Method for producing functional polymer by anionic polymerization method

Abstract

The present invention relates to a method for producing a functional polymer by an anionic polymerization method, according to which it is possible to economically produce a polymer having high chemical uniformity and to carry out an anionic polymerization reaction even at a relatively high temperature compared to conventional methods.

Description

Technical Field

[0001] This invention relates to a method for manufacturing functional polymers by anionic polymerization. Background Technology

[0002] Due to the inherent characteristics of the polymerization method, anionic polymerization offers advantages over other polymerization methods, allowing for easier control of molecular weight based on the molar ratio of initiator and monomer, and maintaining a narrower molecular weight distribution (polydispersity). Anionic polymerization exhibits the characteristics of living polymerization; therefore, as long as protic compounds are absent from the polymerization system, termination reactions, such as ion pair rearrangements, will not occur. Consequently, in the polymerization system, the polymer chains possess active anionic terminals and continue to grow with the introduction of monomers.

[0003] This type of anionic polymerization reaction generates heat during the reaction, leading to side reactions that reduce the homogeneity of the polymer. Therefore, anionic polymerization must be carried out in polar solvents at very low temperatures.

[0004] Furthermore, in anionic polymerization, the reaction occurs immediately at the anionic terminal of the active polymer after monomer injection. Therefore, if rapid and uniform mixing cannot be achieved in the reactor, it will inevitably lead to increased non-uniformity between polymers and a larger molecular weight distribution of the manufactured polymer.

[0005] As disclosed in Japanese Patent Publication No. 7012866, "Method for manufacturing polymer and flow reaction system for manufacturing polymer", a method for manufacturing polymers by performing anionic polymerization reaction through a microflow reaction system has been disclosed.

[0006] Microflow reaction systems offer advantages such as easy control of fluid flow, uniform control of residence time within the reactor, particularly easy control of heat generated or consumed by chemical reactions, and superior mass transfer compared to batch reactors.

[0007] However, in this type of anionic polymerization reaction using existing flow reaction systems, the anionic polymerization initiator and monomer react immediately upon injection into the reactor before they are fully and uniformly mixed. Therefore, the problem of a large molecular weight distribution in the produced polymer still exists.

[0008] Furthermore, this anionic polymerization reaction using existing microflow reactors still requires cryogenic conditions, necessitating separate cooling equipment. However, in the initial stages of anionic polymerization, most of the polymerization occurs rapidly, leading to insufficient heat removal due to the rapid generation of heat. This makes side reactions more likely, hindering the production of polymers with the target molecular weight and molecular weight distribution. To suppress these side reactions, the reactor temperature can be set to extremely low temperatures, but this is highly uneconomical, and the cooling equipment is difficult to maintain, making large-scale production practically impossible. Summary of the Invention

[0009] The problem the invention aims to solve According to one aspect of the present invention, a polymer manufacturing method is provided that can economically produce polymers with high chemical homogeneity.

[0010] Furthermore, according to one aspect of the present invention, a polymer manufacturing method is provided that can perform anionic polymerization reactions at relatively high temperatures compared to existing methods.

[0011] In addition, according to one aspect of the present invention, a polymer manufacturing method is provided for continuously manufacturing high-quality polymers using a microflow reactor.

[0012] The technical problems of this invention are not limited to those described above. Those skilled in the art will have no difficulty understanding the additional technical problems of this invention from the entirety of this specification.

[0013] means for solving problems According to an embodiment of the present invention, a polymer manufacturing method includes: (S1) injecting a first solution comprising one or more solvents selected from the group consisting of ether solvents and nonpolar solvents and a monomer, and a second solution comprising the solvent and an anionic polymerization initiator into a microflow reactor; and (S2) performing anionic polymerization of the monomer in the microflow reactor, wherein the microflow reactor comprises: a body having at least one inlet hole and an outlet hole; microchannels forming flow paths connecting the inlet hole and the outlet hole within the body; a plurality of microchambers arranged along the extension direction of the microchannels and forming an internal space communicating with the flow paths; and a collision medium located within the internal space and colliding with fluid transported within the internal space to convert the flow of fluid within the internal space, wherein the microchannels comprise: an inflow channel connecting the foremost microchamber located in the flow direction of the fluid within the channel to the inlet hole; a connecting channel connecting adjacent microchambers; and an outlet channel connecting the rearmost microchamber located in the flow direction of the fluid within the channel to the outlet hole, wherein the Reynolds number of the inflow channel is... i The number of the discharge channel is less than the Reynolds number (Re). f ).

[0014] According to one embodiment of the polymer manufacturing method, the Reynolds number ratio Re i / Re f It can be between 1.1 and 5.

[0015] According to one embodiment of a polymer manufacturing method, the inlet includes a first inlet for flowing into the first solution and a second inlet for flowing into the second solution, and the inflow channel includes a first inflow channel and a second inflow channel extending from the first inlet and the second inlet respectively to the microchannel located at the foremost end, wherein the Reynolds number (Re i ) is the Reynolds number of the first inflow channel.

[0016] According to one embodiment of the polymer manufacturing method, the Reynolds number (Re) of the inflow channel i The value can range from 100 to 350.

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

[0018] According to one embodiment of the polymer manufacturing method, the anionic polymerization is carried out in a co-solvent environment of the ether solvent and the nonpolar solvent.

[0019] According to one embodiment of the polymer manufacturing method, the Hansen solubility parameter of the co-solvent can be 16 to 20 MPa½.

[0020] According to one embodiment of the polymer manufacturing method, the temperature of the flow path can be from -80 to 60°C.

[0021] According to one embodiment of a polymer manufacturing method, on a plane of the body in the flow path extension direction, the internal space of the microchamber gradually widens from the rear to the front based on the flow direction of the fluid, the front side connection portion connected to the front side microchannel has an inwardly introduced shape, and the inner surface of the internal space is curved.

[0022] According to one embodiment of a polymer manufacturing method, the collision medium has a length extending in a direction perpendicular to the flow direction of the fluid on a plane formed by the body, and bends backward, and the internal space includes branch portions where the fluid collided by the collision medium flows in two directions along both ends of the length direction of the collision medium, and confluence portions where the fluid flowing in the two directions of the collision medium flows in one direction again.

[0023] According to one embodiment of the polymer manufacturing method, the diameter (L1) of the flow path formed by the branch portion and the diameter (L2) of the flow path formed by the confluence portion satisfy the following equation 1: [Formula 1] 1 < (L2 / L1) < 3 In Equation 1, L1 and L2 are measured along a virtual center line, which connects the front connecting portion of the microchannel adjacent to the microchamber to the front side microchannel and the rear connecting portion to the rear side microchannel.

[0024] According to one embodiment of the polymer manufacturing method, the inner diameter (R1) of the flow path formed by the microchannel and the closest distance (D1) between the two ends of the collision medium in the longitudinal direction can satisfy the following equation 2: [Equation 2] 3 <D1 / R1<15。

[0025] According to one embodiment of a polymer manufacturing method, the inner diameter of the rear-end flow path of at least one of the inflow channels and connecting channels may be gradually reduced.

[0026] According to one embodiment of the polymer manufacturing method, the linear velocity of the fluid can be from 0.1 to 1 m / s.

[0027] According to one embodiment of the method for manufacturing a polymer, the monomer may include an aromatic vinyl monomer.

[0028] According to one embodiment of the polymer manufacturing method, the nonpolar solvent may include C5-C8 alkane solvents.

[0029] Invention Effects According to one aspect of the present invention, a method for manufacturing a polymer can economically produce a high-quality polymer with high chemical homogeneity.

[0030] Furthermore, according to one aspect of the polymer manufacturing method of the present invention, anionic polymerization can be carried out at relatively high temperatures, thereby having the advantage of not requiring low-temperature cooling.

[0031] Furthermore, the method for manufacturing polymers according to one aspect of the present invention enables the continuous production of high-quality polymers, thereby providing excellent economic advantages. Attached Figure Description

[0032] Figure 1 This is a perspective view of a microflow reactor according to an embodiment of the present invention.

[0033] Figure 2 It is shown Figure 1 The diagram shows a plan view of the microflow reactor.

[0034] Figure 3 This is a plan view illustrating a microflow reactor according to another embodiment of the present invention.

[0035] Figure 4 This is a plan view showing a microflow reactor according to yet another embodiment of the present invention.

[0036] Figure 5 This is a photograph illustrating a microflow reactor according to an embodiment of the present invention. Detailed Implementation

[0037] Unless otherwise defined, the technical and scientific terms used in this specification have the meanings commonly understood by those skilled in the art. In the following description or drawings, descriptions of well-known functions and structures that do not unnecessarily obscure the essence of the invention are omitted.

[0038] The embodiments of the present invention are provided to illustrate the invention more fully to those skilled in the art. Therefore, the scope of the present invention is not limited to the embodiments described below.

[0039] The terminology used in this description is for the purpose of describing embodiments of the invention and should not be construed as limiting. Unless explicitly stated otherwise, the singular forms include the meaning of the plural forms.

[0040] In this specification, the term "comprising" is an open-ended description that is equivalent to expressions such as "possessing," "containing," "having," or "as a feature," and does not exclude elements, materials, or processes not otherwise listed.

[0041] In this specification, unless otherwise specified, units are based on weight. For example, the units of % or ratio mean weight % or weight ratio, and weight % means the weight of any one component in the composition unless otherwise defined.

[0042] Furthermore, the numerical ranges used in this specification include lower and upper limits and all values ​​within those limits, increments derived from the form and width logic of the defined ranges, all values ​​with double limits, and all possible combinations of upper and lower limits of numerical ranges defined in different forms. Unless otherwise defined in this specification, values ​​outside the defined numerical ranges that may occur due to experimental errors or rounding are also included within the defined numerical ranges.

[0043] In this specification, terms such as "upper," "top," "above," "lower," "below," "side," etc., are based on the accompanying drawings and may actually vary depending on the arrangement direction of the components or constituent elements.

[0044] Furthermore, throughout the specification, when a part is "connected" to other parts, this includes not only "direct connection" but also "indirect connection" with other components in between.

[0045] In this specification, "polymer" means a high molecular weight compound with a weight average molecular weight of 1,000 or more formed by polymerizing monomers, including not only a single polymer (homopolymer) made by polymerizing one monomer, but also a copolymer (copolymer) made by polymerizing two or more monomers.

[0046] In this specification, "fluid" refers to a substance that has fluid properties and is capable of flowing, and specifically to all substances flowing within the microflow reactor. Specifically, the fluid may refer to a first solution, a second solution, and a third solution, or a mixture of two or more of these solutions. As a specific example, the fluid at the front side of the microflow reactor adjacent to the inlet, before the first and second solutions mix, may refer to either the first solution or the second solution; the fluid after the first and second solutions are mixed within the microflow reactor may refer to a mixture of the first and second solutions and the third solution as a reactant. Furthermore, the fluid at the rear side of the microflow reactor adjacent to the outlet may also refer to the third solution.

[0047] This specification describes the invention in detail through various embodiments. However, each embodiment described in the specification is not limited to a single embodiment but should be considered as a combination with other embodiments. Therefore, each claim reference corresponds to only one example, and the technical concept of the invention should not be interpreted as being limited to combinations with the referenced claims. Combinations with various claims are also included within the scope of the technical concept of the invention.

[0048] Existing anionic polymerization reactions using flow reaction systems suffer from the problem of excessively large molecular weight distribution in the produced polymers because the anionic polymerization initiator and monomer react immediately upon injection into the reactor before they are fully and uniformly mixed.

[0049] Furthermore, in traditional anionic polymerization reactions using flow-type reaction systems, the Reynolds number (Re) of the anionic polymerization initiator and monomer is excessively increased to create turbulence in order to achieve a more uniform mixture. However, compared to the applied pressure, this uniform mixing effect is relatively low and may lead to overload of the fluid drive source (pump), thereby causing safety issues.

[0050] Furthermore, existing anionic polymerization reactions via microflow reactors require extremely low temperatures, which results in very high energy consumption of cooling equipment and is highly uneconomical.

[0051] A polymer manufacturing method according to an embodiment of the present invention includes: (S1) injecting a first solution comprising one or more solvents selected from the group consisting of ether solvents and nonpolar solvents and a monomer, and a second solution comprising the solvent and an anionic polymerization initiator into a microflow reactor; and (S2) performing anionic polymerization of the monomer in the microflow reactor.

[0052] The microflow reactor includes: a body having at least one inlet hole and an outlet hole; microchannels forming flow paths connecting the inlet hole and the outlet hole within the body; multiple microchambers arranged along the extension direction of the microchannels and forming an internal space communicating with the flow paths; and a collision medium located within the internal space and colliding with the fluid transported within the internal space to change the flow of the fluid within the internal space. The microchannels include: an inflow channel connecting the foremost microchamber in the flow direction within the channel to the inlet hole; a connecting channel connecting adjacent microchambers; and an outlet channel connecting the rearmost microchamber in the flow direction within the channel to the outlet hole. The Reynolds number of the inflow channel is...i The number of the discharge channel is less than the Reynolds number (Re). f ).

[0053] This polymer manufacturing method maintains a low Reynolds number on the front side of the microflow reactor where the anionic polymerization reaction is carried out (based on the flow direction of the fluid), but achieves uniform mixing and reaction by uniformly mixing the fluid through the microflow reactor.

[0054] Specifically, according to the polymer manufacturing method, the fluid within the microflow reactor exhibits a low Reynolds number and forms laminar flow in the overall flow of the microflow reactor; however, the fluid flowing into the microchamber forms turbulent flow through collisions with the impacting medium. Therefore, although the microflow reactor as a whole exhibits laminar flow, the fluid can be uniformly mixed. Thus, without applying excessive pressure to the fluid, the polymer manufacturing method can achieve uniform mixing of the fluid and can produce high-quality polymers with uniform molecular weight distribution. Specifically, the molecular weight distribution (polydispersity) of the polymer manufactured from the polymer manufacturing method can be controlled to be below 1.5, 1.4, 1.3, 1.2, or 1.1.

[0055] In one implementation, the Reynolds number (Re) in the inflow channel i ) and the Reynolds number in the discharge channel (Re f The ratio of Reynolds numbers (Re) f / Re i The value can be greater than 1 and less than 10, 1.1 to 7, 1.1 to 5, 1.5 to 5, 2 to 5, or 3 to 4.8. Within these ranges, more uniform polymer manufacturing can be achieved.

[0056] In one implementation, the Reynolds number (Re) in the inflow channel i The number is less than the Reynolds number in the discharge channel. f The Reynolds number (R) for laminar flow is not particularly limited, but can be 50 to 500, 80 to 400, 100 to 350, 150 to 300, or 160 to 280. Within these ranges, homogeneous polymers can be produced even at relatively high temperatures. Specifically, anionic polymerization can be carried out at temperatures in the flow path within the microflow reactor at -70 to 60°C, -50 to 60°C, -40 to 60°C, -30 to 50°C, -20 to 50°C, -10 to 50°C, 0 to 40°C, or 20 to 40°C.

[0057] In one embodiment, the inlet includes a first inlet for inflow into the first solution and a second inlet for inflow into the second solution, and the inflow channel may include a first inflow channel and a second inflow channel extending from the first inlet and the second inlet to the microchamber located at the foremost end, respectively. At this time, the Reynolds number (Re...) i The number (Re) can be the Reynolds number of the first inflow channel. That is, the Reynolds number (Re) i () can be the Reynolds number of the first solution flowing in the first inflow channel.

[0058] In one embodiment, the microflow reactor can be a single unit or multiple units. Multiple microflow reactors can be connected in series, in parallel, or in a series-parallel configuration. In the direction of fluid flow, the outlet of the microflow reactor positioned at the front can be connected to the inlet of the microflow reactor positioned at the rear.

[0059] In one embodiment, the Reynolds number (Re) of the discharge channel f When multiple microflow reactors are configured, the measurement can be taken in the discharge channel of the microflow reactor located at the very end of the fluid flow. That is, the Reynolds number (Re) of the discharge channel. f The number can be the Reynolds number of the final product flowing in the discharge channel, i.e., the third solution.

[0060] According to one embodiment, the polymer manufacturing method involves repeatedly varying the diameter of the flow path through microchannels and microcavities, thus causing variations in the linear velocity of the fluid at different locations. Therefore, even with the same flow rate, the linear velocity of the fluid within the microflow reactor can differ depending on the location of the microflow reactor. Specifically, the fastest linear velocity is found in connecting channels with the relatively smallest flow path cross-sectional area, while the slowest linear velocity is found in microcavities with the widest flow path cross-sectional area.

[0061] According to one embodiment, the linear velocity of the fluid within the microflow reactor is not particularly limited as long as it meets the Reynolds number, and can be appropriately adjusted according to the type and properties of the desired polymer. The linear velocity of the fluid can be 0.1 to 1.5 m / s, 0.1 to 1 m / s, 0.1 to 0.9 m / s, 0.2 to 0.8 m / s, or non-limitingly 0.2 to 0.7 m / s. With the fluid linear velocity meeting the aforementioned range, the formation of dead zones (where the fluid stops flowing or its flow velocity drops sharply) can be prevented in the microflow reactor under conditions of collision with the colliding medium. Therefore, the fluid is uniformly mixed throughout the flow path region within the microflow reactor, thereby enabling the production of higher quality polymers.

[0062] The linear velocity of the fluid is measured in a microchannel within the microflow reactor, and therefore can be the average value calculated after more than one measurement. The linear velocity of the fluid can be measured in the first fluid channel.

[0063] Step S1 involves injecting the first and second solutions into the microflow reactor. Through step S1, the types and flow rates of the first and second solutions are adjusted according to the desired polymer type and properties before being injected into the microflow reactor. As a specific example, regardless of the internal capacity of the microflow reactor, the flow rates (flow rates) of the first and second solutions can be adjusted to maintain the linear velocity within the reactor. The size of the external injection path connected to the microflow reactor can be appropriately adjusted according to the internal capacity of the microflow reactor.

[0064] The internal capacity (volume) of the microflow reactor refers to the amount of solution that the microflow reactor can hold. It can refer to the volume formed by the flow paths, namely microchannels and microchambers, and the internal space within the microflow reactor. There is no particular limitation on the internal capacity of the microflow reactor; it is proportional to the internal capacity of the microflow reactor. The flow rates of the first and second solutions injected in step S1 can be adjusted.

[0065] The internal capacity of the microflow reactor can be adjusted according to the diameter and length of the flow path within the microflow reactor and the size of the internal space of the microchamber, or according to the number of interconnected microflow reactors. Specifically, the internal capacity of the microflow reactor can be increased in proportion to the diameter and length of the flow path within the microflow reactor, the size of the internal space of the microchamber, and the number of connected microflow reactors, and the flow rates of the first and second solutions injected in step S1 can be adjusted proportionally.

[0066] As a non-limiting example, when the diameter of the external injection path connecting the microflow reactor to the storage tank storing the first solution is 1 / 8 to 1 / 4 inch, and multiple microflow reactors are connected such that the total internal capacity of the microflow reactors is 60 to 100 mL, the first solution containing the monomer in step S1 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 containing 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.

[0067] As another example, when the diameter of the external injection path connecting the microflow reactor to the storage tank storing the first solution is 1 to 1 / 3 inch, and multiple microflow reactors are connected so that the total internal capacity of the microflow reactors is 2000 to 2200 mL, the first solution containing the monomer in step S1 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 containing 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.

[0068] In other words, step S1, regardless of the internal capacity of the microflow reactor, can adjust the flow rate to make the residence time of the fluid 5 seconds or more, 10 seconds or more, 15 seconds or more, or 20 seconds or more; non-limitingly, the flow rate can be adjusted to make the residence time less than 60 seconds. Specifically, step S1 can adjust the flow rate, i.e., the flow velocity of the first solution and the second solution, to make the residence time of the fluid in the microflow reactor 5 to 60 seconds, 10 to 55 seconds, or 15 to 50 seconds. Within these ranges, a more uniform polymer can be produced.

[0069] As described above, the first solution comprises one or more solvents selected from the group consisting of ether solvents and nonpolar solvents, and a monomer. Specifically, the first solution may contain the monomer in the ether solvent or the monomer in the nonpolar solvent. Alternatively, the monomer may be contained in a co-solvent of an ether solvent and a nonpolar solvent.

[0070] In step S1, the concentration of the monomer in the first solution can be appropriately adjusted according to the type of monomer. However, according to one embodiment, the concentration of the first solution can be 1 to 5 M, 1 to 4 M, 1 to 3 M, or 2 to 3 M, but is not limited thereto. The first solution with the concentration within the aforementioned range has a suitable viscosity for fluid transport, and injection into the microflow reactor can proceed smoothly in step S1.

[0071] The ether solvent contained in the first solution may be an aliphatic aprotic ether solvent or an alicyclic aprotic ether solvent. As a specific example, it may be a mixture of 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), diisopropyl ether, or 1,2-diethoxyethane, but is not limited thereto.

[0072] The nonpolar solvent may specifically be 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 one or more selected from the group consisting of benzene, toluene, butane, pentane, neopentane, hexane, cyclohexane, methylcyclohexane, heptane, and octane. As a specific example, the nonpolar solvent may be a mixture of hexane and heptane. The monomer may be a styrene-based monomer, an acrylate-based monomer, an olefin-based monomer, or a vinyl-based monomer, but is not limited to any particular monomer.

[0073] According to one embodiment, the monomer may include an aromatic vinyl monomer. Specifically, the aromatic vinyl monomer may be styrene, C1-C6 alkoxystyrene, and more specifically, C1-C4 alkoxystyrene.

[0074] Anionic polymerization of alkoxy-substituted styrene monomers is slower than that of unsubstituted styrene. Specifically, the alkoxy group substituted on the phenyl group of styrene acts as an electron-donating group, thus hindering the rapid polymerization reaction as the monomer inserts into the active end of the polymer. Furthermore, the polymerization initiation reaction caused by the complexation of alkoxy-substituted styrene monomers with metal ions is slow. For these reasons, the overall polymerization rate of alkoxy-substituted styrene monomers in anionic polymerization is approximately 10 times lower than that of styrene monomers. On the other hand, the delayed polymerization initiation characteristic offers the advantage that immediate polymerization is not induced when mixing the monomer and initiator solutions, but rather polymerization can begin simultaneously after homogeneous mixing in at least one or more microchambers. This effect is particularly pronounced in microflow reactors with low fluid linear velocities and no turbulence, demonstrating superior operational reliability and economy. Furthermore, the polymerization initiation reaction can be further delayed by the inclusion of nonpolar solvents.

[0075] The second solution comprises one or more solvents selected from the group consisting of ether solvents and nonpolar solvents, and an anionic polymerization initiator. Specifically, the second solution may contain the anionic polymerization initiator in the ether solvent or the nonpolar solvent. Alternatively, the anionic polymerization initiator may be contained in a co-solvent of the ether solvent and the nonpolar solvent.

[0076] However, in order to carry out the anionic polymerization in a co-solvent environment of an ether solvent and a nonpolar solvent, both the solvent of the first solution and the solvent of the second solution can be co-solvents, or the solvent of the first solution and the solvent of the second solution can contain at least one or more different solvents. As a non-limiting example, when the solvent of the first solution is an ether solvent, the solvent of the second solution can be a nonpolar solvent, or a co-solvent environment of an ether solvent and a nonpolar solvent. Alternatively, when the solvent of the first solution is the co-solvent, the solvent of the second solution can be an ether solvent or a nonpolar solvent, or the solvent of the second solution can also be a co-solvent.

[0077] The anionic polymerization initiator may include an organometallic compound. The organometallic compound may be an organoalkali metal compound, such as, but not limited to, ethyl lithium, n-butyllithium, sec-butyllithium, tert-butyllithium, biphenyl lithium, naphthium lithium, 1,1-diphenylhexyllithium, 1,1-diphenyl-3-methylpentyllithium, 1,4-dilithium-2-butene, and 1,6-dilithiumhexane. Specifically, the initiator may be one or a combination of two or more selected from the group consisting of n-butyllithium, sec-butyllithium, and tert-butyllithium.

[0078] According to one embodiment, the concentration of the anionic polymerization initiator in the second solution can be 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, but is not limited thereto. A second solution with a concentration within the aforementioned range has a suitable viscosity for fluid transport, allowing for smooth injection into the microflow reactor in step S1.

[0079] In one embodiment, the anionic polymerization in step S2 can be carried out in a co-solvent environment with ether solvents and nonpolar solvents. With the anionic polymerization performed in the presence of a co-solvent within the microfluidic reactor, the anionic polymerization reaction can proceed even at relatively high temperatures, and high-quality polymers with high chemical homogeneity can be produced economically. Furthermore, the polymer manufacturing method allows for the continuous production of high-quality polymers, thereby improving production efficiency.

[0080] Specifically, as fluids (i.e., the first and second solutions) are injected and transported into channels within the microfluidic reactor, monomers and anionic polymerization initiators mix and react in the presence of a co-solvent.

[0081] Therefore, the polymer manufacturing method does not require cryogenic cooling equipment that consumes excessive amounts of electricity, thus enabling the production of high-quality polymers with greater economic efficiency. Furthermore, the polymer manufacturing method can efficiently produce high-quality polymers with high chemical homogeneity on a large scale.

[0082] According to one embodiment, the Hansen solubility parameter of the co-solvent of the ether solvent and the nonpolar solvent can be 16 to 20, 17 to 19, 18 to 19, or 18.1 to 18.7. Such a co-solvent enables more uniform mixing of the fluid and can increase the anionic polymerization temperature. Furthermore, even after the anionic polymerization reaction, the flow rate of the fluid can be maintained within the stated range, thereby enabling the production of polymers with further improved molecular weight distribution.

[0083] The solubility of Hansen (S) co It can be calculated using the following formula.

[0084] [Calculation formula] S co (MPa ½ ) = (S1×W1)+(S2×W2) In the formula, S1 is the Hansen solubility of the ether solvent, W1 is the weight percentage of the ether solvent in the co-solvent, S2 is the Hansen solubility of the nonpolar solvent, and W2 is the weight of the nonpolar solvent in the co-solvent.

[0085] At this point, the Hansen solubility of each solvent is the known Hansen solubility parameter (based on 25°C, for example, the value known by Charles Hansen, "Hansen Solubility Parameters: A User's Handbook" CRC Press (2007)).

[0086] According to one embodiment, the first and second solutions may have dissolved oxygen removed. Dissolved oxygen removal can be achieved by injecting nitrogen or argon gas into a storage tank containing the solutions. When the first and second solutions, with dissolved oxygen removed in this way, undergo anionic polymerization in a microflow reactor, they can suppress side reactions caused by cavitation due to fluid collisions.

[0087] Step S2 is the step of anionic polymerization of the monomer in the microflow reactor, which involves mixing and reacting the first and second solutions injected into the microflow reactor in step S1 to produce a third solution containing the polymer. In step S2, the monomer undergoes anionic polymerization using the anionic polymerization initiator to produce the polymer.

[0088] The third solution may refer to a mixture of the first and second solutions and their reactants. Specifically, the third solution may include the co-solvent, the product (polymer) of the anionic polymerization reaction, unreacted products, intermediate products, and by-reactants.

[0089] The polymer can be a monopolymer, a random copolymer, or a block copolymer. The random or block copolymer can be a copolymer of two or more monomers; for example, in the case of a copolymer of three or more monomers, it can be a ternary random copolymer in which the three monomers are uniformly present in the polymer chain. As another example, a triblock copolymer can be formed by sequentially injecting three different monomers into the microflow reactor followed by the injection of an anionic polymerization initiator. Alternatively, (M1M2) can be manufactured by pre-mixing two of the three monomers in the microflow reactor without the injection of an anionic polymerization initiator, followed by the injection of an anionic initiator, and finally the injection of the monomers. n (M3) m A diblock copolymer with a specific structure. The polymer thus manufactured can have its type and properties adjusted according to the injection sequence of the first and second solutions, as well as the types and numbers of monomers contained in the first and second solutions.

[0090] According to one aspect of the invention, the properties of the polymer can be adjusted by any one or a combination of two or more of the following means.

[0091] (1) Adjustment of residence time of monomers and anionic polymerization initiators (2) Regulation of fluid velocity in microflow reactor (3) Number and connection structure of microchambers (4) Temperature of the microchamber An increase in flow rate is closely related to residence time. To ensure the reaction time required to achieve the target conversion rate, either the flow rate or the residence time can be adjusted. On the other hand, preferably, if the reaction time is sufficient, a higher flow rate results in a greater mixing effect.

[0092] Furthermore, the shape and length of the overall flow path for fluid movement within the microflow reactor can be adjusted by the number of microchambers and their connection structure, which may also be related to the residence time. The number of microchambers can be 10 to 50, 15 to 40, or 20 to 30, and the microchambers can be connected in series, parallel, or a series-parallel connection. The number of microchambers can be increased as the flow rate increases.

[0093] The temperature within the microcavity can be appropriately adjusted by circulating a known cooling medium. This cooling medium is cooled by a cooler, and the cooled medium contacts the outer wall of the microcavity, thereby regulating the temperature of the fluid flowing through the inner wall of the microcavity and removing heat generated by the exothermic reaction. The temperature within the microcavity can be adjusted to -80 to 60°C, -50 to 60°C, -40 to 60°C, -30 to 50°C, -20 to 50°C, -10 to 50°C, 0 to 40°C, or 20 to 40°C.

[0094] According to one aspect of the polymer manufacturing method of the present invention, after step S2, a further step S3 may be included: injecting a polymerization terminator into a microflow reactor. The polymerization terminator may include, but is not limited to, proton donor compounds such as methanol, halides such as methyl iodide, and other electrophilic substances. Step S3 can terminate the anionic polymerization reaction.

[0095] According to one aspect of the present invention, the polymer manufacturing method can satisfy any one or more of the following conditions.

[0096] Condition 1. The flow rate (velocity) of the first solution is greater than the flow rate (velocity) of the second solution.

[0097] Condition 2. The residence time of the fluid in the microflow reactor is 10 to 50 seconds.

[0098] Condition 3. Inflow rate (Q) in the microflow reactor in (mL / min) and the minimum cross-sectional area of ​​the flow path within the microflow reactor (A)min (cm²) relative to the total flow path length (L) 总 The ratio of , cm) satisfies the following relationship 1.

[0099] [Relation 1] 7 cm² / min ≤ Log(Q in ×(L 总 / Amin)) ≤ 9 cm² / min In condition 3, the inflow rate (Q) in The sum of the flow rates of the first solution (Q1) and the second solution (Q2) (Q1+Q2) is the minimum cross-sectional area of ​​the flow path (A). min The cross-sectional area of ​​the connecting channel in the diametrical direction is called the total flow path length, which is the value of the internal capacity of the microflow reactor divided by the cross-sectional area of ​​the connecting channel.

[0100] Specifically, in condition 1, the ratio (Q1 / Q2) of the flow rate of the first solution (Q1) and the flow rate of the second solution (Q2) can be greater than 1 and less than 5, greater than 1 and less than 4, or greater than 1 and less than 3; in condition 2, the residence time can be 18 to 45 seconds or 20 to 43 seconds; and in condition 3, the Log(Q) of equation 1... in ×(L 总 / Amin)) can be 7.2 cm² / min to 8.8 cm² / min, 7.5 cm² / min to 8.6 cm² / min, 7.6 cm² / min to 8.5 cm² / min or 7.7 cm² / min to 8.4 cm² / min.

[0101] Without limitation, the polymer manufacturing method can satisfy all of the conditions 1 to 3, thus enabling the polymer manufacturing method to produce a more uniform polymer.

[0102] The microfluidic reactor refers to an apparatus for obtaining products through the chemical reaction synthesis of one or more fluids with microchannels of micrometer or larger size. In particular, according to one embodiment of the present invention, the effects of the present invention can be achieved by using the microfluidic reactor.

[0103] Hereinafter, a microflow reactor according to an embodiment of the present invention will be described in detail with reference to the accompanying drawings, but is not limited thereto.

[0104] Figures 1 to 2 A microflow reactor according to an embodiment of the present invention is shown. For ease of explanation, the accompanying drawings show a microflow reactor with an open upper structure, but unlike this, a microflow reactor can actually be a structure with a closed upper part (upper surface).

[0105] Reference Figures 1 to 2 The microflow reactor according to the present invention includes a body 10 having an inlet hole 11 and an outlet hole 13, a microchannel 20, a microchamber 30, and a collision medium 50.

[0106] The body 10 serves as the medium for forming the microchannels 20, microcavities 30, and collision medium 50, providing a flow path for the movement of the first solution to the third solution and a reaction space for the anionic polymerization reaction. The body 10 can be made of a material that is easy to mold, corrosion-resistant, non-flammable, and chemically durable. Specifically, the body 10 can be made of metal, ceramic, plastic, or a composite material thereof.

[0107] As shown in the figure, the body 10 can be a plate-shaped structure forming a plane. The body 10 can extend internally along the surface direction of the plate-shaped structure to form a flow path formed by the microchannels 20 described later. In order to inject the first solution and the second solution internally, the body 10 forms at least one or more inlets 11 and outlets 13 for discharging a third solution to the outside.

[0108] As shown in the figure, the inlet 11 may include a first inlet 11a and a second inlet 11b capable of injecting the first solution and the second solution respectively, but is not limited thereto, and may have one or more. That is, the inlet 11 can be appropriately adjusted according to the type and number of solutions required for the manufacture of the polymer.

[0109] The inlet 11 and outlet 13 of the main body 10 are connected to the flow regulation system, so that the flow rate and velocity can be appropriately adjusted.

[0110] Unlike the figure shown, the body 10 may have a separate plate member (not shown) joined on its upper surface, thereby closing the flow path relative to the upper part of the body 10.

[0111] As shown in the figure, the inlet 11 and outlet 13 can be formed at the edge and adjacent position of the body 10 which has a planar structure, but unlike this, they can also be formed in the central part of the body 10 or the part adjacent thereto.

[0112] The microchannel 20 forms a flow path within the body 10, connecting the inlet hole 11 and the outlet hole 13 on a plane formed by the body 10. The shape of the flow path formed by the microchannel 20 is not particularly limited. As an example, as shown in the figure, the microchannel 20 can form a meandering flow path on a plane formed by the body 10. In this way, the microchannel 20 can integrate the flow path into the body 10, thereby making the reaction system more compact.

[0113] According to one aspect of the invention, the microchannel 20 may include an inflow channel 21 connecting the foremost microchamber 30 and the inlet 11 in the direction of fluid flow within the flow path, a connecting channel 23 connecting adjacent microchambers 30, and an outlet channel 25 connecting the last microchamber 30 and the outlet 13 in the direction of fluid flow within the flow path.

[0114] At this point, the flow direction of the fluid refers to the macroscopic flow of the fluid from the inlet 11 to the outlet 13. The microscopic flow of the fluid converted by the collision medium 50, i.e., the turbulent flow, is ignored. Based on the flow direction of the fluid, the inlet 11 side of the microflow reactor can be divided into the front (or front end) and the outlet 13 side into the rear (or rear end).

[0115] However, when the microchannel 20 forms a serpentine flow path on the body 10, assuming that any microchamber 30 connected to it in a straight line is called a microchamber array, adjacent microchamber arrays can appear to move fluid in opposite directions.

[0116] As the inflow channel 21 has multiple inlets 11, it can correspondingly have multiple inflow channels 11. As a specific example, when the body 10 as shown in the figure includes a first inlet 11 and a second inlet 11, the inflow channel 21 can have a first inflow channel 21a extending from the first inlet 11 and a second inflow channel 21b extending from the second inlet 11. In this case, the first inflow channel 21a and the second inflow channel 21b can be interconnected at the front end of the foremost microchamber 30.

[0117] The connecting channel 23, serving as a flow path for forming the connecting micro-cavities 30, may include a main connecting channel 23 connecting adjacent micro-cavity arrays and sub-connecting channels 23a connecting each micro-cavity 30 within the micro-cavity array. For example... Figures 1 to 2 As shown, it can simultaneously have a main connection channel 23 and a sub-connection channel 23a, but unlike this, as... Figure 3 As shown, the sub-connection channel 23a can also be omitted, and each microchamber 30 can be directly connected.

[0118] The discharge channel 25 serves as a flow path connecting the microchamber 30 located at the rear end and the discharge port 13, allowing the fluid passing through the microchamber 30 to be discharged to the outside of the body 10 through the discharge port 13.

[0119] According to one aspect of the microchannel 20 of the invention, the inner diameter of the rear-end flow path of at least one of the inflow channel 21 and the connecting channel 23 can gradually decrease. That is, the rear end of the inflow channel 21 or the connecting channel 23 can be a tapered shape with a gradually narrowing flow path width. Thus, the flow rate and delivery of fluid can be increased by the microchamber 30 connected to the inflow channel 21 or the connecting channel 23. Therefore, supplying fluid to adjacent microchambers 30 at a fast flow rate continuously and significantly induces excellent mixing and a uniform reaction.

[0120] Multiple microcavities 30 are arranged along the flow path to form an internal space 35 that communicates with the flow path formed by the microchannels 20. The internal space 35 is a conveying path for transporting fluids, and can also be a mixing space where fluids are fully mixed by the collision medium 50.

[0121] According to one aspect of the invention, the internal space 35 of the microchamber 30 gradually widens from rear to front on a plane of the body 10 in the flow path extension direction, based on the flow direction of the fluid. The front-side connecting portion connected to the front-side microchannel 20 can be an inwardly oriented shape. In this case, the inner surface of the internal space 35 can be curved. In other words, as shown, the internal space 35 of the microchamber 30 can be a flattened circle, i.e., a heart shape. Thus, even if the fluid flow changes due to collision with the collision medium 50, the internal space 35 of the microchamber 30 can still flow smoothly along the inner surface of the internal space 35. That is, turbulence occurs within the internal space 35 through the collision medium 50, but this does not impede the flow of fluid from the inlet 11 to the outlet 13, thereby enabling smooth and continuous polymer production.

[0122] The collision medium 50, located within the internal space 35 of the microchamber 30, serves as an obstacle to the fluid flow within the microchamber 30. There are no particular limitations on the collision medium 50, as long as it is a structure capable of creating turbulence within the internal space 35 due to collisions with the fluid flowing inside the microchamber 30. According to one embodiment, the collision medium 50 has a length extending in a direction perpendicular to the fluid flow direction on a plane formed by the body 10, and curves rearward. However, the two ends of the collision medium 50 in the length direction do not contact the inner surface of the microchamber 30.

[0123] At this time, the internal space 35 may include branch portions 36 where the fluid colliding with the collision medium 50 flows in two directions along both ends of the collision medium 50, and a confluence portion 38 where the fluid flowing in the two directions along the collision medium 50 flows again in one direction. Thus, the internal space 35 and the collision medium 50 achieve uniform mixing through the first collision of the fluids via the collision medium 50. After passing through the branch portions 36, the fluids collide a second time in the confluence portion 38, inducing a more uniform mixing and reaction. This maximizes the formation of turbulence while maintaining a constant flow velocity, thereby more smoothly inducing excellent mixing and a uniform reaction of the fluids.

[0124] The diameter L1 of the flow path formed by the branch portion 36 in the internal space 35 and the diameter L2 of the flow path formed by the confluence portion 38 can satisfy the following formula 1.

[0125] [Formula 1] 1 < (L2 / L1) < 3 In Equation 1, L1 and L2 are measured along a virtual centerline that connects the front connecting portion of the microchannel 20 adjacent to the microchamber 30 to the front-side microchannel 20 and the rear connecting portion to the rear-side microchannel 20. Specifically, L2 / L1 can be 1.1 to 2.8, 1.2 to 2.5, or 1.5 to 2.3. Therefore, the fluid is delivered at a high flow rate from the branch portion 36 to the confluence portion 38, resulting in more uniform mixing.

[0126] The length of the collision medium 50 is as described above, and there is no particular limitation as long as it does not contact the inner surface of the microchamber 30. However, in one embodiment, the inner diameter R1 of the flow path formed by the microchannel 20 and the closest distance D1 between the two ends of the collision medium 50 in the longitudinal direction can satisfy the following equation 2.

[0127] [Equation 2] 3 <D1 / R1<15 Specifically, D1 / R1 can be 4 to 13, 5 to 12, or 6 to 10. Therefore, the fluid flowing from the microchannel 20 into the microchamber 30 collides more strongly with the collision medium 50, thereby inducing significantly better mixing and homogeneous reactions.

[0128] According to one embodiment, the flow path formed by the microchannel 20 can be connected between the inlet 11 and the outlet 13 in series, parallel, or series-parallel connection.

[0129] Figure 4A microflow reactor is illustrated, with the flow paths connected in series and parallel between the inlet 11 and the outlet 13. The microflow reactor is thus formed with the flow paths connected in series and parallel, and the microchambers 30 arranged in communication with the flow paths are interconnected in series and parallel. The microchannels 20 may include a series connection portion 20A connecting the flow paths in series and a parallel connection portion 20B connecting them in parallel. As shown, the microchambers located in the parallel connection portion 20B can be positioned parallel to each other. In this case, the parallel microchambers 30 can be interconnected through the parallel connection channel 23b. This allows the microflow reactor to react with a larger volume of fluid, thereby enabling larger-scale production.

[0130] According to one embodiment, the microflow reactors can be multiple and connected in series, parallel, or series-parallel, and each microflow reactor has the same or different internal capacity, so that each microflow reactor operates as a reactor module. Therefore, each microflow reactor can be controlled with different flow rates, residence times, and temperatures.

[0131] The present invention will now be described in detail through specific embodiments. However, these embodiments are merely examples and illustrations of the invention and are not intended to limit the scope of the invention. The scope of the invention is determined by the matters set forth in the claims and those reasonably deduced therefrom.

[0132] (Examples 1 to 17) pass Figure 5 The microflow reactor shown (module size: 162 × 188.5 × 21 mm) is used to produce polymers via anionic polymerization. The internal volume of the microflow reactor is adjusted by the number of connected microflow reactors, and the internal volume (capacity) of each embodiment is described in Table 1 below.

[0133] 4-tert-butoxystyrene, whose concentration is adjusted by solvent and oxygen is removed by argon bubbling, is injected into the first inlet as the first solution, and n-butyllithium (n-BuLi), whose concentration is adjusted by solvent and oxygen is removed by argon bubbling, is injected into the second inlet as the second solution. The concentrations of the first and second solutions and the solvents used in each embodiment are described in Table 1 below.

[0134] Subsequently, a polymerization terminator with a concentration of 1M (solvent: tetrahydrofuran (THF)) was injected into the first inlet. The polymerization terminators used in each embodiment are described in Table 1 below.

[0135] The first solution, the second solution, and the polymerization terminator were injected through a 1 / 8-inch tube. 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 R (the relationship between flow rate, flow path cross-sectional area, and flow path length) calculated from the following Equation 2 are recorded in Table 2.

[0136] [Relationship 2] R (cm² / min) = Log(Q in × (L 总 / A min )) In relation 1, Q in It is the inflow rate (mL / min) within the microflow reactor, that is, the sum of the flow rates of the first solution Q1 and the second solution Q2 (Q1 + Q2), A min It is the minimum cross-sectional area (cm²) of the flow path within the microflow reactor, that is, the cross-sectional area along the diameter of the connecting channel, L. 总 It is the total length of the flow path in cm, that is, the internal capacity (volume) of the microflow reactor divided by the cross-sectional area of ​​the connecting channel.

[0137] In addition, Table 3 lists the linear velocities of the first inflow and outflow channels, and also lists the Reynolds number Re of the first inflow channel calculated from the following mathematical formula. i Reynolds number Re of the discharge channel f and its ratio Re f / Re i .

[0138] [Mathematical expression] Re =

[0139] In the mathematical formula, ρ (kg / m³) represents the fluid density, V (m / s) represents the fluid linear velocity, D (m) represents the diameter of the microchannel, and μ ((Ns) / m²) represents the fluid viscosity. Here, the fluid viscosity is the value measured using an HBDV2T viscometer at 20°C, and the fluid density is the value calculated at 20°C. The diameter of the microchannels (the first inflow channel and the outlet channel) is uniformly calculated to be 25 mm.

[0140] During polymerization, the temperature of the flow path inside the microflow reactor is adjusted by a temperature control unit (TCU system) connected to the microflow reactor, and the total flow rate is measured in the discharge channel at the rear end of the microflow reactor.

[0141] Table 1

[0142] Table 2

[0143] Table 3

[0144] (Comparative Examples 1 and 2) In the described embodiment, the polymer was manufactured using the same method as in the embodiment, except that it was manufactured under the conditions described in Tables 4 and 5 below. The linear velocities in the first inflow channel and the discharge channel are shown in Table 6 below, and the Reynolds number (Re) in the first inflow channel was calculated from the mathematical formula. i ), the Reynolds number in the discharge channel (Re f ) and its ratio (Re f / Re i ) are also listed in Table 6 below.

[0145] (Comparative Examples 3 to 10) In the embodiments described, polymers were manufactured using the same method as in the embodiments, except that a PFA tube (1 / 8-inch inner diameter, Perfluoroalkoxy alkanes tube / Swagelok) was used instead of a microflow reactor. The total volume of the flow path within the PFA tube for each comparative example, the solvents and concentrations of the first and second solutions, and the polymerization terminator of the third solution are described in Table 4 below. The injection flow rates of the first solution, the second solution, and the polymerization terminator for each comparative example, as well as the temperature of the flow path within the microflow reactor, are described in Table 5 below. The Reynolds number Re in the first inflow channel was calculated from the mathematical formula. i Reynolds number Re in the discharge channel f and its ratio Re f / Re i Also listed in Table 6 below.

[0146] (Comparative Examples 11 to 12) In Comparative Examples 1 and 2, polymers were manufactured using the same method as in Comparative Examples 1 and 2, except that a PFA tube (1 / 8-inch inner diameter, perfluoroalkoxyalkane tube / Swagelok) was used instead of a microfluidic reactor.

[0147] Table 4

[0148] Table 5

[0149] Table 6

[0150] <Polymer Evaluation> 1) Conversion rate (%) The conversion rate of the manufactured polymer was calculated using the following formula 1 and is shown in Table 5 below.

[0151] [Calculation Formula 1] Conversion rate (%) = ((moles of 4-tert-butoxystyrene reacted) / (moles of 4-tert-butoxystyrene injected)) × 100 2) Molecular weight, polydispersity The number-average molecular weight (Mn) and polydispersity (PDI) of the polymers manufactured in the examples and comparative examples were measured using gel permeation chromatography (GPC) by Waters Corporation. Shodex KF-801, KF-802, KF-803, and KF-804 columns were used, and Shodex polystyrene was used as the standard sample. Tetrahydrofuran was used as the solvent, the temperature was 40°C, and the flow rate was 1.0 mL / min. The results are shown in Table 5 below.

[0152] 3) Whether side reactions occur As a monomer, p-alkoxystyrene, such as in the case of polymerization reactions involving p-methoxystyrene, exhibits very slow polymerization initiation and rapid termination (J. Polym. Sci. Part A-1 1969, 7, vol 7, pp2859-2873). The occurrence of termination can be easily confirmed by color changes in the polymerization solution. Rapid termination can produce polymers with broad PDI, and may even be accompanied by ring metallation crosslinking reactions, potentially resulting in insoluble precipitates.

[0153] To determine whether side reactions occurred in the polymer manufacturing methods of the Examples and Comparative Examples, the color change of the fluid inside the reactor was observed visually. If the reaction proceeded smoothly without side reactions, the fluid inside the reactor displayed its inherent color, close to red and orange. However, if side reactions occurred, the fluid lost its inherent color and became transparent. Based on this, the color of the fluid inside the reactor was observed to determine whether side reactions occurred, and the results are shown in Table 5 below. Side reactions were marked with "○", and no side reactions occurred with "×".

[0154] Table 7

[0155] Referring to Table 7, the polymers manufactured according to the examples have a PDI closer to 1 compared to the comparative examples, confirming the production of uniform polymers. Furthermore, it can be confirmed that the polymers manufactured from the examples have a lower molecular weight, with a number average molecular weight of approximately 5000, compared to the comparative examples. Moreover, it can be confirmed that the conversion rate in most examples was 100%, and no side reactions occurred.

Claims

1. A method for manufacturing a polymer, wherein, Includes the following steps: S1. The step of injecting a first solution comprising one or more solvents selected from the group consisting of ether solvents and non-polar solvents and a monomer, and a second solution comprising the solvent and an anionic polymerization initiator into a microflow reactor; as well as S2, the step of anionic polymerization of the monomer in the microflow reactor, and The microflow reactor includes: The body has at least one inlet and one outlet. Microchannels form a flow path within the body connecting the inlet and the outlet; Multiple microcavities are arranged along the extension direction of the microchannels, forming an internal space communicating with the flow path; and The collision medium, located within the internal space, collides with and transforms the flow of the fluid within the internal space through collisions. The microchannels include: An inflow channel connects the microchamber, located at the forefront of the fluid flow direction within the channel, to the inflow inlet; Connecting channels link adjacent microchambers; and A discharge channel connects the microchamber located at the rearmost end of the fluid flow direction within the channel to the discharge outlet. The Reynolds number Re in the inflow channel i The Reynolds number Re of the discharge channel is less than that of the discharge channel. f .

2. The method for manufacturing the polymer according to claim 1, wherein, The ratio of the Reynolds number Re i / Re f The values ​​range from 1.1 to 5.

3. The method for manufacturing the polymer according to claim 1, wherein, The inlet ports include a first inlet port for the first solution and a second inlet port for the second solution. The inflow channels include a first inflow channel and a second inflow channel extending from the first inlet and the second inlet to the microchannel located at the foremost end, respectively. Reynolds number Re i Let be the Reynolds number of the first inflow channel.

4. The method for manufacturing the polymer according to claim 1, wherein, The Reynolds number Re in the inflow channel i The range is 100 to 350.

5. The method for manufacturing the polymer according to claim 1, wherein, The concentration of the monomer in the first solution is 1 to 5 M, and the concentration of the anionic polymerization initiator in the second solution is 0.01 to 0.5 M.

6. The method for manufacturing the polymer according to claim 1, wherein, The anionic polymerization is carried out in a co-solvent environment of the ether solvent and the nonpolar solvent.

7. The method for manufacturing the polymer according to claim 6, wherein, The cosolvent has a Hansen solubility of 16 to 20 MPa½.

8. The method for manufacturing the polymer according to claim 1, wherein, The temperature of the flow path is -80 to 60°C.

9. The method for manufacturing the polymer according to claim 1, wherein, On a plane of the body in the direction of flow path extension, The internal space of the microchamber gradually widens from rear to front based on the fluid flow direction, and the front-side connection portion that connects to the front-side microchannel has an inward-facing shape. The inner surface of the internal space is curved.

10. The method for manufacturing the polymer according to claim 1, wherein, The collision medium has a length extending in a direction perpendicular to the flow direction of the fluid on a plane formed by the body, and bends backward. The internal space includes branch portions where the fluid colliding with the colliding medium flows in two directions along both ends of the length of the colliding medium, and confluence portions where the fluid flowing in the two directions along the colliding medium flows in one direction again.

11. The method for manufacturing the polymer according to claim 10, wherein, The diameter L1 of the flow path formed by the branch portion and the diameter L2 of the flow path formed by the confluence portion satisfy the following equation 1: [Formula 1] 1 < (L2 / L1) < 3 In Equation 1, L1 and L2 are measured along a virtual center line, which connects the front connecting portion of the microchannel adjacent to the microchamber to the front side microchannel and the rear connecting portion to the rear side microchannel.

12. The method for manufacturing the polymer according to claim 10, wherein, The inner diameter R1 of the flow path formed by the microchannel and the closest distance D1 between the two ends of the collision medium along its length direction satisfy the following equation 2: [Equation 2] 3 < D1 / R1 < 15.

13. The method for manufacturing the polymer according to claim 1, wherein, The inner diameter of the flow path on the rear end of at least one of the inflow channels and connecting channels gradually decreases.

14. The method for manufacturing the polymer according to claim 1, wherein, The linear velocity of the fluid is 0.1 to 1 m / s.

15. The method for manufacturing the polymer according to claim 1, wherein, The monomers include aromatic vinyl monomers.

16. The method for manufacturing the polymer according to claim 1, wherein, The nonpolar solvents include C5-C8 alkane solvents.

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