Method for manufacturing functional polymers by anionic polymerization

Abstract

The present invention relates to a method for manufacturing functional polymers by anionic polymerization. The polymer manufacturing method according to the present invention can economically produce polymers having high chemical uniformity and enables an anionic polymerization reaction even at a relatively high temperature compared with the prior art.

Description

Method for producing functional polymers by anionic polymerization

[0001] The present invention relates to a method for producing a functional polymer by an anionic polymerization method.

[0002] Anionic polymerization has the advantage of being easier to control molecular weight than other polymerization methods by adjusting the molar ratio of initiator and monomer due to the nature of the polymerization method, and of maintaining a narrow molecular weight distribution (polydispersity). Since anionic polymerization has the characteristics of living polymerization, there is no termination reaction and no termination reaction such as ion pair rearrangement unless a protic compound is present in the polymerization reaction system. Accordingly, in the polymerization reaction system, the polymer chain has the characteristic of continuously growing according to the introduction of monomer while having an active anionic terminal.

[0003] Anionic polymerization reactions such as this one can cause side reactions due to the heat generated during the reaction, reducing the uniformity of the polymer. Therefore, anionic polymerization reactions must be carried out at very low temperatures in a polar solvent.

[0004] In addition, since the anionic polymerization reaction proceeds immediately at the anionic terminal of the active polymer after the injection of the monomer, if rapid and uniform mixing is not achieved within the reactor, the heterogeneity between polymers inevitably increases, and the molecular weight distribution of the polymer produced increases, which is a problem.

[0005] As disclosed in Japanese Patent Publication No. 7012866, “Polymer Production Method and Flow-Type Reaction System for Producing Polymer,” a method for producing a polymer by performing an anionic polymerization reaction through a micro-flow-type reaction system has been disclosed.

[0006] Micro-flow reaction systems have the advantages of easy control of fluid flow and uniform control of residence time within the reactor. In particular, they have the advantage of easy control of heat generated or consumed by chemical reactions and also have advantages over batch reactors in terms of material transfer.

[0007] However, anionic polymerization reaction through a conventional flow-type reaction system such as this still has the problem that the molecular weight distribution of the polymer produced is large because the anionic polymerization initiator and monomer react immediately before they are sufficiently homogeneously mixed when the anionic polymerization initiator and monomer are injected into the reactor.

[0008] Furthermore, conventional anionic polymerization reactions using microflow reactors still require separate cooling facilities because the polymerization reaction must be performed at low temperatures. However, most anionic polymerization reactions proceed rapidly in the early stages of the reaction, and the heat generated by the rapid exotherm is not effectively dissipated, easily causing side reactions. Consequently, it is very difficult to produce polymers with the desired molecular weight and molecular weight distribution. To suppress these side reactions, the reactor temperature can be set to cryogenic temperatures and operated, but this is very uneconomical, and maintenance of the cooling facility is also difficult, making mass production practically difficult.

[0009] According to one aspect of the present invention, a polymer production method capable of economically producing a polymer having high chemical uniformity is provided.

[0010] In addition, according to one aspect of the present invention, a method for producing a polymer capable of anionic polymerization at a relatively high temperature compared to conventional methods is provided.

[0011] In addition, according to one aspect of the present invention, a polymer production method capable of continuously producing a high-quality polymer through a microflow reactor is provided.

[0012] The objectives of the present invention are not limited to the above-described scope. Those skilled in the art will have no difficulty understanding the additional objectives of the present invention from the overall content of this specification.

[0013] According to one embodiment of the present invention, a polymer manufacturing method comprises the steps of (S1) injecting a first solution containing at least one solvent selected from the group consisting of ether solvents and non-polar solvents and a monomer, and a second solution containing the solvent and an anionic polymerization initiator into a microflow reactor; and (S2) anionic polymerizing the monomer in the microflow reactor; wherein the microflow reactor comprises: a main body having at least one inlet hole and an outlet hole formed therein; a microchannel forming a flow path connecting the inlet hole and the outlet hole within the main body; A plurality of microchambers are arranged along the extension direction of the microchannel and form an internal space connected to the flow path, and a collision medium located within the internal space and colliding with the fluid transported within the internal space to change the flow of the fluid within the internal space, and the microchannel includes an inlet channel connecting the microchamber located at the frontmost end in the direction of fluid flow within the flow path and the inlet, a connection channel connecting the microchambers adjacent to each other, and an outlet channel connecting the microchamber located at the rearmost end in the direction of fluid flow within the flow path and the outlet, and the Reynolds number (Re) in the inlet channel i ) is the Reynolds number (Re) in the above discharge channel. f ) is smaller than.

[0014] In a polymer manufacturing method according to one embodiment, the ratio of the Reynolds number (Re f / Re i- ) can be 1.1 to 5.

[0015] In a polymer manufacturing method according to one embodiment, the inlet includes a first inlet through which the first solution is introduced and a second inlet through which the second solution is introduced, respectively, and the inlet channel includes a first inlet channel and a second inlet channel extending from the first inlet and the second inlet to the microchamber located at the most front end, and the Reynolds number (Re) i ) may be the Reynolds number of the first inlet channel.

[0016] In a polymer manufacturing method according to one embodiment, the Reynolds number (Re) in the inlet channel i ) can be between 100 and 350.

[0017] In a polymer manufacturing method according to one embodiment, the concentration of the monomer of the first solution may be 1 to 5 M, and the concentration of the anionic polymerization initiator of the second solution may be 0.01 to 0.5 M.

[0018] In a polymer production method according to one embodiment, the anionic polymerization can be performed in the presence of a co-solvent of the ether solvent and the non-polar solvent.

[0019] In a polymer manufacturing method according to one embodiment, the co-solvent has a Hansen Solubility Parameter of 16 to 20 MPa. ½ It could be.

[0020] In a polymer manufacturing method according to one embodiment, the temperature of the flow path may be -80 to 60°C.

[0021] In a polymer manufacturing method according to one embodiment, on one plane of the main body in the direction in which the flow path extends, the internal space of the microchamber has a shape in which the width gradually increases from the rear to the front based on the flow direction of the fluid, and a front-side connecting portion connected to the front-side microchannel is retracted into the interior, and the inner surface of the internal space may be a curved surface.

[0022] In a polymer manufacturing method according to one embodiment, the collision medium has a length extending in a direction perpendicular to the flow direction of the fluid on one plane formed by the main body, but is curved backward, and the internal space may include a branch portion where the fluid collided by the collision medium flows in both directions along both longitudinal ends of the collision medium, and a confluence portion where the fluid flowing along both directions of the collision medium flows again in one direction.

[0023] In a polymer manufacturing method according to one embodiment, the diameter (L1) of the flow path formed by the branch portion and the diameter (L2) of the flow path formed by the joining portion can satisfy the following equation 1.

[0024] [Formula 1]

[0025] 1 < (L2 / L1) < 3

[0026] In the above equation 1, L1 and L2 is measured along an imaginary center line connecting the front connection portion connected to the front microchannel and the rear connection portion connected to the rear microchannel among the microchannels adjacent to the above microchamber.

[0027] In a polymer manufacturing method according to one embodiment, the inner diameter (R1) of the flow path formed by the microchannel and the shortest distance (D1) between the longitudinal ends of the collision medium can satisfy the following equation 2.

[0028] [Formula 2]

[0029] 3 < D1 / R1< 15

[0030] In a polymer manufacturing method according to one embodiment, at least one of the inlet channel and the connecting channel may have an inner diameter of a rear-end flow path that gradually decreases.

[0031] In a polymer manufacturing method according to one embodiment, the linear velocity of the fluid may be 0.1 to 1 m / s.

[0032] In a polymer manufacturing method according to one embodiment, the monomer may include an aromatic vinyl monomer.

[0033] In a method for producing a polymer according to one embodiment, the non-polar solvent may include a C5-C8 alkane solvent.

[0034] A method for producing a polymer according to one aspect of the present invention can economically produce a high-quality polymer having high chemical uniformity.

[0035] In addition, a method for producing a polymer according to one aspect of the present invention may have the advantage of not requiring low-temperature cooling since anionic polymerization is possible even at relatively high temperatures.

[0036] In addition, a method for producing a polymer according to one aspect of the present invention can continuously produce a high-quality polymer, thereby providing excellent economic benefits.

[0037] Figure 1 is a perspective view illustrating a microflow reactor according to one embodiment of the present invention;

[0038] Figure 2 is a plan view of the microflow reactor shown in Figure 1;

[0039] Figure 3 is a plan view illustrating a microflow reactor according to another embodiment of the present invention;

[0040] Figure 4 is a plan view illustrating a microflow reactor according to another embodiment of the present invention;

[0041] FIG. 5 is a photograph illustrating a microflow reactor according to one embodiment of the present invention.

[0042] Unless otherwise defined, the technical and scientific terms used in this specification have the meaning commonly understood by a person of ordinary skill in the art to which this invention pertains, and descriptions of well-known functions and configurations that may unnecessarily obscure the gist of the present invention in the following description or accompanying drawings are omitted.

[0043] Embodiments of the present invention are provided to more fully explain the present invention to those of ordinary skill in the art. Therefore, the scope of the present invention is not limited to the embodiments described below.

[0044] The terminology used in the description of the present invention is intended solely to describe embodiments of the present invention and is in no way limiting. Unless expressly stated otherwise, singular forms include plural forms.

[0045] The term "includes" in this specification is an open-ended description equivalent to expressions such as "comprises," "contains," "has," or "characterizes," and does not exclude additional elements, materials, or processes not listed.

[0046] Unless otherwise specified, units used herein are based on weight, and as an example, units of % or ratio mean weight% or weight ratio, and weight% means the weight % that any one component of the entire composition occupies in the composition, unless otherwise defined.

[0047] Additionally, the numerical ranges used herein include lower and upper limits and all values ​​within that range, increments logically derived from the shape and width of the defined range, all doubly defined values, and all possible combinations of upper and lower limits of numerical ranges defined in different shapes. Unless otherwise specified herein, values ​​outside the defined numerical range that may arise due to experimental error or rounding of values ​​are also included in the defined numerical range.

[0048] In this specification, terms such as 'top', 'upper part', 'top surface', 'bottom', 'lower part', 'bottom', 'side', etc. are based on the drawings, and in reality, they may vary depending on the direction in which the elements or components are arranged.

[0049] Additionally, throughout the specification, when we say that a part is 'connected' to another part, this includes not only cases where it is 'directly connected', but also cases where it is 'indirectly connected' with other elements in between.

[0050] In this specification, 'polymer' may mean a high molecular weight compound formed by polymerizing monomers and having a weight average molecular weight of 1,000 or more, and includes not only a homopolymer manufactured by polymerizing one monomer but also a copolymer manufactured by polymerizing two or more monomers.

[0051] In this specification, the 'fluid' refers to a material having fluid properties that can flow, and refers to all materials that flow within the microflow reactor. Specifically, the fluid may refer to each of the first solution, the second solution, and the third solution, or a mixture of two or more of the first solution, the second solution, and the third solution. As a specific example, the fluid before the first solution and the second solution are mixed with each other at the front side of the microflow reactor adjacent to the inlet may refer to each of the first solution or the second solution, and after the first solution and the second solution are mixed within the microflow reactor, the fluid may refer to a mixture of the first solution and the second solution and a third solution which is a reactant thereof. In addition, the fluid may refer to the third solution at the rear side of the microflow reactor adjacent to the outlet.

[0052] Although the present invention is described in detail through each embodiment according to the present invention, each embodiment described in the specification should be considered not only to mean a single embodiment but also to mean a combination with other embodiments. Therefore, the citation of a claim in the patent claims is merely an example, and the technical concept of the present invention should not be interpreted solely as a combination with the cited claim, and combinations with various claims also fall within the scope of the technical concept of the present invention.

[0053] Anionic polymerization reactions using conventional flow-type reaction systems have a problem in that, when anionic polymerization initiators and monomers are injected into a reactor, the anionic polymerization initiators and monomers react immediately before they are sufficiently homogeneously mixed, resulting in a large molecular weight distribution of the polymer produced.

[0054] Furthermore, conventional anionic polymerization reactions using flow-through reaction systems force the Reynolds number (Re) of the anionic polymerization initiator and monomer to be relatively uniformly mixed, thereby creating turbulence. However, the homogeneous mixing effect is relatively low compared to the pressure applied, and overloading of the fluid driving source (pump) can occur, which can lead to safety issues.

[0055] In addition, the anionic polymerization reaction using a conventional microflow reactor is very economical because the polymerization reaction must be performed at an extremely low temperature, and the energy consumption of the cooling facility is very high.

[0056] A polymer production method according to one embodiment of the present invention comprises the steps of (S1) injecting a first solution containing at least one solvent selected from the group consisting of ether solvents and non-polar solvents and a monomer, and a second solution containing the solvent and an anionic polymerization initiator into a microflow reactor; and (S2) anionic polymerizing the monomer in the microflow reactor.

[0057] The microflow reactor comprises a main body having at least one inlet hole and an outlet hole formed therein; a microchannel forming a flow path connecting the inlet and the outlet within the main body; a plurality of microchambers arranged along an extension direction of the microchannel and forming an internal space communicated with the flow path; and a collision medium positioned within the internal space to collide with a fluid transported within the internal space and convert a flow of the fluid within the internal space, wherein the microchannel comprises an inlet channel connecting the microchamber located at the frontmost end in the direction of fluid flow within the flow path and the inlet, a connection channel connecting the microchambers adjacent to each other, and an outlet channel connecting the microchamber located at the rearmost end in the direction of fluid flow within the flow path and the outlet. At this time, the Reynolds number (Re) in the inlet channel i ) is the Reynolds number (Re) in the above discharge channel. f ) is characterized by being smaller than that.

[0058] This polymer manufacturing method enables uniform mixing and reaction as the fluid is homogeneously mixed by the microflow reactor, even though a low Reynolds number is maintained at the front side (based on the flow direction of the fluid) of the microflow reactor where the anionic polymerization reaction is performed.

[0059] Specifically, the fluid in the microflow reactor according to the above polymer manufacturing method exhibits a low Reynolds number and forms a laminar flow in the entire flow of the microflow reactor, but the fluid introduced into the microchamber forms a turbulent flow due to collision with the collision medium. Therefore, the fluid can be homogeneously mixed despite exhibiting a laminar flow in the entire microflow reactor. Therefore, the polymer manufacturing method enables homogeneous mixing of the fluid without the need to apply a large pressure to the fluid, and enables the manufacturing of a high-quality polymer with a uniform molecular weight distribution. Specifically, the molecular weight distribution (polydispersity) of the polymer manufactured from the above polymer manufacturing method can be controlled to 1.5 or less, 1.4 or less, 1.3 or less, 1.2 or less, or 1.1 or less.

[0060] In one embodiment, the Reynolds number (Re) in the inlet channel i ) and the Reynolds number (Re) of the above discharge channel f ), that is, the ratio of the Reynolds numbers (Re f / Re i- ) may be greater than 1 and less than 10, 1.1 to 7, 1.1 to 5, 1.5 to 5, 2 to 5, or 3 to 4.8. In the above range, production of a more uniform polymer is possible.

[0061] In one embodiment, the Reynolds number (Re) in the inlet channel i ) is the Reynolds number (Re) in the above discharge channel. f) and the Reynolds number forming a laminar flow is not particularly limited, but may be, without limitation, 50 to 500, 80 to 400, 100 to 350, 150 to 300, or 160 to 280. In the above range, it is possible to produce a uniform polymer even at a relatively high temperature. Specifically, the anionic polymerization reaction may be possible when the temperature of the flow path in the microflow reactor is -70 to 60°C, -50 to 60°C, -40 to 60°C, -30 to 50°C, -20 to 50°C, -10 to 50°C, 0 to 40°C, or 20 to 40°C.

[0062] In one embodiment, the inlet may include a first inlet through which the first solution is introduced and a second inlet through which the second solution is introduced, respectively, and the inlet channel may include a first inlet channel and a second inlet channel extending from the first inlet and the second inlet to the microchamber located at the most forward end. At this time, the Reynolds number (Re i ) may be the Reynolds number of the first inlet channel. That is, the Reynolds number (Re i ) may be the Reynolds number of the first solution flowing in the first inlet channel.

[0063] In one embodiment, the microflow reactor may be provided as a single unit, but alternatively, a plurality of microflow reactors may be arranged. The plurality of microflow reactors may be connected in series, parallel, or series-parallel. In the direction of fluid flow, the outlet of the microflow reactor positioned forward may be connected to the inlet of the microflow reactor positioned backward.

[0064] In one embodiment, the Reynolds number (Re) of the discharge channel f) may be measured in the discharge channel of the microflow reactor located at the rearmost end in the fluid flow when the above microflow reactor is provided in multiple numbers. That is, the Reynolds number (Re) of the discharge channel f ) may be the Reynolds number of the third solution, which is the final product flowing in the above discharge channel.

[0065] According to one embodiment, the polymer manufacturing method changes the linear velocity of the fluid at each location as the diameter of the flow path is repeatedly changed by the microchannels and microchambers. Accordingly, the linear velocity of the fluid within the microflow reactor may differ at each location within the microflow reactor even when the fluid is injected at the same flow rate. Specifically, the linear velocity is fastest in the connecting channel having the smallest flow path cross-sectional area, and the linear velocity is slowest in the microchamber having the largest flow path cross-sectional area.

[0066] In one embodiment, the linear velocity of the fluid within the microflow reactor is not particularly limited as long as it satisfies the Reynolds number, and may be appropriately adjusted depending on the type and properties of the desired polymer. Specifically, the linear velocity of the fluid may be 0.1 to 1.5 m / s, 0.1 to 1 m / s, 0.1 to 0.9 m / s, 0.2 to 0.8 m / s, or, non-limitingly, 0.2 to 0.7 m / s. As the linear velocity of the fluid satisfies the above range, the formation of a dead zone in which the fluid does not flow or the flow velocity rapidly decreases even when the fluid collides with the collision medium within the microflow reactor can be prevented. Accordingly, the fluid is homogeneously mixed throughout the entire flow path area within the microflow reactor, enabling the production of a higher quality polymer.

[0067] The linear velocity of the fluid may be measured in a microchannel within a microflow reactor and may be an average value calculated after measuring at least once. The linear velocity of the fluid may be measured in the first inlet channel.

[0068] The above step (S1) is a step of injecting the first solution and the second solution into the microflow reactor. Through step (S1), the type and flow rate of the first solution and the second solution can be adjusted according to the type and properties of the desired polymer and injected into the microflow reactor. As a specific example, the flow rate (flow rate) of the first solution and the second solution can be adjusted so that the fluid inside the microflow reactor can maintain the linear velocity regardless of the internal capacity of the microflow reactor. The size of the external injection path connected to the microflow reactor can be appropriately adjusted according to the internal capacity of the microflow reactor.

[0069] The internal capacity (volume) of the above microflow reactor refers to the amount of solution that the microflow reactor can accommodate, and may refer to the volume formed by the flow path and internal space formed by the microchannel and microchamber within the microflow reactor. The internal capacity of the microflow reactor is not particularly limited, and the flow rates of the first solution and the second solution injected in step (S1) can be adjusted in proportion to the internal capacity of the microflow reactor.

[0070] The internal capacity of the above microflow reactor can be adjusted according to the diameter and length of the flow path within the microflow reactor and the size of the internal space of the microchamber, or can be adjusted according to the number of microflow reactors that are interconnected. Specifically, the internal capacity of the microflow reactor can be increased in proportion to the diameter and length of the flow path within the microflow reactor, the size of the internal space of the microchamber, and the number of microflow reactors that are connected, and the flow rates of the first solution and the second solution injected in step (S1) can be adjusted in proportion to this.

[0071] As a non-limiting example, when the diameter of the external injection path connecting the microflow reactor and the storage tank in which the first solution is stored is 1 / 8 to 1 / 4 inch, and a plurality of microflow reactors are connected so that the internal volume of the microflow reactor is 60 to 100 mL in total, in the step (S1), the first solution including the monomer may be injected at a flow rate of 70 to 150 mL / min, 80 to 130 mL / min, or 80 to 120 mL / min, and the second solution including the anionic polymerization initiator may be injected at a flow rate of 20 to 80 mL / min, 30 to 70 mL / min, or 40 to 60 mL / min, but is not limited thereto.

[0072] As another example, when the diameter of the external injection path connecting the microflow reactor and the storage tank in which the first solution is stored is 1 to 1 / 3 inch, and a plurality of microflow reactors are connected so that the internal capacity of the microflow reactor is 2000 to 2200 mL in total, in the step (S1), the first solution including the monomer can be injected at a flow rate of 2800 to 6000 mL / min, 3200 to 5200 mL / min, or 3600 to 4000 mL / min, and the second solution including the anionic polymerization initiator can be injected at a flow rate of 800 to 3200 mL / min, 1200 to 2800 mL / min, or 1600 to 2400 mL / min, but is not limited thereto.

[0073] In other words, in the step (S1), the flow rate can be adjusted so that the residence time of the fluid is 5 seconds or more, 10 seconds or more, 15 seconds or more, or 20 seconds or more, regardless of the internal capacity of the microflow reactor, and, without limitation, the flow rate can be adjusted so that the residence time is 60 seconds or less. Specifically, in the step S1), the flow rates, that is, the flow rates of the first solution and the second solution, can be adjusted so that the residence time of the fluid within the microflow reactor is 5 to 60 seconds, 10 to 55 seconds, or 15 to 50 seconds. In the above range, it may be possible to produce a more homogeneous polymer.

[0074] The first solution comprises one or more solvents selected from the group consisting of ether solvents and non-polar solvents as described above, and a monomer. Specifically, the first solution may contain the monomer in the ether solvent, or the monomer in the non-polar solvent. Alternatively, the first solution may contain the monomer in a co-solvent of the ether solvent and the non-polar solvent.

[0075] In the above step (S1), the concentration of the monomer of the first solution can be appropriately adjusted depending on the type of monomer, but according to one embodiment, the concentration of the first solution can be, but is not limited to, 1 to 5 M, 1 to 4 M, 1 to 3 M, or 2 to 3 M. The first solution having a concentration within the above range has an appropriate viscosity for fluid transport, and can be smoothly injected into the microflow reactor in the step (S1).

[0076] The ether solvent included in the first solution may be an aliphatic aprotic ether solvent or an alicyclic aprotic ether solvent. Specific examples thereof include, but are not limited to, diethyl ether, 1,3-dioxolane, 1,2-dimethoxyethane, tetrahydrofuran (THF), 3,5-dimethyl isoxazole, 1,4-dioxane, 4-methyl-1,3-dioxolane, tetraethylene glycol dimethyl ether (TEGDME), isopropyl ether, or 1,2-diethoxyethane, and a mixed solvent thereof.

[0077] The non-polar solvent may be specifically a non-polar hydrocarbon solvent. More specifically, the non-polar solvent may be an aromatic hydrocarbon solvent or an aliphatic hydrocarbon solvent, and even more specifically, the aliphatic hydrocarbon solvent may be a C5-C8 alkane solvent. As a non-limiting example, the non-polar solvent may be at least one selected from the group consisting of benzene, toluene, butane, pentane, neopentane, hexane, cyclohexane, methyl cyclohexane, heptane, and octane. As a specific example, the non-polar solvent may be a mixed solvent of hexane and heptane. The monomer may be a styrene monomer, an acrylate monomer, an olefin monomer, or a vinyl monomer, but is not limited to a specific monomer.

[0078] According to one embodiment, the monomer may include an aromatic vinyl monomer. Specifically, the aromatic vinyl monomer may be styrene, C1-C6 alkoxy styrene, and more specifically, C1-C4 alkoxy styrene.

[0079] Alkoxy-substituted styrene monomers are known to exhibit slower anionic polymerization rates than unsubstituted styrene. That is, the alkoxy group substituted on the phenyl group of styrene has the properties of an electron-donating group, so the polymerization reaction by insertion of the monomer into the living terminal where polymerization occurs does not proceed quickly. In addition, alkoxy-substituted styrene monomers are slow to initiate polymerization by forming a complex with a metal ion. For the same reason as mentioned above, the overall polymerization reaction rate of alkoxy-substituted styrene monomers in anionic polymerization is known to be approximately 10 times lower than that of styrene monomers. On the other hand, the delayed polymerization initiation reaction can provide the advantage of not inducing an immediate polymerization reaction when the monomer and initiator solutions are mixed, but rather of initiating polymerization simultaneously after they are uniformly mixed in at least one microchamber. The aforementioned effects can be particularly effective in improving operational reliability and economic efficiency in microflow reactors, where the fluid velocity is low and turbulence is not formed. Meanwhile, the polymerization initiation reaction may be further delayed due to the inclusion of a non-polar solvent.

[0080] The second solution comprises at least one solvent selected from the group consisting of the ether solvents and non-polar solvents described above, and an anionic polymerization initiator. Specifically, the second solution may comprise an ether solvent containing an anionic polymerization initiator, or a non-polar solvent containing an anionic polymerization initiator. Alternatively, the second solution may comprise an anionic polymerization initiator in a co-solvent of an ether solvent and a non-polar solvent.

[0081] However, so that the anionic polymerization can occur in the presence of a cosolvent of an ether solvent and a non-polar solvent, the solvent of the first solution and the solvent of the second solution may both be cosolvents or may include at least one different solvent. As a non-limiting example, when the solvent of the first solution is an ether solvent, the solvent of the second solution may be a non-polar solvent or a cosolvent of an ether solvent and a non-polar solvent. Alternatively, when the solvent of the first solution is the cosolvent, the solvent of the second solution may be an ether solvent or a non-polar solvent, or the solvent of the second solution may also be a cosolvent.

[0082] The above anionic polymerization initiator may include an organometallic compound. The organometallic compound may be an organic alkali metal compound, and examples thereof include, but are not limited to, ethyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, lithium biphenyl, lithium naphthalene, 1,1-diphenylhexyllithium, 1,1-diphenyl-3-methylpentyllithium, 1,4-dilithio-2-butene, 1,6-dilithiohexane, and the like. Specifically, the initiator may be one or a combination of two or more selected from the group consisting of n-butyllithium, sec-butyllithium, and t-butyllithium.

[0083] According to one embodiment, the concentration of the anionic polymerization initiator in the second solution may be, but is not limited to, 0.01 to 0.5 M, 0.01 to 0.25 M, 0.02 to 0.2 M, or 0.05 to 0.2 M. The second solution having a concentration in the above range has an appropriate viscosity for fluid transport, and can be smoothly injected into the microflow reactor in step (S1).

[0084] In one embodiment, the anionic polymerization in step (S2) can be carried out in the presence of a cosolvent of an ether solvent and a non-polar solvent. Since the anionic polymerization is carried out in the presence of the cosolvent within the microflow reactor, the anionic polymerization reaction is possible even at relatively high temperatures, and a high-quality polymer with high chemical uniformity can be economically produced. In addition, the method for producing the polymer can continuously produce a high-quality polymer, thereby increasing productivity.

[0085] Specifically, as the fluids, i.e., the first solution and the second solution, are injected and transported through the flow path in the microflow reactor, the monomer and the anionic polymerization initiator are mixed and reacted under a cosolvent.

[0086] Accordingly, the polymer manufacturing method eliminates the need for cryogenic cooling equipment, which requires excessive power consumption, enabling the production of high-quality polymers with greater economic efficiency. Furthermore, the polymer manufacturing method enables the efficient mass production of high-quality polymers with high chemical uniformity.

[0087] According to one embodiment, the cosolvent of the ether solvent and the non-polar solvent may have a Hansen Solubility Parameter of 16 to 20, 17 to 19, 18 to 19, or 18.1 to 18.7. Such a cosolvent can achieve more uniform mixing of the fluid and increase the anionic polymerization reaction temperature. In addition, even after the anionic polymerization reaction, the flow rate of the fluid can be satisfied within the above range, thereby enabling the production of a polymer with a further improved molecular weight distribution.

[0088] The above Hansen solubility (S co ) can be calculated using the following formula.

[0089] [Calculation formula]

[0090] S co (MPa ½) = (S1×W1)+(S2×W2)

[0091] In the above formula, S1 is the Hansen solubility of the ether solvent, W1 is the weight% of the ether solvent in the cosolvent, S2 is the Hansen solubility of the nonpolar solvent, and W1 is the weight% of the nonpolar solvent in the cosolvent.

[0092] At this time, the Hansen solubility of each solvent is a known Hansen solubility parameter (based on 25°C, for example, a value known through Charles Hansen, "Hansen Solubility Parameters: A User's Handbook" CRC Press (2007)).

[0093] According to one embodiment, the first solution and the second solution may be free of dissolved oxygen. Removal of dissolved oxygen may be accomplished by injecting nitrogen or argon gas into the storage tank in which the solutions are stored. The first and second solutions, from which dissolved oxygen has been removed, may have the effect of suppressing side reactions caused by cavitation resulting from fluid collisions during an anionic polymerization reaction in a microflow reactor.

[0094] Step (S2) is a step for anionic polymerization of the monomer in the microflow reactor, wherein the first solution and the second solution injected into the microflow reactor through step (S1) are mixed and reacted to produce a third solution containing a polymer. In step (S2), the monomer is anionic polymerized by the anionic polymerization initiator, thereby producing a polymer.

[0095] The third solution may refer to a mixture of the first and second solutions, as well as their reactants. Specifically, the third solution may include the cosolvent, a product (polymer) resulting from the anionic polymerization reaction, unreacted products, intermediate products, and side products.

[0096] The polymer may be a homopolymer, a random copolymer, or a block copolymer. The random or block copolymer may be a copolymer of two or more monomers, and for example, in the case of a copolymer of three or more monomers, it may be a terpolymer in which three monomers are uniformly present in the polymer chain. For another example, when three monomers of different species are sequentially injected into the microflow reactor and then an anionic polymerization initiator is injected, a triblock copolymer may be formed. On the other hand, when two of the three monomers are pre-mixed in the microflow reactor without injecting an anionic polymerization initiator, and then an anionic polymerization initiator is injected and then the last monomer is injected, a diblock copolymer having a structure of (M1M2)n(M3)m may be prepared. The type and properties of the polymer manufactured in this way can be controlled depending on the order of injection of the first and second solutions and the type and number of monomers included in the first and second solutions.

[0097] According to one aspect of the present invention, the polymer can have its properties controlled through one or a combination of two or more of the following means.

[0098] (1) Control of the residence time of monomer and anionic polymerization initiator

[0099] (2) Control of the flow rate of fluid in the microflow reactor

[0100] (3) Number of microchambers and connection structure

[0101] (4) Temperature of the microchamber

[0102] An increase in flow rate is closely related to residence time, and either flow rate or residence time can be adjusted to ensure the necessary reaction time to achieve the target conversion rate. Meanwhile, if reaction time is sufficient, a higher flow rate can be desirable because it enhances the mixing effect.

[0103] Additionally, the shape and length of the entire path through which the fluid moves within the microflow reactor can be controlled by the number of microchambers within the microflow reactor and their connection structure, which may also be related to the residence time. The number of microchambers may be 10 to 50, 15 to 40, or 20 to 30, and the microchambers may be connected in series, parallel, or series-parallel. As the flow rate increases, the number of microchambers can be increased.

[0104] The temperature within the microchamber can be appropriately controlled by circulating a known cooling medium. The cooling medium can be cooled through a cooler, and the cooled cooling medium contacts the outer wall of the microchamber to control the temperature of the fluid flowing along the inner wall of the microchamber, and can remove heat generated by the exothermic reaction. The temperature within the microchamber can be controlled to -80 to 60°C, -50 to 60°C, -40 to 60°C, -30 to 50°C, -20 to 50°C, -10 to 50°C, 0 to 40°C, or 20 to 40°C.

[0105] A polymer production method according to one aspect of the present invention may further include, after step (S2), a step (S3) of injecting a polymerization terminator into a microflow reactor. The polymerization terminator may include, but is not limited to, a proton-donating compound such as methanol, a halide such as methyl iodide, or other electrophilic substances. The anionic polymerization reaction may be terminated through step (S3).

[0106] According to one aspect of the present invention, the polymer production method can satisfy one or more of the following conditions.

[0107] Condition 1. The flow rate (velocity) of the first solution is greater than that of the second solution.

[0108] Condition 2. The residence time of the fluid in the microflow reactor is 10 to 50 seconds.

[0109] Condition 3. Inlet flow rate (Q) in the microflow reactor in , ㎖ / min) and the minimum cross-sectional area of ​​the flow path in the microflow reactor (A min , cm 2 ) for the total length of the euro (L) total, The rain (cm) satisfies the following relationship 1.

[0110] [Relationship 1]

[0111] 7 cm 2 / min ≤ Log(Q in ×(L total / A min ))≤ 9 cm 2 / min

[0112] In the above condition 3, the inflow flow rate (Q in ) means the sum (Q1+Q2) of the flow rate of the first solution (Q1) and the flow rate of the second solution (Q2), and the minimum cross-sectional area of ​​the flow path (A min ) means the cross-sectional area in the diameter direction of the connecting channel, and the total length of the flow path means the value obtained by dividing the internal capacity of the microflow reactor by the cross-sectional area of ​​the connecting channel.

[0113] Specifically, in the above condition 1, the ratio (Q) of the flow rate of the first solution (Q1) and the flow rate of the second solution (Q2) 1 / Q2) may be greater than 1 and less than or equal to 5, greater than 1 and less than or equal to 4, or greater than 1 and less than or equal to 3, and in condition 2, the residence time may be 18 to 45 seconds or 20 to 43 seconds, and in condition 3, the Log(Q) of the above relational expression 1 in ×(L total / A min )) is 7.2 cm 2 / min to 8.8 cm 2 / min, 7.5 cm 2 / min to 8.6 cm 2 / min, 7.6 cm 2 / min to 8.5 cm 2 / min or 7.7 cm 2 / min to 8.4 cm 2 / min may be.

[0114] In an unrelated manner, the above polymer manufacturing method can satisfy all of the above conditions 1 to 3, and such a polymer manufacturing method can produce a more homogeneous polymer.

[0115] The above microfluidic reactor refers to a device used to obtain a product through chemical reaction synthesis of one or more fluids passing through microchannels measuring micrometers or larger. Specifically, according to one embodiment of the present invention, the effects aimed at by the present invention can be achieved by using the microfluidic reactor.

[0116] Hereinafter, a microflow reactor according to one embodiment of the present invention will be described in detail with reference to the drawings, but is not limited thereto.

[0117] Figures 1 and 2 illustrate a microflow reactor according to one embodiment of the present invention. For convenience of explanation, the drawings depict the microflow reactor with an open top; however, in practice, the microflow reactor may have a closed top (upper surface).

[0118] Referring to FIGS. 1 and 2, a microflow reactor according to the present invention includes a main body (10) having an inlet hole (11) and an outlet hole (13), a microchannel (20), a microchamber (30), and an impact medium (50).

[0119] The above main body (10) is a medium in which the microchannel (20), microchamber (30), and collision medium (50) are formed, and provides a flow path through which the first to third solutions move and a reaction space in which anionic polymerization reaction occurs. The above main body (10) may be composed of a material that is easy to mold and has high corrosion resistance, non-flammability, and chemical durability. Specifically, the above main body (10) may be formed of metal, ceramic, plastic, or a composite material thereof.

[0120] As shown in the drawing, the main body (10) may be a plate-shaped structure forming a single plane, and the main body (10) may be formed by extending a flow path by a microchannel (20) to be described later along the plane direction of the plate-shaped structure inside. The main body (10) is formed with at least one inlet (11) through which a first solution and a second solution can be injected inside, and an outlet (13) through which a third solution can be discharged to the outside.

[0121] The above inlet (11) may include a first inlet (11a) and a second inlet (11b) through which the first solution and the second solution can be injected, respectively, as shown in the drawing, but is not limited thereto and may be provided as a single inlet or may be provided in three or more inlets. That is, the above inlet (11) may be appropriately adjusted according to the type and number of solutions required for the production of the polymer to be produced.

[0122] The inlet (11) and outlet (13) of the above main body (10) are connected to a flow control system so that the flow rate and flow speed can be appropriately controlled.

[0123] Unlike what is shown in the drawing, the main body (10) may have a separate plate member (not shown) attached to the upper surface to close the passage to the upper part of the main body (10).

[0124] The above inlet (11) and outlet (13) may be formed at a position adjacent to the edge of the main body (10) provided as a planar structure as shown in the drawing, but of course, they may be formed at the center of the main body (10) or an adjacent portion thereof.

[0125] The above microchannel (20) forms a flow path within the main body (10), and forms a flow path connecting an inlet hole (11) and an outlet hole (13) on one plane formed by the main body (10). The shape of the flow path formed by the microchannel (20) is not particularly limited. For example, as illustrated in the drawing, the microchannel (20) may form a meandering flow path on one plane formed by the main body (10). Such a microchannel (20) can integrate a flow path into the main body (10), thereby making the reaction system more compact.

[0126] The microchannel (20) according to one aspect of the present invention may include an inlet channel (21) connecting the microchamber (30) located at the most forward end in the direction of fluid flow in the flow path and the inlet (11), a connection channel (23) connecting adjacent microchambers (30), and an outlet channel (25) connecting the microchamber (30) located at the most rear end in the direction of fluid flow in the flow path and the outlet (13).

[0127] At this time, the direction of fluid flow refers to the macroscopic flow of fluid from the inlet (11) to the outlet (13). The microscopic flow of fluid converted by the collision medium (50), i.e., the turbulent flow, is ignored. Based on the direction of fluid flow, the inlet (11) side of the microflow reactor can be divided into the front (or front end) and the outlet (13) side can be divided into the rear (or rear end).

[0128] However, as the microchannel (20) forms a meandering path on the main body (10), when assuming that one microchamber (30) and the microchambers (30) connected to it in a straight line are a microchamber array, the adjacent microchamber arrays may appear to have fluids moving in opposite directions.

[0129] As the number of inlets (11) is provided, the number of inlet channels (21) can be provided correspondingly. For example, as shown in the drawing, when the main body (10) includes a first inlet (11) and a second inlet (11), the inlet channel (21) can include a first inlet channel (21a) extending from the first inlet (11) and a second inlet channel (21b) extending from the second inlet (11). At this time, the first and second inlet channels (21a) (21b) can be connected to each other at the front end of the microchamber (30) located at the frontmost end.

[0130] The connecting channel (23) forms a path connecting the microchambers (30), and may include a main connecting channel (23) connecting adjacent microchamber arrays, and a sub-connecting channel (23a) connecting each microchamber (30) within the microchamber array. As illustrated in FIGS. 1 and 2, the main connecting channel (23) and the sub-connecting channel (23a) may be provided simultaneously, but alternatively, as illustrated in FIG. 3, each microchamber (30) may be directly connected without the sub-connecting channel (23a).

[0131] The discharge channel (25) forms a path connecting the microchamber (30) located at the rear end and the discharge port (13), so that the fluid passing through the microchambers (30) can be discharged to the outside of the main body (10) through the discharge port (13).

[0132] In the microchannel (20) according to one aspect of the present invention, at least one of the inlet channel (21) and the connecting channel (23) may have an inner diameter of a flow path at the rear end that gradually decreases. That is, the rear end of the inlet channel (21) or the connecting channel (23) may have a tapered shape in which the width of the flow path gradually decreases. The fluid can be transported at an increased flow rate to the microchamber (30) connected to the inlet channel (21) or the connecting channel (23). Accordingly, the fluid can be supplied to the adjacent microchamber (30) at a high flow rate to continuously induce remarkably excellent mixing and a homogeneous reaction.

[0133] The above microchambers (30) are arranged in multiple numbers along the flow path, forming an internal space (35) that is connected to the flow path formed by the microchannels (20). The internal space (35) can be a transport path through which the fluid is transported, and at the same time, a mixing space through which the fluid can be sufficiently mixed by the collision medium (50).

[0134] According to one aspect of the present invention, the internal space (35) of the microchamber (30) may have a shape in which the width gradually increases from the rear to the front based on the flow direction of the fluid on one plane of the main body (10) in the direction in which the flow path extends, and the front-side connecting portion connected to the front-side microchannel (20) is retracted into the interior. At this time, the inner surface of the internal space (35) may be a curved surface. In other words, the inner space (35) of the microchamber (30) may have a circular shape that is distorted in one direction, i.e., a heart shape, as illustrated in the drawing. The internal space (35) of the microchamber (30) as described above allows the fluid to flow smoothly along the inner surface of the internal space (35) even if the fluid collides with the collision medium (50) and the flow changes. That is, although turbulence of the fluid is generated within the internal space (35) by the collision medium (50), the flow of the fluid from the inlet (11) to the outlet (13) is not obstructed, so that continuous production of the polymer is possible smoothly.

[0135] The above collision medium (50) is located in the internal space (35) of the microchamber (30) and is an obstacle to the fluid flow within the microchamber (30). The collision medium (50) is not particularly limited as long as it has a structure that can form turbulence within the internal space (35) by colliding the fluid flowing within the microchamber (30). According to one embodiment, the collision medium (50) has a length extending in a direction perpendicular to the flow direction of the fluid on one plane formed by the main body (10), and is curved backward. However, both longitudinal ends of the collision medium (50) do not come into contact with the inner surface of the microchamber (30).

[0136] At this time, the internal space (35) may include a branch portion (36) in which the fluid collided by the collision medium (50) flows in both directions along the longitudinal ends of the collision medium (50), and a confluence portion (38) in which the fluid flowing along both directions of the collision medium (50) flows again in one direction. In such an internal space (35) and collision medium (50), the fluid collides for the first time by the collision medium (50) and is homogeneously mixed, and after the fluid collided for the first time passes through the branch portion (36), the fluids collide a second time while facing each other at the confluence portion (38), thereby inducing more uniform mixing and reaction. Accordingly, the formation of turbulence in the fluid can be maximized, while the flow velocity of the fluid can be maintained constant, thereby inducing excellent mixing and homogeneous reaction of the fluid more smoothly.

[0137] The above internal space (35) can satisfy the following equation 1 in terms of the diameter (L1) of the flow path formed by the branch portion (36) and the diameter (L2) of the flow path formed by the joining portion (38).

[0138] [Formula 1]

[0139] 1 < (L2 / L1) < 3

[0140] In the above equation 1, L1 and L2 is measured along an imaginary center line connecting the forward connection portion connected to the forward microchannel (20) and the rear connection portion connected to the rear microchannel (20) among the microchannels (20) adjacent to the microchamber (30). Specifically, L2 / L1 may be 1.1 to 2.8, 1.2 to 2.5, or 1.5 to 2.3. Accordingly, the fluid can be transferred at a high flow rate and mixed more homogeneously when transferred from the branch portion (36) to the confluence portion (38).

[0141] The length by which the above collision medium (50) extends is not particularly limited as long as it is a length that does not contact the inner surface of the microchamber (30) as described above. However, in one embodiment, the inner diameter (R1) of the flow path formed by the microchannel (20) and the shortest distance (D1) between the longitudinal ends of the collision medium (50) can satisfy the following equation 2.

[0142] [Formula 2]

[0143] 3 < D1 / R1< 15

[0144] Specifically, D1 / R1 may be 4 to 13, 5 to 12, or 6 to 10. Accordingly, the fluid flowing into the microchamber (30) from the microchannel (20) can collide more strongly with the collision medium (50), thereby inducing significantly superior mixing and homogeneous reaction.

[0145] According to one embodiment, the flow path formed by the microchannel (20) can be connected in series, in parallel, or in series and parallel between the inlet (11) and the outlet (13).

[0146] Fig. 4 illustrates a microflow reactor in which the inlet (11) and the outlet (13) are connected in series and parallel with each other. In such a microflow reactor, since the flow paths are formed in series and parallel, the microchambers (30) arranged in communication with the flow paths can also be connected in series and parallel with each other. The microchannel (20) can include a series connection portion (20A) in which the flow paths are connected in series, and a parallel connection portion (20B) in which the flow paths are connected in parallel. As illustrated in the drawing, the microchambers located in the parallel connection portion (20B) can be positioned in parallel with each other. In this case, the microchambers (30) that are parallel to each other can be connected to each other through a parallel connection channel (23b). Such a microflow reactor can react a larger amount of fluid, thereby enabling larger-scale production.

[0147] According to one embodiment, the microflow reactors may be connected in series, parallel, or series-parallel in a plurality of units, each having the same or different internal capacity, and each microflow reactor may be operated as a single reactor module. Accordingly, each microflow reactor may be controlled at different flow rates, residence times, and temperatures.

[0148] Hereinafter, the present invention will be described in detail through examples. However, it should be noted that the examples described below are intended only to illustrate and concretize the present invention and are not intended to limit the scope of the invention. This is because the scope of the invention is determined by the matters set forth in the patent claims and matters reasonably inferred therefrom.

[0149] (Examples 1 to 17)

[0150] A polymer was manufactured by anionic polymerization using a microflow reactor (Module size: 162 × 188.5 × 21 (mm)) as shown in Fig. 5. The internal volume of the microflow reactor was controlled by the number of connected microflow reactors, and the internal volume (capacity) for each example is shown in Table 1 below.

[0151] Tert-butoxystyrene (4-tert-butoxy styrene), whose concentration was controlled by the solvent and whose oxygen was removed through argon bubbling, was injected into the first inlet as the first solution, and n-butyllithium (n-BuLi), whose concentration was controlled by the solvent and whose oxygen was removed through argon bubbling, was injected into the second inlet as the second solution. The concentrations of the first and second solutions and the solvents used for each example are shown in Table 1 below.

[0152] Afterwards, a polymerization terminator with a concentration of 1 M (solvent: tetrahydrofuran (THF)) was injected into the first inlet. The polymerization terminator used for each example is listed in Table 1 below.

[0153] The first solution, the second solution, and the polymerization terminator were injected through a 1 / 8 inch tube, and the injection flow rates of the first solution, the second solution, and the polymerization terminator for each example, the temperature of the flow path in the microflow reactor, and R (relationship between flow rate, cross-sectional area of ​​the flow path, and length of the flow path) calculated from the following equation 2 are shown in Table 2.

[0154] [Relationship 2]

[0155] R (cm) 2 / min) = Log(Q in ×(L total / A min ))

[0156] In the above relation 1, Q in is the inlet flow rate (㎖ / min) in the microflow reactor, i.e., the sum (Q1+Q2) of the flow rate of the first solution (Q1) and the flow rate of the second solution (Q2), and A minis the minimum cross-sectional area (cm) of the flow path in the microflow reactor. 2 ), that is, it means the cross-sectional area in the diameter direction of the connecting channel, L total is the total length (cm) of the euro, i.e., the internal capacity (volume) of the microflow reactor divided by the cross-sectional area of ​​the connecting channel.

[0157] In addition, the linear velocities in the first inlet channel and the discharge channel are listed in Table 3 below, and the Reynolds number (Re) in the first inlet channel is calculated from the following mathematical formula. i ), Reynolds number (Re) in the discharge channel f ) and its ratio (Re f / Re i ) are also described in Table 3 below.

[0158] [Mathematical formula]

[0159]

[0160] In the above mathematical formula, ρ(kg / m3) is the density of the fluid, V(m / s) is the linear velocity of the fluid, D(m) is the diameter of the microchannel, μ((Ns) / m 2 ) refers to the viscosity of the fluid. At this time, the viscosity of the fluid was measured using the value measured by the HBDV2T viscometer at 20℃, and the density of the fluid was calculated using the value calculated at 20℃. The diameters of the microchannels (first inlet channel and outlet channel) were calculated to be 25mm.

[0161] During the above polymerization, the temperature of the flow path in the microflow reactor was controlled through a temperature control device (TCU System (Temperature Control Unit)) connected to the microflow reactor, and the total flow rate was measured at the discharge channel located at the rearmost end of the microflow reactor.

[0162]

[0163]

[0164]

[0165] (Comparative examples 1 and 2)

[0166] In the above example, the polymer was manufactured in the same manner as in the example except that the polymer was manufactured under the conditions described in Tables 4 and 5 below. The linear velocities in the first inlet channel and the discharge channel are described in Table 6 below, and the Reynolds number (Re) in the first inlet channel calculated from the above mathematical formula i ), Reynolds number (Re) in the discharge channel f ) and its ratio (Re f / Re i ) are also described in Table 6 below.

[0167] (Comparative examples 3 to 10)

[0168] In the above example, the polymer was manufactured using the same method as in the above example, except that the polymer was manufactured using a PFA tube (inner diameter 1 / 8 inch, Perfluoroalkoxy alkanes tube / Swagelok) instead of a microflow reactor. The total volume of the flow path in the PFA tube for each comparative example, the solvent and concentration of the first and second solutions, and the polymerization terminator for the third solution are shown in Table 4 below, and the input flow rates of the first solution, the second solution, and the polymerization terminator for each comparative example and the temperature of the flow path in the microflow reactor are shown in Table 5 below, and the Reynolds number (Re) in the first inlet channel calculated from the above mathematical formula i ), Reynolds number (Re) in the discharge channel f ) and its ratio (Re f / Re i ) are also described in Table 6 below.

[0169] (Comparative examples 11 and 12)

[0170] In Comparative Examples 1 and 2, a polymer was prepared in the same manner as in Comparative Examples 1 and 2, except that the polymer was prepared using a PFA tube (inner diameter 1 / 8 inch, Perfluoroalkoxy alkanes tube / Swagelok) instead of a microflow reactor.

[0171]

[0172]

[0173]

[0174] Polymer Evaluation

[0175] 1) Conversion rate (%)

[0176] The conversion rate of the polymer manufactured using the following calculation formula 1 was calculated and shown in Table 7 below.

[0177] [Calculation Formula 1]

[0178] Conversion rate (%) = ((number of moles of tert-butoxystyrene reacted) / (number of moles of tert-butoxystyrene introduced)) × 100

[0179] 2) Molecular weight, polydispersity

[0180] The number average molecular weight (Mn) and polydispersity index (PDI) of the polymers manufactured in the examples and comparative examples were measured using gel permeation chromatography (GPC) from Waters. The columns used were Shodex KF-801, KF-802, KF-803, and KF-804, and the standard sample was Shodex polystyrene. The solvent was tetrahydrofuran, the temperature was 40°C, and the flow rate was 1.0 mL / min. The results are shown in Table 5 below.

[0181] 3) Whether there is a side effect

[0182] In polymerization reactions involving p-alkoxystyrene as a monomer, for example, p-methoxystyrene, the polymerization initiation reaction is known to proceed very slowly and the termination reaction to proceed rapidly (J. Polym. Sci. Part A-1 1969, 7, vol 7, pp 2859-2873). The occurrence of the termination reaction can be easily confirmed by the color change of the polymerization solution, and the rapid termination reaction may produce a polymer with a wide PDI or even cause a crosslinking reaction by ring metalation, which may produce an insoluble precipitate.

[0183] To determine whether a side reaction occurred in the polymer manufacturing method according to the examples and comparative examples, the color change of the fluid within the reactor was visually observed. If the reaction proceeds well without a side reaction, the fluid within the reactor exhibits a unique color close to red and orange. However, if a side reaction occurs, the unique color is lost and changes to transparent. Based on this, the presence or absence of a side reaction was determined by observing the color of the fluid within the reactor, and the results are shown in Table 7 below. If a side reaction occurred, it is marked with an "○", and if no side reaction occurred, it is marked with an "×".

[0184]

[0185] Referring to Table 7 above, it was confirmed that the polymer manufactured according to the examples had a PDI closer to 1 than the comparative examples, and that a homogeneous polymer could be manufactured. In addition, it was confirmed that the polymer manufactured from the examples had a lower number average molecular weight of about 5000 than the comparative examples. In addition, it was confirmed that most of the examples had a conversion rate of 100%, and it was confirmed that no side reactions occurred.

Claims

1. (S1) A step of injecting a first solution containing one or more solvents selected from the group consisting of ether solvents and non-polar solvents and a monomer, and a second solution containing the solvent and an anionic polymerization initiator into a microflow reactor; and (S2) a step of anionic polymerizing the monomer in the microflow reactor; The microflow reactor comprises a main body having at least one inlet hole and an outlet hole formed therein; a microchannel forming a flow path connecting the inlet hole and the outlet hole within the main body; a plurality of microchambers arranged along the extension direction of the microchannel and forming an internal space communicated with the flow path; and a collision medium positioned within the internal space to collide with a fluid transported within the internal space and to change the flow of the fluid within the internal space. The microchannel includes an inlet channel connecting the microchamber located at the most forward end in the direction of fluid flow within the path and the inlet, a connection channel connecting the adjacent microchambers, and an outlet channel connecting the microchamber located at the most rear end in the direction of fluid flow within the path and the outlet. Reynolds number (Re) in the above inflow channel i ) is the Reynolds number (Re) in the above discharge channel. f ) smaller than that of a polymer.

2. In paragraph 1, The ratio of the above Reynolds numbers (Re f / Re i- ) is 1.1 to 5, a method for producing a polymer.

3. In paragraph 1, The above inlet includes a first inlet through which the first solution flows in, and a second inlet through which the second solution flows in, respectively. The above inlet channel includes a first inlet channel and a second inlet channel extending from the first inlet port and the second inlet port to the microchamber located at the most forward end, respectively. The above Reynolds number (Re i ) is the Reynolds number of the first inlet channel, a method for producing a polymer.

4. In paragraph 1, Reynolds number (Re) in the above inflow channel i ) is 100 to 350, a method for producing a polymer.

5. In paragraph 1, A method for producing a polymer, wherein the concentration of the monomer in the first solution is 1 to 5 M, and the concentration of the anionic polymerization initiator in the second solution is 0.01 to 0.5 M.

6. In paragraph 1, A method for producing a polymer, wherein the above anionic polymerization is performed in the presence of a co-solvent of the ether solvent and the non-polar solvent.

7. In paragraph 6, The above co-solvent has a Hansen Solubility Parameter of 16 to 20 MPa. ½ A method for producing a polymer.

8. In paragraph 1, A method for producing a polymer, wherein the temperature of the above-mentioned euro is -80 to 60°C.

9. In paragraph 1, On one plane of the main body in the direction in which the above euro extends, The internal space of the above microchamber is gradually wider from the rear to the front based on the flow direction of the fluid, and the front-side connecting portion connected to the front-side microchannel is shaped to be retracted inside. A method for manufacturing a polymer, wherein the inner surface of the above-mentioned internal space is a curved surface.

10. In paragraph 1, The above collision medium has a length extending in a direction perpendicular to the flow direction of the fluid on a plane formed by the body, but is curved backward, A method for manufacturing a polymer, wherein the internal space includes a branch portion where the fluid collided by the collision medium flows in both directions along the longitudinal ends of the collision medium, and a confluence portion where the fluid flowing along both directions of the collision medium flows again in one direction.

11. In paragraph 10, A method for manufacturing a polymer, wherein the diameter (L1) of the flow path formed by the above branch portion and the diameter (L2) of the flow path formed by the above joining portion satisfy the following equation 1. [Formula 1] 1 < (L2 / L1) < 3 (In the above equation 1, L1 and L2 is measured along an imaginary center line connecting the front connection part connected to the front microchannel and the rear connection part connected to the rear microchannel among the microchannels adjacent to the above microchamber.) 12. In paragraph 10, A method for manufacturing a polymer, wherein the inner diameter (R1) of the flow path formed by the above microchannel and the shortest distance (D1) between the longitudinal ends of the collision medium satisfy the following equation 2. [Formula 2] 3 < D1 / R1< 15 13. In paragraph 1, A polymer manufacturing method, wherein at least one of the above inlet channels and connecting channels has an inner diameter of a rear-end flow path that gradually decreases.

14. In paragraph 1, A method for producing a polymer, wherein the linear velocity of the fluid is 0.1 to 1 m / s.

15. In paragraph 1, A method for producing a polymer, wherein the monomer comprises an aromatic vinyl monomer.

16. In paragraph 1, A method for producing a polymer, wherein the above non-polar solvent comprises a C5-C8 alkane solvent.

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