JP6096703B2 - Polymer production method and flow reaction system used therefor - Google Patents

Description

  The present invention relates to a method for producing a polymer and a flow reaction system used therefor.

  Cationic polymerization is a polymerization reaction in which the active species at the growth terminal of the polymer is a cation. In the cationic polymerization reaction, a monomer such as a vinyl compound is polymerized using a cation such as Bronsted acid or Lewis acid as a polymerization initiator.

Cationic polymerization is carried out at a very low temperature in order to suppress side reactions such as chain transfer reaction and termination reaction. For example, in the cationic polymerization of isobutene, in order to obtain a high molecular weight polymer, the temperature is around −100 ° C. A polymerization reaction is performed (Patent Document 1).
In addition, living cationic polymerization that stabilizes the active species at the growth terminal of the polymer to suppress the side reaction and obtain a polymer having a narrow molecular weight distribution has been proposed (for example, Patent Documents 2 and 3). The living cationic polymerization described in Patent Documents 2 and 3 is carried out batchwise. However, since the batch method is a polymerization reaction under mechanical stirring, local unevenness of monomers and polymerization initiators is likely to occur in the reaction system, and there is a limitation in improving the degree of dispersion of the resulting polymer.

  On the other hand, living cationic polymerization using a flow reactor that continuously supplies a polymerization initiator and a monomer to a micromixer is also known. Patent Document 4 describes that a polymer having a narrow molecular weight distribution was obtained by performing cationic polymerization using a flow reactor.

Japanese Patent No. 2775056 JP 7-292038 A JP-A-8-53514 JP 2008-1771 A

  Conventional cationic polymerization initiators include Bronsted acids such as sulfuric acid, methyl sulfuric acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, perchloric acid, boron trifluoride, aluminum chloride, titanium tetrachloride, tin tetrachloride. Lewis acids such as have been used. However, many Bronsted acids are highly reactive and corrosive, and sufficient safety is required. In addition, when a metal Lewis acid is used, a large amount of metal remains in the resulting polymer, which is not suitable for use in polymers such as electronic materials and medical materials in which the metal content in the material is severely restricted. .

  The present invention is a method for continuously producing a polymer by a cationic polymerization reaction using Bronsted acid as a polymerization initiator, which is excellent in handling safety and highly monodispersed in molecular weight distribution. It is an object of the present invention to provide a production method for obtaining a polymer and a flow reaction system used in this production method.

  The present inventor has intensively studied in view of the above problems. Then, a Bronsted acid precursor solution, which is a photoacid generator, is introduced into the flow channel of the flow reaction system, and light irradiation is performed during circulation in the flow channel, so that Bronsted acid is efficiently generated in the flow channel It came to pay attention to. Further, the solution in which the Bronsted acid is generated is directly merged with the cationic polymerizable monomer solution introduced into another flow path of the flow reaction system to cation polymerize the monomer, and this reaction solution is further added to the flow reaction system. Bringed with a reaction terminator introduced in another flow path to neutralize the Bronsted acid, the generation and neutralization of the Bronsted acid can be completed within the flow reaction system flow path. It has been found that a continuous cationic polymerization reaction system with excellent safety can be constructed. Furthermore, the molecular weight distribution of the polymer obtained using the above reaction system was narrow, and it was found that a polymer having a highly monodispersed molecular weight distribution was obtained, and the present invention was completed.

The above object of the present invention has been achieved by the following means.
[1]
A method for producing a polymer that performs a cationic polymerization reaction by a flow reaction,
While introducing the Bronsted acid precursor solution into the first flow channel, the cationic polymerizable monomer solution into the second flow channel, and the polymerization terminator into the third flow channel,
The Bronsted acid precursor is irradiated with light when flowing in the first flow path to generate Bronsted acid, and the solution in which the Bronsted acid is generated and the monomer solution flowing in the second flow path are merged to react. The monomer is cationically polymerized while circulating in the channel, and the polymerization reaction liquid flowing in the reaction channel and the polymerization terminator flowing in the third channel are merged to stop the polymerization reaction to obtain a polymer solution. Manufacturing method.
[2]
The production method according to [1], wherein the BrKasted acid has a pKa of -1.0 or less.
[3]
The production method according to [1], wherein the pKa of the Bronsted acid is −4.0 or less.
[4]
The production method according to any one of [1] to [3], wherein the reaction temperature of the cationic polymerization is −40 ° C. to −10 ° C.
[5]
The equivalent diameter of the flow path at the junction of the first flow path and the second flow path and the equivalent diameter of the flow path at the merge of the reaction flow path and the third flow path are 0.2 mm to 10 mm. [1] The production method according to any one of [4].
[6]
The production method according to any one of [1] to [5], wherein the reaction channel has an equivalent diameter of 0.1 to 50 mm.
[7]
The production method according to any one of [1] to [6], wherein the Bronsted acid precursor is a sulfonium compound.
[8]
The production method according to [7], wherein the sulfonium compound is represented by the following general formula (ZI).

In the general formula ^{(ZI), R 201, R} 202 and ^{R 203} represents an organic group. Z ⁻ represents a non-nucleophilic anion.
[9]
A method for producing a block copolymer in which a cationic polymerization reaction is performed by a flow reaction,
Bronsted acid precursor solution in the first flow path, the first cationic polymerizable monomer solution in the second flow path, the second cationic polymerizable monomer solution in the third flow path, and the polymerization stop in the fourth flow path While introducing each agent and circulating each liquid in each channel,
The Bronsted acid precursor is irradiated with light when flowing in the first flow path to generate a Bronsted acid, and a solution in which the Bronsted acid is generated and a first cationic polymerizable monomer solution flowing in the second flow path are obtained. The first cation polymerizable monomer is cationically polymerized while merging and flowing in the first reaction channel, and the polymerization reaction liquid flowing in the first reaction channel and the second cation flowing in the third channel The second cationic polymerization monomer is cationically polymerized while joining the polymerizable monomer solution and flowing in the second reaction channel, and the polymerization reaction liquid flowing in the second reaction channel and the fourth channel are passed through A production method comprising: joining a circulating polymerization terminator to stop a polymerization reaction to obtain a block copolymer solution.
[10]
A flow reaction system for producing a polymer by a cationic polymerization reaction,
The flow-type reaction system includes a first flow path, a second flow path, a third flow path, a liquid feed pump that sends a solution to each of the first to third flow paths, a first flow path, and a second flow path. A first merging portion where the flow path merges, 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 downstream of the second merging portion And a pipe connected to
A Bronsted acid precursor solution is introduced into the first flow path, a cationic polymerizable monomer solution is introduced into the second flow path, and a polymerization terminator is introduced into the third flow path, respectively.
The Bronsted acid precursor is irradiated with light when flowing through the first flow path to generate Bronsted acid, and the solution in which the Bronsted acid is generated and the monomer solution flowing through the second flow path are formed at the first junction. The above monomers are cationically polymerized when flowing in the reaction tube, and the polymerization reaction liquid and the polymerization terminator flowing in the third flow path are merged at the second merged portion to stop the polymerization reaction. A system that obtains a coalesced solution.
[11]
A flow reaction system for producing a block copolymer by a cationic polymerization reaction,
The flow-type reaction system includes a first flow path, a second flow path, a third flow path, a fourth flow path, a liquid feed pump that sends a solution to each of the first to fourth flow paths, A first merge section where the first flow path and the second flow path merge; a first reaction pipe connected downstream of the first merge section; and a second merge where the first reaction pipe and the third flow path merge. A second reaction tube connected downstream of the second merging portion, a third merging portion where the second reaction tube and the fourth flow path merge, and a pipe connected downstream of the third merging portion Have
Brnsted acid precursor solution in the first channel, first cationic polymerizable monomer solution in the second channel, second cationic polymerizable monomer solution in the third channel, and polymerization in the fourth channel. Stopping agents are introduced by the above-mentioned liquid feed pumps,
The Bronsted acid precursor is irradiated with light when flowing in the first flow path to generate Bronsted acid, and the solution that has generated the Bronsted acid and the first cationic polymerizable monomer that flows in the second flow path are the first. The first cation polymerizable monomer is cation polymerized at the time of flowing in the first reaction tube at the first merging portion, and the second cation polymerizable monomer flowing in the polymerization reaction solution and the third flow path is the second merging portion. The second cationic polymerizable monomer is cationically polymerized at the time of circulation in the second reaction tube, and the polymerization reaction liquid and the polymerization terminator flowing through the fourth flow path are merged at the third convergence part to cause the polymerization reaction. A system for stopping and obtaining a block copolymer solution from the pipe outlet.

  In the present specification, when there are a plurality of substituents, linking groups, and the like (hereinafter referred to as substituents) indicated by specific symbols, or when a plurality of substituents are specified simultaneously or alternatively, It means that a substituent etc. may mutually be same or different. The same applies to the definition of the number of substituents and the like. Further, when there are repetitions of a plurality of partial structures represented by the same indication in the formula, each partial structure or repeating unit may be the same or different. Further, unless otherwise specified, when a plurality of substituents and the like are adjacent (particularly adjacent), they may be connected to each other or condensed to form a ring.

  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 substituent that does not clearly indicate substitution or non-substitution (the same applies to a linking group) means that the group may further have a substituent as long as the intended effect is not impaired. . This is also synonymous for compounds that do not specify substitution / non-substitution.

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

  The production method of the present invention is a method for continuously producing a polymer by a flow method, is excellent in handling safety, and the molecular weight distribution of the obtained polymer is highly monodispersed. The flow reaction system of the present invention is a reaction system suitable for the production method of the present invention.

It is a figure which shows the outline of one Embodiment of the flow type reaction system of this invention. It is a figure which shows the outline of the flow type light irradiation apparatus with which the flow type reaction system of this invention is provided. It is a figure which shows an example of the microreactor which comprises the light-receiving part of a 1st flow path in the flow type reaction system of this invention. It is a figure which shows the outline of another one Embodiment of the flow type reaction system of this invention.

  Hereinafter, the present invention will be described in detail.

[Flow reaction system]
An embodiment of a flow reaction system used in a method for producing a polymer of the present invention (hereinafter referred to as “the production method of the present invention”) will be described with reference to FIG. FIG. 1 is a schematic view showing an example of a flow reaction system used in the present invention. In addition, this invention is not limited to the form shown by drawing except the matter prescribed | regulated by this invention. For example, the equivalent diameter of the flow path constituting the merge portion may be larger or smaller than the equivalent diameter of the flow path, the reaction tube, and the pipe located on the upstream side or the downstream side, and the same. Also good. In addition, the equivalent diameters of the respective flow paths, reaction tubes, and pipes may be the same or different.
A flow reaction system (100) shown in FIG. 1 includes a first flow path (1) having an inlet (A) for introducing a Bronsted acid precursor solution, and an inlet (B) for introducing a cationic polymerizable monomer solution. ), A third channel (3) having an inlet (C) for introducing a polymerization terminator, a first channel (1), and a second channel (2). A first merging section (4) that merges, a reaction pipe (5) connected downstream of the first merging section (4), a second merging section (6) where the reaction pipe (5) and the third flow path merge, A pipe (7) connected downstream of the second junction (6) is provided. A liquid feed pump such as a syringe pump is connected to the introduction port (A), the introduction port (B), and the introduction port (C), and the Bronsted acid precursor solution, the cationic polymerizable monomer solution, and the polymerization termination are performed by this pump. The agent is delivered.
In this specification, “upstream” and “downstream” are used in the direction in which the liquid flows, and the side on which the liquid is introduced (the inlets (A), (B), (C), and (D) in FIGS. Side) is upstream, and the opposite side is downstream.

<First channel>
A Bronsted acid precursor solution is introduced into the first flow path (1), and the Bronsted acid precursor solution is irradiated with light when flowing through the first flow path to generate Bronsted acid.
A part or all of the first flow path (1) is used as a light receiving part (E) for generating a Bronsted acid by irradiating the Bronsted acid precursor with light. The Bronsted acid precursor will be described later.
There is no particular limitation on the form of the light receiving part (E) of the first flow path (1), and the light energy is absorbed by the Bronsted acid precursor flowing through the first flow path, and the Bronsted acid is generated. Not. Moreover, the light-receiving part (E) of the first channel (1) is transmissive to the irradiated light. The irradiated light is actinic rays or radiation. “Actinic ray” or “radiation” in the present specification includes, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV) rays, X rays or electron rays (EB). Further, in this specification, “light” applied to the first flow path means actinic rays or radiation.
In this specification, “light-transmitting” means that 50% or more of the irradiated light amount is transmitted. It is preferable to transmit 80% or more.

  It is preferable that the light receiving part (E) of the first flow path (1) is incorporated in the flow type light irradiation device. An example of a flow type light irradiation apparatus is shown in FIG.

  The flow-type light irradiation device (101) in FIG. 2 is a housing having a light source therein, and a part of the first flow path (1) including the light receiving part (E) is incorporated into the flow-type light irradiation device. ing.

  The flow type light irradiation device (101) includes at least one light source. The structure of the light source is appropriately selected according to the type of Bronsted acid precursor to be used, but is usually an ultraviolet light source. As the light source, for example, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, xenon, an LED (Light-Emitting Diode), or a cold cathode fluorescent tube can be used. From the viewpoint of energy efficiency, a low-pressure mercury lamp, xenon, LED, or cold cathode fluorescent tube is preferable.

The light receiving portion of the first flow path incorporated in the flow type light irradiation device (101) is preferably constituted by a microreactor having a micro flow path. For example, a first substrate having a channel for forming a channel on the substrate is prepared, and a second substrate is bonded so as to cover the groove formed on the first substrate, thereby forming a channel inside. Microreactors can be made. The microreactor is provided with a solution introduction part communicating with the groove (flow path) and a discharge part from which the solution flowing through the reactor comes out, and the introduction part and the discharge part constitute a first flow path. A flow path such as a tube is connected. The introduction part and the discharge part can be formed, for example, by providing a hole that penetrates the first substrate or the second substrate and communicates with the flow path.
An example of the microreactor constituting the light receiving unit is shown in FIG. FIG. 3A shows a first substrate (9) in which a groove (1c) is formed, and FIG. 3 (b) shows a light-transmissive second substrate on the groove (1c) of the first substrate (9). This is a microreactor in which (10) is laminated and the groove (1c) is formed as a flow path. In addition, the shape of the flow path is not limited to the shape shown in FIG. 3, and can be any shape according to the purpose. When the microreactor shown in FIG. 3 is used, the Bronsted acid precursor solution introduced from the introduction port (A) of the first channel (1) flows from the introduction part (1a) of the microreactor into the microreactor. It is introduced into the path (1c). When the microreactor flows through the channel (1c), light is irradiated to the light transmissive second substrate (10) side, and the Bronsted acid precursor absorbs light energy to generate Bronsted acid. The solution containing Bronsted acid is discharged from the discharge part (1b) and flows to the first merge part (4) through the first flow path (1).
The flow-type light irradiation device may include a microreactor accommodating portion that detachably receives the microreactor. At least one of the first substrate (9) and the second substrate (10) is light transmissive, and is disposed with the light transmissive substrate side facing the light source. If both the first substrate and the second substrate are light transmissive, either substrate may be directed to the light source side.
The flow-type light irradiation device including the microreactor having the above-described configuration can irradiate light from the light source more uniformly over the entire flow path of the microreactor, and the light source and the microreactor can be disposed in a close state. As a result, light energy can efficiently reach the Bronsted acid precursor flowing through the microreactor. That is, the acid generation efficiency of the Bronsted acid precursor is excellent.

In the production of the microreactor, the first substrate (9) on which the groove is formed is, for example, a resin substrate made of a fluororesin such as perfluoroalkoxyalkane (PFA) or Teflon (registered trademark), stainless steel, or hastelloy (registered). And a glass substrate made of quartz glass or lime soda glass can be used. From the viewpoint of flexibility, chemical resistance, and cost, PFA, Teflon (registered trademark), stainless steel, and hastelloy are preferable. The thickness of the first substrate (9) is preferably 1000 to 20000 μm.
The second substrate (10) is preferably a glass substrate made of, for example, quartz glass or lime soda glass. The thickness of the second substrate (10) is preferably 500 to 10,000 μm.

The shape of the flow path in the microreactor is not particularly limited. Further, the equivalent diameter of the flow path in the microreactor is preferably 100 to 5000 μm, and more preferably 150 to 2000 μm. 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 (d _eq ) is defined as d _eq = 4 A / p using A: pipe cross-sectional area of the pipe and p: wetting length (inner peripheral length) 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 d _eq = 4a ² / 4a = a for a regular square tube with one side a in the tube cross section, d _eq = a / 3 ^{1/2 for} a regular triangle tube with one side a, and between parallel plates with a channel height h In this flow, d _eq = 2h (for example, see “Mechanical Engineering Encyclopedia” edited by the Japan Society of Mechanical Engineers, 1997, Maruzen Co., Ltd.).
The length of the flow path in the microreactor is preferably 10 mm to 1000 cm. The microreactor is preferably flat. The size of the flat microreactor is preferably such that the area of the front surface (back surface) is 1 to 10,000 cm ² and the thickness is 1 to 10 mm.

  In the flow type light irradiation device, the light source unit may include a temperature adjustment mechanism. Thereby, the heating of the first flow path (1) can be suppressed, and the surface temperature of the light source can be kept in an appropriate range, so that the light output can be stabilized. A flow-type light irradiating device in which the light receiving part is constituted by a microreactor can be obtained commercially. For example, KeyChem-Lumino is commercially available from YMC Co., Ltd.

  The flow-type light irradiation device (101) preferably has the following configuration in addition to the above-described microreactor. That is, it is also preferable to include a light-transmitting cylindrical body provided with a light source therein and a light-transmitting tube that forms a first flow path wound around the outer peripheral surface of the cylindrical body. In this embodiment, since the light-transmitting tube wound around the outer peripheral surface of the light-transmitting cylindrical body is irradiated by the light source unit arranged inside the cylindrical body, the Bronsted acid precursor in the tube It is possible to irradiate the body with light very efficiently, and it is possible to provide a flow-type light irradiation device that is very preferable in terms of reaction efficiency and energy efficiency.

  As the light transmissive tube, for example, a perfluoroalkoxyalkane (PFA), a Teflon (registered trademark) tube, a glass tube made of quartz glass or lime soda glass, or the like can be used. From the viewpoints of flexibility and chemical resistance, PFA and Teflon (registered trademark) are preferable. As the cylindrical body, for example, a cylindrical body made of transparent acrylic resin or fluororesin, or a cylindrical body made of quartz glass or lime soda glass can be used. The transmission diameter of the tube is preferably 0.1 to 10 mm, preferably 0.1 to 5 mm, more preferably 0.5 to 2 mm from the viewpoint of light transmittance. Furthermore, the length of the tube is set in consideration of the time at which the intended reaction is completed, the flow rate of the liquid, and the like, but is preferably 0.1 to 25 m from the viewpoint of pressure loss.

  There is no restriction | limiting in particular in structures other than the light-receiving part (E) of a 1st flow path (1). Usually, a tube having a transmission diameter of about 0.1 mm to 1 cm and a length of about 10 cm to 10 m in total including the upstream side and the downstream side of the light receiving unit (E) is used. 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), Examples include 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.

<Second channel>
The second channel (2) is a channel through which the cationically polymerizable monomer solution introduced from the inlet (B) flows. The cationic polymerizable monomer will be described later.
As the second channel (2), a tube having a transmission diameter of about 0.1 mm to 1 cm and a length of about 10 cm to 10 m is usually used. 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), Examples include 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.

<First junction>
The Bronsted acid precursor solution flowing through the first flow path (1) and the cationic polymerizable monomer solution flowing through the second flow path (2) merge at the first merge section (4). The first merging section (4) serves as a mixer, and the first flow path (1) and the second flow path (2) are merged into one flow path, and a downstream reaction flow path (reaction) The solution is not particularly limited as long as the merged solution can be delivered to the tube (5)). For example, a T-shaped or Y-shaped structure can be used.
The equivalent diameter of the flow path constituting the first merge part (4) (here, the equivalent diameter of the flow path constituting the first merge part (4) is the same as that of the first flow path defined by the manufacturing method of the present invention). The equivalent diameter of the flow path at the junction with the two flow paths is preferably 0.1 mm to 10 mm from the viewpoint of mixing performance, and more preferably 0.2 mm to 10 mm from the viewpoint of pressure loss. The equivalent diameter of the flow path constituting the first merge part (4) is more preferably 0.15 mm to 5.0 mm.
There is no restriction | limiting in particular in the material of the 1st confluence | merging part (4), For example, perfluoro alkoxy alkane (PFA), Teflon (trademark), aromatic polyetherketone type resin, stainless steel, copper (or its alloy), nickel ( Or an alloy thereof, titanium (or an alloy thereof), quartz glass, lime soda glass, or the like can be used.
A commercially available micromixer can be used for the 1st junction part (4) (mixer). For example, a microreactor equipped with an interdigital channel structure; a single mixer and a caterpillar mixer manufactured by Institute, Fleet, Microtechnique Mainz (IMM); a microglass reactor manufactured by Microglass; a cytos manufactured by CPC Systems; YM-1, YM-2 type mixers; Shimadzu GLC's mixing tee and tee (T-shaped connector); GL Sciences' mixing tee and tee (T-shaped connector); Upchurch's 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 connector; T chip reactor; Toray Engineering developed products Micro high mixer, and the like, any can be used in the present invention.

<Reaction tube (reaction channel)>
The Bronsted acid and the cationic polymerizable monomer (hereinafter simply referred to as “monomer”) are mixed in the first junction (4), and the polymerization reaction starts. That is, the monomer in the solution mixed in the first junction (4) is polymerized while flowing through the reaction tube (5).
Although there is no restriction | limiting in particular in the form of reaction tube (5), It is preferable that it is a tube. The preferred material of the reaction tube (5) is the same as that of the second flow path. The residence time of the polymerization reaction can be adjusted by adjusting the equivalent diameter and length of the reaction tube and the flow rate of the liquid feed pump. The residence time may be appropriately adjusted according to the desired molecular weight of the polymer. In general, the longer the residence time, the higher the monomer polymerization rate. Usually, the equivalent diameter of the reaction tube is 0.1 to 50 mm, more preferably 0.1 to 20 mm. The length of the reaction tube is preferably 5 cm to 50 m.

<Third flow path>
The third channel (3) is a channel through which the polymerization terminator introduced from the inlet (C) flows. The polymerization terminator will be described later. The third flow path is also preferably tubular, and the preferred form of the tube is the same as the second flow path.

<Second junction>
The solution in which the polymerization reaction proceeds while flowing through the reaction tube (5) and the polymerization terminator flowing through the third flow path (3) join at the second junction (6). The second merging section (6) serves as a mixer, and merges the reaction tube (5) and the third flow path (3) into one flow path and merges into the downstream pipe (7). The solution is not particularly limited as long as the solution can be delivered. The preferred form of the second junction is the same as the first junction.

<Piping>
In the second merging section (6), the Bronsted acid is neutralized by mixing the solution in which the polymerization reaction is proceeding (the solution containing the polymer having the active species at the growth end) and the polymerization terminator. Within (7), the polymerization reaction stops. The preferable form of piping is the same as the reaction tube (5).
Since the Bronsted acid is neutralized in the pipe (7), the polymer solution discharged from the pipe has a high safety because the reactivity and corrosiveness of the Bronsted acid are suppressed. That is, the production method of the present invention is a method with high handling safety because it can perform from the generation of Bronsted acid to neutralization inside the flow path of the flow reaction system.

  A static mixer may be installed in the reaction tube (5) and the pipe (7). A static mixer is a tubular reactor that incorporates one or more static mixers composed of a number of mixing elements. For example, a known Sulzer type, Kenix type, Toray type, Noritake company type, etc. Can be mentioned. The number of mixing elements is preferably 4 or more, more preferably 6 to 30.

Subsequently, another embodiment of the production method of the present invention will be described below. Another embodiment of the manufacturing method of the present invention is shown in FIG. FIG. 4 is a schematic view showing an example of a flow reaction system used in a method for producing a block copolymer by a cationic polymerization reaction.
In the embodiment shown in FIG. 4, the first channel (11), the light receiving part (E) of the first channel, the second channel (12), the first junction (15), and the first reaction channel (first 1 reaction tube (16)) is respectively the first flow path (1), the light receiving portion (E) of the first flow path, the second flow path (2), the first merging in the embodiment of FIG. 1 described above. Since it is synonymous with a part (4) and a reaction tube (5) and a preferable form is also the same, description is abbreviate | omitted.

In the embodiment of FIG. 4, a cation different from the cation polymerizable monomer (first cation polymerizable monomer) to be introduced into the second channel (12) is introduced into the inlet (C) of the third channel (13). A polymerizable monomer (second cationic polymerizable monomer) is introduced and flows through the third flow path (13). The preferred form of the third channel (13) is the same as that of the second channel (12).
The polymer solution flowing in the first reaction tube (16) is fed to the second merging portion (17) in a state having a cation active species at the growth end, and in the second merging portion (17), the first It merges with the second cationically polymerizable monomer solution flowing through the three flow paths (13). The second merging section (17) has a role of a mixer, and merges the first reaction tube (16) and the third flow path (13) into one flow path, and the downstream second reaction flow path (second flow path). There is no particular limitation as long as the combined solution can be sent out to the two reaction tubes (18)). The preferred form of the second junction is the same as the first junction (15).

  A block copolymer is synthesized in the second reaction tube (18). That is, the second cationic polymerizable monomer is addition-polymerized at the growing end of the polymer that has flowed through the first reaction tube. The preferred form of the second reaction tube (18) is the same as that of the first reaction tube (16).

  The fourth channel (14) is a channel through which the polymerization terminator introduced from the inlet (D) flows. The preferred form of the fourth channel (14) is the same as that of the second channel (12).

  The solution in which the polymerization reaction proceeds while flowing through the second reaction tube (18) and the polymerization terminator flowing through the fourth flow path (14) merge at the third merge portion (19). The second merging section (19) has a role of a mixer. The reaction pipe (18) and the fourth flow path (14) are merged into one flow path and merged into the downstream pipe (20). The solution is not particularly limited as long as the solution can be delivered. The preferred form of the third junction is the same as the first junction.

In the third junction (19), the Bronsted acid is neutralized by mixing the solution in which the polymerization reaction is proceeding (the solution containing the polymer having the active species at the growth end) and the polymerization terminator. Within (20), the polymerization reaction stops. The preferable form of piping is the same as that of the reaction tube (16).
Since the Bronsted acid is neutralized in the pipe (20), the block copolymer solution discharged from the pipe (20) is highly safe because the reactivity and corrosivity of the Bronsted acid are suppressed. That is, the production method of the embodiment of FIG. 4 is also a method with high handling safety because it can be performed from the generation of Bronsted acid to neutralization inside the flow type reaction system.

  In the reaction system shown in FIGS. 1 and 4 above, the flow rate of the liquid flowing through the first flow path, the second flow path, the third flow path, and the fourth flow path is not particularly limited, and the equivalent diameter and length of the flow path are not limited. It is adjusted appropriately depending on the size. For example, the flow rate of the liquid flowing through each of the flow paths can be 0.05 mL / min to 1000 L / min, and preferably 0.1 mL / min to 100 L / min. Further, the flow rate of the liquid flowing through each of the flow paths may be 0.1 mL / min to 10 L / min, 0.1 mL / min to 1 L / min, or 0.1 mL to 100 mL / min. It is good also as 0.1mL-50mL / min. Moreover, the flow rate of the liquid flowing through each flow path may be the same between the flow paths, or may be different for each flow path.

  The composition of the block copolymer can be controlled by adjusting the supply ratio of the first cation polymerizable monomer and the second cation polymerizable monomer or by adjusting the residence time of the reaction liquid in each reaction tube. .

In the production method of the present invention, the polymerization reaction is performed at a low temperature in order to suppress a chain transfer reaction or a termination reaction. Therefore, for example, in the system shown in FIGS. 1 and 4, usually, the space from the downstream of the light receiving part of the first flow path to a part of the pipe is disposed in the low temperature thermostat (8, 21), and the low temperature To maintain.
The reaction temperature at the time of the polymerization reaction in the present invention may be −78 ° C. or lower, which is applied in the conventional batch method. Even in the temperature range of −40 ° C. to −10 ° C., a polymer having a low degree of dispersion can be obtained. Within this temperature range, the polymer can be produced using a cooling device with a simple configuration while suppressing side reactions during polymerization, which is also preferable in that the production cost can be reduced.

  Subsequently, in the production method of the present invention, the Bronsted acid precursor introduced into the first channel, the second channel in the embodiment of FIG. 1 (the second channel and the third channel in the embodiment of FIG. 4). The monomer to be introduced and the polymerization terminator introduced into the third channel (fourth channel in the embodiment of FIG. 4) in the embodiment of FIG. 1 will be described in detail below.

[Bronsted acid precursor]
The Bronsted acid precursor is a compound that generates a Bronsted acid by absorbing the light energy of actinic rays or radiation. The Bronsted acid precursor is not particularly limited as long as it generates a Bronsted acid by absorbing the light energy of actinic rays or radiation. For example, diazonium compound (salt), phosphonium compound (salt), sulfonium compound (salt), iodonium Mention may be made of compounds (salts), imide sulfonates, oxime sulfonates, diazodisulfones, disulfones and o-nitrobenzyl sulfonates. Further, compounds in which a group or a compound that generates an acid upon irradiation with light is introduced into the main chain or side chain of the polymer, for example, US Pat. No. 3,849,137, German Patent No. 3914407, JP-A 63-26653. JP, 55-164824, JP 62-69263, JP 63-146038, JP 63-163452, JP 62-153853, JP 63-146029, etc. Can be used.

  Furthermore, compounds capable of generating an acid by light described in US Pat. No. 3,779,778, European Patent 126,712 and the like can also be used.

  The Bronsted acid precursor used in the present invention preferably has a pKa of Bronsted acid generated by light irradiation of -1.0 or less in order to highly monodisperse the molecular weight distribution of the resulting polymer. It is more preferably −4.0 or less, and further preferably −9.0 or less. The pKa of the Bronsted acid is usually −18.0 or more.

  Moreover, as a preferable example of a Bronsted acid precursor, the compound represented by the following general formula (ZI), (ZII), (ZIII) or (ZIV), and an oxime sulfonate compound can be mentioned.

<Compound of general formula (ZI)>
In formula ^{(ZI), R} 201 ~R ²⁰³ represents an organic group.
The carbon number of the organic group as R ²⁰¹ to R ²⁰³ is preferably 1 to 30, 1 to 20 is more preferable. Moreover, two groups out of R ^{201 to} R ²⁰³ may be bonded to form a ring structure together with S ⁺ . Further, this ring structure may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. The divalent group formed by combining two groups out of R ^{201 to} R ²⁰³ is preferably an alkylene group (preferably a butylene group or a pentylene group).
Further, the compound represented by the general formula (ZI) may be a compound having a plurality of structures represented by the general formula (ZI). For example, at least one of R ^{201 to} R ²⁰³ of the compound represented by the general formula (ZI) has a structure bonded to at least one of R ^{201 to} R ²⁰³ of another compound represented by the general formula (ZI). It may be a compound.

Z ⁻ represents a non-nucleophilic anion. Examples of the non-nucleophilic anion include sulfonate anion, bis (alkylsulfonyl) imide anion, (arylsulfonyl) (alkylsulfonyl) imide anion, bis (arylsulfonyl) imide anion, tris (alkylsulfonyl) methide anion, and Mention may be made of (arylsulfonyl) -bis (alkylsulfonyl) methide anions. In the present specification, “sulfonylimide anion” is also referred to as sulfonimidate and “methide anion” is also referred to as methidate.

When Z ⁻ is a non-nucleophilic anion, decomposition of the compound with time due to intramolecular nucleophilic reaction can be suppressed.

Z ^- If the sulfonate anion include an aliphatic sulfonate anion _{^{(R A -SO 3 -, R}} A is an aliphatic group), an aromatic sulfonic acid anion _{^{(R B -SO 3 -, R}} B is aromatic Group).

The aliphatic group ^RA is preferably an alkyl group or a cycloalkyl group, more preferably a group selected from an alkyl group having 1 to 30 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms (for example, a methyl group or an ethyl group). Propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, A tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an eicosyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, and a boronyl group). The alkyl group and cycloalkyl group preferably have a substituent, and preferred examples of the substituent include a group selected from the substituent group W described later.

The aromatic group R ^B is preferably an aryl group having 6 to 14 carbon atoms (e.g., a group selected from phenyl group, a tolyl group and a naphthyl group). This aryl group may have a substituent, and preferred examples of the substituent include groups selected from the substituent group W described later.

(Substituent group W)
Nitro group, halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), carboxyl group, hydroxyl group, amino group, cyano group, alkoxy group (preferably having 1 to 15 carbon atoms), cycloalkyl group (preferably having carbon number) 3 to 15), aryl group (preferably 6 to 14 carbon atoms), alkoxycarbonyl group (preferably 2 to 7 carbon atoms), acyl group (preferably 2 to 12 carbon atoms), alkoxycarbonyloxy group (preferably carbon 2-7), an alkylthio group (preferably 1-15 carbon atoms), an alkylsulfonyl group (preferably 1-15 carbon atoms), an alkyliminosulfonyl group (preferably 2-15 carbon atoms), an aryloxysulfonyl group ( Preferably 6-20 carbon atoms, alkylaryloxysulfonyl group (preferably 7-20 carbon atoms), cycloalkyl Aryloxy sulfonyl group (preferably having 10 to 20 carbon atoms), an alkyloxyalkyloxy group (preferably having 5 to 20 carbon atoms), and cycloalkylalkyloxyalkyloxy group (preferably 8 to 20 carbon atoms).
When the group selected from the substituent group W has a ring structure such as an aryl group, the ring structure preferably further has a substituent, and the substituent is preferably an alkyl group (preferably having 1 to 15 carbon atoms). .

Z ^- exemplified bis (alkylsulfonyl) imide anion as, (arylsulfonyl) (alkylsulfonyl) imide anion, bis (arylsulfonyl) imide anion and tris (alkylsulfonyl) methide anion, and (arylsulfonyl) - bis (alkylsulfonyl) The alkyl group in the methide anion is selected from an alkyl group having 1 to 5 carbon atoms (preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a pentyl group, and a neopentyl group. The aryl group is preferably an aryl group having 6 to 14 carbon atoms (for example, a group selected from a phenyl group, a tolyl group, and a naphthyl group). The alkyl group having 1 to 5 carbon atoms and the aryl group having 6 to 14 carbon atoms preferably have a substituent. As the substituent, a halogen atom, an alkyl group having a halogen atom as a substituent (preferably having a carbon number of 1 To 12), an alkoxy group having a halogen atom as a substituent (preferably having a carbon number of 1 to 12), an alkylthio group having a halogen atom as a substituent (preferably having a carbon number of 1 to 12), and an alkyl having a halogen atom as a substituent An oxysulfonyl group (preferably having a carbon number of 1 to 12), an aryloxysulfonyl group having a halogen atom as a substituent (preferably having a carbon number of 1 to 12), and a cycloalkylaryloxysulfonyl group having a halogen atom as a substituent (preferably C10-20) and the like, and fluorine atom as a substituent Alkyl group having (preferably 1 to 12 carbon atoms) is more preferred.

As for the non-nucleophilic anion of Z ⁻ , the compound of the general formula (ZI) absorbs light energy and dissociates to generate Bronsted acid (ZH). The pKa of this Bronsted acid is preferably -1.0 or less. In this case, Z ⁻ represents an aliphatic sulfonate anion having a fluorine atom as a substituent at the α-position carbon atom of the sulfonic acid; an aromatic sulfonate anion having a chlorine atom, a fluorine atom or a group having a fluorine atom as a substituent; (Arylsulfonyl) (alkylsulfonyl) imide anion in which aryl group and alkyl group have fluorine atom as substituent, bis (alkylsulfonyl) imide anion in which alkyl group has fluorine atom as substituent, alkyl group is fluorine atom as substituent A tris (alkylsulfonyl) methide anion having an aryl group or an (arylsulfonyl) -bis (alkylsulfonyl) methide anion in which an aryl group and an alkyl group have a fluorine atom as a substituent is preferable.

  Further, the pKa of Bronsted acid generated by absorbing light energy by the compound of the general formula (ZI) is more preferably −4.0 or less. In this case, the aryl group and alkyl group have a fluorine atom as a substituent (arylsulfonyl) (alkylsulfonyl) imide anion, the alkyl group has a fluorine atom as a substituent, bis (alkylsulfonyl) imide anion, and the alkyl group has a substituent. A tris (alkylsulfonyl) methide anion having a fluorine atom, an aryl group and an alkyl group having a fluorine atom as a substituent (arylsulfonyl) -bis (alkylsulfonyl) methide anion, or a bis having an aryl group having a fluorine atom as a substituent (Arylsulfonyl) imide anions are preferred.

The pKa of the Bronsted acid generated when the compound of the general formula (ZI) absorbs light energy is more preferably −9.0 or less. In this case, the alkyl group is preferably a bis (alkylsulfonyl) imide anion having a fluorine atom as a substituent, and the tris (alkylsulfonyl) methide anion having an alkyl group having a fluorine atom as a substituent.
In addition, the pKa of Bronsted acid generated when the compound of the general formula (ZI) absorbs light energy is usually −18.0 or more.

The Bronsted acid (ZH) obtained by dissociating Z ⁻ functions as a polymerization initiator in the production method of the present invention. By reducing the pKa of ZH (by making it a strong acid), the rate of the addition reaction to the monomer, that is, the initiation reaction rate is greatly improved, and the carbocation at the cation polymerization terminal is a non-nucleophilic anion (Z ⁻ ). It is stabilized with. Thereby, side reactions such as termination reaction and transfer reaction are suppressed, and a polymer having a narrow molecular weight distribution can be synthesized.
The pKa of the acid is a calculated value according to Advanced Chemistry Development (ACD / Labs) Software V11.02 (1994-2014 ACD / Labs), or a literature value (for example, J. Phys. Chem. A 2011, 115, 6641-6645). The stated values can be used.
The pKa of Bronsted acid generated from anions (X1) to (X11) constituting the exemplary compounds described below is shown below.

  Preferred forms of the compound represented by the general formula (ZI) include compounds (ZI-1), (ZI-2), and (ZI-3) described below.

-Compound (ZI-1)-
The compound (ZI-1) is an aromatic sulfonium compound in which at least one of R ^{201 to} R ^{203 in} the general formula (ZI) is an aromatic group, that is, a compound having aromatic sulfonium as a cation.

In the aromatic sulfonium compound, all of R ^{201 to} R ²⁰³ may be aromatic groups, or one or two of R ^{201 to} R ²⁰³ are aromatic groups, and the rest are alkyl groups (preferably having 1 to 12 carbon atoms). Or a cycloalkyl group (preferably having 3 to 8 carbon atoms).

  Examples of aromatic sulfonium compounds include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds. When the aromatic group of the aromatic sulfonium compound is an aryl group, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.

  The aromatic group of the aromatic sulfonium compound may have an aromatic heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom and the like. Aromatic heterocyclic groups include, for example, pyrrole residues (groups formed by losing one hydrogen atom from pyrrole), furan residues (groups formed by losing one hydrogen atom from furan) Thiophene residue (group formed by losing one hydrogen atom from thiophene), indole residue (group formed by losing one hydrogen atom from indole), benzofuran residue (hydrogen from benzofuran A group formed by the loss of one atom), a benzothiophene residue (a group formed by the loss of one hydrogen atom from benzothiophene), and the like. When the aromatic sulfonium compound has two or more aromatic groups, the two or more aromatic groups may be the same or different.

When R ²⁰¹ to R ²⁰³ is an aromatic group, it is also preferred that the aromatic group is a form with a substituent. Examples of the substituent include an alkyl group (preferably 1 to 15 carbon atoms), a cycloalkyl group (preferably 3 to 15 carbon atoms), an aryl group (preferably 6 to 14 carbon atoms), and an alkoxy group (preferably Group having 1 to 15 carbon atoms, a halogen atom, a hydroxyl group, or a phenylthio group, more preferably a group selected from a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and a halogen atom. And more preferably an alkyl group having 1 to 4 carbon atoms or a halogen atom. This substituent may be substituted with any one of three R ^{201 to} R ²⁰³ , may be substituted with any two, or may be substituted with all three Good. When R ^{201 to} R ²⁰³ are an aryl group, the substituent is preferably substituted at the para position.

Z ^{− in the} compound (ZI-1) has the same meaning as Z ⁻ described above, and the preferred form is also the same.

-Compound (ZI-2)-
The compound (ZI-2) is a compound in which R ^{201 to} R ²⁰³ in the general formula (ZI) are organic groups having no aromatic ring.

The carbon number of the organic group having no aromatic ring as R ²⁰¹ to R ²⁰³ is preferably 1 to 30, more preferably from 1 to 20.

R ^{201 to} R ²⁰³ are preferably an alkyl group, a cycloalkyl group, an allyl group or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylmethyl group, Particularly preferred is a linear or branched 2-oxoalkyl group.

When R ^{201 to} R ²⁰³ are an alkyl group, it is preferably a linear or branched alkyl group having 1 to 10 carbon atoms (preferably a methyl group, ethyl group, propyl group, butyl group or pentyl group), more preferably carbon. A 2-oxoalkyl group having 1 to 10 carbon atoms or an alkoxycarbonylmethyl group having 1 to 10 carbon atoms. The 2-oxoalkyl group may be linear or branched. A 2-oxoalkyl group is a group in which the carbon atom at the 2-position of the alkyl group is> C═O.

^Also, when R 201 ^{to R 203} is a cycloalkyl group, preferably a cycloalkyl group having 3 to 10 carbon atoms (preferably a cyclopentyl group, a cyclohexyl group, or a norbornyl group), more preferably 3 to 10 carbon atoms 2-oxocycloalkyl group.
A 2-oxocycloalkyl group is a group in which the carbon atom at the 2-position of the cycloalkyl group is> C═O.

When R ²⁰¹ to R ²⁰³ is an alkoxycarbonylmethyl group, the alkoxy group is preferably an alkoxy group having 1 to 5 carbon atoms (preferably a methoxy group, an ethoxy group, a propoxy group, a butoxy group, or pentoxy group).

Z ^{− in the} compound (ZI-2) has the same meaning as Z ⁻ described above, and the preferred form is also the same.

When R ²⁰¹ to R ²⁰³ is an alkyl group or a cycloalkyl group, it is also preferred that the alkyl group and cycloalkyl group is in the form having a substituent. Examples of the substituent include an alkyl group (preferably 1 to 15 carbon atoms), a cycloalkyl group (preferably 3 to 15 carbon atoms), an aryl group (preferably 6 to 14 carbon atoms), and an alkoxy group (preferably C1-15), halogen atom, hydroxyl group, phenylthio group, cyano group and nitro group, more preferably halogen atom, alkoxy group (preferably having 1 to 5 carbon atoms), hydroxyl group, cyano group and nitro group. The group to be selected. This substituent may be substituted with any one of three R ^{201 to} R ²⁰³ , may be substituted with any two, or may be substituted with all three Good.

-Compound (ZI-3)-
Compound (ZI-3) is a compound represented by the following general formula (ZI-3) (a compound having a phenacylsulfonium salt structure).

In General Formula (ZI-3), R ^{1c to} R ^{5c each} represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, or a halogen atom.
R ^6c and R ^7c represent a hydrogen atom, an alkyl group, or a cycloalkyl group.
R ^x and R ^{y each} represents an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group.
Z ^c- has the same meaning as Z ⁻ described above, and the preferred form is also the same.

Any two or more of R ^{1c to} R ^5c , R ^6c and R ^7c , and R ^x and R ^y may be bonded to each other to form a ring structure. This ring structure may contain an oxygen atom, a sulfur atom, an ester bond, or an amide bond. The ring structure is preferably a 5-membered ring or a 6-membered ring.

When R ^{1c to} R ^7c are alkyl groups, they may be either straight chain or branched, preferably an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 12 carbon atoms (preferably methyl Group, ethyl group, linear or branched propyl group, linear or branched butyl group, or linear or branched pentyl group).
Moreover, when R ^<1c > -R <^7c> is a cycloalkyl group, Preferably it is a C3-C8 cycloalkyl group (preferably a cyclopentyl group or a cyclohexyl group).

When R ^{1c to} R ^5c are alkoxy groups, they may be linear, branched or cyclic, preferably have 1 to 10 carbon atoms, more preferably have 1 to 5 carbon atoms and branch. An alkoxy group (preferably a methoxy group, an ethoxy group, a linear or branched propoxy group, a linear or branched butoxy group, a linear or branched pentoxy group), or a cycloalkoxy group having 3 to 8 carbon atoms (preferably a cyclopentyloxy group or A cyclohexyloxy group).

Preferably, any of R ^{1c to} R ^5c is an alkyl group, a cycloalkyl group, or an alkoxy group, and more preferably, the sum of carbon numbers of R ^{1c to} R ^5c is 1 to 15. Thereby, solvent solubility improves more and generation | occurrence | production of a particle is suppressed at the time of a preservation | save.

When R ^x and R ^y are alkyl groups, they may be either linear or branched, preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms (preferably A methyl group, an ethyl group, a linear or branched propyl group, a linear or branched butyl group, or a linear or branched pentyl group), and the 2-position carbon atom of these alkyl groups is> C═O. Also preferred are oxoalkyl groups. The alkyl group is preferably an alkoxycarbonylmethyl group, and the alkoxy group is preferably a linear or branched alkoxy group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms (preferably a methoxy group or an ethoxy group). , A linear or branched propoxy group, a linear or branched butoxy group, a linear or branched pentoxy group), or a C3-C8 cycloalkoxy group (preferably a cyclopentyloxy group or a cyclohexyloxy group).
When R ^x and R ^y are cycloalkyl groups, they are preferably cycloalkyl groups having 3 to 8 carbon atoms (preferably a cyclopentyl group or a cyclohexyl group), and the carbon atom at the 2-position of these cycloalkyl groups is> C = It is also preferable that it is a 2-oxocycloalkyl group which is O.

R ^x and R ^y are preferably an alkyl group or a cycloalkyl group having 4 or more carbon atoms, more preferably an alkyl group having 6 or more carbon atoms, still more preferably an alkyl group having 8 or more carbon atoms, or a cycloalkyl group.

<Compound of general formula (ZII), compound of general formula (ZIII)>
In the general formulas (ZII) and (ZIII), R ^{204 to} R ^{207 each} represents an aromatic group, an alkyl group, or a cycloalkyl group.
In general formula (ZII) in the Z ^- is Z in formula (ZI) ^- in the above formula, a preferred form also the same.

When R ²⁰⁴ to R ²⁰⁷ is an aromatic group, a phenyl group, a naphthyl group are preferred, more preferably a phenyl group. In addition, the aromatic group of R ^{204 to} R ²⁰⁷ may be an aromatic heterocyclic group having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. This aromatic heterocyclic ring is preferably a pyrrole residue (a group formed by losing one hydrogen atom from pyrrole) or a furan residue (a group formed by losing one hydrogen atom from furan). Thiophene residue (group formed by losing one hydrogen atom from thiophene), indole residue (group formed by losing one hydrogen atom from indole), benzofuran residue (hydrogen from benzofuran A group formed by the loss of one atom), or a benzothiophene residue (a group formed by the loss of one hydrogen atom from benzothiophene).

When R ²⁰⁴ to R ²⁰⁷ is an alkyl group, preferably straight-chain or branched alkyl group (preferably methyl group, ethyl group, propyl group, butyl group or pentyl group) having 1 to 10 carbon atoms.
When R ²⁰⁴ to R ²⁰⁷ is a cycloalkyl group, preferably a cycloalkyl group having 3 to 10 carbon atoms (preferably a cyclopentyl group, a cyclohexyl group or a norbornyl group).

The aryl group, alkyl group, and cycloalkyl group represented by R ^{204 to} R ²⁰⁷ may have a substituent. Examples of the substituent include an alkyl group (preferably an alkyl group having 1 to 15 carbon atoms), a cycloalkyl group (preferably a cycloalkyl group having 3 to 15 carbon atoms), and an aryl group (preferably 6 to 15 carbon atoms). Aryl group), an alkoxy group (preferably an alkoxy group having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group.

  The compound represented by the general formula (ZII) is more preferably a diaryliodonium salt. Examples of the diaryliodonium salt include diphenyliodonium trifluoroacetate, diphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, phenyl, 4- (2 ′ -Hydroxy-1'-tetradecaoxy) phenyliodonium trifluoromethanesulfonate, 4- (2'-hydroxy-1'-tetradecaoxy) phenyliodonium hexafluoroantimonate, phenyl, 4- (2'-hydroxy-1) Mention may be made of '-tetradecaoxy) phenyliodonium-p-toluenesulfonate.

  The compound represented by the general formula (ZIII) is more preferably a diazomethane compound. Examples of the diazomethane compound include bis (cyclohexylsulfonyl) diazomethane, bis (t-butylsulfonyl) diazomethane, and bis (p-toluenesulfonyl) diazomethane.

<Compound of general formula (ZIV)>
In the general formula (ZIV), R ²⁰⁸ is an alkyl group having 1 to 6 carbon atoms, preferably a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl. Group or neopentyl group. When R ²⁰⁸ is an alkyl group, this alkyl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group substituted with a halogen atom (preferably having 1 to 12 carbon atoms), an alkoxy group (preferably having 1 to 12 carbon atoms), and an alkylthio group (preferably having 1 to 12 carbon atoms). A group selected from an alkyloxysulfonyl group (preferably having 1 to 12 carbon atoms), an aryloxysulfonyl group (preferably having 1 to 12 carbon atoms) and a cycloalkylaryloxysulfonyl group (preferably having 10 to 20 carbon atoms). And an alkyl group substituted with a fluorine atom (preferably having 1 to 12 carbon atoms) is more preferred.

In general formula (ZIV), A ¹ is a divalent linking group. A ¹ is preferably an ethylene group. The ethylene group also preferably has a substituent. More preferred is a form in which the substituents of the two carbon atoms of the ethylene group are linked to each other to form a ring. A ¹ is more preferably represented by the following formula (ZIV-1).

In the general formula (ZIV-1), L is O, S, or (CH ₂ ) _n , and n is 1 or 2. * Represents a linking site with a carbonyl group in the general formula (ZIV).

  Specific examples of the compound represented by the general formula (ZIV) include, for example, trifluoromethylsulfonyloxybicyclo [2.2.1] hept-5-enedicarboximide, succinimide trifluoromethyl sulfonate, phthalimide trifluoromethyl sulfonate, Examples thereof include N-hydroxynaphthalimide methanesulfonate and N-hydroxy-5-norbornene-2,3-dicarboximidepropanesulfonate.

  Specific examples (compound A) of the compound represented by the general formula (ZI) and the compound represented by the general formula (ZII) are shown below, but the present invention is not limited thereto. Moreover, the cation structure and the anion structure in Table 2 below are shown below Table 2.

  Specific examples of the compound represented by the general formula (ZIII) and the compound represented by the general formula (ZIV) are shown below, but the present invention is not limited thereto.

  Preferred examples of the oxime sulfonate compound as a Bronsted acid precursor used in the present invention, that is, a compound having an oxime sulfonate residue include compounds containing an oxime sulfonate residue represented by the following general formula (b1).

In general formula (b1), R ⁵ represents an alkyl group or an aromatic group.
When R ⁵ is an alkyl group, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable. When R ⁵ is an alkyl group, the alkyl group is substituted with an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (7,7-dimethyl-2-oxonorbornyl). It is also preferable to have a bridged alicyclic group such as a nyl group, preferably a bicycloalkyl group.
When R ⁵ is an aromatic group, an aryl group having 6 to 11 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable. When R ⁵ is an aromatic group, this aromatic group preferably has a lower alkyl group (preferably having 1 to 3 carbon atoms), a lower alkoxy group (preferably having 1 to 3 carbon atoms) or a halogen atom as a substituent. .

  The compound containing an oxime sulfonate residue represented by the above formula (b1) is particularly preferably a compound represented by the following general formula (OS-3), (OS-4) or (OS-5). preferable.

In general formula (OS-3) to formula (OS-5), R ¹ represents an alkyl group or an aromatic group. R ² represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, and R ⁶ represents a halogen atom, an alkyl group, an alkoxy group, a sulfo group, an aminosulfonyl group or an alkoxysulfonyl group. X represents O or S. n represents 1 or 2, and m represents an integer of 0 to 6.

In the general formulas (OS-3) to (OS-5), when R ¹ is an alkyl group, an alkyl group having a total carbon number of 1 to 30 (including carbons of substituents that the alkyl group has) is preferable.
When R ¹ is an alkyl group, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n A group selected from -octyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, and benzyl group is preferable. When R ¹ is a substituted alkyl group, a preferred alkyl group as R ¹ is a halogen atom, alkyloxy group, aryloxy group, alkylthio group, arylthio group, alkyloxycarbonyl group, aryloxycarbonyl group, and A form having a group selected from aminocarbonyl groups is preferred.

In the formulas (OS-3) to (OS-5), when R ¹ is an aromatic group, it may be an aryl group or an aromatic heterocyclic ring.
In the case where R ¹ is an aryl group, an aryl group having a total carbon number of 6 to 30 (including the carbon of the substituent that the aryl group has) is preferable.
When R ¹ is an aryl group, a group selected from a phenyl group, a p-methylphenyl group, a p-chlorophenyl group, a pentachlorophenyl group, a pentafluorophenyl group, an o-methoxyphenyl group, and a p-phenoxyphenyl group is preferable. When R ¹ is a substituted aryl group, a preferred aryl group as R ¹ is a halogen atom, alkyl group, alkyloxy group, aryloxy group, alkylthio group, arylthio group, alkyloxycarbonyl group, aryloxycarbonyl as a substituent. A form having a group selected from a group, an aminocarbonyl group, a sulfonic acid group, an aminosulfonyl group, and an alkoxysulfonyl group is preferable.

Moreover, when R < ¹ > in general formula (OS-3)-(OS-5) is an aromatic heterocyclic group, the total carbon number (including the carbon of the substituent which an aromatic heterocyclic ring has) is 4-30. Is preferred.

When R ¹ is a condensed aromatic heterocyclic ring, at least one ring may be an aromatic heterocyclic ring. For example, the aromatic heterocyclic ring and the benzene ring may be condensed.
When R ¹ is an aromatic heterocyclic ring, one hydrogen atom is selected from a ring selected from the group consisting of a thiophene ring, a pyrrole ring, a thiazole ring, an imidazole ring, a furan ring, a benzothiophene ring, a benzothiazole ring, and a benzimidazole ring. Excluded groups are preferred. When R ¹ is an aromatic heterocycle having a substituent, the aromatic heterocycle preferable as R ¹ is a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyl, as a substituent. A form having a group selected from an oxycarbonyl group, an aryloxycarbonyl group, an aminocarbonyl group, a sulfonic acid group, an aminosulfonyl group, and an alkoxysulfonyl group is preferable.

In general formulas (OS-3) to (OS-5), R ² is preferably a hydrogen atom, an alkyl group, or an aryl group, and more preferably a hydrogen atom or an alkyl group.
In the general formulas (OS-3) to (OS-5), it is preferable that one or two of R ² present in the compound is an alkyl group, an aryl group or a halogen atom, and one is an alkyl group. More preferably an aryl group or a halogen atom, and particularly preferably one is an alkyl group and the rest is a hydrogen atom.

When R ² is an alkyl group, the alkyl group is preferably an alkyl group having 1 to 12 carbon atoms in total (including the substituted carbon of the alkyl group), and more preferably an alkyl group having 1 to 6 carbon atoms in total.
When R ² is an alkyl group, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, n-hexyl group, allyl group, chloromethyl group , A bromomethyl group, a methoxymethyl group, and a benzyl group, preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, and an n-hexyl group. A group selected is preferable, a group selected from a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-hexyl group is more preferable, and methyl is more preferable. When R ² is a substituted alkyl group, a preferred alkyl group as R ² is a halogen atom, alkyloxy group, aryloxy group, alkylthio group, arylthio group, alkyloxycarbonyl group, aryloxycarbonyl group, and A form having a group selected from aminocarbonyl groups is preferred.

When R ² is an aryl group, an aryl group having a total carbon number of 6 to 30 (including the carbon of the substituent that the aryl group has) is preferable.
When R ² is an aryl group, a phenyl group, a p-methylphenyl group, an o-chlorophenyl group, a p-chlorophenyl group, an o-methoxyphenyl group, and a p-phenoxyphenyl group are preferable. In addition, when R ² is a substituted aryl group, a preferred aryl group as R ² is a halogen atom, alkyl group, alkyloxy group, aryloxy group, alkylthio group, arylthio group, alkyloxycarbonyl group, aryl A form having a group selected from an oxycarbonyl group, an aminocarbonyl group, a sulfonic acid group, an aminosulfonyl group, and an alkoxysulfonyl group is preferable.

When R ² is a halogen atom, specifically, it is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Among these, a chlorine atom and a bromine atom are preferable.

In general formulas (OS-3) to (OS-5), X represents O or S, and is preferably O. In general formulas (OS-3) to (OS-5), the ring containing X as a ring constituent atom is a 5-membered ring or a 6-membered ring.
In the general formulas (OS-3) to (OS-5), n represents 1 or 2, and is preferably 1.

When R ⁶ in the above formulas (OS-3) to (OS-5) is an alkyl group, it is preferably an alkyl group having a total carbon number of 1 to 30 (including the number of carbon atoms of the substituent of the alkyl group). .

When R ⁶ is an alkyl group, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n A group selected from -octyl group, n-decyl group, n-dodecyl group, trifluoromethyl group, perfluoropropyl group, perfluorohexyl group, and benzyl group is preferable. When R ⁶ is a substituted alkyl group, the alkyl group preferred as R ⁶ is a halogen atom, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkyloxycarbonyl group, aryloxycarbonyl group, and amino A form having a group selected from carbonyl groups is preferred.

In the case where R ⁶ in the general formulas (OS-3) to (OS-5) is an alkoxy group, an alkoxy group having a total carbon number of 1 to 30 (including carbons as substituents of the alkoxy group) is preferable.

When R ⁶ is an alkoxy group, a methoxy, ethoxy, butoxy, hexyloxy group, phenoxyethyloxy group, trichloromethyloxy group, or ethoxyethyloxy group is preferable. When R ⁶ is a substituted alkoxy group, a preferable alkoxy group as R ⁶ is a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl as a substituent. A form having a group selected from the group is preferred.

When R ⁶ in the general formulas (OS-3) to (OS-5) is an aminosulfonyl group, a methylaminosulfonyl group, a dimethylaminosulfonyl group, a phenylaminosulfonyl group, a methylphenylaminosulfonyl group, or an aminosulfonyl group is preferable.
When R ⁶ in the general formulas (OS-3) to (OS-5) is an alkoxysulfonyl group, a methoxysulfonyl group, an ethoxysulfonyl group, a propyloxysulfonyl group, or a butyloxysulfonyl group is preferable.

  In general formulas (OS-3) to (OS-5), m is preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

  Although the specific example of the oxime sulfonate compound represented by general formula (OS-3)-formula (OS-5) is shown below, this invention is not limited to these.

  The compound having an oxime sulfonate residue represented by the formula (b1) is also preferably a compound represented by the following general formula (b2).

In formula (b2), R ^5a represents an alkyl group or an aryl group. X ¹ represents an alkyl group, an alkoxy group, or a halogen atom. m1 represents an integer of 0 to 3.

When X ¹ is an alkyl group, a linear or branched alkyl group having 1 to 4 carbon atoms is preferable.
When X ¹ is an alkoxy group, preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
When X ¹ is a halogen atom, a chlorine atom or a fluorine atom is preferable.
m1 is preferably 0 or 1.
Wherein (b2), m1 is 1, ^{X 1} is methyl, the substitution position of ^{X 1} is ^{ortho, R 5a} is straight chain alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl A compound that is a 2-oxonorbornylmethyl group or a p-toluyl group is particularly preferable.

  The compound containing an oxime sulfonate residue represented by the formula (b1) is also preferably an oxime sulfonate compound represented by the following general formula (b3).

In formula (b3), R ⁵ has the same meaning as R ⁵ in formula (b1), and X ² represents a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, cyano Represents a group or a nitro group. L represents an integer of 0 to 5.

R ⁵ in the formula (b3) is methyl, ethyl, n-propyl, n-butyl, n-octyl, trifluoromethyl, pentafluoroethyl, perfluoro-n-propyl, perfluoro A fluoro-n-butyl group, p-tolyl group, 4-chlorophenyl group or pentafluorophenyl group is preferred, and an n-octyl group is particularly preferred.
X ² is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group.
L is preferably 0 to 2, and particularly preferably 0 to 1.

  Specific examples of the compound represented by the formula (b3) include α- (methylsulfonyloxyimino) benzyl cyanide, α- (ethylsulfonyloxyimino) benzyl cyanide, α- (n-propylsulfonyloxyimino) benzyl. Cyanide, α- (n-butylsulfonyloxyimino) benzyl cyanide, α- (4-toluenesulfonyloxyimino) benzyl cyanide, α-[(methylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α- [(Ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(n-propylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(n-butylsulfonyloxyimino) -4-methoxyphenyl Acetonitrile, α-[(4-toluene Sulfo) -4-methoxyphenyl] can be mentioned acetonitrile.

  Preferable specific examples of the oxime sulfonate compound represented by the general formula (b2) or (b3) include the following compounds (i) to (ix). Compounds (i) to (ix) can be obtained commercially.

  Among the Bronsted acid precursors that can be used in the present invention described above, it is particularly preferable to use a sulfonium compound represented by the general formula (ZI). The stability of the compound alone and in solution is highest for the sulfonium compound, and the stability over time is the best. Further, by using a sulfonium compound, a polymer having a lower degree of dispersion (narrower molecular weight distribution) can be synthesized. The reason for this is not clear, but it is presumed that the sulfide, which is a decomposition product of the sulfonium compound, formed a dormant species and an appropriate dissociation equilibrium was achieved.

[Cationically polymerizable monomer]
There are no particular limitations on the cationically polymerizable monomer that can be used in the present invention, and any monomer that can be cationically polymerized can be used. For example, J. et al. P. Kennedy et al. (Carbational Polymerization, John Wiley & Sons, 1982); Matyjazewski et al. (Cationic Polymerizations, Marcel Dekker, 1996); Synthesis of Polymers (above), Kodansha Scientific, April 10, 2014; Graduate School Polymer Chemistry, Kodansha Scientific, May 28, 1997 And monomers described in New Experimental Chemistry Course 19, Polymer Chemistry [I], The Chemical Society of Japan, May 20, 1978, and the like. Of these, vinyl derivatives having an electron-donating substituent are preferable because of high cationic polymerizability. Examples of vinyl derivatives having such electron donating substituents are shown below.

(1) A monomer in which a hydrogen atom of an ethylene skeleton is substituted with an alkyl group or an aryl group. For example, isobutylene, styrene, α-methylstyrene, etc. (2) vinyl ethers such as isobutyl vinyl ether, n-butyl vinyl ether, propyl vinyl ether, ethyl vinyl ether, etc. (3) vinyl ethers substituted through hetero atoms, methyl vinyl sulfide, etc. Derivatives such as vinyl sulfides and N-vinylcarbazole

  Among these, isobutyl vinyl ether, n-butyl vinyl ether, propyl vinyl ether, ethyl vinyl ether, α-methyl styrene, methyl vinyl sulfide, N-vinyl carbazole, and the like can be suitably used as monomers having particularly high cationic polymerizability.

Examples of the cationic polymerizable cyclic monomer known to undergo ring-opening polymerization include cyclic ethers, cyclic acetals, cyclic amines, cyclic imino ethers, lactones, and cyclic siloxanes.
Specific examples of the cationic polymerizable cyclic monomer known to undergo ring-opening polymerization include tetrahydrofuran, 1,3-oxolane, 1,3-dioxepane, aziridine (ethyleneimine), and N- (t-butyl). Aziridine, N- (2-tetrahydropyranyl) aziridine, azetidine (trimethyleneimine), 2-oxazoline, ε-caprolactone, 1,3-dioxane-2-one, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, etc. Can be mentioned.

  In the present invention, the polymerization solvent is not particularly limited as long as it is inert to the cation, and specifically, aromatic hydrocarbon solvents such as benzene, toluene and xylene; pentane, hexane, heptane, octane, cyclopentane, cyclohexane Aliphatic hydrocarbon solvents such as methylcyclohexane and decalin; halogenated hydrocarbon solvents such as methyl chloride, methylene chloride, propane chloride, butane chloride, 1,2-dichloroethane, 1,1,2-trichloroethylene, chlorobenzene; It can be appropriately selected from ether solvents such as methyl tert-butyl ether, cyclopentyl methyl ether, and tetrahydropyran; and nitrated hydrocarbon compounds such as nitropropane and nitrobenzene. These organic solvents can be used alone or in combination of two or more.

  The reaction temperature at the time of the polymerization reaction in the present invention can be suitably applied even at −78 ° C. or less, which is applied in the conventional batch method. A temperature range of from ° C to -10 ° C is preferred. This temperature range is preferable in that a polymer can be produced using a cooling device with a simple structure while suppressing side reactions during polymerization, and the production cost can be reduced.

[Polymerization stopper]
The polymerization terminator is not particularly limited as long as it is a liquid that deactivates (neutralizes) a cation that is an active species, and alcohol containing a basic substance or water containing a basic substance is used. Specific examples of this alcohol include methanol, ethanol, propanol, isopropyl alcohol and the like. Examples of basic substances include potassium carbonate, triethylamine, ammonia and the like. The amount of the basic substance in the polymerization terminator is preferably 1 mol to 100 mol with respect to 1 mol of Bronsted acid in the mixed solution combined with the polymer solution.

[Polymer dispersion]
The polymer obtained by the production method of the present invention has a highly monodispersed molecular weight distribution. The dispersity (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the polymer obtained by the production method of the present invention is preferably 1.5 or less, more preferably 1.20 or less, It is more preferably 1.18 or less, further preferably 1.16 or less, and further preferably 1.15 or less.

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

  Cationic polymerization reaction was carried out by a flow reaction system having the configuration shown in FIGS. Details of each part are shown below.

[Flow-type light irradiation device (101)]
Key Chem-Lumino made by YMC Co., Ltd.

[Light receiving portion (E) of first flow path (1)]
Photoreactor manufactured by YMC Co., Ltd. (A quartz glass plate is pressure-bonded to a Teflon (registered trademark) flat channel with a channel width of 1 mm, a channel depth of 750 μm, and a channel length of 91.6 cm)

[light source]
Low pressure mercury lamp manufactured by YMC Co., Ltd. (illuminance at 254 nm: 3.0 mW / cm ² )

[First flow path (1) on the upstream side of the light receiving section (E)]
Teflon tube with an outside diameter of 1/16 inch, an inside diameter of 0.75 mm, and a length of 50 cm

[First flow path (1) on the downstream side of the light receiving section (E)]
A Teflon (registered trademark) tube having an outer diameter of 1/16 inch, an inner diameter of 0.75 mm, and a length of 50 cm, and an SUS316 tube having an outer diameter of 1/16 inch, an inner diameter of 1.0 mm, and a length of 50 cm connected by a SUS316 union.

[Second channel (2)]
SUS316 tube with outer diameter 1/16 inch, inner diameter 1.0mm, length 100cm

[First junction (4)]
Sanko Seiki Kogyo Co., Ltd. SUS316 T-shaped Micromixer (Inner Diameter 0.25mm)

[Reaction tube (5)]
SUS316 tube with an outer diameter of 1/16 inch, an inner diameter of 1.0 mm, and a length of 50 cm

[Third flow path (3)]
SUS316 tube with outer diameter 1/16 inch, inner diameter 1.0mm, length 100cm

[Second junction (6)]
Sanko Seiki Kogyo Co., Ltd. SUS316 T-shaped Micromixer (Inner Diameter 0.50mm)

[Piping (7)]
SUS316 tube with an outer diameter of 1/16 inch, an inner diameter of 1.0 mm, and a length of 50 cm

  As shown in FIG. 1, the space from the upstream of the first merging portion to a part of the piping was immersed in a low temperature thermostat (8) set to −25 ° C.

[Example 1]
A dichloromethane solution of 0.02M triphenylsulfonium trifluoromethanesulfonate (compound A-1, Bronsted acid precursor, resulting Bronsted acid pKa = −3.91) was taken in a 50 ml gust syringe, and a Harvard syringe pump Model11. It set to Plus, and it introduce | transduced continuously with the flow rate of 0.5 mL / min from the inlet (A) of the 1st flow path (1), and liquid-fed. When the first flow path circulated, the photoreactor constituting the light receiving unit (E) was irradiated with ultraviolet rays from the light source.
Take a 0.2M solution of isobutyl vinyl ether in dichloromethane in a 50 ml gust syringe and set it in a syringe pump Model 11 Plus manufactured by Harvard. Continuously at a flow rate of 2.0 mL / min from the inlet (B) of the second flow path (2). Introduced and fed.
A mixed solution of 8.89 g of triethylamine, 10.0 g of methanol, and 100 g of dichloromethane is placed in a 100 ml gust syringe, set in a syringe pump Model 11 Plus manufactured by Harvard, and a flow rate of 0.2 mL from the inlet (C) of the third flow path (3). The solution was continuously introduced at a rate of / min and fed.
After 5 minutes, a solution containing the polymer continuously discharged from the outlet was collected in a sample container. In the collected polymer solution, it was confirmed by pH test paper that the Bronsted acid was neutralized.

  A part of the collected solution was diluted with tetrahydrofuran (THF), and the molecular weight and molecular weight distribution were measured by gel permeation chromatography (GPC). The molecular weight is in terms of polystyrene. The measurement conditions by GPC are shown below.

Apparatus: HLC-8220GPC (manufactured by Tosoh Corporation)
Detector: Differential refractometer (RI 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 weight
Sample injection volume: 100 μL
Data collection time: 5 to 45 minutes after sample injection Sampling pitch: 300 msec

  As a result, no monomer peak was observed, the number average molecular weight (Mn) was 12500, and the molecular weight distribution (Mw / Mn = dispersion degree) was 1.28.

[Example 2]
In Example 1, the dichloromethane solution of triphenylsulfonium trifluoromethanesulfonate was changed to a dichloromethane solution of triphenylsulfonium bis (pentafluorobenzenesulfonyl) imidate (Compound A-4, pKa = -5.00 of the resulting Bronsted acid). A polymer solution was obtained in the same manner as in Example 1 except that. In the obtained polymer solution, it was confirmed by pH test paper that the Bronsted acid was neutralized.
Using the obtained polymer solution, the molecular weight and molecular weight distribution of the polymer were examined in the same manner as in Example 1. As a result, no monomer peak was observed, the number average molecular weight (Mn) was 13,000, and the molecular weight distribution ( Mw / Mn = dispersion degree) was 1.18.

[Example 3]
In Example 1, a solution of triphenylsulfonium trifluoromethanesulfonate in dichloromethane was added to triphenylsulfonium 1,1,2,2,3,3 hexafluoropropane-1,3-disulfonimidate (compound A-3, resulting blene). A polymer solution was obtained in the same manner as in Example 1 except that it was changed to a dichloromethane solution of pKa of Sted acid = -11.55). In the obtained polymer solution, it was confirmed by pH test paper that the Bronsted acid was neutralized.
Using the obtained polymer solution, the molecular weight and molecular weight distribution of the polymer were examined in the same manner as in Example 1. As a result, no monomer peak was observed, the number average molecular weight (Mn) was 12800, and the molecular weight distribution ( Mw / Mn = dispersion degree) was 1.15.

[Example 4]
In Example 1, the dichloromethane solution of triphenylsulfonium trifluoromethanesulfonate was changed to a dichloromethane solution of triphenylsulfonium tris (trifluoromethylsulfonyl) methidate (Compound A-5, pKa of the resulting Bronsted acid = -16.40). A polymer solution was obtained in the same manner as in Example 1 except that. In the obtained polymer solution, it was confirmed by pH test paper that the Bronsted acid was neutralized.
Using the obtained polymer solution, the molecular weight and molecular weight distribution of the polymer were examined in the same manner as in Example 1. As a result, no monomer peak was observed, the number average molecular weight (Mn) was 13100, and the molecular weight distribution ( Mw / Mn = dispersion degree) was 1.12.

[Comparative example]
A polymer solution was obtained in the same manner as in Example 1 except that the dichloromethane solution of triphenylsulfonium trifluoromethanesulfonate in Example 1 was changed to a dichloromethane solution of trifluoromethanesulfonic acid (pKa = −3.91). In the obtained polymer solution, it was confirmed by pH test paper that trifluoromethanesulfonic acid was neutralized.
Using the obtained polymer solution, the molecular weight and molecular weight distribution of the polymer were examined in the same manner as in Example 1. As a result, no monomer peak was observed, the number average molecular weight (Mn) was 16,800, and the molecular weight distribution ( Mw / Mn = dispersion degree) was 1.41.

In the comparative example, trifluoromethanesulfonic acid, which is not a Bronsted acid precursor but a Bronsted acid itself, is directly introduced into the first flow path (1). In this case, the degree of dispersion of the obtained polymer was 1.41.
In contrast, triphenylsulfonium trifluoromethanesulfonate, which is a precursor of trifluoromethanesulfonic acid, was introduced into the first flow path (1), and trifluoromethanesulfonic acid was generated by light irradiation during the flow of the first flow path. In Example 1, the degree of dispersion of the obtained polymer was 1.28, and the molecular weight distribution of the polymer could be further monodispersed.

  Further, from the comparison of Examples 1 to 4, the smaller the pKa of the Bronsted acid generated from the Bronsted acid precursor (the stronger the acid), the narrower the molecular weight distribution of the resulting polymer, and the higher the molecular weight. It was found that a polymer was obtained. The Bronsted acids produced in Examples 2-4 are highly reactive and corrosive and are commercially available and cannot be applied to cationic polymerization. In the present invention, a highly safe Bronsted acid precursor is used to generate a strong acid (Bronsted acid) in the flow path of the reaction system, and neutralization thereof is also completed in the flow path. As a result, it has become possible to obtain a polymer in which the molecular weight distribution is highly monodispersed.

  In addition, in view of the above results obtained with the flow reactor shown in FIG. 1, the block copolymer obtained in the same manner when the block copolymer is formed using the flow reactor shown in FIG. It can be seen that the degree of dispersion of the coalescence is highly enhanced.

DESCRIPTION OF SYMBOLS 100 Flow type reaction system 1 1st flow path 2 2nd flow path 3 3rd flow path 4 1st junction part 5 Reaction tube (reaction flow path)
6 2nd junction part 7 Piping 8 Low temperature thermostatic chamber E 1st flow-path light-receiving part 9 1st board | substrate 10 2nd board | substrate 1a Introducing part 1b Discharge part 1c Groove (flow path)
101 flow type light irradiation device 102 flow type reaction system (block copolymer production)
DESCRIPTION OF SYMBOLS 11 1st flow path 12 2nd flow path 13 3rd flow path 14 4th flow path 15 1st confluence | merging part 16 1st reaction tube (1st reaction flow path)
17 Second junction 18 Second reaction tube (second reaction flow path)
19 3rd junction 20 Piping 21 Low temperature thermostat

Claims (11)

A method for producing a polymer that performs a cationic polymerization reaction by a flow reaction,
While introducing the Bronsted acid precursor solution into the first flow channel, the cationic polymerizable monomer solution into the second flow channel, and the polymerization terminator into the third flow channel,
The Bronsted acid precursor is irradiated with light when flowing in the first flow path to generate Bronsted acid, and the solution in which the Bronsted acid is generated and the monomer solution flowing in the second flow path are joined to react. The monomer is cationically polymerized while flowing in the flow path, and the polymerization reaction liquid flowing in the reaction flow path and the polymerization terminator flowing in the third flow path are merged to stop the polymerization reaction. A manufacturing method comprising obtaining a solution.   The manufacturing method of Claim 1 whose pKa of the said Bronsted acid is -1.0 or less.   The manufacturing method of Claim 1 whose pKa of the said Bronsted acid is -4.0 or less.   The manufacturing method of any one of Claims 1-3 whose reaction temperature of cationic polymerization is -40 degreeC--10 degreeC.   The equivalent diameter of the flow path at the confluence of the first flow path and the second flow path and the equivalent diameter of the flow path at the confluence of the reaction flow path and the third flow path are 0.2 mm to 10 mm. Item 5. The production method according to any one of Items 1 to 4.   The manufacturing method of any one of Claims 1-5 whose equivalent diameter of the said reaction flow path is 0.1-50 mm.   The production method according to claim 1, wherein the Bronsted acid precursor is a sulfonium compound. The manufacturing method of Claim 7 with which the said sulfonium compound is represented with the following general formula (ZI).

In the general formula ^{(ZI), R 201, R} 202 and ^{R 203} represents an organic group. Z ⁻ represents a non-nucleophilic anion. A method for producing a block copolymer in which a cationic polymerization reaction is performed by a flow reaction,
Bronsted acid precursor solution in the first flow path, the first cationic polymerizable monomer solution in the second flow path, the second cationic polymerizable monomer solution in the third flow path, and the polymerization stop in the fourth flow path While introducing each agent and circulating each liquid in each channel,
The Bronsted acid precursor is irradiated with light when flowing in the first flow path to generate a Bronsted acid, a solution that generates the Bronsted acid, and a first cationic polymerizable monomer solution that flows in the second flow path; The first cationic polymerizable monomer is cationically polymerized while flowing in the first reaction channel, and the polymerization reaction solution flowing in the first reaction channel and the second channel flowing in the third channel. The second cationically polymerizable monomer is cationically polymerized while the second cationically polymerizable monomer solution is merged and circulated in the second reaction channel, and the polymerization reaction solution and the fourth flow that circulates in the second reaction channel. A production method comprising: joining a polymerization terminator flowing in a channel to stop a polymerization reaction to obtain a block copolymer solution. A flow reaction system for producing a polymer by a cationic polymerization reaction,
The flow reaction system includes a first flow path, a second flow path, a third flow path, a liquid feed pump that sends a solution to each of the first to third flow paths, a first flow path, and a second flow path. A first merging section where the flow path merges, a reaction tube connected downstream of the first merging section, a second merging section where the reaction pipe and the third flow path merge, and a downstream of the second merging section And a pipe connected to
A Bronsted acid precursor solution is introduced into the first flow path, a cationic polymerizable monomer solution is introduced into the second flow path, and a polymerization terminator is introduced into the third flow path.
The Bronsted acid precursor is irradiated with light when flowing in the first flow path to generate Bronsted acid, and the solution in which the Bronsted acid is generated and the monomer solution flowing in the second flow path are formed in the first junction. The monomers are cationically polymerized during circulation in the reaction tube, the polymerization reaction liquid and the polymerization terminator flowing through the third flow path are merged at the second merge part to stop the polymerization reaction, and the polymerization reaction is stopped from the pipe outlet. A system that obtains a coalesced solution. A flow reaction system for producing a block copolymer by a cationic polymerization reaction,
The flow reaction system includes a first flow path, a second flow path, a third flow path, a fourth flow path, and a liquid feed pump that sends a solution to each of the first to fourth flow paths, A first merge section where the first flow path and the second flow path merge; a first reaction pipe connected downstream of the first merge section; and a second merge where the first reaction pipe and the third flow path merge. A second reaction tube connected downstream of the second merging portion, a third merging portion where the second reaction tube and the fourth flow path merge, and a pipe connected downstream of the third merging portion Have
Brnsted acid precursor solution in the first channel, first cationic polymerizable monomer solution in the second channel, second cationic polymerizable monomer solution in the third channel, and polymerization in the fourth channel. A stop agent is introduced by each of the liquid feed pumps,
The Bronsted acid precursor is irradiated with light when flowing in the first flow path to generate Bronsted acid, and the solution that has generated the Bronsted acid and the first cationic polymerizable monomer that flows in the second flow path are the first. The first cation polymerizable monomer merges at one merging portion and cation polymerizes when flowing in the first reaction tube, and the second cation polymerizable monomer flowing in the polymerization reaction solution and the third flow path becomes the second merging portion. The second cationic polymerizable monomer is cationically polymerized at the time of circulation in the second reaction tube, and the polymerization reaction liquid and the polymerization terminator flowing through the fourth flow path are merged at the third convergence part to cause the polymerization reaction. A system that stops and obtains a block copolymer solution from the piping outlet.

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