Method for manufacturing functional polymers by anionic polymerization

Abstract

The present invention relates to a method for manufacturing functional polymers by anionic polymerization. The polymer manufacturing method according to the present invention can economically produce polymers having high chemical uniformity.

Description

Method for producing functional polymers by anionic polymerization

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

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

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

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

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

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

[0007] However, conventional anionic polymerization reactions using microflow reactors still require the polymerization reaction to be performed at extremely low temperatures, requiring separate cooling equipment. However, the entire reactant is not uniformly cooled (heated) and side reactions easily occur, making it very difficult to produce a polymer with the target molecular weight. Furthermore, because the cooling equipment must be set to extremely low temperatures, its operation is very uneconomical and its maintenance is also difficult, making mass production practically difficult.

[0008] In addition, the anionic polymerization reaction using the conventional flow-type reaction system has the problem that the molecular weight distribution of the polymer produced is still large because the anionic polymerization initiator and monomer immediately react before they are sufficiently homogeneously mixed when injected into the reactor. Furthermore, the anionic polymerization reaction using the conventional flow-type reaction system cannot produce a proton polymer, and thus the development of a technology for mass production of a proton polymer using a single flow-type reaction system is further demanded.

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

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

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

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

[0013] According to one embodiment of the present invention, a 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 an aprotic monomer containing a protecting group, and a second solution containing the solvent and an anionic polymerization initiator into a first microflow reactor; (S2) injecting the aprotic monomer containing a protecting group into the first microflow reactor into which the first and second solutions are injected, thereby producing a third solution containing an aprotic polymer; (S3) injecting a fourth solution containing a deprotecting agent into a second microflow reactor connected to a rear end of the first microflow reactor into which the third solution is injected; And (S4) a step of performing a deprotection reaction of the aprotic polymer in the second microflow reactor into which the third solution and the fourth solution are injected to produce a fifth solution containing a protic polymer; wherein the microflow reactor comprises a main body having at least one inlet hole through which a fluid is introduced and an outlet hole through which a fluid is discharged; a microchannel forming a flow path connecting the inlet and the outlet within the main body; a plurality of microchambers arranged along an extension direction of the microchannel and forming an internal space communicated with the flow path; and a collision medium positioned within the internal space to collide with a fluid transported within the internal space and to convert a flow of the fluid within the internal space.

[0014] In a polymer production method according to one embodiment, the anionic polymerization can be performed in the presence of a co-solvent of an ether solvent and a non-polar solvent.

[0015] In a polymer manufacturing method according to one embodiment, the cosolvent may have a Hansen Solubility Parameter of 16 to 20.

[0016] In a polymer production method according to one embodiment, the anionic polymerization initiator may be an organic alkali metal.

[0017] In a polymer manufacturing method according to one embodiment, the first solution or the second solution may further include an organic metal having magnesium, aluminum or zinc as a metal species.

[0018] In a polymer manufacturing method according to one embodiment, after the step (S2) and before the step (S3), a step (S2.5) of introducing a polymerization terminator to terminate polymerization may be further included.

[0019] In a polymer manufacturing method according to one embodiment, the deprotecting agent may be at least one selected from the group consisting of hydrochloric acid (HCl), hydrobromic acid (HBr), sulfuric acid, nitric acid, trifluoroacetic acid (TFA), methanesulfonic acid (MsOH), p-toluenesulfonic acid (pTSA), and trimethylsilyl chloride (TMSCl).

[0020] In a polymer manufacturing method according to one embodiment, the quantum polymer may have a polydispersity index of 1.1 or less.

[0021] In a polymer manufacturing method according to one embodiment, the temperature of the flow path may be -80 to 60°C.

[0022] In a polymer manufacturing method according to one embodiment, on one plane of the main body in the direction in which the flow path extends, the internal space of the microchamber has a shape in which the width gradually increases from the rear to the front based on the flow direction of the fluid, and a front-side connecting portion connected to the front-side microchannel is retracted into the interior, and the inner surface of the internal space may be a curved surface.

[0023] In a polymer manufacturing method according to one embodiment, the collision medium has a length extending in a direction perpendicular to the flow direction of the fluid on one plane formed by the main body, but is curved backward, and the internal space may include a branch portion where the fluid collided by the collision medium flows in both directions along both longitudinal ends of the collision medium, and a confluence portion where the fluid flowing along both directions of the collision medium flows again in one direction.

[0024] In a polymer manufacturing method according to one embodiment, the diameter (L1) of the flow path formed by the branch portion and the diameter (L2) of the flow path formed by the joining portion can satisfy the following equation 1.

[0025] [Formula 1]

[0026] 1 < (L2 / L1) < 3

[0027] In the above equation 1, L1 and L2 is measured along an imaginary center line connecting the forward connection portion connected to the forward microchannel and the backward connection portion connected to the rear microchannel among the microchannels adjacent to the above microchamber.

[0028] In a polymer manufacturing method according to one embodiment, the inner diameter (R1) of the flow path formed by the microchannel and the shortest distance (D1) between the longitudinal ends of the collision medium can satisfy the following equation 2.

[0029] [Formula 2]

[0030] 3 < D1 / R1< 15

[0031] In a polymer manufacturing method according to one embodiment, the microchannel may include an inlet channel connecting the microchamber located at the most forward end in the direction of fluid flow in the channel and the inlet, a connection channel connecting the microchambers adjacent to each other, and an outlet channel connecting the microchamber located at the most rearward end in the direction of fluid flow in the channel and the outlet.

[0032] In a polymer manufacturing method according to one embodiment, at least one of the inlet channel and the connecting channel may have an inner diameter of a rear-end flow path that gradually decreases.

[0033] In a polymer manufacturing method according to one embodiment, the linear velocity of the fluid may be 0.1 to 1 m / s.

[0034] In a method for producing a polymer according to one embodiment, the protecting group-containing aprotic monomer may include a protecting group-containing aprotic aromatic vinyl monomer.

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

[0036] A method for producing a polymer according to one aspect of the present invention can economically produce a high-quality polymer having high chemical uniformity.

[0037] In addition, a method for producing a polymer according to one aspect of the present invention may have the advantage of not requiring low-temperature cooling since anionic polymerization reaction is possible even at relatively high temperatures.

[0038] 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.

[0039] Figure 1 is a perspective view illustrating a microflow reactor according to one embodiment of the present invention;

[0040] Figure 2 is a plan view of the microflow reactor shown in Figure 1;

[0041] Figure 3 is a plan view illustrating a microflow reactor according to another embodiment of the present invention;

[0042] Figure 4 is a plan view illustrating a microflow reactor according to another embodiment of the present invention;

[0043] FIG. 5 is a photograph illustrating a microflow reactor according to one embodiment of the present invention.

[0044] Unless otherwise defined, the technical and scientific terms used in this specification have the meaning commonly understood by a person of ordinary skill in the art to which this invention pertains, and descriptions of well-known functions and configurations that may unnecessarily obscure the gist of the present invention in the following description or accompanying drawings are omitted.

[0045] Embodiments of the present invention are provided to more fully explain the present invention to those of ordinary skill in the art. Therefore, the scope of the present invention is not limited to the embodiments described below.

[0046] The terminology used in the description of the present invention is intended solely to describe embodiments of the present invention and is in no way limiting. Unless expressly stated otherwise, singular forms include plural forms.

[0047] The term "includes" in this specification is an open-ended description equivalent to expressions such as "comprises," "contains," "has," or "characterizes," and does not exclude additional elements, materials, or processes not listed.

[0048] Unless otherwise specified, units used herein are based on weight, and as an example, units of % or ratio mean weight% or weight ratio, and weight% means the weight % that any one component of the entire composition occupies in the composition, unless otherwise defined.

[0049] Additionally, the numerical ranges used herein include lower and upper limits and all values ​​within that range, increments logically derived from the shape and width of the defined range, all doubly defined values, and all possible combinations of upper and lower limits of numerical ranges defined in different shapes. Unless otherwise specified herein, values ​​outside the defined numerical range that may arise due to experimental error or rounding of values ​​are also included in the defined numerical range.

[0050] In this specification, terms such as 'top', 'upper part', 'top surface', 'bottom', 'lower part', 'bottom', 'side', etc. are based on the drawings, and in reality, they may vary depending on the direction in which the elements or components are arranged.

[0051] 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.

[0052] In this specification, 'polymer' may mean a high molecular weight compound formed by polymerizing monomers and having a weight average molecular weight of 1,000 or more, and includes not only a homopolymer manufactured by polymerizing one monomer but also a copolymer manufactured by polymerizing two or more monomers.

[0053] In this specification, "fluid" refers to a material having fluidic properties capable of flowing, and refers to all materials flowing within the microflow reactor (collectively referred to as the first and second microflow reactors). Specifically, the fluid may refer to each of the first to fifth solutions, or a mixture of two or more different types of the first to fifth solutions.

[0054] As a specific example, with respect to the first microflow reactor, the fluid before the first solution and the second solution are mixed together at the front side of the first microflow reactor adjacent to the inlet may refer to the first solution or the second solution, respectively, and the fluid after the first solution and the second solution are mixed within the first microflow reactor may refer to a mixture of the first solution and the second solution and a third solution which is a reactant thereof. In addition, the fluid at the rear side of the first microflow reactor adjacent to the outlet may refer to the third solution.

[0055] In addition, with respect to the second microflow reactor, the fluid before the third solution and the fourth solution are mixed at the front side of the second microflow reactor adjacent to the inlet may refer to the third solution or the fourth solution, respectively, and the fluid after the third solution and the fourth solution are mixed within the second microflow reactor may refer to a mixture of the third solution and the fourth solution and a fifth solution which is a reactant thereof. In addition, the fluid at the rear side of the second microflow reactor adjacent to the outlet may refer to the fifth solution.

[0056] In this specification, the third solution may refer to a mixture of the first solution and the second solution and their reactants, and the fifth solution may refer to a mixture of the third solution and the fourth solution and their reactants. Specifically, the third solution and the fifth solution may include a solvent, a product resulting from a polymerization reaction or a deprotection reaction (protic or aprotic polymer), unreacted products, intermediate products, and side products.

[0057] Although the present invention is described in detail through each embodiment according to the present invention, each embodiment described in the specification should be considered not only to mean a single embodiment but also to mean a combination with other embodiments. Therefore, the citation of a claim in the patent claims is merely an example, and the technical concept of the present invention should not be interpreted solely as a combination with the cited claim, and combinations with various claims also fall within the scope of the technical concept of the present invention.

[0058] Conventional anionic polymerization reactions using flow-through reaction systems require extremely low temperatures, resulting in extremely high energy consumption for cooling equipment, making them extremely uneconomical. Furthermore, when the anionic polymerization initiator and monomer are injected into the reactor, the reaction between the anionic polymerization initiator and the monomer begins immediately before they are fully and homogeneously mixed, resulting in a high molecular weight distribution of the resulting polymer. In particular, conventional flow-through anionic polymerization reactions have the disadvantage of making it impossible to produce proton-sensitive polymers.

[0059] According to one embodiment of the present invention, a method for producing a polymer comprises: (S1) a step of injecting a first solution containing at least one solvent selected from the group consisting of ether solvents and non-polar solvents and an aprotic monomer containing a protecting group, and a second solution containing the solvent and an anionic polymerization initiator into a first microflow reactor; (S2) a step of anionic polymerizing the aprotic monomer containing a protecting group in the first microflow reactor into which the first and second solutions are injected to produce a third solution containing an aprotic polymer; (S3) a step of injecting a fourth solution containing a deprotecting agent into a second microflow reactor connected to the rear end of the first microflow reactor and into which the third solution is injected; and (S4) a step of performing a deprotection reaction of the aprotic polymer in the second microflow reactor into which the third and fourth solutions are injected to produce a fifth solution containing a protic polymer.

[0060] The microflow reactor comprises a main body having at least one inlet hole and an outlet hole through which a fluid is discharged; a microchannel forming a flow path connecting the inlet hole and the outlet hole within the main body; a plurality of microchambers arranged along an extension direction of the microchannel and forming an internal space communicated with the flow path; and a collision medium positioned within the internal space to collide with a fluid transported within the internal space and to change the flow of the fluid within the internal space.

[0061] The above polymer manufacturing method can be broadly divided into a polymerization step (steps (S1) and (S2)) for manufacturing an aprotic polymer containing a protecting group, and a deprotection step (steps (S3) and (S4)) for performing a deprotection reaction of the manufactured aprotic polymer to manufacture a protic polymer. This polymer manufacturing method can continuously produce high-quality protic polymers having homogeneous chemical uniformity despite including a polymerization step and a deprotection step by manufacturing through the microflow reactor.

[0062] Specifically, in the polymer manufacturing method, the fluids in the microflow reactor (collectively referred to as the first and second microflow reactors) collide with the collision medium, forming turbulence in the flow of the fluids, so that the fluids can be homogeneously mixed. In addition, the reaction conditions (e.g., the temperature and internal capacity of the flow path) of the microflow reactors in which each step is performed can be controlled differently. Accordingly, the polymerization step and the deprotection step can be homogeneously performed under optimal conditions for each microflow reactor. Accordingly, the polymer manufacturing method not only enables the continuous performance of the polymerization step and the deprotection step having different reaction conditions, but also enables the production of a proton polymer having a target molecular weight despite the continuous performance of the polymerization step and the deprotection step. Furthermore, the molecular weight distribution of the produced proton polymer can be improved. Specifically, the polydispersity index of the proton polymer produced through the polymer manufacturing method can be 1.1 or less, or 1.0 to 1.1, or 1.0 to 1.08.

[0063] In addition, this polymer manufacturing method is easier to manufacture and can have better productivity because, unlike batch manufacturing, it does not require a step of dissolving the aprotic polymer manufactured in the polymerization step by adding an organic solvent after the polymerization step.

[0064] The first and second microflow reactors may each be provided as a single unit, but alternatively, they may each be connected in multiple units. Specifically, in a reactor in which three or more microflow reactors are connected, the microflow reactor in which the polymerization step is performed may be referred to as the first microflow reactor, and the microflow reactor in which the deprotection step is performed may be referred to as the second microflow reactor.

[0065] The first and second microflow reactors may have the same or different internal capacities. The internal capacities of each microflow reactor can be appropriately adjusted depending on the type of aprotic monomer produced in the polymerization step and the type of protic polymer produced in the deprotection step. In other words, the residence time of the fluid can be appropriately controlled by adjusting the internal capacities of each of the first and second microflow reactors depending on the anionic polymerization rate of the aprotic monomer and the deprotection reaction rate of the aprotic polymer.

[0066] According to one embodiment, the polymer manufacturing method changes the linear velocity of the fluid at each location as the diameter of the flow path is repeatedly changed by the microchannels and microchambers. Accordingly, the linear velocity of the fluid within the microflow reactor may differ at each location within the microflow reactor even when the fluid is injected at the same flow rate. Specifically, the linear velocity is fastest in the connecting channel having the smallest flow path cross-sectional area, and the linear velocity is slowest in the microchamber having the largest flow path cross-sectional area.

[0067] In one embodiment, the linear velocity (flow rate) of the fluid within the microflow reactor can be appropriately controlled depending on the type and properties of the desired aprotic or protic polymer. Specifically, the linear velocity of the fluid may be 0.1 to 1.5 m / s, 0.1 to 1 m / s, 0.1 to 0.9 m / s, 0.2 to 0.8 m / s, or, non-limitingly, 0.2 to 0.7 m / s. When the linear velocity of the fluid satisfies the above range, turbulence due to collision with the collision medium within the first and second microflow reactors can be smoothly formed, while the formation of a dead zone in which the fluid does not flow or the flow rate rapidly decreases can be prevented. Accordingly, the fluid is homogeneously mixed throughout the entire flow path area within the microflow reactor, enabling the production of a higher quality polymer.

[0068] The linear velocity of the fluid may be measured in a microchannel within a microflow reactor and may be an average value calculated after measuring at least once. The linear velocity of the fluid may be measured in any one of a microchannel connecting an inlet and an adjacent microchamber (an inlet channel described below), a microchannel connecting an outlet and an adjacent microchamber (an outlet channel described below), and a microchannel connecting adjacent microchambers (a connecting channel described below). Specifically, the linear velocity may be measured in the inlet channel or the microchannel.

[0069] The internal capacity (volume) of the above microflow reactor refers to the amount of solution that the microflow reactor can accommodate, and may refer to the volume formed by the flow path and internal space formed by the microchannel and microchamber within the microflow reactor. The internal capacity of the microflow reactor is not particularly limited, and the flow rates of the first and second solutions injected in step (S1) or the flow rates of the third and fourth solutions injected in step (S3) can be adjusted in proportion to the internal capacity of the microflow reactor.

[0070] The internal capacity of the above microflow reactor can be adjusted according to the diameter and length of the flow path within the microflow reactor and the size of the internal space of the microchamber, or can be adjusted according to the number of interconnected microflow reactors. Specifically, the internal capacity of the microflow reactor can increase 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 interconnected microflow reactors.

[0071] The above step (S1) is a step of injecting the first solution and the second solution into the first microflow reactor. Depending on the type and properties of the desired aprotic polymer, the type and flow rate of the first solution and the second solution can be adjusted through step (S1) and injected into the first microflow reactor. As a specific example, regardless of the internal capacity of the microflow reactor, the flow rates (flow rates) of the first solution and the second solution can be adjusted so that the fluid within the microflow reactor can maintain the linear velocity. The size of the external injection path connected to the first microflow reactor can be appropriately adjusted according to the internal capacity of the first microflow reactor.

[0072] 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 such that the internal volume of the microflow reactor is 60 to 100 mL in total, the step (S1) may inject the first solution containing the protecting group-containing aprotic monomer 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 may be injected at a flow rate of 20 to 80 mL / min, 30 to 70 mL / min, or 40 to 60 mL / min, but is not limited thereto.

[0073] As another example, when the diameter of the external injection path connecting the microflow reactor and the storage tank in which the first solution is stored is 1 to 1 / 3 inch, and a plurality of microflow reactors are connected so that the internal capacity of the microflow reactor is 2000 to 2200 mL in total, in the step (S1), the first solution including the monomer can be injected at a flow rate of 2800 to 6000 mL / min, 3200 to 5200 mL / min, or 3600 to 4000 mL / min, and the second solution including the anionic polymerization initiator can be injected at a flow rate of 800 to 3200 mL / min, 1200 to 2800 mL / min, or 1600 to 2400 mL / min, but is not limited thereto.

[0074] In other words, regardless of the internal capacity of the microflow reactor, the flow rates of the first solution and the second solution can be controlled so that the residence time of the fluid is 5 seconds or more, 10 seconds or more, 15 seconds or more, or 20 seconds or more. In a non-limiting example, the flow rates of the first solution and the second solution can be controlled so that the residence time of the fluid is 60 seconds or less. Specifically, the flow rates, i.e., the flow rates of the first solution and the second solution, can be controlled so that the flow rates are 5 to 60 seconds, 10 to 55 seconds, or 15 to 50 seconds. In the above range, it may be possible to produce a more homogeneous aprotic polymer.

[0075] The first solution comprises at least one solvent selected from the group consisting of ethereal solvents and non-polar solvents as described above, and an aprotic monomer containing a protecting group. Specifically, the first solution may comprise an ethereal solvent containing an aprotic monomer containing a protecting group, or a non-polar solvent containing the aprotic monomer containing a protecting group. Alternatively, the first solution may comprise a co-solvent of an ethereal solvent and a non-polar solvent containing the aprotic monomer containing a protecting group.

[0076] In the step (S1), the concentration of the protecting group-containing aprotic monomer in the first solution can be appropriately adjusted depending on the type of the protecting group-containing aprotic 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 a concentration within the above range has an appropriate viscosity for fluid transport, and can be smoothly injected into the first microflow reactor in the step (S1).

[0077] 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.

[0078] The non-polar solvent may be specifically a non-polar hydrocarbon solvent. More specifically, the non-polar solvent may be an aromatic hydrocarbon solvent or an aliphatic hydrocarbon solvent, and even more specifically, the aliphatic hydrocarbon solvent may be a C5-C8 alkane solvent. As a non-limiting example, the non-polar solvent may be at least one selected from the group consisting of benzene, toluene, butane, pentane, neopentane, hexane, cyclohexane, methyl cyclohexane, heptane, and octane. As a specific example, the non-polar solvent may be a mixed solvent of hexane and heptane.

[0079] The above-mentioned protecting group-containing aprotic monomer may include a protecting group-containing aprotic aromatic vinyl monomer. The above-mentioned protecting group-containing aprotic aromatic vinyl monomer may be any one or a combination of two or more selected from the group consisting of alkoxystyrene monomers, alkoxyalkyloxystyrene monomers, alkanoyloxystyrene monomers, alkoxycarbonyloxystyrene monomers, alkoxycarbonylalkyloxystyrene monomers, and alkylsilyloxystyrene monomers. As a specific example, the above-mentioned protecting group-containing aprotic aromatic vinyl monomer is p-methoxystyrene, m-methoxystyrene, p-ethoxystyrene, m-ethoxystyrene, p-propoxystyrene, m-propoxystyrene, p-isopropoxystyrene, m-isopropoxystyrene, pn-butoxystyrene, mn-butoxystyrene, p-isobutoxystyrene, m-isobutoxystyrene, p-tert-butoxystyrene, mtert-butoxystyrene, p-methoxymethoxystyrene, m-methoxymethoxystyrene, p-(1-ethoxyethoxy)styrene, m-(1-ethoxyethoxy)styrene, p-(2-ethoxyethoxy)styrene, m-(2-ethoxyethoxy)styrene p-(2-tetrahydropyranyl)oxystyrene, Examples thereof include m-(2-tetrahydropyranyl)oxystyrene, p-acetoxystyrene, m-acetoxystyrene, ptert-butylcarbonyloxystyrene, m-tert-butylcarbonyloxystyrene, p-methoxycarbonyloxystyrene, m-methoxycarbonyloxystyrene, p-tert-butoxycarbonyloxystyrene, m-tert-butoxycarbonyloxystyrene, p-tert-butoxycarbonylmethyloxystyrene, m-tert-butoxycarbonyloxymethylstyrene, p-trimethylsilyloxystyrene, m-trimethylsilyloxystyrene, p-tert-butyldimethylsilyloxystyrene, m-tert-butyldimethylsilyloxystyrene, etc.More specifically, the protecting group-containing aprotic monomer may be any one or a combination of two or more selected from the group consisting of p-tert-butoxystyrene, m-tert-butoxystyrene, p-methoxymethoxystyrene, m-methoxymethoxystyrene, p-(1-ethoxyethoxy)styrene, m-(1-ethoxyethoxy)styrene, p-(2-ethoxyethoxy)styrene, m-(2-ethoxyethoxy)styrene p-(2-tetrahydropyranyl)oxystyrene, and m-(2-tetrahydropyranyl)oxystyrene.

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

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

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

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

[0084] In one embodiment, the first solution or the second solution may further include an organometallic having magnesium, aluminum or zinc as a metal species. Specifically, the organometallic may be di-n-butylmagnesium, di-t-butylmagnesium, di-sec-butylmagnesium, n-butyl-sec-butylmagnesium, n-butyl-ethylmagnesium, di-n-amylmagnesium, dibenzylmagnesium, diphenylmagnesium, diethylzinc, di-n-butylzinc, trimethylaluminum, triethylaluminum, triisobutylaluminum or tri-n-hexylaluminum. Specifically, the organometallic may be one or a combination of two or more selected from the group consisting of di-n-butylmagnesium, di-t-butylmagnesium and di-sec-butylmagnesium.

[0085] In an exemplary embodiment, the molar ratio of the anionic polymerization initiator: organometallic may be, but is not limited to, 1:8 to 20, specifically 1:8 to 20, and more specifically 1:8 to 20. However, when the molar ratio is satisfied, an anionic polymer having a narrower molecular weight distribution and a number average molecular weight of 10,000 g / mol or less can be produced.

[0086] According to one embodiment, the first solution and the second solution may be free of dissolved oxygen. Removal of dissolved oxygen may be accomplished by injecting nitrogen or argon gas into the storage tank in which the solutions are stored. The first and second solutions, from which dissolved oxygen has been removed, may have the effect of suppressing side reactions caused by cavitation resulting from fluid collisions during an anionic polymerization reaction in a microflow reactor.

[0087] The above step (S2) is a step in which the first solution and the second solution injected into the first microflow reactor through step S1) are mixed and reacted to produce a third solution including an aprotic polymer. That is, step (S2) is a step in which the aprotic monomer containing the protecting group undergoes anionic polymerization reaction by an anionic polymerization initiator to produce an aprotic polymer. In step (S2), the fluids in the first microflow reactor collide with a collision medium, and turbulence is formed in the flow of the fluids, so that the fluids can be homogeneously mixed. Due to this, the aprotic polymer produced in the first microflow reactor can have high chemical uniformity. Specifically, the molecular weight distribution (polydispersity) of the aprotic polymer produced from the first microflow reactor can have a polydispersity index of 1.1 or less, or 1.0 to 1.1, or 1.0 to 1.08.

[0088] The above-described aprotic polymer may be a homopolymer or copolymer containing repeating units derived from the above-described styrene monomer. In addition, the above-described protected anionic polymer may be a homopolymer containing one type of repeating unit.

[0089] The aprotic polymer may not contain repeating units containing phenol groups (or phenolic hydroxyl groups). Furthermore, the aprotic polymer may refer to a polymer that does not contain repeating units containing phenolic hydroxyl groups and only contains repeating units derived from styrenic monomers in which all phenolic hydroxyl groups are protected by protecting groups.

[0090] In one embodiment, the anionic polymerization in step (S2) can be carried out in the presence of a cosolvent of an ether solvent and a non-polar solvent. This polymer production method, since the anionic polymerization is carried out in the presence of the cosolvent within the first microflow reactor, enables anionic polymerization even at relatively high temperatures and economically produces a high-quality polymer with high chemical uniformity.

[0091] Specifically, as the fluids, i.e., the first solution and the second solution, are injected and transported through the channels in the first microflow reactor, the protecting group-containing aprotic monomer and the anionic polymerization initiator mix and react under a cosolvent. At this time, the fluids collide with the collision medium, and turbulence is formed in the flow of the fluids, allowing the fluids to be homogeneously mixed. As a result, the polymer production method enables anionic polymerization even at relatively high temperatures, as the fluids are homogeneously mixed under the cosolvent.

[0092] According to one embodiment, the anionic polymerization reaction may be possible when the temperature of the flow path in the first microflow reactor is -70 to 60°C, -50 to 60°C, -40 to 60°C, -30 to 50°C, -20 to 50°C, -10 to 50°C, 0 to 40°C, or 20 to 40°C. Accordingly, the polymer production method does not require an ultra-low temperature cooling facility requiring excessive power consumption, and thus can produce a high-quality polymer with higher economic efficiency.

[0093] According to one embodiment, the cosolvent of the ether solvent and the non-polar solvent may have a Hansen Solubility Parameter of 16 to 20, 17 to 19, 18 to 19, or 18.1 to 18.7. Such a cosolvent can achieve more uniform mixing of the fluid and increase the anionic polymerization reaction temperature. In addition, even after the anionic polymerization reaction, the flow rate of the fluid can be satisfied within the above range, thereby enabling the production of a polymer with a further improved molecular weight distribution.

[0094] The above Hansen solubility (S co ) can be calculated using the following formula.

[0095] [Calculation formula]

[0096] S co( MPa ½ ) = (S1×W1)+(S2×W2)

[0097] In the above formula, S1 is the Hansen solubility of the ether solvent, W1 is the weight% of the ether solvent in the cosolvent, S2 is the Hansen solubility of the nonpolar solvent, and W1 is the weight% of the nonpolar solvent in the cosolvent.

[0098] At this time, the Hansen solubility of each solvent is a known Hansen solubility parameter (based on 25°C, for example, a value known through Charles Hansen, "Hansen Solubility Parameters: A User's Handbook" CRC Press (2007)).

[0099] According to one aspect of the present invention, the properties of the aprotic polymer can be controlled through one or a combination of two or more of the following means.

[0100] (1) Control of the residence time of aprotic monomer containing a protecting group and anionic polymerization initiator

[0101] (2) Control of the flow rate of fluid in the microflow reactor

[0102] (3) Number of microchambers and connection structure

[0103] (4) Temperature of the microchamber

[0104] An increase in flow rate is closely related to residence time, and either flow rate or residence time can be adjusted to ensure the necessary reaction time to achieve the target conversion rate. Meanwhile, if reaction time is sufficient, a higher flow rate can be desirable because it enhances the mixing effect.

[0105] Additionally, the shape and length of the entire path through which the fluid moves within the microflow reactor can be controlled by the number of microchambers within the microflow reactor and their connection structure, which may be related to the residence time. The number of microchambers may be 10 to 50, 15 to 40, or 20 to 30, and the microchambers may be connected in series, in parallel, or in series-parallel. As the flow rate increases, the number of microchambers can be increased.

[0106] The temperature within the microchamber can be appropriately controlled by circulating a known cooling medium. The cooling medium can be cooled through a cooler, and the cooled cooling medium contacts the outer wall of the microchamber to control the temperature of the fluid flowing along the inner wall of the microchamber, and can remove heat generated by the exothermic reaction. The temperature within the microchamber can be controlled to -80 to 60°C, -50 to 60°C, -40 to 60°C, -30 to 50°C, -20 to 50°C, -10 to 50°C, 0 to 40°C, or 20 to 40°C.

[0107] Step (S3) is a step of injecting a fourth solution containing a deprotecting agent into a second microflow reactor, which is connected to the rear end of the first microflow reactor and into which the third solution is injected. That is, it is a step of injecting the third solution and the fourth solution into the second microflow reactor. Through step (S3), the flow rates (velocities) of the third solution and the fourth solution can be adjusted according to the type and properties of the desired quantum polymer and injected into the second microflow reactor.

[0108] As a specific example, regardless of the internal capacity of the microflow reactor, the flow rates (flow rates) of the third and fourth solutions can be adjusted so that the fluid within the microflow reactor can maintain the linear velocity. The size of the injection path connected to the second microflow reactor can be appropriately adjusted according to the internal capacity of the second microflow reactor.

[0109] As a non-limiting example, the flow rates, i.e., the flow rates of the third solution and the fourth solution, can be adjusted so that the residence time of the fluid within the microflow reactor is 10 to 300 seconds, 20 to 200 seconds, or 30 to 100 seconds, regardless of the internal capacity of the microflow reactor, but the present invention is not limited thereto.

[0110] The fourth solution above contains a deprotecting agent as described above, and the deprotecting agent may be one or more acid catalysts selected from the group consisting of hydrochloric acid (HCl), hydrobromic acid (HBr), sulfuric acid, nitric acid, trifluoroacetic acid (TFA), methanesulfonic acid (MsOH), p-toluenesulfonic acid (pTSA), and trimethylsilyl chloride (TMSCl). The deprotecting agent can deprotect the terminal of the aprotic anionic polymer.

[0111] In the above step (S3), the concentration of the deprotecting agent of the fourth solution can be appropriately adjusted depending on the concentration of the third solution. In non-limiting examples, the concentration of the fourth solution can be 1 to 60 w%, 5 to 50 w%, 10 to 40 w%, or 20 to 40 w%, but is not limited thereto.

[0112] The fourth solution may further include the solvent for smooth injection into the second microflow reactor and miscibility with the third solution. As a non-limiting example, the solvent included in the fourth solution may be an ether solvent or a non-polar solvent.

[0113] According to one embodiment, the fourth solution may be one from which dissolved oxygen has been removed. The removal of dissolved oxygen is as described above.

[0114] Step (S4) is a step in which the third solution and the fourth solution injected into the second microflow reactor through step (S3) are mixed and reacted to produce a fifth solution containing a proton polymer. That is, this is a step in which the aproton polymer undergoes a deprotection reaction by a deprotection agent to produce a proton polymer. Step (S4) is a step in which the fluids in the second microflow reactor collide with a collision medium, and turbulence is formed in the flow of the fluids, so that the fluids can be homogeneously mixed and the deprotection reaction can occur. Specifically, the molecular weight distribution (polydispersity) of the proton polymer produced from the second microflow reactor may have a polydispersity index of 1.1 or less, or 1.0 to 1.1, or 1.0 to 1.08.

[0115] The above-mentioned quantum polymer is a terminal of the above-mentioned aprotic polymer deprotected, and the above-mentioned quantum polymer may be a terminal of the above-mentioned aprotic polymer deprotected and converted with a conversion rate of 90% or more, preferably 99% or more, and more preferably 99.9% or more.

[0116] In the above step (4), the temperature of the flow path within the second microflow reactor is not particularly limited as long as the deprotection reaction can be smoothly performed. In non-limiting terms, the deprotection reaction may be possible when the temperature of the flow path within the second microflow reactor is 0 to 80°C, 10 to 70°C, 20 to 70°C, 30 to 70°C, or 40 to 70°C.

[0117] According to one embodiment, after the step (S2) and before the step (S3), the method may further include a step (S2.5) of introducing a polymerization terminator to terminate polymerization. The polymerization terminator may include, but is not limited to, a proton-donating compound such as methanol, a halide such as methyl iodide, or other electrophilic substances. The anionic polymerization reaction may be terminated through the step (S2.5). The introduction of the polymerization terminator in the step (S2,5) is not particularly limited as long as it can be injected into the third solution before being mixed with the fourth solution. As a non-limiting example, the polymerization terminator may be injected into a first microflow reactor located at a relatively rear end among the plurality of first microflow reactors. Alternatively, at least two or more microflow reactors may be additionally connected separately between the first microflow reactor and the second microflow reactor so that the polymerization termination reaction by the polymerization terminator may be further performed.

[0118] The above microfluidic reactor refers to a device used to obtain a product through chemical reaction synthesis of one or more fluids passing through microchannels measuring micrometers or larger. Specifically, according to one embodiment of the present invention, the effects aimed at by the present invention can be achieved by using the microfluidic reactor.

[0119] 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.

[0120] Figures 1 and 2 illustrate a microflow reactor according to one embodiment of the present invention. For convenience of explanation, the drawings depict the microflow reactor with an open top; however, in practice, the microflow reactor may have a closed top (upper surface).

[0121] Referring to FIGS. 1 and 2, a microflow reactor according to the present invention includes a main body (10) having an inlet hole (11) and an outlet hole (13), a microchannel (20), a microchamber (30), and an impact medium (50).

[0122] The above main body (10) is a medium in which the microchannel (20), microchamber (30), and collision medium (50) are formed, and provides a flow path through which the first to third solutions move and a reaction space in which anionic polymerization reaction occurs. The above main body (10) may be composed of a material that is easy to mold and has high corrosion resistance, non-flammability, and chemical durability. Specifically, the above main body (10) may be formed of metal, ceramic, plastic, or a composite material thereof.

[0123] As shown in the drawing, the main body (10) may be a plate-shaped structure forming a single plane, and the main body (10) may be formed by extending a flow path by a microchannel (20) to be described later along the plane direction of the plate-shaped structure inside. The main body (10) is formed with at least one inlet (11) through which a first solution and a second solution can be injected inside, and an outlet (13) through which a third solution can be discharged to the outside.

[0124] The above inlet (11) may include a first inlet (11a) and a second inlet (11b) through which the first solution and the second solution can be injected, respectively, as shown in the drawing, but is not limited thereto and may be provided as a single inlet or may be provided in three or more inlets. That is, the above inlet (11) may be appropriately adjusted according to the type and number of solutions required for the production of the polymer to be produced.

[0125] The inlet (11) and outlet (13) of the above main body (10) are connected to a flow control system so that the flow rate and flow speed can be appropriately controlled.

[0126] Unlike what is shown in the drawing, the main body (10) may have a separate plate member (not shown) attached to the upper surface to close the passage to the upper part of the main body (10).

[0127] The above inlet (11) and outlet (13) may be formed at a position adjacent to the edge of the main body (10) provided as a planar structure as shown in the drawing, but of course, they may be formed at the center of the main body (10) or an adjacent portion thereof.

[0128] The above microchannel (20) forms a flow path within the main body (10), and forms a flow path connecting an inlet hole (11) and an outlet hole (13) on one plane formed by the main body (10). The shape of the flow path formed by the microchannel (20) is not particularly limited. For example, as illustrated in the drawing, the microchannel (20) may form a meandering flow path on one plane formed by the main body (10). Such a microchannel (20) can integrate a flow path into the main body (10), thereby making the reaction system more compact.

[0129] The microchannel (20) according to one aspect of the present invention may include an inlet channel (21) connecting the microchamber (30) located at the most forward end in the direction of fluid flow in the flow path and the inlet (11), a connection channel (23) connecting adjacent microchambers (30), and an outlet channel (25) connecting the microchamber (30) located at the most rear end in the direction of fluid flow in the flow path and the outlet (13).

[0130] At this time, the direction of fluid flow refers to the macroscopic flow of fluid from the inlet (11) to the outlet (13). The microscopic flow of fluid converted by the collision medium (50), i.e., the turbulent flow, is ignored. Based on the direction of fluid flow, the inlet (11) side of the microflow reactor can be divided into the front (or front end) and the outlet (13) side can be divided into the rear (or rear end).

[0131] However, as the microchannel (20) forms a meandering path on the main body (10), when assuming that one microchamber (30) and the microchambers (30) connected to it in a straight line are a microchamber array, the adjacent microchamber arrays may appear to have fluids moving in opposite directions.

[0132] As the number of inlets (11) is provided, the number of inlet channels (21) can be provided correspondingly. For example, as shown in the drawing, when the main body (10) includes a first inlet (11) and a second inlet (11), the inlet channel (21) can include a first inlet channel (21a) extending from the first inlet (11) and a second inlet channel (21b) extending from the second inlet (11). At this time, the first and second inlet channels (21a) (21b) can be connected to each other at the front end of the microchamber (30) located at the frontmost end.

[0133] The connecting channel (23) forms a path connecting the microchambers (30), and may include a main connecting channel (23) connecting adjacent microchamber arrays, and a sub-connecting channel (23a) connecting each microchamber (30) within the microchamber array. As illustrated in FIGS. 1 and 2, the main connecting channel (23) and the sub-connecting channel (23a) may be provided simultaneously, but alternatively, as illustrated in FIG. 3, each microchamber (30) may be directly connected without the sub-connecting channel (23a).

[0134] The discharge channel (25) forms a path connecting the microchamber (30) located at the rear end and the discharge port (13), so that the fluid passing through the microchambers (30) can be discharged to the outside of the main body (10) through the discharge port (13).

[0135] In the microchannel (20) according to one aspect of the present invention, at least one of the inlet channel (21) and the connecting channel (23) may have an inner diameter of a flow path at the rear end that gradually decreases. That is, the rear end of the inlet channel (21) or the connecting channel (23) may have a tapered shape in which the width of the flow path gradually decreases. The fluid can be transported at an increased flow rate to the microchamber (30) connected to the inlet channel (21) or the connecting channel (23). Accordingly, the fluid can be supplied to the adjacent microchamber (30) at a high flow rate to continuously induce remarkably excellent mixing and a homogeneous reaction.

[0136] The above microchambers (30) are arranged in multiple numbers along the flow path, forming an internal space (35) that is connected to the flow path formed by the microchannels (20). The internal space (35) can be a transport path through which the fluid is transported, and at the same time, a mixing space through which the fluid can be sufficiently mixed by the collision medium (50).

[0137] According to one aspect of the present invention, the internal space (35) of the microchamber (30) may have a shape in which the width gradually increases from the rear to the front based on the flow direction of the fluid on one plane of the main body (10) in the direction in which the flow path extends, and the front-side connecting portion connected to the front-side microchannel (20) is retracted into the interior. At this time, the inner surface of the internal space (35) may be a curved surface. In other words, the inner space (35) of the microchamber (30) may have a circular shape that is distorted in one direction, i.e., a heart shape, as illustrated in the drawing. The internal space (35) of the microchamber (30) as described above allows the fluid to flow smoothly along the inner surface of the internal space (35) even if the fluid collides with the collision medium (50) and the flow changes. That is, although turbulence of the fluid is generated within the internal space (35) by the collision medium (50), the flow of the fluid from the inlet (11) to the outlet (13) is not obstructed, so that continuous production of the polymer is possible smoothly.

[0138] The above collision medium (50) is located in the internal space (35) of the microchamber (30) and is an obstacle to the fluid flow within the microchamber (30). The collision medium (50) is not particularly limited as long as it has a structure that can form turbulence within the internal space (35) by colliding the fluid flowing within the microchamber (30). According to one embodiment, the collision medium (50) has a length extending in a direction perpendicular to the flow direction of the fluid on one plane formed by the main body (10), and is curved backward. However, both longitudinal ends of the collision medium (50) do not come into contact with the inner surface of the microchamber (30).

[0139] At this time, the internal space (35) may include a branch portion (36) in which the fluid collided by the collision medium (50) flows in both directions along the longitudinal ends of the collision medium (50), and a confluence portion (38) in which the fluid flowing along both directions of the collision medium (50) flows again in one direction. In such an internal space (35) and collision medium (50), the fluid collides for the first time by the collision medium (50) and is homogeneously mixed, and after the fluid collided for the first time passes through the branch portion (36), the fluids collide a second time while facing each other at the confluence portion (38), thereby inducing more uniform mixing and reaction. Accordingly, the formation of turbulence in the fluid can be maximized, while the flow velocity of the fluid can be maintained constant, thereby inducing excellent mixing and homogeneous reaction of the fluid more smoothly.

[0140] The above internal space (35) can satisfy the following equation 1 in terms of the diameter (L1) of the flow path formed by the branch portion (36) and the diameter (L2) of the flow path formed by the joining portion (38).

[0141] [Formula 1]

[0142] 1 < (L2 / L1) < 3

[0143] In the above equation 1, L1 and L2 is measured along an imaginary center line connecting the forward connection portion connected to the forward microchannel (20) and the rear connection portion connected to the rear microchannel (20) among the microchannels (20) adjacent to the microchamber (30). Specifically, L2 / L1 may be 1.1 to 2.8, 1.2 to 2.5, or 1.5 to 2.3. Accordingly, the fluid can be transferred at a high flow rate and mixed more homogeneously when transferred from the branch portion (36) to the confluence portion (38).

[0144] The length by which the above collision medium (50) extends is not particularly limited as long as it is a length that does not contact the inner surface of the microchamber (30) as described above. However, in one embodiment, the inner diameter (R1) of the flow path formed by the microchannel (20) and the shortest distance (D1) between the longitudinal ends of the collision medium (50) can satisfy the following equation 2.

[0145] [Formula 2]

[0146] 3 < D1 / R1< 15

[0147] Specifically, D1 / R1 may be 4 to 13, 5 to 12, or 6 to 10. Accordingly, the fluid flowing into the microchamber (30) from the microchannel (20) can collide more strongly with the collision medium (50), thereby inducing significantly superior mixing and homogeneous reaction.

[0148] According to one embodiment, the flow path formed by the microchannel (20) can be connected in series, in parallel, or in series and parallel between the inlet (11) and the outlet (13).

[0149] Fig. 4 illustrates a microflow reactor in which the inlet (11) and the outlet (13) are connected in series and parallel with each other. In such a microflow reactor, since the flow paths are formed in series and parallel, the microchambers (30) arranged in communication with the flow paths can also be connected in series and parallel with each other. The microchannel (20) can include a series connection portion (20A) in which the flow paths are connected in series, and a parallel connection portion (20B) in which the flow paths are connected in parallel. As illustrated in the drawing, the microchambers located in the parallel connection portion (20B) can be positioned in parallel with each other. In this case, the microchambers (30) that are parallel to each other can be connected to each other through a parallel connection channel (23b). Such a microflow reactor can react a larger amount of fluid, thereby enabling larger-scale production.

[0150] According to one embodiment, the microflow reactors are connected in series in multiple units, so that each microflow reactor can be operated as a single reactor module. Accordingly, each microflow reactor can be controlled at different flow rates, residence times, and temperatures.

[0151] Hereinafter, the present invention will be described in detail through examples. However, it should be noted that the examples described below are intended only to illustrate and concretize the present invention and are not intended to limit the scope of the invention. This is because the scope of the invention is determined by the matters set forth in the patent claims and matters reasonably inferred therefrom.

[0152] (Examples 1 to 15)

[0153] 1) Polymerization stage

[0154] Polymers were manufactured through a microflow reactor (Module size: 162 × 188.5 × 21 (mm), internal capacity: 8 ml) as shown in Fig. 5. The internal volume (internal capacity) of the microflow reactor was controlled by the number of connected microflow reactors, and the internal volumes for each example are listed in Table 1 below.

[0155] p-tert-butoxy styrene and 1M di-n-butyl magnesium, whose concentration was controlled by the solvent and whose oxygen was removed through argon bubbling, were injected into the first inlet as the first solution, and n-butyl lithium (n-BuLi), whose concentration was controlled by the solvent and whose oxygen was removed through argon bubbling, was injected into the second inlet as the second solution. The concentrations of the first and second solutions and the solvents used for each example are shown in Table 1 below. At this time, di-n-butyl magnesium of the first solution was injected so that the molar ratio (di-n-butyl magnesium : butyl lithium) with n-butyl lithium (n-BuLi) of the second solution was 10:1.

[0156] 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 residence time of the fluid in the microflow reactor are shown in Table 2 below.

[0157] Thereafter, a polymerization terminator with a concentration of 1 M (solvent: tetrahydrofuran (THF)) was injected into the inlet of the first microflow reactor located at the rearmost stage among the first microflow reactors. The polymerization terminators used for each example are listed in Table 1 below.

[0158] 2) Deprotection stage

[0159] The fourth solution, HBr (48 wt%, sigma Aldrich), diluted 5 times, was injected into the inlet of the second microflow reactor located at the front end of the second microflow reactor. The flow rate of the fourth solution for each example is shown in Table 2 below. The temperature of the flow path in the second microflow reactor was maintained at 60°C.

[0160] The internal flow path temperatures of the first and second microflow reactors were controlled and maintained through a temperature control unit (TCU System (Temperature Control Unit)) connected to each microflow reactor.

[0161]

[0162]

[0163] (Comparative examples 1 to 8)

[0164] In the examples, the polymer was manufactured in the same manner as in the examples, except that the polymer was manufactured using a PFA tube (inner diameter 1 / 8 inch, Perfluoroalkoxy alkanes tube / Swagelok) instead of a microflow reactor. The total volume of the flow path in the PFA tube for each comparative example, the solvent and concentration of the first and second solutions, and the polymerization terminator of the third solution are shown in Table 3 below, and the input flow rates of the first solution, the second solution, the polymerization terminator, and the fourth solution 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.

[0165]

[0166]

[0167] Polymer Evaluation

[0168] 1) Conversion rate (%)

[0169] The conversion rates of the aprotic polymers manufactured in the polymerization stages of the examples and comparative examples were calculated using the following calculation formula 1 and are shown in Table 5 below.

[0170] [Calculation Formula 1]

[0171] Conversion rate (%) = ((number of moles of tert-butoxystyrene reacted) / (number of moles of tert-butoxystyrene introduced)) × 100

[0172] 2) Molecular weight, polydispersity

[0173] The number average molecular weight (Mn) and polydispersity index (PDI) of the aprotic polymer and protic polymer prepared in the polymerization step and deprotection step of the examples and comparative examples are shown in Tables 5 and 6, respectively. The number average molecular weight (Mn) and polydispersity index (PDI) were measured using gel permeation chromatography (GPC) from Waters. Shodex KF-801, KF-802, KF-803, and KF-804 columns were used, and Shodex polystyrene was used as the standard sample. The solvent was tetrahydrofuran, the temperature was 40 ℃, and the flow rate was 1.0 mL / min.

[0174] 3) Whether there is a side effect

[0175] In order to determine whether a side reaction occurred during the polymerization step of the polymer manufacturing method according to the examples and comparative examples, the color change of the fluid inside the reactor was visually observed. If the polymerization reaction proceeds well without a side reaction, the fluid inside the reactor exhibits a unique color close to red and orange. However, if a side reaction occurs, the unique color is lost and changes to transparent. Based on this, the presence or absence of a side reaction was determined by observing the color of the fluid inside the reactor, and the results are shown in Table 5 below. If a side reaction occurred, it was marked with a "○", and if no side reaction occurred, it was marked with a "×".

[0176]

[0177]

[0178] Referring to Tables 5 and 6 above, it was confirmed that the aprotic polymer and the protic polymer manufactured according to the examples had a PDI closer to 1 than the comparative examples, and that homogeneous polymers could be manufactured. In addition, it was confirmed that the aprotic polymer and the protic polymer manufactured from the examples had a lower number average molecular weight of about 5000 than the comparative examples. That is, it was confirmed that both the polymerization reaction and the deprotection reaction were performed uniformly in the examples compared to the comparative examples, and that high-quality polymers could be manufactured. In addition, it was confirmed that most of the examples had a conversion rate of 100%, and it was confirmed that no side reactions occurred.

Claims

1. (S1) A step of injecting a first solution containing at least one solvent selected from the group consisting of ether solvents and non-polar solvents and an aprotic monomer containing a protecting group, and a second solution containing the solvent and an anionic polymerization initiator into a first microflow reactor; (S2) A step in which the aprotic monomer containing the protecting group is anionically polymerized in the first microflow reactor into which the first solution and the second solution are injected to produce a third solution containing the aprotic polymer; (S3) a step of injecting a fourth solution containing a deprotecting agent into a second microflow reactor connected to the rear end of the first microflow reactor and into which a third solution is injected; and (S4) a step of performing a deprotection reaction of the aprotic polymer in the second microflow reactor into which the third and fourth solutions are injected to produce a fifth solution containing a proton polymer; The above microflow reactor comprises a main body having at least one inlet hole through which a fluid is introduced and an outlet hole through which a fluid is discharged; a microchannel forming a flow path connecting the inlet and the outlet within the main body; a plurality of microchambers arranged along an extension direction of the microchannel and forming an internal space communicated with the flow path; and a collision medium positioned within the internal space to collide with a fluid transported within the internal space and to change the flow of the fluid within the internal space.

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

3. In paragraph 2, A method for producing a polymer, wherein the above co-solvent has a Hansen Solubility Parameter of 16 to 20.

4. In paragraph 1, A method for producing a polymer, wherein the anionic polymerization initiator is an organic alkali metal.

5. In paragraph 1, A method for producing a polymer, wherein the first solution or the second solution further contains an organic metal having magnesium, aluminum or zinc as a metal species.

6. In paragraph 1, After the above step (S2), before the above step (S3), (S2.5) A method for producing a polymer, further comprising a step of terminating polymerization by introducing a polymerization terminator.

7. In paragraph 1, A method for producing a polymer, wherein the above-mentioned deprotecting agent is at least one selected from the group consisting of hydrochloric acid (HCl), hydrobromic acid (HBr), sulfuric acid, nitric acid, trifluoroacetic acid (TFA), methanesulfonic acid (MsOH), p-toluenesulfonic acid (pTSA), and trimethylsilyl chloride (TMSCl).

8. In paragraph 1, A method for producing a polymer, wherein the above quantum polymer has a polydispersity index of 1.1 or less.

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

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

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

12. In paragraph 11, A method for manufacturing a polymer, wherein the diameter (L1) of the flow path formed by the above branch portion and the diameter (L2) of the flow path formed by the above joining portion satisfy the following equation 1. [Formula 1] 1 < (L2 / L1) < 3 (In the above equation 1, L1 and L2 is measured along an imaginary center line connecting the front connection part connected to the front microchannel and the rear connection part connected to the rear microchannel among the microchannels adjacent to the above microchamber.) 13. In paragraph 11, A method for manufacturing a polymer, wherein the inner diameter (R1) of the flow path formed by the above microchannel and the shortest distance (D1) between the longitudinal ends of the collision medium satisfy the following equation 2. [Formula 2] 3 < D1 / R1< 15 14. In paragraph 1, A method for producing a polymer, wherein the microchannel comprises an inlet channel connecting the microchamber located at the most forward end in the direction of fluid flow within the path and the inlet, a connection channel connecting the microchambers adjacent to each other, and an outlet channel connecting the microchamber located at the most rearward end in the direction of fluid flow within the path and the outlet.

15. In paragraph 14, A polymer manufacturing method, wherein at least one of the above inlet channels and connecting channels has an inner diameter of a rear-end flow path that gradually decreases.

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

17. In paragraph 1, A method for producing a polymer, wherein the above-mentioned protecting group-containing aprotic monomer comprises a protecting group-containing aprotic aromatic vinyl monomer.

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

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