KR102089236B1 - Brominated polyphenylenesulfide based by polyphenylenesulfide and method for producing the same - Google Patents

Abstract

The present invention relates to a cationically conductive polymer and a method for manufacturing the same, and more particularly, to a novel polymer material formed by modifying an aromatic hydrocarbon-based polymer, polyphenylene sulfide (PPS), and a method for manufacturing the same.

Description

Brominated polyphenylenesulfide based by polyphenylenesulfide and method for producing the same}

The present invention relates to a cationically conductive polymer and a method for manufacturing the same, and more particularly, to a novel polymer material formed by modifying an aromatic hydrocarbon-based polymer, polyphenylene sulfide (PPS), and a method for manufacturing the same.

Energy-efficient or eco-friendly new secondary batteries are attracting attention. In particular, large-sized secondary batteries are strongly required to store natural energy such as wind power. Among them, the redox flow battery is suitable for large-sized secondary batteries because of its excellent charge and discharge cycle resistance and safety.

Examples of the current application of the ion exchange membrane to the industrial field include an electrodialysis process for desalination and purification, an electrolysis process for water decomposition, and a diffusion dialysis process for recovering acid from an acidic waste solution, and an electrolysis process for ultra pure production. In particular, interest in ion-exchange membranes has increased in recent years, suggesting the possibility that the ion-exchange membranes may exhibit excellent performance in polymer electrolyte fuel cells or redox flow cells.

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

Among the fuel cells, a polymer electrolyte fuel cell, a direct methanol fuel cell, and a direct boron hydride fuel cell employ a cation exchange membrane that is a cation or hydrogen ion conducting 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 battery is a battery that causes an oxidation-reduction reaction of vanadium in a vanadium sulfate solution and obtains energy according to the circulation of a pump. The basic structure of a redox flow battery is a tank that stores the electrolyte and a pump that circulates the electrolyte , Consisting of a polymer electrolyte membrane located between the anode and cathode and the two electrodes. As the polymer electrolyte membrane, a cation or anion exchange membrane that maintains ion balance between the anodes is used.

The electrode material is divided into a carbon felt electrode and an inert electrode, and the active material is dissolved in an acidic aqueous solution containing all metals such as V, Fe, Cr, Cu, Ti, Mn, and Sn. At this time, it is preferable to use a polymer membrane having a high ion permeability, and commercially available polymer membranes include Nafion of DuPont, USA, CMV, AMV, and DMV of Asai Glass of Japan. Among them, Nafion, a polymer having relatively good chemical stability and high hydrogen ion conductivity, is a hydrogen perfluoride-based polymer, but has a high cost, poor dimensional stability, and high permeability. Specifically, since vanadium ions are also discarded during charging and discharging, there is also a problem that the amount of active material in the electrolyte decreases, the charge and discharge cycles deteriorate significantly, and the environmental load upon disposal is large.

In order to solve the problems of the existing commercially available polymer membranes, research into new hydrocarbon-based conductive materials having relatively low permeability has been actively conducted, and examples thereof include polyimide, polyetheretherketone, and polyether. Polyethersulfone, polybenzimidazole, and the like.

However, these hydrocarbon-based polymer electrolyte membranes also have a high water content during hydration, resulting in poor dimensional stability, and low membrane / electrode interface stability, making it difficult to realize excellent performance of a redox flow battery (RFB), and ion to improve them There is a need to develop a polymer electrolyte membrane with improved conductivity and permeability characteristics. In addition, development of cationic polymer technology is urgently required to improve water treatment devices, especially durability.

The present inventor completed the present invention by developing a technique for preparing sulfonated polymers based on polyphenylene sulfide (PPS) as a result of research efforts to solve the above problems.

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

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

Another object of the present invention is to provide a cationic conductive polymer electrolyte membrane having excellent dimensional stability, mechanical, thermal, and chemical stability while securing price competitiveness compared to a commercially available polymer membrane including a PPS-based sulfonated polymer.

Another object of the present invention is to include a cation-conducting polymer electrolyte membrane, including a cation-conducting exchange membrane that maintains a level equal to or higher than that of a commercially available membrane. It is to provide a water treatment device.

The objects of the present invention are not limited to the objects mentioned above, and other objects not mentioned will 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].

[Formula 1]

Here, n and m are real numbers greater than 0 as a mole fraction.

In addition, the present invention is a dissolution step of preparing a PPS solution by dissolving polyphenylene sulfide (PPS); It provides a brominated polyphenylene sulfide production method comprising; and a bromination step of brominating the PPS contained in the PPS solution.

In a preferred embodiment, the bromination step is performed by adding a brominated precursor material to the PPS solution to react and obtaining a 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 carried out by reacting the PPS with 1-chloronaphthalene and sulfuric acid.

In addition, the present invention provides a cationic polymer electrolyte membrane comprising a brominated polyphenylene sulfide (bPPS) or bPPS prepared by any one of the above-described manufacturing methods.

In addition, the present invention provides an energy storage device including the cationic polymer electrolyte membrane described above.

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

In addition, the present invention provides a water treatment device comprising the cationic polymer electrolyte 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. In particular, brominated polyphenylene sulfide (bPPS) is an intermediate for preparing PPS-based sulfonated polymers, thereby significantly improving the sulfonation efficiency of PPS. I can do it.

In addition, the cationic conductive polymer electrolyte membrane of the present invention is excellent in dimensional stability, mechanical, thermal and chemical stability while securing price competitiveness compared to commercially available polymer membranes including PPS-based sulfonated polymers.

In addition, according to the energy storage device and the water treatment device of the present invention, a cationic conductive exchange membrane that maintains a level equal to or higher than that of a commercially available membrane by including a cationic conductive polymer electrolyte membrane is also excellent in stability during operation, thereby greatly improving long-term stability of the system. You can.

The technical effects of the present invention are not limited to the above-mentioned ranges, and even if not explicitly mentioned, the effects of the invention that can be recognized by those skilled in the art from the description of specific contents for carrying out the invention described below are also Of course it is included.

1 is a schematic diagram of a known vanadium-based redox flow battery.
Figure 2 is a process schematic diagram for producing a brominated polyphenylene sulfide (bPPS) based on PPS.
3 is a process schematic diagram of manufacturing a bsPPS polymer from bPPS.
4 is a graph showing the results of measuring FT-IR of PPS, bPPS, and bsPPS.

The terms used in the present invention are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, terms such as “include” or “have” are intended to indicate that a feature, number, step, operation, component, part, or combination thereof described in the specification exists, or that one or more other features or It should be understood that the existence or addition possibilities of numbers, steps, actions, components, parts or combinations thereof are not excluded in advance.

Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by a person skilled in the art to which the present invention pertains. Terms, such as those defined in a commonly used dictionary, should be interpreted as having meanings consistent with meanings in the context of related technologies, and are not to be interpreted as ideal or excessively formal meanings unless explicitly defined in the present invention. Does not.

Hereinafter, the technical configuration 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 and may be embodied in other forms. The same reference numerals used to describe the present invention throughout the specification indicate the same components.

The technical feature of the present invention is an intermediate for preparing PPS-based sulfonated polymers formed by modifying PPS and PPS-based sulfonated polymers, through which brominated polyphenylene sulfide (bPPS) capable of significantly improving the sulfonation efficiency of PPS Is in That is, the new PPS-based sulfonated polymer of the present invention is because the cationic polymer electrolyte membrane has low active material permeability and cationic conductivity and durability, and thus has properties suitable for redox flow batteries and water treatment devices.

Example 1

According to the process conditions shown in Figure 2, bPPS was obtained by performing the reaction as follows.

1. PPS dissolution step

The reactor temperature was set to 210 ° C, 1-chloronaphthalene 36g and sulfuric acid 6g were added to PPS 2.5g, and the mixture was stirred vigorously for about 240 minutes, and the reactor temperature was cooled to 138 ° C.

2. PPS bromination stage

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

(2) In order to evaporate the organic solvent, the reactor temperature was maintained at 138 ° C., and the reaction was further performed for 3 hours.

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

(4) The precipitate was put in isopropyl alcohol (hereinafter referred to as 'IPA') to precipitate again, and then washed several times.

(5) bPPS was prepared by drying the product after washing for 5 hours in a dryer maintained at 80 ° C.

Example 2

According to the process conditions shown in Figure 3, bsPPS was obtained by performing the reaction as follows.

1. bPPS dissolution step

To the three-necked reaction, 2.5 g of bPPS prepared in Example 1 and 42 g of Chloroform were added.

2. bPPS sulfonation stage

(1) 2.68 g of chlorosulfuric acid was added dropwise to the reaction mixture for 30 minutes using a burette.

(2) The mixture was reacted with stirring at 138 ° C for 4 hours. Then, it was cooled to room temperature and washed with DI Water.

(3) bsPPS was prepared by drying the product after washing for 5 hours in a dryer maintained at 80 ° C.

Experimental Example

In order to check whether the bPPS prepared in Example 1 and the bsPPS prepared in Example 2 were brominated and sulfonated, PPS was used as a control and analyzed by FT-IR, and the results are shown in FIG. 4.

It can be seen from FIG. 4 that shows the results of FT-IR data analysis that bPPS is a bromine group, bsPPS is a sulfonyl group, and a bromine group is introduced into the bsPPS.

That is, when comparing the bPPS and PPS peaks, it can be seen that the COC bond is bromine in the phenyl ring when the new peak is formed near 1,300 cm ^-1 , indicating that it has been brominated.

In addition, when comparing the bsPPS and PPS peaks, it can be seen that a new peak was formed by a functional group due to ?? SO ₂ -Stretching vibration, Stretching vibration of the SO ₃ H group near 1,030, 650 cm ^-1 , which proves sulfonation. .

Accordingly, it is shown that in a situation in which it is difficult to obtain a sulfonated polymer by modifying PPS, the bPPS and bsPPS of the present invention can be sulfonated very efficiently through bromination of PPS.

The present invention has been shown and described with reference to preferred embodiments as described above, but is not limited to the above-described embodiments and is within the scope of the present invention to those skilled in the art to which the present invention pertains. By this, various changes and modifications will be possible.

Claims (9)

Brominated polyphenylene sulfide represented by the following [Formula 1].
[Formula 1]

Here, n and m are real numbers greater than 0 as a mole fraction.
A dissolution step of preparing a PPS solution by dissolving polyphenylene sulfide (PPS); And
Brominated polyphenylene sulfide production method comprising a; bromination step of brominating the PPS contained in the PPS solution.
According to claim 2,
The bromination step is a method of producing a brominated polyphenylene sulfide, characterized in that it comprises a step of reacting by adding a brominated precursor to the PPS solution and obtaining a brominated polyphenylene sulfide (bPPS) from the reactant.
The method of claim 3,
The brominated precursor material is N-bromosuccinimide (NBS) method for producing brominated polyphenylene sulfide.
According to claim 2,
The dissolving step is a brominated polyphenylene sulfide production method characterized in that the PPS is carried out by reacting with 1-chloronaphthalene and sulfuric acid.
A cationic polymer electrolyte membrane comprising the brominated polyphenylene sulfide (bPPS) of claim 1 or bPPS prepared by the method of any one of claims 2 to 5.
An energy storage device comprising the cationic polymer electrolyte membrane of claim 6.
The method of claim 7,
The energy storage device is an energy storage device characterized in that the redox flow battery.
A water treatment device comprising the cationic polymer electrolyte membrane of claim 6.

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