Method for producing polymer

Abstract

To provide a method for producing a polymer by employing an alkoxysilyl group-containing monomer while controlling molecular weight and molecular weight distribution.SOLUTION: A method for producing a polymer comprises an anionic polymerization step in which an alkoxysilyl group-containing monomer is subjected to anionic polymerization using a microreactor in the presence of an initiator represented by the following general formula (1), wherein, in the general formula (1), one of R1 and R2 is an aryl group and the other is an aryl group or an alkyl group having 1-10 carbon atoms.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a polymer. [Background technology]

[0002] In recent years, chemical reactions using minute containers called microreactors have been studied in the field of chemical synthesis (see, for example, Non-Patent Documents 1 and 2). The microreactor is a minute container equipped with a flow path capable of mixing multiple liquids and an inlet path that is connected to the flow path and introduces liquids into the flow path. The multiple liquids supplied through the inlet path of the microreactor join together in the flow path, where they are mixed and a reaction occurs.

[0003] It is believed that reactions using the microreactors enable precise control of residence time, precise temperature control, and high-speed mixing, and are expected to improve conversion and selectivity compared to conventional batch-type reactions, and are attracting attention as a highly efficient production method.

[0004] On the other hand, anionic polymerization is a powerful tool for synthesizing styrene-based polymers due to its fast reaction rate. However, the polymerization of functionalized styrene is severely limited by the reactivity of the functional groups, and therefore has not been thoroughly studied. Anionic polymerization of halogenated styrenes using a microreactor has been reported (see, for example, Patent Document 1), but anionic polymerization using an alkoxysilyl group-containing monomer has not been reported.

[0005] Therefore, a method for producing a polymer using an alkoxysilyl group-containing monomer while controlling the molecular weight and molecular weight distribution has not yet been provided, and there is a strong demand for such a method to be provided promptly. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Patent Publication No. 2021-138946

[0007] [Non-Patent Document 1] Chimia 2002 56:636 [Non-patent document 2] Tetrahedron) 2002 58:4735-4757 Summary of the Invention [Problem to be solved by the invention]

[0008] The present invention aims to solve the above-mentioned problems in the prior art and to achieve the following object: That is, the present invention aims to provide a method for producing a polymer by using an alkoxysilyl group-containing monomer while controlling the molecular weight and molecular weight distribution. [Means for solving the problem]

[0009] As a result of intensive research conducted by the present inventors to achieve the above object, a method for producing a polymer, comprising an anionic polymerization step of anionically polymerizing an alkoxysilyl group-containing monomer using a microreactor in the presence of an initiator represented by the following general formula (1) (wherein, in the general formula (1), R 1 and R 2 The present inventors have found that by using an alkoxysilyl group-containing monomer, one of which is an aryl group and the other is an aryl group or an alkyl group having 1 to 10 carbon atoms, a method for producing a polymer while controlling the molecular weight and molecular weight distribution can be provided. [ka]

[0010] The present invention is based on the above findings by the present inventors, and the means for solving the above problems are as follows: <1> A method for producing a polymer, comprising an anionic polymerization step of anionically polymerizing an alkoxysilyl group-containing monomer using a microreactor in the presence of an initiator represented by the following general formula (1): 1 and R 2 one of which is an aryl group and the other is an aryl group or an alkyl group having 1 to 10 carbon atoms). [ka] [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a method for producing a polymer while controlling the molecular weight and molecular weight distribution by using an alkoxysilyl group-containing monomer. [Brief explanation of the drawings]

[0012] [Figure 1] FIG. 1 is a schematic diagram of a flow microreactor used in an example of a method for producing an initiator. [Figure 2] FIG. 2 is a schematic diagram of a flow microreactor used in an example of the production method of the present invention. [Figure 3] FIG. 3 is a schematic diagram of a flow microreactor used in an example of the production method of the present invention. [Figure 4] FIG. 4 is a schematic diagram of a flow microreactor used in an example of the production method of the present invention. [Figure 5] FIG. 5 shows GPC spectra of the polymers obtained in Comparative Examples 1, 4, and 7. [Figure 6] FIG. 6 shows GPC spectra of the polymers obtained in Example 1, Comparative Example 11, Comparative Example 14, and Comparative Example 20. [Figure 7] FIG. 7 shows GPC spectra of the polymers obtained in Example 1, Comparative Example 22, and Comparative Example 23. [Figure 8] FIG. 8 shows the GPC spectra of the polymers obtained in Examples 3 to 6. [Figure 9] FIG. 9 shows GPC spectra of the polymers obtained in Examples 7, 11, and 12. [Figure 10] FIG. 10 shows the GPC spectra of the polymers obtained in Examples 13 and 14. [Figure 11] FIG. 11 shows the GPC spectra of the polymers obtained in Examples 15 to 17. [Figure 12] FIG. 12 shows the GPC spectra of the polymers obtained in Examples 23 to 26. [Figure 13] FIG. 13 shows the GPC spectra of the polymers obtained in Examples 27 to 30. [Figure 14] FIG. 14 shows GPC spectra of the polymers obtained in Examples 31, 33, 37, 41, and 45. [Figure 15] FIG. 15 shows GPC spectra of the polymers obtained in Examples 32, 34, 38, 42, and 46. [Figure 16] FIG. 16 shows the GPC spectra of the polymers obtained in Examples 45 to 48. [Figure 17] FIG. 17 shows GPC spectra of the polymers obtained in Examples 49, 53, 57, and 61. [Figure 18] FIG. 18 shows GPC spectra of the polymers obtained in Examples 50, 54, 58, and 62. [Figure 19] FIG. 19 shows the GPC spectra of the polymers obtained in Examples 61 and 62. [Figure 20] FIG. 20 is a MALDI-TOF MS spectrum of the polymer obtained in Example 69. [Figure 21] FIG. 21 shows GPC spectra of the polymers obtained in Examples 70 to 77. [Figure 22] FIG. 22 shows GPC spectra of the polymers obtained in Examples 99 to 103. [Figure 23]FIG. 23 is a MALDI-TOF MS spectrum of the polymer obtained in Example 111. DETAILED DESCRIPTION OF THE INVENTION

[0013] (Polymer manufacturing method) The method for producing the polymer includes an anionic polymerization step and may further include other steps.

[0014] <Anionic polymerization process> The anionic polymerization step is a step in which an alkoxysilyl group-containing monomer is anionically polymerized in the presence of an initiator using a flow microreactor. The anionic polymerization step may be a step of introducing the alkoxysilyl group-containing monomer and the initiator into a micromixer in the flow microreactor.

[0015] -Alkoxysilyl group-containing monomer- The alkoxysilyl group-containing monomer is a monomer having an alkoxysilyl group. The alkoxysilyl group-containing monomer is not particularly limited and can be appropriately selected depending on the purpose. For example, a monomer represented by the following general formula (2) (where R 3 is a hydrogen atom; R 4 represents a hydrogen atom, a chlorine atom, an alkyl group having 1 to 4 carbon atoms, or a trimethylsilyl group; X represents an alkoxysilyl group; and a represents the number of the alkoxysilyl groups (X) and is an integer of 1 to 4. [ka]

[0016] Among the monomers represented by the general formula (2), those in which a is 1 are preferred from the viewpoint of producing a polymer while controlling the molecular weight and molecular weight distribution, and R 4 is a hydrogen atom and a is 1, and R 4 and R 3is a hydrogen atom and a is 1, and trimethoxysilylstyrene, triethoxysilylstyrene, methoxydimethylsilylstyrene, ethoxydimethylsilylstyrene, ethoxydiethylsilylstyrene, dimethoxymethylsilylstyrene, or diethoxyethylsilylstyrene is particularly preferred, and 4-trimethoxysilylstyrene, 4-triethoxysilylstyrene, 4-methoxydimethylsilylstyrene, 4-ethoxydimethylsilylstyrene, or 4-ethoxydiethylsilylstyrene is most preferred.

[0017] The lower limit of the concentration of the alkoxysilyl group-containing monomer is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.01 M or more, 0.05 M or more, 0.1 M or more, 0.3 M or more, 0.5 M or more, or 0.8 M or more, and among these, 0.8 M or more is more preferable. The upper limit of the concentration of the alkoxysilyl group-containing monomer is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 10 M or less, 5 M or less, or 1 M or less. It is preferable that the numerical range has a lower limit value and an upper limit value that are either of the numerical values ​​shown as the lower limit value and either of the numerical values ​​shown as the upper limit value.

[0018] The lower limit of the rate (flow rate) at which the alkoxysilyl group-containing monomer is introduced into the micromixer in the flow microreactor is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 3 mL / min or more, 5 mL / min or more, 9 mL / min or more, 12 mL / min or more, 16 mL / min or more, or 20 mL / min or more. The upper limit of the rate (flow rate) at which the alkoxysilyl group-containing monomer is introduced into the micromixer in the flow microreactor is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 100 mL / min or less, or 50 mL / min or less. It is preferable that the numerical range has a lower limit value and an upper limit value that are either of the numerical values ​​shown as the lower limit value and either of the numerical values ​​shown as the upper limit value.

[0019] -Initiator- The initiator is represented by the following general formula (1). [ka]

[0020] In the general formula (1), "s-Bu" represents a sec-butyl group (-CH(CH3)CH2CH3), and "Li" represents a lithium group.

[0021] In the general formula (1), R 1 and R 2 One of them is an aryl group, and the other is an aryl group or an alkyl group having 1 to 10 carbon atoms. Among these, from the viewpoint of producing a polymer while controlling the molecular weight and molecular weight distribution, R 1 and R 2 Preferably, one of the groups is an alkyl group having 1 to 10 carbon atoms.

[0022] The alkyl group having 1 to 10 carbon atoms is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoint of producing a polymer while controlling the molecular weight and molecular weight distribution, however, an alkyl group having 1 to 8 carbon atoms is preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, an alkyl group having 1 to 4 carbon atoms is even more preferred, an alkyl group having 1 to 2 carbon atoms is particularly preferred, and a methyl group is most preferred.

[0023] The aryl group is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include a phenyl group, a tolyl group, and an o-xylyl group. Among these, a phenyl group is preferred from the viewpoint of producing a polymer while controlling the molecular weight and molecular weight distribution.

[0024] Examples of the compound represented by the general formula (1) include a compound represented by the following structural formula (1) (DPHLi ((3-methyl-1,1-diphenylpentyl)lithium)), a compound represented by the following structural formula (2) (2PHLi), and a compound represented by the following structural formula (3) (3POLi). Among these, the compound (2PHLi) represented by the following structural formula (2) is preferred from the viewpoint of producing a polymer while controlling the molecular weight and molecular weight distribution. [ka] [ka] [ka]

[0025] The lower limit of the concentration of the initiator is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.01M or more, 0.03M or more, 0.04M or more, or 0.05M or more. The upper limit of the concentration of the initiator is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 10M or less, 5M or less, 1M or less, 0.5M or less, or 0.1M or less. It is preferable that the numerical range has a lower limit value and an upper limit value that are either of the numerical values ​​shown as the lower limit value and either of the numerical values ​​shown as the upper limit value.

[0026] The lower limit of the rate (flow rate) at which the initiator is introduced into the micromixer in the flow microreactor is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 3 mL / min or more, 5 mL / min or more, 7 mL / min or more, 12 mL / min or more, 16 mL / min or more, or 20 mL / min or more. The upper limit of the rate (flow rate) at which the initiator is introduced into the micromixer in the flow microreactor is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 100 mL / min or less, or 50 mL / min or less. It is preferable that the numerical range has a lower limit value and an upper limit value that are either of the numerical values ​​shown as the lower limit value and either of the numerical values ​​shown as the upper limit value.

[0027] The lower limit of the amount of the alkoxysilyl group-containing monomer relative to the initiator is not particularly limited and can be appropriately selected depending on the purpose. However, from the viewpoint of producing a polymer while controlling the molecular weight and molecular weight distribution, the amount is preferably 1 molar equivalent or more, 10 molar equivalents or more, 20 molar equivalents or more, or 30 molar equivalents or more. The upper limit of the amount of the alkoxysilyl group-containing monomer relative to the initiator is not particularly limited and can be appropriately selected depending on the purpose. However, from the viewpoint of producing a polymer while controlling the molecular weight and molecular weight distribution, the upper limit is preferably 100 molar equivalents or less, or 50 molar equivalents or less. It is preferable that the numerical range has a lower limit value and an upper limit value that are either of the numerical values ​​shown as the lower limit value and either of the numerical values ​​shown as the upper limit value.

[0028] The lower limit of the reaction temperature (temperature at which the anionic polymerization step is carried out) between the alkoxysilyl group-containing monomer and the initiator is not particularly limited and can be appropriately selected depending on the purpose. However, from the viewpoint of producing a polymer while controlling the molecular weight and molecular weight distribution, the lower limit is preferably −80° C. or higher, −60° C. or higher, or −40° C. or higher. The upper limit of the reaction temperature (temperature at which the anionic polymerization step is carried out) between the alkoxysilyl group-containing monomer and the initiator is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoint of producing a polymer while controlling the molecular weight and molecular weight distribution, the upper limit is preferably 0°C or lower, more preferably -20°C or lower, even more preferably -25°C or lower, even more preferably -30°C or lower, and particularly preferably -35°C or lower. It is preferable that the numerical range has a lower limit value and an upper limit value that are either of the numerical values ​​shown as the lower limit value and either of the numerical values ​​shown as the upper limit value.

[0029] The initiator represented by the general formula (1) is preferably one obtained by reacting sec-BuLi with an alkylaryl compound.

[0030] The lower limit of the amount of the alkoxysilyl group-containing monomer relative to the sec-BuLi is not particularly limited and can be appropriately selected depending on the purpose. However, from the viewpoint of producing a polymer while controlling the molecular weight and molecular weight distribution, the amount is preferably 1 molar equivalent or more, 10 molar equivalents or more, 20 molar equivalents or more, or 30 molar equivalents or more. The upper limit of the amount of the alkoxysilyl group-containing monomer relative to the sec-BuLi is not particularly limited and can be appropriately selected depending on the purpose. However, from the viewpoint of producing a polymer while controlling the molecular weight and molecular weight distribution, the upper limit is preferably 100 molar equivalents or less, or 50 molar equivalents or less. It is preferable that the numerical range has a lower limit value and an upper limit value that are either of the numerical values ​​shown as the lower limit value and either of the numerical values ​​shown as the upper limit value.

[0031] --Initiator manufacturing method-- The method for producing the initiator is not particularly limited and can be appropriately selected depending on the purpose. For example, a method of reacting sec-BuLi with an alkylaryl compound can be mentioned. The method for producing the initiator may include a step of introducing the sec-BuLi and the alkylaryl compound into a micromixer in the flow microreactor.

[0032] The alkylaryl compound is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include alkylbenzene compounds.

[0033] The alkylbenzene compound is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include methylstyrene compounds such as α-methylstyrene, β-methylstyrene, 2-methylstyrene (o-methylstyrene), 3-methylstyrene (m-methylstyrene), 4-methylstyrene (p-methylstyrene), 1,5-dimethylstyrene, and 2,4-dimethylstyrene; and ethylstyrene compounds such as α-ethylstyrene, β-ethylstyrene, 2-ethylstyrene (o-ethylstyrene), 3-ethylstyrene (m-ethylstyrene), 4-ethylstyrene (p-ethylstyrene), 1,5-diethylstyrene, and 2,4-diethylstyrene. Examples of such divinylbenzenes include 1,2-divinylbenzene (o-divinylbenzene), 1,3-divinylbenzene (m-divinylbenzene), 1,4-divinylbenzene (p-divinylbenzene), 1,2-bis(1-methylethenyl)benzene (o-bis(1-methylethenyl)benzene), 1,3-bis(1-methylethenyl)benzene (m-bis(1-methylethenyl)benzene), 1,4-bis(1-methylethenyl)benzene (p-bis(1-methylethenyl)benzene), 1,2,3-tris(1-methylethenyl)benzene, 1,2,4-tris(1-methylethenyl)benzene, and 1,3,5-tris(1-methylethenyl)benzene. Among these, from the viewpoint of producing a polymer while controlling the molecular weight and molecular weight distribution, a methylstyrene compound or an ethylstyrene compound is preferred, a methylstyrene compound is more preferred, and α-methylstyrene is even more preferred.

[0034] The molar equivalent of the alkylaryl compound is not particularly limited and can be appropriately selected depending on the purpose. However, from the viewpoint of producing a polymer while controlling the molecular weight and molecular weight distribution, it is preferably greater than the molar equivalent of sec-BuLi.

[0035] The lower limit of the amount of the alkylaryl compound relative to the sec-BuLi is not particularly limited and can be appropriately selected depending on the purpose. However, from the viewpoint of producing a polymer while controlling the molecular weight and molecular weight distribution, the amount is preferably 1 molar equivalent or more, more preferably 1.2 molar equivalents or more, even more preferably 1.5 molar equivalents or more, even more preferably 1.8 molar equivalents or more, particularly preferably 1.9 molar equivalents or more, and most preferably 2 molar equivalents or more. The upper limit of the amount of the alkylaryl compound relative to the sec-BuLi is not particularly limited and can be appropriately selected depending on the purpose. However, from the viewpoint of producing a polymer while controlling the molecular weight and molecular weight distribution, the upper limit is preferably 5 molar equivalents or less, more preferably 4 molar equivalents or less, even more preferably 3 molar equivalents or less, particularly preferably 2.5 molar equivalents or less, and most preferably 2.2 molar equivalents or less. It is preferable that the numerical range has a lower limit value and an upper limit value that are either of the numerical values ​​shown as the lower limit value and either of the numerical values ​​shown as the upper limit value.

[0036] The lower limit of the reaction temperature between the sec-BuLi and the alkylaryl compound is not particularly limited and can be appropriately selected depending on the purpose. However, from the viewpoint of producing a polymer while controlling the molecular weight and molecular weight distribution, the reaction temperature is preferably 0°C or higher, more preferably 5°C or higher, even more preferably 10°C or higher, and particularly preferably 15°C or higher. The upper limit of the reaction temperature between the sec-BuLi and the alkylaryl compound is not particularly limited and can be appropriately selected depending on the purpose. However, from the viewpoint of producing a polymer while controlling the molecular weight and molecular weight distribution, the upper limit is preferably 40°C or lower, more preferably 35°C or lower, and even more preferably 25°C or lower. It is preferable that the numerical range has a lower limit value and an upper limit value that are either of the numerical values ​​shown as the lower limit value and either of the numerical values ​​shown as the upper limit value.

[0037] The lower limit of the rate (flow rate) at which the sec-BuLi is introduced into the micromixer in the flow microreactor is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.5 mL / min or more, 1 mL / min or more, 1.5 mL / min or more, or 2 mL / min or more. The upper limit of the rate (flow rate) at which the sec-BuLi is introduced into the micromixer in the flow microreactor is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 100 mL / min or less, 50 mL / min or less, or 10 mL / min or less. It is preferable that the numerical range has a lower limit value and an upper limit value that are either of the numerical values ​​shown as the lower limit value and either of the numerical values ​​shown as the upper limit value.

[0038] The lower limit of the rate (flow rate) at which the alkylaryl compound is introduced into the micromixer in the flow microreactor is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.5 mL / min or more, 1 mL / min or more, 3 mL / min or more, or 5 mL / min or more. The upper limit of the rate (flow rate) at which the alkylaryl compound is introduced into the micromixer in the flow microreactor is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 100 mL / min or less, 50 mL / min or less, or 10 mL / min or less. It is preferable that the numerical range has a lower limit value and an upper limit value that are either of the numerical values ​​shown as the lower limit value and either of the numerical values ​​shown as the upper limit value.

[0039] The lower limit of the concentration of sec-BuLi is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.01M or more, 0.05M or more, 0.1M or more, 0.15M or more, or 0.2M or more. The upper limit of the concentration of sec-BuLi is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 10 M or less, 5 M or less, 1 M or less, or 0.5 M or less. It is preferable that the numerical range has a lower limit value and an upper limit value that are either of the numerical values ​​shown as the lower limit value and either of the numerical values ​​shown as the upper limit value.

[0040] The lower limit of the alkylaryl concentration is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.01M or more, 0.05M or more, or 0.1M or more. The upper limit of the alkylaryl concentration is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 10 M or less, 5 M or less, 1 M or less, or 0.5 M or less. It is preferable that the numerical range has a lower limit value and an upper limit value that are either of the numerical values ​​shown as the lower limit value and either of the numerical values ​​shown as the upper limit value.

[0041] -Microreactor- The microreactor is not particularly limited and can be appropriately selected depending on the purpose. Examples include a microreactor (hereinafter sometimes referred to as a "flow microreactor") that is equipped with a mixing means and a flow channel, and further equipped with other means as necessary. The mixing means and the flow passage may be of an integral type or of a separate type.

[0042] The mixing means is a means capable of mixing two or more types of liquids. The flow passage is a pipe through which a liquid can flow, and is connected to at least one of the mixing means.

[0043] By using the flow microreactor, it is possible to shorten the residence time from the production to the next reaction for a compound with low stability, thereby suppressing side reactions. Furthermore, the flow microreactor has excellent cooling efficiency, and therefore can suppress side reactions caused by heat generated in an exothermic reaction.

[0044] --Integrated flow microreactor-- The mixing means and the flow passage of the integrated flow microreactor may be a substrate-type micromixer.

[0045] The substrate-type micromixer is made of a substrate having passages formed inside or on the surface thereof, and is sometimes called a microchannel. The substrate-type micromixer is not particularly limited and can be appropriately selected depending on the purpose. Examples include the mixer having fine flow channels for mixing described in International Publication No. 96 / 30113; and the mixer described in the literature "Microreactors," Chapter 3, by W. Ehrfeld, V. Hessel, and H. Lowe, published by Wiley-VCH.

[0046] In the substrate-type micromixer, the mixing means and the flow path are configured by minute flow paths that can mix a plurality of liquids.

[0047] In addition to the flow paths, the substrate-type micromixer is preferably formed with inlet paths that communicate with the flow paths and introduce a plurality of liquids into the flow paths. That is, it is preferable that the flow paths are branched on the upstream side depending on the number of the inlet paths.

[0048] The number of the inlet channels is not particularly limited and can be appropriately selected depending on the purpose, but it is preferable that the multiple liquids to be mixed are introduced through separate inlet channels and merged in the flow channel for mixing. Alternatively, one liquid may be pre-loaded in the flow channel, and the other liquids may be introduced through the inlet channels.

[0049] --Separate flow microreactor-- The separate flow microreactor comprises a mixing means and a flow passage connected thereto.

[0050] The mixing means is not particularly limited as long as it can mix two or more liquids, and can be appropriately selected depending on the purpose. For example, a pipe joint type micromixer can be used.

[0051] The pipe joint type micromixer has a flow path formed therein and, if necessary, a connecting member that connects the flow path formed therein with the flow passage. The connection method of the connecting member is not particularly limited and can be appropriately selected from known connection methods depending on the purpose, and examples thereof include a threaded type, a union type, a butt welding type, a plug welding type, a socket welding type, a flange type, a bite type, a flare type, and a mechanical type.

[0052] In addition to the flow paths, it is preferable that inlet paths communicating with the flow paths and introducing multiple liquids into the flow paths are formed inside the pipe joint type micromixer. That is, it is preferable that the flow paths are branched upstream depending on the number of the inlet paths. When the number of the inlet paths is two, the pipe joint type micromixer can be, for example, T-shaped or Y-shaped, and when the number of the inlet paths is three, it can be, for example, cross-shaped. Note that it is also possible to configure the micromixer so that one liquid is pre-loaded into the flow path and the other liquids are introduced through the inlet paths.

[0053] The material of the pipe joint type micromixer is not particularly limited and can be appropriately selected depending on requirements such as heat resistance, pressure resistance, solvent resistance, and ease of processing. Examples include stainless steel, titanium, copper, nickel, aluminum, silicon, fluororesins such as Teflon (registered trademark) and PFA (perfluoroalkoxy resin), and TFAA (trifluoroacetamide).

[0054] As the pipe joint type micro mixer, commercially available products can be used, such as the YM-1 type mixer and YM-2 type mixer manufactured by Yamatake Corporation; mixing tees and tees (T-shaped connectors) manufactured by Shimadzu GLC Corporation; the Micro High Mixer developed by Toray Engineering; union tees manufactured by Swagelok Corporation; and a T-shaped micro mixer manufactured by Sanko Seiki Kogyo Co., Ltd.

[0055] The method of mixing two or more raw materials in the mixing means is not particularly limited and can be appropriately selected depending on the purpose, and examples include mixing by laminar flow, mixing by turbulent flow, etc. Among these, mixing by laminar flow (static mixing) is preferred in that it allows for more efficient reaction control and heat removal.

[0056] Since the flow paths in the mixing means are minute, the liquids introduced into the mixing means tend to naturally flow in a laminar manner, and are mixed by diffusing in a direction perpendicular to the flow. In mixing by laminar flow, branching points and confluences may be provided in the flow paths to divide the laminar cross section of the flowing liquids, thereby increasing the mixing speed. Furthermore, when turbulent mixing (dynamic mixing) is performed in the flow path of the mixing means, the laminar flow can be changed to turbulent flow by adjusting the flow rate and the shape of the flow path (the three-dimensional shape of the liquid-contacting portion, the shape of the flow path such as bending, the roughness of the wall surface, etc.). Mixing by turbulent flow has the advantages of better mixing efficiency and faster mixing speed than mixing by laminar flow.

[0057] Here, a smaller inner diameter of the flow path in the mixing means can shorten the diffusion distance of molecules, thereby shortening the time required for mixing and improving the mixing efficiency. Furthermore, a smaller inner diameter of the flow path increases the ratio of surface area to volume, making it easier to control the temperature of the liquid, for example, by removing the heat of reaction. On the other hand, if the inner diameter of the flow path is too small, the pressure loss when the liquid flows increases, and a special high-pressure pump is required for the liquid delivery, which may increase the manufacturing cost. Furthermore, the liquid delivery flow rate is limited, which may also limit the structure of the micromixer.

[0058] The inner diameter of the flow path in the mixing means is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 50 μm to 4 mm, more preferably 100 μm to 3 mm, even more preferably 250 μm to 2 mm, and particularly preferably 500 μm to 1 mm. If the inner diameter is less than 50 μm, pressure loss may increase. If the inner diameter is more than 4 mm, the surface area per unit volume becomes small, which may result in difficulty in rapid mixing and removal of reaction heat. On the other hand, if the inner diameter is within the particularly preferred range, it is advantageous in that more rapid mixing can be achieved and reaction heat can be removed more efficiently. More specifically, the inner diameter of the flow path formed inside the mixing means is preferably 50 μm to 1,000 μm, more preferably 100 μm to 800 μm, and even more preferably 250 μm to 500 μm.

[0059] The cross-sectional area of ​​the flow channel is not particularly limited and can be appropriately selected depending on the purpose. 2 ~16mm 2 is preferable, and 1,000 μm 2 ~4.0mm 2 is more preferable, and 10,000 μm 2 ~2.1mm 2 is more preferable, and 190,000 μm 2 ~1mm 2 is particularly preferred.

[0060] The cross-sectional shape of the flow channel is not particularly limited and can be appropriately selected depending on the purpose. Examples include a circle, a rectangle, a semicircle, and a triangle.

[0061] The flow path is not particularly limited as long as it is a tube that is connected to at least one of the mixing means and allows a liquid to flow through it, and can be appropriately selected depending on the purpose. The configuration of the flow path, such as its inner diameter, outer diameter, length, material, etc., can be appropriately selected depending on the desired reaction.

[0062] The flow passage is used, for example, when supplying raw materials to the mixing means. The flow channel is used, for example, when supplying a reaction product of two or more substances mixed by the mixing means to a subsequent mixing means, while the reaction may continue to occur within the flow channel.

[0063] The flow path can be a commercially available product, such as a stainless steel tube manufactured by GL Sciences Inc. (outer diameter 1 / 16 inch (1.58 mm), inner diameter selectable from 250 μm, 500 μm, and 1,000 μm, tube length adjustable by the user).

[0064] The material of the flow path is not particularly limited, and the materials exemplified as the materials of the mixing means can be suitably used.

[0065] The inner diameter of the flow path is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 50 μm to 4 mm, more preferably 100 μm to 3 mm, even more preferably 250 μm to 2 mm, and particularly preferably 500 μm to 1 mm. More specifically, the inner diameter of the flow path is preferably 50 μm to 1,000 μm, more preferably 100 μm to 800 μm, and even more preferably 250 μm to 500 μm.

[0066] The inner diameter of the flow passage connected downstream of the mixing means is preferably 50 μm to 4 mm, more preferably 100 μm to 2 mm, and even more preferably 500 μm to 1 mm.

[0067] The flow rate of the liquid in the flow channel for supplying the raw materials is not particularly limited and can be appropriately selected depending on the purpose, and may be, for example, 1 mL / min to 20 mL / min, 2 mL / min to 15 mL / min, or 3 mL / min to 10 mL / min.

[0068] The residence time of the reaction liquid in the flow channel through which the reaction liquid flows is not particularly limited and can be appropriately selected depending on the purpose, and may be, for example, 0.001 seconds to 10 seconds.

[0069] The lower limit of the length of the flow channel between the micromixer in which the sec-BuLi and the alkylaryl compound are reacted and the micromixer in which the anionic polymerization is carried out is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 100 cm or more, more preferably 150 cm or more, even more preferably 170 cm or more, and particularly preferably 190 cm or more. The upper limit of the length of the flow channel between the micromixer in which the sec-BuLi and the alkylaryl compound are reacted and the micromixer in which the anionic polymerization is carried out is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 300 cm or less, more preferably 280 cm or less, even more preferably 250 cm or less, and particularly preferably 230 cm or less.

[0070] --Other means-- The other means is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include a liquid delivery means and a temperature control means.

[0071] The liquid delivery means is not particularly limited as long as it can supply various raw materials to the flow passage of the flow microreactor, and can be appropriately selected depending on the purpose. For example, a pump can be used.

[0072] The pump is not particularly limited and can be appropriately selected from those that can be used industrially. However, it is preferable to use a pump that does not generate pulsation during liquid transfer, and examples thereof include a plunger pump, a gear pump, a rotary pump, and a diaphragm pump.

[0073] The temperature control means is not particularly limited as long as it can control the temperatures of the mixing means and the flow channel of the flow microreactor, and can be appropriately selected depending on the purpose.

[0074] <Other processes> The other steps are not particularly limited and can be appropriately selected depending on the purpose. Examples of the other steps include a step of producing an initiator before the anionic polymerization step, a functional group substitution step after the anionic polymerization step, and a polymerization termination step after the anionic polymerization step.

[0075] -Initiator manufacturing process before anionic polymerization process- The step of producing an initiator before the anionic polymerization step is a step of reacting the sec-BuLi with an alkylaryl compound before the anionic polymerization step. The step of reacting the sec-BuLi with the alkylaryl compound is as described in the above-mentioned method for producing the initiator. The step of producing an initiator prior to the anionic polymerization step may be a step of introducing the sec-BuLi and the alkylaryl compound into a micromixer in the flow microreactor.

[0076] -Functional Group Substitution Step After the Anionic Polymerization Step- The functional group substitution step after the anionic polymerization step is a step of converting the silicon-on substituents of the polymer obtained after the anionic polymerization step (post-functionalization).

[0077] The method for converting the silicon-containing substituent is not particularly limited and can be appropriately selected depending on the purpose. For example, a method of mixing the obtained polymer with a functional group-substituting agent can be mentioned. The functional group substitution step after the anionic polymerization step may be a step of introducing the polymer obtained in the anionic polymerization step and the functional group substitution agent into a micromixer in the flow microreactor.

[0078] The functional group substitution agent is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include Grignard reagents, methyllithium, and phenyllithium. The Grignard reagent is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include methyl magnesium chloride, vinyl magnesium chloride, and n-butyl magnesium chloride.

[0079] The lower limit of the concentration of the functional group substitution agent is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.01 M or more, 0.05 M or more, 0.1 M or more, 0.5 M or more, 0.8 M or more, or 1 M or more. The upper limit of the concentration of the functional group substitution agent is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 10 M or less, 5 M or less, or 1 M or less. It is preferable that the numerical range has a lower limit value and an upper limit value that are either of the numerical values ​​shown as the lower limit value and either of the numerical values ​​shown as the upper limit value.

[0080] The lower limit of the amount of the functional group substitution agent relative to the alkoxysilyl group-containing monomer is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 1 molar equivalent or more, more preferably 5 molar equivalents or more, even more preferably 10 molar equivalents or more, and particularly preferably 15 molar equivalents or more. The upper limit of the amount of the functional group-substituting agent relative to the alkoxysilyl group-containing monomer is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 20 molar equivalents or less. It is preferable that the numerical range has a lower limit value and an upper limit value that are either of the numerical values ​​shown as the lower limit value and either of the numerical values ​​shown as the upper limit value.

[0081] By adjusting the amount of the functional group substitution agent (the amount of the functional group substitution agent relative to the alkoxysilyl group-containing monomer), it is possible to control the post-functionalization rate, such as the methylation rate, of the resulting polymer. Post-functionalization can improve the stability of the resulting polymer.

[0082] The lower limit of the reaction temperature between the polymer obtained in the anionic polymerization step and the functional group substitution agent is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0°C or higher, 20°C or higher, 50°C or higher, or 60°C or higher. The upper limit of the reaction temperature between the polymer obtained in the reflux anionic polymerization step and the functional group substitution agent is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 100° C. or lower. It is preferable that the numerical range has a lower limit value and an upper limit value that are either of the numerical values ​​shown as the lower limit value and either of the numerical values ​​shown as the upper limit value.

[0083] The reaction between the polymer obtained in the anionic polymerization step and the functional group substitution agent can be carried out under reflux conditions using a thermostatic bath. The lower limit of the temperature of the thermostatic bath is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0°C or higher, 20°C or higher, 50°C or higher, or 80°C or higher. The upper limit of the temperature of the thermostatic bath is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 100° C. or lower. It is preferable that the numerical range has a lower limit value and an upper limit value that are either of the numerical values ​​shown as the lower limit value and either of the numerical values ​​shown as the upper limit value.

[0084] The functional group substitution step after the anionic polymerization step may be carried out using a batch reactor or a flow microreactor. From the viewpoint of consistently and efficiently performing the initiator production step, the anionic polymerization reaction, the functional group substitution step, and the polymerization termination step using a flow microreactor, it is preferable to perform the functional group substitution step after the anionic polymerization step using a flow microreactor.

[0085] The lower limit of the rate (flow rate) at which the functional group substitution agent is introduced into the micromixer in the flow microreactor is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 1 mL / min or more, 3 mL / min or more, 5 mL / min or more, or 8 mL / min or more. The upper limit of the speed (flow rate) at which the functional group substitution agent is introduced into the micromixer in the flow microreactor is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 100 mL / min or less, 50 mL / min or less, or 10 mL / min or less. It is preferable that the numerical range has a lower limit value and an upper limit value that are either of the numerical values ​​shown as the lower limit value and either of the numerical values ​​shown as the upper limit value.

[0086] When the functional group substitution step after the anionic polymerization step is carried out using a flow microreactor, it is preferable to carry out a polymerization termination step after the functional group substitution step after the anionic polymerization step.

[0087] -Polymerization termination step after the anionic polymerization step- The polymerization termination step after the anionic polymerization step is a step of terminating the polymerization after the anionic polymerization step (quenching step).

[0088] The method for terminating the polymerization is not particularly limited and can be appropriately selected depending on the purpose. For example, a method of mixing the obtained polymer with a polymerization terminator (quenching agent) can be mentioned. The polymerization termination step after the anionic polymerization step may be a step of introducing the polymer obtained in the anionic polymerization step and the polymerization terminator into a micromixer in the flow microreactor.

[0089] The polymerization terminator is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include methanol and hydrochloric acid.

[0090] The lower limit of the concentration of the polymerization terminator is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.01M or more, 0.05M or more, 0.1M or more, or 0.3M or more. The upper limit of the concentration of the polymerization terminator is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 10M or less, 5M or less, 1M or less, or 0.5M or less. It is preferable that the numerical range has a lower limit value and an upper limit value that are either of the numerical values ​​shown as the lower limit value and either of the numerical values ​​shown as the upper limit value.

[0091] The lower limit of the amount of the polymerization terminator relative to the sec-BuLi is not particularly limited and can be appropriately selected depending on the purpose. However, from the viewpoint of producing a polymer while controlling the molecular weight and molecular weight distribution, the amount is preferably 1 molar equivalent or more, more preferably 1.5 molar equivalents or more, even more preferably 2 molar equivalents or more, particularly preferably 2.3 molar equivalents or more, and most preferably 2.5 molar equivalents or more. The upper limit of the amount of the polymerization terminator relative to the amount of sec-BuLi is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 20 molar equivalents or less. It is preferable that the numerical range has a lower limit value and an upper limit value that are either of the numerical values ​​shown as the lower limit value and either of the numerical values ​​shown as the upper limit value.

[0092] The lower limit of the reaction temperature between the polymer obtained in the anionic polymerization step and the polymerization terminator is not particularly limited and can be appropriately selected depending on the purpose. However, from the viewpoint of producing a polymer while controlling the molecular weight and molecular weight distribution, the lower limit is preferably −80° C. or higher, −60° C. or higher, or −40° C. or higher. The upper limit of the reaction temperature between the polymer obtained in the anionic polymerization step and the polymerization terminator is not particularly limited and can be appropriately selected depending on the purpose. However, from the viewpoint of producing a polymer while controlling the molecular weight and molecular weight distribution, the upper limit is preferably −20° C. or lower, more preferably −25° C. or lower, even more preferably −30° C. or lower, and particularly preferably −35° C. or lower. It is preferable that the numerical range has a lower limit value and an upper limit value that are either of the numerical values ​​shown as the lower limit value and either of the numerical values ​​shown as the upper limit value.

[0093] The lower limit of the rate (flow rate) at which the polymerization terminator is introduced into the micromixer in the flow microreactor is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.5 mL / min or more, 1 mL / min or more, 3 mL / min or more, or 4 mL / min or more. The upper limit of the rate (flow rate) at which the polymerization terminator is introduced into the micromixer in the flow microreactor is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 100 mL / min or less, 50 mL / min or less, or 10 mL / min or less. It is preferable that the numerical range has a lower limit value and an upper limit value that are either of the numerical values ​​shown as the lower limit value and either of the numerical values ​​shown as the upper limit value.

[0094] The lower limit of the total rate (total flow rate) of the rate (flow rate) at which the sec-BuLi is introduced into the micromixer (first micromixer) in the flow microreactor, the rate (flow rate) at which the alkylaryl compound is introduced into the micromixer (first micromixer) in the flow microreactor, the rate (flow rate) at which the alkoxysilyl group-containing monomer is introduced into the micromixer (second micromixer) in the flow microreactor, and the rate (flow rate) at which the polymerization terminator is introduced into the micromixer (third micromixer) in the flow microreactor is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoint of producing a polymer while controlling the molecular weight and molecular weight distribution, the lower limit is preferably 5 mL / min or more, more preferably 10 mL / min or more, and even more preferably 15 mL / min or more. The upper limit of the total rate (total flow rate) of the rate (flow rate) at which the sec-BuLi is introduced into the micromixer (first micromixer) in the flow microreactor, the rate (flow rate) at which the alkylaryl compound is introduced into the micromixer (first micromixer) in the flow microreactor, the rate (flow rate) at which the alkoxysilyl group-containing monomer is introduced into the micromixer (second micromixer) in the flow microreactor, and the rate (flow rate) at which the polymerization terminator is introduced into the micromixer (third micromixer) in the flow microreactor is not particularly limited and can be appropriately selected depending on the purpose. However, from the viewpoint of producing a polymer while controlling the molecular weight and molecular weight distribution, the upper limit is preferably 100 mL / min or less, 50 mL / min or less, or 30 mL / min or less. It is preferable that the numerical range has a lower limit value and an upper limit value that are either of the numerical values ​​shown as the lower limit value and either of the numerical values ​​shown as the upper limit value.

[0095] The lower limit of the length of the flow channel between the micromixer in the flow microreactor, into which the alkoxysilyl group-containing monomer is introduced (second micromixer: the micromixer that performs the anionic polymerization), and the micromixer in the flow microreactor, into which the polymerization terminator is introduced (third micromixer), is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 5 cm or more, 10 cm or more, or 20 cm or more. There is no particular upper limit to the length of the flow channel between the micromixer in the flow microreactor (second micromixer: the micromixer that performs the anionic polymerization) into which the alkoxysilyl group-containing monomer is introduced and the micromixer in the flow microreactor (third micromixer) into which the polymerization terminator is introduced. The upper limit may be appropriately selected depending on the purpose, but from the viewpoint of producing a polymer while controlling the molecular weight and molecular weight distribution, the upper limit is preferably 200 cm or less, more preferably 100 cm or less, and even more preferably 50 cm or less. It is preferable that the numerical range has a lower limit value and an upper limit value that are either of the numerical values ​​shown as the lower limit value and either of the numerical values ​​shown as the upper limit value.

[0096] The order of carrying out the functional group substitution step after the anionic polymerization step and the polymerization termination step after the anionic polymerization step is not particularly limited and can be appropriately selected depending on the purpose.

[0097] (Initiator for polymerization of alkoxysilyl group-containing monomers) The initiator for polymerization of the alkoxysilyl group-containing monomer is the same as the initiator described above.

[0098] (Method of producing an initiator for polymerization of alkoxysilyl group-containing monomers) The method for producing the initiator for polymerization of the alkoxysilyl group-containing monomer is the same as the method for producing the initiator described above.

[0099] (polymer) The polymer can be produced by the above-mentioned method for producing a polymer.

[0100] The polymer is not particularly limited and can be appropriately selected depending on the purpose. For example, the polymer may be a polymer represented by the following general formula (3).

[0101] [ka] In the general formula (3), m represents the degree of polymerization and is an integer of 1 or more; 5 represents an aryl group or an alkyl group having 1 to 10 carbon atoms; X represents an alkoxysilyl group; and a represents the number of the alkoxysilyl groups (X) and is an integer of 1 to 4.

[0102] In the general formula (3), m is not particularly limited as long as it is an integer of 1 or more and can be appropriately selected depending on the purpose, but is preferably 5 or more, more preferably 10 or more, even more preferably 15 or more, particularly preferably 20 or more, and most preferably 25 or more.

[0103] R in the general formula (3) 5 is not particularly limited as long as it is an aryl group or an alkyl group having 1 to 10 carbon atoms and can be appropriately selected depending on the purpose, but is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably a methyl group.

[0104] The molecular weight distribution (polydispersity index (PDI): Mw / Mn) of the polymer is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 1.8 or less, more preferably 1.5 or less, even more preferably 1.3 or less, even more preferably 1.2 or less, and particularly preferably 1.1 or less. The molecular weight distribution is measured by the following GPC analysis.

[0105] -GPC analysis- The analysis was carried out in THF (Fujifilm Wako Pure Chemical Industries, Ltd.) at 40 °C using a SHIMADZU Prominence equipped with a Shodex LF-604 column. The reflectance index (RI) was recorded on a Shodex RI-504. The molecular weight distribution (polydispersity index (PDI): Mw / Mn) was determined by a calibration curve obtained from commercially available polystyrene. Prior to GPC analysis, the solution was filtered through a 13 mm PTFE (hydrophobic) 0.45 μm syringe filter (Tomsic Corporation).

[0106] Here, an example of a flow microreactor that can be suitably used in the method for producing a polymer or the method for producing an initiator, and a method for producing a polymer using the same will be described with reference to the drawings.

[0107] FIG. 1 is a schematic diagram showing an example of a flow microreactor used in an example of a method for producing an initiator represented by general formula (1). The flow microreactor shown in FIG. 1 includes one mixing means and three flow paths.

[0108] The flow passage P1 is connected to the mixing means M1. The flow passage P2 is connected to the mixing means M1. The flow passage R1 is connected to the mixing means M1 and also serves as a reaction section.

[0109] The alkylaryl compound is supplied to the mixing means M1 through a flow path P1. The sec-BuLi is supplied to the mixing means M1 through a flow path P2. Then, the alkylaryl compound and the sec-BuLi are mixed in the mixing means M1, and an addition reaction starts in the resulting liquid to produce the initiator represented by the general formula (1).

[0110] FIG. 2 is a schematic diagram showing an example of a flow microreactor. The flow microreactor shown in FIG. 2 has two mixing means and five flow passages.

[0111] The flow passage P1 is connected to the mixing means M1. The flow passage P2 is connected to the mixing means M1. The flow passage P3 is connected to the mixing means M2. The flow path R1 is connected to the mixing means M1 and the mixing means M2. The flow path R1 also serves as a reaction section. The flow passage R2 is connected to the mixing means M2 and also serves as a reaction section.

[0112] The initiator represented by the general formula (1) is supplied to the mixing means M1 through a flow path P1. The alkoxysilyl group-containing monomer is supplied to the mixing means M1 through a flow path P2. Then, the initiator represented by the general formula (1) and the alkoxysilyl group-containing monomer are mixed in the mixing means M1, and in the resulting liquid, living anionic polymerization of the alkoxysilyl group-containing monomer is initiated using the initiator represented by the general formula (1) as an anionic polymerization initiator, producing a living polymer. The liquid undergoing the polymerization reaction flows through the flow path R1, which also serves as the reaction section, while polymerizing. The resulting polymer is a living polymer. Therefore, in order to terminate the active ends, a solution containing a polymerization terminator (e.g., methanol) is circulated through the flow path P3 and mixed with the polymer solution by the mixing means M2, thereby carrying out the termination reaction.

[0113] FIG. 3 is a schematic diagram showing an example of a flow microreactor. The flow microreactor shown in FIG. 3 has three mixing means and seven flow passages.

[0114] The flow passage P1 is connected to the mixing means M1. The flow passage P2 is connected to the mixing means M1. The flow passage P3 is connected to the mixing means M2. The flow passage P4 is connected to the mixing means M3. The flow path R1 is connected to the mixing means M1 and the mixing means M2. The flow path R1 also serves as a reaction section. The flow passage R2 is connected to the mixing means M2 and the mixing means M3. The flow passage R2 also serves as a reaction section. The flow passage R3 is connected to the mixing means M3 and also serves as a reaction section.

[0115] The alkylaryl compound is supplied to the mixing means M1 through flow path P1. The sec-BuLi is supplied to the mixing means M1 through flow path P2. Then, the alkylaryl compound and the sec-BuLi are mixed in the mixing means M1, and an addition reaction starts in the resulting liquid, producing the initiator represented by general formula (1). The liquid during the reaction flows through flow path R1, which also serves as the reaction section, while reacting.

[0116] The liquid containing the initiator represented by the general formula (1) flowing through the flow path R1 is introduced into the mixing means M2. In the mixing means M2, the liquid is mixed with the alkoxysilyl group-containing monomer supplied from the flow path P3, and in the resulting liquid, living anionic polymerization of the alkoxysilyl group-containing monomer is initiated using the initiator represented by the general formula (1) as an anionic polymerization initiator, to produce a living polymer. The liquid undergoing the polymerization reaction flows through the flow path R2, which also serves as the reaction section, while polymerizing. The resulting polymer is a living polymer. Therefore, in order to terminate the active ends, a solution containing a polymerization terminator (e.g., methanol) is circulated through the flow path P4 and mixed with the polymer solution by the mixing means M3 to carry out the termination reaction.

[0117] FIG. 4 is a schematic diagram showing an example of a flow microreactor. The flow microreactor shown in FIG. 4 has four mixing means and nine flow passages.

[0118] The flow passage P1 is connected to the mixing means M1. The flow passage P2 is connected to the mixing means M1. The flow passage P3 is connected to the mixing means M2. The flow passage P4 is connected to the mixing means M3. The flow passage P5 is connected to the mixing means M4. The flow path R1 is connected to the mixing means M1 and the mixing means M2. The flow path R1 also serves as a reaction section. The flow passage R2 is connected to the mixing means M2 and the mixing means M3. The flow passage R2 also serves as a reaction section. The flow path R3 is connected to the mixing means M3 and the mixing means M4. The flow path R3 also serves as a reaction section. The flow passage R4 is connected to the mixing means M4 and also serves as a reaction section.

[0119] The alkylaryl compound is supplied to the mixing means M1 through the flow path P1. The sec-BuLi is supplied to the mixing means M1 through the flow path P2. Then, the alkylaryl compound and the sec-BuLi are mixed in the mixing means M1, and an addition reaction starts in the resulting liquid, producing the initiator represented by the general formula (1). The liquid during the reaction flows through the flow path R1, which also serves as the reaction section, while reacting.

[0120] The liquid containing the initiator represented by the general formula (1) flowing through the flow path R1 is introduced into the mixing means M2. In the mixing means M2, the liquid is mixed with the alkoxysilyl group-containing monomer supplied from the flow path P3, and in the resulting liquid, living anionic polymerization of the alkoxysilyl group-containing monomer is initiated using the initiator represented by the general formula (1) as an anionic polymerization initiator, to produce a living polymer. The liquid undergoing the polymerization reaction flows, for example, through flow channel R2, which also serves as a reaction section, while undergoing polymerization. The liquid containing the living polymer flowing through flow channel R2 is introduced into mixing means M3. In mixing means M3, the liquid is mixed with the functional group substitution agent supplied through flow channel P4, and the silicon-bonded substituents of the living polymer are converted in the resulting liquid, which then flows through flow channel R3, also serving as a reaction section. To terminate the active ends of the resulting polymer, a solution containing a polymerization terminator (e.g., methanol) is circulated through flow channel P5, and the resulting polymer is mixed with the polymer solution in mixing means M4 to carry out a termination reaction. [Example]

[0121] Examples of the present invention will be described below, but the present invention is not limited to these examples in any way.

[0122] <1. Polymer Production 1. Anionic Polymerization Using a Batch Reactor> [ka]

[0123] (Comparative Example 1) Anionic polymerization of 4-trimethoxysilylstyrene was carried out using a batch reactor. To compare only the polymerization reaction process, the polymerization initiator was prepared using a flow microreactor, and the subsequent steps were carried out in a batch reactor.

[0124] To prepare the polymerization initiator, we used a flow microreactor system shown in Figure 1, which consists of one V-type micromixer (M1, manufactured by Sanko Seiki Kogyo Co., Ltd.), one microtube reactor (R1, manufactured by GL Sciences), and two pre-cooling units (100 cm, manufactured by GL Sciences).

[0125] The flow microreactor system was placed in a bath at 20°C. α-Methylstyrene (0.09 M THF solution, manufactured by Tokyo Chemical Industry Co., Ltd., flow rate: 4.22 mL / min, 1.5 molar equivalents relative to sec-BuLi) and sec-BuLi (0.15 M THF solution, manufactured by Kanto Chemical Co., Inc., flow rate: 1.69 mL / min) were introduced into M1 (φ = 250 μm) using a syringe pump, and the mixture (polymerization initiator solution 2-phenyl-4-methylhex-2-yl lithium (2PHLi)) was passed through R1 (inner diameter 1000 μm, 200 cm).

[0126] A 15-second portion of the polymerization initiator solution was stored in a recovery flask. 4-Trimethoxysilylstyrene (0.564 M THF solution, manufactured by Tokyo Chemical Industry Co., Ltd., 1.5 mL, 10 molar equivalents) was immediately added dropwise to the recovery flask containing the polymerization initiator solution. After stirring at 0°C for 10 seconds, the reaction was quenched with methanol. After 3 seconds, a methyl Grignard reagent (methylmagnesium chloride, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 12 molar equivalents) was added and the reaction was continued at 25°C for 12 hours with stirring to convert the silicon-containing substituents (post-functionalization). After quenching with methanol, the reaction mixture was treated with saturated aqueous ammonium chloride (NH4Cl) and brine. The solution was diluted with THF and filtered. The results of gel permeation chromatography (GPC) analysis according to the method described below in "-GPC analysis-" are shown in Table 1, and the GPC chart is shown in FIG.

[0127] -GPC analysis- The analysis was carried out in THF (Fujifilm Wako Pure Chemical Industries, Ltd.) at 40 °C using a SHIMADZU Prominence equipped with a Shodex LF-604 column. The reflectance index (RI) was recorded on a Shodex RI-504. Mn was determined using a calibration curve obtained from commercially available polystyrene. Prior to GPC analysis, the solution was filtered through a 13 mm syringe filter (Tomsic Corporation) with 0.45 μm PTFE (hydrophobic).

[0128] [Table 1]

[0129] (Comparative Example 2) A polymer was produced and analyzed in the same manner as in Comparative Example 1, except that stirring was carried out for 120 seconds after the dropwise addition of 4-trimethoxysilylstyrene. The results are shown in Table 1.

[0130] (Comparative Example 3) A polymer was produced and analyzed in the same manner as in Comparative Example 1, except that stirring was carried out for 30 minutes after the dropwise addition of 4-trimethoxysilylstyrene. The results are shown in Table 1.

[0131] Comparative Example 4 A polymer was produced and analyzed in the same manner as in Comparative Example 1, except that stirring after the dropwise addition of 4-trimethoxysilylstyrene was carried out at −40° C. The results are shown in Table 1 and FIG.

[0132] (Comparative Example 5) A polymer was produced and analyzed in the same manner as in Comparative Example 1, except that stirring after the dropwise addition of 4-trimethoxysilylstyrene was carried out for 120 seconds at −40° C. The results are shown in Table 1.

[0133] (Comparative Example 6) A polymer was produced and analyzed in the same manner as in Comparative Example 1, except that stirring after the dropwise addition of 4-trimethoxysilylstyrene was carried out for 30 minutes at −40° C. The results are shown in Table 1.

[0134] (Comparative Example 7) A polymer was produced and analyzed in the same manner as in Comparative Example 1, except that stirring after the dropwise addition of 4-trimethoxysilylstyrene was carried out at −78° C. The results are shown in Table 1 and FIG.

[0135] (Comparative Example 8) A polymer was produced and analyzed in the same manner as in Comparative Example 1, except that stirring after the dropwise addition of 4-trimethoxysilylstyrene was carried out for 120 seconds at −78° C. The results are shown in Table 1.

[0136] (Comparative Example 9) A polymer was produced and analyzed in the same manner as in Comparative Example 1, except that stirring after the dropwise addition of 4-trimethoxysilylstyrene was carried out for 30 minutes at −78° C. The results are shown in Table 1.

[0137] The results in Table 1 and Figure 5 show that when anionic polymerization was performed using a batch reactor rather than a microreactor (flow microreactor), the molecular weight and dispersion could not be controlled under any of the conditions, and it was found that it is difficult to control the anionic polymerization of 4-trimethoxysilylstyrene in a batch reactor. Furthermore, because the methylation conditions with the methyl Grignard reagent were not optimized, it is possible that some methoxy groups remain. In Table 1, "-" indicates that the polymer was not detected by GPC, possibly due to insolubilization caused by cross-linking.

[0138] <2 Polymer Production 2 Anionic Polymerization Using a Microreactor> [ka]

[0139] The effects of polymerization initiators on the anionic polymerization of 4-trimethoxysilylstyrene were investigated using a flow microreactor. The polymerization initiator used was 2PHLi prepared from α-methylstyrene and s-BuLi, alkyllithiums such as n-BuLi (n-butyllithium) and s-BuLi (sec-butyllithium), or DPHLi ((1,1-diphenylhexyl)lithium) prepared from 1,1-diphenylethylene and n-BuLi.

[0140] Example 1 As shown in Figure 2, a flow microreactor system was used, which consisted of one V-type micromixer (M1: manufactured by Sanko Seiki Kogyo Co., Ltd.), one T-type micromixer (M2: manufactured by Sanko Seiki Kogyo Co., Ltd.), two microtube reactors (R1 and R2: manufactured by GL Sciences), and three 100 cm pre-cooling units (P1, P2, and P3: manufactured by GL Sciences).

[0141] The flow microreactor system was placed in a −40° C. bath, and 4-trimethoxysilylstyrene (0.33 M THF solution, manufactured by Tokyo Chemical Industry Co., Ltd., flow rate: 9 mL / min, 10 molar equivalents) and 2-phenyl-4-methylhex-2-yl lithium (2PHLi) (0.05 M THF / hexane solution, flow rate: 5.91 mL / min, 1 molar equivalent) prepared by the following method were mixed in M1 (φ=500 μm), and the mixture was transferred to R1 (inner diameter: 1000 μm, 100 cm, t R1 =3.16s). The resulting solution was introduced into M2 (φ=500 μm), and methanol (0.1 M THF solution, flow rate: 3.38 mL / min, 1.1 molar equivalents) was introduced thereinto, and the mixture was transferred to R2 (inner diameter 1000 μm, 100 cm, t R2 =2.58s). After reaching a steady state, an aliquot of the product solution was collected for 10 seconds, and a methyl Grignard reagent (methylmagnesium chloride, Fujifilm Wako Pure Chemical Industries, Ltd., 10 molar equivalents relative to the monomer) was added and stirred at 25 °C for 0.5 hours to convert the silicon-containing substituents (post-functionalization). After quenching with methanol, the reaction was treated with saturated aqueous ammonium chloride (NH4Cl) and brine. The solution was diluted with THF and filtered. The resulting solution was analyzed by gel permeation chromatography (GPC) in the same manner as in Comparative Example 1. The results are shown in Table 2 and FIG.

[0142] -2PHLi manufacturing method- 2PHLi was produced by mixing α-methylstyrene (THF solution, manufactured by Tokyo Chemical Industry Co., Ltd.) with 0.6 equivalents of s-BuLi (hexane solution, manufactured by Kanto Chemical Co., Inc.) relative to α-methylstyrene at 20°C using a flow microreactor.

[0143] [Table 2]

[0144] (Comparative Example 10) The flow microreactor system was placed in a bath at 0°C, and a polymer was produced and analyzed in the same manner as in Example 1, except that n-BuLi (hexane solution, manufactured by Kanto Chemical Co., Inc.) was used as the polymerization initiator instead of 2PHLi. The results are shown in Table 2.

[0145] (Comparative Example 11) A polymer was produced and analyzed in the same manner as in Example 1, except that n-BuLi (manufactured by Kanto Chemical Co., Inc.) was used as the polymerization initiator instead of 2PHLi. The results are shown in Table 2 and FIG.

[0146] (Comparative Example 12) The flow microreactor system was placed in a bath at −78° C., and a polymer was produced and analyzed in the same manner as in Example 1, except that n-BuLi (manufactured by Kanto Chemical Co., Inc.) was used as the polymerization initiator instead of 2PHLi. The results are shown in Table 2.

[0147] (Comparative Example 13) The flow microreactor system was placed in a bath at 0°C, and a polymer was produced and analyzed in the same manner as in Example 1, except that s-BuLi (hexane solution, manufactured by Kanto Chemical Co., Inc.) was used as the polymerization initiator instead of 2PHLi. The results are shown in Table 2.

[0148] (Comparative Example 14) A polymer was produced and analyzed in the same manner as in Example 1, except that s-BuLi (manufactured by Kanto Chemical Co., Inc.) was used as the polymerization initiator instead of 2PHLi. The results are shown in Table 2 and FIG.

[0149] (Comparative Example 15) The flow microreactor system was placed in a bath at −78° C., and a polymer was produced and analyzed in the same manner as in Example 1, except that s-BuLi (manufactured by Kanto Chemical Co., Inc.) was used as the polymerization initiator instead of 2PHLi. The results are shown in Table 2.

[0150] (Comparative Example 16) A polymer was produced and analyzed in the same manner as in Comparative Example 13, except that the amount of 4-trimethoxysilylstyrene was changed from 10 molar equivalents to 20 molar equivalents (the flow rate of s-BuLi was half that of Comparative Example 13). The results are shown in Table 2.

[0151] (Comparative Example 17) A polymer was produced and analyzed in the same manner as in Comparative Example 14, except that the amount of 4-trimethoxysilylstyrene was changed from 10 molar equivalents to 20 molar equivalents (the flow rate of s-BuLi was half that of Comparative Example 13). The results are shown in Table 2.

[0152] (Comparative Example 18) A polymer was produced and analyzed in the same manner as in Comparative Example 15, except that the amount of 4-trimethoxysilylstyrene was changed from 10 molar equivalents to 20 molar equivalents (the flow rate of s-BuLi was half that of Comparative Example 13). The results are shown in Table 2.

[0153] (Comparative Example 19) The flow microreactor system was placed in a 0°C bath, and a polymer was produced and analyzed in the same manner as in Example 1, except that DPHLi ((1,1-diphenylhexyl)lithium) prepared from 1,1-diphenylethylene and n-BuLi, prepared by the following method, was used as the polymerization initiator instead of 2PHLi. The results are shown in Table 2.

[0154] (Comparative Example 20) A polymer was produced and analyzed in the same manner as in Example 1, except that DPHLi ((1,1-diphenylhexyl)lithium) prepared from 1,1-diphenylethylene and n-BuLi, prepared by the following method, was used instead of 2PHLi as the polymerization initiator. The results are shown in Table 2 and FIG. 6.

[0155] (Comparative Example 21) The flow microreactor system was placed in a bath at -78°C, and a polymer was produced and analyzed in the same manner as in Example 1, except that DPHLi ((1,1-diphenylhexyl)lithium) prepared from 1,1-diphenylethylene and n-BuLi, prepared by the following method, was used as the polymerization initiator instead of 2PHLi. The results are shown in Table 2.

[0156] -Method for producing DPHLi ((1,1-diphenylhexyl)lithium) prepared from 1,1-diphenylethylene and n-BuLi- DPHLi ((1,1-diphenylhexyl)lithium) was produced by adding 0.6 molar equivalents of n-BuLi (Kanto Chemical Co., Inc.) to a 1,1-diphenylethylene THF solution (prepared by adding THF (Fujifilm Wako Pure Chemical Industries, Ltd.) to 1,1-diphenylethylene (Tokyo Chemical Industry Co., Ltd.)) dropwise at 0°C and stirring for 1 hour.

[0157] The results in Table 2 and Figure 6 show that the molecular weight and dispersion were best controlled when anionic polymerization was performed using a microreactor (flow microreactor) with 2PHLi as the polymerization initiator. Note that because the methylation conditions with the methyl Grignard reagent were not optimized, some methoxy groups may remain. In Table 2, "-" indicates that data could not be collected due to blockage, which is thought to be due to the influence of an increase in molecular weight.

[0158] <3 Polymer Production 3 Anionic Polymerization Using a Microreactor> [ka]

[0159] Furthermore, we investigated the polymerization initiators in the anionic polymerization of 4-trimethoxysilylstyrene using a flow microreactor. As the polymerization initiator, 2PHLi prepared from α-methylstyrene and s-BuLi, or alkyllithium such as n-BuLi or s-BuLi was used. By increasing the flow rate, the mixing efficiency was improved, and the methylation of silicon-containing substituents was fully achieved under conditions that strongly promoted post-functionalization.

[0160] Example 2 As shown in Figure 2, a flow microreactor system was used, which consisted of one V-type micromixer (M1: manufactured by Sanko Seiki Kogyo Co., Ltd.), one T-type micromixer (M2: manufactured by Sanko Seiki Kogyo Co., Ltd.), two microtube reactors (R1 and R2: manufactured by GL Sciences), and three 100 cm pre-cooling units (P1, P2, and P3: manufactured by GL Sciences).

[0161] The flow microreactor system was placed in a bath at −40° C., and 4-trimethoxysilylstyrene (0.846 M THF solution, manufactured by Tokyo Chemical Industry Co., Ltd., flow rate: 12 mL / min, 30 molar equivalents) and 2-phenyl-4-methylhex-2-yl lithium (2PHLi) (0.043 M THF / hexane solution, flow rate: 7.875 mL / min, 1 molar equivalent) prepared by the method described above (Example 1) were mixed in M1 (φ=500 μm), and the mixture was transferred to R1 (inner diameter: 1000 μm, 25 cm, t R1 =0.59s). The resulting solution was introduced into M2 (φ=500 μm), and methanol (0.15 M THF solution, flow rate: 4.5 mL / min, 2 molar equivalents) was introduced thereto, and the mixture was transferred to R2 (inner diameter 1000 μm, 100 cm, t R2 =1.93s). After reaching a steady state, an aliquot of the product solution was collected for 10 seconds, and a methyl Grignard reagent (methylmagnesium chloride, Merck, 16 molar equivalents relative to the monomer) was added. The mixture was stirred under reflux conditions (oil bath temperature 100 °C) for 3 hours to convert the silicon-containing substituents (post-functionalization). After quenching with methanol, the mixture was treated with saturated aqueous ammonium chloride (NH4Cl) and brine. The solution was diluted with THF and filtered. The resulting solution was analyzed by gel permeation chromatography (GPC) in the same manner as in Comparative Example 1. The results are shown in Table 3 and FIG.

[0162] [Table 3]

[0163] (Comparative Example 22) A polymer was produced and analyzed in the same manner as in Example 1, except that n-BuLi (manufactured by Kanto Chemical Co., Inc.) was used as the polymerization initiator instead of 2PHLi. The results are shown in Table 3 and FIG.

[0164] (Comparative Example 23) A polymer was produced and analyzed in the same manner as in Example 1, except that s-BuLi (manufactured by Kanto Chemical Co., Inc.) was used as the polymerization initiator instead of 2PHLi. The results are shown in Table 3 and FIG.

[0165] The results in Table 3 and FIG. 7 show that the molecular weight and dispersion are best controlled when anionic polymerization is carried out using a microreactor (flow microreactor) using 2PHLi as a polymerization initiator.

[0166] <4 Polymer Production 4 Anionic Polymerization Using a Microreactor> [ka]

[0167] In order to investigate the reaction conditions for anionic polymerization using a microreactor (flow microreactor) with 2PHLi as a polymerization initiator, the residence time and reaction temperature of the polymerization reaction were investigated.

[0168] Example 3 As shown in Figure 3, a flow microreactor system was used, which consisted of two V-type micromixers (M1 and M2: manufactured by Sanko Seiki Kogyo Co., Ltd.), one T-type micromixer (M3: manufactured by Sanko Seiki Kogyo Co., Ltd.), three microtube reactors (R1, R2, and R3: manufactured by GL Sciences), and four 100 cm pre-cooling units (P1, P2, P3, and P4: manufactured by GL Sciences).

[0169] The flow reactor consisting of P1, P2, M1 and R1 was cooled at 20°C, and the flow reactor consisting of P3, P4, M2, M3, R2 and R3 was cooled at 20°C. The first half (flow reactor consisting of P1, P2, M1, and R1) and the second half (flow reactor consisting of P3, P4, M2, M3, R2, and R3) of the stainless steel reactor were connected with a PTFE tube. α-Methylstyrene (0.09 M THF solution, flow rate: 4.22 mL / min, 1.5 molar equivalents relative to sec-BuLi) and sec-BuLi (0.15 M THF solution, flow rate: 1.69 mL / min) were introduced into M1 (φ = 250 μm) using a syringe pump, and the mixture (initiator solution) was passed through R1 (inner diameter 1000 μm, 212.5 cm).

[0170] Next, the initiator solution and 4-trimethoxysilylstyrene (0.285 M THF solution, flow rate: 9.0 mL / min, 10 molar equivalents) were mixed in M2 (φ=500 μm), and the mixture was passed through R2 (inner diameter 1000 μm, 100 cm). The obtained solution was introduced into M3 (φ=500 μm), and methanol (0.0825 M THF solution, flow rate: 3.38 mL / min, 1.1 molar equivalents) was introduced thereto, and the mixture was passed through R3 (inner diameter 1000 μm, 100 cm). After reaching a steady state, an aliquot of the product solution was collected for 10 seconds, and a methyl Grignard reagent (methylmagnesium chloride, Fujifilm Wako Pure Chemical Industries, Ltd. or Merck, 12 molar equivalents relative to the monomer) was added and stirred at 25 °C for 3 hours to convert the silicon-containing substituents (post-functionalization). After quenching with methanol, the reaction was treated with saturated aqueous ammonium chloride (NH4Cl) and brine. The solution was diluted with THF and filtered. The resulting solution was analyzed by gel permeation chromatography (GPC) in the same manner as in Comparative Example 1. The results are shown in Table 4 and FIG.

[0171] [Table 4]

[0172] Example 4 Except for changing the length of R2 from 100 cm to 200 cm, a polymer was produced and analyzed in the same manner as in Example 3. The results are shown in Table 4 and Figure 8.

[0173] Example 5 Except for changing the length of R2 from 100 cm to 300 cm, a polymer was produced and analyzed in the same manner as in Example 3. The results are shown in Table 4 and Figure 8.

[0174] Example 6 Except for changing the length of R2 from 100 cm to 400 cm, a polymer was produced and analyzed in the same manner as in Example 3. The results are shown in Table 4 and Figure 8.

[0175] Example 7 A polymer was produced and analyzed in the same manner as in Example 3, except that the flow reactor composed of P3, P4, M2, M3, R2, and R3 was cooled to 0° C. The results are shown in Table 4 and FIG. The stainless steel reactors in the cooling baths at different temperatures were connected with PTFE tubes. This was also the case in Examples 8 to 12.

[0176] Example 8 A polymer was produced and analyzed in the same manner as in Example 3, except that the flow reactor consisting of P3, P4, M2, M3, R2, and R3 was cooled to 0°C and the length of R2 was changed from 100 cm to 200 cm. The results are shown in Table 4.

[0177] Example 9 A polymer was produced and analyzed in the same manner as in Example 3, except that the flow reactor consisting of P3, P4, M2, M3, R2, and R3 was cooled to 0°C and the length of R2 was changed from 100 cm to 300 cm. The results are shown in Table 4.

[0178] Example 10 A polymer was produced and analyzed in the same manner as in Example 3, except that the flow reactor consisting of P3, P4, M2, M3, R2, and R3 was cooled to 0°C and the length of R2 was changed from 100 cm to 400 cm. The results are shown in Table 4.

[0179] Example 11 A polymer was produced and analyzed in the same manner as in Example 3, except that the flow reactor consisting of P3, P4, M2, M3, R2, and R3 was cooled to −78° C. The results are shown in Table 4 and FIG.

[0180] Example 12 A polymer was produced and analyzed in the same manner as in Example 3, except that the flow reactor consisting of P3, P4, M2, M3, R2, and R3 was cooled to −40° C. The results are shown in Table 4 and FIG.

[0181] Example 13 A polymer was produced and analyzed in the same manner as in Example 12, except that the amount of 4-trimethoxysilylstyrene was changed from 10 molar equivalents to 30 molar equivalents (the concentration of α-methylstyrene was 0.846 M). The results are shown in Table 5 and Figure 10.

[0182] [Table 5]

[0183] Example 14 Polymers were prepared and analyzed in the same manner as in Example 13, except that the amount of 4-trimethoxysilylstyrene was changed from 10 to 30 molar equivalents (the concentration of α-methylstyrene was 0.846 M) and the length of R2 was changed from 100 cm to 300 cm. The results are shown in Table 5 and Figure 10. In Table 6, "-" means that the variance was not calculated due to multimodality.

[0184] Example 15 A polymer was produced and analyzed in the same manner as in Example 7, except that the amount of 4-trimethoxysilylstyrene was changed from 10 molar equivalents to 20 molar equivalents (the concentration of α-methylstyrene was 0.564 M). The results are shown in Table 6 and Figure 11.

[0185] [Table 6]

[0186] Example 16 A polymer was produced and analyzed in the same manner as in Example 12, except that the amount of 4-trimethoxysilylstyrene was changed from 10 molar equivalents to 20 molar equivalents (the concentration of α-methylstyrene was 0.564 M). The results are shown in Table 6 and Figure 11.

[0187] Example 17 Polymers were prepared and analyzed in the same manner as in Example 12, except that the amount of 4-trimethoxysilylstyrene was changed from 10 to 20 molar equivalents (the concentration of α-methylstyrene was 0.564 M) and the length of R2 was changed from 100 cm to 300 cm. The results are shown in Table 6 and Figure 11.

[0188] The results in Tables 4 to 6 and Figures 8 to 11 show that when anionic polymerization was performed using a microreactor (flow microreactor) with 2PHLi as the polymerization initiator, increasing the residence time of R2 increased the dispersion. Lowering the cooling temperature of the flow reactor consisting of P3, P4, M2, M3, R2, and R3 from 20°C to -40°C reduced the molecular weight and narrowed the dispersion. This is likely due to the suppression of side reactions such as dimerization by shortening the residence time and lowering the reaction temperature. It is possible that some methoxy groups remained because the methylation conditions with the methyl Grignard reagent were not optimized.

[0189] <5 Polymer Production 5 Anionic Polymerization Using a Microreactor> [ka]

[0190] We investigated the effect of mixing efficiency on the polymerization of 4-trimethoxysilylstyrene when performing anionic polymerization using a microreactor (flow microreactor) with 2PHLi as the polymerization initiator. Specifically, we set flow rates by multiplying each flow rate by a variable as the liquid transport condition so that the equivalent ratio of each raw material did not change, and evaluated the dispersion of the polymer obtained under conditions of low flow rate, i.e., conditions where the mixing performance of the mixer was poor.

[0191] Example 18 As shown in Figure 3, a flow microreactor system was used, which consisted of two V-type micromixers (M1 and M2: manufactured by Sanko Seiki Kogyo Co., Ltd.), one T-type micromixer (M3: manufactured by Sanko Seiki Kogyo Co., Ltd.), three microtube reactors (R1, R2, and R3: manufactured by GL Sciences), and four 100 cm pre-cooling units (P1, P2, P3, and P4: manufactured by GL Sciences).

[0192] The flow reactor consisting of P1, P2, M1 and R1 was cooled to 20°C, and the flow reactor consisting of P3, P4, M2, M3, R2 and R3 was cooled to -40°C. The stainless steel reactors in cooling baths at different temperatures were connected with PTFE tubing. α-Methylstyrene (0.12 M THF solution, flow rate: 5.625 mL / min, 1.5 molar equivalents relative to sec-BuLi) and sec-BuLi (0.2 M hexane solution, flow rate: 2.25 mL / min) were introduced into M1 (φ = 250 μm) using a syringe pump, and the mixture (initiator solution) was passed through R1 (inner diameter 1000 μm, 212.5 cm).

[0193] Next, the initiator solution and 4-trimethoxysilylstyrene (0.375 M THF solution, manufactured by Tokyo Chemical Industry Co., Ltd., flow rate: 12.0 mL / min, 10 molar equivalents) were mixed in M2 (φ=500 μm), and the mixture was passed through R2 (inner diameter 1000 μm, 100 cm). The obtained solution was introduced into M3 (φ=500 μm), and methanol (0.11 M THF solution, flow rate: 4.5 mL / min, 1.1 molar equivalents) was introduced thereto, and the mixture was passed through R3 (inner diameter 1000 μm, 100 cm). After 50 seconds of flow until the flow reached a steady state (50 seconds of stabilization time), an aliquot of the product solution was collected for 10 seconds, and a methyl Grignard reagent (methylmagnesium chloride, Fujifilm Wako Pure Chemical Industries, Ltd., 12 molar equivalents relative to the monomer) was added and stirred at 25 °C for 20 minutes to convert the silicon-containing substituents (post-functionalization). After quenching with methanol, the reaction was treated with saturated aqueous ammonium chloride (NH4Cl) and brine. The solution was diluted with THF and filtered. The resulting solution was analyzed by gel permeation chromatography (GPC) in the same manner as in Comparative Example 1. The results are shown in Tables 7 and 8.

[0194] [Table 7]

[0195] Example 19 A polymer was produced and analyzed in the same manner as in Example 18, except that the concentrations of α-methylstyrene, s-BuLi, 4-trimethoxysilylstyrene, and methanol were each 3 / 4 as shown in Table 7. The results are shown in Table 7.

[0196] Example 20 A polymer was produced and analyzed in the same manner as in Example 18, except that the concentrations of α-methylstyrene, s-BuLi, 4-trimethoxysilylstyrene, and methanol were each 3 / 4 as shown in Table 7, and the total flow rate of α-methylstyrene, s-BuLi, 4-trimethoxysilylstyrene, and methanol was 6.1 mL / min, which is 1 / 4 of the 24.4 mL / min. The results are shown in Table 7.

[0197] Example 21 A polymer was produced and analyzed in the same manner as in Example 18, except that the concentrations of α-methylstyrene, s-BuLi, 4-trimethoxysilylstyrene, and methanol were each half as shown in Table 7. The results are shown in Table 7.

[0198] Example 22 A polymer was produced and analyzed in the same manner as in Example 18, except that the concentrations of α-methylstyrene, s-BuLi, 4-trimethoxysilylstyrene, and methanol were each half as shown in Table 7, and the total flow rate of α-methylstyrene, s-BuLi, 4-trimethoxysilylstyrene, and methanol was 12.2 mL / min, which is half of the 24.4 mL / min. The results are shown in Table 7.

[0199] Example 23 A polymer was produced and analyzed in the same manner as in Example 18, except that the concentrations of α-methylstyrene, s-BuLi, 4-trimethoxysilylstyrene, and methanol were each 3 / 4, the total flow rate of α-methylstyrene, s-BuLi, 4-trimethoxysilylstyrene, and methanol was 18.3 mL / min (3 / 4 of 24.4 mL / min), and the stabilization time was changed from 50 seconds to 30 seconds. The results are shown in Table 8 and Figure 12.

[0200] [Table 8]

[0201] Example 24 A polymer was produced and analyzed in the same manner as in Example 18, except that the concentrations of α-methylstyrene, s-BuLi, 4-trimethoxysilylstyrene, and methanol were each 3 / 4, the total flow rate of α-methylstyrene, s-BuLi, 4-trimethoxysilylstyrene, and methanol was 18.3 mL / min (3 / 4 of 24.4 mL / min), and the stabilization time was changed from 50 seconds to 40 seconds. The results are shown in Table 8 and Figure 12.

[0202] Example 25 A polymer was produced and analyzed in the same manner as in Example 18, except that the concentrations of α-methylstyrene, s-BuLi, 4-trimethoxysilylstyrene, and methanol were each 3 / 4, and the total flow rate of α-methylstyrene, s-BuLi, 4-trimethoxysilylstyrene, and methanol was 18.3 mL / min, which is 3 / 4 of the 24.4 mL / min. The results are shown in Table 8 and Figure 12.

[0203] Example 26 A polymer was produced and analyzed in the same manner as in Example 18, except that the concentrations of α-methylstyrene, s-BuLi, 4-trimethoxysilylstyrene, and methanol were each 3 / 4, the total flow rate of α-methylstyrene, s-BuLi, 4-trimethoxysilylstyrene, and methanol was 18.3 mL / min (3 / 4 of 24.4 mL / min), and the stabilization time was changed from 50 seconds to 70 seconds. The results are shown in Table 8 and Figure 12.

[0204] Example 27 A polymer was produced and analyzed in the same manner as in Example 18, except that the concentrations of α-methylstyrene, s-BuLi, 4-trimethoxysilylstyrene, and methanol were each 3 / 4, the total flow rate of α-methylstyrene, s-BuLi, 4-trimethoxysilylstyrene, and methanol was 12.2 mL / min (half of 24.4 mL / min), and the stabilization time was changed from 50 seconds to 30 seconds. The results are shown in Table 8 and Figure 13.

[0205] Example 28 A polymer was produced and analyzed in the same manner as in Example 18, except that the concentrations of α-methylstyrene, s-BuLi, 4-trimethoxysilylstyrene, and methanol were each changed to 3 / 4, the total flow rate of α-methylstyrene, s-BuLi, 4-trimethoxysilylstyrene, and methanol was changed to 12.2 mL / min (half of 24.4 mL / min), and the stabilization time was changed from 50 seconds to 40 seconds. The results are shown in Table 8 and Figure 13.

[0206] Example 29 A polymer was produced and analyzed in the same manner as in Example 18, except that the concentrations of α-methylstyrene, s-BuLi, 4-trimethoxysilylstyrene, and methanol were each 3 / 4 and the total flow rate of α-methylstyrene, s-BuLi, 4-trimethoxysilylstyrene, and methanol was 12.2 mL / min, half of the 24.4 mL / min. The results are shown in Table 8 and Figure 13.

[0207] Example 30 A polymer was produced and analyzed in the same manner as in Example 18, except that the concentrations of α-methylstyrene, s-BuLi, 4-trimethoxysilylstyrene, and methanol were each 3 / 4, the total flow rate of α-methylstyrene, s-BuLi, 4-trimethoxysilylstyrene, and methanol was 12.2 mL / min (half of 24.4 mL / min), and the stabilization time was changed from 50 seconds to 70 seconds. The results are shown in Table 8 and Figure 13.

[0208] The results in Tables 7 and 8 and Figures 12 and 13 show that when anionic polymerization was performed using a microreactor (flow microreactor) with 2PHLi as the polymerization initiator, decreasing the flow rate (total flow rate of 6.1 mL / min or 12.2 mL / min) increased the variance to about 1.5, whereas increasing the flow rate (total flow rate of 18.3 mL / min or 24.4 mL / min) decreased the variance. The effect of concentration was not significant within the range investigated.

[0209] <6 Polymer Production 6 Anionic Polymerization Using a Microreactor> [ka]

[0210] Anionic polymerization was carried out using a microreactor (flow microreactor) with 2PHLi as a polymerization initiator, and the residence time and reaction temperature of the polymerization reaction were investigated when 20 molar equivalents of monomer were used.

[0211] Example 31 As shown in Figure 3, a flow microreactor system was used, which consisted of two V-type micromixers (M1 and M2: manufactured by Sanko Seiki Kogyo Co., Ltd.), one T-type micromixer (M3: manufactured by Sanko Seiki Kogyo Co., Ltd.), three microtube reactors (R1, R2, and R3: manufactured by GL Sciences), and four 100 cm pre-cooling units (P1, P2, P3, and P4: manufactured by GL Sciences).

[0212] The flow reactor consisting of P1, P2, M1 and R1 was cooled at 20°C, and the flow reactor consisting of P3, P4, M2, M3, R2 and R3 was cooled at 20°C. The first half (flow reactor consisting of P1, P2, M1, and R1) and the second half (flow reactor consisting of P3, P4, M2, M3, R2, and R3) of the stainless steel reactor were connected with a PTFE tube. α-Methylstyrene (0.09 M THF solution, flow rate: 4.22 mL / min, 1.5 molar equivalents relative to sec-BuLi) and sec-BuLi (0.15 M hexane solution, flow rate: 1.69 mL / min) were introduced into M1 (φ = 250 μm) by a syringe pump, and the mixture (initiator solution) was passed through R1 (inner diameter 1000 μm, 212.5 cm).

[0213] Next, the initiator solution and 4-trimethoxysilylstyrene (0.564 M THF solution, manufactured by Tokyo Chemical Industry Co., Ltd., flow rate: 9.0 mL / min, 20 molar equivalents) were mixed in M2 (φ=500 μm), and the mixture was passed through R2 (inner diameter 1000 μm, 50 cm). The obtained solution was introduced into M3 (φ=500 μm), and methanol (0.0827 M THF solution, flow rate: 3.38 mL / min, 1.1 molar equivalents) was introduced thereto, and the mixture was passed through R3 (inner diameter 1000 μm, 100 cm). After reaching a steady state, an aliquot of the product solution was collected for 10 seconds, and a methyl Grignard reagent (methylmagnesium chloride, Merck, 24 molar equivalents relative to the monomer) was added. The mixture was stirred under reflux (oil bath temperature 100 °C) for 2.5 hours to convert the silicon-containing substituents (post-functionalization). After quenching with methanol, the reaction was treated with saturated aqueous ammonium chloride (NH4Cl) and brine. The solution was diluted with THF and filtered. The resulting solution was analyzed by gel permeation chromatography (GPC) in the same manner as in Comparative Example 1. The results are shown in Table 9 and FIG.

[0214] [Table 9]

[0215] Example 32 A polymer was produced and analyzed in the same manner as in Example 31, except that the length of R2 was changed from 50 cm to 100 cm. The results are shown in Table 9 and Figure 15.

[0216] Example 33 A polymer was produced and analyzed in the same manner as in Example 31, except that the flow reactor consisting of P3, P4, M2, M3, R2, and R3 was cooled to 0° C. The results are shown in Table 9 and FIG. The stainless steel reactors in the cooling baths at different temperatures were connected with PTFE tubes. This was also the case in Examples 34 to 48.

[0217] Example 34 A polymer was produced and analyzed in the same manner as in Example 31, except that the flow reactor consisting of P3, P4, M2, M3, R2, and R3 was cooled to 0°C and the length of R2 was changed from 50 cm to 100 cm. The results are shown in Table 9 and Figure 15.

[0218] Example 35 A polymer was produced and analyzed in the same manner as in Example 31, except that the flow reactor consisting of P3, P4, M2, M3, R2, and R3 was cooled to 0°C and the length of R2 was changed from 50 cm to 200 cm. The results are shown in Table 9.

[0219] Example 36 A polymer was produced and analyzed in the same manner as in Example 31, except that the flow reactor consisting of P3, P4, M2, M3, R2, and R3 was cooled to 0°C and the length of R2 was changed from 50 cm to 300 cm. The results are shown in Table 9.

[0220] Example 37 A polymer was produced and analyzed in the same manner as in Example 31, except that the flow reactor consisting of P3, P4, M2, M3, R2, and R3 was cooled to −20° C. The results are shown in Table 9 and FIG.

[0221] Example 38 A polymer was produced and analyzed in the same manner as in Example 31, except that the flow reactor consisting of P3, P4, M2, M3, R2, and R3 was cooled to -20°C and the length of R2 was changed from 50 cm to 100 cm. The results are shown in Table 9 and Figure 15.

[0222] Example 39 A polymer was produced and analyzed in the same manner as in Example 31, except that the flow reactor consisting of P3, P4, M2, M3, R2, and R3 was cooled to -20°C and the length of R2 was changed from 50 cm to 200 cm. The results are shown in Table 9.

[0223] Example 40 A polymer was produced and analyzed in the same manner as in Example 31, except that the flow reactor consisting of P3, P4, M2, M3, R2, and R3 was cooled to -20°C and the length of R2 was changed from 50 cm to 300 cm. The results are shown in Table 9.

[0224] Example 41 A polymer was produced and analyzed in the same manner as in Example 31, except that the flow reactor consisting of P3, P4, M2, M3, R2, and R3 was cooled to −40° C. The results are shown in Table 9 and FIG.

[0225] Example 42 A polymer was produced and analyzed in the same manner as in Example 31, except that the flow reactor consisting of P3, P4, M2, M3, R2, and R3 was cooled to -40°C and the length of R2 was changed from 50 cm to 100 cm. The results are shown in Table 9 and Figure 15.

[0226] Example 43 A polymer was produced and analyzed in the same manner as in Example 31, except that the flow reactor consisting of P3, P4, M2, M3, R2, and R3 was cooled to -40°C and the length of R2 was changed from 50 cm to 200 cm. The results are shown in Table 9.

[0227] Example 44 A polymer was produced and analyzed in the same manner as in Example 31, except that the flow reactor consisting of P3, P4, M2, M3, R2, and R3 was cooled to -40°C and the length of R2 was changed from 50 cm to 300 cm. The results are shown in Table 9.

[0228] Example 45 A polymer was produced and analyzed in the same manner as in Example 31, except that the flow reactor consisting of P3, P4, M2, M3, R2, and R3 was cooled to −78° C. The results are shown in Table 9, Figures 14 and 16.

[0229] Example 46 A polymer was produced and analyzed in the same manner as in Example 31, except that the flow reactor consisting of P3, P4, M2, M3, R2, and R3 was cooled to -78°C and the length of R2 was changed from 50 cm to 100 cm. The results are shown in Table 9 and Figures 15 and 16.

[0230] Example 47 A polymer was produced and analyzed in the same manner as in Example 31, except that the flow reactor consisting of P3, P4, M2, M3, R2, and R3 was cooled to -78°C and the length of R2 was changed from 50 cm to 200 cm. The results are shown in Table 9 and Figure 16.

[0231] Example 48 A polymer was produced and analyzed in the same manner as in Example 31, except that the flow reactor consisting of P3, P4, M2, M3, R2, and R3 was cooled to -78°C and the length of R2 was changed from 50 cm to 300 cm. The results are shown in Table 9 and Figure 16.

[0232] The results in Table 9 and Figures 14 to 16 show that when anionic polymerization is performed using a microreactor (flow microreactor) with 2PHLi as the polymerization initiator and 20 molar equivalents of monomer, if the monomer remains unconsumed, the GPC spectrum (not showing a normal distribution) becomes significantly distorted. This is thought to be due to crosslinking by siloxane bonds.

[0233] <7 Polymer Production 7 Anionic Polymerization Using a Microreactor> [ka]

[0234] Anionic polymerization was carried out using a microreactor (flow microreactor) with 2PHLi as a polymerization initiator, and the residence time and reaction temperature of the polymerization reaction were investigated when 30 molar equivalents of monomer were used.

[0235] Example 49 As shown in Figure 3, a flow microreactor system was used, which consisted of two V-type micromixers (M1 and M2: manufactured by Sanko Seiki Kogyo Co., Ltd.), one T-type micromixer (M3: manufactured by Sanko Seiki Kogyo Co., Ltd.), three microtube reactors (R1, R2, and R3: manufactured by GL Sciences), and four 100 cm pre-cooling units (P1, P2, P3, and P4: manufactured by GL Sciences).

[0236] The flow reactor consisting of P1, P2, M1 and R1 was cooled to 20°C, and the flow reactor consisting of P3, P4, M2, M3, R2 and R3 was cooled to 0°C. The stainless steel reactors in cooling baths at different temperatures were connected with PTFE tubing. α-Methylstyrene (0.09 M THF solution, flow rate: 4.22 mL / min, 1.5 molar equivalents relative to sec-BuLi) and sec-BuLi (0.15 M hexane solution, flow rate: 1.69 mL / min) were introduced into M1 (φ = 250 μm) by a syringe pump, and the mixture (initiator solution) was passed through R1 (inner diameter 1000 μm, 212.5 cm).

[0237] Next, the initiator solution and 4-trimethoxysilylstyrene (0.846 M THF solution, manufactured by Tokyo Chemical Industry Co., Ltd., flow rate: 9.0 mL / min, 30 molar equivalents) were mixed in M2 (φ=500 μm), and the mixture was passed through R2 (inner diameter 1000 μm, 50 cm). The obtained solution was introduced into M3 (φ=500 μm), and methanol (0.0827 M THF solution, flow rate: 3.38 mL / min, 1.1 molar equivalents) was introduced thereto, and the mixture was passed through R3 (inner diameter 1000 μm, 100 cm). After reaching a steady state, an aliquot of the product solution was collected for 10 seconds, and a methyl Grignard reagent (methylmagnesium chloride, Merck, 16 molar equivalents relative to the monomer) was added. The mixture was stirred under reflux conditions (oil bath temperature 100 °C) for 3 hours to convert the silicon-containing substituents (post-functionalization). After quenching with methanol, the mixture was treated with saturated aqueous ammonium chloride (NH4Cl) and brine. The solution was diluted with THF and filtered. The resulting solution was analyzed by gel permeation chromatography (GPC) in the same manner as in Comparative Example 1. The results are shown in Table 10 and FIG.

[0238] [Table 10]

[0239] Example 50 A polymer was produced and analyzed in the same manner as in Example 49, except that the length of R2 was changed from 50 cm to 100 cm. The results are shown in Table 10 and Figure 18.

[0240] Example 51 A polymer was produced and analyzed in the same manner as in Example 49, except that the length of R2 was changed from 50 cm to 200 cm. The results are shown in Table 10.

[0241] Example 52 A polymer was produced and analyzed in the same manner as in Example 49, except that the length of R2 was changed from 50 cm to 300 cm. The results are shown in Table 10.

[0242] Example 53 A polymer was produced and analyzed in the same manner as in Example 49, except that the flow reactor consisting of P3, P4, M2, M3, R2, and R3 was cooled to −20° C. The results are shown in Table 10 and FIG.

[0243] Example 54 A polymer was produced and analyzed in the same manner as in Example 49, except that the flow reactor consisting of P3, P4, M2, M3, R2, and R3 was cooled to -20°C and the length of R2 was changed from 50 cm to 100 cm. The results are shown in Table 10 and Figure 18.

[0244] Example 55 A polymer was produced and analyzed in the same manner as in Example 49, except that the flow reactor consisting of P3, P4, M2, M3, R2, and R3 was cooled to -20°C and the length of R2 was changed from 50 cm to 200 cm. The results are shown in Table 10.

[0245] Example 56 A polymer was produced and analyzed in the same manner as in Example 49, except that the flow reactor consisting of P3, P4, M2, M3, R2, and R3 was cooled to -20°C and the length of R2 was changed from 50 cm to 300 cm. The results are shown in Table 10.

[0246] Example 57 A polymer was produced and analyzed in the same manner as in Example 49, except that the flow reactor consisting of P3, P4, M2, M3, R2, and R3 was cooled to −40° C. The results are shown in Table 10 and FIG.

[0247] Example 58 A polymer was produced and analyzed in the same manner as in Example 49, except that the flow reactor consisting of P3, P4, M2, M3, R2, and R3 was cooled to -40°C and the length of R2 was changed from 50 cm to 100 cm. The results are shown in Table 10 and Figure 18.

[0248] Example 59 A polymer was produced and analyzed in the same manner as in Example 49, except that the flow reactor consisting of P3, P4, M2, M3, R2, and R3 was cooled to -40°C and the length of R2 was changed from 50 cm to 200 cm. The results are shown in Table 10.

[0249] Example 60 A polymer was produced and analyzed in the same manner as in Example 49, except that the flow reactor consisting of P3, P4, M2, M3, R2, and R3 was cooled to -40°C and the length of R2 was changed from 50 cm to 300 cm. The results are shown in Table 10.

[0250] Example 61 A polymer was produced and analyzed in the same manner as in Example 49, except that the flow reactor consisting of P3, P4, M2, M3, R2, and R3 was cooled to −78° C. The results are shown in Table 10 and Figures 17 and 19.

[0251] Example 62 A polymer was produced and analyzed in the same manner as in Example 49, except that the flow reactor consisting of P3, P4, M2, M3, R2, and R3 was cooled to -78°C and the length of R2 was changed from 50 cm to 100 cm. The results are shown in Table 10 and Figures 18 and 19.

[0252] Example 63 A polymer was produced and analyzed in the same manner as in Example 49, except that the flow reactor consisting of P3, P4, M2, M3, R2, and R3 was cooled to -78°C and the length of R2 was changed from 50 cm to 200 cm. The results are shown in Table 10.

[0253] Example 64 A polymer was produced and analyzed in the same manner as in Example 49, except that the flow reactor consisting of P3, P4, M2, M3, R2, and R3 was cooled to −78°C and the length of R2 was changed from 50 cm to 300 cm. The results are shown in Table 10.

[0254] The results in Table 10 and Figures 17 to 19 show that when anionic polymerization is performed using a microreactor (flow microreactor) with 2PHLi as the polymerization initiator and 30 molar equivalents of monomer, if the monomer remains unconsumed, the GPC spectrum (not showing a normal distribution) becomes significantly distorted. This is thought to be due to crosslinking by siloxane bonds.

[0255] <8. Study of methylation using a batch reactor> As a post-functionalization, after polymerization of 4-trimethoxysilylstyrene, the resulting polymer was converted to functional groups with a methyl Grignard reagent. Therefore, we investigated the methylation rate with a methyl Grignard reagent.

[0256] Example 65 The polymer was prepared in the same manner as in Example 7, except that the post-functionalization reaction time was changed from 3 hours to 4 hours. By the method described below in "-1H NMR-", 1 The methylation rate was analyzed by H NMR, and the results are shown in Table 11.

[0257] - 1 H NMR Using Varian MERCURYplus-400 or JEOL JNM-ECZ400S 1 H NMR measurements were carried out. The protons of the methoxy group on the silicon atom are observed in the range of 3.3 to 3.4 ppm, and the protons of the methyl group on the silicon atom are observed in the range of 0.1 to 0.4 ppm. Therefore, the methylation rate was evaluated based on the peak integrated value in each range.

[0258] [Table 11]

[0259] Example 66 The polymer was prepared and analyzed in the same manner as in Example 65, except that the post-functionalization reaction temperature was changed from 25° C. to 60° C. The results are shown in Table 11.

[0260] Example 67 The polymer was prepared and analyzed in the same manner as in Example 16, except that the amount of methyl Grignard reagent was changed from 12 to 18 molar equivalents, the post-functionalization reaction temperature was changed from 25° C. to 60° C., and the post-functionalization reaction time was changed from 3 to 4 hours. The results are shown in Table 11.

[0261] Example 68 A polymer was prepared and analyzed in the same manner as in Example 67, except that the amount of methyl Grignard reagent was changed from 18 molar equivalents to 24 molar equivalents, post-functionalization was performed under reflux conditions (oil bath temperature 100°C), and the post-functionalization reaction time was changed from 4 hours to 2 hours. The results are shown in Table 11.

[0262] Example 69 A polymer was produced and analyzed in the same manner as in Example 41, except that the amount of methyl Grignard reagent was changed from 24 molar equivalents to 16 molar equivalents and the reaction time was changed from 2.5 hours to 3 hours. The results are shown in Table 11. The polymer obtained in Example 69 was subjected to MALDI-TOF-MS analysis using the method described below in "-MALDI / TOFMS-". The results are shown in Figure 20. It was found that the repeating unit was 176, and that all three trimethoxy groups on the silicon atom had been converted to methyl groups.

[0263] -MALDI / TOFMS- Mass spectrometry was performed using a Bruker Daltonics UltrafleXtreme MALDI-TOF mass spectrometer. The polymers were dissolved in THF and applied to the plate. DCTB was used as the matrix, and sodium or silver salts were used as additives as appropriate.

[0264] From the results in Table 11 and FIG. 20, it was found that the methylation rate can be adjusted by adjusting the amount of methyl Grignard reagent, the reaction temperature and reaction time of post-functionalization.

[0265] <9. Polymer Stability Study> [ka]

[0266] Anionic polymerization was carried out using a microreactor (flow microreactor), and the stability of the obtained polymer was investigated.

[0267] Example 70 As shown in Figure 3, a flow microreactor system was used, which consisted of two V-type micromixers (M1 and M2: manufactured by Sanko Seiki Kogyo Co., Ltd.), one T-type micromixer (M3: manufactured by Sanko Seiki Kogyo Co., Ltd.), three microtube reactors (R1, R2, and R3: manufactured by GL Sciences), and four 100 cm pre-cooling units (P1, P2, P3, and P4: manufactured by GL Sciences).

[0268] The flow reactor consisting of P1, P2, M1 and R1 was cooled to 20°C, and the flow reactor consisting of P3, P4, M2, M3, R2 and R3 was cooled to -40°C. The stainless steel reactors in cooling baths at different temperatures were connected with PTFE tubing. α-Methylstyrene (0.12 M THF solution, flow rate: 5.625 mL / min, 1.5 molar equivalents relative to sec-BuLi) and sec-BuLi (0.2 M hexane solution, flow rate: 2.25 mL / min) were introduced into M1 (φ = 250 μm) using a syringe pump, and the mixture (initiator solution) was passed through R1 (inner diameter 1000 μm, 212.5 cm).

[0269] Next, the initiator solution and 4-trimethoxysilylstyrene (0.375 M THF solution, manufactured by Tokyo Chemical Industry Co., Ltd., flow rate: 12.0 mL / min, 10 molar equivalents) were mixed in M2 (φ=500 μm), and the mixture was passed through R2 (inner diameter 1000 μm, 100 cm). The obtained solution was introduced into M3 (φ=500 μm), and methanol (0.11 M THF solution, flow rate: 4.5 mL / min, 1.1 molar equivalents) was introduced thereto, and the mixture was passed through R3 (inner diameter 1000 μm, 100 cm). After steady state was reached, an aliquot of the product solution was collected for 10 seconds, diluted with THF, and filtered. The resulting solution was analyzed by gel permeation chromatography (GPC) on the same day as the polymerization (within about 3 hours) in the same manner as in Comparative Example 1. The results are shown in the lower left part of FIG.

[0270] Example 71 A polymer was produced and analyzed in the same manner as in Example 70, except that the amount of 4-trimethoxysilylstyrene was changed from 10 molar equivalents to 20 molar equivalents. The results are shown in the lower left corner of Figure 21.

[0271] Example 72 A polymer was produced and analyzed in the same manner as in Example 70, except that the amount of 4-trimethoxysilylstyrene was changed from 10 molar equivalents to 30 molar equivalents. The results are shown in the lower left corner of Figure 21.

[0272] Example 73 The polymer was produced and analyzed in the same manner as in Example 70, except that the analysis was carried out by gel permeation chromatography (GPC) one day (approximately 18 hours) after polymerization. The results are shown in the lower left of Figure 21.

[0273] Example 74 A polymer was produced and analyzed in the same manner as in Example 70, except that the amount of 4-trimethoxysilylstyrene was changed from 10 molar equivalents to 20 molar equivalents, and analysis was performed by gel permeation chromatography (GPC) one day (approximately 18 hours) after polymerization. The results are shown in the lower left corner of Figure 21.

[0274] Example 75 A polymer was produced and analyzed in the same manner as in Example 70, except that the amount of 4-trimethoxysilylstyrene was changed from 10 molar equivalents to 30 molar equivalents, and analysis was performed by gel permeation chromatography (GPC) one day (approximately 18 hours) after polymerization. The results are shown in the lower left corner of Figure 21.

[0275] Example 76 The polymer produced in Example 69 was analyzed by gel permeation chromatography (GPC), and the results are shown in the lower right corner of Figure 21.

[0276] Example 77 The polymer produced in Example 69 was analyzed by gel permeation chromatography (GPC) after 11 days, and the results are shown in the lower right of FIG.

[0277] As shown in Figure 21, when the polymer obtained by the method of the present invention was analyzed by GPC on the same day as polymerization, a shoulder peak was observed in the GPC spectrum. When the polymer was analyzed by GPC again one day after polymerization, it was found that the GPC spectrum shifted significantly toward the higher molecular weight side. On the other hand, by converting the methoxy groups of the polymer obtained by the method of the present invention to methyl groups, the spectrum of the polymer remained unchanged even after 11 days. This is thought to be due to crosslinking by siloxane bonds.

[0278] <10 Polymer Production 8 Anionic Polymerization Using Microreactors> The effects of residence time and reaction temperature on anionic polymerization using a microreactor (flow microreactor) were investigated using 2PHLi as a polymerization initiator.

[0279] [ka]

[0280] Example 78 As shown in Figure 3, a flow microreactor system was used, which consisted of two V-type micromixers (M1 and M2: manufactured by Sanko Seiki Kogyo Co., Ltd.), one T-type micromixer (M3: manufactured by Sanko Seiki Kogyo Co., Ltd.), three microtube reactors (R1, R2, and R3: manufactured by GL Sciences), and four 100 cm pre-cooling units (P1, P2, P3, and P4: manufactured by GL Sciences).

[0281] The flow reactor consisting of P1, P2, M1 and R1 was cooled to 20°C, and the flow reactor consisting of P3, P4, M2, M3, R2 and R3 was cooled to 0°C. The stainless steel reactors in cooling baths at different temperatures were connected with PTFE tubing. α-Methylstyrene (0.09 M THF solution, flow rate: 4.22 mL / min, 1.5 molar equivalents relative to sec-BuLi) and sec-BuLi (0.15 M hexane solution, flow rate: 1.69 mL / min) were introduced into M1 (φ = 250 μm) by a syringe pump, and the mixture (initiator solution) was passed through R1 (inner diameter 1000 μm, 212.5 cm).

[0282] Next, the initiator solution and 4-trimethoxysilylstyrene (0.846 M THF solution, manufactured by Tokyo Chemical Industry Co., Ltd., flow rate: 9.0 mL / min, 30 molar equivalents) were mixed in M2 (φ=500 μm), and the mixture was passed through R2 (inner diameter 1000 μm, 12.5 cm). The obtained solution was introduced into M3 (φ=500 μm), and methanol (0.0827 M THF solution, flow rate: 3.38 mL / min, 1.1 molar equivalents) was introduced thereto, and the mixture was passed through R3 (inner diameter 1000 μm, 100 cm). After reaching a steady state, an aliquot of the product solution was collected for 10 seconds, and a methyl Grignard reagent (methylmagnesium chloride, Merck, 16 molar equivalents relative to the monomer) was added. The mixture was stirred under reflux conditions (oil bath temperature 100 °C) for 3 hours to convert the silicon-containing substituents (post-functionalization). After quenching with methanol, the mixture was treated with saturated aqueous ammonium chloride (NH4Cl) and brine. The solution was diluted with THF and filtered. The resulting solution was analyzed by gel permeation chromatography (GPC) in the same manner as in Comparative Example 1. The results are shown in Table 12.

[0283] [Table 12]

[0284] Example 79 A polymer was produced and analyzed in the same manner as in Example 78, except that the length of R2 was changed from 12.5 cm to 25 cm. The results are shown in Table 12.

[0285] (Example 80) A polymer was produced and analyzed in the same manner as in Example 78, except that the length of R2 was changed from 12.5 cm to 400 cm. The results are shown in Table 12.

[0286] [ka]

[0287] Example 81 As shown in Figure 3, a flow microreactor system was used, which consisted of two V-type micromixers (M1 and M2: manufactured by Sanko Seiki Kogyo Co., Ltd.), one T-type micromixer (M3: manufactured by Sanko Seiki Kogyo Co., Ltd.), three microtube reactors (R1, R2, and R3: manufactured by GL Sciences), and four 100 cm pre-cooling units (P1, P2, P3, and P4: manufactured by GL Sciences).

[0288] The flow reactor consisting of P1, P2, M1 and R1 was cooled to 20°C, and the flow reactor consisting of P3, P4, M2, M3, R2 and R3 was cooled to -20°C. The stainless steel reactors in cooling baths at different temperatures were connected with PTFE tubing. α-Methylstyrene (0.09 M THF solution, flow rate: 4.22 mL / min, 1.5 molar equivalents relative to sec-BuLi) and sec-BuLi (0.15 M hexane solution, flow rate: 1.69 mL / min) were introduced into M1 (φ = 250 μm) by a syringe pump, and the mixture (initiator solution) was passed through R1 (inner diameter 1000 μm, 212.5 cm).

[0289] Next, the initiator solution and 4-trimethoxysilylstyrene (0.846 M THF solution, manufactured by Tokyo Chemical Industry Co., Ltd., flow rate: 9.0 mL / min, 30 molar equivalents) were mixed in M2 (φ=500 μm), and the mixture was passed through R2 (inner diameter 1000 μm, 12.5 cm). The obtained solution was introduced into M3 (φ=500 μm), and methanol (0.0827 M THF solution, flow rate: 3.38 mL / min, 1.1 molar equivalents) was introduced thereto, and the mixture was passed through R3 (inner diameter 1000 μm, 100 cm). After reaching a steady state, an aliquot of the product solution was collected for 10 seconds, and a methyl Grignard reagent (methylmagnesium chloride, Merck, 16 molar equivalents relative to the monomer) was added. The mixture was stirred under reflux conditions (oil bath temperature 100 °C) for 3 hours to convert the silicon-containing substituents (post-functionalization). After quenching with methanol, the mixture was treated with saturated aqueous ammonium chloride (NH4Cl) and brine. The solution was diluted with THF and filtered. The resulting solution was analyzed by gel permeation chromatography (GPC) in the same manner as in Comparative Example 1. The results are shown in Table 13.

[0290] [Table 13]

[0291] Example 82 A polymer was produced and analyzed in the same manner as in Example 81, except that the length of R2 was changed from 12.5 cm to 25 cm. The results are shown in Table 13.

[0292] Example 83 A polymer was produced and analyzed in the same manner as in Example 81, except that the length of R2 was changed from 12.5 cm to 400 cm. The results are shown in Table 13.

[0293] [ka]

[0294] Example 84 As shown in Figure 3, a flow microreactor system was used, which consisted of two V-type micromixers (M1 and M2: manufactured by Sanko Seiki Kogyo Co., Ltd.), one T-type micromixer (M3: manufactured by Sanko Seiki Kogyo Co., Ltd.), three microtube reactors (R1, R2, and R3: manufactured by GL Sciences), and four 100 cm pre-cooling units (P1, P2, P3, and P4: manufactured by GL Sciences).

[0295] The flow reactor consisting of P1, P2, M1 and R1 was cooled to 20°C, and the flow reactor consisting of P3, P4, M2, M3, R2 and R3 was cooled to -40°C. The stainless steel reactors in cooling baths at different temperatures were connected with PTFE tubing. α-Methylstyrene (0.09 M THF solution, flow rate: 4.22 mL / min, 1.5 molar equivalents relative to sec-BuLi) and sec-BuLi (0.15 M hexane solution, flow rate: 1.69 mL / min) were introduced into M1 (φ = 250 μm) by a syringe pump, and the mixture (initiator solution) was passed through R1 (inner diameter 1000 μm, 212.5 cm).

[0296] Next, the initiator solution and 4-trimethoxysilylstyrene (0.846 M THF solution, manufactured by Tokyo Chemical Industry Co., Ltd., flow rate: 9.0 mL / min, 30 molar equivalents) were mixed in M2 (φ=500 μm), and the mixture was passed through R2 (inner diameter 1000 μm, 300 cm). The obtained solution was introduced into M3 (φ=500 μm), and methanol (0.0827 M THF solution, flow rate: 3.38 mL / min, 1.1 molar equivalents) was introduced thereto, and the mixture was passed through R3 (inner diameter 1000 μm, 100 cm). After reaching a steady state, an aliquot of the product solution was collected for 10 seconds, and a methyl Grignard reagent (methylmagnesium chloride, Merck, 16 molar equivalents relative to the monomer) was added. The mixture was stirred under reflux conditions (oil bath temperature 100 °C) for 3 hours to convert the silicon-containing substituents (post-functionalization). After quenching with methanol, the mixture was treated with saturated aqueous ammonium chloride (NH4Cl) and brine. The solution was diluted with THF and filtered. The resulting solution was analyzed by gel permeation chromatography (GPC) in the same manner as in Comparative Example 1. The results are shown in Table 14.

[0297] [Table 14]

[0298] Example 85 A polymer was produced and analyzed in the same manner as in Example 84, except that the length of R2 was changed from 300 cm to 350 cm. The results are shown in Table 14.

[0299] Example 86 A polymer was produced and analyzed in the same manner as in Example 84, except that the length of R2 was changed from 300 cm to 400 cm. The results are shown in Table 14.

[0300] [ka]

[0301] Example 87 As shown in Figure 3, a flow microreactor system was used, which consisted of two V-type micromixers (M1 and M2: manufactured by Sanko Seiki Kogyo Co., Ltd.), one T-type micromixer (M3: manufactured by Sanko Seiki Kogyo Co., Ltd.), three microtube reactors (R1, R2, and R3: manufactured by GL Sciences), and four 100 cm pre-cooling units (P1, P2, P3, and P4: manufactured by GL Sciences).

[0302] The flow reactor consisting of P1, P2, M1 and R1 was cooled to 20°C, and the flow reactor consisting of P3, P4, M2, M3, R2 and R3 was cooled to 0°C. The stainless steel reactors in cooling baths at different temperatures were connected with PTFE tubing. α-Methylstyrene (0.12 M THF solution, flow rate: 4.22 mL / min, 2 molar equivalents relative to sec-BuLi) and sec-BuLi (0.15 M hexane solution, flow rate: 1.69 mL / min) were introduced into M1 (φ = 250 μm) using a syringe pump, and the mixture (initiator solution) was passed through R1 (inner diameter 1000 μm, 212.5 cm).

[0303] Next, the initiator solution and 4-trimethoxysilylstyrene (0.846 M THF solution, manufactured by Tokyo Chemical Industry Co., Ltd., flow rate: 9.0 mL / min, 30 molar equivalents) were mixed in M2 (φ=500 μm), and the mixture was passed through R2 (inner diameter 1000 μm, 50 cm). The obtained solution was introduced into M3 (φ=500 μm), and methanol (0.0827 M THF solution, flow rate: 3.38 mL / min, 1.1 molar equivalents) was introduced thereto, and the mixture was passed through R3 (inner diameter 1000 μm, 100 cm). After reaching a steady state, an aliquot of the product solution was collected for 10 seconds, and a methyl Grignard reagent (methylmagnesium chloride, Merck, 16 molar equivalents relative to the monomer) was added. The mixture was stirred under reflux conditions (oil bath temperature 100 °C) for 3 hours to convert the silicon-containing substituents (post-functionalization). After quenching with methanol, the mixture was treated with saturated aqueous ammonium chloride (NH4Cl) and brine. The solution was diluted with THF and filtered. The resulting solution was analyzed by gel permeation chromatography (GPC) in the same manner as in Comparative Example 1. The results are shown in Table 15.

[0304] [Table 15]

[0305] Example 88 A polymer was produced and analyzed in the same manner as in Example 87, except that the length of R2 was changed from 50 cm to 200 cm. The results are shown in Table 15.

[0306] Example 89 A polymer was produced and analyzed in the same manner as in Example 87, except that the length of R2 was changed from 50 cm to 350 cm. The results are shown in Table 15.

[0307] The results in Tables 12 to 15 show that the dispersion tends to widen under conditions of long residence times, and this tendency becomes more pronounced as the polymerization temperature increases. However, it was found that increasing the equivalent weight of α-methylstyrene can suppress side reactions that occur when the residence time is long. This is thought to be because the α-methylstyrene remaining after the generation of 2PHLi caps the active terminals of the polymer.

[0308] <11 Polymer Production 9 Anionic Polymerization Using Microreactors> We investigated the effect of the equivalent amount of methanol, a quenching agent (polymerization terminator), on anionic polymerization using a microreactor (flow microreactor) with 2PHLi as a polymerization initiator.

[0309] [ka]

[0310] Example 90 As shown in Figure 3, a flow microreactor system was used, which consisted of two V-type micromixers (M1 and M2: manufactured by Sanko Seiki Kogyo Co., Ltd.), one T-type micromixer (M3: manufactured by Sanko Seiki Kogyo Co., Ltd.), three microtube reactors (R1, R2, and R3: manufactured by GL Sciences), and four 100 cm pre-cooling units (P1, P2, P3, and P4: manufactured by GL Sciences).

[0311] The flow reactor consisting of P1, P2, M1 and R1 was cooled to 20°C, and the flow reactor consisting of P3, P4, M2, M3, R2 and R3 was cooled to -40°C. The stainless steel reactors in cooling baths at different temperatures were connected with PTFE tubing. α-Methylstyrene (0.09 M THF solution, flow rate: 4.22 mL / min, 1.5 molar equivalents relative to sec-BuLi) and sec-BuLi (0.15 M hexane solution, flow rate: 1.69 mL / min) were introduced into M1 (φ = 250 μm) by a syringe pump, and the mixture (initiator solution) was passed through R1 (inner diameter 1000 μm, 212.5 cm).

[0312] Next, the initiator solution and 4-trimethoxysilylstyrene (0.846 M THF solution, manufactured by Tokyo Chemical Industry Co., Ltd., flow rate: 9.0 mL / min, 30 molar equivalents) were mixed in M2 (φ=500 μm), and the mixture was passed through R2 (inner diameter 1000 μm, 300 cm). The obtained solution was introduced into M3 (φ=500 μm), and methanol (0.0827 M THF solution, flow rate: 3.38 mL / min, 1.1 molar equivalents relative to sec-BuLi) was introduced thereto, and the mixture was passed through R3 (inner diameter 1000 μm, 200 cm). After reaching a steady state, an aliquot of the product solution was collected for 10 seconds, and a methyl Grignard reagent (methylmagnesium chloride, Merck, 16 molar equivalents relative to the monomer) was added. The mixture was stirred under reflux conditions (oil bath temperature 100 °C) for 3 hours to convert the silicon-containing substituents (post-functionalization). After quenching with methanol, the mixture was treated with saturated aqueous ammonium chloride (NH4Cl) and brine. The solution was diluted with THF and filtered. The resulting solution was analyzed by gel permeation chromatography (GPC) in the same manner as in Comparative Example 1. The results are shown in Table 16.

[0313] [Table 16]

[0314] Example 91 Polymers were prepared and analyzed in the same manner as in Example 90, except that the amount of methanol was changed from 1.1 molar equivalents to 2.0 molar equivalents (methanol concentration: 0.15 M) and the length of R3 was changed from 200 cm to 100 cm. The results are shown in Table 16.

[0315] Example 92 Polymers were prepared and analyzed in the same manner as in Example 90, except that the amount of methanol was changed from 1.1 molar equivalents to 2.5 molar equivalents (to give a methanol concentration of 0.188 M) and the length of R3 was changed from 200 cm to 100 cm. The results are shown in Table 16.

[0316] [ka]

[0317] Example 93 As shown in Figure 3, a flow microreactor system was used, which consisted of two V-type micromixers (M1 and M2: manufactured by Sanko Seiki Kogyo Co., Ltd.), one T-type micromixer (M3: manufactured by Sanko Seiki Kogyo Co., Ltd.), three microtube reactors (R1, R2, and R3: manufactured by GL Sciences), and four 100 cm pre-cooling units (P1, P2, P3, and P4: manufactured by GL Sciences).

[0318] The flow reactor consisting of P1, P2, M1 and R1 was cooled to 20°C, and the flow reactor consisting of P3, P4, M2, M3, R2 and R3 was cooled to -40°C. The stainless steel reactors in cooling baths at different temperatures were connected with PTFE tubing. α-Methylstyrene (0.12 M THF solution, flow rate: 4.22 mL / min, 2.0 molar equivalents relative to sec-BuLi) and sec-BuLi (0.15 M hexane solution, flow rate: 1.69 mL / min) were introduced into M1 (φ = 250 μm) using a syringe pump, and the mixture (initiator solution) was passed through R1 (inner diameter 1000 μm, 212.5 cm).

[0319] Next, the initiator solution and 4-trimethoxysilylstyrene (0.846 M THF solution, manufactured by Tokyo Chemical Industry Co., Ltd., flow rate: 9.0 mL / min, 30 molar equivalents) were mixed in M2 (φ=500 μm), and the mixture was passed through R2 (inner diameter 1000 μm, 300 cm). The obtained solution was introduced into M3 (φ=500 μm), and methanol (0.0827 M THF solution, flow rate: 3.38 mL / min, 1.1 molar equivalents) was introduced thereto, and the mixture was passed through R3 (inner diameter 1000 μm, 200 cm). After reaching a steady state, an aliquot of the product solution was collected for 10 seconds, and a methyl Grignard reagent (methylmagnesium chloride, Merck, 16 molar equivalents relative to the monomer) was added. The mixture was stirred under reflux conditions (oil bath temperature 100 °C) for 3 hours to convert the silicon-containing substituents (post-functionalization). After quenching with methanol, the mixture was treated with saturated aqueous ammonium chloride (NH4Cl) and brine. The solution was diluted with THF and filtered. The resulting solution was analyzed by gel permeation chromatography (GPC) in the same manner as in Comparative Example 1. The results are shown in Table 17.

[0320] [Table 17]

[0321] Example 94 Polymers were prepared and analyzed in the same manner as in Example 93, except that the amount of methanol was changed from 1.1 molar equivalents to 2.0 molar equivalents (to give a methanol concentration of 0.15 M) and the length of R3 was changed from 200 cm to 100 cm. The results are shown in Table 17.

[0322] Example 95 Polymers were prepared and analyzed in the same manner as in Example 93, except that the amount of methanol was changed from 1.1 molar equivalents to 2.5 molar equivalents (to give a methanol concentration of 0.188M) and the length of R3 was changed from 200 cm to 100 cm. The results are shown in Table 17.

[0323] The results in Tables 16 and 17 show that when the methanol equivalent is low, the reaction is not terminated quickly, and as a result, a polymer with a wide dispersion is obtained, similar to when the polymerization time is extended.

[0324] <12 Polymer Production 10 Anionic Polymerization Using Microreactors> [ka]

[0325] The effect of the equivalent weight of α-methylstyrene on anionic polymerization was investigated using 2PHLi as a polymerization initiator in a microreactor (flow microreactor).

[0326] Example 96 As shown in Figure 3, a flow microreactor system was used, which consisted of two V-type micromixers (M1 and M2: manufactured by Sanko Seiki Kogyo Co., Ltd.), one T-type micromixer (M3: manufactured by Sanko Seiki Kogyo Co., Ltd.), three microtube reactors (R1, R2, and R3: manufactured by GL Sciences), and four 100 cm pre-cooling units (P1, P2, P3, and P4: manufactured by GL Sciences).

[0327] The flow reactor consisting of P1, P2, M1 and R1 was cooled to 20°C, and the flow reactor consisting of P3, P4, M2, M3, R2 and R3 was cooled to -40°C. The stainless steel reactors in cooling baths at different temperatures were connected with PTFE tubing. α-Methylstyrene (0.06 M THF solution, flow rate: 5.625 mL / min, 1 molar equivalent relative to sec-BuLi) and sec-BuLi (0.15 M hexane solution, flow rate: 2.25 mL / min) were introduced into M1 (φ = 250 μm) by a syringe pump, and the mixture (initiator solution) was passed through R1 (inner diameter 1000 μm, 212.5 cm).

[0328] Next, the initiator solution and 4-trimethoxysilylstyrene (0.846 M THF solution, manufactured by Tokyo Chemical Industry Co., Ltd., flow rate: 12.0 mL / min, 30 molar equivalents) were mixed in M2 (φ=500 μm), and the mixture was passed through R2 (inner diameter 1000 μm, 400 cm). The obtained solution was introduced into M3 (φ=500 μm), and methanol (0.15 M THF solution, flow rate: 4.50 mL / min, 2 molar equivalents) was introduced thereto, and the mixture was passed through R3 (inner diameter 1000 μm, 100 cm). After reaching a steady state, an aliquot of the product solution was collected for 10 seconds, and a methyl Grignard reagent (methylmagnesium chloride, Merck, 16 molar equivalents relative to the monomer) was added. The mixture was stirred under reflux conditions (oil bath temperature 100 °C) for 3 hours to convert the silicon-containing substituents (post-functionalization). After quenching with methanol, the mixture was treated with saturated aqueous ammonium chloride (NH4Cl) and brine. The solution was diluted with THF and filtered. The resulting solution was analyzed by gel permeation chromatography (GPC) in the same manner as in Comparative Example 1. The results are shown in Table 18.

[0329] [Table 18]

[0330] Example 97 A polymer was prepared and analyzed in the same manner as in Example 96, except that the amount of α-methylstyrene was changed from 1 molar equivalent to 2 molar equivalents (the concentration of α-methylstyrene was 0.12 M). The results are shown in Table 18.

[0331] Example 98 A polymer was produced and analyzed in the same manner as in Example 96, except that the flow reactor consisting of P3, P4, M2, M3, R2, and R3 was cooled to 20°C and the amount of α-methylstyrene was changed from 1 molar equivalent to 2 molar equivalents (α-methylstyrene concentration was 0.12 M). The results are shown in Table 18.

[0332] The results in Table 18 show that by using 2 molar equivalents of α-methylstyrene, the molecular weight approaches the theoretical value and a polymer with relatively controlled dispersion can be obtained.

[0333] <13 Polymer Production 11 Anionic Polymerization Using a Microreactor> [ka]

[0334] The effect of the monomer equivalent weight on anionic polymerization was investigated using 2PHLi as a polymerization initiator in a microreactor (flow microreactor).

[0335] Example 99 As shown in Figure 3, a flow microreactor system was used, which consisted of two V-type micromixers (M1 and M2: manufactured by Sanko Seiki Kogyo Co., Ltd.), one T-type micromixer (M3: manufactured by Sanko Seiki Kogyo Co., Ltd.), three microtube reactors (R1, R2, and R3: manufactured by GL Sciences), and four 100 cm pre-cooling units (P1, P2, P3, and P4: manufactured by GL Sciences).

[0336] The flow reactor consisting of P1, P2, M1 and R1 was cooled to 20°C, and the flow reactor consisting of P3, P4, M2, M3, R2 and R3 was cooled to -40°C. The stainless steel reactors in cooling baths at different temperatures were connected with PTFE tubing. α-Methylstyrene (0.12 M THF solution, flow rate: 5.625 mL / min, 2 molar equivalents relative to sec-BuLi) and sec-BuLi (0.15 M hexane solution, flow rate: 2.25 mL / min) were introduced into M1 (φ = 250 μm) by a syringe pump, and the mixture (initiator solution) was passed through R1 (inner diameter 1000 μm, 212.5 cm).

[0337] Next, the initiator solution and 4-trimethoxysilylstyrene (0.846 M THF solution, manufactured by Tokyo Chemical Industry Co., Ltd., flow rate: 4 mL / min, 10 molar equivalents) were mixed in M2 (φ=500 μm), and the mixture was passed through R2 (inner diameter 1000 μm, 100 cm). The obtained solution was introduced into M3 (φ=500 μm), and methanol (0.375 M THF solution, flow rate: 4.5 mL / min, 5 molar equivalents) was introduced thereto, and the mixture was passed through R3 (inner diameter 1000 μm, 100 cm). After reaching a steady state, an aliquot of the product solution was collected for 10 seconds, and methyllithium (Kanto Chemical Co., Ltd., 6 molar equivalents relative to the monomer) was added and stirred at 0 °C for 1 minute to convert the silicon-containing substituents (post-functionalization). After quenching with methanol, the reaction was treated with saturated aqueous ammonium chloride (NH4Cl) and brine. The solution was diluted with THF and filtered. The resulting solution was analyzed by gel permeation chromatography (GPC) in the same manner as in Comparative Example 1. The results are shown in Table 19 and FIG.

[0338] [Table 19]

[0339] Example 100 A polymer was prepared and analyzed in the same manner as in Example 99, except that the amount of 4-trimethoxysilylstyrene was changed from 10 to 20 molar equivalents and the flow rate of 4-trimethoxysilylstyrene was changed from 4 mL / min to 8 mL / min. The results are shown in Table 19 and Figure 22.

[0340] Example 101 A polymer was prepared and analyzed in the same manner as in Example 99, except that the amount of 4-trimethoxysilylstyrene was changed from 10 to 30 molar equivalents and the flow rate of 4-trimethoxysilylstyrene was changed from 4 mL / min to 12 mL / min. The results are shown in Table 19 and Figure 22.

[0341] Example 102 Polymers were prepared and analyzed in the same manner as in Example 99, except that the amount of 4-trimethoxysilylstyrene was changed from 10 to 40 molar equivalents and the flow rate of 4-trimethoxysilylstyrene was changed from 4 mL / min to 16 mL / min. The results are shown in Table 19 and Figure 22.

[0342] (Example 103) A polymer was prepared and analyzed in the same manner as in Example 99, except that the amount of 4-trimethoxysilylstyrene was changed from 10 to 50 molar equivalents and the flow rate of 4-trimethoxysilylstyrene was changed from 4 mL / min to 20 mL / min. The results are shown in Table 19 and Figure 22.

[0343] The results in Table 19 and Figure 22 show that the number-average molecular weight increases linearly with the monomer equivalent. Furthermore, narrow-dispersity polymers with molecular weight distributions of 1.07 to 1.10 were obtained. Furthermore, it was found that post-functionalization is possible using not only Grignard reagents but also methyllithium.

[0344] <14 Post-functionalization study> [ka]

[0345] We investigated the conditions for post-functionalization after anionic polymerization using a microreactor (flow microreactor) using 2PHLi as a polymerization initiator.

[0346] Example 104 As shown in Figure 3, a flow microreactor system was used, which consisted of two V-type micromixers (M1 and M2: manufactured by Sanko Seiki Kogyo Co., Ltd.), one T-type micromixer (M3: manufactured by Sanko Seiki Kogyo Co., Ltd.), three microtube reactors (R1, R2, and R3: manufactured by GL Sciences), and four 100 cm pre-cooling units (P1, P2, P3, and P4: manufactured by GL Sciences).

[0347] The flow reactor consisting of P1, P2, M1 and R1 was cooled to 20°C, and the flow reactor consisting of P3, P4, M2, M3, R2 and R3 was cooled to -40°C. The stainless steel reactors in cooling baths at different temperatures were connected with PTFE tubing. α-Methylstyrene (0.12 M THF solution, flow rate: 5.63 mL / min, 2 molar equivalents relative to sec-BuLi) and sec-BuLi (0.15 M hexane solution, flow rate: 2.25 mL / min) were introduced into M1 (φ = 250 μm) using a syringe pump, and the mixture (initiator solution) was passed through R1 (inner diameter 1000 μm, 212.5 cm).

[0348] Next, the initiator solution and 4-trimethoxysilylstyrene (0.846 M THF solution, manufactured by Tokyo Chemical Industry Co., Ltd., flow rate: 12 mL / min, 30 molar equivalents) were mixed in M2 (φ=500 μm), and the mixture was passed through R2 (inner diameter 1000 μm, 50 cm). The obtained solution was introduced into M3 (φ=500 μm), and methanol (0.38 M THF solution, flow rate: 4.5 mL / min, 5 molar equivalents) was introduced thereto, and the mixture was passed through R3 (inner diameter 1000 μm, 100 cm). After reaching a steady state, an aliquot of the product solution was collected for 10 seconds, and a methyl Grignard reagent (methylmagnesium chloride, Fujifilm Wako Pure Chemical Industries, Ltd., 12 molar equivalents relative to the monomer) was added and stirred at 60 °C for 3 hours to convert the silicon-containing substituents (post-functionalization). After quenching with methanol, the reaction was treated with saturated aqueous ammonium chloride (NH4Cl) and brine. The solution was diluted with THF and filtered. The resulting solution was analyzed by gel permeation chromatography (GPC) in the same manner as in Comparative Example 1, and the methylation rate was analyzed in the same manner as in Example 65. The results are shown in Table 20.

[0349] [Table 20]

[0350] Example 105 A polymer was prepared and analyzed in the same manner as in Example 104, except that the amount of 4-trimethoxysilylstyrene was changed from 30 to 10 molar equivalents and the amount of methyl Grignard reagent was changed from 12.0 to 8.0 molar equivalents. The results are shown in Table 20.

[0351] Example 106 A polymer was prepared and analyzed in the same manner as in Example 104, except that the amount of 4-trimethoxysilylstyrene was changed from 30 to 10 molar equivalents and the amount of methyl Grignard reagent was changed from 12.0 to 7.0 molar equivalents. The results are shown in Table 20.

[0352] (Example 107) A polymer was prepared and analyzed in the same manner as in Example 104, except that the amount of 4-trimethoxysilylstyrene was changed from 30 to 10 molar equivalents and the amount of methyl Grignard reagent was changed from 12.0 to 6.0 molar equivalents. The results are shown in Table 20.

[0353] Example 108 A polymer was prepared and analyzed in the same manner as in Example 104, except that the amount of 4-trimethoxysilylstyrene was changed from 30 to 10 molar equivalents and the amount of methyl Grignard reagent was changed from 12.0 to 5.0 molar equivalents. The results are shown in Table 20.

[0354] Example 109 A polymer was prepared and analyzed in the same manner as in Example 104, except that the amount of 4-trimethoxysilylstyrene was changed from 30 to 10 molar equivalents and the amount of methyl Grignard reagent was changed from 12.0 to 4.0 molar equivalents. The results are shown in Table 20.

[0355] Example 110 A polymer was prepared and analyzed in the same manner as in Example 104, except that the amount of 4-trimethoxysilylstyrene was changed from 30 to 10 molar equivalents and the amount of methyl Grignard reagent was changed from 12.0 to 3.5 molar equivalents. The results are shown in Table 20.

[0356] Example 111 A polymer was prepared and analyzed in the same manner as in Example 104, except that the amount of 4-trimethoxysilylstyrene was changed from 30 to 10 molar equivalents and the amount of methyl Grignard reagent was changed from 12.0 to 3.0 molar equivalents. The results are shown in Table 20. By adding 3 equivalents of methyl Grignard reagent (methylmagnesium chloride) to the monomer, 71% of the trimethoxy groups were methylated, resulting in the synthesis of a silicon-containing polymer with one methoxy group and two methyl groups on the silicon. The MALDI-TOFMS spectrum of this polymer is shown in Figure 23. The repeating unit of this polymer was confirmed to be 192.10.

[0357] Example 112 A polymer was prepared and analyzed in the same manner as in Example 104, except that the amount of 4-trimethoxysilylstyrene was changed from 30 to 10 molar equivalents and the amount of methyl Grignard reagent was changed from 12.0 to 2.5 molar equivalents. The results are shown in Table 20.

[0358] Example 113 A polymer was prepared and analyzed in the same manner as in Example 104, except that the amount of 4-trimethoxysilylstyrene was changed from 30 to 10 molar equivalents and the amount of methyl Grignard reagent was changed from 12.0 to 2.0 molar equivalents. The results are shown in Table 20.

[0359] Previously, post-functionalization involved the use of an excess amount of Grignard reagent on the resulting polymer to completely methylate the silicon-containing substituents. The results in Table 20 show that the methylation rate can be controlled by relaxing the reaction conditions of the post-functional group and adjusting the equivalent weight of the Grignard reagent.

[0360] 15. Post-functionalization using microreactors [ka]

[0361] Anionic polymerization was carried out using a microreactor (flow microreactor) with 2PHLi as a polymerization initiator, and post-functionalization using the microreactor was investigated.

[0362] Example 114 As shown in Figure 4, a flow microreactor system was used, which consisted of three V-type micromixers (M1, M2, and M3: manufactured by Sanko Seiki Kogyo Co., Ltd.), one T-type micromixer (M4: manufactured by Sanko Seiki Kogyo Co., Ltd.), four microtube reactors (R1, R2, R3, and R4: manufactured by GL Sciences), and five 100 cm pre-cooling units (P1, P2, P3, P4, and P5: manufactured by GL Sciences).

[0363] The flow reactor consisting of P1, P2, M1, and R1 was cooled at 20°C, the flow reactor consisting of P3, M2, and R2 was cooled at -40°C, and the flow reactor consisting of P4, P5, M3, M4, R3, and R4 was cooled at 20°C. The stainless steel reactors in the cooling baths at different temperatures were connected with PTFE tubing (however, the flow reactor consisting of P3, M2, and R2 was not connected to the flow reactor consisting of P4, P5, M3, M4, R3, and R4). α-Methylstyrene (0.12 M THF solution, flow rate: 5.63 mL / min, 2 molar equivalents relative to sec-BuLi) and sec-BuLi (0.15 M hexane solution, flow rate: 2.25 mL / min) were introduced into M1 (φ = 250 μm) using a syringe pump, and the mixture (initiator solution) was passed through R1 (inner diameter 1000 μm, 212.5 cm).

[0364] Next, the initiator solution and 4-trimethoxysilylstyrene (0.28 M THF solution, manufactured by Tokyo Chemical Industry Co., Ltd., flow rate: 5.99 mL / min, 5 molar equivalents) were mixed in M2 (φ=500 μm), and the mixture was passed through R2 (inner diameter 1000 μm, 50 cm). The obtained solution was introduced into M3 (φ=500 μm), and methyllithium (0.80 M diethyl ether solution, flow rate: 8.45 mL / min, 4.0 molar equivalents relative to the monomer) was introduced thereto, and the mixture was passed through R3 (inner diameter 1000 μm, 200 cm). In addition, polymer synthesis and methylation were carried out in the flow microreactor system shown in Figure 4, with P5, M4, and R4 removed, and the reaction solution obtained from the R3 outlet was quenched by receiving (treating) it with a saturated aqueous solution of ammonium chloride (NH4Cl) (approximately 4 mL). The obtained solution was introduced into M4 (φ=500 μm), and methanol (0.38 M THF solution, flow rate: 4.5 mL / min, 5 molar equivalents) was introduced thereto, and the mixture was passed through R4 (inner diameter 1000 μm, 100 cm). After steady state was reached, aliquots of the product solution were collected for 10 seconds, and the resulting solutions were analyzed by gel permeation chromatography (GPC) as in Comparative Example 1 and for methylation rate as in Example 65. The results are shown in Table 21.

[0365] [Table 21]

[0366] Example 115 A polymer was produced and analyzed in the same manner as in Example 114, except that the flow rate of methyllithium was changed from 8.45 mL / min to 6.33 mL / min, the amount of methyllithium was changed from 4.0 molar equivalents to 3.0 molar equivalents, and P5, M4, and R4 were not removed from the flow microreactor system shown in Figure 4. The results are shown in Table 21.

[0367] The results in Table 21 show that post-functionalization (methylation), which was previously performed in a batch reactor, can be incorporated into a flow microreactor system, and the entire process from polymerization initiator preparation, polymerization reaction, post-functionalization, and reaction quenching can be performed using a flow microreactor.

[0368] <16 Grignard Reagents> [ka]

[0369] Anionic polymerization was carried out using a microreactor (flow microreactor) with 2PHLi as a polymerization initiator, and post-functionalization (Grignard reagent) using the microreactor was then investigated.

[0370] Example 116 A polymer was produced and analyzed in the same manner as in Example 99, except that instead of adding methyllithium and stirring at 0°C for 1 minute, post-functionalization was performed using a Grignard reagent (methylmagnesium chloride, Fujifilm Wako Pure Chemical Industries, Ltd., 16 molar equivalents relative to the monomer) and stirring under reflux conditions (oil bath temperature 80°C) for 3 hours. As shown in the first row of Table 22, the number average molecular weight of the obtained polymer was 7,400, and the molecular weight distribution (Mw / Mn) was 1.11. 1 The methylation rate as analyzed by 1 H NMR was 98 mol %.

[0371] [Table 22]

[0372] Example 117 A polymer was produced and analyzed in the same manner as in Example 86, except that instead of performing post-functionalization by adding methyllithium and stirring at 0°C for 1 minute, a Grignard reagent (Tokyo Chemical Industry Co., Ltd., 16 molar equivalents relative to the monomer) was used and post-functionalization was performed by stirring under reflux conditions (oil bath temperature 80°C) for 3 hours. As shown in the second row of Table 22, the number average molecular weight of the obtained polymer was 8700, and the molecular weight distribution (Mw / Mn) was 1.17. 1 The methylation rate as analyzed by 1 H NMR was 100 mol %.

[0373] Example 118 A polymer was produced and analyzed in the same manner as in Example 99, except that instead of carrying out post-functionalization by adding methyllithium and stirring at 0°C for 1 minute, post-functionalization was carried out by using n-BuLi (manufactured by Kanto Chemical Co., Inc., 16 molar equivalents relative to the monomer) as a functional group substitution agent and stirring at 25°C for 5 minutes. As shown in the third row of Table 22, the number average molecular weight of the obtained polymer was 10,800, and the molecular weight distribution (Mw / Mn) was 1.12. 1 The methylation rate as analyzed by 1 H NMR was 100 mol %.

[0374] Example 119 A polymer was produced and analyzed in the same manner as in Example 99, except that instead of carrying out post-functionalization by adding methyllithium and stirring at 0°C for 1 minute, post-functionalization was carried out by using phenyllithium (manufactured by Kanto Chemical Co., Inc., 16 molar equivalents relative to the monomer) as a functional group substitution agent and stirring at 25°C for 5 minutes. As shown in the fourth row of Table 22, the number average molecular weight of the obtained polymer was 8,200, and the molecular weight distribution (Mw / Mn) was 1.10. 1 The methylation rate as analyzed by 1 H NMR was 100 mol %.

[0375] From the above, when methyl Grignard or vinyl Grignard was used as the functional group substitution agent, complete post-functionalization was achieved, resulting in silicon-containing polymers bearing methyl and vinyl groups on the silicon.Furthermore, when n-butyllithium or phenyllithium was used as the functional group substitution agent, complete post-functionalization was achieved, resulting in silicon-containing polymers bearing butyl and phenyl groups on the silicon.

[0376] <17 Polymerization of 4-methoxydimethylsilylstyrene using a microreactor> [ka]

[0377] Anionic polymerization using a microreactor (flow microreactor) was carried out using 2PHLi as a polymerization initiator and 4-methoxydimethylsilylstyrene as a monomer.

[0378] Example 120 As shown in Figure 3, a flow microreactor system was used, which consisted of two V-type micromixers (M1 and M2: manufactured by Sanko Seiki Kogyo Co., Ltd.), one T-type micromixer (M3: manufactured by Sanko Seiki Kogyo Co., Ltd.), three microtube reactors (R1, R2, and R3: manufactured by GL Sciences), and four 100 cm pre-cooling units (P1, P2, P3, and P4: manufactured by GL Sciences).

[0379] The flow reactor consisting of P1, P2, M1 and R1 was cooled to 20°C, and the flow reactor consisting of P3, P4, M2, M3, R2 and R3 was cooled to -40°C. The stainless steel reactors in cooling baths at different temperatures were connected with PTFE tubing. α-Methylstyrene (0.04 M THF solution, flow rate: 5.625 mL / min, 2 molar equivalents relative to sec-BuLi) and sec-BuLi (0.05 M hexane solution, flow rate: 2.25 mL / min) were introduced into M1 (φ = 250 μm) using a syringe pump, and the mixture (initiator solution) was passed through R1 (inner diameter 1000 μm, 212.5 cm).

[0380] Next, the initiator solution and 4-methoxydimethylsilylstyrene (0.282 M THF solution, manufactured by Tokyo Chemical Industry Co., Ltd., flow rate: 4.0 mL / min, 10 molar equivalents) were mixed in M2 (φ=500 μm), and the mixture was passed through R2 (inner diameter 1000 μm, 200 cm). The obtained solution was introduced into M3 (φ=500 μm), and methanol (0.125 M THF solution, flow rate: 4.5 mL / min, 5 molar equivalents) was introduced thereto, and the mixture was passed through R3 (inner diameter 1000 μm, 100 cm). After reaching a steady state, an aliquot of the product solution was collected for 10 seconds, and methyllithium (Kanto Chemical Co., Ltd., 6 molar equivalents relative to the monomer) was added and stirred at 25°C for 5 minutes to convert the silicon-containing substituents (post-functionalization). After quenching with methanol, the reaction was treated with saturated aqueous ammonium chloride (NH4Cl) and brine. The solution was diluted with THF and filtered. The resulting solution was analyzed by gel permeation chromatography (GPC) in the same manner as in Comparative Example 1. The results are shown in Table 23.

[0381] [Table 23]

[0382] Example 121 A polymer was prepared and analyzed as in Example 120, except that the amount of 4-methoxydimethylsilylstyrene was changed from 10 to 15 molar equivalents and the flow rate of 4-methoxydimethylsilylstyrene was changed from 4.0 mL / min to 6.0 mL / min. The results are shown in Table 23.

[0383] Example 122 Polymers were prepared and analyzed in the same manner as in Example 120, except that the amount of 4-methoxydimethylsilylstyrene was changed from 10 to 20 molar equivalents and the flow rate of 4-methoxydimethylsilylstyrene was changed from 4.0 mL / min to 8.0 mL / min. The results are shown in Table 23.

[0384] Example 123 Polymers were prepared and analyzed in the same manner as in Example 120, except that the amount of 4-methoxydimethylsilylstyrene was changed from 10 to 25 molar equivalents and the flow rate of 4-methoxydimethylsilylstyrene was changed from 4.0 mL / min to 10.0 mL / min. The results are shown in Table 23.

[0385] Example 124 Polymers were prepared and analyzed in the same manner as in Example 120, except that the amount of 4-methoxydimethylsilylstyrene was changed from 10 to 30 molar equivalents and the flow rate of 4-methoxydimethylsilylstyrene was changed from 4.0 mL / min to 12.0 mL / min. The results are shown in Table 23.

[0386] Example 125 Polymers were prepared and analyzed as in Example 120, except that the concentration of α-methylstyrene was changed from 0.04 M to 0.12 M, the concentration of sec-BuLi was changed from 0.05 M to 0.15 M, the concentration of 4-methoxydimethylsilylstyrene was changed from 0.282 M to 0.846 M, and the flow rate of 4-methoxydimethylsilylstyrene was changed from 4.0 mL / min to 3.0 mL / min. The results are shown in Table 23.

[0387] Example 126 Polymers were prepared and analyzed as in Example 120, except that the concentration of α-methylstyrene was changed from 0.04 M to 0.12 M, the concentration of sec-BuLi was changed from 0.05 M to 0.15 M, the concentration of 4-methoxydimethylsilylstyrene was changed from 0.282 M to 0.846 M, the amount of 4-methoxydimethylsilylstyrene was changed from 10 to 15 molar equivalents, and the flow rate of 4-methoxydimethylsilylstyrene was changed from 4.0 mL / min to 4.5 mL / min. The results are shown in Table 23.

[0388] Example 127 Polymers were prepared and analyzed as in Example 120, except that the concentration of α-methylstyrene was changed from 0.04 M to 0.12 M, the concentration of sec-BuLi was changed from 0.05 M to 0.15 M, the concentration of 4-methoxydimethylsilylstyrene was changed from 0.282 M to 0.846 M, the amount of 4-methoxydimethylsilylstyrene was changed from 10 to 20 molar equivalents, and the flow rate of 4-methoxydimethylsilylstyrene was changed from 4.0 mL / min to 6.0 mL / min. The results are shown in Table 23.

[0389] Example 128 Polymers were prepared and analyzed as in Example 120, except that the concentration of α-methylstyrene was changed from 0.04 M to 0.12 M, the concentration of sec-BuLi was changed from 0.05 M to 0.15 M, the concentration of 4-methoxydimethylsilylstyrene was changed from 0.282 M to 0.846 M, the amount of 4-methoxydimethylsilylstyrene was changed from 10 molar equivalents to 25 molar equivalents, and the flow rate of 4-methoxydimethylsilylstyrene was changed from 4.0 mL / min to 7.5 mL / min. The results are shown in Table 23.

[0390] Example 129 Polymers were prepared and analyzed as in Example 120, except that the concentration of α-methylstyrene was changed from 0.04 M to 0.12 M, the concentration of sec-BuLi was changed from 0.05 M to 0.15 M, the concentration of 4-methoxydimethylsilylstyrene was changed from 0.282 M to 0.846 M, the amount of 4-methoxydimethylsilylstyrene was changed from 10 molar equivalents to 30 molar equivalents, and the flow rate of 4-methoxydimethylsilylstyrene was changed from 4.0 mL / min to 9.0 mL / min. The results are shown in Table 23.

[0391] Example 130 Polymers were prepared and analyzed as in Example 120, except that the concentration of α-methylstyrene was changed from 0.04 M to 0.12 M, the concentration of sec-BuLi was changed from 0.05 M to 0.15 M, the concentration of 4-methoxydimethylsilylstyrene was changed from 0.282 M to 0.846 M, the amount of 4-methoxydimethylsilylstyrene was changed from 10 molar equivalents to 35 molar equivalents, and the flow rate of 4-methoxydimethylsilylstyrene was changed from 4.0 mL / min to 10.5 mL / min. The results are shown in Table 23.

[0392] The results in Table 23 show that polymerization control using a flow microreactor is possible when 4-methoxydimethylsilylstyrene is used as the monomer, just as it was when 4-trimethoxysilylstyrene was used. Furthermore, the higher the concentration, the more precisely the polymer dispersion was controlled. This is thought to be because, at high concentrations, the polymer growth reaction, which is an intermolecular reaction, proceeds more predominantly.

[0393] The present invention includes, for example, the following aspects. <1> A method for producing a polymer, comprising an anionic polymerization step of anionically polymerizing an alkoxysilyl group-containing monomer using a microreactor in the presence of an initiator represented by the following general formula (1): 1 and R 2 one of which is an aryl group and the other is an aryl group or an alkyl group having 1 to 10 carbon atoms). [ka] <2> the aryl group is a phenyl group, <1> 2. A method for producing the polymer described in claim 1. <3> In the general formula (1), R 1 and R 2 one of the groups is an alkyl group having 1 to 10 carbon atoms, <1> 2. A method for producing the polymer described in claim 1. <4> The initiator represented by the general formula (1) is obtained by reacting sec-BuLi with an alkylaryl compound. <1> 2. A method for producing the polymer described in claim 1. <5> the amount of the alkylaryl compound is greater than the molar equivalent of the sec-BuLi; <4> 2. A method for producing the polymer described in claim 1. <6> The anionic polymerization step is carried out at 0° C. or higher. <1> 2. A method for producing the polymer described in claim 1. <7> a functional group substitution step is carried out after the anionic polymerization step; <1> 2. A method for producing the polymer described in claim 1. <8> A polymerization termination step is carried out after the anionic polymerization step. <1> 2. A method for producing the polymer described in claim 1.

Claims

1. A method for producing a polymer, comprising an anionic polymerization step of anionically polymerizing an alkoxysilyl group-containing monomer using a microreactor in the presence of an initiator represented by the following general formula (1): 【Chemistry 1】 However, in the general formula (1), R １ and R ２ One of the groups is an aryl group, and the other is an aryl group or an alkyl group having 1 to 10 carbon atoms.

2. The method for producing a polymer according to claim 1 , wherein the aryl group is a phenyl group.

3. In the general formula (1), R １ and R ２ 2. The method for producing a polymer according to claim 1, wherein one of the groups is an alkyl group having 1 to 10 carbon atoms.

4. 2. The method for producing a polymer according to claim 1, wherein the initiator represented by the general formula (1) is obtained by reacting sec-BuLi with an alkylaryl compound.

5. The method for producing a polymer according to claim 4, wherein the amount of the alkylaryl compound is greater than the molar equivalent of the sec-BuLi.

6. The method for producing a polymer according to claim 1 , wherein the anionic polymerization step is carried out at 0° C. or higher.

7. The method for producing a polymer according to claim 1 , wherein a functional group substitution step is carried out after the anionic polymerization step.

8. The method for producing a polymer according to claim 1 , wherein a polymerization termination step is carried out after the anionic polymerization step.

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