JP2015131873A - Method of producing polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of producing a block-copolymer having a weight-average molecular weight greater than 10,000 and a narrow molecular-weight distribution using a microreactor.SOLUTION: A method of producing a block-copolymer includes: a first process of obtaining a styrene polymer having a molecular weight of not less than 100 by living anion polymerization using a microreactor provided with a flow pass capable of mixing a plurality of liquids; a second process of reacting active terminals of the styrene polymer obtained by the first process with diphenylethylene by a time before the active terminal-substituted diphenylethylene are deactivated after completing a reaction of the active terminals of the styrene polymer with the diphenylethylene; and a third process of polymerizing an intermediate polymer obtained by the second process in which diphenylethylene is added to the active terminals of the styrene polymer with a polymerizable monomer other than styrene by living anion polymerization to obtain a polymer having a degree of polymerization of not less than 100.

Description

  The present invention relates to a method for producing a high molecular weight styrenic block copolymer using a microreactor.

  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 introduced 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).

  However, the molecular weights of the block copolymers obtained by these prior arts are several thousand in weight average molecular weight, and the production of those having a weight average molecular weight exceeding 10,000 has not been disclosed.

JP 2009-67999 A JP 2010-180353 A

  The problem to be solved by the present invention is to provide a method for producing a block copolymer having a weight average molecular weight exceeding 10,000 and having a narrow molecular weight distribution using a microreactor.

  As a result of earnest research to solve the above problems, the present inventors have specified a time for reacting diphenylethylene with the active terminal of the styrene polymer when a styrene block copolymer is obtained using a microreactor. By making it into the range, it was found that a styrenic block copolymer having a weight average molecular weight exceeding 10,000 and having a narrow molecular weight distribution was obtained, and the present invention was completed.

That is, the present invention is a method for producing a block copolymer having a styrene polymer block having a polymerization degree of 100 or more and a polymer block of a polymerizable monomer other than styrene having a polymerization degree of 100 or more,
Using a microreactor with a channel that can mix multiple liquids,
A first step of living anionic polymerization of styrene in the presence of a polymerization initiator for a time sufficient to achieve a degree of polymerization of 100 or more;
Diphenylethylene is added to the active terminal of the styrene polymer obtained in the first step, and the time is longer than the time required for the reaction between the active terminal of the styrene polymer and diphenylethylene to be completed. A second step of reacting in the time required before the active end replaced with diphenylethylene is deactivated;
In the presence of a polymerization initiator, a polymerization monomer other than styrene is added to the intermediate polymer in which diphenylethylene is added to the active terminal of the styrene polymer obtained in the second step, and the degree of polymerization is 100 or more. The present invention provides a method for producing a block copolymer, comprising a third step of conducting living anion polymerization for a sufficient time.

  By using the block copolymer production method of the present invention, a styrenic block copolymer having a weight average molecular weight exceeding 10,000 can be obtained, and therefore it is suitably used for applications requiring a high molecular weight. be able to. In particular, it can be used for block copolymer lithography applications utilizing a self-organized structure of a high molecular weight block copolymer, which is one of the next-generation semiconductor microfabrication technologies.

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. 4 is a chart of gel permeation chromatography (GPC) of the polymer obtained in Example 1. FIG. 5 is a chart of gel permeation chromatography (GPC) of the polymer obtained in Example 2. FIG. 6 is a chart of gel permeation chromatography (GPC) of the polymer obtained in Example 3. FIG. 7 is a chart of gel permeation chromatography (GPC) of the polymer obtained in Example 4. FIG. FIG. 8 is a chart of gel permeation chromatography (GPC) of the polymer obtained in Comparative Example 1. FIG. 9 is a chart of gel permeation chromatography (GPC) of the polymer obtained in Comparative Example 2. 10 is a chart of gel permeation chromatography (GPC) of the polymer obtained in Comparative Example 3. FIG.

The block polymer production method of the present invention is a production of a block copolymer having a styrene polymer block having a polymerization degree of 100 or more and a polymer block of a polymerizable monomer other than styrene having a polymerization degree of 100 or more. A method,
Using a microreactor with a channel that can mix multiple liquids,
A first step of living anionic polymerization of styrene in the presence of a polymerization initiator for a time sufficient to achieve a degree of polymerization of 100 or more;
Diphenylethylene is added to the active terminal of the styrene polymer obtained in the first step, and the time is longer than the time required for the reaction between the active terminal of the styrene polymer and diphenylethylene to be completed. A second step of reacting in the time required before the active end replaced with diphenylethylene is deactivated;
In the presence of a polymerization initiator, a polymerization monomer other than styrene is added to the intermediate polymer in which diphenylethylene is added to the active terminal of the styrene polymer obtained in the second step, and the degree of polymerization is 100 or more. It includes a third step in which living anion polymerization is performed for a sufficient time.

  Examples of polymerizable monomers other than styrene used in the third step of the method for producing a block copolymer of the present invention include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec. -Butyl (meth) acrylate, t-butyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) ) Acrylate (lauryl (meth) acrylate), tridecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate (stearyl (meth) Acrylate), nonadecyl (meth) acrylate, icosanyl (meth) acrylate and other alkyl (meth) acrylates; benzyl (meth) acrylate, phenylethyl (meth) acrylate and other aromatic (meth) acrylates; cyclohexyl (meth) acrylate, isobornyl (Meth) acrylate having a cyclic compound such as (meth) acrylate; methoxypolyethylene glycol mono (meth) acrylate, methoxypolypropylene glycol mono (meth) acrylate, octoxypolyethylene glycol mono (meth) acrylate, octoxypolypropylene glycol mono (meta ) Acrylate, Lauroxypolyethylene glycol mono (meth) acrylate, Lauroxypolypropylene glycol mono (meth) acrylate , Stearoxy polyethylene glycol mono (meth) acrylate, stearoxy polypropylene glycol mono (meth) acrylate, allyloxy polyethylene glycol mono (meth) acrylate, allyloxy polypropylene glycol mono (meth) acrylate, nonylphenoxy polyethylene glycol mono (meth) acrylate , Alkyl group-terminated polyalkylene glycol mono (meth) acrylates such as nonylphenoxypolypropylene glycol mono (meth) acrylate, silane-based (meth) acrylates such as trimethylsiloxyethyl (meth) acrylate; dialkylsiloxy group, diphenylsiloxy group, tri (Meth) acrylates having siloxy groups such as alkylsiloxy groups and triphenylsiloxy groups; (Meth) acrylate having a sesquioxane group; fluorine-based (meth) acrylate such as perfluoroalkylethyl (meth) acrylate; glycidyl (meth) acrylate, epoxy (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) ) Acrylate, trimethylolpropane tri (meth) acrylate, tetramethylene glycol tetra (meth) acrylate, 2-hydroxy-1,3-diaacryloxypropane, 2,2-bis [4- (acryloxymethoxy) phenyl] propane 2,2-bis [4- (acryloxyethoxy) phenyl] propane, dicyclopentenyl (meth) acrylate tricyclodecanyl (meth) acrylate, tris (acryloxyethyl) isocyanurate (Meth) acrylate compounds such as urethane (meth) acrylate; (meth) acrylates having an alkylamino group such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, etc. It is done. Further examples include conjugated monomers such as acrylonitrile, 1,3-butadiene, isoprene, and vinylpyridine. These other polymerizable monomers can be used alone or in combination of two or more.

  Examples of the perfluoroalkylethyl (meth) acrylate include 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, and 2- (perfluorooctyl) ethyl. (Meth) acrylate etc. are mentioned.

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

  The first step in the method for producing a block copolymer of the present invention is a step for producing a styrene polymer block by subjecting styrene to living anion polymerization in the presence of a polymerization initiator. In this first step, the reaction is carried out for a time sufficient for the degree of polymerization of the styrene polymer to be 100 or more. As the time required for setting the degree of polymerization of the styrene polymer to 100 or more, the styrene polymer obtained by living anion polymerization is sampled while changing the time required for the first step, and the degree of polymerization of styrene is 100. It is preferable to set the time more than the above. Specifically, the time required for the first step is preferably 15 seconds or longer. The degree of polymerization of the styrene polymer was determined by measuring the molecular weight using gel permeation chromatography (hereinafter abbreviated as “GPC”) by polymerizing only styrene in the presence of a polymerization initiator, and measuring the residual monomer. This can be confirmed by measuring the polymerization reaction rate.

  The second step in the production method of the block copolymer of the present invention is a step of reacting the active terminal of the styrene polymer obtained in the first step with diphenylethylene. The reaction is carried out for a time sufficient for the reaction with ethylene to be completed, and for the time required before the active end of the styrene polymer replaced with diphenylethylene is deactivated. The required time is obtained by sampling a styrene polymer reacted with diphenylethylene, confirming the reaction rate of diphenylethylene, obtaining the time required for sufficient reaction of diphenylethylene, and other than styrene in the third step. It is preferable to set the time required in the second step by determining the reactivity with the polymerizable monomer (reaction rate of the polymerizable monomer other than styrene). Specifically, the time required for the second step is preferably in the range of 10 to 35 seconds, and more preferably in the range of 15 to 30 seconds. In the block copolymer production method of the present invention, the time required for the second step is the same as the time from the end of the first step to the start of the third step in the present invention.

  Further, in the third step of the method for producing a block copolymer of the present invention, the polymerizable monomer other than styrene is added to the intermediate polymer in which diphenylethylene is added to the active terminal of the styrene polymer obtained in the second step. Is a process of producing a block copolymer having a styrene polymer block and a polymer block of a polymerizable monomer other than styrene by living anion polymerization in the presence of a polymerization initiator. In this third step, the reaction is carried out for a time sufficient for the degree of polymerization of the polymer block of a polymerizable monomer other than styrene to be 100 or more. As the time required for setting the degree of polymerization of the polymer block of a polymerizable monomer other than styrene to 100 or more, a block copolymer obtained by living anion polymerization is used while changing the time required for the third step. It is preferable to sample and set the degree of polymerization of the polymerizable monomer other than styrene to be equal to or more than 100 hours. Specifically, the time required for the third step is preferably 20 seconds or longer. The degree of polymerization of a polymer of a polymerizable monomer other than styrene is determined by measuring the molecular weight of only styrene by the above method, and then measuring the molecular weight of the final block copolymer using GPC. It can confirm by measuring a polymerization reaction rate by measuring.

  The time required for the above-mentioned first to third steps is the size and length of the inner diameter of the tube reactor used for introducing each reactant into the next step after mixing the raw materials in each step with a micromixer, By adjusting the feeding speed of the solution of the reaction product of the styrene polymer and diphenylethylene, it can be adjusted to a desired time range. The end point of the required time in the third step is the time when the living anion polymerization is terminated with methanol or the like.

  As the polymerization initiator, organic lithium can be used. For example, methyl lithium, ethyl lithium, propyl lithium, butyl lithium (n-butyl lithium, sec-butyl lithium, isobutyl lithium, t-butyl lithium, etc.), Alkyl lithium such as pentyl lithium and hexyl lithium; alkoxyalkyl lithium such as methoxymethyl lithium and ethoxymethyl lithium; α-methylstyryl lithium; 1,1-diphenylhexyl lithium, 1,1-diphenyl-3-methylpentyl lithium; Diarylalkyllithium such as 3-methyl-1,1-diphenylpentyllithium; alkenyllithium such as vinyllithium, allyllithium, propenyllithium, butenyllithium; ethynyllithium, butini Alkynyl lithium such as 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 and 2-quinolyl lithium And heterocyclic lithium; alkyl lithium magnesium complexes such as tri (n-butyl) magnesium lithium and trimethyl magnesium 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.

  As the solution concentration of the polymerization initiator, the concentration of the polymerizable monomer can be increased, the designed molecular weight can be increased, and the growth terminal concentration can be increased so that the polymerization can proceed stably. The range of 0.005M to 0.1M is preferable, the range of 0.01 to 0.08M is more preferable, and the range of 0.02 to 0.06M is more preferable. In addition, as an organic solvent in which a polymerization initiator is diluted or dissolved to form a solution, the solubility of the polymerization initiator, the stability of the polymerization initiator activity, and the styrene polymer or block copolymer formed in the polymerization step In view of the solubility of hydrocarbons, hydrocarbon solvents such as hexane, cyclohexane, benzene, toluene, and xylene are preferable.

  In the living anionic polymerization in the first step and the third step, 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 prevent the nucleophilic reaction of the polymerization initiator (anion) to the ester bond existing in the structure of the polymerizable monomer other than styrene or the structure of the polymer obtained by the polymerization reaction. It is thought that there is. 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.

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

  The reaction temperature in the first step and the second step is preferably in the range of 0 to 50 ° C., because the reaction can be completed in a short time and the liquid viscosity in the microreactor can be lowered as much as possible. The range of is more preferable. In addition, the reaction temperature in the third step is preferably in the range of −90 to 0 ° C., more preferably in the range of −50 to −10 ° C., in view of the polymerization stability of polymerizable monomers other than styrene. A range of −40 to −20 ° C. is more preferable.

  When the styrene used in the first step and the polymerizable monomer other than styrene used in the third step are introduced into the microreactor as a solution, the concentration of the solution is 3M (mol / L, the same applies hereinafter). The above is preferable, the range of 3 to 10M is more preferable, and the range of 4 to 8M is more preferable.

  In order to introduce a solution of a polymerizable monomer and a polymerization initiator into a microreactor flow path at a higher concentration than in the conventional method and to allow living anion polymerization to proceed smoothly, It is necessary to reliably feed a polymer solution of a high viscosity polymerizable monomer formed by polymerization. Further, in the third step of the method for producing a block copolymer of the present invention, a polymerizable monomer was introduced into the flow path in the microreactor, and diphenylethylene was added to the styrene polymer obtained in the second step. When producing a block copolymer by living anion polymerization with an intermediate polymer, a solution of the intermediate polymer obtained by adding diphenylethylene to the styrene polymer obtained in the second step having a high viscosity, and a low viscosity third Even though the viscosity of the polymerizable monomer introduced into the macroreactor in the process is greatly different, the mixture is surely mixed and living anionic polymerized, and the formed high-viscosity block copolymer is reliably fed. Must be able to liquid. As such a pump that reliably introduces a highly viscous solution into the flow path of the microreactor, a plunger pump capable of high-pressure liquid feeding and having a very small pulsating flow is preferable.

  In addition, as the liquid feeding pressure when the polymerizable monomer, the polymerization initiator, and the produced intermediate polymer solution are introduced into the flow path of the microreactor, the polymer can be efficiently produced. The range of -32MPa is preferable, the range of 3-20MPa is more preferable, and the range of 4-15MPa is further more preferable. As a pump capable of feeding at such a pressure, a plunger pump for liquid chromatography is preferable, and a double plunger pump is more preferable. Further, a method in which a damper is attached to the outlet of the double plunger pump to feed the liquid while suppressing the pulsating flow is more preferable.

  The microreactor used in the method for producing a block copolymer of the present invention is provided with a flow path capable of mixing a plurality of liquids, but preferably has a heat transfer reaction vessel provided with flow paths. What has a heat-conductive reaction container in which the microtubular channel was formed is more preferable, and what has a 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.

  In the present invention, a preferred form of the micromixer system for mixing two or more kinds of polymerizable monomers or polymer solutions is introduced into the flow channel of the microreactor at a higher concentration than the conventional method, and the living anion. In order to allow the polymerization to proceed smoothly, a micromixer that can mix a high-concentration polymerizable monomer solution and a polymerization initiator solution in a short time is preferable.

  The micromixer is a flow path capable of mixing a plurality of liquids included in the microreactor. As the micromixer, a commercially available micromixer can be used. For example, an interdigital channel structure is used. Equipped with microreactor, Institute Furle Microtechnic Mainz (IMM) single mixer and caterpillar mixer; Microglass microglass reactor; CPC Systems Cytos; Yamatake YM-1, YM-2 Type mixers; mixing tees and tees (T-shaped connectors) manufactured by Shimadzu GLC; IMT chip reactors manufactured by Micro Chemical Engineering Co., Ltd .; micro-high mixer developed by Toray Engineering Co., Ltd., all of which can be used in the present invention.

  Furthermore, as a preferred form of the micromixer system, in particular in the second embodiment, the second polymerizable monomer solution is introduced into the flow path in the microreactor to polymerize the first polymerizable monomer. In order to prepare a block copolymer by living anion polymerization with a polymer solution, an intermediate polymer solution obtained by polymerizing a first polymerizable monomer having a high viscosity, and a second polymerizable monomer having a low viscosity A micromixer system that can reliably mix the body solution with a large difference in viscosity is preferable.

  Such a micromixer system is preferably a micromixer in which a relatively wide flow path space is formed at the junction with respect to the liquid introduction flow path to the micromixer. By using such a micromixer system, an intermediate polymer solution in which the high-viscosity first polymerizable monomer is reliably polymerized while the low-viscosity second polymerizable monomer solution is stably supplied. And a second polymerizable monomer solution having a low viscosity can be mixed.

  As a micromixer in which a relatively wide flow path space is formed at the joining portion with respect to the liquid introduction flow path to the micromixer, the first polymerizable monomer is used even if it is a metal integrated micromixer. A process plate having a flow path through which the polymerized intermediate polymer solution passes and a process plate having a flow path through which the second polymerizable monomer solution pass are stacked one above the other, and these two types are formed at the flow path outlet. You may combine the micromixer which mixes these solutions, and the micromixer which has a flow path through which the solution after mixing passes.

  Moreover, the flow path inner diameter of the inlet part of the micromixer is preferably in the range of 0.1 to 1.0 mm, and more preferably in the range of 0.2 to 0.6 mm. Moreover, the flow path inner diameter of the inlet part of the micromixer is preferably in the range of 1 to 5 times the flow path inner diameter of the inlet part, which can increase the yield of polymer per unit time and improve the mixing efficiency. Therefore, the range of 1.5 to 3 times is more preferable.

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, semiconductor, or the like.

  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 inlets and outlets 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 introduced from the end surface 1b, discharged as a fluid β to the end surface 1c, and a temperature control fluid γ is introduced from the side surface 1e. And is discharged to the side surface 1d. The planar view shape of the chemical reaction device 1 is not limited to the rectangular shape as illustrated, and may be a square shape or a rectangular shape in which the distance between the side surfaces 1d and 1e is longer than that between the end surfaces 1b and 1c.

<Micromixer 1 used in Examples>
The microreactor 1 used in the present embodiment includes 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.

  The methods for measuring the number average molecular weight, weight average molecular weight, and residual monomer amount of the polymers produced in the examples and comparative examples are as follows.

[Method for measuring number average molecular weight and weight average molecular weight]
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the polymers obtained in Examples and Comparative Examples were measured by the 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
First, the following five types of solutions were prepared.
(1) Styrene (4.0 M) Solution In a 200 mL eggplant flask substituted with argon gas, 83.6 g (92.0 mL) of styrene (hereinafter referred to as “St”) and tetrahydrofuran (hereinafter referred to as “St”) using a syringe. This is abbreviated as “THF.”) By taking 102 mL and stirring, 200 mL of a 4.0 M solution of St was prepared.
(2) Methyl methacrylate (3.4 M), lithium chloride (0.11 M) solution 83.8 g of methyl methacrylate (hereinafter abbreviated as “MMA”) using a syringe in a 300 mL eggplant flask substituted with argon gas. (88.0 mL) and 107 mL of THF were collected, and then 55.0 ml of a THF solution (manufactured by Tokyo Chemical Industry Co., Ltd.) of 0.5 M lithium chloride (hereinafter abbreviated as “LiCl”) was collected and stirred using a syringe. Thus, 250 mL of a solution having a MMA concentration of 3.4 M and a LiCl concentration of 0.11 M was prepared.
(3) n-Butyllithium (0.055M) solution Into a 200 mL eggplant flask substituted with argon gas, 146.8 mL of hexane was collected using a syringe and then cooled with ice. After cooling, 3.2 mL of a 2.6 M n-butyllithium (hereinafter abbreviated as “n-BuLi”) solution was sampled and stirred to prepare 150 mL of a 0.055 M solution of n-BuLi.
(4) Diphenylethylene (0.165M) solution In a 200 mL eggplant flask substituted with argon gas, 4.46 g (4.3 mL) of diphenylethylene (hereinafter abbreviated as “DPE”) and THF145. By taking 7 mL and stirring, 150 mL of a 0.165 M solution of DPE was prepared.
(5) Methanol (1.5 M) solution In a 100 mL eggplant flask substituted with argon gas, 2.48 g of methanol and 46.9 mL of THF were collected using a syringe and stirred to prepare 50 mL of a 1.5 M solution of methanol. did.

  Next, living anion copolymerization of St and MMA was performed by the following operation. A microreactor device comprising a micromixer comprising three T-shaped saddle joints and a tube reactor connected downstream of the micromixer, four plunger pumps ("PU714" manufactured by GL Science), and St Each eggplant flask prepared with a solution, n-BuLi solution, DPE solution, and MMA solution was connected, and each plunger solution was set so that each solution could be sent to the microreactor apparatus.

From the upstream of a reactor composed of a micromixer with a joint diameter of 250 μm, a tube reactor having an inner diameter of 1 mm, a length of 212.5 cm, an inner diameter of 2.18 mm, and an length of 8 cm, the St solution is 4.0 mL / min, n-BuLi The solution was fed and mixed at a rate of 2.0 mL / min, and St anionic polymerization was performed by controlling the St polymerization reaction time to 19.6 seconds. Subsequently, the St polymerization solution obtained from the upstream of the reactor composed of a micromixer having a heel joint diameter of 500 μm and a static mixer having an inner diameter of 1 mm, a length of 262.5 cm + a length of 12 cm (volume of 0.504 cm ³ ), The St polymerization solution and DPE were reacted by feeding and mixing the DPE solution at a rate of 2.0 mL / min and controlling the DPE reaction time to 19.2 seconds. The polymerization of St and the reaction of St polymerization solution and DPE were carried out by immersing the micromixer and tube reactor in a constant temperature bath at 25 ° C. Finally, the reaction solution of St and diphenylethylene obtained from the upstream of the reactor composed of a micromixer with a diameter of 500 μm and a tube reactor with an inner diameter of 1 mm, a length of 200 cm + an inner diameter of 2.18 mm, and a length of 120 cm The MMA solution was fed and mixed at a rate of 5.0 mL / min to control the polymerization reaction time of MMA to 27.8 seconds, and living anion copolymerization of St and MMA was performed. Living anionic copolymerization of St and MMA was performed by immersing a micromixer and a tube reactor in a thermostatic bath at -30 ° C. Finally, the polymer solution from the microreactor outlet was collected in a sample bottle containing 0.75 ml of methanol solution for 30 seconds to obtain a polymer solution. An overall view of the microreactor used in Example 1 is shown in FIG.

  From the amount of residual monomers in the obtained polymer solution, the St reaction rate (polymer pass-through rate) was 100%, and the MMA reaction rate (polymer pass-through rate) was 99.0%. Moreover, the number average molecular weight (Mn) of the obtained polymer is 28,400 with respect to the design molecular weight 30,632, the weight average molecular weight (Mw) is 33,500, and the dispersity (Mw / Mn) is 1. .18. A chart of GPC is shown in FIG. From the GPC chart, a single peak was obtained, indicating that the residual ratio of the unpolymerized St polymer was very low.

(Example 2)
From the upstream of the reactor composed of a tube reactor from the upstream of the reactor composed of a micromixer with a joint diameter of 500 μm and a static mixer having an inner diameter of 1 mm, length of 212.5 cm + length of 12 cm (volume of 0.504 cm ³ ) The resulting St polymerization solution and DPE solution were mixed by feeding at a rate of 2.0 mL / min, and the reaction time of St polymerization solution and DPE was controlled by controlling the DPE reaction time to 15.5 seconds. A block copolymer of St and MMA was prepared in the same manner as in Example 1 except for the above.

  From the amount of residual monomers in the obtained polymer solution, the St reaction rate (polymer pass-through rate) was 100%, and the MMA reaction rate (polymer pass-through rate) was 98.6%. A GPC chart is shown in FIG. The GPC chart shows two peaks presumed to be composed of an unpolymerized St polymer with a block copolymer of St and MMA, but the residual ratio of the unpolymerized St polymer was found to be low. . From the peak presumed to be the block copolymer portion of St and MMA in GPC, the number average molecular weight (Mn) of the obtained polymer is 35,400 with respect to the designed molecular weight 30,632, and the weight average molecular weight (Mw) Was 38,700, and the dispersity (Mw / Mn) was 1.09.

(Example 3)
From the upstream of the reactor composed of a tube reactor from the upstream of the reactor composed of a micromixer with a joint diameter of 500 μm and a static mixer having an inner diameter of 1 mm, length of 412.5 cm + length of 12 cm (volume of 0.504 cm ³ ) The St polymerization solution and the DPE solution were fed at a rate of 2.0 mL / min and mixed, and the reaction time of the DPE was controlled to 28 seconds, whereby the St polymerization solution and the DPE were reacted. Otherwise, a block copolymer of St and MMA was prepared in the same manner as in Example 1.

  From the amount of residual monomers in the obtained polymer solution, the St reaction rate (polymer pass-through rate) was 100%, and the MMA reaction rate (polymer pass-through rate) was 96.2%. A chart of GPC is shown in FIG. The GPC chart shows two peaks presumed to be composed of an unpolymerized St polymer with a block copolymer of St and MMA, but the residual ratio of the unpolymerized St polymer was found to be low. . From the peak presumed to be the block copolymer portion of St and MMA in GPC, the number average molecular weight (Mn) of the obtained polymer was 38,800 with respect to the designed molecular weight 30,632, and the weight average molecular weight (Mw) Was 42,700, and the dispersity (Mw / Mn) was 1.10.

Example 4
First, the following five types of solutions were prepared.
(1) St (5.0 M) solution In a 200 mL eggplant flask substituted with argon gas, St4.00 g (104 mL) and 76 mL of THF were collected using a syringe and stirred to obtain 180 mL of a 5.0 M solution of St. Prepared.
(2) MMA (4.2 M), lithium chloride (0.14 M) solution In a 300 mL eggplant flask substituted with argon gas, MMA 92.2 g (97.5 mL) and THF 92 mL were collected using a syringe, and then the syringe was inserted. Then, 60.5 ml of 0.5 M LiCl in THF was collected and stirred to prepare 220 mL of a solution having a MMA concentration of 4.2 M and a LiCl concentration of 0.14 M.
(3) n-BuLi (0.069M) solution In a 200 mL eggplant flask substituted with argon gas, 117 mL of hexane was collected using a syringe, and then ice-cooled. After cooling, 3.2 mL of a 2.6 M n-BuLi solution was collected and stirred to prepare 120 mL of a 0.069 M solution of n-BuLi.
(4) DPE (0.344M) solution In a 200 mL eggplant flask replaced with argon gas, 7.46 g (7.2 mL) of DPE and 113 mL of THF were collected using a syringe and stirred to obtain 120 mL of a 0.344 M solution of DPE. Was prepared.
(5) Methanol (1.5 M) solution In a 100 mL eggplant flask substituted with argon gas, 2.48 g of methanol and 46.9 mL of THF were collected using a syringe and stirred to prepare 50 mL of a 1.5 M solution of methanol. did.
Next, a block copolymer of St and MMA was prepared in the same manner as in Example 1.

  From the amount of residual monomers in the obtained polymer solution, the St reaction rate (polymer pass-through rate) was 100%, and the MMA reaction rate (polymer pass-through rate) was 98.1%. Moreover, the number average molecular weight (Mn) of the obtained polymer is 32,400 with respect to the design molecular weight 30,632, the weight average molecular weight (Mw) is 37,400, and the dispersity (Mw / Mn) is 1. .15. A GPC chart is shown in FIG. From the GPC chart, a single peak was obtained, indicating that the residual ratio of the unpolymerized St polymer was very low.

(Comparative Example 1)
From the upstream of the reactor composed of a micromixer with a joint diameter of 500 μm and a tube reactor from the upstream of the reactor composed of an inner diameter of 1 mm and a length of 62.5 cm, the obtained St polymerization solution and DPE solution The mixture was sent and mixed at a rate of 0.0 mL / min, and the reaction time of DPE was controlled to 3.6 seconds. A block copolymer of St and MMA was prepared.

  From the amount of residual monomers in the obtained polymer solution, the St reaction rate (polymer pass-through rate) was 99.9%, and the MMA reaction rate (polymer pass-through rate) was 87.6%. A chart of GPC is shown in FIG. The GPC chart shows two peaks presumed to be composed of a St polymer that is not copolymerized with a block copolymer of St and MMA, and it was found that the residual ratio of the unpolymerized St polymer is large. From the peak presumed to be the block copolymer portion of St and MMA in GPC, the number average molecular weight (Mn) of the obtained polymer was 44,000 with respect to the designed molecular weight of 30,632, and the weight average molecular weight (Mw) Was 47,900 and the dispersity (Mw / Mn) was 1.09. It turned out that the difference of the number average molecular weight value of the block copolymer part of St and MMA and a design molecular weight is large compared with the Example.

(Comparative Example 2)
From the upstream of a reactor composed of a micromixer with a joint diameter of 500 μm, a tube reactor having an inner diameter of 1 mm, a length of 400 cm, an inner diameter of 2.18 mm, and a length of 80 cm, 2.0 mL of the obtained St polymerization solution and DPE solution The reaction was carried out in the same manner as in Example 1 except that the St polymerization solution was reacted with DPE by controlling the DPE reaction time to 37.9 seconds. A MMA block copolymer was prepared.

  From the amount of residual monomers in the obtained polymer solution, the St reaction rate (polymer pass-through rate) was 98.6%, and the MMA reaction rate (polymer pass-through rate) was 91.8%. A chart of GPC is shown in FIG. The GPC chart shows two peaks presumed to be composed of a St polymer that is not copolymerized with a block copolymer of St and MMA, and it was found that the residual ratio of the unpolymerized St polymer is large. From the peak presumed to be the block copolymer portion of St and MMA in GPC, the number average molecular weight (Mn) of the obtained polymer is 43,500 with respect to the designed molecular weight 30,632, and the weight average molecular weight (Mw) Was 47,100, and the dispersity (Mw / Mn) was 1.08. It turned out that the difference of the number average molecular weight value of the block copolymer part of St and MMA and a design molecular weight is large compared with the Example.

(Comparative Example 3)
From the upstream side of a 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 150 cm, the St solution is sent at a rate of 4.0 mL / min and the n-BuLi solution is sent at a rate of 2.0 mL / min. The living anionic polymerization of St was performed by controlling the polymerization reaction time of St to 11.8 seconds. Subsequently, the obtained St polymerization solution and the DPE solution were sent at a rate of 2.0 mL / min from the upstream of the reactor composed of 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 125 cm. The St polymerization solution and DPE were reacted by controlling the DPE reaction time to 7.4 seconds. The polymerization of St and the reaction of St polymerization solution and DPE were carried out by immersing the micromixer and tube reactor in a constant temperature bath at 25 ° C. Finally, the reaction solution of St and diphenylethylene and the MMA solution obtained from the upstream of the reactor composed of 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 were added at 4.0 mL / By feeding and mixing at a rate of min, the polymerization reaction time of MMA was controlled to 18.8 seconds, and living anion copolymerization of St and MMA was performed. Living anionic copolymerization of St and MMA was performed by immersing a micromixer and a tube reactor in a thermostatic bath at -30 ° C. Finally, the polymer solution from the microreactor outlet was collected in a sample bottle containing 0.75 ml of methanol solution for 30 seconds to obtain a polymer solution. Otherwise, a block copolymer of St and MMA was prepared in the same manner as in Example 1.

  From the amount of residual monomers in the resulting polymer solution, the St reaction rate (polymer pass-through rate) was 85.0%, and the MMA reaction rate (polymer pass-through rate) was 74.2%. A chart of GPC is shown in FIG. The GPC chart shows two peaks presumed to be composed of a St polymer that is not copolymerized with a block copolymer of St and MMA, and it was found that the residual ratio of the unpolymerized St polymer is large. From the peak presumed to be the block copolymer portion of St and MMA in GPC, the number average molecular weight (Mn) of the obtained polymer is 40,200 with respect to the designed molecular weight of 30,632, and the weight average molecular weight (Mw) Was 44,400 and the dispersity (Mw / Mn) was 1.10. It turned out that the difference of the number average molecular weight value of the block copolymer part of St and MMA and a design molecular weight is large compared with the Example.

  Table 1 shows the required time in each step of Examples 1 to 4 and Comparative Examples 1 to 3, the reaction rate of the obtained block copolymer, the degree of polymerization, and the molecular weight.

DESCRIPTION OF SYMBOLS 1 ... Microreactor α ... Fluid mixed fluid β ... Fluid reaction fluid γ ... Temperature control fluid 1b ... End face of chemical reaction device 1c・ ・ ・ Chemical reaction device end face 1d ･ ･ ･ Chemical reaction device side face 1e ･ ･ ･ Chemical reaction device side face 2 ･ ･ ･ First plate (process plate)
2b ··· end surface of the first plate 2c ··· end surface of the first plate 2d ··· side surface of the first plate 2e ··· side surface of the first plate 3 ··· second plate ( Temperature control plate)
3a ··· surface of the second plate 3b ··· end surface of the second plate 3c ··· end surface of the second plate 3d ··· side surface of the second plate 3e ··· side surface of the second plate 6 ... Temperature groove with cross-sectional groove shape 6a ... Main flow channel with cross-sectional groove shape 6b ... Supply channel with cross-sectional groove shape 6c ... Discharge side flow path 30 ... Connector 31 ... Joint part 32 ... Joint part

Claims (6)

A method for producing a block copolymer having a styrene polymer block having a polymerization degree of 100 or more and a polymer block of a polymerizable monomer other than styrene having a polymerization degree of 100 or more,
Using a microreactor with a channel that can mix multiple liquids,
A first step of living anionic polymerization of styrene in the presence of a polymerization initiator for a time sufficient to achieve a degree of polymerization of 100 or more;
Diphenylethylene is added to the active terminal of the styrene polymer obtained in the first step, and the time is longer than the time required for the reaction between the active terminal of the styrene polymer and diphenylethylene to be completed. A second step of reacting in the time required before the active end replaced with diphenylethylene is deactivated;
In the presence of a polymerization initiator, a polymerization monomer other than styrene is added to the intermediate polymer in which diphenylethylene is added to the active terminal of the styrene polymer obtained in the second step, and the degree of polymerization is 100 or more. A method for producing a block copolymer, comprising a third step of conducting a living anion polymerization for a sufficient time.   The method for producing a block copolymer according to claim 1, wherein the reaction temperature in the first step and the second step is in the range of 0 to 30 ° C, and the reaction temperature in the third step is in the range of -40 to -10 ° C. .   The method for producing a polymer according to claim 1 or 2, wherein the time required for the second step is in the range of 10 to 35 seconds.   The method for producing a polymer according to any one of claims 1 to 3, wherein the time required for the first step is 15 seconds or longer, and the time required for the third step is 20 seconds or longer.   The method for producing a polymer according to any one of claims 1 to 4, wherein the styrene and a polymerizable monomer other than styrene are introduced into a macroreactor in a solution having a concentration of 3M or more.   The method for producing a polymer according to any one of claims 1 to 5, wherein the polymerizable monomer other than styrene is a (meth) acrylate compound.

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