JP2005272804A - Process for preparing polymer by cation polymerization - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a process for preparing a polymer having a narrow molecular weight distribution by cation polymerization efficiently and to provide a process for preparing this polymer efficiently and safely without using protonic acids, Lewis acids and the like and without burdening a heavy load on the environment. <P>SOLUTION: A reaction apparatus having a micro mixer and a flowing-type reactor connected with it are used. A cation polymerizing monomer and a cation are separately supplied to the micro mixer side of this reaction apparatus and are mixed. Then, the monomer is cation-polymerized. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a polymer by cationic polymerization. More specifically, the present invention uses a reactor having a micromixer and a flow-type reactor connected to the micromixer, and cationically polymerizes a cationic polymerizable monomer in a homogeneous system, thereby effectively producing a polymer having a narrow molecular weight distribution. The present invention relates to a method for producing the polymer, and a method for producing the polymer safely and effectively without causing much load on the environment, and provides a novel living cationic polymerization method.

In recent years, microchemical process technology has attracted attention as bringing about innovative changes in chemical synthesis. In this microchemical process technology, a microdevice that performs a chemical reaction is called a microreactor, and a device for mixing is called a micromixer.
The micromixer is mostly laminar, such as having a small channel diameter, and mixing ultimately depends on molecular diffusion. In this mixing by diffusion, the time for mixing is proportional to the square of the diffusion distance. For example, when two liquids are mixed using a T-shaped channel system, (1) collision of two liquid flows by applying high-speed energy, and (2) one component is made into many flows. (3) Mixing of two components by dividing the two liquids introduced from two directions into multiple layers, and (4) Increasing the flow velocity, thereby allowing the liquid to flow. A method of reducing the diffusion distance in the direction, (5) mixing by laminating and rearranging a two-component flow in laminar flow, (6) stirring, ultrasonic, electric, thermal energy, etc. (7) Mixing performed by intermittently blowing small liquid sections, and the like.
Depending on the purpose of use and the type of reaction, it is properly selected from the various micromixers.

  As an example of a reaction using a micromixer, for example, a radical polymerizable monomer and a polymerization initiator are mixed by a micromixer that mixes using a fine flow path, and then polymerized to obtain a polymer. A production method of a radical polymer is disclosed in which formation of a high molecular weight component is suppressed and formation of a precipitate in a tubular polymerization reactor is avoided (see, for example, Patent Document 1). However, this technique is a technique applied to radical polymerization, and a technique using a micromixer for cationic polymerization has not been known so far.

On the other hand, a microreactor generally refers to a device that performs a reaction in a fine microchannel having an internal structure of about 1 μm to 1 mm. Such a microreactor is, for example, (1) capable of being synthesized in a minute amount from the organic synthesis surface, (2) has a large surface area per unit volume (flow rate), and (3) temperature control is extremely easy. There are (4) reaction at the interface efficiently, (5) time, cost and environmental load can be reduced, and (6) reaction in a sealed system is possible, so there are toxic and dangerous compounds. Can be synthesized safely, (7) It is possible to prevent contamination by small scale, closed system, and (8) Efficient mixing, separation and purification of products by utilizing the laminar flow unique to microchannels It has features such as being applicable.
In industrial applications, it is potentially possible to increase production by (i) increasing the number without changing the size of the microchannel (numbering up) (conventional experiments). (B) The intermediate trial steps necessary for transferring the results obtained in the laboratory to the factory are omitted.) (B) It is possible to start production early at low cost. ) It is possible to quickly transfer the experimental results to production. In addition, (d) there is an advantage that a plant for industrial production can be small.

By the way, for cationic polymerization, conventionally, as a cationic polymerization catalyst, generally, a protonic acid such as sulfuric acid, phosphoric acid, perchloric acid, or a Lewis acid such as boron trifluoride, aluminum chloride, titanium tetrachloride, tin tetrachloride or the like. As a cocatalyst, a compound having a lone electron pair such as water, alcohol, acid, ether, or halogen compound has been used. However, these protonic acids and Lewis acids are highly reactive, and many of them have dangerous properties, and there are problems such as requiring great consideration for safe handling and high environmental impact. Have.
The present inventors have previously reported that a cation can be generated by an electrical method, not by a chemical method using the above-described compound, and can be used for a Friedel-Crafts reaction (for example, Non-patent document 1). However, there has not yet been reported an example in which a cation generated by such an electrical method is applied to cationic polymerization.
In cationic polymerization, when the polymerization reaction is carried out under ordinary mechanical stirring, local unevenness of the catalyst concentration occurs in the reaction system, and as a result, the resulting polymer has a wide molecular weight distribution. There was also a problem that it was easy.

  Furthermore, conventionally, the living polymerization system in the cationic polymerization has realized the living polymerization by stabilizing the polymer growth terminal with a catalyst component as a principle, and generally has a drawback that the reaction rate is slow. Moreover, in living polymerization that produces one polymer from one active species, the use of a special catalyst is a significant cost increase factor. At the same time, when a metal catalyst is used, many metal residues are contained in the synthesized polymer. Existed.

Japanese translation of PCT publication No. 2002-512272 “Chemical Communication”, page 354 (2003)

  Under such circumstances, the object of the present invention is (1) a method for efficiently producing a polymer by cationic polymerization having a narrow molecular weight distribution, and (2) safely without using a protonic acid or a Lewis acid, Another object of the present invention is to provide a method for efficiently producing the polymer by a method having a small environmental load.

As a result of intensive research to achieve the above object, the present inventors have used a device having a micromixer and a flow-type reactor connected to the reaction device as a reaction device. The monomer and the cation (preferably a cation generated by electrolytic oxidation of the cation precursor) are separately supplied and mixed to polymerize the monomer, and then the reaction solution is supplied from the reactor side. It was found that the purpose can be achieved by extracting. The present invention has been completed based on such findings.
That is, the present invention
(1) Using a reactor having a micromixer and a flow-type reactor connected to the micromixer, a cationically polymerizable monomer and a cation are separately supplied to the micromixer side of the reactor, and both are mixed. A method for producing a polymer by cationic polymerization, wherein the monomer is cationically polymerized in a reactor;
(2) The cation according to (1) above, wherein the micromixer has a structure in which the flow paths for introducing the cationic polymerizable monomer and the cation are alternately formed in layers in the range of 1 to 500 μm in width. A method for producing a polymer by polymerization,
(3) The method for producing a polymer by cationic polymerization according to the above (1) or (2), wherein the cation is generated by electrolytic oxidation of a cation precursor,
(4) The method for producing a polymer by cationic polymerization according to (3) above, wherein the cation is generated by a cation pool method,
(5) The method for producing a polymer by cationic polymerization according to any one of (1) to (4) above, wherein the flow reactor has one or more reaction tubes having an inner diameter of 5 mm or less, and (6 ) The method for producing a polymer according to any one of (1) to (5) above, wherein the cationic polymerization is living cationic polymerization.
Is to provide.

According to the present invention, a polymer having a narrow molecular weight distribution is effectively produced by cationically polymerizing a cationic polymerizable monomer in a homogeneous system using a reaction apparatus having a micromixer and a flow-type reactor connected thereto. By using a cation generated by electrolysis of a cation precursor and a method, it is possible to provide a method for producing the polymer safely and effectively without giving much load to the environment.
Furthermore, according to the present invention, there is provided an economical living cation polymerization method that does not sacrifice the reaction rate by a method that does not rely on stabilization of the polymer growth terminal (without using a catalyst for living polymerization). Can do.
Polymerization active species and monomers are mixed at high speed using a micromixer, and excellent temperature control (removal of reaction heat) and laminar flow formation are achieved by using a fine reaction tube. Living polymerization can be realized by minimizing the influence of external factors such as temperature non-uniformity of the field and existence of residence time distribution. In addition, according to such a distribution method, synthesis of a block copolymer or the like can be easily performed by sequentially reacting monomers.

In the method for producing a polymer by cationic polymerization according to the present invention, as a reaction apparatus, an apparatus having a micromixer and a flow-type reactor connected to the micromixer is used. The system and the cation are separately supplied, both are mixed, the monomer is cationically polymerized, and then the reaction solution is extracted from the reactor side.
The cationic polymerizable monomer used in this cationic polymerization is not particularly limited as long as it is a monomer capable of cationic polymerization, but a vinyl derivative having an electron-donating substituent is highly cationic polymerizable. This is preferable. Typical examples of the vinyl derivative having such an electron-donating substituent include derivatives such as isobutylene, styrene, and α-methylstyrene in which the ethylene skeleton is substituted with an alkyl group or an aryl group, and heteroatoms. And vinyl ethers, vinyl sulfides, and derivatives such as N-vinyl carbazole substituted therewith. Among these, monomers having particularly high cationic polymerization include isobutyl vinyl ether, n-butyl vinyl ether, methyl vinyl sulfide, N-vinyl carbazole, α-methyl styrene and the like.

  On the other hand, as the cation, one generated by electrolytic oxidation of a cation precursor is preferable because of good stability. As the cation precursor, for example, compounds having a trimethylsilyl group such as the following compounds (1) to (4) are preferably used.

Electrolytic oxidation of these cation precursors can generate a cation pool, and this cation pool is preferably used for cation polymerization.
For example, the following cation pools (5) and (6) can be generated by electrolytic oxidation of the compounds (1) and (4), respectively.

As a method for generating a cation pool by electrolytic oxidation of a cation precursor, for example, the following method can be used.
A two-chamber electrolyzer was prepared in which a carbon felt was attached to the anode chamber, a platinum plate was attached to the cathode chamber, and a glass filter was used as a diaphragm. 8.0 mL of methylene chloride solution of 0.3 M tetrabutylammonium tetrafluoroborate (Bu ₄ NBF ₄ ) and compound (4) (90.0 mg, 0.414 mmol) were placed in the anode chamber, and 0.3 M Bu ₄ NBF ₄ was placed in the cathode chamber. After adding 8.0 mL of methylene chloride solution and trifluoromethanesulfonic acid (144.6 mg, 0.964 mmol), constant current electrolysis (5.0 mA) was performed at −78 ° C. while stirring with a magnetic stirrer. A cation pool (6) was generated in the anode chamber by flowing an electric quantity of 2.5 F / mol.

  Other examples of the cation pool include (7) to (9).

There is no particular limitation on the quantitative ratio of the cationic polymerizable monomer and the cation in the cationic polymerization, but the molar ratio of the cationic polymerizable monomer and the cation precursor used to generate the cation is usually 10%. : About 1 to 100: 1 is appropriate.
Moreover, there is no restriction | limiting in particular as a polymerization solvent, For example, a hydrocarbon compound, a halogenated hydrocarbon compound, a nitrated hydrocarbon compound etc. can be used.
Furthermore, regarding the polymerization temperature, the activation energy of cationic polymerization is extremely lower than that of radical polymerization. Therefore, there are many systems in which the polymerization reaction proceeds rapidly even at low temperatures of −50 ° C. or lower. Moreover, since the activation energy of chain transfer or termination reaction is larger than that of the growth reaction, the side reaction is suppressed and the high molecular weight polymer is obtained as the polymerization is performed at a lower temperature.

  The micromixer in the reaction apparatus used in the present invention is a micro mixer capable of performing high-speed and high-efficiency mixing of a liquid containing a cationic polymerizable monomer and a liquid containing a cation by taking advantage of the characteristics of the micro space. There is no particular limitation on the structure as long as it is a chemical device. For example, the flow paths for introducing the cationic polymerizable monomer and the cation are alternately formed in layers within a width range of 1 to 500 μm. What has a structure can mention preferably. The width of each channel is preferably 10 to 50 μm, more preferably 25 to 40 μm.

FIG. 1 is a schematic diagram illustrating an example of a micromixer used in the present invention, and FIG. 2 is a schematic diagram illustrating a mixing state of a reaction solution in the micromixer.
The micromixer includes an upper housing 14 provided with a first supply pipe 11, a second supply pipe 12, an outflow pipe 13 and the like, and a bottom housing 16 provided with a micromixing unit 15.
A solution containing a cation polymerizable monomer from the first supply pipe 11 (hereinafter simply referred to as a monomer solution) is a solution containing a cation from the second supply pipe 12 (hereinafter simply referred to as a cation solution). The monomer solution and the cation solution enter the micromixing unit 15.
As shown in FIG. 2, the micromixing unit 15 is formed by folding a bellows-like band-shaped element to form a plurality of zigzag flow paths parallel to the vertical direction, and there are opposed element folding side surfaces. . The plurality of zigzag microchannels having an inlet on one side surface and the plurality of zigzag microchannels having an inlet on the other side surface are separated by an element wall, and the plurality of first channels, A plurality of second flow paths are alternately provided in the width direction.
The monomer solution and the cation solution entering the micromixing unit 15 from both directions rise in a separated state in each of the plurality of zigzag microchannels. Then, it is mixed at the upper outlet of the micromixing section 15 and supplied to the reactor of the flow type connected to the micromixer through the outflow pore 17 and the outflow pipe 13 in a homogeneously mixed state.

As the micromixer having such a structure, for example, a micromixer developed by Institute of Microtechnik Mainz (abbreviation: IMM) can be used.
In the present invention, the mixing type in the micromixer is not particularly limited, and may be any of a cross flow type, a cocurrent type, a counter flow type, a spiral flow type, and the like.

In the present invention, it is desirable to select conditions such that the polymerization reaction does not occur in the micromixer as much as possible. When a polymerization reaction occurs in the micromixer, polymerization occurs before the monomer and cation are completely homogeneously mixed, and a polymer having a desired narrow molecular weight distribution may not be obtained. Problems such as blockage of the flow path in the micromixer occur. Therefore, ideally, only mixing is performed by a micromixer, and the completely homogeneous mixed solution is sent to a flow-type reactor connected to the micromixer, and cationic polymerization is performed in the reactor.
In the present invention, the reactor of the flow format may be any flow format and is not particularly limited, and various types of reactors can be used. However, a reactor having one or more reaction tubes having an inner diameter of 5 mm or less. preferable. If the inner diameter of the reaction tube is 5 mm or less, the temperature of the reaction zone can be controlled sufficiently uniformly, but it is more preferably 2 mm or less.
The reaction solution that has passed through the reactor is immediately stopped at the outlet of the reaction tube, and a polymer having a narrow molecular weight distribution, which is the object of the present invention, can be obtained by recovering the polymer by a known method. . The polymerization reaction termination treatment can be performed by introducing the reaction solution into a polymerization terminator bath provided at the outlet of the reaction tube or by mixing with a polymerization terminator solution using a micromixer.
According to such a method of the present invention, a polymer having a narrow molecular weight distribution can be effectively produced by cationic polymerization, and the polymer is effective without causing a burden on the environment safely. Can be manufactured automatically.
Furthermore, according to the method of the present invention, high concentration mixing of monomers, excellent temperature control by using a fine reaction tube and laminar flow formation make it possible to achieve nonuniform concentration of polymerization active species and monomers and temperature of reaction field. The influence of external factors such as uniformity and existence of residence time distribution can be minimized, and living polymerization can be realized.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
Example 1
The cationic polymerizable monomer and the cation are separately introduced into a micromixer manufactured by IMM having a flow path width of 25 μm in the mixing section, and a reaction tube having an inner diameter of 2 mm and a length of 150 mm is provided from the outlet of the micromixer. The experimental apparatus discharged after the assembly was assembled, and the temperature was maintained at −78 ° C. except for the reaction liquid discharge section. In addition, the inside of the reaction apparatus was sufficiently replaced with argon before starting the reaction.
Generated from 5 mL (0.625 g, 6.25 mmol / 5 mL) of a 1.25 mol / L n-butyl vinyl ether solution in methylene chloride and a 0.05 mol / L methylene chloride solution of compound (4) at −78 ° C. 5 mL of the cation pool (6) was circulated through the reactor at a flow rate of 5.0 mL / min with a syringe pump (Harvard, model 11), and a 25 mass% aqueous ammonia solution was added to the outlet of the reaction tube with methanol. A container containing the double diluted solution was provided, and the reaction was terminated by collecting the reaction solution in the container.
After the end of circulation, the reaction solution remaining in the reaction apparatus was extruded with air and collected in the same container. After the solvent was distilled off under reduced pressure, the obtained solution was added with 7 mL of water and extracted three times with 30 mL of hexane. Next, the organic layer was dried over anhydrous sodium sulfate, and then subjected to a silica gel short column (40 mm; eluted with 150 mL of hexane) to remove Bu ₄ NBF ₄ derived from the cation pool. The obtained solution was dried to obtain 0.413 g of a polymer (polyvinyl ether) (yield 66%).
The number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of this polymer were determined by gel permeation chromatography (GPC) measurement. Two columns of Shodex K-804L and Shodex K-805L are arranged in series, and calibration is performed using a commercially available styrene polymer as a standard sample with an RI detector using chloroform as a developing solvent at 40 ° C., Mn and Mw / Mn were measured. As a result, Mn = 5400 and Mw / Mn = 1.23.

Comparative Example 1
At −78 ° C., 5 mL of the cation pool (6) generated from a 0.05 mol / L methylene chloride solution of the compound (4) was stirred by a magnetic stirrer in a reactor immersed in a low temperature bath at −78 ° C. 1.25 mol / L of n-butyl vinyl ether (0.625 g, 6.25 mmol / 5 mL) in methylene chloride (5 mL) (cooled to −78 ° C.) was transferred by a syringe pump (Harvard, model 11), The flow rate was 5.0 mL / min. Immediately after the addition was completed, 4 mL of a solution obtained by diluting a 25 mass% aqueous ammonia solution 20-fold with methanol was added to terminate the reaction. After the solvent was distilled off under reduced pressure, the obtained solution was added with 7 mL of water and extracted three times with 30 mL of hexane. Next, the organic layer was dried over anhydrous sodium sulfate, and then subjected to a silica gel short column (40 mm; eluted with 150 mL of hexane) to remove Bu ₄ NBF ₄ derived from the cation pool. The obtained solution was dried to obtain 0.481 g of a polymer (polyvinyl ether) (yield 77%).
The number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of this polymer were determined by gel permeation chromatography (GPC) measurement in the same manner as in Example 1. As a result, Mn = 8300 and Mw / Mn = 1.70.

Comparative Example 2
In Comparative Example 1, the same procedure as in Comparative Example 1 was carried out except that the cation pool (6) was added to the n-butyl vinyl ether solution at a flow rate of 5.0 mL / min. As a result, the yield was 0.600 g (96% yield), Mn = 20000, and Mw / Mn = 1.95.

  As is clear from the comparison between Example 1 and Comparative Examples 1 and 2, it can be seen that Example 1 has a polymer with a narrow molecular weight distribution.

Example 2
In Example 1, it implemented like Example 1 except the density | concentration of the n-butyl vinyl ether solution having been 2.5 mol / L (1.25 g, 12.5 mmol / 5 mL). As a result, the yield was 0.988 g (yield 79%), and Mn = 11000 and Mn / Mw = 1.23.

Comparative Example 3
In Comparative Example 1, the same procedure as in Comparative Example 1 was performed except that the concentration of the n-butyl vinyl ether solution was 2.5 mol / L (1.25 g, 12.5 mmol / 5 mL). As a result, the yield was 1.200 g (96% yield), and Mn = 14000 and Mw / Mn = 2.26.

Comparative Example 4
In Comparative Example 3, the same procedure as in Comparative Example 3 was carried out except that the cation pool (6) was added to the n-butyl vinyl ether solution at a flow rate of 5.0 mL / min. As a result, the yield was 1.212 g (yield 97%), and Mn = 24000 and Mw / Mn = 2.32.

  As is apparent from the comparison between Example 2 and Comparative Examples 3 and 4, it can be seen that Example 2 yielded a polymer having a narrow molecular weight distribution.

Example 3
A polymerization initiator (cation precursor) and a monomer are introduced into a micromixer manufactured by IMM having a flow path width of 25 μm in the mixing section, and passed through a reaction tube having an inner diameter of 1 mm and a length of 100 mm from the outlet of the micromixer. An experimental apparatus for discharging a solution containing a polymer after assembling with a reaction terminator was assembled with a micromixer manufactured by Yamatake Corporation (see JP 2002-346353), and the temperature was maintained at −78 ° C. except for the reaction solution discharge part. I tried to sag. Further, the inside of the reaction apparatus was sufficiently replaced with argon before starting the reaction.
A cation pool (5) generated from a 0.5 mol / L methylene chloride solution of n-butyl vinyl ether and a 0.05 mol / L methylene chloride solution of the compound (1) at −78 ° C. was added to a syringe pump (Harvard). It was made to distribute | circulate to said reactor at each flow rate of 5.0 mL / min using the model 11) (residence time 0.48 second in a reaction tube), and 0.83 mol / L of diisopropylamine was used as a reaction terminator. The reaction was terminated by introducing methylene chloride solution at a flow rate of 3.0 mL / min. After the inside of the apparatus was sufficiently replaced, the reaction solution was collected for 0.2 minutes to obtain 2.6 mL of the reaction solution.
After the solvent was distilled off under reduced pressure, the obtained solution was added with 7 mL of water and extracted three times with 30 mL of hexane. Next, after drying the organic layer on anhydrous sodium sulfate, it was applied to a silica gel short column (length: 40 mm) and eluted with 150 mL of hexane to remove Bu ₄ NBF ₄ . The obtained solution was dried to obtain 0.050 g of a polymer (polyvinyl ether) (yield: 100%).
The number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of this polymer were determined by gel permeation chromatography (GPC) measurement under the same conditions as in Example 1. As a result, Mn = 1500 and Mw / Mn = 1.40.

Example 4
In Example 3, it implemented like Example 3 except the density | concentration of the n-butyl vinyl ether solution having been 1.25 mol / L. As a result, the yield was 0.125 g (yield 100%), and Mn = 2900 and Mw / Mn = 1.26.

Example 5
In Example 3, it implemented like Example 3 except the density | concentration of n-butyl vinyl ether solution having been 1.75 mol / L. As a result, the yield was 0.175 g (yield 100%), and Mn = 4400 and Mw / Mn = 1.17.

Example 6
In Example 3, it implemented like Example 3 except the density | concentration of the n-butyl vinyl ether solution having been 2.5 mol / L. As a result, the yield was 0.25 g (yield 100%), and Mn = 6700 and Mw / Mn = 1.14.

Example 7
In Example 3, it implemented like Example 3 except the density | concentration of the n-butyl vinyl ether solution having been 3.75 mol / L. As a result, the yield was 0.375 g (yield 100%), and Mn = 1500 and Mw / Mn = 1.54.

  When plotting the relationship between the “ratio of the monomer to the polymerization initiator” and the “number average molecular weight of the produced polymer” for Examples 3 to 7, linearity is obtained as shown in FIG. 3, and this polymerization is living polymerization. I understand that.

Comparative Example 5
At −78 ° C., 5 mL of cation pool (5) generated from a 0.05 mol / L methylene chloride solution of compound (1) was stirred by a magnetic stirrer in a reactor immersed in a low temperature bath at −78 ° C. 5 mL of a 2.5 mol / L n-butyl vinyl ether methylene chloride solution (cooled to −78 ° C.) was added at a flow rate of 5.0 mL / min using a syringe pump (Harvard Model 11). Immediately after the addition, 3 mL of a 0.83 mol / L diisopropylamine methylene chloride solution was quickly added to terminate the reaction.
After the solvent was distilled off from the obtained solution under reduced pressure, 7 mL of water was added, and extraction was performed 3 times with 30 mL of hexane. After drying the organic layer over anhydrous sodium sulfate, it was applied to a silica gel short column (length 40 mm) and eluted with 150 mL of hexane to remove Bu ₄ NBF ₄ . The resulting solution was dried to obtain 1.25 g of a polymer (polyvinyl ether) (yield 100%). The number average molecular weight (Mn) and the molecular weight distribution (Mw / Mn) were determined by gel permeation chromatography (GPC) measurement in the same manner as in Example 1. As a result, Mn = 5700 and Mw / Mn = 2.56.

Comparative Example 6
At −78 ° C., 5 mL of a cation pool (5) generated from a 0.05 mol / L methylene chloride solution of Compound (1) in 5 mL of a 2.5 mol / L n-butyl vinyl ether solution in methylene chloride (at −78 ° C. This was carried out in the same manner as in Comparative Example 5 except that the cooled one) was added at a flow rate of 5.0 mL / min using a syringe pump (Harvard model 11). As a result, the polymer yield was 1.25 g (yield 100%), and Mn = 13100 and Mw / Mn = 2.25.

Comparative Example 7
At −78 ° C., 5 mL of a 2.5 mol / L n-butyl vinyl ether methylene chloride solution and 5 mL of a cation pool (5) generated from a 0.05 mol / L methylene chloride solution of compound (1) (at −78 ° C. This was carried out in the same manner as in Comparative Example 5, except that a cooled one) was simultaneously added to the reaction vessel with stirring at a flow rate of 5.0 mL / min using a syringe pump (Harvard model 11). As a result, the polymer yield was 1.25 g (yield 100%), and Mn = 24500 and Mw / Mn = 2.43.

  From Comparative Examples 5 to 7, it can be seen that when the reaction apparatus of the present invention is not used, the polymerization has a broad molecular weight distribution and clearly has no living property.

  The method for producing a polymer by cationic polymerization of the present invention uses a reaction apparatus having a micromixer and a flow reactor connected to the micromixer, and cationic polymerization of the cationic polymerizable monomer in a homogeneous system, thereby achieving a narrow molecular weight distribution. The polymer can be effectively produced, and the polymer can be produced safely and effectively without causing a heavy load on the environment.

1 is an overall schematic diagram of an example of a micromixer used in the present invention (cited from IMM “Micromixer Operation Manual” (May 2002)). It is a schematic diagram which shows the mixing state of the reaction liquid in the micromixer of FIG. About Examples 3-7, the relationship between "the ratio of the monomer with respect to a polymerization initiator" and "the number average molecular weight of a production | generation polymer" is plotted.

Explanation of symbols

11 First supply pipe 12 Second supply pipe 13 Outflow pipe 14 Upper housing 15 Micromixing section 16 Bottom housing 17 Outflow pore

Claims (6)

  Using a reactor having a micromixer and a flow-type reactor connected to the micromixer, a cationically polymerizable monomer and a cation are separately supplied to the micromixer side of the reactor and mixed together. A method for producing a polymer by cationic polymerization, wherein the body is cationically polymerized in a reactor.   2. The polymer of cationic polymerization according to claim 1, wherein the micromixer has a structure in which the flow paths for introducing the cationic polymerizable monomer and the cation are alternately formed in layers in a range of 1 to 500 μm in width. Production method.   The method for producing a polymer by cationic polymerization according to claim 1 or 2, wherein the cation is generated by electrolytic oxidation of a cation precursor.   The method for producing a polymer by cationic polymerization according to claim 3, wherein the cation is generated by a cation pool method.   The method for producing a polymer by cationic polymerization according to any one of claims 1 to 4, wherein the flow reactor has one or more reaction tubes having an inner diameter of 5 mm or less. Cationic polymerization is living cationic polymerization, The manufacturing method of the polymer in any one of Claims 1-5.

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