithium is particularly preferable because it has high reactivity and can accelerate the initiation reaction. Among butyllithiums, n-butyllithium is preferable because of its high stability in a solution state. For example, when sec-butyllithium is used, it does not dissolve in the solution and gradually precipitates in the suspension state, which may cause a problem in terms of quality stability in industrial production of the polymer. Moreover, t-butyllithium is very flammable and ignitable, and is not very suitable for industrial production. The said organolithium compound may be used individually by 1 type, and may use 2 or more types together.

  Examples of the organic magnesium compound include di-n-butylmagnesium, di-t-butylmagnesium, di-s-butylmagnesium, n-butyl-s-butylmagnesium, n-butyl-ethylmagnesium, di-n-amylmagnesium, Examples thereof include dibenzylmagnesium and diphenylmagnesium.

There is no restriction | limiting in particular in content of the anionic polymerization initiator in the liquid B, The monomer concentration of the liquid A, the introduction | transduction flow rate of the liquid A, etc. are considered, and it adjusts suitably according to the objective. The content of the anionic polymerization initiator in the liquid B is usually 0.01 to 20% by mass, more preferably 0.01 to 15% by mass, further preferably 0.01 to 10% by mass, and 0.05 More preferably, it is 10 mass%.
Further, from the viewpoint of controlling the molecular weight of the polymer, the molar concentration of the anionic polymerization initiator in the liquid B is preferably 0.008 to 1.6M, more preferably 0.01 to 1.6M, and 0.01 to 0.00. 8M is more preferable.

  The introduction amount of liquid A and liquid B is based on the assumption that the equivalent ratio of the anionic polymerizable monomer and the anionic polymerization initiator in the mixed liquid starts when it is assumed that both liquids are homogeneously mixed in the junction (C1). The monomer is preferably 5 to 5000 equivalents, more preferably 10 to 5000 equivalents, and particularly preferably 10 to 1000 equivalents relative to 1 equivalent of the agent. In particular, it is advantageous in that a polymer having a molecular weight substantially equal to the theoretical value can be obtained by setting the equivalent ratio within the above-mentioned particularly preferable range. That is, when the monomer is a compound having one polymerizable functional group, the amount of the monomer used is preferably 5 to 5000 mol, more preferably 10 to 5000 mol, and more preferably 10 to 1000 mol with respect to 1 mol of the initiator. Particularly preferred.

<Merging section (C1)>
The liquid A flowing through the anionic polymerizable monomer supply flow path (1) and the liquid B flowing through the anionic polymerization initiator supply flow path (2) are merged at the merge section (C1). The merge part (C1) has a role of a mixer, and the anion polymerizable monomer supply flow path (1) and the anion polymerization initiator supply flow path (2) are merged into one flow path, and the merge part (C1) If the solution which joined the reaction pipe | tube (4) connected with the downstream edge part of this can be sent out, it will not restrict | limit in particular. In the embodiment of FIG. 1, a T-shaped connector is used as the junction (C1).
The equivalent diameter of the flow path in the merge part (C1) is preferably 0.2 to 10 mm from the viewpoint of improving the mixing performance, and more preferably 1 to 5 mm from the viewpoint of further suppressing the pressure loss.

There are no particular restrictions on the material of the junction (C1). For example, perfluoroalkoxyalkane (PFA), Teflon (registered trademark), aromatic polyetherketone resin, stainless steel, copper (or its alloy), nickel (or its) Alloys), titanium (or alloys thereof), quartz glass, lime soda glass, and other materials can be used.
A commercially available micromixer can be used for the junction (C1). For example, Micrograss Reactor manufactured by Microglass; Cytos manufactured by CPC Systems; YM-1 and YM-2 mixers manufactured by Yamatake Corporation; Mixing tee and tee (T-shaped connector) manufactured by Shimadzu GLC; Tee (T-shaped connector); Upchurch mixing tee and tee (T-shaped connector); Upchurch mixing tee and tee (T-shaped connector); Valco mixing tee and tee (T-shaped connector); Swagelok T-shaped connectors and the like can be mentioned, and any of them can be used in the production method of the present invention.

<Reaction tube (4)>
Liquid A and Liquid B are merged and mixed at the merge section (C1), then flow into the reaction tube (4), which is the reaction channel, and anion polymerization while flowing through the reaction tube (4) downstream Monomer is anionically polymerized.
There is no restriction | limiting in particular in the form of reaction tube (4), and a tube is used normally. The preferable material of the reaction tube (4) is the same as the preferable material of the anionic polymerizable monomer supply channel (1) described above. Moreover, the reaction time of anion polymerization can be adjusted by the equivalent diameter and length of the reaction tube (4), the flow rate setting of the liquid feed pump, and the like. What is necessary is just to adjust suitably the residence time of the reaction liquid which distribute | circulates the inside of a reaction tube (4) according to the molecular weight of the polymer desired. Usually, the equivalent diameter of the reaction tube (4) is 0.1 to 50 mm, more preferably 0.2 to 20 mm, still more preferably 0.4 to 15 mm, still more preferably 0.7 to 10 mm. More preferably, it is 1-5 mm. Further, the length of the reaction tube (4) is preferably 0.05 to 50 m, more preferably 0.5 to 30 m, further preferably 1 to 30 m, and further preferably 2 to 30 m.

<Polymerization terminator supply channel (3)>
The polymerization terminator supply channel (3) is a channel for supplying the polymerization terminator introduced from the introduction port (III) to the junction (C2). The equivalent diameter of the polymerization terminator supply channel (3) is preferably 1 to 8 mm, more preferably 1 to 8 mm, further preferably 1 to 6 mm, and further preferably 1 to 4 mm. Moreover, there is no restriction | limiting in particular in the length of a polymerization terminator supply flow path (3), For example, it can comprise with a tube about 10 cm-10 m in length (preferably 30 cm-5 m). A preferred material for the polymerization terminator supply channel (3) is the same as the preferred material for the anionic polymerizable monomer supply channel (1) described above.

-Polymerization terminator-
The polymerization terminator is not particularly limited as long as it is a liquid containing a component that deactivates an anion that is an active species (polymerization termination component). An aqueous solution or an organic solution containing alcohol and / or an acidic substance as a polymerization termination component ( For example, tetrahydrofuran (THF), methyl tertiary butyl ether, dioxane, cyclopentyl methyl ether, toluene and the like are used as a solvent. In addition, a liquid containing an electrophilic agent such as an alkyl halide or chlorosilane as a polymerization termination component can be used as the polymerization termination agent.
Examples of the alcohol as the polymerization termination component include methanol, ethanol, propanol, isopropyl alcohol, and the like.

Examples of the acidic substance as the polymerization termination component include acetic acid and hydrochloric acid.
Examples of the alkyl halide as the polymerization termination component include alkyl bromide and alkyl iodide.
The amount of the polymerization termination component such as alcohol, acidic substance, electrophile and the like contained in the polymerization terminator is 1 mol to 100 mol with respect to 1 mol of the polymerization initiator in the mixed solution combined with the polymer solution. It is preferable to do this.

  The flow rate at which the polymerization terminator is introduced from the introduction port (III) is not particularly limited and can be appropriately selected depending on the purpose. For example, it can be set to 1-1000 mL / min, 2-500 mL / min is more preferable, and 4-200 mL / min is further more preferable. If the flow rate is within the above range, rapid mixing is possible, and the risk of pressure loss is reduced.

<Merging section (C2)>
The polymerization reaction liquid in which the anionic polymerization reaction proceeds while flowing in the reaction tube (4) and the polymerization stopper flowing in the polymerization stopper supply channel (3) join at the junction (C2). . The junction (C2) has the role of a mixer, and the reaction tube (4) and the polymerization terminator supply channel (3) are merged into one channel and the solution is merged into the downstream pipe (5). If it can send out, it will not be restrict | limited in particular. In the embodiment of FIG. 1, the junction (C2) uses a T-shaped connector.
The equivalent diameter of the flow path in the junction (C2) is preferably 0.2 to 10 mm from the viewpoint of improving the mixing performance, and more preferably 1 to 10 mm from the viewpoint of further suppressing the pressure loss.
There is no restriction | limiting in particular in the material of a junction part (C2), What consists of the same material as what was demonstrated by the junction part (C1) mentioned above can be used. In addition, a specific example of the micromixer that can be used as the junction (C2) is the same as the specific example of the micromixer that can be used as the junction (C1).

<Piping (5)>
The mixed solution containing the polymerization reaction solution and the polymerization terminator reacts while flowing through the pipe (5), the anion is deactivated, and the polymerization is stopped.
The pipe (5) can be constituted by a tube, and the equivalent diameter thereof is preferably 1 to 50 mm, more preferably 1 to 10 mm, from the viewpoint of controlling the liquid temperature of the flowing liquid more precisely. The length of the pipe (5) may be appropriately adjusted according to the equivalent diameter, the flow rate, and the desired molecular weight of the polymer, and is preferably 1 to 10 m, and more preferably 1 to 5 m. The preferable material of the pipe (5) is the same as the preferable material of the anionic polymerizable monomer supply channel (1) described above.
The liquid temperature of the liquid flowing through the pipe (5) is not particularly limited, but it is preferable that at least the upstream side is the same as the liquid temperature of the liquid flowing through the reaction tube (4) as shown in FIG. .
The flow rate of the liquid flowing through the pipe (5) is the sum of the flow rate of the liquid flowing through the polymerization terminator supply channel (3) and the flow rate of the liquid flowing through the reaction tube (4).
The target polymer can be obtained by collecting the liquid downstream of the pipe (5).

Another embodiment of the flow reaction system for carrying out the production method of the present invention will be described with reference to FIG. The embodiment of FIG. 2 is the same as the embodiment of FIG. 1 except that the anionically polymerizable monomer supply channel (1) is branched into two channels in the middle. In the embodiment of FIG. 2, the anionic polymerizable monomer supply channel (1) is branched into two channels on the way, and these two branched channels are at the junction (C3) which is a cross-shaped connector. , Are introduced from the connection ports facing each other and merge. In this embodiment, the anion polymerization initiator supply channel (2) through which the liquid B flows is connected to a connection port of the junction (C3) facing the connection site of the reaction tube (4). By branching the anionic polymerizable monomer supply channel (1) in this way, the monomer and initiator are mixed more quickly and more homogeneously in the junction (C3), and the molecular weight distribution of the resulting polymer is further increased. The polymer can be narrowed and a highly monodispersed polymer can be obtained. The cross connector preferably has an inner diameter of 1 to 10 mm.
Commercially available products can be widely used as the cross connector. Examples of commercially available products include a cross connector manufactured by Upchurch; a union cross manufactured by swagelok; a four-way joint manufactured by EYELA, and the like.

In the embodiment of FIG. 2, the anionic polymerizable monomer supply channel (1) is branched into two channels, but it may be branched into three or more channels, and this embodiment is also an embodiment of the present invention. As preferred. Further, the anionic polymerization monomer supply flow path (1) is branched, or the anionic polymerization initiator supply flow path (1) is branched without branching the anionic polymerization monomer supply flow path (1), and the junction It is good also as a form made to join, and such a form is also contained in embodiment of this invention. Among them, the anionic polymerizable monomer supply flow path (1) is branched into two or more and the anionic polymerization initiator supply flow path (2) is not branched, or the anionic polymerization initiator supply flow path (2) is formed. It is preferable to adopt a form branched into two or more. The relationship between the number of branches in the anionic polymerizable monomer supply channel (1) and the number of branches in the anion polymerization initiator supply channel (2) is more preferably designed as shown in i) or ii) below.
i) A mode in which the number of branches of the anionic polymerizable monomer supply channel (1) is 2, and the anion polymerization initiator supply channel (2) has no branches.
ii) The number of branches in the anion polymerizable monomer supply channel (1) is 3 or more, the number of branches in the anion polymerization initiator supply channel (2) is 2 or more, and the anion polymerizable monomer supply channel (1 ) Has a larger number of branches than the number of branches in the anionic polymerization initiator supply channel (2).

The total of the number of channels through which liquid A circulates and the number of channels through which liquid B circulates connected to the junction of liquid A and liquid B is preferably 3-10, and 3-8 It is more preferable that it is 3-6, it is further more preferable, and it is further more preferable that it is 3-5. In this case, it is preferable that the number of branches of the anionic polymerizable monomer supply channel (1) is larger than the number of branches of the anionic polymerization initiator supply channel (2).
The junction part to which such a number of flow paths can be connected can be constituted by a connector having a number of connection ports corresponding to the number of connected flow paths. For example, if a 6-way connector is used, the total number of channels through which liquid A flows and the number of channels through which liquid B flows can be five, and the remaining one connection port can be used as a discharge port. A reaction tube can be connected to the outlet.
Commercially available products can be widely used as connectors having five or more connection ports that can be used in the present invention. Examples of these commercially available products include a 6-way joint manufactured by EYELA, a 6-way joint manufactured by Sugiyama Corporation, and a 6-port manifold manufactured by Upchurch.
A connector having five or more connection ports preferably has an inner diameter of 1 to 10 mm.

  In the above description, the flow path having a branch has one introduction port and the flow path is branched in the middle. However, a form in which a plurality of introduction ports for one solution may be provided is also possible. Are also included in the embodiments of the present invention. For example, a plurality of anion polymerizable monomer supply channels (1) may be prepared, and the plurality of anion polymerizable monomer supply channels (1) may be merged at the junction. The same applies to the anionic polymerization initiator supply channel (2).

  1 and 2, the residence time (reaction time) is preferably 15 seconds or longer, more preferably 20 to 1800 seconds, and even more preferably 20 to 600 seconds. The residence time (reaction time) in the embodiment of FIGS. 1 and 2 is the time from when the liquid mixture of liquid A and liquid B is introduced into the reaction tube (4) until it is discharged from the outlet of the pipe (5). means.

Next, still another embodiment of the flow reaction system used in the production method of the present invention will be described. FIG. 3 is a schematic view showing an example of a flow reaction system used in a method for producing a block copolymer by an anionic polymerization reaction.
In the embodiment shown in FIG. 3, an anion polymerizable monomer supply channel (1) having an inlet (I), an anionic polymerization initiator supply channel (2) having an inlet (II), and an inlet (III ) Having a polymerization terminator supply channel (3), the junction (C1) where the anion polymerizable monomer supply channel (1) and the anion polymerization initiator supply channel (2) are merged, and this junction The reaction tube (4) and the pipe (5) connected to the downstream end of (C1) are each an anion polymerizable monomer supply channel (I) having an introduction port (I) in the embodiment of FIG. 1) an anionic polymerization initiator supply channel (2) provided with an inlet (II), a polymerization terminator supply channel (3) provided with an inlet (III), the anionic polymerizable monomer supply channel (1) ) And the anionic polymerization initiator supply channel (2) join together (C1), This is synonymous with the reaction pipe (4) and the pipe (5) connected to the downstream end of the merging section (C1), and the preferred form is also the same.

The embodiment of FIG. 3 has an anion polymerizable monomer supply channel (6) in addition to the anion polymerizable monomer supply channel (1) in the embodiment of FIG. 1 described above. In the embodiment of FIG. 3, an anion polymerizable monomer (hereinafter referred to as “first anion polymerizable monomer”) introduced from the inlet (I) and flowing through the anion polymerizable monomer supply channel (1). The anion polymerizable monomer (hereinafter referred to as “second anion polymerizable monomer”) introduced from the introduction port (IV) and flowing through the anion polymerizable monomer supply channel (6) is of a kind different from each other. Monomer. By carrying out like this, the block copolymer comprised from two types of different blocks can be obtained. The types of the first anionic polymerizable monomer and the second anionic polymerizable monomer are preferably selected from the preferred anionic polymerizable monomers described in the embodiment of FIG.
The first anionic polymerizable monomer and the second anionic polymerizable monomer may be circulated in the flow path as they are, but are normally circulated in the flow pipe in a solution state (hereinafter, anionic polymerizable monomer supply flow path). (1) The liquid containing the first anionic polymerizable monomer that circulates in the interior is referred to as “liquid A1”, and includes the second anionic polymerizable monomer that circulates in the anionic polymerizable monomer supply channel (6). The liquid is referred to as “Liquid A2.”) As the solvent used for the liquid A1 and the liquid A2, those described as the solvent that can be used for the liquid A can be preferably used. The solvent used for the liquid A1 and the solvent used for the liquid A2 may be the same as or different from each other.
The content of the anionic polymerizable monomer in the liquid A1 and the content of the anionic polymerizable monomer in the liquid A2 are each independently usually 1 to 100% by mass, more preferably 3 to 70% by mass. -50 mass% is more preferable, and 10-40 mass% is further more preferable.
In addition, the molar concentration of the anionic polymerizable monomer in the liquid A1 and the molar concentration of the anionic polymerizable monomer in the liquid A2 are each independently preferably 0.5 to 10M, and more preferably 0.5 to 5M.

  In the embodiment of FIG. 3, the polymer solution flowing through the reaction tube (4) reaches the joining part (C4) in a state having an anion active species at its growth end, and in the joining part (C4), the liquid A2 To join. The junction (C4) has a role of a mixer, and joins the reaction tube (4) and the anion polymerizable monomer supply channel (6) into one channel, and a downstream reaction tube ( It will not be restrict | limited especially if the solution which merged to 7) can be sent out. The form of the joining part (C4) is the same as the joining part (C2) described in the form of FIG.

  A block copolymer is produced in the reaction tube (7). That is, the second anionic polymerizable monomer undergoes addition polymerization at the growing end of the polymer that has flowed through the reaction tube (4). The preferred form of the reaction tube (7) is the same as the preferred form of the reaction tube (4) described in the form of FIG.

In the embodiment of FIG. 3, the polymerization reaction liquid containing the block copolymer that circulates in the reaction tube (7) joins in the polymerization terminator supply flow path (3) and the merging section (C2). The form of the joining part (C2) is the same as the joining part (C2) in the embodiment of FIG. 1, and the preferred form is also the same.
The polymerization reaction liquid containing the block copolymer is mixed with the polymerization terminator in the junction (C2), and the polymerization reaction is completely stopped while circulating in the pipe (5).

In the embodiment of FIG. 3, the flow rate for introducing the liquid A1 from the inlet (I) is appropriately selected according to the purpose in consideration of the equivalent diameter of the flow path, the concentration of the liquid B, the introduction flow rate of the liquid B, and the like. Can do. For example, 1 to 2000 mL / min is preferable, 5 to 500 mL / min is more preferable, 10 to 200 mL / min is further preferable, and 10 to 100 mL / min is further preferable.
Similarly, the flow rate when introducing the liquid A2 from the inlet (IV) is preferably 1 to 2000 mL / min, more preferably 5 to 500 mL / min, further preferably 10 to 200 mL / min, and 10 to 100 mL / min. Is more preferable.
In the embodiment of FIG. 3, the flow rate when introducing the liquid B of the anionic polymerization initiator from the inlet (II) is faster than 10 mL / min and not more than 500 mL / min (that is, more than 10 mL / min and 500 mL / min). The following. By setting the flow rate of the liquid B within the above range, the polymer that can increase the mixing efficiency in the joining portion can be monodispersed, and the concern about pressure loss is also reduced. The flow rate when introducing the liquid B is preferably 11 to 200 mL / min, more preferably 12 to 100 mL / min, and still more preferably 12 to 50 mL / min.
In the embodiment of FIG. 3, the flow rate B of the liquid B introduced from the introduction port (II) is slower than the flow rate A1 of the liquid A1 introduced from the introduction port (I) from the viewpoint of controlling the molecular weight of the polymer. It is preferable. The ratio between the flow velocity A1 and the flow velocity B is preferably [flow velocity A1] / [flow velocity B] = 20/1 to 1.5 / 1, and more preferably [flow velocity A1] / [flow velocity B] = 10/1 to 2/1. preferable.

  The introduction amount of the liquid A1 and the liquid B is the equivalent ratio of the anionic polymerizable monomer and the anionic polymerization initiator in the mixed liquid, assuming that the liquid A1 and the liquid B are homogeneously mixed in the merging portion (C1). However, the monomer is preferably 5 to 5000 equivalents, more preferably 10 to 5000 equivalents, and particularly preferably 10 to 1000 equivalents with respect to 1 equivalent of the initiator. In particular, it is advantageous in that a polymer having a molecular weight substantially equal to the theoretical value can be obtained by setting the equivalent ratio within the above-mentioned particularly preferable range. That is, when the monomer is a compound having one polymerizable functional group, the amount of the monomer used is preferably 5 to 5000 mol, more preferably 10 to 5000 mol, and more preferably 10 to 1000 mol with respect to 1 mol of the initiator. Particularly preferred.

  In the embodiment of FIG. 3, the introduction flow rate of the polymerization terminator introduced from the introduction port (III) is not particularly limited and can be appropriately selected according to the purpose. For example, it can be set to 1-1000 mL / min, 2-500 mL / min is more preferable, 4-200 mL / min is further more preferable, and 4-100 mL / min is further more preferable. If the flow rate is within the above range, rapid mixing is possible, and the risk of pressure loss is reduced.

  In the embodiment of FIG. 3, the areas represented by R2 and R3 mean that they are arranged in a thermostatic bath. The temperature in R2 is preferably controlled so that the liquid temperature becomes −100 ° C. to 40 ° C. (preferably −80 ° C. to 20 ° C., more preferably −50 ° C. to 10 ° C.). Moreover, it is preferable that the temperature in R3 is controlled so that the liquid temperature becomes −100 ° C. to 0 ° C. (preferably −80 ° C. to −10 ° C., more preferably −70 ° C. to −20 ° C.). In particular, when the second anionic polymerizable monomer is an acrylic monomer or a methacrylate monomer, by setting the temperature in R3 within the above preferred temperature range, side reactions can be suppressed and a polymer with a lower degree of dispersion can be obtained. .

Another embodiment of a flow reaction system for obtaining a block copolymer by the production method of the present invention will be described with reference to FIG. The embodiment of FIG. 4 is the same as the embodiment of FIG. 3 except that the first anionically polymerizable monomer supply channel (1) is branched into two channels on the way.
In the embodiment of FIG. 4, the first anionically polymerizable monomer supply channel (1) is branched into two channels on the way, and the two branched channels are cross-shaped structures (cross connectors). In the joining portion (C3), the two are introduced from the connecting ports facing each other and join together. In this embodiment, the anion polymerization initiator supply channel (2) through which the liquid B flows is connected to a connection port of the junction (C3) facing the connection site of the reaction tube (4). Thus, by branching the first anionic polymerizable monomer supply channel (1), the monomer and the initiator are mixed more quickly and more homogeneously in the junction (C3). The molecular weight distribution can be further narrowed, and a highly monodispersed block copolymer can be synthesized.
In the embodiment of FIG. 4, the first anionic polymerizable monomer supply channel (1) is branched into two channels, but it may be branched into three or more channels, and such an embodiment is also the present invention. It is preferable as an embodiment. In addition, the anion polymerization initiator supply channel (2) is branched without branching the first anion polymerizable monomer supply channel (1) or without branching the first anion polymerizable monomer supply channel (1). May be branched and merged at the junction, and such an embodiment is also included in the embodiment of the present invention. Among them, the first anionic polymerizable monomer supply channel (1) is branched into two or more and the anionic polymerization initiator supply channel (2) is not branched, or the anion polymerization initiator supply channel ( It is preferable to adopt a form in which 2) is branched into two or more. The relationship between the number of branches in the first anionic polymerizable monomer supply channel (1) and the number of branches in the anion polymerization initiator supply channel (2) is more preferably designed as in the following iii) or iv).

iii) A form in which the number of branches of the first anionic polymerizable monomer supply channel (1) is 2, and the anion polymerization initiator supply channel (2) has no branches.
iv) The number of branches in the first anionic polymerizable monomer supply channel (1) is 3 or more, the number of branches in the anionic polymerization initiator supply channel (2) is 2 or more, and the anionic polymerizable monomer supply flow A mode in which the number of branches in the channel (1) is greater than the number of branches in the anionic polymerization initiator supply channel (2).

The total of the number of flow paths through which liquid A1 circulates and the number of flow paths through which liquid B circulates, connected to the junction of liquid A1 and liquid B, is preferably 3-10, and 3-8 It is more preferable that it is 3-6, it is further more preferable, and it is further more preferable that it is 3-5. In this case, it is preferable that the number of branches in the first anionic polymerizable monomer supply channel (1) is larger than the number of branches in the anion polymerization initiator supply channel (2).
The junction part to which such a number of flow paths can be connected can be constituted by a connector having a number of connection ports corresponding to the number of connected flow paths. For example, if a 6-way connector is used, the total of the number of channels through which the liquid A1 flows and the number of channels through which the liquid B flows can be five. A reaction tube can be connected to the outlet.

  In the above description, the flow path having a branch has one introduction port and the flow path is branched in the middle. However, a form in which a plurality of introduction ports for one solution may be provided is also possible. Are also included in the embodiments of the present invention. For example, a plurality of first anion polymerizable monomer supply channels (1) may be prepared, and the plurality of anion polymerizable monomer supply channels (1) may be merged at a junction. The same applies to the anionic polymerization initiator supply channel (2).

FIG. 5 is a schematic view showing still another embodiment for carrying out the production method of the present invention. The embodiment of FIG. 5 is different from the embodiment of FIG. 4 in that the polymerization reaction liquid containing the polymer obtained by polymerizing the first anionic polymerizable monomer and the liquid A2 containing the second anionic polymerizable monomer are merged. And a step of joining the polymerization reaction solution and the liquid C containing the polymerization control agent at the joining portion (C5) and reacting the inside of the reaction tube (9) in the downstream. In the embodiment of FIG. 5, the liquid C is introduced from the introduction port (V) and circulates in the polymerization control agent supply flow path (8) toward the junction (C5).
The polymerization control agent is used to further increase the degree of dispersion of the resulting block copolymer. For example, by using at least one of an alkali metal alkoxide, an alkali metal salt and an alkaline earth metal salt as a polymerization controller, the living anion at the growth terminal of the polymer obtained by polymerizing the first anionic polymerizable monomer is stabilized. Thus, the addition reaction of the second anionic polymerizable monomer to the growth terminal can be stably performed.

  The alkali metal alkoxide used as the polymerization controller is preferably a lithium alkoxide, specifically, a C1-C24 alcohol such as methanol, ethanol, isopropanol, 2-butanol, octanol, benzyl alcohol, diethylene glycol monomethyl ether, cyclohexanol, or the like. These lithium salts can be used, and these can be used alone or in combination of two or more.

  Specific examples of the alkali metal salt and alkaline earth metal salt used as the polymerization controller include mineral salts and halides such as sodium, potassium, barium, magnesium sulfate, nitrate, borate. be able to. More specifically, lithium, barium chloride, bromide, iodide, lithium borate, magnesium nitrate, sodium chloride, potassium chloride and the like can be mentioned. Among these, lithium halides such as lithium chloride, lithium bromide, lithium iodide or lithium fluoride are preferable, and lithium chloride is particularly preferable. These can be used alone or in combination of two or more.

  The total amount of the alkali metal alkoxide, alkali metal salt and alkaline earth metal salt can be used in any amount as long as the polymerization is not affected. For example, it can be used at 1/10 to 100 times mol, preferably 1/2 to 20 times mol, of the amount of anionic polymerization initiator used. By using it at 1/2 to 20 times mol, a polymer with controlled molecular weight and molecular weight distribution can be produced more stably and with good reproducibility.

In the liquid C, the total content of alkali metal alkoxide, alkali metal salt and alkaline earth metal salt is generally 0.01 to 10% by mass, preferably 0.1 to 5% by mass.
Further, the molar concentration of the alkali metal alkoxide, alkali metal salt and alkaline earth metal salt in the liquid C is preferably 0.01 to 5M, more preferably 0.02 to 1M.
The solvent used in the liquid C is not particularly limited as long as the polymerization control agent can be dissolved. Tetrahydrofuran, dioxane, trioxane, methyl tertiary butyl ether, cyclopentyl methyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, and these And derivatives thereof.

Further, when the second anionic polymerizable monomer introduced into the second anionic polymerizable monomer supply channel (6) is a (meth) acrylic acid ester, an ethylene derivative having a low anionic polymerization activity alone as a polymerization control agent Is preferably added. Thereby, the side reaction of superposition | polymerization can be suppressed. Examples of such ethylene derivatives include 1,1-diphenylethylene (DPE), 1,1-di (p-tolyl) ethylene, 1,1-di (o-tolyl) ethylene, and alphamethylstyrene. .
When the liquid C contains an ethylene derivative, the content is preferably 0.1 to 20% by mass, and more preferably 0.5 to 10% by mass. Moreover, 0.01-5M is preferable and, as for the molar concentration of the ethylene derivative in the liquid C, 0.05-1M is more preferable.

  In the embodiment of FIGS. 4 and 5, the areas represented by R <b> 2 and R <b> 3 mean that they are arranged in the thermostat. The temperature in R2 is preferably controlled so that the liquid temperature becomes −100 ° C. to 40 ° C. (preferably −80 ° C. to 20 ° C., more preferably −50 ° C. to 10 ° C.). The temperature in R3 is such that the liquid temperature is −100 ° C. to 0 ° C. (preferably −80 ° C. to −10 ° C., more preferably −2 ° C.), particularly when the second anionic polymerizable monomer is an acrylic monomer or a methacrylate monomer. It is preferable that the temperature is controlled to be 70 ° C to -20 ° C.

  The composition of the block copolymer obtained by the production method of the present invention is such that the supply ratio of the first anionic polymerizable monomer and the second anionic polymerizable monomer is adjusted, or the residence time of the reaction liquid in each reaction tube is adjusted. It can be controlled by adjusting.

  3 to 5, the residence time (reaction time) is preferably 20 seconds or more, more preferably 20 to 1800 seconds, and even more preferably 20 to 600 seconds. The residence time (reaction time) in the embodiment of FIGS. 3 to 5 is the time from when the liquid mixture of liquid A and liquid B is introduced into the reaction tube (4) until it is discharged from the outlet of the pipe (5). Means.

According to the method for producing a polymer of the present invention (including the method for producing a block copolymer), even if the polymer to be produced has a large molecular weight, the molecular weight distribution can be highly monodispersed. For example, even if the polymer has a number average molecular weight exceeding 50,000, the dispersity (weight average molecular weight (Mw) / number average molecular weight (Mn)) can be suppressed to less than 1.1.
The degree of dispersion of the polymer or block copolymer obtained by the production method of the present invention is preferably less than 1.1, more preferably 1.09 or less, still more preferably 1.08 or less, and still more preferably Is 1.07 or less.

  As mentioned above, although this invention was demonstrated with the preferable embodiment, this invention is not limited to the said embodiment at all except the matter prescribed | regulated by this invention. For example, the reaction tubes (4, 7), the second anion polymerizable monomer supply channel (6), the polymerization control agent supply channel (8), and the reaction tube (9) are the anion polymerizable monomer supply flow of FIG. It is good also as a form which has a branched structure which was demonstrated with the path, and merges downstream. Moreover, it is good also as a form which has multiple 2nd anion polymerizable monomer supply flow paths (6) and polymerization control agent supply flow paths (8), respectively, and merges downstream.

  The present invention will be described below in more detail based on examples, but the present invention is not limited to these examples.

[Example 1]
A polymer was synthesized by an anionic polymerization reaction using the flow reaction system having the configuration shown in FIG. Details of each part are shown below.

Liquid feed pump (not shown):
All used PU716B manufactured by GL Sciences Inc., and a pulse damper HPD-1, a back pressure valve manufactured by Tescom (44-2361-24), and a relief valve RHA manufactured by IBS (4 MPa) were sequentially installed on the flow outlet side.

Low temperature bath (R1):
A tabletop small-sized cryogenic water tank CBi-270A was used and set to 0 ° C.

Anion polymerizable monomer supply channel (1):
One SUS tube was divided into two by a T-shaped connector.
More specifically, an upchurch T-connector (U-429, 1.0 mm inner diameter) is connected to a SUS316 tube having an outer diameter of 1/16 inch, an inner diameter of 1.0 mm, and a length of 50 cm. The anion polymerizable monomer supply flow path (1) was formed by connecting two SUS316 tubes each having an outer diameter of 1/16 inch, an inner diameter of 1.0 mm, and a length of 3 cm so as to face each other.

Anionic polymerization initiator supply channel (2):
A SUS316 tube having an outer diameter of 1/16 inch, an inner diameter of 1.0 mm, and a length of 50 cm was used.

Junction (C3) (cross connector):
A cross connector (U-431, inner diameter 1.0 mm) manufactured by Upchurch was used.
Two SUS316 tubes connected to the T-shaped connector constituting the anionic polymerizable monomer supply channel (1) so as to face each other are connected to two connection ports facing each other among the four connection ports of the cross connector. Respectively. The anion polymerization initiator supply channel (2) was connected to one of the remaining two connection ports, and the remaining connection port was used as a discharge port for sending out the liquid.

Reaction tube (4):
SUS316 tube with outer diameter 1/16 inch, inner diameter 1.0 mm, length 50 cm, outer diameter 3 mm, inner diameter 2 mm, length 8 m SUS316 tube, and outer diameter 1/16 inch, inner diameter 1.0 mm, length 50 cm SUS316 tubes were sequentially connected by a SUS316 union and used as a reaction tube (4).

Polymerization terminator supply channel (3):
A SUS316 tube having an outer diameter of 1/16 inch, an inner diameter of 1.0 mm, and a length of 50 cm was used.

Junction (C2) (T-shaped connector):
An upchurch T-connector (U-429, inner diameter 1.0 mm) was used.
The reaction tube (4) and the polymerization terminator supply channel (3) were respectively connected to two connection ports facing each other among the three connection ports of the T-connector. The remaining connection port was used as a discharge port for feeding out the liquid.

Piping (5):
A SUS316 tube having an outer diameter of 1/16 inch, an inner diameter of 1.0 mm, and a length of 1 m was used.

Liquid A containing a monomer introduced into the anionically polymerizable monomer supply channel (1):
<Styrene / Tetrahydrofuran (THF)>
Wako Pure Chemicals THF (deoxygenated grade) and Wako Pure Chemicals styrene (special grade) were added to a 5 LSUS tank to prepare 4 L of 2M-styrene / THF solution. This solution was dehydrated with molecular sieve 3A to obtain liquid A.
In this example, the description “xM−y / z” means a solution in which y is dissolved in the solvent z, and the y concentration in this solution is xM.

Liquid B containing an initiator introduced into the anionic polymerization initiator supply channel (2):
<N-Butyllithium (nBuLi) / Toluene>
Toluene (deoxygenated grade) made by Wako Pure Chemical Industries was added to a 5 LSUS tank and cooled to 0 ° C. NBuLi (1.6M-nBuLi / hexane solution) manufactured by Kanto Kagaku was added and titrated with menthol / bipyridine to prepare 4L of 0.018M-nBuLi / toluene solution.

Polymerization terminator introduced into the polymerization terminator supply channel (3):
<Methanol (MeOH) / THF>
Wako Pure Chemicals THF (deoxygenated grade) and Wako Pure Chemicals MeOH (deoxygenated grade) were added to a 3 LSUS tank to prepare 4 L of a 0.5 M MeOH / THF solution, which was used as a polymerization terminator.

Liquid feeding conditions:
Liquid A (2M-styrene / THF): 40.0 mL / min
Liquid B (0.018M-nBuLi / toluene): 19.1 mL / min
Polymerization terminator (MeOH / THF): 10.0 mL / min

Flow path time:
Reaction tube (4): about 26 seconds Pipe (5): about 1 second Residence time: about 27 seconds

take out:
100 mL of a solution containing the polymer (polystyrene) was collected from the outlet of the pipe (5) (86 seconds), dropped into 1000 mL of 10 times the volume of this solution, and the precipitated white precipitate was collected by filtration. The collected white precipitate was dried at 80 ° C. under vacuum to obtain 11.8 g of polystyrene (production capacity: 494 g / h). A part of the obtained polystyrene was dissolved in THF, and the molecular weight and molecular weight distribution were measured by gel permeation chromatography (GPC). As a result, the number average molecular weight (Mn) was 25200, and the molecular weight distribution (dispersion degree, Mw / Mn) was 1.03.
In this specification, GPC was measured under the following conditions.
Apparatus: HLC-8220GPC (manufactured by Tosoh Corporation)
Detector: Differential refractometer (RI (Refractive Index) detector)
Precolumn: TSKGUARDCOLUMN HXL-L 6mm x 40mm (manufactured by Tosoh Corporation)
Sample side column: The following three columns are directly connected (all manufactured by Tosoh Corporation).
・ TSK-GEL GMHXL 7.8mm x 300mm
・ TSK-GEL G4000HXL 7.8mm x 300mm
・ TSK-GEL G2000HXL 7.8mm x 300mm
Reference side column: TSK-GEL G1000HXL 7.8 mm x 300 mm
Thermostatic bath temperature: 40 ° C
Moving bed: THF
Sample-side moving bed flow rate: 1.0 mL / min Reference-side moving bed flow rate: 1.0 mL / min Sample concentration: 0.1% by mass
Sample injection volume: 100 μL
Data collection time: 5 to 45 minutes after sample injection Sampling pitch: 300 msec

[Example 2]
In Example 1, a polymer was produced in the same manner as in Example 1 except that the liquid B was changed to a 0.25M-nBuLi / toluene solution. The number average molecular weight (Mn) of the obtained polystyrene was 1800, and the molecular weight distribution (dispersion degree, Mw / Mn) was 1.08.

[Example 3]
In Example 1, a polymer was produced in the same manner as in Example 1 except that the liquid B was changed to a 0.13M-nBuLi / toluene solution. The number average molecular weight (Mn) of the obtained polystyrene was 3530, and the molecular weight distribution (dispersion degree, Mw / Mn) was 1.05.

[Example 4]
In Example 1, a polymer was produced in the same manner as in Example 1 except that the liquid B was changed to a 0.03M-nBuLi / toluene solution. The number average molecular weight (Mn) of the obtained polystyrene was 14100, and the molecular weight distribution (dispersion degree, Mw / Mn) was 1.03.

[Example 5]
In Example 1, a polymer was produced in the same manner as in Example 1 except that the flow rate for introducing the liquid A was changed to 50 mL / min and the liquid B was changed to a 0.008 M-nBuLi / toluene solution. The number average molecular weight (Mn) of the obtained polystyrene was 67000, and the molecular weight distribution (dispersion degree, Mw / Mn) was 1.09.

[Example 6]
A polymer was produced in the same manner as in Example 1 except that the anionic polymerization initiator supply channel (2) in Example 1 was changed to a SUS316 tube having an outer diameter of 3 mm, an inner diameter of 2 mm, and a length of 50 cm. The number average molecular weight (Mn) of the obtained polystyrene was 25100, and the molecular weight distribution (dispersion degree, Mw / Mn) was 1.04.

[Example 7]
A polymer was produced in the same manner as in Example 1, except that the anionic polymerization initiator supply channel (2) in Example 1 was changed to a SUS316 tube having an outer diameter of 6 mm, an inner diameter of 5 mm, and a length of 50 cm. The number average molecular weight (Mn) of the obtained polystyrene was 24900, and the molecular weight distribution (dispersion degree, Mw / Mn) was 1.03.

[Example 8]
A polymer was produced in the same manner as in Example 1 except that the anionic polymerization initiator supply channel (2) in Example 1 was changed to a SUS316 tube having an outer diameter of 10 mm, an inner diameter of 8 mm, and a length of 150 cm. The number average molecular weight (Mn) of the obtained polystyrene was 24700, and the molecular weight distribution (dispersion degree, Mw / Mn) was 1.04.

[Comparative Example 1]
The anion polymerizable monomer supply channel (1) and the anion polymerization initiator supply channel (2) of Example 1 were both changed to SUS316 tubes having an outer diameter of 1/16 inch, an inner diameter of 0.25 mm, and a length of 50 cm. Except for the above, production of a polymer was attempted in the same manner as in Example 1. However, the pressure inside the system exceeded 4 MPa, so that the liquid could not be fed, and the polymer could not be obtained continuously and stably.

[Example 9]
In Example 1, a polymer was produced in the same manner as in Example 1 except that the flow rate for introducing the liquid A was changed to 15.5 mL / min and the flow rate for introducing the liquid B was changed to 12 mL / min. The number average molecular weight (Mn) of the obtained polystyrene was 15400, and the molecular weight distribution (dispersion degree, Mw / Mn) was 1.04.

[Example 10]
In Example 1, the flow rate for introducing the liquid A was changed to 80 mL / min, the flow rate for introducing the liquid B was changed to 38 mL / min, and the flow rate for introducing the polymerization terminator was further changed to 20 mL / min. A polymer was produced in the same manner as in Example 1. The number average molecular weight (Mn) of the obtained polystyrene was 25100, and the molecular weight distribution (dispersion degree, Mw / Mn) was 1.03.

[Comparative Example 2]
In Example 1, the flow rate for introducing the liquid A was changed to 4 mL / min, the flow rate for introducing the liquid B was changed to 1.9 mL / min, and the flow rate for introducing the polymerization terminator was further changed to 1 mL / min. Except for the above, a polymer was produced in the same manner as in Example 1. The number average molecular weight (Mn) of the obtained polystyrene was 26700, and the molecular weight distribution (dispersion degree, Mw / Mn) was 1.13.
The polystyrene production capacity of the reaction system of Comparative Example 2 was 46 g / hour.

[Comparative Example 3]
In Example 1, the flow rate for introducing the liquid A was changed to 8 mL / min, the flow rate for introducing the liquid B was changed to 3.8 mL / min, and the flow rate for introducing the polymerization terminator was further changed to 2 mL / min. Except for the above, a polymer was produced in the same manner as in Example 1. The number average molecular weight (Mn) of the obtained polystyrene was 26200, and the molecular weight distribution (dispersion degree, Mw / Mn) was 1.11.
Moreover, the polystyrene production capacity of the reaction system of Comparative Example 3 was 91 g / hour.

[Example 11]
A polymer was produced in the same manner as in Example 1 except that Example 1 was changed as follows.
<Anion polymerizable monomer supply channel (1)>
One SUS tube was divided into three by a cross connector. More specifically, an upchurch cross connector (U-431, 1.0 mm inner diameter) is connected to a SUS316 tube having an outer diameter of 1/16 inch, an inner diameter of 1.0 mm, and a length of 50 cm. Three SUS316 tubes each having an outer diameter of 1/16 inch, an inner diameter of 1.0 mm, and a length of 3 cm were connected to one connection port.
<Anionic polymerization initiator supply channel (2)>
An upchurch T-connector (U-429, 1.0 mm inner diameter) is connected to a SUS316 tube having an outer diameter of 1/16 inch, an inner diameter of 1.0 mm, and a length of 50 cm. The outer diameter of the T-connector is 1/16. Two SUS316 tubes having an inch, an inner diameter of 1.0 mm, and a length of 3 cm were connected.
<Merging section (C3)>
The cross connector used as the junction (C3) was changed to a 6-way connector. Three SUS316 tubes (length 3 cm) connected to the cross connector constituting the anionic polymerizable monomer supply flow path (1) and the T-connector constituting the anionic polymerization initiator supply flow path (2) Sugiyama Shoji Co., Ltd. connected two SUS316 tubes (length: 3 cm) so that the connection ports of the anionic polymerizable monomer supply flow path (1) and the anionic polymerization initiator supply flow path (2) alternate. It was connected to a hexagonal joint (6-1 / 8F-1.0, inner diameter 1.0 mm).
The number average molecular weight (Mn) of the obtained polystyrene was 24900, and the molecular weight distribution (dispersion degree, Mw / Mn) was 1.03.

[Example 12]
In Example 1, the cross connector used as the junction (C3) was changed to a T-shaped connector (that is, a polymer was produced in the embodiment of FIG. 1). As the T-shaped connector, an upchurch T-connector (U-429, inner diameter 1.0 mm) was used. As the anionic polymerizable monomer supply channel (1), an SUS316 tube having an outer diameter of 1/16 inch, an inner diameter of 1.0 mm, and a length of 50 cm was used. Other than that, a polymer was produced in the same manner as in Example 1.
The number average molecular weight (Mn) of the obtained polystyrene was 24000, and the molecular weight distribution (dispersion degree, Mw / Mn) was 1.07.

[Example 13]
In Example 1, a polymer was produced in the same manner as in Example 1 except that the solvent of the liquid B was changed from toluene to hexane. The number average molecular weight (Mn) of the obtained polystyrene was 21300, and the molecular weight distribution (dispersion degree, Mw / Mn) was 1.04.
When hexane is used as the solvent of the liquid B, the molecular weight distribution can be highly monodispersed as in the case of using toluene. On the other hand, the monomer conversion was smaller than when toluene was used, the molecular weight of the polymer obtained was slightly smaller, and the yield was lower.

[Example 14]
A block copolymer was synthesized by an anionic polymerization reaction using a flow reaction system having the configuration shown in FIG. Details of each part are shown below.

Liquid feed pump (not shown):
All used PU716B manufactured by GL Sciences Inc., and a pulse damper HPD-1, a back pressure valve manufactured by Tescom (44-2361-24), and a relief valve RHA manufactured by IBS (4 MPa) were sequentially installed on the flow outlet side.

Low temperature bath (R2):
A tabletop small-sized cryogenic water tank CBi-270A was used and set to 0 ° C.

Low temperature bath (R3):
A PSL-2000 made by EYELA was used as a low temperature thermostat and set to −50 ° C.

Anion polymerizable monomer supply channel (1):
One SUS tube was divided into two by a T-shaped connector.
More specifically, an upchurch T-connector (U-429, 1.0 mm inner diameter) is connected to a SUS316 tube having an outer diameter of 1/16 inch, an inner diameter of 1.0 mm, and a length of 50 cm. The anion polymerizable monomer supply flow path (1) was formed by connecting two SUS316 tubes each having an outer diameter of 1/16 inch, an inner diameter of 1.0 mm, and a length of 3 cm so as to face each other.

Anionic polymerization initiator supply channel (2):
A SUS316 tube having an outer diameter of 1/16 inch, an inner diameter of 1.0 mm, and a length of 50 cm was used.

Junction (C3) (cross connector):
A cross connector (U-431, inner diameter 1.0 mm) manufactured by Upchurch was used.
Two SUS316 tubes connected to the T-shaped connector constituting the anionic polymerizable monomer supply channel (1) so as to face each other are connected to two connection ports facing each other among the four connection ports of the cross connector. Respectively. The anion polymerization initiator supply channel (2) was connected to one of the remaining two connection ports, and the remaining connection port was used as a discharge port for sending out the liquid.

Reaction tube (4):
SUS316 tube with outer diameter 1/16 inch, inner diameter 1.0 mm, length 50 cm, outer diameter 3 mm, inner diameter 2 mm, length 8 m SUS316 tube, and outer diameter 1/16 inch, inner diameter 1.0 mm, length 50 cm SUS316 tubes were sequentially connected by a SUS316 union and used as a reaction tube (4).

Polymerization control agent supply flow path (8):
A SUS316 tube having an outer diameter of 1/16 inch, an inner diameter of 1.0 mm, and a length of 50 cm was used.

Junction (C5) (T-shaped connector):
An upchurch T-connector (U-429, inner diameter 1.0 mm) was used.
The reaction tube (4) and the polymerization control agent supply channel (8) were respectively connected to two connection ports facing each other among the three connection ports of the T-connector. The remaining connection port was used as a discharge port for feeding out the liquid.

Reaction tube (9):
SUS316 tube with outer diameter 1/16 inch, inner diameter 1.0 mm, length 5 cm, outer diameter 3 mm, inner diameter 2 mm, length 3 m SUS316 tube, and outer diameter 1/16 inch, inner diameter 1.0 mm, length 4 m SUS316 tubes were sequentially connected with a SUS316 union and used as a reaction tube (9).

Anion polymerizable monomer supply channel (6):
A SUS316 tube having an outer diameter of 1/16 inch, an inner diameter of 1.0 mm, and a length of 50 cm was used.

Junction (C4) (T-shaped connector):
T-type union tee (SS-3M0-3, inner diameter 2.4 mm) manufactured by Swagelok was used.
The reaction tube (9) and the anion polymerizable monomer supply channel (6) were respectively connected to two connection ports facing each other among the three connection ports of the T-connector. The remaining connection port was used as a discharge port for feeding out the liquid.

Reaction tube (7):
SUS316 tube with outer diameter 1/16 inch, inner diameter 1.0 mm, length 5 cm, SUS316 tube with outer diameter 4 mm, inner diameter 3 mm, length 2 m, and SUS316 tube with outer diameter 3 mm, inner diameter 2 mm, length 1.1 m Were sequentially connected by SUS316 union and used as a reaction tube (7).

Polymerization terminator supply channel (3):
A SUS316 tube having an outer diameter of 1/16 inch, an inner diameter of 1.0 mm, and a length of 50 cm was used.

Junction (C2) (T-shaped connector):
An upchurch T-connector (U-429, inner diameter 1.0 mm) was used.
The reaction tube (7) and the polymerization terminator supply channel (3) were respectively connected to two connection ports facing each other among the three connection ports of the T-connector. The remaining connection port was used as a discharge port for feeding out the liquid.

Piping (5):
A SUS316 tube having an outer diameter of 1/16 inch, an inner diameter of 1.0 mm, and a length of 1 m was used.

Liquid A1: containing the first monomer introduced into the anionic polymerizable monomer supply channel (1)
<Styrene / THF>
Wako Pure Chemicals THF (deoxygenated grade) and Wako Pure Chemicals styrene (special grade) were added to a 5 LSUS tank to prepare 4 L of 2M-styrene / THF solution. This solution was dehydrated with molecular sieve 3A to obtain liquid A1.

Liquid B containing an initiator introduced into the anionic polymerization initiator supply channel (2):
<NBuLi / Toluene>
Toluene (deoxygenated grade) made by Wako Pure Chemical Industries was added to a 5 LSUS tank and cooled to 0 ° C. NBuLi (1.6M-nBuLi / hexane solution) manufactured by Kanto Kagaku was added and titrated with menthol / bipyridine to prepare 4L of 0.018M-nBuLi / toluene solution.

Liquid C containing a polymerization control agent introduced into the polymerization control agent supply channel (8):
<1,1-diphenylethylene (DPE) & LiCl / THF>
To a 5 L eggplant flask, THF (deoxygenated grade) manufactured by Wako Pure Chemical Industries, Ltd. and lithium chloride (purity 99%) manufactured by Wako Pure Chemical Industries, Ltd. were added. Macromolecules, 2009, vol. 42, p. Chemical dehydration was performed by the method described in 8835, and 3 L of 0.09M-LiCl / THF was prepared. To this solution, DPE distilled from n-butyllithium was added so as to have a concentration of 0.15 M to obtain liquid C.

Liquid A2 containing the second monomer introduced into the anionically polymerizable monomer supply channel (6):
<Methyl methacrylate (MMA) / THF>
Wako Pure Chemicals THF (deoxygenated grade) and Wako Pure Chemicals methyl methacrylate (special grade) were added to a 5 LSUS tank to prepare 4 L of 2M-MMA / THF solution. This solution was dehydrated with molecular sieve 3A to obtain liquid A2.

Polymerization terminator introduced into the polymerization terminator supply channel (3):
<MeOH / THF>
Wako Pure Chemicals THF (deoxygenated grade) and Wako Pure Chemicals MeOH (deoxygenated grade) were added to a 3 LSUS tank to prepare 4 L of a 0.5 M MeOH / THF solution, which was used as a polymerization terminator.

Liquid feeding conditions:
Liquid A1 (2M-styrene / THF): 40.1 mL / min
Liquid B (0.018M-nBuLi / toluene): 18.2 mL / min
Liquid C (DPE & LiCl / THF): 11.1 mL / min
Liquid A2 (2M-MMA / THF): 42.1 mL / min
Polymerization terminator (0.5M-MeOH / THF): 10.0 mL / min

Flow path time:
Reaction tube (4): about 26 seconds Reaction tube (9): about 11 seconds Reaction tube (7): about 40 seconds Pipe (5): about 9 seconds Residence time: about 86 seconds

take out:
1 L of the solution containing the polymer was collected from the outlet of the pipe (5) (for 8 minutes), dropped into 10 L of 10 times the volume of this solution, and the precipitated white precipitate was collected by filtration. The collected white precipitate was dried at 80 ° C. under vacuum to obtain 110 g of a polystyrene-b-polymethylmethacrylate block copolymer (manufacturing capacity: 825 g / h). A part of the obtained block copolymer was dissolved in THF, and the molecular weight and molecular weight distribution were measured by gel permeation chromatography (GPC). As a result, the number average molecular weight (Mn) was 43800, and the molecular weight distribution (dispersion degree, Mw / Mn) was 1.06. When 1H-NMR spectrum was measured using heavy acetone as a measurement solvent, the component composition ratio (molar ratio: styrene / MMA) was 51/49.

[Example 15]
In Example 14, a block copolymer was produced in the same manner as in Example 14 except that the liquid feeding conditions were changed as follows.
Liquid feeding conditions:
Liquid A1 (2M-styrene / THF): 25.0 mL / min
Liquid B (0.018M-nBuLi / toluene): 17.8 mL / min
Liquid C (DPE & LiCl / THF): 11.1 mL / min
Liquid A2 (2M-MMA / THF): 35.0 mL / min
Polymerization terminator (0.5M-MeOH / THF): 10.0 mL / min
The resulting block copolymer has a number average molecular weight (Mn) of 27400, a molecular weight distribution (dispersity, Mw / Mn) of 1.04, and a component composition ratio (molar ratio: styrene / MMA) of 48/52. there were.

[Example 16]
A block polymer was produced in the same manner as in Example 14 except that the anionic polymerization initiator supply channel (2) in Example 14 was changed to a SUS316 tube having an outer diameter of 3 mm, an inner diameter of 2 mm, and a length of 50 cm. The number average molecular weight (Mn) of the obtained block copolymer was 44000, the molecular weight distribution (dispersion degree, Mw / Mn) was 1.05, and the component composition ratio (molar ratio: styrene / MMA) was 50/50. It was.

[Comparative Example 4]
The anionic polymerizable monomer supply channel (1) and the anionic polymerization initiator supply channel (2) of Example 14 were both changed to SUS316 tubes having an outer diameter of 1/16 inch, an inner diameter of 0.5 mm, and a length of 50 cm. Except for the above, an attempt was made to produce a block copolymer in the same manner as in Example 14. However, the pressure inside the system exceeded 4 MPa, so that the liquid could not be fed, and the polymer could not be obtained continuously and stably.

[Example 17]
In Example 14, a block copolymer was produced in the same manner as in Example 14 except that the liquid feeding conditions were changed as follows.
Liquid feeding conditions:
Liquid A1 (2M-styrene / THF): 19.0 mL / min
Liquid B (0.04M-nBuLi / toluene): 12.2 mL / min
Liquid C (DPE & LiCl / THF): 22.2 mL / min
Liquid A2 (2M-MMA / THF): 35.0 mL / min
Polymerization terminator (0.5M-MeOH / THF): 10.0 mL / min
The resulting block copolymer has a number average molecular weight (Mn) of 13,000, a molecular weight distribution (dispersity, Mw / Mn) of 1.05, and a component composition ratio (molar ratio: styrene / MMA) of 49/51. there were.

[Comparative Example 5]
In Example 14, a block copolymer was produced in the same manner as in Example 14 except that the liquid feeding conditions were changed as follows.
Liquid feeding conditions:
Liquid A1 (2M-styrene / THF): 2.5 mL / min
Liquid B (0.018M-nBuLi / toluene solution): 1.8 mL / min
Liquid C (DPE & LiCl / THF): 1.1 mL / min
Liquid A2 (2M-MMA / THF): 3.5 mL / min
Polymerization terminator (0.5M-MeOH / THF): 1.0 mL / min
The obtained block copolymer has a number average molecular weight (Mn) of 46400, a molecular weight distribution (dispersion degree, Mw / Mn) of 1.11, and a component composition ratio (molar ratio: styrene / MMA) of 53/47. there were.

[Example 18]
In Example 14, a block copolymer was produced in the same manner as in Example 14 except that the liquid to be introduced and the flow rate were as follows, and that the block copolymer was taken out as follows.
Liquid A1 (1.1M-4-tert-butylstyrene / THF): 18.0 mL / min
Liquid B (0.015M-nBuLi / toluene): 12.0 mL / min
Liquid C (DPE & LiCl / THF, DPE concentration 0.15M, LiCl concentration 0.09M): 6.0 mL / min
Liquid A2 (0.53M-2-methoxyethyl methacrylate / THF): 18.0 mL / min
Polymerization terminator (0.3M-MeOH / THF): 6.0 mL / min

take out:
From the outlet of the pipe (5), 1.2 L of a solution containing the block copolymer was collected (20 minutes). 2.4 L of ethyl acetate was added to this solution, and it was separated and washed with 1 L of 0.1 M hydrochloric acid (2 times) and 1 L of pure water (4 times), and the organic layer was concentrated under reduced pressure to 1 L. This was dropped into 5 L of a mixed solution of hexane / isopropyl alcohol (IPA) (50/50), and the precipitated white precipitate was collected by filtration, dried at 80 ° C. under vacuum, and 87 g of poly tert-butylstyrene-b— Polymethoxyethyl methacrylate was obtained (production capacity: 261 g / h). The number average molecular weight (Mn) of this block copolymer was 25100, and the molecular weight distribution (Mw / Mn) was 1.08. Moreover, the component composition ratio (molar ratio: t-butylstyrene / 2-methoxyethyl methacrylate) was 71/29.

[Example 19]
A polymer was produced in the same manner as in Example 14 except that Example 14 was changed as follows.
<Anion polymerizable monomer supply channel (1)>
A single SUS tube was divided into three by a cross connector (three-branch structure). More specifically, an upchurch cross connector (U-431, 1.0 mm inner diameter) is connected to a SUS316 tube having an outer diameter of 1/16 inch, an inner diameter of 1.0 mm, and a length of 50 cm. Three SUS316 tubes each having an outer diameter of 1/16 inch, an inner diameter of 1.0 mm, and a length of 3 cm were connected to one connection port.
<Anionic polymerization initiator supply channel (2)>
An upchurch T-connector (U-429, 1.0 mm inner diameter) is connected to a SUS316 tube having an outer diameter of 1/16 inch, an inner diameter of 1.0 mm, and a length of 50 cm. The outer diameter of the T-connector is 1/16. Two SUS316 tubes having an inch, an inner diameter of 1.0 mm, and a length of 3 cm were connected.
<Merging section (C3)>
The cross connector used as the junction (C3) was changed to a 6-way connector. Three SUS316 tubes (length 3 cm) connected to the cross connector constituting the anionic polymerizable monomer supply flow path (1) and the T-connector constituting the anionic polymerization initiator supply flow path (2) Sugiyama Shoji Co., Ltd. connected two SUS316 tubes (length: 3 cm) so that the connection ports of the anionic polymerizable monomer supply flow path (1) and the anionic polymerization initiator supply flow path (2) alternate. It was connected to a hexagonal joint (6-1 / 8F-1.0, inner diameter 1.0 mm).
The number average molecular weight (Mn) of the obtained polystyrene was 44000, the molecular weight distribution (dispersion degree, Mw / Mn) was 1.06, and the component composition ratio (molar ratio: styrene / MMA) was 51/49.

  As shown in each of the above Examples, the polymer production method of the present invention can obtain a polymer with a highly monodispersed molecular weight distribution continuously and stably with high productivity. I understood.

100, 200, 300, 400, 500 Flow type reaction system I, II, III, IV, V Inlet 1, 6 Anion polymerizable monomer supply flow path 2 Anion polymerization initiator supply flow path 3 Polymerization stopper supply flow path 4 , 7, 9 Reaction tube 5 Piping 8 Polymerization control agent supply flow path C1, C2, C3, C4, C5 Merging section R1, R2, R3 Low temperature constant temperature bath

Claims (20)

A method for producing a polymer that performs an anionic polymerization reaction by a flow-type reaction,
The liquid A containing an anionic polymerizable monomer, the liquid B containing an anionic polymerization initiator, and a polymerization terminator are introduced into different flow paths, and the respective liquids are circulated in the respective flow paths. The anionic polymerizable monomer is anionically polymerized while the combined liquid flows downstream in the reaction flow path, and the polymerization reaction liquid flowing in the reaction flow path and the polymerization terminator are merged. Including stopping the
The equivalent diameter of the flow path into which the liquid A is introduced and the flow path into which the liquid B is introduced is 1 to 10 mm,
The equivalent diameter of the flow path at the junction of the liquid A and the liquid B is 0.2 to 10 mm,
The flow rate for introducing the liquid A is 10 to 2000 mL / min,
The flow rate for introducing the liquid B is more than 10 mL / min and 500 mL / min or less,
A method for producing a polymer, wherein the anionic polymerization initiator is alkyl lithium.
However, when the anionic polymerization initiator is butyl lithium, the butyl lithium is n-butyl lithium.   The production method according to claim 1, wherein the length of the reaction path is 3 to 50 m.   The sum of the number of flow paths through which the liquid A circulates and the number of flow paths through which the liquid B circulates is 3 to 10 connected to the confluence portion of the liquid A and the liquid B. 2. The production method according to 2.   The manufacturing method according to claim 1, wherein the number of flow paths through which the liquid A flows is greater than the number of flow paths through which the liquid B flows.   The manufacturing method of any one of Claims 1-4 which makes the equivalent diameter of the flow path of the confluence | merging part of the said liquid A and the said liquid B 1-10 mm. The production method according to any one of claims 1 to 5 , wherein n-butyllithium is used as the anionic polymerization initiator. The liquid B contains an aromatic hydrocarbon, a manufacturing method of any one of claims 1-6. A method for producing a block copolymer that performs an anionic polymerization reaction by a flow-type reaction,
The liquid A1 containing the first anionic polymerizable monomer, the liquid B containing the anionic polymerization initiator, the liquid A2 containing the second anionic polymerizable monomer, and the polymerization terminator are introduced into different flow paths, respectively. The liquid A1 and the liquid B are circulated in the flow path, and the combined liquid anionically polymerizes the first anionic polymerizable monomer while flowing downstream in the first reaction flow path,
The polymerization reaction liquid flowing in the first reaction channel and the liquid A2 are merged, and the merged liquid anionically polymerizes the second anionic polymerizable monomer while flowing downstream in the second reaction channel, 2 merging a polymerization reaction liquid and a polymerization terminator flowing in the reaction flow path to stop the polymerization reaction,
The equivalent diameter of the flow path into which the liquid A1 is introduced and the flow path into which the liquid B is introduced is 1 to 10 mm,
The equivalent diameter of the flow path at the junction of the liquid A1 and the liquid B is 0.2 to 10 mm,
The flow rate for introducing the liquid A1 is 10 to 2000 mL / min,
The flow rate for introducing the liquid B is more than 10 mL / min and 500 mL / min or less,
A method for producing a block copolymer, wherein the anionic polymerization initiator is alkyl lithium.
However, when the anionic polymerization initiator is butyl lithium, the butyl lithium is n-butyl lithium. The manufacturing method of Claim 8 which makes the length of a 1st reaction flow path 3 m or more and 50 m or less. Connecting to the junction portion between the liquid B and the liquid A1, the liquid A1 is the number of channels and said solution B to 3-10 present the total number of channels to be distributed to the distribution, according to claim 8 or 9. The production method according to 9 . The manufacturing method according to any one of claims 8 to 10 , wherein the number of flow paths through which the liquid A1 flows is greater than the number of flow paths through which the liquid B flows. The anionic polymerization initiator used n- butyl lithium as, any one method according to claim 8-11. The liquid B contains an aromatic hydrocarbon, a manufacturing method of any one of claims 8-12. The liquid A1 and the liquid B are merged, and after the merged liquid anionically polymerizes the first anionic polymerizable monomer while flowing downstream in the first reaction channel, the first reaction channel before merging the polymerization reaction liquid flowing through said liquid A2 and a polymerization reaction liquid flowing through the first reaction channel comprises merging a liquid C containing polymerization control agents, claims 8 to 14. The manufacturing method according to any one of items 13 . A flow reaction system for producing a polymer by an anionic polymerization reaction,
The first flow path through which the anionic polymerizable monomer flows, the second flow path through which the anionic polymerization initiator flows, the third flow path through which the polymerization terminator flows, and the first flow path and the second flow path merge. A first junction, a reaction tube connected downstream of the first junction, a second junction where the reaction tube and the third flow path merge, and a pipe connected downstream of the second junction Have
The equivalent diameters of the first channel and the second channel are both 1 to 10 mm,
The total of the number of the first flow paths and the number of the second flow paths connected to the first merge portion is 3 to 10,
A flow reaction system in which the anionic polymerization initiator is alkyllithium.
However, when the anionic polymerization initiator is butyl lithium, the butyl lithium is n-butyl lithium. The flow type reaction system according to claim 15 , wherein the number of the first flow paths connected to the first merge part is larger than the number of the second flow paths connected to the first merge part. A flow reaction system for producing a block copolymer by an anionic polymerization reaction,
A first flow path through which the first anionic polymerizable monomer flows, a second flow path through which the anionic polymerization initiator flows, a third flow path through which the second anionic polymerizable monomer flows, and a polymerization stopper flow. A fourth flow path, a first merge section where the first flow path and the second flow path merge, a first reaction tube connected downstream of the first merge section, a first reaction tube, and a third flow path Of the second merging portion, the second reaction tube connected downstream of the second merging portion, the third merging portion where the second reaction tube and the fourth flow path merge, and the third merging portion A pipe connected downstream,
The equivalent diameters of the first channel and the second channel are both 1 to 10 mm,
The total of the number of the first flow paths and the number of the second flow paths connected to the first merge portion is 3 to 10,
A flow reaction system in which the anionic polymerization initiator is alkyllithium.
However, when the anionic polymerization initiator is butyl lithium, the butyl lithium is n-butyl lithium. The flow type reaction system according to claim 17 , wherein the number of the first flow paths connected to the first merge part is larger than the number of the second flow paths connected to the first merge part. A flow reaction system for producing a block copolymer by an anionic polymerization reaction,
A first flow path through which the first anionic polymerizable monomer flows, a second flow path through which the anionic polymerization initiator flows, a third flow path through which the polymerization control agent flows, and a second anionic polymerizable monomer flow through. A fourth flow path, a fifth flow path through which the polymerization terminator circulates, a first merge section where the first flow path and the second flow path merge, and a first reaction connected downstream of the first merge section. A pipe, a second merging portion where the first reaction tube and the third flow path merge, a second reaction pipe connected downstream of the second merging section, and the second reaction pipe and the fourth flow path merge. Connected to the third merging portion, the third reaction tube connected downstream of the third merging portion, the fourth merging portion where the third reaction tube and the fifth flow path merge, and the downstream of the fourth merging portion. Pipes, and
The equivalent diameters of the first channel and the second channel are both 1 to 10 mm,
The total of the number of the first flow paths and the number of the second flow paths connected to the first merge portion is 3 to 10,
A flow reaction system in which the anionic polymerization initiator is alkyllithium.
However, when the anionic polymerization initiator is butyl lithium, the butyl lithium is n-butyl lithium. The flow type reaction system according to claim 19 , wherein the number of the first flow paths connected to the first merge part is larger than the number of the second flow paths connected to the first merge part.

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