WO2025048579A1 - Method for manufacturing functional polymer by anionic polymerization method - Google Patents

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 polymer by anionic polymerization method

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

Anionic polymerization has the advantage of being easier to control molecular weight by changing the molar ratio of the initiator and monomer compared to other polymerization methods due to the characteristics 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 unless a protic compound exists in the polymerization reaction system, and there is no termination reaction such as ion pair rearrangement. Accordingly, in the polymerization reaction system, the polymer chain has the characteristic of continuously growing according to the injection of the monomer while having an active anionic terminal.

Such anionic polymerization reactions cause side reactions due to the heat generated during the reaction, which reduces the uniformity of the polymer. Therefore, anionic polymerization reactions must be carried out at very low temperatures in polar solvents.

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

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 is disclosed.

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

However, anionic polymerization reaction using a conventional flow-type reaction system such as this still has a problem in 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.

In addition, although the conventional flow-type reaction system enables efficient heat control using a heat medium, in the case of anionic polymerization, a local temperature surge (hot spot) may occur within the reaction system due to rapid heat generation at the early stage of the reaction due to rapid reaction polymerization. In the anionic polymerization using the conventional flow-type reaction system, a temperature gradient of the reactants occurs depending on the location within the reaction path due to the explosive heat generated at the early stage of the polymerization reaction. To this end, operation can be performed by increasing the flow rate of the reactant or the refrigerant or by 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 demand for the development of a manufacturing technology capable of polymerizing high-quality polymers using a flow-type reaction system while maintaining economical operation and long-term reliability.

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

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.

The tasks of the present invention are not limited to the above-described contents. Those with ordinary knowledge in the technical field to which the present invention belongs will have no difficulty in understanding additional tasks of the present invention from the overall contents of this specification.

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 paths through which the heat medium is transported to the upper and lower layers of the reaction layer, respectively.

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 paths.

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 switches the flow of the fluid within the internal space.

In a polymer manufacturing method according to one embodiment, the first temperature regulating layer may include a temperature regulating plate which is spaced apart from the upper portion of the reaction plate in the main body and has 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 in the first heat medium passage to induce transport of the heat medium transported in the first heat medium passage, and the second temperature regulating layer may include a second heat medium channel which forms the second heat medium passage on the bottom surface of the main body, and a plurality of second induction media positioned in the second heat medium passage to induce transport of the heat medium transported in the second heat medium passage.

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.

In a method for producing a polymer according to one embodiment, the anionic polymerization can be performed in a co-solvent of an ether solvent and a non-polar solvent.

In a method for producing a polymer according to one embodiment, the flow rate of the first solution may be greater than the flow rate of the second solution.

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

[Relationship 1]

7.6 ㎝ ² /min ≤Log(Q _in Х(L _total /A _min )) ≤8.5 ㎝ ² /min

(In the above relational expression 1, the inflow rate (Q _in ) means the sum (Q ₁ +Q ₂ ) of the flow rate of the first solution (Q ₁ ) and the flow rate of the second solution (Q ₂ ), the minimum cross-sectional area of the flow path (A _min ) means the diametric cross-sectional area of the 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.)

In a method for producing a polymer according to one embodiment, the concentration of the monomer in the first solution may be 1 to 5 M.

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.

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 in which the fluid collided by the collision medium flows in both directions along both longitudinal ends of the collision medium, and a confluence portion in which the fluid flowing along both directions of the collision medium flows again in one direction.

In a polymer manufacturing method according to one embodiment, the diameter (L ₁ ) of the channel formed by the branch portion and the diameter (L ₂ ) of the channel formed by the joining portion can satisfy the following equation 1.

[Formula 1]

1 < (L ₂ /L ₁ ) < 3

In the above equation 1, L ₁ and L ₂ is measured along an imaginary center line connecting the anterior connection portion connected to the anterior microchannel and the posterior connection portion connected to the posterior microchannel among the microchannels adjacent to the above microchamber.

In a polymer manufacturing method according to one embodiment, the inner diameter (R ₁ ) of the reaction path formed by the microchannel and the shortest distance (B ₁ ) between the longitudinal ends of the collision medium can satisfy the following equation 2.

[Formula 2]

3 < B ₁ /R ₁ < 15

In a polymer manufacturing method according to one embodiment, the microchannel may include an inlet channel connecting the microchamber located most forward 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 most rearward in the direction of fluid flow in the reaction channel and the fluid outlet.

In a method for producing a polymer according to one embodiment, the monomer may include an aromatic vinyl monomer.

In a method for producing a polymer according to one embodiment, the nonpolar solvent may include a C5-C8 alkane solvent.

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.

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.

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

Figure 2 is a plan view showing the reaction layer of the microflow reactor shown in Figure 1.

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

Unless otherwise defined, 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 belongs, 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.

The embodiments of the present invention are provided to more completely explain the present invention to those with average knowledge in the art. Therefore, the scope of the present invention is not limited to the embodiments described below.

The terminology used in the description of the present invention is for the purpose of describing embodiments of the present invention only and should not be taken to be limiting. Unless clearly used otherwise, the singular form includes the plural form.

The term "comprises," as used herein, is an open-ended description equivalent to the expressions "comprises," "contains," "has," or "characterized by," and does not exclude additional elements, materials, or processes not listed herein.

Unless otherwise specified, units used in this specification are based on weight, and as an example, units of % or ratio mean weight% or weight ratio, and weight% means the weight % that one component occupies in the composition among the entire composition unless otherwise defined.

In addition, the numerical range used in this specification includes the 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 the upper and lower limits of the numerical range defined in different shapes. Unless otherwise specifically defined herein, values outside the numerical range that may arise due to experimental error or rounding of values are also included in the defined numerical range.

In this specification, terms such as ‘top’, ‘upper part’, ‘top surface’, ‘bottom’, ‘lower part’, ‘bottom’, and ‘side’ are based on the drawings, and may actually vary depending on the direction in which elements or components are arranged.

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.

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 more than one of the first solution, the second solution, and the third solution. As a specific example, 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, the fluid 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.

In this specification, the 'heat medium' refers to a medium that transfers heat and can cool or heat a fluid through heat exchange with the fluid in 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 used as a refrigerant or a heat medium in the past. As a non-limiting example, the heat medium may be a heat transfer oil such as silicone oil or mineral oil, heat transfer nanofluids, ethylene glycol, propylene glycol, etc.

In this specification, the term '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.

In this specification, the present invention is described in detail through each embodiment according to the present invention, but each embodiment described in the specification should be considered not only to mean one embodiment but also to mean a combination with other embodiments. Therefore, the citation of a claim in the scope of the patent claims is only an example, and the technical idea of the present invention should not be interpreted only as a combination with the cited claim, and a combination with various claims is also included in the scope of the technical idea of the present invention.

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

In addition, although the conventional flow-type reaction system enables efficient heat control using a heat medium, in the case of anionic polymerization, due to rapid heat generation at the initial stage of the reaction due to rapid reaction polymerization, a local temperature surge (hot spot) occurs within the reaction system, and a temperature gradient of the reactants occurs depending on the location within the reaction path. To this end, operation can be performed by increasing the flow rate of the reactant or the heat medium or further reducing the temperature of the heat medium, but there are problems in that the pump pressure increases and energy consumption due to low-temperature cooling is high. 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, a high-quality polymer can be manufactured, and thus the present invention has been completed.

A polymer manufacturing 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 an ether solvent and a non-polar solvent 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.

The above 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.

This method of manufacturing a polymer using a microflow reactor can effectively control the rapid exotherm of an anionic polymerization reaction by increasing the heat exchange area through two temperature control layers that surround the reaction layer from above and below. Accordingly, side reactions due to the reaction heat can be suppressed, so that the desired polymer can be produced with a high conversion rate and high purity.

To explain in more detail, when the first and second solutions are mixed and 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 described above, the reaction heat can be quickly removed by the heat medium flowing over the upper and lower surfaces of the reaction layer. By increasing the flow rates of the first and second solutions in the microflow reactor, 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.

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.

This polymer manufacturing method can solve the problem of pump overload because the pump pressure can be maintained low, and even though the fluid is transported in a laminar flow, a sufficient heat removal effect can be achieved because 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 non-homogeneous due to non-uniform mixing of the fluid, which may lower the quality of the polymer manufactured, but since the fluid in 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. As a result, the polymer manufacturing method can homogeneously mix the fluid even though the fluid is transported in a laminar flow.

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, so that the polymerization reaction does not occur immediately, and thus the generation of reaction heat may be delayed. Accordingly, since polymerization is not carried out before uniform mixing is achieved, but rather after uniform mixing in a microchamber, it has the advantage of being able to manufacture a chemically uniform polymer. That is, the above polymer manufacturing method can manufacture a high-quality polymer having a low molecular weight distribution, and can use a relatively high concentration of reactants through efficient heat control, thereby increasing the production amount per unit time. Furthermore, since stable heat control is possible despite the continuous process, a high-quality polymer can be produced for a long time. Specifically, the molecular weight distribution (polydispersity) of the polymer manufactured through the above 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.

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 increase 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 over the entire reaction layer area by rapid heat transfer by parallel flow and high heat transfer efficiency by 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 time, so that continuous production of a more homogeneous polymer can be possible.

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.

The above fluid inflow 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 inflow 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 inflow region may refer to the region including the fluid inlet, the inflow channel, and the microchamber located at the most forward end and the microchambers located in the same row, 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 inflow region and the fluid discharge region. In addition, the heat medium inflow 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 inflow region, and the fluid transfer region are projected in the upper and lower direction of the main body.

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 to each other. The heat transfer efficiency is improved, so that the rapid reaction heat generated during the anionic polymerization reaction can be quickly removed.

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 to each other in series, parallel, or series-parallel. In the direction of fluid flow, the outlet of the microflow reactor arranged forward may be connected to the inlet of the microflow reactor arranged backward.

According to one embodiment, the polymer manufacturing method changes the linear velocity of the fluid at each position in the reaction path as the diameter of the path is repeatedly changed by the microchannel and microchamber. Accordingly, the linear velocity of the fluid in the reaction layer may be different at each position in the reaction layer even if the fluid is injected at the same flow rate. Specifically, the linear velocity is the fastest in the microchannel having the smallest cross-sectional area of the path, and the slowest in the microchamber having the widest cross-sectional area of the path.

In one embodiment, the linear velocity of the fluid within the reaction layer is not particularly limited as long as continuous production of the polymer is possible, and may be appropriately controlled 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, so that a higher quality polymer can be produced.

In one embodiment, the average residence time of the fluid within the reaction layer is 10 to 50 seconds, and the passage 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 passage 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.

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 in the microflow reactor, the polymerization reaction is slower in initiation than in a typical anionic polymerization reaction, and the polymerization reaction rate is also slower, 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 performed without increasing the flow rate of the heat medium or decreasing the temperature of the heat medium in the microflow reactor, and the anionic polymerization reaction is possible even at a relatively high temperature, and a high-quality polymer can be economically manufactured.

The step (S1) above 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 rates 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 ports to be supplied to the reaction layer, and supplies the heat medium to the first and second temperature-control 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.

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, that is, the path formed by the microchannel and microchamber, and the internal space. 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 controlled in proportion to the internal capacity of the reaction layer.

The internal capacity of the above reaction layer can be controlled according to the diameter and length of the reaction path in the reaction layer and the size of the internal space of the microchamber, or can be controlled 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 path in 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 controlled in proportion to these.

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 total internal volume of the reaction layer is 60 to 100 mL, in the step (S1), the first solution including the monomer can 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 can 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.

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 total internal capacity of the reaction layer is 2000 to 2200 mL, 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.

The above first solution contains 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.

According to one embodiment, the cosolvent of the ether solvent and the nonpolar 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 make mixing of the fluid more uniform and increase the anionic polymerization reaction temperature. In addition, since the flow rate of the fluid can be satisfied within the above range even after the anionic polymerization reaction, it may be possible to manufacture a polymer with a further improved molecular weight distribution.

The above Hansen solubility (S _co ) can be calculated using the following formula.

[Calculation formula]

S _co( MPa ^½ ₎ = (S ₁ ×W ₁ )+(S ₂ ×W ₂ )

In the above formula, S ₁ is the Hansen solubility of the ether solvent, W ₁ is the weight% of the ether solvent in the cosolvent, S ₂ is the Hansen solubility of the nonpolar solvent, and W ₁ is the weight% of the nonpolar solvent in the cosolvent.

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

In the step (S1), the concentration of the monomer of the first solution can be appropriately adjusted depending on the type of the monomer. According to one embodiment, the concentration of the first solution may 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 the concentration in the above range has an appropriate viscosity for fluid transport, and can be smoothly injected into the microflow reactor in the step (S1).

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.

The nonpolar solvent may be specifically a nonpolar hydrocarbon solvent. More specifically, the nonpolar solvent may be an aromatic hydrocarbon solvent or an aliphatic hydrocarbon solvent, and more specifically, the aliphatic hydrocarbon solvent may be a C5-C8 alkane solvent. As a non-limiting example, the nonpolar 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 nonpolar 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.

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

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

However, in order for the anionic polymerization to 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 may be 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.

The above anionic polymerization initiator may include an organometallic compound. The organometallic compound may be an organoalkali 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.

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 in the above range has an appropriate viscosity for transporting a fluid and can be smoothly injected into the microflow reactor in step (S1).

According to one embodiment, the first solution and the second solution may be those from which dissolved oxygen has been removed. The removal of dissolved oxygen may be performed by injecting nitrogen or argon gas into a storage tank in which the solution is stored. In this way, the first solution and the second solution from which dissolved oxygen has been removed may have the effect of suppressing side reactions caused by cavitation resulting from collision of fluids during an anionic polymerization reaction in a microflow reactor.

Step (S2) is a step of anionic polymerization of the monomer in the microflow reactor, and 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.

The third solution may mean a mixture of the first solution and the second solution, and all of their reactants. Specifically, the third solution may include the cosolvent, a product (polymer) resulting from the anionic polymerization reaction, unreacted substances, intermediate substances, and side products.

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, when it is 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 kinds are sequentially injected into the microflow reactor and then an anionic polymerization initiator is injected, a triblock copolymer can be formed. Meanwhile, when two of the three monomers are mixed in advance 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 can be produced. The type and properties of the polymer manufactured in this manner 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.

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.

(1) Control of residence time of monomer and anionic polymerization initiator

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

(3) Number of microchambers and connection structure

(4) Temperature of the microchamber

The increase in flow rate is closely related to the residence time, and the flow rate or residence time can be adjusted to secure the necessary reaction time to achieve the target conversion rate. On the other hand, if the reaction time is sufficient, a higher flow rate may be desirable because it increases the mixing effect.

In addition, 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, and this may also be related to the residence time. The number of the 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.

The temperature inside the microchamber can be adjusted by circulating the heat medium in the first and second temperature control layers. When performing the step S1), the heat medium can be injected into the first and second temperature control layers simultaneously with the first solution and the second solution. Alternatively, the first solution and the second solution 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.

A polymer manufacturing 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 halogenide such as methyl iodide, and other electrophilic substances. The anionic polymerization reaction may be terminated through step (S3).

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

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

Condition 2. The ratio of the inlet flow rate (Q _in , ㎖/min) in the microflow reactor and the total length of the reaction channel (L _total, cm) to the minimum cross-sectional area of the reaction channel (A _min , cm ² ) satisfies the following relationship 1.

[Relationship 1]

7 cm ² /min ≤ Log(Q _in ×(L _total /A _min ))≤ 9 cm ² /min

In the above condition 2, the inlet flow rate (Q _in ) means the sum ₍ Q ₁ +Q 2 ) of the flow rates of the first solution (Q ₁ ) and the second solution (Q ₂ ), the minimum cross-sectional area of the reaction channel (A _min ) means the cross-sectional area in the diameter direction of the microchannel (the connecting channel described later), and the total length of the reaction channel means the value obtained by dividing the internal capacity of the reaction layer by the cross-sectional area of the connecting channel.

Specifically, in the above condition 1, the ratio (Q ₁ / Q 2 ) of the flow rate of the first solution (Q ₁ ) to the flow rate of the second solution ₍ Q ₂ ) 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 the above condition 2 ^, Log (Q _in × (L _total / A _min )) of the above relationship 1 may be 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.

Without limitation, the above polymer manufacturing method can satisfy all of the above conditions 1 to 2, and such a polymer manufacturing method can manufacture a more homogeneous polymer.

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 of micrometer or larger in size. In particular, according to one embodiment of the present invention, the effect aimed at by the present invention can be realized by using the above microfluidic reactor.

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.

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 body.

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).

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 partitioned into three layers so that each layer of the microflow reactor (100) can be distinguished. The main body (10) is formed with an inlet (11)(14) and an outlet (13)(12) so as to receive and discharge the fluid and heat medium into the inside. Specifically, the fluid inlet (11), the fluid outlet (13), the heat medium inlet (14), and the 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 the upper and lower sides of the reaction layer (30), is discharged through the heat medium discharge port (12).

The main body (10) is a panel-shaped structure with a hollow 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 provided with metal, ceramic, plastic, or a composite material thereof.

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, as shown in the drawing, but is not limited thereto and may be provided as a single one or may be provided in 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 be introduced through the upper surface of the main body (10) into the reaction layer (30) to supply a fluid from the outside of the main body (10) to the reaction layer (30). 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). Accordingly, the fluid does not flow into the first temperature control layer (50).

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 connected to the reaction passageway (30b), but is not connected to 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).

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) form a channel that is introduced to the second temperature control layer (70), but is connected to the first heat medium path (50a) of the first temperature control layer (50) and the second heat medium path (50a) (not shown) of the second temperature control layer (70), so that the heat medium is not supplied to the reaction layer (30).

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

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.

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 microchannels (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 the fluid transported within the internal space and converts the flow of the fluid within the internal space.

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

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, as shown in the drawing, the microchannel (35) can form a path that meanders on one plane formed by the reaction plate (31). Such a microchannel (35) can integrate the reaction path (30b), thereby making the reaction system more compact.

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 position in the direction of fluid flow in the reaction channel (30b) and a fluid inlet port (11), a connection channel (34) connecting adjacent microchambers (37), and an outlet channel (38) connecting a microchamber (37) located at the rearmost position in the direction of fluid flow in the reaction channel (30b) and a fluid outlet (13).

At this time, the direction of the fluid flow refers to the macroscopic flow of the fluid from the fluid inlet (11) to the fluid outlet (13). The microscopic flow of the fluid, i.e., the turbulent flow, which is switched by the collision medium (39) is ignored. Based on the direction of the 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).

However, as the 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 be seen as having fluids moving in opposite directions.

As the fluid inlets (11) are provided in multiple numbers, the inlet channels (32) may be provided in multiple numbers correspondingly. As a specific example, when the main body (10) includes a first fluid inlet and a second fluid inlet (11) as shown in the drawing, 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.

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) in the microchamber array. As shown 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).

The discharge channel (38) forms a path connecting the microchamber (37) located at the rearmost 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).

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

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 in which the fluid can be sufficiently mixed by the collision medium (39).

According to one aspect of the present invention, the internal space (36) of the microchamber (37) may have a shape in which, based on the flow direction of the fluid, the width thereof gradually increases from the rear to the front 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 drawn inward. 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 have a one-way distorted circle, 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 when the fluid collides with the collision medium (39) and the flow changes. That is, although turbulence of the fluid occurs 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.

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 that extends 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 ends of the collision medium (39) in the longitudinal direction do not come into contact with the inner surface of the microchamber (37).

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 face each other and collide for the second time 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 rate of the fluid can be maintained constant, thereby inducing excellent mixing and homogeneous reaction of the fluid more smoothly.

The internal space (36) above can satisfy the following equation 1 in terms of the diameter (L ₁ ) of the flow path formed by the branch portion (36a) and the diameter (L ₂ ) of the flow path formed by the joining portion (36b).

[Formula 1]

1 < (L ₂ /L ₁ ) < 3

In the above equation 1, L ₁ and L ₂ is measured along an imaginary center line connecting a forward connection portion connected to the forward microchannel (35) and a rear connection portion connected to the rear microchannel (35) among the microchannels (35) adjacent to the microchamber (37). Specifically, L ₂ /L ₁ may be 1.1 to 2.8, 1.2 to 2.5, or 1.5 to 2.3. Accordingly, the fluid may be transferred at a fast flow rate and mixed more homogeneously when transferred from the branching portion to the confluence portion.

The length by which the above collision medium (39) extends is not particularly limited as long as it is a length that does not contact the inner surface of the microchamber (37) as described above. However, in one embodiment, the inner diameter (R ₁ ) of the flow path formed by the microchannel (35) and the shortest distance (B ₁ ) between the longitudinal ends of the collision medium (39) can satisfy the following equation 2.

[Formula 2]

3 < B ₁ /R ₁ < 15

Specifically, B ₁ /R ₁ can 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 excellent mixing and homogeneous reaction.

According to one embodiment, the reaction 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). Since the paths of such a microflow reactor (100) are formed in series and in parallel, the microchambers (37) arranged in communication with the paths can also be connected in series and in parallel with each other. The microchannel (35) can include a series connection part in which the paths are connected in series and a parallel connection part in which the paths are connected in parallel. The microchambers (37) located in the parallel connection part can be positioned in parallel with 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 more mass production.

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

Specifically, the first temperature control layer (50) includes a temperature control plate having a first heat medium channel (51) formed on one surface thereof, which is spaced apart from the upper portion of the reaction plate (31) in the main body (10) and forms the first heat medium path (50a), and a plurality of first induction media (53) positioned within the first heat medium path (50a) and inducing transport of the heat medium transported within the first heat medium path (50a), and the second temperature control layer (70) includes a second heat medium channel forming the second heat medium path on the bottom surface of the main body (10), and a plurality of second induction media positioned within the second heat medium path and inducing transport of the heat medium transported within the second heat medium path.

The 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 in parallel with each other. As described above, 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) by the reaction plate (31) and the temperature control plate. The temperature control plate is a medium in which the first heat medium path (50a) is formed, and in which the first heat medium channel (51) and the first induction medium (53) are formed.

The first and second heat medium channels (51) are formed by being introduced onto the bottom surface of the temperature control plate and the main body (10), respectively, and extend in the direction of the surface of the bottom surface of the temperature control plate and 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 the 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.

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 pieces 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 such may play a role in guiding the heat medium in each passage so that it can flow along the shape of the first and second heat medium passages (50a). Accordingly, it is possible to prevent a dead zone in which the heat medium does not flow but stagnates or has a low flow speed from being formed within the first and second heat medium passages (50a), thereby enabling the heat transfer efficiency to occur more smoothly.

As described above, the fluid inlet area (A ₁ ) may mean an area including the fluid inlet (11), the inlet channel (32), and the microchamber (37) located at the most forward end and the microchambers (37) located in the same row, and the fluid discharge area (A ₃ ) may mean an area including the fluid discharge area (13), the discharge channel (38) (38), and the microchamber (37) located at the most rear end and the microchambers (37) located in the same row, and the fluid transfer area (A ₂ ) may mean an area including the microchannels (35) and microchambers (37) connecting the fluid inlet area (A ₁ ) and the fluid discharge area (A ₃ ).

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 one reactor module. Accordingly, each microflow reactor (100) can be controlled at different flow rates, residence times, and temperatures.

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

(Examples 1 to 18)

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 listed in Table 1 below.

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 a 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 a second solution. The concentrations of the first and second solutions and the solvents used for each example are listed in Table 1 below.

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.

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 directions of the heat medium and the 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 relational expression 2 is shown in Table 2.

[Relationship 2]

R (cm ² /min) = Log(Q _in ×(L _total /A _min ))

In the above equation 1, Q _in represents the inlet flow rate (㎖/min) inside the microflow reactor, i.e., the sum (Q ₁ +Q ₂ ) of the flow rates of the first solution (Q ₁ ) and the second solution (Q ₂ ), A _min represents the minimum cross-sectional area (cm ² ) of the flow path inside the microflow reactor, i.e., the cross-sectional area in the diametric direction of the connecting channel, and L _total represents the total length (cm) of the flow path, i.e., the internal capacity (volume) of the microflow reactor divided by the cross-sectional area of the connecting channel.

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 unit (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.

(Comparative examples 1 to 8)

In the examples, the polymer was manufactured in the same manner as in the examples, except that the polymer was manufactured using PFA tubing (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 of the third solution are shown in Table 3 below, and the injection 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.

(Comparative Example 9)

The 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 solvent and concentration of the first and second solutions, and the polymerization terminator of the third solution are shown in Table 3 below, and the injection 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.

<Polymer Evaluation>

1) Conversion rate (%)

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

[Calculation formula 1]

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

2) Molecular weight, polydispersity

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) of 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.

3) Whether there is any side effect

In order 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 in the reactor was observed with the naked eye. If the reaction proceeds well without a side reaction, the fluid in the reactor exhibits a unique color close to red and orange, but if a side reaction occurred, it loses its unique color and changes to transparent. Based on this, the color of the fluid in the reactor was observed to determine whether a side reaction occurred, and the results are shown in Table 5 below. If a side reaction occurred, it was marked with "○", and if a side reaction did not occur, it was marked with "×".

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 low molecular weight of about 5000 in number average molecular weight compared to the comparative examples. In addition, it was confirmed that most of the examples had a conversion rate of 100% and that no side reaction occurred.

Claims (16)

(S1) a step of injecting a first solution containing one or more solvents and a monomer 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; 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. In the first paragraph, 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. In the first paragraph, 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 switches the flow of the fluid within the internal space. In the third paragraph, The above first temperature control layer is, A temperature control plate having a first heat medium channel formed on one surface and spaced apart from the upper portion of the reaction plate in the above body and forming the first heat medium path, and a plurality of first induction media positioned in the first heat medium path and inducing the transport of the heat medium transported in the first heat medium path, 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 inducing media positioned within the second heat medium path and inducing heat medium transport within the second heat medium path. In the first paragraph, 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. In the first paragraph, 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. In the first paragraph, A method for producing a polymer, wherein the flow rate of the first solution is greater than the flow rate of the second solution. In the first paragraph, A method for producing a polymer, wherein the ratio of the inflow rate (Q _in , ㎖/min) into the reaction layer and the total length (L _total , ㎝) of the flow path in the reaction layer to the minimum cross-sectional area (A _min , ㎝ ² ) of the flow path in the reaction layer satisfies the following relationship 1. [Relationship 1] 7.6 cm ² /min ≤Log(Q _in ×(L _total /A _min ))≤8.5 cm ² /min (In the above relational expression 1, the inflow rate (Q _in ) means the sum (Q ₁ +Q ₂ ) of the flow rate of the first solution (Q ₁ ) and the flow rate of the second solution (Q ₂ ), the minimum cross-sectional area of the flow path (A _min ) means the diametric cross-sectional area of the 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.) In the first paragraph, A method for producing a polymer, wherein the concentration of the monomer in the first solution is 1 to 5 M. In the first paragraph, On one plane of the reaction plate in the direction in which the reaction path extends, The internal space of the above microchamber gradually widens 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 such that it is retracted inside. A method for manufacturing a polymer, wherein the inner surface of the above internal space is a curved surface. In the first paragraph, 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 above reaction body, but is curved backwards, A method for manufacturing a polymer, wherein the internal space includes a branch portion in which a fluid collided with the collision medium flows in both directions along both longitudinal ends of the collision medium, and a confluence portion in which a fluid flowing along both directions of the collision medium flows again in one direction. In Article 11, A method for manufacturing a polymer, wherein the diameter (L ₁ ) of the flow path formed by the branch portion and the diameter (L ₂ ) of the flow path formed by the joining portion satisfy the following equation 1. [Formula 1] 1 < (L ₂ /L ₁ ) < 3 (In the above equation 1, L ₁ and L ₂ is measured along an imaginary center line connecting the anterior connection portion connected to the anterior microchannel and the posterior connection portion connected to the posterior microchannel among the microchannels adjacent to the above microchamber.) In Article 11, A method for manufacturing a polymer, wherein the inner diameter (R ₁ ) of the reaction path formed by the above microchannel and the shortest distance (B ₁ ) between the longitudinal ends of the collision medium satisfy the following equation 2. [Formula 2] 3 < B ₁ /R ₁ < 15 In the first paragraph, A method for producing a polymer, wherein the microchannel includes an inlet channel connecting the microchamber located most forward in the direction of fluid flow in the reaction path and the fluid inlet, a connection channel connecting the microchambers adjacent to each other, and an outlet channel connecting the microchamber located most rearward in the direction of fluid flow in the reaction path and the fluid outlet. In the first paragraph, A method for producing a polymer, wherein the monomer comprises an aromatic vinyl monomer. In the first paragraph, A method for producing a polymer, wherein the nonpolar solvent comprises a C5-C8 alkane solvent.

Images