Preparation method of polymer

Abstract

In this application, a method for manufacturing a polymer having desired molecular weight characteristics and solubility in a solvent, and having a monomer composition freely and diversely designed according to the purpose, can be effectively produced without unnecessary components with excellent polymerization efficiency and conversion rate, and a dispersion containing the polymer formed by the method.

Description

Technology Field

[0001] The present application relates to a method for manufacturing a polymer and a polymer manufactured by the method. Background Technology

[0002] Various methods for synthesizing polythiophene, a conductive polymer, are known, and representative methods include those utilizing oxidation reactions and radical reactions.

[0003] In the method utilizing oxidation reactions, polythiophene is produced by oxidizing thiophene monomers dissolved or dispersed in a solvent and then binding the oxidized monomers together. In this method, an oxidizing agent is added to the solvent and an external magnetic field is applied to carry out polymerization; however, because the polymer produced by polymerization is in a doped state, the polymerized chains tend to easily bond with each other, leading to a problem where solubility in the solvent decreases as polymerization progresses. Consequently, it is difficult to obtain high molecular weight products because products with a molecular weight exceeding a certain level precipitate.

[0004] A method for manufacturing conductive polymers using metal ligand catalysts is also known; however, this method is complex because it requires not only sufficient removal of oxygen and moisture during the polymerization process but also blocking their influx during the reaction, and it is not easy to completely remove the applied catalyst after polymerization.

[0005] Although a method of producing polymers by inducing an oxidation reaction through light irradiation is also known, it is difficult to obtain high molecular weight products using this method, and while a redox catalyst is required for polymerization, it is also difficult to remove the catalyst from the product. The problem to be solved

[0006] This application relates to a method for manufacturing a polymer and to the polymer itself. One objective of this application is to provide a method for manufacturing a target polymer that can be produced with excellent polymerization efficiency and conversion rate without consumption or alteration during the polymerization process. Another objective of this application is to provide a method for manufacturing a polymer that has a large molecular weight at a target level and exhibits excellent solubility in various solvents. Another objective of this application is to provide a method for manufacturing a polymer that eliminates the need for or minimizes the use of a catalyst, thereby minimizing or substantially eliminating the amount of catalyst in the product. Another objective of this application is to provide a method for manufacturing a polymer that can easily achieve copolymerization between various types of monomers. Another objective of this application is to provide a polymer dispersion containing the polymer manufactured as described above. means of solving the problem

[0007] Among the physical properties mentioned in this specification, if the measured temperature and / or pressure affects the value of the physical property, unless specifically stated otherwise, said physical property refers to the physical property measured at room temperature and / or atmospheric pressure.

[0008] In this application, the term "room temperature" refers to a natural temperature that is not heated or cooled, and may mean, for example, any temperature within the range of about 10°C to 30°C, 25°C, or 23°C.

[0009] In this application, the term "atmospheric pressure" refers to pressure that is not specifically reduced or increased, and can be approximately 1 atmosphere, which is the same as normal atmospheric pressure.

[0010] The method for manufacturing the polymer of the present application may, in one example, be a method for manufacturing a conductive polymer, and for example, a method for manufacturing polythiophene. In this specification, the term polythiophene means a polymer comprising about 50 mol% or more, 55 mol% or more, 60 mol% or more, 65 mol% or more, 70 mol% or more, 75 mol% or more, 80 mol% or more, 85 mol% or more, or 90 mol% or more of the polymerization units of a thiophene-based monomer relative to the total polymerization units. The upper limit of the ratio of the polymerization units of the thiophene-based monomer within polythiophene is not particularly limited and may, for example, be 100 mol% or less, 95 mol% or less, or 90 mol% or less.

[0011] The above thiophene series monomer can be represented, for example, by the following chemical formula 1.

[0012] [Chemical Formula 1]

[0013]

[0014] In Chemical Formula 1, R1 and R2 are each independently hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkyl carbonyl group, an aryl carbonyl group, an aryl carbonyloxy group, an alkyl carbonyloxy group, a carboxyl group, or an aryl group, or are connected to each other to form a ring structure, and R3 and R4 are each independently hydrogen, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, or an aryl group, and at least one of R3 and R4 is a halogen atom.

[0015] In this application, the terms alkyl group, alkylene group, or alkoxy group may mean a straight-chain or branched-chain alkyl group, alkylene group, or alkoxy group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms, or a cyclic alkyl group, alkylene group, or alkoxy group having 3 to 20 carbon atoms, 3 to 16 carbon atoms, 3 to 12 carbon atoms, 3 to 8 carbon atoms, or 3 to 6 carbon atoms.

[0016] In this application, the terms alkenyl group, alkynylene group, alkynyl group, or alkynylene group may, unless specifically otherwise defined, mean a straight-chain or branched-chain alkenyl group or alkynyl group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms, or a cyclic alkenyl group or alkynyl group having 3 to 20 carbon atoms, 3 to 16 carbon atoms, 3 to 12 carbon atoms, 3 to 8 carbon atoms, or 3 to 6 carbon atoms.

[0017] In this specification, the terms aryl group or arylene group refer to benzene or a derivative thereof; a compound or derivative thereof in which two benzenes are bonded by sharing one or two carbon atoms; a compound or derivative thereof in which two benzenes are bonded by any linker; or a compound in which three or more benzene compounds are bonded together, wherein the bonded benzene compounds are bonded by sharing one or two carbon atoms or are connected by any linker, and the aryl group or arylene group is derived from a compound or derivative thereof. The aryl group may be an aryl group or arylene group having 6 to 30 carbon atoms, 6 to 24 carbon atoms, 6 to 18 carbon atoms, or 6 to 12 carbon atoms. Optionally, one or more substituents may be substituted on the aryl group or arylene group.

[0018] The above alkyl group, alkylene group, alkoxy group, alkenyl group, alkynylene group, alkynyl group, alkynylene group, arylene group and / or aryl group may optionally be substituted with one or more substituents, wherein examples of substituents include, but are not limited to, glycidyl group, glycidoxyalkyl group, acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, hydroxyl group, carboxyl group, epoxy group, alkyl group, alkylene group, alkoxy group, alkenyl group, alkynylene group, alkynyl group, alkynylene group and / or aryl group.

[0019] In Chemical Formula 1, at least one or two of R3 and R4 are halogen atoms. Examples of halogen atoms included in Chemical Formula 1 may include fluorine, chlorine, bromine, or iodine, and suitably iodine.

[0020] In the manufacturing method of the present application, radicals are generated at the R3 and / or R4 portions of the halogen atoms, and then a polymerization reaction may proceed.

[0021] In one example, R1 and R2 of Chemical Formula 1 may be connected to each other to form a ring structure. In this case, the monomer of Chemical Formula 1 may be represented by the following Chemical Formula 2.

[0022] [Chemical Formula 2]

[0023]

[0024] In Chemical Formula 2, R3 and R4 may be the halogen atoms, and L may be a chain forming the ring structure.

[0025] In the above, the chain may have 3 to 10 chain-forming atoms. A chain-forming atom is an atom that forms the chain of L, examples of which include carbon, oxygen, nitrogen, or sulfur, and in appropriate examples, may be carbon or oxygen. In determining the number of chain-forming atoms, atoms other than those present in the chain-forming region are not considered. For example, one or more substituents may be optionally substituted in the chain; in such cases, the number of atoms present in said substituents is not included in the number of chain-forming atoms, and if a chain-forming atom is carbon or nitrogen to which a hydrogen atom is bonded, said hydrogen atom is not counted as a chain-forming atom. Furthermore, if there are two or more oxygen or sulfur atoms each as chain-forming atoms, said oxygen or sulfur atoms do not exist adjacent to each other in the chain structure.

[0026] In the compound of Chemical Formula 1, at least one of R1 and R2 is a substituent containing an oxygen atom, or the ring structure formed by connecting R1 and R2 of Chemical Formula 1 may contain an oxygen atom.

[0027] That is, in Chemical Formula 1, at least one or both of R1 and R2 may be an alkoxy group, an alkyl carbonyl group, an aryl carbonyl group, an aryl carbonyl oxy group, an alkyl carbonyl oxy group, or a carboxyl group, and suitably may be an alkoxy group.

[0028] In addition, when R1 and R2 in Formula 1 are connected to each other to form a ring structure, the chain formed by R1 and R2 forming the ring structure (e.g., L in Formula 2) may contain at least one oxygen atom. In this case, the number of oxygen atoms included in the chain is one or two or more, and the upper limit is not specifically limited, but for example, 10 or fewer, 9 or fewer, 8 or fewer, 7 or fewer, 6 or fewer, 5 or fewer, 4 or fewer, 3 or fewer, or 2 or fewer. Also, when there are two or more oxygen atoms in the chain, those oxygen atoms may not be adjacent to each other. In other words, between the two or more oxygen atoms, for example, carbon or nitrogen atoms may exist, and suitably, carbon atoms may exist.

[0029] In a suitable example, the chain by R1 and R2 may have 3 to 10 chain-forming atoms, and the chain-forming atoms may be carbon or oxygen, and at least 1 or 2 to 5, 2 to 4, 2 to 3, or 2 oxygen atoms that are not adjacent to each other.

[0030] Compounds of this type can allow the polymerization reaction to proceed more effectively by lowering the oxidation potential of the compound through the non-covalent electron pair of the oxygen atom.

[0031] For example, the monomer of Formula 1 containing an oxygen atom may be represented by any one of Formulas 3 to 5 below.

[0032] [Chemical Formula 3]

[0033]

[0034] In Chemical Formula 3, R3 and R4 are each independently hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkyl carbonyl group, an aryl carbonyl group, or an aryl group, or are connected to each other to form a ring structure, and R1 and R2 are each independently hydrogen, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, or an aryl group, and at least one of R1 and R2 is a halogen atom.

[0035] [Chemical Formula 4]

[0036]

[0037] [Chemical Formula 5]

[0038]

[0039] In chemical formula 4 or 5, R3 and R4 are each independently hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkyl carbonyl group, an aryl carbonyl group, an aryl carbonyloxy group, an alkyl carbonyloxy group, a carboxyl group, or an aryl group, R1 and R2 are each independently hydrogen, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, or an aryl group, at least one of R1 and R2 is a halogen atom, and m is a number within the range of 1 to 4.

[0040] In Formula 3, R3 and R4 are suitably alkyl groups, alkenyl groups, alkynyl groups or aryl groups, or alkyl groups, and suitable examples for R1 and R2 in Formulas 3 to 5 are the same as R3 and R4 in Formula 1.

[0041] As thiophene-based monomers applied in the polymerization process of the present application, the above-described monomers are all monomers containing halogen atoms, and can serve as initiators or radical generators for the polymerization process. In one example, the thiophene-based monomers applied in the polymerization process of the present application may be a mixture of the above-described monomers containing halogen atoms and monomers not containing halogen atoms. By applying such monomer compositions, the reaction can be controlled so that the photoarylation mechanism predominates over the photocondensation mechanism in the polymerization mechanism, and as a result, high molecular weight conductive polymers can be formed more effectively.

[0042] Accordingly, in one example, the mixture applied to the polymerization process may include a non-halogenated thiophene series monomer, which may be, for example, a compound of Chemical Formula 6 below.

[0043] [Chemical Formula 6]

[0044]

[0045] In Chemical Formula 6, R1 and R2 are each independently hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkyl carbonyl group, an aryl carbonyl group, an aryl carbonyloxy group, an alkyl carbonyloxy group, a carboxyl group, or an aryl group, or are connected to each other to form a ring structure, and R3 and R4 are each independently hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, or an aryl group, and at least one of R3 and R4 is a hydrogen atom.

[0046] The specific details regarding these non-halogenated monomers are identical to those described for the halogenated monomers, except that they do not contain halogens.

[0047] For example, in Chemical Formula 6, at least one or two of R3 and R4 are hydrogen atoms that are not halogen atoms.

[0048] In addition, in one example, when R1 and R2 of Chemical Formula 6 are connected to each other to form a ring structure, the monomer of Chemical Formula 6 can be represented by the following Chemical Formula 7.

[0049] [Chemical Formula 7]

[0050]

[0051] In Chemical Formula 7, R3 and R4 may be the hydrogen atoms, and L may be a chain forming the ring structure, where the specific details regarding the chain are the same as in Chemical Formula 2.

[0052] In the compound of Formula 6 above, at least one of R1 and R2 is a substituent containing an oxygen atom, or the ring structure formed by connecting R1 and R2 of Formula 1 may contain an oxygen atom. That is, in Formula 6, at least one or both of R1 and R2 may be an alkoxy group, an alkyl carbonyl group, an aryl carbonyl group, an aryl carbonyl oxy group, an alkyl carbonyl oxy group, or a carboxyl group, and suitably may be an alkoxy group.

[0053] In addition, when R1 and R2 in Chemical Formula 6 are connected to each other to form a ring structure, the chain formed by R1 and R2 forming the ring structure (e.g., L in Chemical Formula 2) may contain at least one oxygen atom. In this case, the number of oxygen atoms included in the chain is one or two or more, and the upper limit is not specifically limited, but for example, 10 or fewer, 9 or fewer, 8 or fewer, 7 or fewer, 6 or fewer, 5 or fewer, 4 or fewer, 3 or fewer, or 2 or fewer. Also, when there are two or more oxygen atoms in the chain, those oxygen atoms may not be adjacent to each other. In other words, between the two or more oxygen atoms, for example, carbon or nitrogen atoms may exist, and suitably, carbon atoms may exist. In a suitable example, the chain by R1 and R2 may have 3 to 10 chain-forming atoms, said chain-forming atoms may be carbon or oxygen, and may be oxygen atoms such that at least 1, 2 to 5, 2 to 4, 2 to 3, or 2 chain-forming atoms exist separately from each other. The advantages of this type of compound are as described above.

[0054] For example, the monomer of the above formula 6 containing an oxygen atom may be represented by any one of the following formulas 8 to 10.

[0055] [Chemical Formula 8]

[0056]

[0057] In Chemical Formula 8, R3 and R4 are each independently hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkyl carbonyl group, an aryl carbonyl group, or an aryl group, or are connected to each other to form a ring structure, and R1 and R2 are each independently hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, or an aryl group, and at least one of R1 and R2 is a hydrogen atom.

[0058] [Chemical Formula 9]

[0059]

[0060] [Chemical Formula 10]

[0061]

[0062] In chemical formula 9 or 10, R3 and R4 are each independently hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkyl carbonyl group, an aryl carbonyl group, an aryl carbonyloxy group, an alkyl carbonyloxy group, a carboxyl group, or an aryl group, R1 and R2 are each independently hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, or an aryl group, at least one of R1 and R2 is a hydrogen atom, and m is a number within the range of 1 to 4.

[0063] In Formula 8, R3 and R4 are suitably alkyl groups, alkenyl groups, alkynyl groups or aryl groups, or alkyl groups, and suitable examples for R1 and R2 in Formulas 8 to 10 are the same as R3 and R4 in Formula 1.

[0064] As described above, when a mixture of halogenated thiophene monomers and non-halogenated thiophene monomers is applied as a monomer, the ratio between them is not particularly limited. For proper polymerization to proceed, for example, when based on compounds of Formula 1 and Formula 6, the ratio (Halo / (Halo+H)) of the number of moles of halogen atoms (Halo) contained in R3 and R4 of Formula 1 and the number of moles of hydrogen atoms (H) contained in R3 and R4 of the compound of Formula 6 may be in the range of 0.001 to 99. The above ratio (Halo / (Halo+H)) may be approximately 0.01 or more, 0.05 or more, 0.1 or more, 0.15 or more, 0.2 or more, 0.25 or more, 0.3 or more, 0.35 or more, 0.4 or more, 0.45 or more, or 0.5 or more in other examples, or 95 or less, 90 or less, 85 or less, 80 or less, 75 or less, 70 or less, 65 or less, 60 or less, 55 or less, 50 or less, 45 or less, 40 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, or 10 or less. Polymerization can be carried out effectively within this range to obtain a high molecular weight product.

[0065] Among the matters regarding the mole ratio of halogen atoms and hydrogen atoms based on the compounds of Chemical Formulas 1 and 6 above, the matters regarding the mole ratio of halogen atoms and hydrogen atoms based on R3 and R4 of Chemical Formulas 1 and 6 are applied equally to the halogen atoms and hydrogen atoms of R3 and R4 of Chemical Formulas 2 and 7, and are applied equally to the halogen atoms and hydrogen atoms of R1 and R2 of Chemical Formulas 3 to 5 and Chemical Formulas 8 to 10.

[0066] That is, the ratio (Halo / (Halo+H)) of the number of moles of halogen atoms (Halo) contained in R3 and R4 of Formula 1 and / or 2 and / or R1 and R2 of Formulas 3 to 5 in the entire thiophene monomer undergoing the polymerization reaction, and the number of moles of hydrogen atoms (H) contained in R3 and R4 of the compound of Formula 6 and / or 7 and / or R1 and R2 of Formulas 8 to 10, can satisfy the above range.

[0067] The manufacturing method of the present application may include a step of irradiating light while the thiophene-based monomer as described above is dissolved in a solvent.

[0068] Through this process, radicals are generated at the sites where halogen atoms are present in the thiophene-based monomer, and a chain reaction occurs to form a polymer. If necessary, additional monomers may be present in the solvent in addition to the thiophene-based monomer.

[0069] Accordingly, the manufacturing method of the present application includes the step of irradiating light onto a mixture comprising a monomer of Formula 1 and a solvent as a thiophene-based monomer.

[0070] In the first aspect of the present application, a solvent that does not contain hydrogen atoms may be used as the solvent applied in the above manufacturing method.

[0071] The inventors have discovered that a solvent containing hydrogen atoms absorbs halogen radicals and / or halogen molecules generated during the polymerization process. When halogen radicals and / or halogen molecules generated during the polymerization process are absorbed and depleted by the solvent, it becomes difficult to generate active radicals, and thus, further reactions between monomers or macromolecules produced by polymerization and other monomers do not proceed, making it impossible to obtain the desired high molecular weight product. In one aspect of the present application, the depletion of halogen radicals and / or halogen molecules can be prevented by applying a solvent that does not contain hydrogen atoms as the solvent.

[0072] In the second aspect of the present application, the step of irradiating light onto a mixture comprising the solvent and a thiophene-based monomer may be carried out in at least two steps. For example, the step of irradiating light may include a first step of irradiating the mixture with light having a wavelength of 450 nm or less and a second step of irradiating the mixture with light having a wavelength exceeding 450 nm.

[0073] For example, the first and second steps may be performed consecutively without interruption, or after performing the first step, the irradiation of light may be stopped for a certain period of time, and then the second step may be performed by irradiating light of a wavelength greater than 450 nm at an appropriate time. Additionally, while the second step is being performed, only light of a wavelength greater than 450 nm may be irradiated, or light of a wavelength of 450 nm or less may also be irradiated along with the light.

[0074] The wavelength of the light irradiated in the first step above may be 100 nm or more, 150 nm or more, 200 nm or more, 250 nm or more, 300 nm or more, or 350 nm or more, or 400 nm or less.

[0075] In addition, the wavelength of the light irradiated in the second step may be approximately 900 nm or less, 850 nm or less, 800 nm or less, 750 nm or less, 700 nm or less, 650 nm or less, 600 nm or less, or 550 nm or less, or 460 nm or more, 480 nm or more, or 500 nm or more.

[0076] In order to generate radicals during the polymerization process of the manufacturing method of the present application and to form a target polymer of high molecular weight through a chain reaction, it is required that irradiated light be absorbed by the monomer or the macromolecule formed by the polymerization of the monomer to generate radicals in a chain reaction. However, since the wavelength of light efficiently absorbed by the monomer and the wavelength of light efficiently absorbed by the macromolecule formed by the polymerization of the monomers are different, if light of the same wavelength is continuously irradiated during the polymerization process, the radical generation efficiency of at least one of the monomer and the macromolecule decreases, making it difficult to produce a polymer of the target molecular weight.

[0077] The inventors have confirmed that the problem can be solved and the desired polymer can be produced by performing the first step for an appropriate amount of time and then changing the wavelength of the light being irradiated or by additionally irradiating another light to perform the second step.

[0078] The two methods of the present application may be performed simultaneously or independently of each other. That is, in the manufacturing method of applying the specific solvent (a solvent that does not contain hydrogen atoms), the irradiation of light may or may not be carried out in the two steps described above, and in the method of carrying out the irradiation of light in two steps, a solvent that does not contain hydrogen atoms may or may not be used.

[0079] Suitablely, by applying the two above-mentioned suns simultaneously, the desired polymer can be formed more efficiently.

[0080] In the method described above, the present application enables the production of a polymer having a high molecular weight at a desired level with excellent polymerization efficiency and conversion rate, without the generation of byproducts during the polymerization process or the deterioration of the target product. Since the polymer is produced by radical-induced chain polymerization in the present application, excessive doping by halogen anions, etc., does not occur in the polymer, as in oxidation methods that apply oxidizing agents; therefore, the polymer can exhibit excellent solubility in various solvents. Furthermore, in the manufacturing method of the present application, the use of a catalyst is not required, or if necessary, only a small amount is applied to form the desired polymer; thus, the catalyst is absent or present in small amounts in the final product, and therefore, the desired polymer can be obtained with high purity without an additional process for separating the catalyst. According to the manufacturing method of the present application, various monomers that form polymers by radical reaction, in addition to the thiophene-based monomer, can be easily applied to easily produce copolymers of the thiophene-based monomer and other monomers, thereby enabling easy and efficient production.

[0081] In the manufacturing method of the first and second embodiments of the present application, a step of irradiating a mixture of a solvent and a thiophene monomer with light is performed. In this process, there are no specific limitations on the ratio of the thiophene monomer in the mixture, and an appropriate ratio of thiophene monomer can be applied considering the desired polymer. In one example, the concentration of the thiophene monomer may be within the range of about 0.01 mol / L to 1 mol / L. The concentration of the thiophene monomer may be the concentration of the monomer in the solvent. In other examples, the concentration may be about 0.05 mol / L or more, 0.1 mol / L or more, 0.15 mol / L or more, 0.2 mol / L or more, 0.25 mol / L or more, 0.3 mol / L or more, 0.35 mol / L or more, 0.4 mol / L or more, 0.45 mol / L or more, or 0.5 mol / L or more. Within this range, effective polymerization of monomers can be induced, and the solubility of the polymerized polymer can also be stably maintained.

[0082] As described above, in the method for manufacturing a polymer of the present application, the consumption of halogen radicals and halogen molecules can be prevented by not applying a solvent having hydrogen atoms. Accordingly, the mixture in the method for manufacturing the first embodiment may include only a solvent that does not have hydrogen atoms as a solvent, and may substantially not include a solvent having hydrogen atoms. In the above, "substantially not applying a solvent having hydrogen atoms" may mean that the proportion of the solvent having hydrogen atoms in the mixture is about 1 wt% or less, 0.5 wt% or less, 0.1 wt% or less, 0.05 wt% or less, 0.01 wt% or less, 0.005 wt% or less, 0.001 wt% or less, 0.0005 wt% or less, 0.0001 wt% or less, 0.00005 wt% or less, or 0.00001 wt% or less. Furthermore, the lower limit of the proportion of the solvent is 0 wt%.

[0083] As for the solvent that does not contain hydrogen atoms, various solvents may be used without special limitations as long as they do not contain hydrogen atoms. Examples of such solvents include bromotrichloromethane (CBrCl3), tetrachloromethane (CCl4), or dibromodichloromethane (CBr2Cl2), but are not limited thereto.

[0084] In the manufacturing method of the present application, any one of the above solvents may be selected, and if necessary, two or more mixed solvents may be applied.

[0085] In the manufacturing method of the present application, when light irradiation is performed in two stages, the time for which each stage is applied is not particularly limited. In one example, in the first stage, the total energy from the irradiated light is approximately 0.01 W / cm² 2 Up to 20W / cm 2 It can be performed at a level that is appropriate. Since if the total energy is excessively small, radical formation is not carried out efficiently, and if it is excessively high, photodegradation may occur in the products, etc., it can be adjusted to an appropriate range in consideration of this.

[0086] The above second step can adjust the total energy of the irradiated light to a level similar to that of the above first step. Since if the total energy is too low, radical formation is not efficiently carried out, and if it is too high, photodegradation may occur in the product, etc., it can be adjusted to an appropriate range in consideration of this. Meanwhile, if the light irradiated in the second step is pulsed light as described below, the total energy is the average energy.

[0087] The light irradiation performed in the second step above may be carried out using a pulsed light source, for example, a pulsed laser light source. By pulse irradiating with such long-wavelength light, polymerization can be performed stably while efficiently preventing photodegradation caused by the irradiated light. In this case, the frequency of the pulsed light source can be adjusted within a range of about 1 to 20 Hz. In other examples, the frequency may be about 2 Hz or higher, 3 Hz or higher, 4 Hz or higher, 5 Hz or higher, 6 Hz or higher, 7 Hz or higher, 8 Hz or higher, 9 Hz or higher, or 10 Hz or higher, or about 19 Hz or lower, 18 Hz or lower, 17 Hz or lower, 16 Hz or lower, 15 Hz or lower, 14 Hz or lower, 13 Hz or lower, 12 Hz or lower, 11 Hz or lower, or 10 Hz or lower.

[0088] According to one example of the present application, when the first and second steps are carried out together, a step of additionally supplying a halogen source may be additionally performed at an appropriate time (e.g., between the first and second steps).

[0089] Through this, the polymerization process can be carried out more effectively while maintaining or improving the radical generation efficiency. Known compounds can be used as halogen sources without special limitations, for example, fluorine molecules (F2), chlorine molecules (Cl2), bromine molecules (Br2), or iodine molecules (I2), and suitably, iodine molecules (I2). In addition, perchloric acid (HClO4), etc., can be added together with the halogen molecules to facilitate the supply of halogen.

[0090] In the manufacturing method of the present application, a polymer having a desired level of molecular weight characteristics and solubility in a solvent can be formed with excellent polymerization efficiency without the use of a separate catalyst or other components through the above method.

[0091] The present application also relates to a polymer dispersion comprising a polymer and a solvent prepared in the manner described above.

[0092] For example, the polymer may include a polymerization unit of the following chemical formula 11, as a polymerization unit formed by a thiophene-based monomer of chemical formula 1 and / or 6.

[0093] The polymerization unit of the following chemical formula 11 is a polymerization unit formed by connecting the R3 and R4 portions in the above chemical formulas 1 and / or 6. Accordingly, the specific details regarding R1 and R2 in the following chemical formula 11 are the same as the details regarding R1 and R2 in the above chemical formulas 1 and 6.

[0094] [Chemical Formula 11]

[0095]

[0096] In addition, in Chemical Formula 11, n represents the degree of polymerization of the thiophene monomer and is any number, for example, may be a number within the range of about 4 to 200.

[0097] The content in which the monomers of Chemical Formula 1 and / or 6 are polymerized to form the unit of Chemical Formula 11 may be applied in the same way to monomers of other chemical formulas.

[0098] For example, when the polymerization unit is formed from the monomer of Formula 2 and / or 7, the R3 and R4 portions of the monomer of Formula 2 and / or 7 are connected to form a chain, so the polymerization unit can be represented by the following Formula 12.

[0099] [Chemical Formula 12]

[0100]

[0101] In Chemical Formula 12, L is the same as L in Chemical Formula 2 and / or 7, and n is any number, for example, a number within the range of 4 to 200.

[0102] In addition, the above content can be applied in the same way as in the manner in which the R1 and R2 portions form a chain in the halogenated thiophene monomers of chemical formulas 3 to 5, and in the manner in which the R1 and R2 portions form a chain in the non-halogenated thiophene monomers of chemical formulas 8 to 10.

[0103] The above polymer may contain polymerization units of the above-mentioned thiophene-based monomer in an amount of about 50 mol% or more, 55 mol% or more, 60 mol% or more, 65 mol% or more, 70 mol% or more, 75 mol% or more, 80 mol% or more, 85 mol% or more, or 90 mol% or more relative to the total polymerization units. The upper limit of such polymerization unit ratio is not specifically limited and, for example, may be 100 mol% or less, 95 mol% or less, or 90 mol% or less.

[0104] The above polymer may contain only polymerization units of thiophene monomers of the same structure, or it may simultaneously contain polymerization units of two or more thiophene monomers of different structures. For example, the above polymer may simultaneously contain polymerization units of different specific structures (e.g., R1 and R2 having different structures in Formula 11, or L having different structures in Formula 12) while having structures within the structural categories of the polymerization units of Formulas 11 and 12 described above, or within the structural categories of the polymerization units of Formulas 3 to 5 and / or Formulas 8 to 10. The above polymer containing two or more polymerization units of thiophene monomers simultaneously may be in the form of a so-called random copolymer, block copolymer, or gradient copolymer.

[0105] In addition, the polymer may simultaneously include other types of monomers in addition to the polymerization units of the thiophene-based monomer, and in such cases, the polymer may be in the form of a so-called random copolymer, block copolymer, or gradient copolymer.

[0106] The above polymer may have a large molecular weight and is manufactured by the method of the present application described above. For example, the molecular weight of the polymer may be approximately 2,000 g / mol or more, 2,500 g / mol or more, 3,000 g / mol or more, 3,500 g / mol or more, 4,000 g / mol or more, 4,500 g / mol or more, 5,000 g / mol or more, 5,500 g / mol or more, 6,000 g / mol or more, 6,500 g / mol or more, 7,000 g / mol or more, 7,500 g / mol or more, 8,000 g / mol or more, 8,500 g / mol or more, 9,000 g / mol or more, 9,500 g / mol or more, 10,000 g / mol or more, 15,000 g / mol or more, 20,000 g / mol or more, or 25,000 g / mol or more. The above molecular weight may be the number average molecular weight (Mn), which is a converted value for standard polystyrene measured by a gel permeation chromatograph (GPC). The upper limit of the above molecular weight is not specifically limited. For example, the above molecular weight may be about 1,000,000 g / mol or less, 500,000 g / mol or less, 100,000 g / mol or less, 50,000 g / mol or less, 40,000 g / mol or less, or 30,000 g / mol or less.

[0107] The polymer in the above dispersion may exhibit an appropriate molecular weight distribution (PDI, the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn) (Mw / Mn)). For example, the molecular weight distribution may be about 1.5 or less. In other examples, the molecular weight distribution may be about 1.45 or less or 1.4 or less, or 1 or more, 1.05 or more, 1.1 or more, 1.15 or more, 1.2 or more, 1.25 or more, or 1.3 or more. Such a molecular weight distribution can be obtained by the manufacturing method of the present application described above.

[0108] In one example, the solvent included in the polymer dispersion is a solvent that does not contain the aforementioned hydrogen atoms, and may be bromotrichloromethane (CBrCl3), tetrachloromethane (CCl4), or dibromodichloromethane (CBr2Cl2), but is not limited thereto.

[0109] The proportion of the polymer in the above dispersion is not particularly limited, and for example, the proportion of the polymer in the dispersion may be about 0.1 to 10 weight percent.

[0110] The above dispersion is prepared by the method of the present application described above, and since a catalyst is not substantially applied during the manufacturing process, it may not substantially contain a catalyst component. The catalyst component is a catalyst component typically applied to the production of conductive polymers such as polythiophene, and specifically, as an oxidizing agent used in an oxidation reaction, examples may include transition metal ligand catalysts such as FeCl3, MnO2, CuCl2, Fe(tosylate), Na2S2O8, etc., or 1,3-bis(diphenylphosphino)propane]dichloronickel(II).

[0111] Since the polymer dispersion does not substantially contain the catalyst component, the proportion of the catalyst component in the dispersion may be about 1 wt% or less, 0.5 wt% or less, 0.1 wt% or less, 0.05 wt% or less, 0.01 wt% or less, 0.005 wt% or less, 0.001 wt% or less, 0.0005 wt% or less, 0.0001 wt% or less, 0.00005 wt% or less, or 0.00001 wt% or less. The lower limit of the proportion of the catalyst component is 0 wt%.

[0112] The polymer dispersion of the present application as described above can be applied to various uses. As the proportion of unnecessary components, such as catalyst components, is minimized as described above, and the polymer itself possesses excellent molecular weight characteristics, it can exhibit significantly superior performance compared to existing conductive polymers even when applied to applications where existing conductive polymers are used. Effects of the invention

[0113] The present application provides a method for manufacturing a polymer and a polymer. The present application provides a manufacturing method capable of effectively producing a polymer having desired molecular weight characteristics and solubility in a solvent, with a monomer composition freely and diversely designed according to the purpose, without unnecessary components and with excellent polymerization efficiency and conversion rate, and a dispersion containing the polymer formed by said manufacturing method. Brief explanation of the drawing

[0114] FIGS. 1 to 4 are of the compounds synthesized in the synthesis examples. 1 This is the H-NMR result. FIGS. 5 to 15 show the polymer synthesized in the examples. 1 It is the result of H-NMR, UV-vis spectrum analysis, or GPC analysis. Specific details for implementing the invention

[0115] The present application will be specifically described through the following examples, but the scope of the present application is not limited by the following examples.

[0117] 1. NMR Analysis Method

[0118] In the examples and synthesis examples 1 H-NMR analysis was performed at room temperature using an NMR spectrometer including a Bruker UltraShield (300 MHz) spectrometer equipped with a triple resonance 5 mm probe. The analyte was diluted to a concentration of approximately 10 mg / ml in the NMR measurement solvent (CDCl3), and the chemical shift was expressed in ppm.

[0120] 2. GPC(Gel Permeation Chromatograph)

[0121] Number-average molecular weight (Mn) and molecular weight distribution were measured using Gel Permeation Chromatography (GPC). Polymers such as those in the examples were placed in 5 mL vials and diluted in chloroform to a concentration of approximately 1 mg / mL. Subsequently, the standard sample for calibration and the sample to be analyzed were filtered through a syringe filter (pore size: 0.45 μm) and then measured. Waters Empower 3 was used as the analysis program; the weight-average molecular weight (Mw) and number-average molecular weight (Mn) were determined by comparing the sample elution time with the calibration curve, respectively, and the molecular weight distribution (PDI) was calculated using the ratio (Mw / Mn). The GPC measurement conditions are as follows.

[0122] <GPC 측정 조건>

[0123] Device: Waters 2414

[0124] Column: Used 3 Waters Styragel columns

[0125] Solvent: THF

[0126] Column temperature: 35℃

[0127] Sample concentration: 1 mg / mL, 1 mL injection

[0128] Standard Sample: Polystyrene (Mp: 3900000, 723000, 316500, 52200, 31400, 7200, 3940, 485)

[0130] 3. UV-vis Spectrum Analysis

[0131] UV-vis spectra were performed using an Agilent Technologies Cary 50 UV-Vis spectrophotometer (Manufacturer: Agilent Technologies, Product Name: Cary 50), by placing chloroform in a transparent quartz cuvette (45 mm × 12.5 mm × 12.5 mm), calibrating in the wavelength range of 200 nm to 1000 nm, and then measuring the absorption rate of a sample diluted with chloroform in the said wavelength range.

[0133] Synthesis Examples 1 and 2

[0134] Compound 1 (DBuProDOT) and Compound 2 (DIBBuProDOT) in Reaction Scheme 1 below were synthesized in the following manner.

[0135] [Reaction Equation 1]

[0136]

[0138] Synthesis of Compound 1

[0139] 6 g (41.61 mmol, 1 eq) of 3,4-dimethoxythiophene and 10.187 g (54.10 mmol, 1.3 eq) of 2,2-dibutyl-1,3-propanediol were dissolved in 200 mL of toluene with 500 mg of p-toluenesulfonic acid. The mixture was refluxed at 120°C, and the methanol produced by the transetherification of the reactants was removed using a Type 4A molecular sieve packed with a Soxhlet extractor. After refluxing for 24 hours, the mixture was quenched with water, extracted with ethyl acetate, washed with brine, and dried over MgSO4. The solvent was evaporated using a rotary evaporator, and the residue was purified by column chromatography with a methylene chloride / hexane (1:4) elution to obtain the target product (Compound 1). FIG. 1 shows the target product. 1 This is the H-NMR spectrum.

[0141] Synthesis of Compound 2

[0142] 5 g (18.63 mmol, 1 eq) of Compound 1 was dissolved in chloroform and stirred with 9.22 g (40.98 mmol, 1 eq) of n-iodosuccinimide and a few drops of acetic acid. The mixture was quenched with deionized water and washed with sodium thiosulfate to remove excess iodine, then dried over MgSO4 and evaporated under vacuum. The residue was purified by column chromatography with a methylene chloride / hexane (1:8) elution to obtain the target product (Compound 2). FIG. 2 shows the target product. 1 This is the H-NMR spectrum.

[0144] Synthesis Examples 3 and 4

[0145] Compound 3 (DEHProDOT) and Compound 4 (DIDEHProDOT) in Reaction Scheme 2 below were synthesized in the following manner.

[0146] [Reaction Equation 2]

[0147]

[0149] Synthesis of Compound 3

[0150] 5 g (34.68 mmol, 1 eq) of 3,4-dimethoxythiophene and 10.9 g (41.61 mmol, 1.2 eq) of 2,2-bis(bromomethyl)-1,3-propanediol were dissolved in 200 mL of toluene with 500 mg of p-toluenesulfonic acid. The mixture was refluxed at 120°C, and the methanol produced by the transetherification of the reactants was removed using a Type 4A molecular sieve packed with a Soxhlet extractor. After refluxing for 24 hours, the mixture was quenched with water, extracted with ethyl acetate, washed with brine, and dried over MgSO4. The solvent was evaporated using a rotary evaporator, and the residue was purified by column chromatography with a methylene chloride / hexane (1:2) elution to obtain the target product (DBrProDOT).

[0151] 2.924 g (60% with oil, 73.09 mmol, 5.0 eq) of NaH was placed in a 250 mL round-bottom flask, vacuum-purged, and then filled with argon three times. 100 mL of anhydrous dimethylformamide (anhydrous DMF) was added at 0°C, and the cooled solution was stirred at room temperature for 2 hours. 4.19 g (32.164 mmol, 2.2 eq) of 2-ethylhexanol was dissolved in 20 mL of dimethylformamide (DMF), and after adding it dropwise to the NaH solution, the mixture was stirred at room temperature for 6 hours. A mixture in which 5 g (14.62 mmol, 1 eq) of the obtained target product (DBrProDOT) was dissolved in 20 mL of dimethylformamide (DMF) was added to the stirred solution. The prepared solution was refluxed at 80°C for 24 hours, cooled to room temperature, quenched with 1N HCl dropwise, and extracted three times with diethyl ether. The organic layer was washed with 1N HCl and brine, dried over MgSO4, and then evaporated under vacuum. The residue was purified by column chromatography with a methylene chloride / hexane (1:4) elution to obtain the target product (Compound 3). Figure 3 shows the target product. 1 This is the H-NMR spectrum.

[0153] Synthesis of Compound 4

[0154] 5 g (11.35 mmol, 1 eq) of Compound 3 was dissolved in chloroform and stirred with 5.615 g (24.96 mmol, 2.2 eq) of n-iodosuccinimide and a few drops of acetic acid. The mixture was quenched with deionized water and washed with sodium thiosulfate to remove excess iodine, then dried over MgSO4 and evaporated under vacuum. The residue was purified by column chromatography with a methylene chloride / hexane (1:8) elution to obtain the target product (Compound 4). FIG. 4 shows the target product. 1 This is the H-NMR spectrum.

[0156] Example 1.

[0157] A polymer was synthesized using compounds 1 and 2 prepared in Synthesis Examples 1 and 2. The compounds were dissolved in bromotrichloromethane (CBrCl3), a solvent, at a molar ratio of 1:2 (compound 1:compound 2), and polymerization was initiated by irradiating the solution with LED light of 365 nm (Step 1). The solvent was used after purging with argon. After confirming that most of the monomers (compounds 1 and 2) were consumed, 2.0 mmol of I2 and a few drops of HClO4 were added, and the light source was changed to a q-switched pulsed laser of 532 nm (2 mJ / cm2, 10 Hz) to continue the polymerization (Step 2). During the reaction, aliquots were taken at regular intervals, and UV-vis absorbance was measured after diluting with chloroform. The above partial sample was also rinsed with sodium thiosulfate (Na2S2O3) and dedoped with hydrazine (N2H4) to obtain a neutralized polymer product after removing separate iodine molecules, and dissolved in chloroform to perform UV-vis absorbance and GPC (Gel Permeation Chromatograph) analysis.

[0158] Figure 5 is a UV-vis absorbance spectrum confirmed while performing the first step of Example 1 above, and Figure 6 is a GPC analysis result confirmed while performing the first step above.

[0159] In Figure 5, the absorbance of a partial sample according to the irradiation time (0, 24, 48, and 72 hours) of the 365 nm wavelength LED light source of the first stage is shown as a bold line, and the absorbance of a partial sample that has undergone de-doping by I2 washing is also shown as a dotted line for each time period (24, 48, and 72 hours).

[0160] Looking at the solid line in Fig. 5, the main absorption of the partial sample is observed in the range of 600 to 1,000 nm, and it can be seen that as the irradiation time of the LED light source increases, the main absorption peak shifts to the long wavelength region. This indicates that the conjugated length gradually increases as the first stage progresses. In the case of the dedoped sample (dotted line), as the irradiation time of the LED light increases, absorption shifting to the long wavelength region while vibrating in the range of 400 to 600 nm was also observed. In particular, the shoulder peak observed near 570 nm indicates enhanced intermolecular π-π* transitions of the product with a higher molecular weight. The trend shown in Fig. 5 is also consistent with the GPC analysis results (Fig. 6). As shown in Fig. 6, the retention time in GPC analysis decreases as the UV irradiation (LED light irradiation) time increases, and it demonstrates that the molecular weight of the polymer (polymer) increases with the consumption of the monomer (Compound 1). After 72 hours of LED light irradiation, the number-average molecular weight (Mn) of the product (conductive polymer) was approximately 2,200 g / mol, and the molecular weight distribution (PDI) was approximately 1.20. The photograph in Fig. 6 shows the precipitate of the high molecular weight component generated as polymerization proceeded. Meanwhile, Fig. 10 shows the polymer formed in Example 1 1 The H-NMR spectrum (blue line) is shown.

[0162] Example 2.

[0163] A polymer was synthesized in the same manner as in Example 1, except that compounds 3 and 4 prepared in Synthesis Examples 3 and 4 were used (the molar ratio of compounds 3 and 4 was 1:2 (compound 4:compound 3)). Fig. 7 is the UV-vis spectrum observed in the first step of the above process, and Fig. 8 is the GPC spectrum. As shown in Figs. 7 and 8, the behavior of the UV-vis spectrum and GPC spectrum in the first step of the above process was similar to that of Example 1. However, in the case of Example 2, no precipitate was formed due to the bulky side chains (diethylhexyl methoxy) of compounds 3 and 4. Fig. 9 is the GPC spectrum in the second step of the above process (532 nm pulsed laser irradiation). From Fig. 9, it can be seen that the number-average molecular weight, initially at approximately 3,000 g / mol, significantly increased to about 29,500 g / mol (molecular weight distribution: 1.35) after 12 hours of pulsed laser irradiation. Meanwhile, Fig. 10 shows the polymer formed in Example 2. 1 The H-NMR spectrum (green line) is shown.

[0165] Examples 3 to 5.

[0166] Using Compound 2 prepared in Synthesis Example 2 and Compound 3 prepared in Synthesis Example 3, polymerization was carried out in the same manner as in Example 1 while varying the ratios. The ratios were controlled to 1:2 (Compound 2:Compound 3, Example 3), 1:4 (Compound 2:Compound 3, Example 4), and 1:6 (Compound 2:Compound 3, Example 5), respectively. Figures 11 to 13 are UV-vis spectra confirmed during the first step of Examples 3 to 5, respectively, and it can be confirmed that they exhibit the same trend as in Example 1.

[0167] FIG. 14 shows the polymers synthesized in Examples 3 to 5. 1 The H-NMR spectrum is shown.

[0168] Figure 15 is a GPC spectrum confirmed as the second step of Example 3 proceeds, and it can be seen that the molecular weight shows a tendency to increase as the irradiation time of the 532 nm pulsed laser increases. That is, looking at Figure 15, at the start of the second step, the number average molecular weight was approximately 2,800 g / mol (molecular weight distribution: about 1.2), but as the second step proceeds, it can be seen that the number average molecular weight increases to about 27,000 g / mol (molecular weight distribution: 1.25).

Claims

Claim 1 A method for preparing a polymer comprising the step of irradiating light onto a mixture comprising a solvent that does not contain hydrogen atoms and a compound of the following chemical formula 1: [Chemical Formula 1] In Chemical Formula 1, R1 and R2 are each independently hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkyl carbonyl group, an aryl carbonyl group, an aryl carbonyloxy group, an alkyl carbonyloxy group, a carboxyl group, or an aryl group, or are connected to each other to form a ring structure, and R3 and R4 are each independently hydrogen, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, or an aryl group, and at least one of R3 and R4 is a halogen atom. Claim 2 A method for preparing a polymer according to claim 1, wherein the solvent not containing hydrogen atoms is bromotrichloromethane (CBrCl3), tetrachloromethane (CCl4), or dibromodichloromethane (CBr2Cl2). Claim 3 A method for manufacturing a polymer according to claim 1, wherein the mixture does not contain a solvent having hydrogen atoms. Claim 4 A method for preparing a polymer comprising: a first step of irradiating a mixture comprising a solvent and a compound of Chemical Formula 1 below with light having a wavelength of 450 nm or less, and a second step of irradiating light by changing the wavelength of the irradiated light to greater than 450 nm: [Chemical Formula 1] In Chemical Formula 1, R1 and R2 are each independently hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkyl carbonyl group, an aryl carbonyl group, an aryl carbonyloxy group, an alkyl carbonyloxy group, a carboxyl group, or an aryl group, or are connected to each other to form a ring structure, and R3 and R4 are each independently hydrogen, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, or an aryl group, and at least one of R3 and R4 is a halogen atom. Claim 5 A method for manufacturing a polymer, wherein the solvent in claim 4 is a solvent that does not contain hydrogen atoms. Claim 6 In claim 4, a method for manufacturing a polymer in which the mixture does not contain a solvent having hydrogen atoms. Claim 7 A method for manufacturing a polymer according to claim 4, wherein a halogen source is additionally supplied between the first and second steps. Claim 8 A method for manufacturing a polymer in which the light irradiated in the second step is irradiated with a pulsed light source, in claim 4. Claim 9 A method for preparing a polymer according to claim 1 or 4, wherein at least one of R1 and R2 of Formula 1 is a substituent comprising an oxygen atom. Claim 10 A method for manufacturing a polymer comprising oxygen atoms, wherein the ring structure formed by connecting R1 and R2 of Formula 1 in claim 1 or 4. Claim 11 A method for preparing a polymer in which R3 and R4 of Chemical Formula 1 are halogen atoms, in claim 1. Claim 12 A method for preparing a polymer according to claim 1 or 4, wherein the compound of Formula 1 has the structure of Formula 2 below: [Formula 2] In Chemical Formula 2, R3 and R4 are each independently hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkyl carbonyl group, an aryl carbonyl group, or an aryl group, or are connected to each other to form a ring structure, and R1 and R2 are each independently hydrogen, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, or an aryl group, and at least one of R1 and R2 is a halogen atom. Claim 13 A method for preparing a polymer represented by the following chemical formula 3, wherein the compound of chemical formula 1 is the compound of chemical formula 1: [Chemical formula 3] In Chemical Formula 3, R3 and R4 are halogen atoms, and L is a divalent chain having 3 to 7 chain-forming atoms. Claim 14 In claim 13, a method for manufacturing a polymer in which the divalent chain comprises carbon atoms and oxygen atoms. Claim 15 A method for preparing a polymer represented by the following chemical formula 4 or 5, wherein the compound of chemical formula 1 is the compound of chemical formula 1: [Chemical formula 4] [Chemical Formula 5] In chemical formula 4 or 5, R3 and R4 are each independently hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkyl carbonyl group, an aryl carbonyl group, an aryl carbonyloxy group, an alkyl carbonyloxy group, a carboxyl group, or an aryl group, R1 and R2 are each independently hydrogen, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, or an aryl group, at least one of R1 and R2 is a halogen atom, and m is a number within the range of 1 to 4. Claim 16 A method for preparing a polymer according to claim 1 or 4, wherein the compound further comprises a compound represented by the following chemical formula 6: [Chemical Formula 6] In Chemical Formula 6, R1 and R2 are each independently hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkyl carbonyl group, an aryl carbonyl group, an aryl carbonyloxy group, an alkyl carbonyloxy group, a carboxyl group, or an aryl group, or are connected to each other to form a ring structure, and R3 and R4 are each independently hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, or an aryl group. Claim 17 A method for preparing a polymer according to claim 16, wherein the ratio (Halo / (Halo+H)) of the number of moles of halogen atoms (Halo) contained in R3 and R4 of Formula 1 and the number of moles of hydrogen atoms (H) contained in R3 and R4 of the compound of Formula 6 is within the range of 0.001 to 99. Claim 18 A polymer dispersion comprising a polymer unit of the following chemical formula 11, a number average molecular weight of 2,000 g / mol or more, a solvent, and a polymer dispersion comprising an oxidizing agent and a transition metal ligand catalyst component in a ratio of 1 wt% or less: [Chemical Formula 11] In Chemical Formula 11, R1 and R2 are each independently hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkyl carbonyl group, an aryl carbonyl group, an aryl carbonyloxy group, an alkyl carbonyloxy group, a carboxyl group, or an aryl group, or are connected to each other to form a ring structure, and n is any number. Claim 19 In claim 18, the polymer is represented by Chemical Formula 11, wherein the polymer dispersion comprises two or more different polymerization units, R1 and R2 of Chemical Formula 11. Claim 20 In claim 18, a polymer dispersion in which n in Chemical Formula 11 is in the range of 4 to 200. Claim 21 In claim 18, a polymer dispersion having a molecular weight distribution of 1.5 or less. Claim 22 delete

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