WO2015174591A1 - High-density sulfonated multiblock polymer and electrochemical system comprising same - Google Patents

Abstract

The present invention relates to a method for preparing a multiblock copolymer, the method comprising the steps of: (A) dissolving a hydrophobic oligomer in a first solvent to obtain a first solution; (B) dissolving a hydrophilic oligomer in a second solvent to obtain a second solution; and (C) bringing the first solution and the second solution into contact with each other, to an electrolyte membrane for an electrochemical battery, containing the multiblock copolymer thus prepared, and to an electrochemical battery comprising the same. The method for preparing a multiblock copolymer according to the present invention has advantages of: increasing the molecular weight, ion-exchange capacity, and yield of the copolymer; improving the uniformity of the molecular weight; having improved proton ion conductivity under a low-humidity condition; and obtaining very improved proton ion conductivity in all humidity regions, compared with the conventional commercial fluorinated electrolyte membrane.

Description

High density sulfonated multiblock type polymer and electrochemical system including the same

The present invention relates to a high density sulfonated multiblock type polymer and an electrochemical system including the same.

Efforts have recently been made to improve the long-term performance of electrolyte membranes, a key component of fuel cells. High ionic conductivity at low humidity is a very important factor for improving price performance and improving performance.

Of the various types of electrolyte membranes, perfluorinated electrolyte membranes are very expensive (800 $ / m ² ) due to complex manufacturing processes, despite the superior mechanical strength and electrochemical properties, and low glass transition temperatures due to fluorinated structures. It works as a disadvantage.

As an alternative to the perfluorinated electrolyte membrane, the development of a hydrocarbon polymer has been actively carried out. The hydrocarbon polymer electrolyte membrane shows a very high ion conductivity in the high humidity region, but shows a tendency of very low ion conductivity in the low humidity region. Compared to the perfluorinated electrolyte membrane, it is known that the rate of water migration is slow due to the low phase separation between the hydrophilic and hydrophobic components containing sulfonic acid groups, and the concentration of protons dissociated is low due to the acidity of the sulfonic acid groups. In order to overcome this problem, recently, a multiblock polymer having a hydrophilic block and a hydrophobic block has been synthesized to achieve high ionic conductivity.

In addition, it is important to have high ion conductivity at low humidity to improve the performance of the fuel cell while maintaining the price competitiveness. Recently, development of (multi) block hydrocarbon polymers capable of competing with Nafion, a commercially available fluorine polymer, has been actively conducted. Such a multiblock polymer has a structure in which hydrophilic blocks and hydrophobic blocks are alternately connected.

Among them, the chemical structure and ionicity of the hydrophilic block into which the sulfonic acid group is introduced play a decisive role in improving the ionic conductivity, and if possible, the development of a hydrophilic block having a high ion exchange capacity (Ion Exchange Capacity, IEC) is required.

In the case of synthesizing block polymers using a hydrophilic block having such a very high IEC, it has been pointed out that synthesis of high molecular weight block polymers due to the poor solubility of the hydrophilic block. To date, no success of block polymers containing very high IEC has been reported. In this patent, a method of increasing the solubility of hydrophilic oligomers has been introduced to obtain a high molecular weight block polymer.

Accordingly, the present invention is to provide a sulfonic acid multiblock type polymer having a high density of the sulfonic acid group of the hydrophilic block has an improved ion conductivity, in particular a very high molecular weight, an electrochemical system including the same and a method for producing the same.

One aspect of the invention is (A) dissolving hydrophobic oligomer in a first solvent to obtain a first solution, (B) dissolving hydrophilic oligomer in a second solvent to obtain a second solution, (C) agent It relates to a method for producing a multiblock copolymer comprising the step of contacting the first solution and the second solution.

Another aspect of the invention relates to an electrolyte membrane for an electrochemical system comprising a multiblock copolymer prepared according to various embodiments of the invention.

Another aspect of the invention relates to an electrochemical system comprising a multiblock copolymer prepared according to various embodiments of the invention.

According to the method for producing a multiblock copolymer according to the present invention, not only the molecular weight and ion exchange capacity and the yield of the copolymer can be improved, but also the molecular weight uniformity can be improved.

In addition, the multiblock copolymer according to the present invention has improved proton ion conductivity under low-humidity conditions, and can obtain a very improved effect of proton ion conductivity in the full-humidity region compared with the conventional fluorinated commercial electrolyte membrane.

1 shows the GPC results of the multiblock copolymer prepared in Example 1a.

Figure 2 shows the NMR results of the multiblock copolymer prepared in Example 1a.

Figure 3 shows the GPC results of the multiblock copolymer prepared in Example 1b.

Figure 4 shows the NMR results of the multiblock copolymer prepared in Example 1b.

Figure 5 shows the humidity dependence of the proton conductivity measured at 80 ℃. Here, Δ and □ are data of the multiblock copolymers prepared in Examples 1a and 1b, respectively, and ○ and ▽ show data of Aquivion and NRE 212, which are commercially available polymers.

One aspect of the invention is (A) dissolving hydrophobic oligomer in a first solvent to obtain a first solution, (B) dissolving hydrophilic oligomer in a second solvent to obtain a second solution, (C) agent It relates to a method for producing a multiblock copolymer comprising the step of contacting the first solution and the second solution.

Typically, in order to prepare a block copolymer, polymerization is carried out by adding a hydrophilic oligomer and a hydrophobic oligomer to the same solvent. When the multiblock copolymer of the present invention is polymerized in the same solvent, the molecular weight is increased. There is a limit. Therefore, in the present invention, it was confirmed that the multiblock copolymer can be obtained at a high molecular weight by dissolving each other in different solvents as described above and contacting them with the above configuration.

According to one embodiment, step (C) may be performed by adding a second solution to the first solution. In the case where phase separation occurs between the first solution and the second solution, the second solution in which the hydrophilic oligomer is dissolved in the first solution in which the hydrophobic oligomer is dissolved has an ion exchange capacity (IEC) value. This is because a largely increased multiblock copolymer can be synthesized.

According to another embodiment, the dosing can be performed by dropwise addition. As such, it was confirmed that by dropwise addition, the amount of precipitated in the solution can be reduced, and the amount of unreacted oligomer can be reduced as compared with the case where the amount of unreacted oligomer can be increased, thereby increasing the obtainable polymer yield.

According to another embodiment, the dosing can be performed by adding dropwise at the same time interval. As such, it was confirmed that a multiblock copolymer having a uniform molecular weight could be obtained by maintaining the same time interval of dropwise dropping.

According to another embodiment, the first solvent may be selected from dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), DMF, NMP, diphenylsulfone, chlorobenzene and a mixture of two or more thereof. Of these, the use of dimethylacetamide (DMAc) is advantageous over other solvents in terms of dissolving hydrophobic oligomers.

According to another embodiment, the second solvent may be selected from dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), DMF, NMP, diphenylsulfone, chlorobenzene and a mixture of two or more thereof. Of these, the use of dimethyl sulfoxide (DMSO) is advantageous over other solvents in terms of dissolving hydrophilic oligomers.

According to another embodiment, a mixed solvent in which DMAc and DMSO are mixed at a volume ratio of 100: 0.5 to 5 is used as the first solvent, and a mixture of DMSO and DMac is mixed at a volume ratio of 100: 0.5 to 5 as the second solvent. Solvent is used. In the case of using such a mixed solvent, compared with the case of using a single solvent, it was confirmed that the molecular weight is greatly increased and the thermal and mechanical properties of the block copolymer are greatly improved.

According to another embodiment, the hydrophobic oligomer has a structure of Formula 1, the hydrophilic oligomer has a structure of Formula 2 or Formula 3, the multiblock copolymer has a structure of Formula 4.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

In this case, P is one selected from H, K, Na, Si (CH ₃ ) ₃ ; Q is one selected from F, Cl, and NO ₂ ; R is an inorganic cation selected from H, K, Li, Na, Rb, Cs or N ⁺ R ₁ R ₂ R ₃ R ₄ (ammonium), P ⁺ R ₁ R ₂ R ₃ R ₄ (phosphonium), N ⁺ NR ₁ R ₂ R ₃ R ₄ R ₅ (imidazorium), NH ⁺ R ₁ R ₂ R ₃ R ₄ R ₅ (pyridinium), pyrrolidium, sulfonium; X and Y are each a number in the range of 5-50; N is an integer from 2 to 50.

R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ are the same as or different from each other, and each independently a C ₁ to C ₇ linear or branched alkyl group. Examples of such alkyl include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the like.

In addition, the above R ₁ , R ₂ , R ₃ , R ₄ are the same as or different from each other, and each independently a linear or branched aromatic. Examples of such aromatics include, but are not limited to, benzyl, phenyl, biphenyl, and the like.

In addition, the above R ₁ , R ₂ , R ₃ , R ₄ may be the same or different from each other, and each independently may contain a C ₁ to C ₇ linear or branched alkyl group and aromatic at the same time.

In particular, when using R as the organic cation, the molecular weight and polydispersity index (PDI) can be improved, and it was confirmed that the inorganic cation is preferable.

As mentioned above, in the polymerization of the hydrophobic oligomer and the hydrophilic oligomer, higher molecular weights can be obtained when the polymerization is performed by dissolving in different solvents, respectively, as compared with polymerization in the same solvent.

In particular, in the case of preparing the multi-block copolymer of the above structure through the hydrophobic oligomer and hydrophilic oligomer of the structure as described above, in addition to the high molecular weight can be obtained, even if the time interval of drop-by-dropping does not necessarily keep the same It was further confirmed that there is another advantage of obtaining a multiblock copolymer of uniform molecular weight.

According to another embodiment, the step (A) may be carried out by further adding a catalyst to the first solvent, wherein the catalyst which may be used is potassium carbonate, NaOH, KOH, CsF and mixtures of two or more thereof. . As described above, by further adding a catalyst to prepare a hydrophobic oligomer solution, it was confirmed that the molecular weight can be further increased compared to the other case.

According to another embodiment, the step (A) may be carried out by further adding a catalyst to the second solvent, wherein the catalyst that may be used is potassium carbonate, NaOH, KOH, CsF and mixtures of two or more thereof. . As described above, by further adding a catalyst to prepare a hydrophilic oligomer solution, it was confirmed that the molecular weight can be further increased compared to the case.

In particular, when the above catalyst is used to prepare both the hydrophilic oligomer and the hydrophobic oligomer, unlike the case where the catalyst is used in only one case, the molecular weight of the polymerized multiblock copolymer becomes more uniform and thus the polydipersity index , PDI) was significantly lowered.

According to another embodiment, the dosage of the catalyst is preferably adjusted to 0.1 to 10 mmol per 10 mL of the first solvent. When the catalyst input amount is less than the lower limit of the following range, even if the catalyst input amount is increased, there is no effect of increasing the molecular weight. When the catalyst input amount is exceeded, the catalyst is increased within the above range because the molecular weight decreases. It is preferable to add.

According to another embodiment, when an excess calcium carbonate is added to the above catalyst when preparing a block copolymer from hydrophilic oligomer and hydrophobic oligomer, the molecular weight of the polymerized multiblock copolymer becomes more uniform and thus the polydispersity index ( polydipersity index, PDI) was found to be significantly lower. This is because calcium carbonate converts HF, a by-product of the reaction, into insoluble Ca ₂ F, thereby inhibiting the decomposition reaction. At this time, potassium carbonate is preferably added in 5 to 100 times the amount of the catalyst in a molar ratio.

Another aspect of the present invention relates to an electrolyte membrane for an electrochemical cell including a multiblock copolymer prepared according to various embodiments of the present invention.

Another aspect of the invention relates to an electrochemical cell comprising a multiblock copolymer prepared according to various embodiments of the invention.

Examples of electrochemical cells to which the present invention may be applied include, but are not limited to, a fuel cell, a battery, a redox flow battery, a direct methanol fuel cell, a metal / air rechargeable battery, and the like.

Hereinafter, various embodiments of the present invention will be described in more detail.

The hydrophilic oligomer portion (hydrophilic segment) of the present invention has an extremely high hydrophilicity since it has a high density of sulfonic acid group concentration.

Due to such extremely high hydrophilicity, hydrophilic and hydrophobic segment precursors are respectively purified and synthesized, and in particular, hydrophilic segment precursors are purified using an improved purification method such as dialysis. In addition, this improved purification method allows the synthesis of high molecular weight block copolymers.

In addition, the high partial ion exchange capacity of the hydrophilic segment enables the synthesis of sulfonated multiblock polymers showing high ion conductivity.

As a result, it has an improved proton ion conductivity under low-humidity conditions, and shows better proton ion conductivity in the entire humidity range than the conventional fluorinated commercial electrolyte membrane.

That is, one embodiment of the present invention relates to a sulfonated polymer electrolyte showing a high ion conductivity and a method for manufacturing the same, and to produce a multiblock copolymer showing a high ion conductivity, a hydrophilic segment block having a very high concentration of sulfonic acid groups. Should be used.

These hydrophilic segments include sulfonated polysulfones, sulfonated polyether ketones, sulfonated poly (para-) phenylenes, sulfonated polyimides, sulfonated polybenzimidazoles, mainly as sulfonated polyether sulfones as shown in the examples. You can choose from.

In addition, the molecular weight of the hydrophilic oligomer usable in the present invention may be 2,000 to 100,000 Da, has a very high ion exchange capacity, and is characterized by having a halogen terminal (-F, -Cl).

On the other hand, the hydrophobic oligomer can be selected from polyether ketone, sulfonated polysulfone, sulfonated polyacetal, sulfonated poly (p-phenylene), sulfonated polyimide, sulfonated polybenzimidazole, etc. in addition to the structures shown in the examples. In addition, the use of partially fluorinated hydrophobic oligomers is also preferred and has a halogen terminal or a hydroxyl group terminal.

Polymerization using sulfonated oligomers as precursors facilitates the control of ion exchange capacity and the synthesis of high molecular weight multiblock copolymers due to high purity.

Hereinafter, the present invention will be described in more detail with reference to examples and the like, but the scope and contents of the present invention are not limited or interpreted by the following examples. Moreover, it is clear that a person skilled in the art can easily carry out the present invention, in which no experimental results are specifically presented, based on the disclosure of the present invention including the following examples.

Example

Preparation Example 1a: Synthesis of High Ion Conductive Hydrophilic Precursor Oligomer (1)

[Scheme 1]

In a 100 mL three-necked flask, a condenser connected to a cooling water and a mechanical stirrer were connected and purged with nitrogen. Pre-dried sodium 3,3`-disulfonated-4,4`-difluorodiphenyl sulfone (8.0 mmol, 3.67 g), potassium hydroquinone sulfonate (7.3 mmol, 1.66 g), potassium carbonate (8.7 mmol, 1.21 g), DMSO 16 mL was added to the above three-neck flask and reacted at 130 ° C. The reaction was monitored by GPC in 1 hour increments and maintained in the same state until reaching the desired molecular weight, and the reaction was terminated after about 24 hours.

10 g of celite was added to the solution to which the reaction was completed, followed by stirring for 1 hour. The solution was purified by permeation with a membrane filter to obtain a solution from which the precipitate was removed. This solution was dropped dropwise into 500 mL isopropyl alcohol to obtain a precipitate, and then filtered through a membrane filter to obtain a hydrophilic precursor oligomer as a precipitate.

The precipitate thus obtained was completely dissolved in 100 mL of ultrapure water and dialyzed with a 1,000 kDa dialysis network. The salinity of the external aqueous solution was continuously measured during dialysis, and the external aqueous solution was continuously exchanged until the salinity no longer increased. When the salinity of the external aqueous solution no longer increased, the solution in the dialysis membrane was dried with a reduced pressure evaporator, and the resulting high ion conductivity hydrophilic precursor oligomer was dried completely through vacuum drying.

Preparation Example 1b: Synthesis of High Ion Conductive Hydrophilic Precursor Oligomer (2)

[Scheme 2]

In a 100 mL three-necked flask, a condenser connected to a cooling water and a mechanical stirrer were connected and purged with nitrogen. Pre-dried sodium 3,3`-disulfonated-4,4`-difluorodiphenyl sulfone (3.1 mmol, 1.41 g), disodium 3,6-dihydroxynaphthalene-2,7-disulphonate (2.8 mmol, 1.02 g), potassium carbonate (3.4 mmol, 0.47 g) and 6 mL of DMSO were added to the three neck flask and reacted at 130 ° C. The reaction was monitored by GPC in 1 hour increments and maintained in the same state until reaching the desired molecular weight, and the reaction was terminated after about 24 hours.

10 g of celite was added to the solution containing the above reaction and stirred for 1 hour. The solution was purified by permeation with a membrane filter to obtain a solution from which the precipitate was removed. This solution was dropped dropwise into 500 mL isopropyl alcohol to obtain a precipitate, and then filtered through a membrane filter to obtain a hydrophilic precursor oligomer as a precipitate.

The precipitate thus obtained was completely dissolved in 100 mL of ultrapure water and dialyzed with a 1,000 kDa dialysis network. The salinity of the external aqueous solution was continuously measured during dialysis, and the external aqueous solution was continuously exchanged until the salinity no longer increased. When the salinity of the external aqueous solution no longer increased, the solution in the dialysis membrane was dried with a reduced pressure evaporator, and the obtained hydrophilic precursor oligomer showing high ion conductivity was dried completely through vacuum drying.

Preparation Example 1c: Synthesis of Hydrophobic Precursor Oligomer

Scheme 3

In a 100 mL three-necked flask, a condenser connected to a cooling water and a mechanical stirrer were connected and purged with nitrogen. Pre-dried bis (4-fluorophenyl) sulfone (14.4 mmol, 3.67 g), 4,4'-dihydroxy biphenyl (15.9 mmol, 2.95 g), potassium carbonate (19.0 mmol, 2.63 g) and 28 mL DMAc Put into a three-neck flask of the reaction at 120 ℃. Monitored by GPC in 30 minutes, the same state until the desired molecular weight was maintained and the reaction was terminated after about 2 hours.

10 g of celite was added to the solution to which the reaction was completed, followed by stirring for 1 hour. The solution was purified by permeation with a membrane filter to obtain a solution from which the precipitate was removed. The solution was dropped in methanol dropwise to obtain a precipitate, which was then filtered through a membrane filter to obtain a precipitate.

The obtained precipitate thus obtained was once more rinsed in methanol, filtered through a membrane filter to obtain a hydrophobic precursor oligomer, and then dried completely by vacuum drying.

Example 1a: Multiblock Copolymerization Polymerization

[Scheme 4]

In a 100 mL three-necked flask, a condenser connected to a cooling water and a mechanical stirrer were connected and purged with nitrogen. The hydrophilic precursor oligomer (0.1 mmol, 0.76 g) of the above-prepared Example 1a was dissolved in 2.5 mL of DMSO to obtain a hydrophilic oligomer solution. Similarly, the hydrophobic precursor oligomer (0.1 mmol, 0.42 g of the above-prepared Example 1c) was dried. ) Was dissolved in 1.5 mL of DMAc to prepare a hydrophobic oligomer solution. Two solutions thus obtained were simultaneously injected into the three-necked flask and potassium carbonate (1 mmol, 0.14 g) was added to polymerize at 130 ° C. After the reaction was completed by dropping the solution dropwise in water to obtain a precipitate, and filtered with a membrane filter to obtain a precipitate only. The precipitate thus obtained was completely dried by vacuum drying.

GPC results and NMR results of the multiblock copolymer thus prepared are shown in FIGS. 1 and 2, respectively. In addition, Figure 5 shows the humidity dependence of the proton conductivity measured at 80 ℃.

Example 1b: Multiblock Copolymerization Polymerization

[Scheme 5]

In a 100 mL three-necked flask, a condenser connected to a cooling water and a mechanical stirrer were connected and purged with nitrogen. The hydrophilic precursor oligomer (0.1 mmol, 0.608 g) of the above-prepared Example 1b was dissolved in 2.5 mL of DMSO to obtain a hydrophilic oligomer solution. Similarly, the hydrophobic precursor oligomer (0.1 mmol, 0.54 g of the above-prepared Example 1c) was obtained. ) Was dissolved in 1.5 mL of DMAc to prepare a hydrophobic oligomer solution. Two solutions thus obtained were simultaneously injected into the three-necked flask and potassium carbonate (1 mmol, 0.14 g) was added to polymerize at 130 ° C. Otherwise, the experiment was performed under the conditions according to Example 1a. After the reaction was completed by dropping the solution dropwise in water to obtain a precipitate, and filtered with a membrane filter to obtain a precipitate only. The precipitate thus obtained was completely dried by vacuum drying.

The GPC and NMR results of the multiblock copolymer thus prepared are shown in FIGS. 3 and 4, respectively. In addition, Figure 5 shows the humidity dependence of the proton conductivity measured at 80 ℃.

Example 2: Multiblock Copolymerization

Instead of simultaneously injecting the hydrophobic oligomer solution and the hydrophilic oligomer solution into the three-necked flask, the hydrophobic oligomer was first dissolved together with the catalyst in the three-necked flask, and the hydrophilic oligomer solution was slowly injected to increase the molecular weight without causing precipitation. Except, the experiment was conducted in the same manner as in Example 1a. As a result, the ion exchange capacity (IEC) was measured at 3.2 meq / g, it was confirmed that compared with Example 1a above.

Example 3: Multiblock Copolymerization

The hydrophilic oligomer solution was dropped dropwise into the hydrophobic oligomer solution, but the polymerization was conducted in the same manner as in Example 2 except that the polymerization was performed by uniformly adding the injection interval within the range of 1 to 3 seconds. As a result, the dry mass of the finally obtained copolymer was measured to be 0.94 g, which was further increased to 0.83 g of Example 2.

Example 4: Multiblock Copolymerization Polymerization

The hydrophilic oligomer solution was dropped drop by drop into the hydrophobic oligomer solution, but the polymerization was conducted in the same manner as in Example 3 except that the polymerization was performed by uniformly adding the input interval to 1 second. As a result, the polydispersity index (PDI) of the finally obtained copolymer was observed to be lower than that of Example 3, confirming that the obtained polymer molecular weight became more uniform.

Example 5: Multiblock Copolymerization Polymerization

The experiment was conducted in the same manner as in Example 4, except that calcium carbonate was further added in a ratio of 10 mmol per mmol of potassium carbonate to prepare a hydrophobic oligomeric solution. As a result, the number average molecular weight of the finally obtained copolymer was observed to be 193 kDa, confirming that the molecular weight increased compared with 151 kDa of Example 4.

Example 7: Multiblock Copolymerization Polymerization

The experiment was carried out in the same manner as in Example 4 except that calcium carbonate was further added in a ratio of 10 mmol per mmol of the solution to prepare a hydrophilic oligomer solution. As a result, the number average molecular weight of the finally obtained copolymer was observed to be 365 kDa, confirming that the molecular weight increased significantly compared with 151 kDa of Example 4.

Comparative Example 1: Multiblock Copolymer One-Pod Polymerization (1)

In a 100 mL three-necked flask, a condenser connected to a cooling water and a mechanical stirrer were connected and purged with nitrogen. The hydrophilic precursor oligomer (0.1 mmol, 0.76 g) of Preparation Example 1a above and the hydrophobic precursor oligomer (0.1 mmol, 0.41 g) of Preparation Example 1c were previously dried prior to polymerization, followed by potassium carbonate (1.0 mmol, 0.14 g). 5 mL of a single solvent DMSO was placed in a three-necked flask and polymerized at 130 ° C. The reaction was monitored by GPC in 1 hour increments and maintained in the same state until reaching the desired molecular weight, and the reaction was terminated after about 24 hours. After the reaction was completed by dropping the solution dropwise in water to obtain a precipitate, and filtered with a membrane filter to obtain a precipitate only. The precipitate thus obtained was completely dried by vacuum drying. As a result, it was confirmed that the number average molecular weight of the final obtained copolymer was only about 10% level compared with Example 1.

Comparative Example 2: Multiblock Copolymer One-Pod Polymerization (2)

The experiment was conducted in the same manner as in Comparative Example 1 except that a single solvent DMAc instead of a single solvent DMSO was used. As a result, it was confirmed that the number average molecular weight of the final obtained copolymer was only about 10% level compared with Example 1.

Claims (21)

1. (A) dissolving hydrophobic oligomer in a first solvent to obtain a first solution,

   (B) dissolving the hydrophilic oligomer in a second solvent to obtain a second solution,

   (C) a method for producing a multiblock copolymer comprising contacting a first solution with a second solution.
2. The method of claim 1, wherein step (C) is performed by adding a second solution to the first solution.
3. The method according to claim 2, wherein the dosing is carried out by dropwise addition.
4. The method according to claim 3, wherein the dosing is performed by dropwise addition at the same time intervals.
5. The method of claim 1, wherein the first solvent is selected from dimethyl acetamide (DMAc), dimethyl sulfoxide (DMSO), DMF, NMP, diphenyl sulfone, chlorobenzene and a mixture of two or more thereof. Copolymer production method.
6. The method of claim 1, wherein the second solvent is selected from dimethyl acetamide (DMAc), dimethyl sulfoxide (DMSO), DMF, NMP, diphenyl sulfone, chlorobenzene and a mixture of two or more thereof. Copolymer production method.
7. The method of claim 1, wherein the hydrophobic oligomer has the structure of Formula 1:

   [Formula 1]

   

   The hydrophilic oligomer has the structure of Formula 2 or Formula 3:

   [Formula 2]

   

   [Formula 3]

   

   The multiblock copolymer has the structure of formula 4:

   [Formula 4]

   

   P is one selected from H, K, Na, and Si (CH ₃ ) ₃ ;

   Q is one selected from F, Cl, and NO ₂ ;

   R is an inorganic cation selected from H, K, Li, Na, Rb, Cs or N ⁺ R ₁ R ₂ R ₃ R ₄ (ammonium), P ⁺ R ₁ R ₂ R ₃ R ₄ (phosphonium), N ⁺ NR ₁ R ₂ R ₃ R ₄ R ₅ (imidazorium), NH ⁺ R ₁ R ₂ R ₃ R ₄ R ₅ (pyridinium), pyrrolidium, sulfonium;

   X and Y are each a number in the range of 5-50;

   N is an integer from 2 to 50;

   Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ are the same as or different from each other, each independently a C ₁ to C ₇ multi-block copolymer production method characterized in that the linear or branched alkyl group.
8. According to claim 7, The alkyl group is multi-block air, characterized in that selected from methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert- butyl group Incorporation method.
9. The method according to claim 8, wherein R ₁ , R ₂ , R ₃ , R ₄ are the same as or different from each other, and each independently a linear or branched aromatic group;

   The aromatic group is a method for producing a multiblock copolymer, characterized in that selected from benzyl, phenyl, biphenyl.
10. According to claim 1, wherein the step (A) is carried out by further adding a catalyst to the first solvent,

    The catalyst is a method of producing a multiblock copolymer, characterized in that selected from potassium carbonate, NaOH, KOH, CsF and mixtures of two or more thereof.
11. According to claim 1, wherein the step (B) is carried out by further adding a catalyst to the second solvent,

    The catalyst is a method of producing a multiblock copolymer, characterized in that selected from potassium carbonate, NaOH, KOH, CsF and mixtures of two or more thereof.
12. The method of claim 1, wherein the step (A) is performed by further adding a first catalyst to the first solvent,

    The step (B) is performed by further adding a second catalyst to the second solvent,

    The first catalyst and the second catalyst are the same as or different from each other, each independently a method of producing a multiblock copolymer, characterized in that potassium carbonate, NaOH, KOH, CsF and mixtures of two or more thereof.
13. The method of claim 10, wherein the amount of the catalyst is added in a ratio of 0.1 to 10 mmol per 10 mL of the first solvent.
14. The method of claim 1, wherein the first solvent and the second solvent are different from each other.
15. According to claim 1, (i) performing the step (A) by further adding calcium carbonate only to the first solvent,

    (ii) performing step (B) by further adding calcium carbonate only to the second solvent, or

    (iii) a method of preparing a block copolymer, characterized in that steps (A) and (B) are performed by further adding calcium carbonate to both the first solvent and the second solvent.
16. The method of claim 1, wherein the first solvent is a mixed solvent of DMAc and DMSO in a volume ratio of 100: 0.5 to 5,

    The second solvent is a block copolymer production method characterized in that the mixed solvent of DMSO and DMac in a volume ratio of 100: 0.5 to 5.
17. An electrolyte membrane for an electrochemical cell comprising a multiblock copolymer prepared by the method according to any one of claims 1 to 15.
18. An electrochemical cell comprising a multiblock copolymer prepared by the method according to any one of claims 1 to 15.
19. An electrochemical cell comprising a multiblock copolymer prepared by the method according to any one of claims 1 to 15,

    The electrochemical cell is any one selected from a fuel cell, a battery, a redox flow battery (redox flow battery), a direct methanol fuel cell, a metal / air rechargeable battery.
20. An electrochemical system comprising a multiblock copolymer prepared by the process according to any one of claims 1 to 15.
21. An electrochemical system comprising the electrochemical cell according to claim 18.

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