JP2014189749A - Method for producing polymer - Google Patents

Abstract

Production capable of carrying out living anionic polymerization of a polymerizable monomer having a long chain alkyl group at a reaction temperature that can be produced industrially, and further obtaining a polymer having a long chain alkyl group with a narrow molecular weight distribution Provide a method.
A polymerization initiator containing a polymerizable monomer (A) having a long-chain alkyl group is converted into a polymerization initiator (C) using a microreactor having a flow path capable of mixing a plurality of liquids. A method for producing a polymer that undergoes living anionic polymerization in the presence of Furthermore, when obtaining a block copolymer, the intermediate polymer obtained by carrying out living anion polymerization of the first polymerizable monomer and the polymerization initiator (C) in the microreactor, and the second polymerization In the method for producing a polymer in which a living monomer is polymerized with living anionic polymer, a polymerizable monomer having a long chain alkyl group in at least one of the first polymerizable monomer and the second polymerizable monomer ( A method for producing a polymer using a material containing A) is used.
[Selection figure] None

Description

  The present invention relates to a method for producing a polymer using a microreactor. More specifically, the present invention relates to a method for producing a polymer having a long-chain alkyl group with a very narrow molecular weight distribution using living anionic polymerization.

  In recent years, a drastic review of the manufacturing method of chemical products has been urged due to soaring petroleum energy. Among them, interest in microreactors is increasing in the field of chemical synthesis. A microreactor is a device that performs chemical reactions in a small space using a micro container, and it is not necessary to introduce a large-scale device, and it is expected to reduce investment costs and manufacturing costs. Therefore, it is widely used for chemical reactions using microreactors. It has been studied.

  Specifically, the microreactor is a micro container provided with a flow path capable of mixing a plurality of liquids, and an introduction path that communicates with the flow path and introduces the liquid into the flow path. A typical one is from several μm to several hundred μm. The plurality of liquids supplied through the introduction path of the microreactor are mixed together by the flow path to cause a reaction.

  In the reaction using a microreactor, it is considered that precise flow control of the reaction solution, temperature control, and rapid mixing are possible, and the conversion rate and selectivity are compared with the batch-type reaction that has been carried out conventionally. Improvement is expected, and it is attracting attention as a highly efficient production method. A new technology for synthesizing polymers with a narrow molecular weight distribution using a microreactor, a method capable of producing a polymer efficiently and at a high conversion without using a special cooling device, and blocking in a continuous process A method capable of producing a copolymer is disclosed (for example, see Patent Documents 1 and 2).

  On the other hand, living anion polymerization is considered to be one of the best polymerization methods because it allows precise polymer design (especially molecular weight control) as a polymer production method. Therefore, there is a problem that an ultra-low temperature cooling facility is required because the polymerizable monomer and the polymerization initiator must be mixed while being cooled to −78 ° C. or lower. In addition, in order to align the initiation reaction of living anion polymerization, the polymerizable monomer has to be added in a mist form or in a low concentration (for example, less than 1.5M), which is not suitable for mass production. .

JP 2009-67999 A JP 2010-180353 A

  The problem to be solved by the present invention is that a living anion polymerization of a polymerizable monomer having a long chain alkyl group can be carried out at a reaction temperature that can be produced industrially, and a long chain alkyl having a very narrow molecular weight distribution. It is providing the manufacturing method from which the polymer which has group is obtained.

  As a result of diligent research to solve the above-mentioned problems, the present inventors can industrially manufacture by performing living anion polymerization of a polymerizable monomer having a long-chain alkyl group using a microreactor. The inventors have found that a polymer having a long-chain alkyl group with a very narrow molecular weight distribution can be efficiently produced at the reaction temperature, and completed the present invention.

  That is, the present invention uses a microreactor provided with a flow channel capable of mixing a plurality of liquids to convert a polymerizable monomer containing a polymerizable monomer (A) having a long-chain alkyl group into a polymerization initiator ( The present invention provides a method for producing a polymer, characterized in that living anionic polymerization is carried out in the presence of C).

In the present invention, the first polymerizable monomer and the polymerization initiator (C) are introduced into the flow path in the microreactor using a microreactor having a flow path capable of mixing a plurality of liquids. A first step of living anionic polymerization to form an intermediate polymer;
The intermediate polymer and a second polymerizable monomer are introduced into the microreactor, and the polymerizable monomer having the long chain alkyl group at the growth terminal of the intermediate polymer is introduced into the microreactor. A second step of forming a block copolymer by living anionic polymerization;
A method for producing a polymer, comprising a polymerizable monomer (A) having a long-chain alkyl group in at least one of the first polymerizable monomer and the second polymerizable monomer The present invention provides a method for producing a polymer characterized in that:

  By using the method for producing a polymer of the present invention, a living anion polymerization of a polymerizable monomer having a long chain alkyl group can be carried out at a reaction temperature that can be produced industrially, and the molecular weight distribution is very narrow. A polymer having a long-chain alkyl group can be produced. In the method for producing a polymer of the present invention, a block copolymer having a polymer block having a long-chain alkyl group and a polymer block having other functional groups can also be produced. The polymer having a long-chain alkyl group produced by the production method of the present invention is useful as a functional material in various applications by utilizing the characteristics resulting from the long-chain alkyl group of the polymer. .

FIG. 1 is a schematic perspective view showing the overall configuration of an example of a microreactor used in the production method of the present invention. FIG. 2 is a schematic horizontal cross-sectional view showing the overall configuration of an example of a microreactor used in the production method of the present invention. FIG. 3 is a simplified reaction procedure of Example 1. FIG. 4 is a simplified reaction procedure of Example 2. FIG. 5 is a simplified reaction procedure of Example 3.

  The method for producing a polymer of the present invention has the following two aspects.

  A 1st aspect uses the microreactor provided with the flow path which can mix a some liquid, the polymerizable monomer containing the polymerizable monomer (A) which has a long-chain alkyl group, and a polymerization initiator (C) is introduced into a flow path in the microreactor and is subjected to living anion polymerization to obtain a polymer. In this first embodiment, the polymerizable monomer (A) having a long chain alkyl group alone may be used as the polymerizable monomer used as a raw material for the polymer. The polymer (A) and other polymerizable monomer (B) other than the polymerizable monomer (A) having a long-chain alkyl group may be used in combination.

On the other hand, the second embodiment uses a microreactor having a flow path capable of mixing a plurality of liquids, and transfers the first polymerizable monomer and the polymerization initiator (C) to the flow path in the microreactor. A first step of introducing and living anionic polymerization to form an intermediate polymer;
The intermediate polymer and a second polymerizable monomer are introduced into the microreactor, and the polymerizable monomer having the long chain alkyl group at the growth terminal of the intermediate polymer is introduced into the microreactor. A second step of forming a block copolymer by living anionic polymerization;
In the method for producing a polymer, at least one of the first polymerizable monomer and the second polymerizable monomer contains a polymerizable monomer (A) having a long-chain alkyl group. Is a method for obtaining a polymer. That is, the polymerizable monomer used in the first step and the polymerizable monomer used in the second step need only contain the polymerizable monomer (A) having a long-chain alkyl group. Other polymerizable monomers (B) other than the polymerizable monomer (A) having a long-chain alkyl group to be described later can be used as the polymerizable monomer used in addition to the above.

  The long-chain alkyl group of the polymerizable monomer (A) is preferably an alkyl group having 8 to 30 carbon atoms, more preferably an alkyl group having 10 to 20 carbon atoms, and 12 to 18 carbon atoms. More preferred is an alkyl group. Specific examples of the polymerizable monomer (A) include decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate (lauryl (meth) acrylate), tridecyl (meth) acrylate, pentadecyl ( Examples include meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate (stearyl (meth) acrylate), nonadecyl (meth) acrylate, icosanyl (meth) acrylate, and the like. These polymerizable monomers (A) can be used alone or in combination of two or more.

  On the other hand, as other polymerizable monomer (B) other than the polymerizable monomer (A) having a long-chain alkyl group, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl Alkyl (meth) acrylates such as (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate; aromatics such as benzyl (meth) acrylate ( Silane (meth) acrylates such as trimethylsiloxyethyl (meth) acrylate; (meth) acrylates having an epoxy group such as glycidyl (meth) acrylate; dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate , Dimethylamino (Meth) acrylates having an alkylamino group such as propyl (meth) acrylate; acrylamide compounds such as (meth) acrylamide, N, N-dimethylacrylamide, N-methylol (meth) acrylamide, isopropylacrylamide, diacetone acrylamide; Vinylpyridine compounds such as vinylpyridine, 4-vinylpyridine and naphthylvinylpyridine; alkylpolyalkylene glycol mono (meth) acrylates such as methoxypolyethylene glycol mono (meth) acrylate and methoxypolypropylene glycol mono (meth) acrylate; perfluoroalkylethyl Fluorine-based (meth) acrylates such as (meth) acrylate; styrene, styrene derivatives (p-dimethylsilylstyrene, (p-vinylpheny ) Methyl sulfide, p-hexynyl styrene, p-methoxy styrene, p-tert-butyldimethylsiloxy styrene, o-methyl styrene, p-methyl styrene, p-tert-butyl styrene, α-methyl styrene, etc.), vinyl naphthalene , Vinyl anthracene, aromatic vinyl compounds such as 1,1-diphenylethylene; methyl (meth) acrylate, ethyl (meth) acrylate, t-butyl methacrylate, n-butyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (Meth) acrylate, epoxy (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylene glycol te La (meth) acrylate, 2-hydroxy-1,3-diaacryloxypropane, 2,2-bis [4- (acryloxymethoxy) phenyl] propane, 2,2-bis [4- (acryloxyethoxy) phenyl ] (Meth) acrylate compounds such as propane, dicyclopentenyl (meth) acrylate tricyclodecanyl (meth) acrylate, tris (acryloxyethyl) isocyanurate, urethane (meth) acrylate; 1,3-butadiene, 2-methyl Examples include conjugated dienes such as -1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and 1,3-cyclohexadiene. These other polymerizable monomers can be used alone or in combination of two or more.

  Further, the alkyl group in the perfluoroalkylethyl methacrylate is not particularly limited, and specific examples of perfluoroalkylethyl methacrylate include 2- (perfluorobutyl) ethyl methacrylate and 2- (perfluorohexyl) ethyl. Methacrylate, 2- (perfluorooctyl) ethyl methacrylate and the like.

  In the present invention, “(meth) acrylate” refers to one or both of methacrylate and acrylate.

  In the method for producing a polymer according to the first aspect, by using only a polymerizable monomer (A) having a long chain alkyl group as a raw material for the polymer, a polymerizable monomer having a long chain alkyl group is used. A homopolymer of the body (A) is obtained. Further, in addition to the polymerizable monomer (A) having a long-chain alkyl group, the polymerizable monomer (B) is also used in combination with the polymerizable monomer (A) having a long-chain alkyl group and the above-mentioned A random copolymer with the polymerizable monomer (B) is obtained.

  On the other hand, in the method for producing a polymer according to the second embodiment, a block polymerizable copolymer is obtained by using a single polymerizable monomer for each of the first polymerizable monomer and the second polymerizable monomer. A polymer can be produced. For example, as the first polymerizable monomer, only one kind of the polymerizable monomer (B) is used, and as the second polymerizable monomer, a polymerizable monomer having a long-chain alkyl group is used. By using only the body (A), an AB type block copolymer can be produced.

  In the method for producing a polymer according to the second aspect, a plurality of types of polymerizable monomers are used as the first polymerizable monomer and the second polymerizable monomer. A copolymer having a plurality of different polymer blocks can be obtained.

  In the method for producing a polymer according to the second aspect, in addition to the polymerization reaction in the first step and the polymerization reaction in the second step, the intermediate polymer obtained in the second step, and the first step And a polymerizable monomer of a different type from the polymerizable monomer used in the second step is introduced into the microreactor, and the third polymerizable property is added to the growth terminal of the intermediate polymer obtained in the second step. A ternary block copolymer may be formed by performing a third step of forming a block copolymer by subjecting the monomer to living anion polymerization.

  In the living anion polymerization in the first and second aspects, in addition to the polymerizable monomer and the polymerization initiator, lithium chloride, lithium perchlorate, N, N, N ′, N ′ -The presence of one or more additives selected from the group consisting of tetramethylethylenediamine and pyridine makes it possible to perform living anionic polymerization, which usually needs to be performed at a low temperature, in a temperature range that can be industrially produced. Here, these additives are polymerization initiators for ester bonds existing in the structure of the polymerizable monomer used in the first aspect or the second aspect or the structure of the polymer obtained by the polymerization reaction ( It is thought that it has a function to prevent nucleophilic reaction of anion). The amount of these additives used can be adjusted as appropriate according to the amount of the polymerization initiator. However, since the polymerization reaction rate is increased and the molecular weight of the resulting polymer can be easily controlled, the polymerization is initiated. 0.05-10 mol is preferable with respect to 1 mol of agent, and 0.1-5 mol is more preferable.

  In the second aspect, at least one of the polymerization reaction in the first step and the polymerization reaction in the second step, lithium chloride, lithium perchlorate, N, N, N ′, N′-tetra One or more additives selected from the group consisting of methylethylenediamine and pyridine can be present, but the additive is present only in the polymerization reaction in the first step and only in the polymerization reaction in the second step. Alternatively, it may be present in the polymerization reaction in both the first step and the second step.

  The polymerizable monomer, the polymerization initiator, and the additive are preferably diluted or dissolved using an organic solvent and introduced into the microreactor as a solution.

  Examples of the organic solvent include hydrocarbon solvents such as pentane, octane, cyclohexane, benzene, toluene, xylene, decalin, tetralin, and derivatives thereof; diethyl ether, tetrahydrofuran (THF), 1,4-dioxane, 1, Examples include ether solvents such as 2-dimethoxyethane, diethylene glycol dimethyl ether and diglyme. These organic solvents can be used alone or in combination of two or more.

  As the concentration of the polymerizable monomer in the organic solvent solution, the production amount of the polymer per unit time becomes good, and the heat of the polymerization reaction can be efficiently removed. L, the same shall apply hereinafter) is preferred, a range of 0.05 to 3M is more preferred, and a range of 0.1 to 2M is particularly preferred.

  As the polymerization initiator, organic lithium can be used. For example, methyllithium, ethyllithium, propyllithium, butyllithium (n-butyllithium, sec-butyllithium, iso-butyllithium, tert-butyllithium, etc.) ), Alkyllithium such as pentyllithium and hexyllithium; alkoxyalkyllithium such as methoxymethyllithium and ethoxymethyllithium; α-methylstyryllithium; 1,1-diphenylhexyllithium and 1,1-diphenyl-3-methylpentryl Diarylalkyllithium such as lithium and 3-methyl-1,1-diphenylpentyllithium; alkenyllithium such as vinyllithium, allyllithium, propenyllithium and butenyllithium; ethynyllithium Alkynyl lithium such as butynyl lithium, pentynyl lithium and hexynyl lithium; aralkyl lithium such as benzyl lithium and phenylethyl lithium; aryl lithium such as phenyl lithium and naphthyl lithium; 2-thienyl lithium, 4-pyridyl lithium, 2- Heterocyclic lithium such as quinolyl lithium; alkyl lithium magnesium complex such as tri (n-butyl) magnesium lithium and trimethylmagnesium lithium; Among these, alkyl lithium is preferable because the polymerization reaction can be efficiently advanced, and n-butyl lithium and sec-butyl lithium are preferable among them. In addition, n-butyllithium is more preferable because it is easily available industrially and has high safety. These polymerization initiators can be used alone or in combination of two or more.

  Further, as described above, these polymerization initiators are preferably diluted or dissolved using an organic solvent and introduced into the microreactor as a solution. Examples of the organic solvent used include solubility of the polymerization initiator and Tetrahydrofuran (THF) is preferred because of its high solvation with respect to the counter cation and high polymerization rate.

  Moreover, it is preferable to introduce diphenylethylene or a derivative thereof (hereinafter abbreviated as “diphenylethylene etc.”) into the microreactor together with organic lithium which is a polymerization initiator. By using diphenylethylene or the like, it becomes a bulky polymerization initiator due to the phenyl group, so that the activity of the polymerization initiator can be weakened, so when using a (meth) acrylate monomer as a polymerizable monomer, There is an advantage that side reaction can be suppressed and living anionic polymerization can be appropriately controlled. In addition, even if diphenylethylene etc. introduce | transduce into a microreactor separately from organic lithium which is a polymerization initiator, and mix in a microreactor, it mixes with organic lithium which is a polymerization initiator beforehand, diphenylethylene etc. and organic After forming a reaction product with lithium, it may be introduced into a microreactor.

  The concentration of the polymerization initiator in the organic solvent solution is such that the polymerization reaction can proceed efficiently, and precipitation of insoluble substances during the polymerization that causes clogging of the microreactor flow path can be suppressed. The range of 001 to 1M is preferable, the range of 0.002 to 0.75M is more preferable, the range of 0.01 to 0.5M is more preferable, and the range of 0.02 to 0.2M is particularly preferable.

  In the second aspect of the present invention, the intermediate polymer obtained in the first step is brought into contact with the polymerizable monomer (A) having a long-chain alkyl group in the second step to perform a living anion polymerization reaction. The intermediate polymer is preferably introduced into the microreactor in the form of a solution dissolved in an organic solvent.

  The microreactor used in the production method of the present invention is provided with a flow channel capable of mixing a plurality of liquids, but preferably has a heat transfer reaction vessel provided with a flow channel, and a microtubular flow channel is provided inside. What has the formed heat conductive reaction container is more preferable, and what has the heat conductive reaction container which laminated | stacked the heat conductive plate-shaped structure in which the several groove part was formed in the surface is especially preferable.

  The living anion polymerization reaction in the present invention can be carried out at a temperature of −78 ° C. or lower, which is the reaction temperature in the conventional batch method, in both the first and second aspects, but is industrially feasible. It can be performed even at a temperature of −40 ° C. or higher, and can be performed at −28 ° C. or higher. A reaction temperature of −40 ° C. or higher is preferable because a polymer can be produced using a cooling device having a simple structure, and the production cost can be reduced. Moreover, it is preferable that the temperature is −28 ° C. or higher because a polymer can be produced using a cooling device having a simpler configuration, and the production cost can be greatly reduced.

  A micromixer is mentioned as a channel which can mix a plurality of liquids with which a microreactor used for the present invention is provided. As this micromixer, it is possible to use a commercially available micromixer, for example, a microreactor equipped with an interdigital channel structure, a single mixer manufactured by Institute, Futur, Microtechnique Mainz (IMM), and Caterpillar mixer; Microglass reactor manufactured by Microglass; Cytos manufactured by CPC Systems; YM-1 and YM-2 mixer manufactured by Yamatake Corporation; Mixing tee and tee (T-shaped connector) manufactured by Shimadzu GLC; Examples include IMT chip reactor; Toray Engineering Development Micro-High Mixer, etc., any of which can be used in the present invention.

  Furthermore, as a preferred form of the micromixer system, a process plate having a flow path for a polymer and a process plate having a flow path for a polymerization initiator are stacked one above the other, and the two fluids are combined at the flow path outlet. It is preferable to combine a mixer and a micromixer having a flow path through which the fluid after joining passes.

  The reaction channel described in the above formation method is a combination of at least two members and the space formed between the members is used as the reaction channel. It may be used as a reaction channel. The flow rate of flowing the flow path is such that the Reynolds number in the reaction vessel of the fluid containing the polymerizable monomer, the polymerization initiator, and the additive is continuously controlled at 2 to 300, so that the polymerizable monomer Further, the mixing property of the fluid containing the polymerization initiator and the additive is further enhanced by the turbulent flow effect, whereby the production can be performed more efficiently.

  Here, by controlling the movement of the fluid in the flow path with a value larger than Reynolds number 2, the mixing property of the fluid containing the polymerizable monomer, the polymerization initiator, and the additive is not remarkably deteriorated. It is preferable because it is possible to prevent the problem that the production efficiency is deteriorated without causing a reaction in a short time, and the reaction is completed without increasing the residence time. Further, it is difficult to control the Reynolds number to be over 300.

  The Reynolds number in the present invention is calculated according to the following formula (1).

Reynolds number = (D × u × ρ) / μ (1)
Here, D (inner diameter of the flow path), u (average flow velocity), ρ (fluid density), and μ (fluid viscosity).

As the reaction apparatus used in the production method of the present invention, a reaction apparatus in which a flow path is installed in a heat transfer reaction vessel is preferable. Since the flow path is a microtubule, heating can be quickly controlled. preferable. As the microtubular channel, a channel having a void size with a channel cross-sectional area of 0.1 to 4.0 mm ² is preferable for controlling the polymerization reaction temperature. In the present invention, “cross section” means a cross section perpendicular to the flow direction in the flow path, and “cross sectional area” means the area of the cross section.

  The cross-sectional shape of the channel is a square, a rectangle including a rectangle, a polygon including a trapezoid, a parallelogram, a triangle, a pentagon, etc. (a shape with rounded corners, a high aspect ratio, ie including a slit shape) It may be a star shape, a semicircle, a circle including an ellipse, or the like. The cross-sectional shape of the channel need not be constant.

  The method for forming the reaction channel is not particularly limited, but in general, the member (X) having a plurality of grooves on the surface is laminated and bonded to the other surface (Y) on the surface having the grooves. And is formed as a space between the member (X) and the member (Y).

  The channel may further be provided with a heat exchange function. In that case, for example, a groove for flowing the temperature adjusting fluid is provided on the surface of the member (X), and another member is bonded or laminated on the surface provided with the groove for flowing the temperature adjusting fluid. What is necessary is just to fix. In general, a member (X) having a groove on the surface and a member (Y) provided with a groove for flowing a temperature-controlled fluid include a surface provided with a groove, and a surface provided with a groove of another member. A flow path may be formed by fixing the opposite surface, and a plurality of these members (X) and members (Y) may be fixed alternately.

  At this time, the groove formed on the member surface may be formed as a so-called groove lower than the peripheral portion thereof, or may be formed between the walls standing on the member surface. The method of providing the groove on the surface of the member is arbitrary, and for example, methods such as injection molding, solvent casting method, melt replica method, cutting, etching, photolithography (including energy beam lithography), and laser ablation can be used.

  The layout of the flow paths in the member may be in the form of a straight line, a branch, a comb, a curve, a spiral, a zigzag, or any other arrangement according to the purpose of use.

  The flow path is, for example, a mixing field, an extraction field, a separation field, a flow rate measurement unit, a detection unit, a liquid storage tank, a membrane separation mechanism, a connection port to the inside or outside of the device, a tangential line, a development path for chromatography or electrophoresis Further, it may be connected to a part of the valve structure (portion surrounding part), a pressurizing mechanism, a depressurizing mechanism or the like.

  The outer shape of the member need not be particularly limited, and can take a shape according to the purpose of use. The shape of the member may be, for example, a plate shape, a sheet shape (including a film shape, a ribbon shape, etc.), a coating film shape, a rod shape, a tube shape, and other complicated shapes. External dimensions such as thickness are preferably constant. The material of the member is arbitrary, and may be, for example, a polymer, glass, ceramic, metal, or semiconductor.

  As described above, the reaction apparatus used in the production method of the present invention is preferably a reaction apparatus having a flow path installed in a heat transfer reaction vessel, and may be a tube immersed in an oil bath or a water bath. Furthermore, as a reaction apparatus comprising a heat transfer reaction vessel in which a channel is formed, a reaction apparatus having a structure in which a heat transfer plate-like structure having a plurality of grooves formed on the surface is laminated can be used.

  Examples of such a reaction apparatus include an apparatus in which the channel (hereinafter sometimes simply referred to as “microchannel”) is provided in a member used as a chemical reaction device.

  Hereinafter, a schematic configuration example of a microreactor provided with a flow channel in a preferable form used in the present invention will be described with reference to FIGS.

  In the chemical reaction device 1, a plurality of first plates (2 in FIG. 1) and second plates (3 in FIG. 1) having the same rectangular plate shape in FIG. Configured. Each one first plate is provided with a flow path (4 in FIG. 1; hereinafter referred to as a reaction flow path) (hereinafter, the plate provided with the reaction flow path is referred to as a process plate). Further, the second plate is provided with a temperature control fluid channel (6 in FIG. 1; hereinafter referred to as a temperature control channel) (hereinafter, the plate provided with the temperature control channel is referred to as a temperature control plate). ). And as shown in FIG. 2, those supply ports and discharge ports are distributed and arranged in each region of the end surface 1b, 1c, side surface 1d, 1e of the device for chemical reaction 1, and in these regions, the polymerizable monomer The joint part 32 which consists of the connector 30 and the joint part 31 for flowing the fluid (alpha) containing a body, a polymerization initiator, and an additive, and the temperature control fluid (gamma) is each connected.

Via these joints, a fluid α containing a polymerizable monomer, a polymerization initiator, and an additive is supplied from the end surface 1b, discharged to the end surface 1c as a fluid β, and a temperature-controlled fluid γ is supplied from the side surface 1e. And is discharged to the side surface 1d. The planar view shape of the device for chemical reaction 1 is not limited to the rectangular shape as shown in the figure, and may be a square shape or a rectangular shape having a longer distance between the side surfaces 1d and 1e than between the end surfaces 1b and 1c.

<Micromixer used in Examples>
The microreactor used in this example is configured to include a micromixer made of a T-shaped pipe joint and a tube reactor connected downstream of the micromixer. As the micromixer, a special order product manufactured by Sanko Seiki Kogyo Co., Ltd. was used (it is possible to request the manufacture based on the description of this example and obtain an equivalent product). Note that the micromixer used in this example has a part of the first introduction path, the second introduction path, and the flow path in which these are merged, and any of them is included in the micromixer. The inner diameter is the same. Therefore, hereinafter, these inner diameters are collectively referred to as “the inner diameter of the micromixer”.

[Method for measuring number average molecular weight and weight average molecular weight]
The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the polymers obtained in Examples and Comparative Examples were measured by gel permeation chromatography (GPC) method under the following conditions.

Measuring device: High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were connected in series.
"TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000" (7.8 mm ID x 30 cm) x 1 "TSKgel G3000" (7.8 mm ID x 30 cm) x 1 “TSKgel G2000” (7.8 mm ID × 30 cm) × 1 detector: RI (differential refractometer)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Injection amount: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4 mass%)
Standard sample: A calibration curve was prepared using the following standard polystyrene.

(Standard polystyrene)
"TSKgel standard polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel standard polystyrene A-5000" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-1" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel standard polystyrene F-550" manufactured by Tosoh Corporation

[Measurement method of residual monomer amount]
The polymer solutions obtained in Examples and Comparative Examples were measured under the following conditions using gas chromatography (“GC-2014F type” manufactured by Shimadzu Corporation) to determine the amount of residual monomers.
Column: Wide bore capillary column manufactured by Shimadzu Corporation Detector: FID (hydrogen flame ionization detector)
Column temperature: 70-250 ° C
Injection volume: 1 μL (tetrahydrofuran diluted solution)

Example 1
The following three types of solutions were prepared.
(1) Lauryl methacrylate mixture (0.5 M) solution In a 300 mL eggplant flask substituted with argon gas, a lauryl methacrylate mixture (“Blemmer SLMA-H” manufactured by NOF Corporation, 43% by mass and tridecyl methacrylate was used). Mixture of 56% by mass of decyl methacrylate; hereinafter abbreviated as “SLMA”) 15.7 g (18.1 mL) and tetrahydrofuran (hereinafter abbreviated as “THF”) 101.8 mL were collected and stirred. 120 mL of a 0.5 M solution of SLMA was prepared.
(2) Diphenylhexyllithium (0.05M) solution (polymerization initiator solution)
In a 100 mL eggplant flask substituted with argon gas, 0.45 g (0.5 mL) of diphenylethylene and 48.56 mL of THF were collected using a syringe, and then cooled by being immersed in a container immersed in ice water. After cooling, 0.94 mL of a 2.6 M hexane solution of n-butyllithium was collected using a syringe and stirred to prepare 50 mL of a 0.05 M solution of diphenylhexyllithium (hereinafter abbreviated as “DPhLi”). did.
(3) Methanol (0.33M) solution In a 100 mL eggplant flask substituted with argon gas, 0.53 g (0.64 mL) of methanol (hereinafter abbreviated as “MeOH”) and 49.4 mL of THF were added using a syringe. By collecting and stirring, 50 mL of a 0.33 M solution of MeOH was prepared.

  Next, living anionic polymerization of SLMA was performed by the following operation. Two syringe pumps (“Syringe Pump Model 11 Plus” manufactured by Harvard) were installed in a microreactor device equipped with a micromixer consisting of two T-shaped saddle joints and a tube reactor connected downstream of the micromixer. The 50 mL gust syringe that sucked each of the three types of solutions obtained above was set in the syringe pump. From the upstream side of the reactor composed of a micromixer with a joint diameter of 250 μm and a tube reactor with an inner diameter of 1 mm and a length of 200 cm, the SLMA solution is fed at a rate of 6 mL / min and the DPhLi solution at a rate of 2 mL / min and mixed. Then, living anionic polymerization of SLMA was carried out, and a MeOH solution was fed at a rate of 1.5 mL / min in a reactor composed of a micromixer with a 500 mm joint diameter and a tube reactor with an inner diameter of 1 mm and a length of 100 cm. The polymerization reaction was stopped by mixing. The reaction temperature was adjusted to −28 ° C. by burying the entire microreactor in a constant temperature layer. A simplified reaction procedure of Example 1 is shown in FIG.

  From the amount of residual monomers in the obtained polymer solution, the reaction rate (polymer pass-through rate) was 98.4%. Moreover, the number average molecular weight (Mn) of the obtained polymer was 11,000, the weight average molecular weight (Mw) was 13,500, and dispersion degree (Mw / Mn) was 1.23. From these results, it was confirmed that a polymer having a very narrow molecular weight distribution was obtained.

(Example 2)
The following solutions were prepared.
(1) DMAMA / SLMA (0.3M) mixed solution In a 300 mL eggplant flask substituted with argon gas, 3.96 g (4.24 mL) of DMAMA, 15.7 g (18.1 mL) of SLMA, and 97.66 mL of THF were added using a syringe. By collecting and stirring, 120 mL of a mixed solution having a concentration of DMAM and SLMA of 0.5 M each was prepared.
The DPhLi (0.05M) solution and the MeOH (0.33M) solution were prepared in the same manner as in Example 1.

  Next, a random copolymer was produced by living anionic polymerization of DMAMA and SLMA by the following operation. Two syringe pumps (“Syringe Pump Model 11 Plus” manufactured by Harvard) were installed in a microreactor device equipped with a micromixer consisting of two T-shaped saddle joints and a tube reactor connected downstream of the micromixer. A 50 mL gust syringe that sucked the two types of solutions obtained above was set in the syringe pump. A DMAMA / SLMA mixed solution and a DPhLi solution were fed at a rate of 6 mL / min and 2 mL / min from upstream of a reactor composed of a micromixer having a joint diameter of 250 μm and a tube reactor having an inner diameter of 1 mm and a length of 400 cm. By mixing, living anionic polymerization of DMAMA and SLMA was performed. The polymerization solution was stopped by putting the obtained polymer solution into a container containing a predetermined amount of MeOH solution to obtain a solution of a random copolymer of DMAMA and SLMA. The reaction temperature was adjusted to 0 ° C. by burying the entire microreactor in a constant temperature layer. A simplified reaction procedure of Example 2 is shown in FIG.

  From the amount of residual monomers in the obtained polymer solution, the DMAMA reaction rate (polymer pass-through rate) was 98.6%, and the SLMA reaction rate (polymer pass-through rate) was 95.9%. Moreover, the number average molecular weight (Mn) of the obtained polymer was 11,420, the weight average molecular weight (Mw) was 13,700, and dispersion degree (Mw / Mn) was 1.20. From these results, it was confirmed that a random copolymer having a very narrow molecular weight distribution was obtained. A simplified reaction procedure of Example 2 is shown in FIG.

(Comparative Example 1)
A random copolymer was produced by free radical polymerization of SLMA and DMAMA using a batch reactor. A four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen gas inlet tube was charged with 66.5 g of butyl acetate and heated to 80 ° C. When the same temperature was reached, 66.5 g of SLMA, DMAMA3. 5 g and a mixture prepared by dissolving 0.49 g of 2,2′-azobis (2-methylbutyronitrile) in 3.6 g of butyl acetate were added dropwise over 3.5 hours, and the temperature was raised to 90 ° C. after completion of the addition, Reaction was performed at the same temperature for 10 hours to obtain an SLMA-DMAMA random copolymer solution.

  The number average molecular weight (Mn) of the obtained polymer was 18,700, the weight average molecular weight (Mw) was 33,000, and the dispersity (Mw / Mn) was 1.76. From these results, it was confirmed that in free radical polymerization, only a polymer having a broad molecular weight distribution was obtained as compared with the polymer obtained in Example 2 using living anion polymerization.

(Example 3)
The following solutions were prepared.
(1) Polymerizable monomer (0.5M) solution having an alkylamino group In a 300 mL eggplant flask substituted with argon gas, dimethylaminoethyl methacrylate (hereinafter abbreviated as “DMAMA”) is used with a syringe. .9 g (8.4 mL) and 91.6 mL of THF were collected and stirred to prepare 100 mL of a 0.5 M solution of DMAMA.
The SLMA (0.5M) solution, DPhLi (0.05M) solution, and MeOH (0.33M) solution were prepared in the same manner as in Example 1.

  Next, a block copolymer was produced by living anionic polymerization of DMAMA and SLMA by the following operation. Three syringe pumps (“Syringe Pump Model 11 Plus” manufactured by Harvard) were added to a microreactor device equipped with a micromixer composed of two T-shaped saddle joints and a tube reactor connected downstream of the micromixer. The 50 mL gust syringe that sucked each of the three types of solutions obtained above was set in the syringe pump. First, a DMAMA solution is sent at a rate of 2.5 mL / min and a DPhLi solution is sent at a rate of 2 mL / min from the upstream of a reactor composed of a micromixer with a diameter of 250 μm and a tube reactor with an inner diameter of 1 mm and a length of 100 cm. As a result, a living anionic polymerization of DMAMA was performed to obtain a DMAMA polymer solution. Next, the obtained DMAMA polymer solution and the SLMA solution were sent at a rate of 6 mL / min from the upstream of the reactor constituted by a micromixer with a spear joint diameter of 500 μm and a tube reactor with an inner diameter of 1 mm and a length of 400 cm. Liquid anionic copolymerization of DMAMA and SLMA was performed by liquefying. The resulting polymer solution was put into a container containing a predetermined amount of MeOH solution to stop the polymerization reaction, and a DMAMA / SLMA block copolymer solution was obtained. The reaction temperature was adjusted to −28 ° C. by burying the entire microreactor in a constant temperature layer. A simplified reaction procedure of Example 3 is shown in FIG.

  From the amount of residual monomers in the obtained polymer solution, the DMAMA reaction rate (polymer pass-through rate) was 100%, and the SLMA reaction rate (polymer pass-through rate) was 99%. Moreover, the number average molecular weight (Mn) of the obtained polymer was 9,510, the weight average molecular weight (Mw) was 13,250, and dispersity (Mw / Mn) was 1.39. From these results, it was confirmed that a block copolymer having a narrow molecular weight distribution was obtained. In the free radical polymerization as in Comparative Example 1, it is difficult to produce a block copolymer even if two kinds of polymerizable monomers are used.

Example 4
The following solutions were prepared.
(1) Stearyl methacrylate (0.5 M) solution In a 300 mL eggplant flask substituted with argon gas, stearyl methacrylate (“Light Ester S” manufactured by Kyoeisha Chemical Co., Ltd .; hereinafter abbreviated as “StMA”) was used. 20.2 g (23.5 mL) and 96.5 mL of THF were collected and stirred to prepare 120 mL of a 0.5 M solution of StMA.

  A living anionic polymerization of StMA was performed in the same manner as in Example 1 except that the 0.5 M solution of StMA obtained above was used instead of the 0.5 M solution of SLMA used in Example 1. A solution of a homopolymer of StMA was obtained. From the amount of residual monomers in the polymer solution obtained, the StMA reaction rate (polymer pass-through rate) was 95.9%. Moreover, the number average molecular weight (Mn) of the obtained polymer was 17,270, the weight average molecular weight (Mw) was 24,000, and dispersion degree (Mw / Mn) was 1.39. From these results, it was confirmed that a polymer having a narrow molecular weight distribution was obtained.

(Example 5)
Instead of the 0.5M solution of SLMA used in Example 3, the 0.5M solution of StMA obtained in Example 4 was used, and the flow rate of the StMA solution was changed to 3 mL / min. By operating, living anion copolymerization of DMAMA and StMA was performed to obtain a solution of a block copolymer of DMAMA and StMA. From the amount of residual monomers in the obtained polymer solution, the DMAMA reaction rate (polymer pass-through rate) was 100%, and the StMA reaction rate (polymer pass-through rate) was 99.9%. Moreover, the number average molecular weight (Mn) of the obtained polymer was 12,770, the weight average molecular weight (Mw) was 18,100, and dispersity (Mw / Mn) was 1.42. From these results, it was confirmed that a block copolymer having a narrow molecular weight distribution was obtained.

  Table 1 shows the polymerization reaction conditions in Examples 1 to 5 and Comparative Example 1 and the characteristic values of the obtained polymer.

1 …… Microreactor

Claims (4)

  Using a microreactor having a flow path capable of mixing a plurality of liquids, a polymerizable monomer containing a polymerizable monomer (A) having a long-chain alkyl group is removed in the presence of a polymerization initiator (C). A method for producing a polymer, characterized by carrying out living anion polymerization. Using a microreactor equipped with a flow channel capable of mixing a plurality of liquids, the first polymerizable monomer and the polymerization initiator (C) are introduced into the flow channel in the microreactor to perform living anion polymerization, A first step of forming an intermediate polymer;
The intermediate polymer and a second polymerizable monomer are introduced into the microreactor, and the polymerizable monomer having the long chain alkyl group at the growth terminal of the intermediate polymer is introduced into the microreactor. A second step of forming a block copolymer by living anionic polymerization;
A method for producing a polymer, comprising a polymerizable monomer (A) having a long-chain alkyl group in at least one of the first polymerizable monomer and the second polymerizable monomer And a method for producing a polymer.   The first polymerizable monomer contains a (meth) acrylate having an alkylamino group, and the second polymerizable monomer has a long-chain alkyl group (A) Or the first polymerizable monomer contains a polymerizable monomer (A) having a long-chain alkyl group, and the second polymerizable monomer The method for producing a polymer according to claim 2, which comprises (meth) acrylate having an alkylamino group.   4. The polymer according to claim 1, wherein the polymerizable monomer (A) having a long-chain alkyl group is a polymerizable monomer having an alkyl group having 8 to 30 carbon atoms. Production method.

Images