Method for manufacturing functional polymer by anionic polymerization method

Abstract

The present invention relates to a method for manufacturing a functional polymer by an anionic polymerization method. The method for manufacturing a polymer according to the present invention can economically manufacture a polymer having high chemical uniformity, and enables an anionic polymerization reaction even at a relatively high temperature compared to 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 advantages of easy control of heat generated or consumed by chemical reactions and material transfer compared to batch reactors.

[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] In addition, conventional flow-type reaction systems enable efficient heat control using a heat medium, but in the case of anionic polymerization, rapid heat generation occurs in the early stage of the reaction due to rapid reaction polymerization, which can cause local temperature surges (hot spots) within the reaction system. Anionic polymerization using conventional flow-type reaction systems also causes a temperature gradient of the reactants depending on the location within the reaction path due to the explosive heat generated in the early stage of the polymerization reaction. To address this, operation can be performed by increasing the flow rate of the reactants or refrigerant or reducing the temperature of the refrigerant, but this has the problems of increased pump pressure and high energy consumption due to low-temperature cooling. Accordingly, there is a need for the development of a manufacturing technology that can polymerize high-quality polymers using a flow-type reaction system while maintaining economical operation and long-term reliability.

[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 polymer production method capable of continuously producing a high-quality polymer through a microflow reactor is provided.

[0011] 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.

[0012] According to one embodiment of the present invention, a method for producing a polymer 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, a second solution containing the solvent and an anionic polymerization initiator, and a heat medium 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 fluid inlet through which the first solution and the second solution are introduced, a fluid outlet through which a third solution containing a polymer obtained by anionic polymerization of the monomer is discharged, a heat medium inlet through which a heat medium is introduced, and a heat medium outlet through which the heat medium is discharged; a reaction layer connecting the fluid inlet and the fluid outlet within the main body and forming a reaction path through which the first solution, the second solution, and the third solution are transported; It includes first and second temperature control layers which connect the heat medium inlet and the heat medium outlet and form first and second heat medium passages through which the heat medium is transported to the upper and lower layers of the reaction layer, respectively.

[0013] In a polymer manufacturing method according to one embodiment, parallel flow and counter flow of the fluid and the heat medium can occur in parallel in the first and second heat medium passages.

[0014] In a polymer manufacturing method according to one embodiment, the reaction layer may include a reaction plate that divides the main body into upper and lower parts and has microchannels formed on one surface to form the reaction path, a plurality of microchambers arranged along the extension direction of the microchannels on the reaction plate and forming an internal space communicated with the reaction path, and a collision medium that collides with a fluid transported within the internal space and converts the flow of the fluid within the internal space.

[0015] In a polymer manufacturing method according to one embodiment, the first temperature control layer may include a temperature control plate spaced apart from the upper portion of the reaction plate in the main body and having a first heat medium channel formed on one surface thereof to form the first heat medium passage, and a plurality of first induction media positioned within the first heat medium passage to induce transport of the heat medium transported within the first heat medium passage, and the second temperature control layer may include a second heat medium channel forming the second heat medium passage on the bottom surface of the main body, and a plurality of second induction media positioned within the second heat medium passage to induce transport of the heat medium transported within the second heat medium passage.

[0016] In a polymer manufacturing method according to one embodiment, the average residence time of the fluid in the reaction layer is 10 to 50 seconds, and the flow path can be maintained at -80 to 60°C.

[0017] In a polymer production method according to one embodiment, the anionic polymerization can be performed in the presence of a co-solvent of an ether solvent and a non-polar solvent.

[0018] In a polymer manufacturing method according to one embodiment, the flow rate of the first solution may be greater than the flow rate of the second solution.

[0019] In a polymer manufacturing method according to one embodiment, the inflow rate (Q) into the reaction layer in, ㎖ / min) and the minimum cross-sectional area (A) of the flow path in the reaction layer min , cm 2 ) for the total length of the flow path within the reaction layer (L) total , cm) can satisfy the following relationship 1.

[0020] [Relationship 1]

[0021] 7.6 cm 2 / min ≤Log(Q in Х(L total / A min ))≤8.5 cm 2 / min

[0022] (In the above relational expression 1, 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 diameter-direction cross-sectional area of ​​the above microchannel, and the total length of the flow path is the value obtained by dividing the internal capacity of the reaction layer by the minimum cross-sectional area of ​​the flow path.

[0023] In a polymer manufacturing method according to one embodiment, the concentration of the monomer in the first solution may be 1 to 5 M.

[0024] In a polymer manufacturing method according to one embodiment, on one plane of the reaction plate in the direction in which the reaction 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.

[0025] 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 reaction 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.

[0026] 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.

[0027] [Formula 1]

[0028] 1 < (L2 / L1) < 3

[0029] 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.

[0030] In a polymer manufacturing method according to one embodiment, the inner diameter (R1) of the reaction path formed by the microchannel and the shortest distance (B1) between the longitudinal ends of the collision medium can satisfy the following equation 2.

[0031] [Formula 2]

[0032] 3 < B1 / R1< 15

[0033] In a polymer manufacturing method according to one embodiment, the microchannel may include an inlet channel connecting the microchamber located at the most forward end in the direction of fluid flow in the reaction channel and the fluid inlet, a connection channel connecting the microchambers adjacent to each other, and an outlet channel connecting the microchamber located at the most rearward end in the direction of fluid flow in the reaction channel and the fluid outlet.

[0034] In a polymer manufacturing method according to one embodiment, the monomer may include an aromatic vinyl monomer.

[0035] In a method for producing a polymer according to one embodiment, the non-polar solvent may include a C5-C8 alkane solvent.

[0036] 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.

[0037] 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.

[0038] Figure 1 is a perspective view illustrating a microflow reactor according to one embodiment of the present invention;

[0039] Figure 2 is a plan view showing the reaction layer of the microflow reactor illustrated in Figure 1;

[0040] Figure 3 is a plan view illustrating the first temperature control layer of the microflow reactor illustrated in Figure 1.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] In this specification, 'fluid' means a material having fluid properties that can flow, and refers to all materials that flow within a reaction layer. Specifically, the fluid may mean 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 fluid inlet may mean 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 mean a mixture of the first solution and the second solution and a third solution which is a reactant thereof. In addition, the fluid may mean the third solution at the rear side of the microflow reactor adjacent to the outlet.

[0050] In this specification, the term "heat medium" refers to a medium that transfers heat and can cool or heat a fluid through heat exchange with the fluid within the reaction layer. The heat medium may be a refrigerant or a heat medium, and is not particularly limited as long as it is a material that has been conventionally used as a refrigerant or heat medium. Non-limiting examples of the heat medium include heat transfer oils such as silicone oil or mineral oil, heat transfer nanofluids, ethylene glycol, propylene glycol, and the like.

[0051] 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.

[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] In addition, although conventional flow-type reaction systems enable efficient heat control using a heat medium, in the case of anionic polymerization, due to rapid reaction polymerization, rapid heat generation occurs at the early stage of the reaction, resulting in a local temperature surge (hot spot) within the reaction system, and a temperature gradient of the reactants depending on the location within the reaction path. To address this, operation can be achieved by increasing the flow rate of the reactant or heat medium, or further reducing the temperature of the heat medium, but this has the problem of increased pump pressure and high energy consumption due to low-temperature cooling. The inventors of the present invention have conducted in-depth research to improve the economic feasibility and reliability of the anionic polymerization process using a flow-type reaction system, and as a result, have discovered that the economic feasibility and reliability can be improved through the design of the flow-type reaction system and polymerization reaction conditions, and at the same time, high-quality polymers can be produced, and thus the present invention has been completed.

[0055] 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, a second solution containing the solvent and an anionic polymerization initiator, and a heat medium into a microflow reactor; and (S2) anionic polymerizing the monomer in the microflow reactor.

[0056] The microflow reactor comprises a main body having at least one fluid inlet through which the first solution and the second solution are introduced, a fluid outlet through which a third solution including a polymer obtained by anionic polymerization of the monomer is discharged, a heat medium inlet through which a heat medium is introduced, and a heat medium outlet through which the heat medium is discharged; a reaction layer connecting the fluid inlet and the fluid outlet within the main body and forming a reaction path through which the first solution, the second solution, and the third solution are transported; first and second temperature control layers connecting the heat medium inlet and the heat medium outlet and forming first and second heat medium paths through which the heat medium is transported to upper and lower layers of the reaction layer, respectively.

[0057] This method of manufacturing polymers using a microflow reactor effectively controls the rapid exothermicity of anionic polymerization by increasing the heat exchange area through two temperature-controlled layers surrounding the reaction bed from above and below. This suppresses side reactions caused by the reaction heat, enabling the production of the desired polymer with high conversion and purity.

[0058] To explain in more detail, when the first and second solutions are mixed in the flow path, the polymerization reaction can proceed rapidly due to the characteristics of anionic polymerization, which can generate explosive reaction heat. However, as mentioned above, the reaction heat can be quickly removed by the heat medium flowing around the upper and lower surfaces of the reaction bed. In the microflow reactor, by increasing the flow rates of the first and second solutions, turbulent flow can be formed in the reaction flow path, and at the same time, the reaction heat can be removed by the high linear velocity of the fluid. However, the increase in flow rate inevitably leads to an increase in the pressure of the pump, and a high pump pressure can cause an increase in operating cost and a decrease in long-term reliability. Furthermore, when the flow rate of the fluid is increased while maintaining the same monomer concentration, the reaction heat generated in the microflow reactor increases proportionally, so the flow rate of the heat medium must be increased proportionally. Therefore, the problem described above due to the increase in pump pressure is also aggravated.

[0059] According to one embodiment, the reaction layer may include a reaction plate dividing the main body into upper and lower parts and having microchannels formed on one surface to form the reaction path, a plurality of microchambers arranged along the extension direction of the microchannels on the reaction plate and forming an internal space communicated with the reaction path, and a collision medium that collides with a fluid transported within the internal space and converts the flow of the fluid within the internal space, wherein the fluid can move in a laminar flow in the reaction path.

[0060] This polymer manufacturing method can solve the problem of pump overload by maintaining a low pump pressure, and even though the fluid is transported in a laminar flow, a sufficient heat removal effect can be achieved as the heat medium flows on both the upper and lower sides of the fluid layer. However, since the fluid is transported in a laminar flow, the polymerization reaction may be inhomogeneous due to non-uniform mixing of the fluid, which may lower the quality of the polymer produced. However, since the fluid within the reaction path of the reaction layer collides with the collision medium, turbulence is formed in the flow of the fluid, so that the fluid can be homogeneously mixed. Therefore, the polymer manufacturing method can achieve homogeneous mixing of the fluid even though the fluid is transported in a laminar flow.

[0061] Meanwhile, since the above anionic polymerization is carried out in the presence of a co-solvent of an ether solvent and a non-polar solvent, the anionic polymerization initiation reaction is significantly slower than the typical anionic polymerization initiation reaction, and the polymerization reaction does not occur immediately, which may delay the generation of reaction heat. Accordingly, since polymerization does not occur before uniform mixing is achieved, but rather after uniform mixing is achieved in the microchamber, it has the advantage of enabling the production of a chemically homogeneous polymer. In other words, the above polymer production method enables the production of high-quality polymers with low molecular weight distribution, and can use relatively high concentrations of reactants through efficient heat control, thereby increasing the production volume per unit time. Furthermore, stable heat control is possible despite the continuous process, so that high-quality polymers can be produced for a long time. Specifically, the molecular weight distribution (polydispersity) of the polymer produced through the above production 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.

[0062] In one embodiment, parallel and countercurrent flows of the fluid and the heat medium can occur in parallel in the first and second heat medium passages. Such a polymer production method can further enhance heat exchange efficiency by simultaneously obtaining heat exchange effects according to countercurrent and parallel flows without a separate temperature control device. Such a polymer production method can uniformly distribute the temperature difference between the heat medium and the fluid throughout the entire reaction layer due to rapid heat transfer by the parallel flow and high heat transfer efficiency by the countercurrent flow. Accordingly, the heat exchange efficiency between the fluid and the heat medium is increased, and the heat of the fluid can be stably removed for a long period of time, enabling continuous production of a more homogeneous polymer.

[0063] In another embodiment, the reaction path may be divided into a fluid inlet region, a fluid transfer region, and a fluid discharge region, and the first and second heat medium paths may be divided into a heat medium discharge region, a heat medium transfer region, and a heat medium inlet region, and may be positioned at positions corresponding to the fluid inlet region, the fluid transfer region, and the fluid discharge region, respectively.

[0064] The fluid inlet region and the heat medium discharge region may refer to the forward portion in the fluid flow direction of the reaction layer, the fluid discharge region and the heat medium inlet region may refer to the rear portion, and the fluid transfer region and the heat medium transfer region may refer to the middle portion. Specifically, the fluid inlet region may refer to the region including the fluid inlet port, the inlet channel, and the microchamber located at the most forward end and the microchambers located in the same row, which will be described later, the fluid discharge region may refer to the region including the fluid discharge port, the discharge channel, and the microchamber located at the most rear end and the microchambers located in the same row, and the fluid transfer region may refer to the region including the microchannels and microchambers connecting the fluid inlet region and the fluid discharge region. In addition, the heat medium inlet region, the heat medium discharge region, and the heat medium transfer region may refer to the region in which the fluid discharge region, the fluid inlet region, and the fluid transfer region are projected in the vertical direction of the main body.

[0065] The fluid in the fluid inflow region and the heat medium in the heat medium discharge region, and the fluid in the fluid discharge region and the heat medium in the heat medium inflow region, can form countercurrents with each other. Heat transfer efficiency is improved, so that the rapid reaction heat generated during the anionic polymerization reaction can be quickly removed.

[0066] 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.

[0067] According to one embodiment, the polymer manufacturing method changes the linear velocity of the fluid at each location in the reaction flow path as the diameter of the flow path is repeatedly changed by the microchannels and microchambers. Accordingly, the linear velocity of the fluid within the reaction layer may differ at each location in the reaction layer even when the fluid is injected at the same flow rate. Specifically, the linear velocity is fastest in the microchannel 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.

[0068] In one embodiment, the linear velocity of the fluid within the reaction layer is not particularly limited as long as it is within a range that allows continuous production of the polymer, and may be appropriately adjusted depending on the type and properties of the desired polymer. Specifically, the linear velocity of the fluid may be 0.01 to 10 m / s, 0.1 to 8 m / s, 0.5 to 5 m / s, or 1 to 4 m / s in the microchannel. When 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 reaction layer can be prevented. Accordingly, the fluid is homogeneously mixed throughout the entire reaction path, enabling the production of a higher quality polymer.

[0069] In one embodiment, the average residence time of the fluid within the reaction layer is 10 to 50 seconds, and the flow path is maintained at -80 to 60°C. Specifically, the residence time may be 5 to 60 seconds, 10 to 55 seconds, or 15 to 50 seconds, regardless of the internal capacity (internal volume) of the reaction layer, and the temperature of the flow path within the reaction layer may be controlled by the heat medium and may be -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. In the above range, it is possible to produce a polymer having a more homogeneous molecular weight.

[0070] In one embodiment, the anionic polymerization 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 polymerization reaction is initiated more slowly than in a conventional anionic polymerization reaction, and the polymerization reaction rate is also slow, so that the generation of reaction heat does not occur only in a local area, and the generation of reaction heat can also be delayed. Accordingly, heat removal can be easily carried out within the microflow reactor without increasing the flow rate of the heat medium or decreasing the temperature of the heat medium, and the anionic polymerization reaction is possible even at relatively high temperatures, and a high-quality polymer can be produced economically.

[0071] The above step (S1) is a step of injecting the first solution and the second solution and the heat medium into the microflow reactor. Depending on the type and properties of the target polymer, the type and flow rate of the first solution and the second solution, and the temperature and flow rate of the heat medium can be adjusted through step (S1) to be injected into the microflow reactor. Specifically, step (S1) supplies the first solution and the second solution to the fluid inlet to supply them to the reaction layer, and supplies the heat medium to the first and second temperature-controlled layers. At this time, regardless of the internal capacity of the reaction layer, the flow rates (flow rates) of the first solution and the second solution can be adjusted so that the fluid can maintain the linear velocity within the reaction layer. The size of the external injection path connected to the microflow reactor can be appropriately adjusted according to the internal capacity of the reaction layer. The heat medium can be injected with the temperature and flow rate adjusted according to the properties of the target polymer.

[0072] The internal capacity (volume) of the above reaction layer refers to the amount of solution that the reaction layer in the microflow reactor can accommodate, and may refer to the volume formed by the reaction path, i.e., the path and internal space formed by the microchannel and microchamber. The internal capacity of the reaction layer is not particularly limited, and the flow rates of the first solution and the second solution injected in step S1) may be adjusted in proportion to the internal capacity of the reaction layer.

[0073] The internal capacity of the above reaction layer can be adjusted according to the diameter and length of the reaction channel within the reaction layer 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 reaction layer can increase in proportion to the diameter and length of the channel within the reaction layer, the size of the internal space of the microchamber, and the number of microflow reactors that are connected (the number of reaction layers), and the flow rates of the first solution and the second solution injected in step S1) can be adjusted in proportion to this.

[0074] 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 reaction layer 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.

[0075] 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 volume of the reaction layer 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.

[0076] 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.

[0077] 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.

[0078] The above Hansen solubility (S co ) can be calculated using the following formula.

[0079] [Calculation formula]

[0080] S co( MPa ½ ) = (S1×W1)+(S2×W2)

[0081] 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.

[0082] 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)).

[0083] In the above step (S1), the concentration of the monomer of the first solution can be appropriately adjusted depending on the type of monomer. 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).

[0084] 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.

[0085] 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.

[0086] 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.

[0087] 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.

[0088] 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.

[0089] 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.

[0090] According to one embodiment, the concentration of 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 within the above range has an appropriate viscosity for fluid transport, and can be smoothly injected into the microflow reactor in step (S1).

[0091] 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.

[0092] Step (S2) is a step of anionic polymerization of the monomer in the microflow reactor, wherein the anionic polymerization reaction can be performed in the reaction layer whose temperature is controlled through step (S1). In step (S2), the monomer is anionic polymerized by the anionic polymerization initiator, and a polymer is produced.

[0093] 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.

[0094] 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.

[0095] 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.

[0096] (1) Control of the residence time of monomer and anionic polymerization initiator

[0097] (2) Control of the flow rate of fluid in the microflow reactor (reaction layer)

[0098] (3) Number of microchambers and connection structure

[0099] (4) Temperature of the microchamber

[0100] 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.

[0101] Additionally, the shape and length of the entire path through which the fluid moves within the reaction layer can be controlled through the number of microchambers within the reaction layer 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. The microchambers may be connected in series, in parallel, or in series-parallel, and the number of microchambers may be increased as the flow rate increases.

[0102] The temperature inside the microchamber can be adjusted by circulating a heat medium in the first and second temperature control layers. When performing step S1), the heat medium can be injected into the first and second temperature control layers simultaneously with the first and second solutions. Alternatively, the first and second solutions can be injected after the heat medium is injected. The injected heat medium contacts the upper and lower surfaces of the reaction layer, respectively, to control the temperature of the flowing fluid, and can remove heat generated by the exothermic reaction.

[0103] 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 is supplied to the reaction layer and 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).

[0104] According to one aspect of the present invention, the polymer production method may further satisfy one or both of the following conditions.

[0105] Condition 1. The flow rate (velocity) of the first solution is greater than that of the second solution.

[0106] Condition 2. Inlet flow rate (Q) in the microflow reactor in , ㎖ / min) and the minimum cross-sectional area of ​​the reaction path (A min , cm 2) for the total length of the reaction Euro (L) total, The rain (cm) satisfies the following relationship 1.

[0107] [Relationship 1]

[0108] 7 cm 2 / min ≤ Log(Q in ×(L total / A min ))≤ 9 cm 2 / min

[0109] In the above condition 2, 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 reaction path (A min ) refers to the cross-sectional area in the diameter direction of the microchannel (connecting channel described later), and the total length of the reaction path refers to the value of the internal capacity of the reaction layer divided by the cross-sectional area of ​​the connecting channel.

[0110] 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) can 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, Log(Q) of the above relation 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.

[0111] In an unrelated manner, the above polymer manufacturing method can satisfy all of the above conditions 1 and 2, and such a polymer manufacturing method can produce a more homogeneous polymer.

[0112] 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.

[0113] 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.

[0114] Figures 1 to 3 illustrate a microflow reactor according to one embodiment of the present invention. For convenience of explanation, the bonding structure of each layer is omitted, and unlike the drawings, the microflow reactor may be formed as an integral unit.

[0115] Referring to FIGS. 1 to 3, a microflow reactor (100) according to one embodiment of the present invention includes a main body (10), a reaction layer (30), and first and second temperature control layers (50) (70).

[0116] The above main body (10) is for receiving the fluid and heat medium from the outside, and the inside of the main body (10) is divided into three layers so that each layer of the microflow reactor (100) can be distinguished. The main body (10) is formed with inlets (11)(14) and outlets (13)(12) so as to receive and discharge the fluid and heat medium into the inside. Specifically, the fluid inlet (11), fluid outlet (13), heat medium inlet (14), and heat medium outlet (12) described above are formed on the upper part of the main body (10), and the first solution and the second solution are introduced into the reaction layer (30) through the fluid inlet (11), and after undergoing an anionic polymerization reaction, are discharged to the outside of the main body (10) through the fluid outlet (13) in the state of a third solution containing a polymer. At this time, the heat medium introduced through the heat medium inlet (14) simultaneously with the fluid introduction is distributed to the first temperature control layer (50) and the second temperature control layer (70), respectively, and after controlling the temperature of both the upper and lower sides of the reaction layer (30), is discharged through the heat medium discharge port (12).

[0117] The main body (10) is a panel-shaped structure with an empty space formed inside, and can be formed of a material that is easy to form and has high corrosion resistance, non-flammability, and chemical durability. Specifically, the main body (10) can be formed of metal, ceramic, plastic, or a composite material thereof.

[0118] As shown in the drawing, the fluid inlet (11) of the main body (10) may include a first fluid inlet (11a) and a second fluid inlet (11b) into which a first solution and a second solution can be injected, respectively, but is not limited thereto and may be provided as a single one or three or more. That is, the fluid inlet (11) may be appropriately adjusted according to the type and number of solutions required for the production of the polymer to be produced. The fluid inlet (11) may penetrate from the upper surface of the main body (10) to the reaction layer (30) to supply a fluid to the reaction layer (30) from the outside of the main body (10). At this time, the fluid inlet (11) forms a flow path that is connected to the reaction flow path (30b), but is not connected to the heat medium flow path (50a) of the first temperature control layer (50). Therefore, the fluid does not flow into the first temperature control layer (50).

[0119] The fluid discharge port (13) of the main body (10) may also penetrate from the upper surface of the main body (10) to the reaction layer (30) to supply the fluid of the reaction layer (30) inside the main body (10) to the outside of the main body (10). At this time, the fluid discharge port (13) also forms a passageway that is in communication with the reaction passageway (30b), but is not in communication with the heat medium passageway (50a) of the first temperature control layer (50). Accordingly, the fluid inside the reaction layer (30) may not be discharged to the first temperature control layer (50).

[0120] The heat medium inlet (14) and the heat medium outlet (12) of the main body (10) can penetrate from the upper surface of the main body (10) to the second temperature control layer (70) located at the lowest layer, so as to inject the heat medium into the main body (10) or discharge the heat medium inside the main body (10) to the outside. Specifically, the heat medium inlet (14) and the heat medium outlet (12) are introduced to the second temperature control layer (70), but form a flow path that is connected to the first heat medium flow path (50a) of the first temperature control layer (50) and the second heat medium flow path (50a) (not shown) of the second temperature control layer (70), so that the heat medium is not supplied to the reaction layer (30).

[0121] The inlet ports (11) (14) and outlet ports (13) (12) of the above main body (10) are connected to a flow control system so that the flow rate and flow velocity can be appropriately controlled.

[0122] The above inlets (11) (14) and outlets (13) (12) may be formed at positions adjacent to the edges of the main body (10) as shown in the drawing, but of course, they may be formed at the center of the main body (10) or at a portion adjacent thereto.

[0123] The above reaction layer (30) is located in the middle layer of the main body (10), and includes a reaction plate (31) that divides the main body (10) into upper and lower parts and has a microchannel (35) formed on one surface to form the reaction path (30b), a plurality of microchambers (37) arranged along the extension direction of the microchannels (35) on the reaction plate (31) and forming an internal space communicated with the reaction path (30b), and a collision medium (39) that collides with a fluid transported in the internal space and converts the flow of the fluid in the internal space.

[0124] The above reaction plate (31) is a planar structure and is positioned to partition the internal space of the main body (10). The reaction plate (31) is a medium in which a reaction path (30b) through which a fluid is transported is formed, and a microchannel (35), microchamber (37), and collision medium (39) are formed, which will be described later.

[0125] Specifically, the microchannel (35) is formed by being introduced onto the reaction plate (31) and extends in the surface direction of the reaction plate (31) to form a reaction path (30b). The microchannel (35) forms a path connecting the fluid inlet (11) and the fluid outlet (13). The shape of the path formed by the microchannel (35) is not particularly limited. For example, the microchannel (35) may form a path that meanders on one plane formed by the reaction plate (31), as illustrated in the drawing. Such a microchannel (35) can integrate the reaction path (30b), thereby making the reaction system more compact.

[0126] The microchannel (35) according to one aspect of the present invention may include an inlet channel (32) connecting a microchamber (37) located at the frontmost end in the direction of fluid flow in the reaction channel (30b) and a fluid inlet (11), a connection channel (34) connecting adjacent microchambers (37), and an outlet channel (38) connecting a microchamber (37) located at the rearmost end in the direction of fluid flow in the reaction channel (30b) and a fluid outlet (13).

[0127] At this time, the direction of fluid flow refers to the macroscopic flow of fluid from the fluid inlet (11) to the fluid outlet (13). The microscopic flow of fluid converted by the collision medium (39), i.e., the turbulent flow, is ignored. Based on the direction of fluid flow, the fluid inlet (11) side can be divided into the front (or front end), and the fluid outlet (13) side can be divided into the rear (or rear end).

[0128] However, as the above microchannel (35) forms a meandering path on the reaction plate (31), when assuming that one microchamber (37) and the microchambers (37) connected to it in a straight line are microchamber arrays, the adjacent microchamber arrays may appear to have fluids moving in opposite directions.

[0129] As the fluid inlets (11) are provided in multiple numbers, the inlet channels (32) may be provided in multiple numbers correspondingly. For example, as shown in the drawing, when the main body (10) includes a first fluid inlet and a second fluid inlet (11), the inlet channel (32) may include a first inlet channel (32b) extending from the first fluid inlet (11) and a second inlet channel (32a) extending from the second fluid inlet (11). At this time, the first and second inlet channels (32) may be connected to each other at the front end of the microchamber (37) located at the frontmost end.

[0130] The connecting channel (34) forms a path connecting the microchambers (37), and may include a main connecting channel (34) connecting adjacent microchamber (37) arrays, and a sub-connecting channel (34a) connecting each microchamber (37) within the microchamber array. As illustrated in Fig. 2, the main connecting channel (34) and the sub-connecting channel (34a) may be provided simultaneously, but alternatively, each microchamber (37) may be directly connected without the sub-connecting channel (34a).

[0131] The discharge channel (38) forms a path connecting the microchamber (37) located at the rear end and the fluid discharge port (13), so that the fluid passing through the microchambers (37) can be discharged to the outside of the main body (10) through the discharge port (13).

[0132] In the microchannel (35) according to one aspect of the present invention, at least one of the inlet channel (32) and the connecting channel (34) 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 (32) or the connecting channel (34) 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 (37) connected to the inlet channel (32) or the connecting channel (34). Accordingly, the fluid can be supplied at a high flow rate to the adjacent microchamber (37) to continuously induce remarkably excellent mixing and a homogeneous reaction.

[0133] The above microchambers (37) are arranged in multiple numbers along the reaction path (30b) and form an internal space that is connected to the reaction path (30b) formed by the microchannel (35). The internal space 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 (39).

[0134] According to one aspect of the present invention, the internal space (36) of the microchamber (37) 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 reaction plate (31) in the direction in which the reaction path (30b) extends, and the front-side connecting portion connected to the front-side microchannel (35) is retracted into the interior. At this time, the inner surface of the internal space (36) may be a curved surface. In other words, the inner space (36) of the microchamber (37) may be a circular shape distorted in one direction, i.e., a heart shape, as illustrated in the drawing. The internal space (36) of the microchamber (37) as described above allows the fluid to flow smoothly along the inner surface of the internal space (36) even if the fluid collides with the collision medium (39) and the flow changes. That is, although turbulence of the fluid is generated within the internal space (36) by the collision medium (39), the flow of the fluid from the fluid inlet (11) to the fluid outlet (13) is not obstructed, so that continuous production of the polymer is possible smoothly.

[0135] The above collision medium (39) is located in the internal space (36) of the microchamber (37) and is an obstacle to the fluid flow within the microchamber (37). The collision medium (39) is not particularly limited as long as it has a structure that can form turbulence within the internal space (36) by colliding the fluid flowing within the microchamber (37). According to one embodiment, the collision medium (39) has a length extending in a direction perpendicular to the flow direction of the fluid on one plane formed by the reaction plate (31), but is curved backward. However, both longitudinal ends of the collision medium (39) do not come into contact with the inner surface of the microchamber (37).

[0136] At this time, the internal space (36) may include a branch portion (36a) in which the fluid collided by the collision medium (39) flows in both directions along the longitudinal ends of the collision medium (39), and a confluence portion (36b) in which the fluid flowing along both directions of the collision medium (39) flows again in one direction. In such an internal space (36) and collision medium (39), the fluid collides for the first time by the collision medium (39) and is homogeneously mixed, and after the fluid collided for the first time passes through the branch portion (36a), the fluids collide a second time while facing each other at the confluence portion (36b), 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 (36) can satisfy the following equation 1 in terms of the diameter (L1) of the flow path formed by the branch portion (36a) and the diameter (L2) of the flow path formed by the joining portion (36b).

[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 (35) and the rear connection portion connected to the rear microchannel (35) among the microchannels (35) adjacent to the microchamber (37). 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 branching portion to the confluence portion.

[0141] The length of the above-described collision medium (39) is not particularly limited as long as it does not contact the inner surface of the microchamber (37) as described above. However, in one embodiment, the inner diameter (R1) of the flow path formed by the microchannel (35) and the shortest distance (B1) between the longitudinal ends of the collision medium (39) can satisfy the following equation 2.

[0142] [Formula 2]

[0143] 3 < B1 / R1< 15

[0144] Specifically, B1 / R1 may be 4 to 13, 5 to 12, or 6 to 10. Accordingly, the fluid flowing into the microchamber (37) from the microchannel (35) can collide more strongly with the collision medium (39), thereby inducing significantly superior mixing and a homogeneous reaction.

[0145] According to one embodiment, the reaction flow path (30b) formed by the microchannel (35) can be connected in series, in parallel, or in series and parallel between the fluid inlet (11) and the fluid outlet (13). In such a microflow reactor (100), since the flow paths are formed in series and in parallel, the microchambers (37) arranged in communication with the flow paths can also be connected in series and in parallel with each other. The microchannel (35) can include a series connection portion in which the flow paths are connected in series, and a parallel connection portion in which the flow paths are connected in parallel. The microchambers (37) located in the parallel connection portion can be positioned in parallel to each other. At this time, the microchambers (37) that are parallel to each other can be connected to each other through the parallel connection channels (34)(34). Such a microflow reactor (100) can react a larger amount of fluid, thereby enabling larger-scale production.

[0146] The first temperature control layer (50) and the second temperature control layer (70) are located at the uppermost and lowermost layers of the main body (10), respectively, and form a heat medium path (50a) through which the heat medium is transported.

[0147] Specifically, the first temperature control layer (50) includes a temperature control plate that is spaced apart from the upper portion of the reaction plate (31) in the main body (10) and has a first heat medium channel (51) formed on one surface thereof to form the first heat medium passage (50a), and a plurality of first induction media (53) positioned within the first heat medium passage (50a) to induce the transport of the heat medium transported within the first heat medium passage (50a), and the second temperature control layer (70) includes a second heat medium channel that forms the second heat medium passage on the bottom surface of the main body (10), and a plurality of second induction media positioned within the second heat medium passage to induce the transport of the heat medium transported within the second heat medium passage.

[0148] The above temperature control plate is a planar structure spaced apart from the reaction plate (31), and the reaction plate (31) and the temperature control plate are provided parallel to each other. By the reaction plate (31) and the temperature control plate, the main body (10) can be divided into three layers in which the first temperature control layer (50) - reaction layer (30) - second temperature control layer (70) are sequentially laminated (from top to bottom) as described above. The temperature control plate is a medium in which a first heat medium passage (50a) is formed, and in which a first heat medium channel (51) and a first induction medium (53) are formed.

[0149] The first and second heat medium channels (51) are formed by being introduced onto the temperature control plate and the bottom surface of the main body (10), respectively, and extend in the direction of the surface of the temperature control plate and the bottom surface of the main body (10) to form first and second heat medium flow paths (50a), respectively. The shapes of the first and second heat medium flow paths (50a) are not particularly limited as long as they are shapes in which parallel and countercurrent flows of the fluid and heat medium can occur in parallel within the heat medium flow path. For example, the first heat medium flow path (50a) may form a flow path that meanders on one plane formed by the temperature control plate.

[0150] The first and second induction media (53) are formed to protrude on the first and second heat medium passages (50a), respectively, and are arranged in multiple numbers spaced apart from each other along the direction of the first and second heat medium passages (50a). The shapes of the first and second induction media (53) are not particularly limited, but both ends of the first and second induction media (53) may be formed as curved surfaces so as not to impede the flow of fluid in the direction of the heat medium flow. The first and second induction media (53) as described above may guide the heat medium in each passage to flow along the shape of the first and second heat medium passages (50a). Accordingly, it is possible to prevent the formation of a dead zone in which the heat medium does not flow but stagnates or the flow speed is reduced within the first and second heat medium passages (50a), thereby enabling the heat transfer efficiency to occur more smoothly.

[0151] As described above, the fluid inlet area (A1) may refer to an area including a fluid inlet (11), an inlet channel (32), and a microchamber (37) located at the front end and microchambers (37) located in the same row, and the fluid discharge area (A3) may refer to an area including a fluid discharge area (13), a discharge channel (38) (38), and a microchamber (37) located at the rear end and microchambers (37) located in the same row, and the fluid transfer area (A2) may refer to an area including microchannels (35) and microchambers (37) connecting the fluid inlet area (A1) and the fluid discharge area (A3).

[0152] According to one embodiment, the microflow reactors (100) are connected in series with each other in multiple numbers, so that each microflow reactor (100) can be operated as a single reactor module. Accordingly, each microflow reactor (100) can be controlled at different flow rates, residence times, and temperatures.

[0153] 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.

[0154] (Examples 1 to 18)

[0155] A polymer was manufactured by anionic polymerization using a microflow reactor (Module size: 162 × 188.5 × 21 (mm)) as shown in Fig. 1. 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.

[0156] 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.

[0157] 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.

[0158] 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 the direction of the heat medium and fluid in the inlet flow path area are shown in Table 2 below. In addition, R (relationship between flow rate, flow path cross-sectional area, and flow path length) calculated from the following equation 2 is shown in Table 2.

[0159] [Relationship 2]

[0160] R (cm) 2 / min) = Log(Q in ×(L total / A min ))

[0161] 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 min is 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.

[0162] During the above polymerization, silicone oil was supplied as a heat medium to the heat medium inlet (14) of the microflow reactor through a temperature control device (TCU System (Temperature Control Unit)) connected to the microflow reactor to control the temperature of the flow path in the microflow reactor, and the total flow rate was measured at the discharge channel located at the rearmost end of the microflow reactor.

[0163]

[0164]

[0165] (Comparative examples 1 to 8)

[0166] In the examples, the polymer was manufactured in the same manner as in the examples, except that the polymer was manufactured using a PFA tube (1 / 8 inch inner diameter, 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 3 below, and the input flow rates of the first solution, the second solution, and the polymerization terminator for each comparative example, the temperature of the flow path in the microflow reactor, and the residence time of the fluid in the microflow reactor are shown in Table 4 below.

[0167] (Comparative Example 9)

[0168] A polymer was manufactured using the same microflow reactor as in the above example. However, the heat medium, silicone oil, was introduced into the heat medium outlet (12) instead of the heat medium inlet (14), so that the heat medium and the fluid formed countercurrents in the fluid inlet area and the fluid outlet area. The total volume of the flow path in the PFA tube, the solvents and concentrations of the first and second solutions, and the polymerization terminator of the third solution are shown in Table 3 below, and the input flow rates of the first solution, the second solution, and the polymerization terminator, the temperature of the flow path in the microflow reactor, and the residence time of the fluid in the microflow reactor are shown in Table 4 below.

[0169]

[0170]

[0171] Polymer Evaluation

[0172] 1) Conversion rate (%)

[0173] The conversion rate of the polymer manufactured using the following calculation formula 1 was calculated and shown in Table 5 below.

[0174] [Calculation Formula 1]

[0175] Conversion rate (%) = ((number of moles of tert-butoxystyrene reacted) / (number of moles of tert-butoxystyrene introduced)) × 100

[0176] 2) Molecular weight, polydispersity

[0177] 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 used was tetrahydrofuran, the temperature was 40°C, and the flow rate was 1.0 mL / min. The results are shown in Table 5 below.

[0178] 3) Whether there is a side effect

[0179] 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 smoothly 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 5 below. If a side reaction occurred, it was marked with a "○", and if no side reaction occurred, it was marked with a "×".

[0180]

[0181] Referring to Table 5 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 and monomers selected from the group consisting of ether solvents and non-polar solvents, a second solution containing the solvent and an anionic polymerization initiator, and a heat medium 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 fluid inlet through which the first solution and the second solution are introduced, a fluid outlet through which a third solution including a polymer obtained by anionic polymerization of the monomer is discharged, a heat medium inlet through which a heat medium is introduced, and a heat medium outlet through which the heat medium is discharged; a reaction layer connecting the fluid inlet and the fluid outlet within the main body and forming a reaction path through which the first solution, the second solution, and the third solution are transported; and first and second temperature control layers connecting the heat medium inlet and the heat medium outlet and forming first and second heat medium paths through which the heat medium is transported to upper and lower layers of the reaction layer, respectively.

2. In paragraph 1, A method for producing a polymer, wherein parallel flow and counter flow of the fluid and the heat medium occur in parallel in the first and second heat medium passages.

3. In paragraph 1, The above reaction layer is, A method for producing a polymer, comprising: a reaction plate dividing the main body into upper and lower parts and having microchannels formed on one surface to form the reaction path; a plurality of microchambers arranged along the extension direction of the microchannels on the reaction plate and forming an internal space communicated with the reaction path; and a collision medium that collides with a fluid transported within the internal space and converts the flow of the fluid within the internal space.

4. In paragraph 3, The first temperature control layer is, A temperature control plate having a first heat medium channel formed on one surface thereof and spaced apart from the upper portion of the reaction plate within the body, and a plurality of first induction media positioned within the first heat medium channel to induce the transport of the heat medium transported within the first heat medium channel, The second temperature control layer is, A method for producing a polymer, comprising a second heat medium channel forming the second heat medium path on the bottom surface of the main body, and a plurality of second induction media positioned within the second heat medium path and inducing heat medium transport within the second heat medium path.

5. In paragraph 1, A method for producing a polymer, wherein the average residence time of the fluid in the reaction layer is 10 to 50 seconds, and the flow path is maintained at -80 to 60°C.

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

7. In paragraph 1, A method for producing a polymer, wherein the flow rate of the first solution is greater than the flow rate of the second solution.

8. In paragraph 1, The inflow rate (Q) in the above reaction layer in , ㎖ / min) and the minimum cross-sectional area (A) of the flow path in the reaction layer min , cm 2 ) for the total length of the flow path within the reaction layer (L) total , cm) of a polymer, wherein the ratio satisfies the following relational expression 1. [Relationship 1] 7.6 ㎝ 2 / min ≤Log(Q in ×(L total / A min ))≤8.5 ㎝ 2 / min (In the above relational expression 1, 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 diameter-direction cross-sectional area of ​​the above microchannel, and the total length of the flow path is the value obtained by dividing the internal capacity of the reaction layer by the minimum cross-sectional area of ​​the flow path.

9. In paragraph 1, A method for producing a polymer, wherein the concentration of the monomer in the first solution is 1 to 5 M.

10. In paragraph 1, On one plane of the reaction plate in the direction in which the reaction path 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.

11. In paragraph 1, The above collision medium has a length extending in a direction perpendicular to the flow direction of the fluid on one plane formed by the reaction 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.

12. In paragraph 11, 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.) 13. In paragraph 11, A method for manufacturing a polymer, wherein the inner diameter (R1) of the reaction path formed by the above microchannel and the shortest distance (B1) between the longitudinal ends of the collision medium satisfy the following equation 2. [Formula 2] 3 < B1 / R1< 15 14. In paragraph 1, A method for producing a polymer, wherein the microchannel comprises an inlet channel connecting the microchamber located at the most forward end in the direction of fluid flow in the reaction channel and the fluid inlet, a connection channel connecting the microchambers adjacent to each other, and an outlet channel connecting the microchamber located at the most rearward end in the direction of fluid flow in the reaction channel and the fluid outlet.

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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