KR20180052208A - Brominated polyphenylenesulfide based by polyphenylenesulfide, method for producing the same, brominated and sulfonated polyphenylenesulfide and manufacturing method using the same - Google Patents

Abstract

The present invention relates to polyphenylene sulfide-based brominated polyphenylene sulfide, a method for manufacturing the same, brominated and sulfonated polyphenylene sulfide using the same, and a method for manufacturing the same. According to an embodiment of the present invention, the method for manufacturing brominated polyphenylene sulfide comprises a dissolution step and a bromination step. According to the present invention, the polyphenylene sulfide-based brominated polyphenylene sulfide, the method for manufacturing the same, the brominated and sulfonated polyphenylene sulfide using the same, and the method for manufacturing the same can provide excellent chemical stability.

Description

TECHNICAL FIELD The present invention relates to a polyphenylene sulfide-based brominated polyphenylene sulfide, a process for producing the same, a brominated and sulfonated polyphenylene sulfide using the same, and a process for producing the same. the same}

TECHNICAL FIELD The present invention relates to a cationic conductive polymer and a method for producing the same, and more particularly, to a novel polymer material formed by modifying polyphenylene sulfide (PPS), which is an aromatic hydrocarbon polymer, and a method for producing the same.

New secondary batteries, which are energy efficient and environmentally friendly, have attracted attention. In particular, large secondary batteries are strongly required to store natural energy such as wind power. Among them, Redox flow cells are suitable for large secondary batteries because they are excellent in charge cycle resistance and safety.

Current applications of ion exchange membranes in industry include electrodialysis for desalting and purification, electrodialysis for water degradation, diffusion dialysis for recovering acids from acidic papermaking, and electrodemulsion for ultra pure water production. Particularly recently, interest in ion exchange membranes has increased as the ion exchange membrane shows the possibility of exhibiting excellent performance of a polymer electrolyte fuel cell or a redox flow cell.

On the other hand, the principle of generating electricity in the fuel cell is that when the fuel is supplied through the fuel electrode, the fuel is divided into hydrogen ions and electrons, and hydrogen ions combine with oxygen supplied from the air electrode through the electrolyte membrane to generate water. The electrons separated from the fuel of the fuel electrode proceed to an electrochemical reaction that generates a current through an external circuit to generate electricity and heat.

Among the above fuel cells, a polymer electrolyte fuel cell, direct methanol as a fuel cell, and a direct boron hydride fuel cell adopt a cation exchange membrane as a cation or a hydrogen ion conductive electrolyte membrane as an electrolyte. Here, the direct boron hydride fuel cell can use both a cation exchange membrane and an anion exchange membrane.

In general, a redox flow cell is a cell that generates redox reaction of vanadium in a vanadium sulfate solution according to circulation of a pump and obtains energy. The basic structure of a redox flow battery is a tank for storing an electrolyte and a pump , An anode and a cathode, and a polymer electrolyte membrane located between the two electrodes. As the polymer electrolyte membrane, a cation or anion exchange membrane for keeping ion balance between the positive and negative electrodes is used.

The electrode material is divided into a carbon felt electrode and an inactive electrode. The active material is dissolved in an acidic aqueous solution containing a metal such as V, Fe, Cr, Cu, Ti, Mn and Sn. As the polymer membrane used herein, it is preferable to use a polymer having a high ion selectivity. Examples of commercially available polymer membranes include Nafion manufactured by DuPont of America, CMV, AMV and DMV of Asagi Glass, Japan. Of these, Nafion, which is relatively high in chemical stability and high in hydrogen ion conductivity, is superior in performance but has not been widely practically used because of its disadvantage of high unit cost, poor dimensional stability, and high permeability. Concretely, since the vanadium ions are also thrown away during the charging and discharging, the amount of active material in the electrolytic solution is decreased, the charging and discharging cycle is remarkably deteriorated, and the environmental load at the time of disposal is large.

In order to solve the problems of the conventional commercialized polymer membrane, researches on a new hydrocarbon-based proton conductive material having a relatively low permeability have been actively conducted. Typical examples thereof include polyimide, polyetheretherketone, Polyethersulfone, polybenzimidazole, and the like.

However, such a hydrocarbon-based polymer electrolyte membrane also has a problem of low dimensional stability due to high moisture content at the time of hydration and low membrane / electrode interface stability, which makes it difficult to realize excellent performance of a redox flow cell (RFB) A polymer electrolyte membrane having improved conductivity and permeability characteristics needs to be developed. In addition, the development of water treatment equipment, particularly cationic polymer technology, is urgently required to improve durability.

As a result of efforts to solve the above problems, the present inventors have completed the present invention by developing a technique for producing a sulfonated polymer based on polyphenylene sulfide (PPS).

Accordingly, an object of the present invention is to provide a PPS-based sulfonated polymer formed by modifying PPS and a method for producing the same.

Another object of the present invention is to provide brominated polyphenylene sulfide (bPPS), which is an intermediate for producing a PPS-based sulfonated polymer, and a method for producing the same.

It is still another object of the present invention to provide a cation-conductive polymer electrolyte membrane including a PPS-based sulfonated polymer, which is superior in cost competitiveness compared to a commercialized polymer membrane, and is excellent in dimensional stability, mechanical, thermal and chemical stability.

Still another object of the present invention is to provide an energy storage device and a method of manufacturing the same, which can improve the long-term stability of the system by including a cation conductive exchange membrane which maintains a level equal to or higher than that of the compatibilized membrane by including a cation- And a water treatment apparatus.

The objects of the present invention are not limited to the above-mentioned objects, and other objects not mentioned can be clearly understood by those skilled in the art from the following description.

In order to achieve the object of the present invention described above, the present invention provides a brominated polyphenylene sulfide represented by the following formula (1).

[Chemical Formula 1]

Where n and m are real numbers greater than zero as a mole fraction.

The present invention also provides a method for producing a PPS solution, comprising: a dissolving step of dissolving polyphenylene sulfide (PPS) to prepare a PPS solution; And a step of brominating PPS contained in the PPS solution by brominating the brominated polyphenylene sulfide.

In a preferred embodiment, the bromination step is carried out comprising a reaction step of adding a brominated precursor material to the PPS solution and reacting, and obtaining brominated polyphenylene sulfide (bPPS) from the reactant.

In a preferred embodiment, the brominated precursor material is N-bromosuccinimide (NBS).

In a preferred embodiment, the dissolving step is performed by reacting the PPS with 1-chloronaphthalene and sulfuric acid.

The present invention also provides brominated and sulfonated polyphenylene sulfides represented by the following formula (2).

(2)

Where n, m, and L are real numbers greater than zero as a mole fraction.

The present invention also provides a method for producing a bPPS solution, comprising dissolving bPPS to prepare a bPPS solution; And sulfonating the bPPS contained in the bPPS solution. The present invention also provides a method for producing a brominated and sulfonated polyphenylene sulfide.

In a preferred embodiment, the sulfonation step is carried out comprising a reaction step in which the sulfonated precursor material is added to the bPPS solution and reacted, and the step of obtaining brominated and sulfonated polyphenylene sulfide (bsPPS) from the reactant.

In a preferred embodiment, the sulfonated precursor material is a halogenated sulfonic acid.

In a preferred embodiment, the halogenated sulfonic acid is at least one selected from the group consisting of ClSO ₃ H, (CH ₃ ) ₃ SiSO ₃ Cl, (CF ₃ ) ₃ SiSO ₃ Cl.

In a preferred embodiment, the dissolution step is performed by reacting the bPPS with chloroform.

The present invention also provides a cationic polyelectrolyte membrane comprising the above-described brominated and sulfonated polyphenylene sulfide (bsPPS) or bsPPS prepared by any one of the above-described production methods.

The present invention also provides an energy storage device comprising the above-described cationic polymer electrolyte membrane.

In a preferred embodiment, the energy storage device is a redox flow cell.

The present invention also provides a water treatment apparatus comprising the cationic polyelectrolyte membrane described above.

The present invention has the following excellent effects.

First, the PPS-based sulfonated polymer of the present invention is formed by modifying PPS. Particularly, brominated polyphenylene sulfide (bPPS) is an intermediate for preparing a PPS-based sulfonated polymer, thereby remarkably improving the sulfonation efficiency of PPS .

In addition, according to the cationic conductive polymer electrolyte membrane of the present invention, cost competitiveness against commercialized polymer membranes including PPS-based sulfonated polymers is secured, and dimensional stability, mechanical, thermal and chemical stability are excellent.

In addition, according to the energy storage device and the water treatment device of the present invention, since the cationic conductive exchange membrane that includes the cation-conductive polymer electrolyte membrane and maintains a level equal to or higher than that of the compatibilized membrane is included, stability during driving is also excellent, .

Although the present invention has been fully described by way of example with reference to the accompanying drawings, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, Of course.

1 is a schematic diagram of a known vanadium redox flow cell.
2 is a schematic view of a process for producing PPS-based brominated polyphenylene sulfide (bPPS).
3 is a schematic view of a process for producing a bsPPS polymer from bPPS.
4 is a graph showing FT-IR of PPS, bPPS, and bsPPS measured.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present application, the terms "comprising" or "having ", and the like, are intended to specify the presence of stated features, integers, steps, operations, elements, parts, or combinations thereof, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, parts, or combinations thereof.

Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries are to be interpreted as having a meaning consistent with the meaning of the context in the relevant art and, unless expressly defined in the present invention, are to be interpreted as an ideal or overly formal sense Do not.

Hereinafter, the technical structure of the present invention will be described in detail with reference to the accompanying drawings and preferred embodiments.

However, the present invention is not limited to the embodiments described herein but may be embodied in other forms. Like reference numerals used to describe the present invention throughout the specification denote like elements.

A technical feature of the present invention is to provide an intermediate for preparing a PPS-based sulfonated polymer and a PPS-based sulfonated polymer formed by modifying PPS, thereby providing brominated polyphenylene sulfide (bPPS) capable of remarkably improving the sulfonation efficiency of PPS, . That is, the cationic polyelectrolyte membrane containing the novel PPS-based sulfonated polymer of the present invention maintains low active material permeability, cation conductivity, and durability, and has characteristics suitable for redox flow cells and water treatment apparatuses.

Example 1

According to the process conditions shown in FIG. 2, the following reaction was carried out to obtain bPPS.

1. PPS lysis step

36 g of 1-chloronaphthalene and 6 g of sulfuric acid were added to 2.5 g of PPS, the mixture was vigorously stirred with a stirrer for about 240 minutes, and the reactor temperature was cooled to 138 캜.

2. PPS bromination step

(1) 9.8 g of NBS and 0.115 g of azobisisobutyronitrile (hereinafter referred to as 'AIBN') as a initiator were added and reacted for about 3.5 hours.

(2) The reactor temperature was maintained at 138 占 폚 for evaporating the organic solvent, and the reaction was further continued for 3 hours.

(3) After completion of the reaction, the reaction mixture was cooled to room temperature and the reaction product was precipitated in 500 ml of benzene.

(4) The precipitate was precipitated again in isopropyl alcohol (IPA) and then washed several times.

(5) The washed product was dried in a dryer maintained at 80 캜 for 5 hours to produce bPPS.

Example 2

The following reaction was carried out according to the process conditions shown in FIG. 3 to obtain bsPPS.

1. bPPS lysis step

2.5 g of the bPPS prepared in Example 1 and 42 g of chloroform were added to the three-neck reaction vessel.

2. bPPS Sphoning step

(1) Using burette, 2.68 g of chlorosulfuric acid was added to the reaction vessel for 30 minutes and added.

(2) The reaction was carried out with stirring at 138 DEG C for 4 hours. After that, it was cooled to room temperature and DI water was washed.

(3) The washed product was dried in a dryer maintained at 80 캜 for 5 hours to produce bsPPS.

Experimental Example

The bPPS prepared in Example 1 and the bsPPS prepared in Example 2 were analyzed by FT-IR using PPS as a control group in order to confirm the bromination and sulphonation. The results are shown in Fig.

From FIG. 4 showing the result of FT-IR data analysis, it can be seen that bPPS is introduced into the bromine group, and bsPPS is introduced into the bsPPS with the sulfonyl group and the bromine group.

That is, comparing bPPS and PPS peaks shows that a COC bond is bromine in the phenyl ring, indicating that a new peak is formed near 1,300 cm ^-1 , indicating that it is brominated.

Further, when the bsPPS and the PPS peaks are compared, it can be seen that a new peak due to the functional group due to the SO ₂ -stretching vibration and the stretching vibration of the SO ₃ H group is formed near 1,030 and 650 cm ^-1 , which proves sulfonation .

Therefore, in a situation where it is difficult to modify a PPS to obtain a sulfonated polymer, the bPPS and bsPPS of the present invention can be sulfonated very efficiently through bromination of PPS.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is clearly understood that the same is by way of illustration and example only and is not to be taken by way of limitation, Various changes and modifications will be possible.

Claims (15)

A brominated polyphenylene sulfide represented by the following formula (1).
[Chemical Formula 1]

Where n and m are real numbers greater than zero as a mole fraction.
A dissolving step of dissolving polyphenylene sulfide (PPS) to prepare a PPS solution; And
And brominating the PPS contained in the PPS solution to bromine the brominated polyphenylene sulfide.
3. The method of claim 2,
Wherein the bromination step is performed by adding a brominated precursor material to the PPS solution, and reacting the brominated polyphenylene sulfide and the brominated polyphenylene sulfide to obtain brominated polyphenylene sulfide (bPPS) from the reactant. The method of claim 3,
Wherein the brominated precursor material is N-bromosuccinimide (NBS).
3. The method of claim 2,
Wherein the dissolving step is carried out by reacting the PPS with 1-chloronaphthalene and sulfuric acid.
Brominated and sulfonated polyphenylene sulfides represented by the following formula (2).
(2)

Where n, m, and L are real numbers greater than zero as a mole fraction.
a dissolving step of dissolving bPPS to prepare a bPPS solution; And
And sulfonating the bPPS contained in the bPPS solution to form a sulfonated polyphenylene sulfide.
8. The method of claim 7,
Wherein the sulfonation step is carried out comprising a reaction step of adding a sulfonated precursor material to the bPPS solution and reacting and a step of obtaining brominated and sulfonated polyphenylene sulfide (bsPPS) from the reactant. Lt; / RTI >
9. The method of claim 8,
Wherein the sulfonated precursor material is a halogenated sulfonic acid. ≪ RTI ID = 0.0 > 11. < / RTI >
10. The method of claim 9,
Wherein the halogenated sulfonic acid is at least one selected from the group consisting of ClSO ₃ H, (CH ₃ ) ₃ SiSO ₃ Cl, and (CF ₃ ) ₃ SiSO ₃ Cl.
8. The method of claim 7,
Wherein said dissolving step is carried out by reacting said bPPS with chloroform.
A cationic polyelectrolyte membrane comprising the brominated and sulfonated polyphenylene sulfide (bsPPS) of claim 6 or the bsPPS produced by the process of any one of claims 7 to 11.
An energy storage device comprising the cationic polymer electrolyte membrane of claim 12.
14. The method of claim 13,
Wherein the energy storage device is a redox flow battery.
12. A water treatment apparatus comprising the cationic polymer electrolyte membrane of claim 12.

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