KR101977936B1 - Solution polymerization method of polyphenylene sulfide and polyphenylene sulfide polymer prepared thereby - Google Patents

Abstract

The present invention relates to: a solution polymerization manufacturing method of polyphenylene sulfide to which a high heat-resistant solvent is applied; and a polymer of polyphenylene sulfide obtained from the same. More specifically, the present invention relates to a manufacturing method which makes easy removal of iodine in an existing melt polymerization method by solution polymerization in polyphenylene sulfide polymerization by using the high heat-resistant solvent and makes a process of production and removal of salt in the existing melt polymerization method to be easier. Polyphenylene sulfide, which is a heat-resistant polymer having a controlled sulfur content according to the present invention, can easily be used as an electrode material of a secondary battery and a smart material having a self-healing function because of easy removal of by-products and easy adjustment of sulfur content and copolymerization.

Description

[0001] The present invention relates to a solution polymerization method of polyphenylene sulfide and a solution polymerization method of polyphenylene sulfide and polyphenylene sulfide polymer prepared thereby,

The present invention relates to a solution polymerization preparation method of polyphenylene sulfide to which a high heat resistant solvent is applied and a polyphenylene sulfide polymer obtained therefrom.

More specifically, solution polymerization of polyphenylene sulfide during solution polymerization using a high heat-resistant solvent makes it easier to remove the iodine from the existing melt polymerization method. In addition, And a polymer film having a scratch self-healing function of a positive electrode active material, an anode material, and a scratch self-healing function of a lithium-sulfur battery of a polyphenylene sulfide copolymer produced by such a method and having a high sulfur content will be.

Polyphenylenesulfide (PPS) is a polymer polymer having a structure in which sulfur is bonded to a benzene ring. It is a crystalline engineering plastic having excellent heat resistance (heat distortion temperature of 270 ° C. or higher) and flame retardancy. Is a resin having sufficient flame retardancy.

The polymerization method of PPS can be roughly classified into a solution polymerization method and a melt polymerization method. In the solution polymerization method, paradichlorobenzene (p-DCB), sodium sulfide (Na ₂ S) or sodium hydrogen sulfide can be obtained in a polar solvent under high temperature and high pressure. This reaction is a dehydration reaction to produce sodium chloride salt (NaCl) Reaction. Removal of the sodium chloride produced in this process is a very important process, and weakness and defects can occur if the removal is not done well. Japanese Unexamined Patent Application, First Publication No. Hei 8-183858 and Korean Patent No. 10-1475658 are known prior arts.

 On the other hand, the melt polymerization can be achieved at high temperature and high vacuum of 300 ° C or higher using para-diiodo benzene (DIB) and sulfur, and iodine (I) is produced as a by-product. Removal of iodine is very important in the melt polymerization process and has a great effect on the production of high molecular weight polymers. It is also difficult to remove iodine as a by-product in the melt polymerization method, as the salt produced as a by-product in the conventional solution polymerization method adversely affects the processing or the like during processing of the PPS. A related art related to this is Korean Patent No. 10-1549205.

Despite these problems, PPS has a very high melting point and heat distortion temperature, which is widely used where heat resistance is required, and is excellent in flame retardancy and chemical resistance and is not well soluble in organic solvents. In addition, it has excellent mechanical and thermal properties and insulation properties and is widely used for heat-resistant products and metal products, and is widely used as a thermosetting material.

Accordingly, the present inventors have studied to increase the sulfur content and the problem of the removal of iodine in the melt polymerization method while studying the polyphenylene sulfide polymerization, and have found that by using the monomers used in the conventional melt polymerization method, It is confirmed that the polymerization can control the sulfur content, and the present invention has been completed.

Japanese Patent Application Laid-Open No. 8-183858 Korean Patent No. 10-1475658 Korean Patent No. 10-1549205

The present invention has been developed in order to solve the above problems, and it is an object of the present invention to solve the problems in the solution polymerization method and the melt polymerization method and to provide a method for removing salts as by-products in the solution polymerization method and removing the by- It is an object of the present invention to provide a solution polymerization method using a high heat resistant solvent.

The present invention also provides a method for producing polyphenylene sulfide by effectively removing the iodine generated during the solution polymerization of para-diiodobenzene and sulfur, the production of polyphenylene sulfide having a high sulfur content, and the use of various monomers We want to provide merger.

The present invention also provides a battery field of polyphenylene sulfide having a high sulfur content and a method of application to a polymer film having a scratch self-healing function.

The present invention provides a method for solution polymerization of polyphenylene sulfide using a high heat resistant solvent to solve the above problems.

More specifically, the present invention provides a process for producing polyphenylene sulfide which effectively removes iodine by adding solution of para-diiodobenzene and sulfur in which no salt is formed in solution.

The present invention also provides polyphenylene sulfide, which is a copolymer of various monomers with a high content of sulfur produced by the above method.

In addition, the present invention provides an electrode material of a lithium-sulfur battery using a polyphenylene sulfide polymer having a greatly increased sulfur content and a polymer resin having a thermoreversible self-healing function.

The polyphenylene sulfide according to the present invention is easy to remove by-products, can control the content of sulfur and is easy to copolymerize, and thus various materials can be manufactured and applied.

The heat-resistant polymer having the sulfur content controlled according to the present invention can be utilized as an electrode material of a secondary battery, a smart material having a self-healing function, and the like.

Figure 1 shows FT-IR spectra of polyphenylene sulfide prepared according to one embodiment of the present invention.
FIG. 2 is a graph showing a differential scanning calorimetry (DSC) result of measuring the glass transition temperature according to the sulfur content of polyphenylene sulfide prepared according to an embodiment of the present invention.
FIG. 3 is a photograph showing a thermoreversible self-healing function of a polyphenylene sulfide polymer film produced according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail. The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.

The present invention provides a solution polymerization method of polyphenylene sulfide using an aromatic dihalogen compound and sulfur in a high heat-resistant solvent.

In the preparation method according to the present invention, the aromatic dihalogen compound may be any one of compounds having the chemical structures of the following Chemical Formulas (1) to (2).

≪ Formula 1 >

(2)

X-Aryl-X

,

,

중 어느 하나일 수 있다.In Formula 1 or Formula 2, X is any one of Cl, Br, and I, Aryl is

,

,

. ≪ / RTI >

More preferably, the aromatic dihalogen compound may be para-diiodobenzene.

The present invention also provides a method for increasing the content of sulfur in a polyphenylene sulfide polymer and a method for copolymerizing with other comonomers.

In the production process according to the present invention, the comonomer may be added together with the existing monomer at the start of the polymerization reaction. By injecting these comonomers together, it is possible to reduce the number of experimental steps and more simply provide a copolymer of polyphenylene sulfide.

In the production process according to the present invention, the weight ratio of sulfur to be used may be in the range of 32.9 wt% to 52.8 wt%.

In the preparation method according to the present invention, the solution polymerization method may be carried out at a reaction temperature of 150 to 250 ° C. When the reaction temperature of the polymerization is lower than 150 ° C, the reactivity of sulfur is lowered. When the polymerization temperature is higher than 250 ° C, deformation of the high heat resistant solvent may occur, and more preferably the reaction proceeds in the range of 150 to 250 ° C.

The polyphenylene sulfide polymer according to the present invention can be prepared according to the following Reaction Scheme 1.

<Reaction Scheme 1>

Further, the polyphenylene sulfide copolymer according to the present invention can be produced by the method of the following reaction formula (2).

<Reaction Scheme 2>

,

,

중 어느 하나일 수 있다.In this case,

,

,

. &Lt; / RTI &gt;

The polyphenylene sulfide resin thus prepared was analyzed for the content of sulfur by an elemental analyzer as described in the following examples. The glass transition temperature according to the sulfur content was 93 to 37 ° C, and the polyphenylene sulfide was sulfur Depending on the content, it can be used as high-performance engineering plastics. Sulfur-rich polymers can also be applied as lithium-sulfur batteries or self-healing materials.

The polyphenylene sulfide polymer produced according to the method of the present invention can be used as a cathode active material for a lithium sulfur battery together with a carbon-based material, and also can be used for the production of a lithium sulfur battery including a cathode including the cathode active material, .

BRIEF DESCRIPTION OF THE DRAWINGS The above and other objects, features and advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, in which: FIG. In particular, the technical idea of the present invention and its core structure and action are not limited by this. In addition, the content of the present invention can be implemented by various other types of equipment, and is not limited to the embodiments and examples described herein.

&Lt; Comparative Example 1 > Preparation of polyphenylene sulfide polymer (reaction in sulfolane)

In the polymerization of a PPS homopolymer, 0.32 g of elemental sulfur (S) and 3.3 g of p-diiodobenzene (DIB) were added to a 100 ml two-neck round bottom flask And add 11 ml of sulfolane. Connect nitrogen on one side and connect pipe on the other side. Connections can be heated using heating tapes and the trap is filled with distilled water. Allow nitrogen to flow for at least one hour before raising the temperature. The experiments were conducted in a nitrogen atmosphere and heated at 50, 100, and 150 ° C for 30 minutes, respectively, and heated at 160, 170, and 180 ° C for 10 minutes, respectively. And the mixture was heated at 200 占 폚 for 1 hour and at 250 占 폚 for 2 hours and 30 minutes. The product was extracted with toluene using Soxhlet extraction to remove iodine (I) and sulfur, but there was no residue.

&Lt; Comparative Example 2 > Preparation of polyphenylene sulfide polymer (reaction in NMP)

In the polymerization of a PPS homopolymer, 0.32 g of elemental sulfur (S) and 3.3 g of p-diiodobenzene (DIB) were added to a 100 ml two-neck round bottom flask And 3.5 ml of N-methylpyrrolidone (NMP) is added. Connect nitrogen on one side and connect pipe on the other side. Connections can be heated using heating tapes and the trap is filled with distilled water. Allow nitrogen to flow for at least one hour before raising the temperature. The experiment was conducted in a nitrogen atmosphere and heated at 150, 160, 170, 180, 190, 200, and 210 ° C for 30 minutes, respectively, and heated at 220 ° C for 3 hours. The product was extracted with toluene using Soxhlet extraction to remove iodine (I) and sulfur, but there was no residue.

&Lt; Comparative Example 3 > Preparation of polyphenylene sulfide polymer (S / DIB = 0.5 / 1 molar ratio reaction)

In the polymerization of the polyphenylene sulfide polymer (PPS homopolymer), 0.16 g of elemental sulfur (S) and 3.3 g of p-diiodobenzene (DIB) were placed in a 100 ml two-neck round bottom flask And add 5 ml of silicone oil (KF-54). Connect nitrogen on one side and connect pipe on the other side. Connections can be heated using heating tapes and the trap is filled with distilled water. The experiment was carried out in a nitrogen atmosphere and heated at 60 ° C and 130 ° C for 30 minutes, respectively, and then overheated at 230 ° C. The molecular weight of the product was low and the product was made into powder. The product was subjected to Soxhlet extraction with toluene to remove iodine (I) and sulfur. Elemental analysis showed a measured value (wt%) of carbon 78.0% hydrogen 4.6% sulfur 17.5%.

&Lt; Comparative Example 4 > Preparation of polyphenylene sulfide polymer (S / DIB = 0.8 / 1 molar ratio reaction)

In the polymerization of the PPS homopolymer, 0.26 g of elemental sulfur (S) and 3.3 g of p-diiodobenzene (DIB) were placed in a 100 ml two-neck round bottom flask And add 5 ml of silicone oil (KF-54). Connect nitrogen on one side and connect pipe on the other side. Connections can be heated using heating tapes and the trap is filled with distilled water. The experiment was carried out in a nitrogen atmosphere and heated at 60 ° C and 130 ° C for 30 minutes, respectively, and then overheated at 230 ° C. The molecular weight of the product was low and the product was made into powder. The product was subjected to Soxhlet extraction with toluene to remove iodine (I) and sulfur. Elemental analysis showed a measured value (weight%) of carbon 70.8% hydrogen 4.2% sulfur 25.2%.

&Lt; Comparative Example 5 > Preparation of polyphenylene sulfide polymer (reaction in air)

In the polymerization of the PPS homopolymer, 0.32 g of elemental sulfur (S) and 3.3 g of p-diiodobenzene (DIB) were placed in a 100 ml round bottom flask Add 5 ml of silicone oil (KF-54). Experiments were conducted in air and heated at 60 ° C and 130 ° C for 30 minutes, respectively, and then over-night heated at 230 ° C. The molecular weight of the product was low and the elemental analysis showed a measured value (weight%) of 65.2% of carbon and 3.9% of sulfur and 31.1% of sulfur.

&Lt; Comparative Example 6 > Preparation of polyphenylene sulfide polymer (reaction at 150 DEG C)

In the polymerization of a PPS homopolymer, 0.32 g of elemental sulfur (S) and 3.3 g of p-diiodobenzene (DIB) were added to a 100 ml two-neck round bottom flask And add 5 ml of silicone oil (KF-54). Connect nitrogen on one side and connect pipe on the other side. Connections can be heated using heating tapes and the trap is filled with distilled water. The experiment was conducted in a nitrogen atmosphere, heated at 60 ° C for 30 minutes, and over-nested at 150 ° C. The product was extracted with toluene using Soxhlet extraction to remove iodine (I) and sulfur, but there was no residue.

&Lt; Comparative Example 7 > Preparation of polyphenylene sulfide polymer (reaction at 200 DEG C)

In the polymerization of a PPS homopolymer, 0.32 g of elemental sulfur (S) and 3.3 g of p-diiodobenzene (DIB) were added to a 100 ml two-neck round bottom flask And add 5 ml of silicone oil (KF-54). Connect nitrogen on one side and connect pipe on the other side. Connections can be heated using heating tapes and the trap is filled with distilled water. The experiment was carried out in a nitrogen atmosphere and heated at 60 ° C and 130 ° C for 30 minutes, respectively, and then overheated at 200 ° C. The product was extracted with toluene using Soxhlet extraction to remove iodine (I) and sulfur, and elemental analysis showed a measured value (weight%) of carbon 65.1% hydrogen 4.1% sulfur 30.9%. Also, the glass transition temperature (T _g ) of the resin was 85 ° C.

&Lt; Comparative Example 8 > Preparation of polyphenylene sulfide polymer (reaction at 250 DEG C)

In the polymerization of a PPS homopolymer, 0.32 g of elemental sulfur (S) and 3.3 g of p-diiodobenzene (DIB) were added to a 100 ml two-neck round bottom flask And add 5 ml of silicone oil (KF-54). Connect nitrogen on one side and connect pipe on the other side. Connections can be heated using heating tapes and the trap is filled with distilled water. The experiment was conducted in a nitrogen atmosphere and heated for 30 minutes at 60 ° C and 130 ° C, respectively, and then overheated at 250 ° C. The product was extracted with toluene using Soxhlet extraction to remove iodine (I) and sulfur. Elemental analysis showed a measured value (weight%) of carbon 64.2% hydrogen 3.9% sulfur 32.1%. The glass transition temperature (T _g ) of the resin was also found to be 92 ° C.

Example 1 Production of polyphenylene sulfide polymer (S / DIB = 1/1 mole ratio reaction)

In the polymerization of a PPS homopolymer, 0.32 g of elemental sulfur (S) and 3.3 g of p-diiodobenzene (DIB) were added to a 100 ml two-neck round bottom flask And add 5 ml of silicone oil (KF-54). Connect nitrogen on one side and connect pipe on the other side. Connections can be heated using heating tapes and the trap is filled with distilled water. Allow nitrogen to flow for at least one hour before raising the temperature. The experiment was conducted in a nitrogen atmosphere and heated at 60 ° C and 150 ° C for 30 minutes, respectively, and then overheated at 230 ° C. The product was extracted with toluene using Soxhlet extraction to remove iodine (I) and sulfur to obtain a clean product. The resin produced under these conditions showed peaks at 3060 cm ^-1 (CH) and 1080 cm ^-1 (CS) of FT-IR and the measured value (wt%) of carbon 63.8% hydrogen 3.8% sulfur 32.9% ) And about 1.1 of sulfur per benzene were polymerized. The glass transition temperature (T _g ) of the resin was also found to be 93 ° C.

&Lt; Example 2 > Preparation of polyphenylene sulfide polymer (S / DIB = 2/1 reaction)

In the polymerization of the PPS homopolymer, 0.64 g of elemental sulfur (S) and 3.3 g of p-diiodobenzene (DIB) were added to a 100 ml two-neck round bottom flask And add 5 ml of silicone oil (KF-54). Connect nitrogen on one side and connect pipe on the other side. Connections can be heated using heating tapes and the trap is filled with distilled water. Allow nitrogen to flow for at least one hour before raising the temperature. The experiment was carried out in a nitrogen atmosphere and heated at 60 ° C and 130 ° C for 30 minutes, respectively, and then overheated at 230 ° C. The product was extracted with toluene using Soxhlet extraction to remove iodine (I) and sulfur to obtain a clean product. The resin produced under these conditions showed peaks at 3060 cm ^-1 (CH) and 1080 cm ^-1 (CS) of FT-IR and the measured value (weight%) of carbon 51.3% hydrogen 3.2% sulfur 44.8% ), And about two sulfur atoms per benzene were polymerized. Further, the glass transition temperature (T _g ) of the resin was 51 ° C.

Example 3 Preparation of Polyphenylene Sulfide Polymer (S / DIB = 3/1)

In the polymerization of the PPS homopolymer, 0.96 g of elemental sulfur (S) and 3.3 g of p-diiodobenzene (DIB) were added to a 100 ml two-neck round bottom flask And add 5 ml of silicone oil (KF-54). Connect nitrogen on one side and connect pipe on the other side. Connections can be heated using heating tapes and the trap is filled with distilled water. Allow nitrogen to flow for at least one hour before raising the temperature. The experiment was carried out in a nitrogen atmosphere and heated at 60 ° C and 130 ° C for 30 minutes, respectively, and then overheated at 230 ° C. The product was extracted with toluene using Soxhlet extraction to remove iodine (I) and sulfur to obtain a clean product. The resin produced under these conditions showed peaks at 3060 cm ^-1 (CH) and 1080 cm ^-1 (CS) of FT-IR and the measured value (weight%) of carbon 44.3% hydrogen 2.6% sulfur 52.8% ) And about 2.7 of sulfur per benzene were polymerized. Further, the glass transition temperature (T _g ) of the resin was 37 ° C.

Example 4 Preparation of Polyphenylene Sulfide Polymer (S / DIB = 5/1)

In the polymerization of a PPS homopolymer, 1.6 g of elemental sulfur (S) and 3.3 g of p-diiodobenzene (DIB) were added to a 100 ml two-neck round bottom flask And add 5 ml of silicone oil (KF-54). Connect nitrogen on one side and connect pipe on the other side. Connections can be heated using heating tapes and the trap is filled with distilled water. Allow nitrogen to flow for at least one hour before raising the temperature. The experiment was carried out in a nitrogen atmosphere and heated at 60 ° C and 130 ° C for 30 minutes, respectively, and then overheated at 230 ° C. The product was extracted with toluene using Soxhlet extraction to remove iodine (I) and sulfur to obtain a clean product. The resin produced under these conditions showed peaks at 3060 cm ^-1 (CH) and 1080 cm ^-1 (CS) of FT-IR and the measured value (weight%) of carbon 32.2% hydrogen 1.7% sulfur 69.8% ) And about 5.5 of sulfur per benzene were polymerized. Also, the glass transition temperature (T _g ) of the resin was 28 ° C.

Example 5 Preparation of Polyphenylene Sulfide Polymer (S / DIB = 6/1)

In polymerizing a PPS homopolymer, 1.92 g of elemental sulfur (S) and 3.3 g of p-diiodobenzene (DIB) were added to a 100 ml two-neck round bottom flask And add 5 ml of silicone oil (KF-54). Connect nitrogen on one side and connect pipe on the other side. Connections can be heated using heating tapes and the trap is filled with distilled water. Allow nitrogen to flow for at least one hour before raising the temperature. The experiment was carried out in a nitrogen atmosphere and heated at 60 ° C and 130 ° C for 30 minutes, respectively, and then overheated at 230 ° C. The product was extracted with toluene using Soxhlet extraction to remove iodine (I) and sulfur to obtain a clean product. The resin produced under these conditions showed peaks at 3060 cm ^-1 (CH) and 1080 cm ^-1 (CS) of FT-IR and the measured value (wt%) of carbon 30.2% hydrogen 1.6% sulfur 71.6% ) And about 6 sulfur per benzene were polymerized. Further, the glass transition temperature (T _g ) of the resin was 21 ° C.

Example 6 Preparation of polyphenylene sulfide copolymer (using comonomer DIPS)

0.32 g of elemental sulfur (S), 2.9 g of p-diiodobenzene (DIB), 4,4'-diiodide (DIB) were added to polymerize the polyphenylene sulfide copolymer Add 0.47 g of 4,4'-diiododiphenyl sulfone (DIPS) to a 100 ml two-neck round bottom flask and add 5 ml of silicone oil (KF-54). Connect nitrogen on one side and connect pipe on the other side. Connections can be heated using heating tapes and the trap is filled with distilled water. Allow nitrogen to flow for at least one hour before raising the temperature. The experiment was carried out in a nitrogen atmosphere and heated at 60 ° C and 130 ° C for 30 minutes, respectively, and then overheated at 230 ° C. The product was extracted with toluene using Soxhlet extraction to remove iodine (I) and sulfur to obtain a clean product. The resin produced under these conditions showed peaks at 3060 cm ^-1 (CH), 1080 cm ^-1 (CS) and 1320 cm ^-1 (S = O) of FT-IR and 52.2% hydrogen 3.2 And a measured value (% by weight) of sulfur sulfur 41.5%. Further, the glass transition temperature (T _g ) of the resin was 83 ° C.

Example 7 Preparation of Polyphenylene Sulfide Copolymer (Using Comonomer DIBP)

0.32 g of elemental sulfur (S) and 2.9 g of p-diiodobenzene (DIB), 4,4-diiodobenzene (DIB) were added in the polymerization of the polyphenylene sulfide copolymer 0.41 g of phenyl (4,4-diiodobipenyl: DIBP) is placed in a 100 ml two-neck round bottom flask and 5 ml of silicone oil (KF-54) is added. Connect nitrogen on one side and connect pipe on the other side. Connections can be heated using heating tapes and the trap is filled with distilled water. Allow nitrogen to flow for at least one hour before raising the temperature. The experiment was carried out in a nitrogen atmosphere and heated at 60 ° C and 130 ° C for 30 minutes, respectively, and then overheated at 230 ° C. The product was extracted with toluene using Soxhlet extraction to remove iodine (I) and sulfur to obtain a clean product. The resin produced under these conditions showed peaks at 3060 cm ^-1 (CH), 1080 cm ^-1 (CS) and 730 cm ^-1 (biphenyl) of FT-IR, And a measured value (% by weight) of 29.1%. The glass transition temperature (T _g ) of the resin was also found to be 106 ° C.

&Lt; Example 8 > Preparation of polyphenylene sulfide copolymer (using comonomer DIBA)

In the polymerization of a polyphenylene sulfide copolymer (PPS copolymer), 0.32 g of elemental sulfur (S), 2.9 g of p-diiodobenzene (DIB), 2.5 g of 2,5-diiodobenzoic acid 0.37 g of 2,5-diiodo benzoic acid (DIBA) is placed in a 100 ml two-neck round bottom flask and 5 ml of silicone oil (KF-54) is added. Connect nitrogen on one side and connect pipe on the other side. Connections can be heated using heating tapes and the trap is filled with distilled water. Allow nitrogen to flow for at least one hour before raising the temperature. The experiment was carried out in a nitrogen atmosphere and heated at 60 ° C and 130 ° C for 30 minutes, respectively, and then overheated at 230 ° C. The product was extracted with toluene using Soxhlet extraction to remove iodine (I) and sulfur to obtain a clean product. The resin produced under these conditions showed peaks at 3060 cm ^-1 (CH), 1080 cm ^-1 (CS) 1636 cm ^-1 and 1728 cm ^-1 (C = O) of FT-IR, (Weight%) of 65.1% hydrogen 3.6% sulfur 28.5%. The glass transition temperature (T _g ) of the resin was also found to be 101 ° C.

The results of the glass transition temperature (T _g ) and sulfur content (%) of the monomers of Comparative Examples 1 to 8 and Examples 1 to 8 and solvent used are summarized in Table 1 below.

The mole ratio Solvent used Polymerization temperature
(° C) Polymerization environment T _g
(° C) Sulfur content
(weight%) Sulfur input DIB input Comonomer and
input Comparative Example 1 One One - sulfolane 230 nitrogen - - Comparative Example 2 One One - NMP 230 nitrogen - - Comparative Example 3 0.5 One - 실리콘 油 230 nitrogen - 17.5 Comparative Example 4 0.8 One - 실리콘 油 230 nitrogen - 25.2 Comparative Example 5 One One - 실리콘 油 230 Waiting - 31.1 Comparative Example 6 One One - 실리콘 油 150 nitrogen - - Comparative Example 7 One One - 실리콘 油 200 nitrogen 85 30.9 Comparative Example 8 One One - 실리콘 油 250 nitrogen 92 32.1 Example 1 One One - 실리콘 油 230 nitrogen 93 32.9 Example 2 2 One - 실리콘 油 230 nitrogen 51 45.8 Example 3 3 One - 실리콘 油 230 nitrogen 37 52.8 Example 4 5 One - 실리콘 油 230 nitrogen 28 69.8 Example 5 6 One - 실리콘 油 230 nitrogen 21 71.6 Example 6 One 0.9 DIPS 0.1 실리콘 油 230 nitrogen 83 41.5 Example 7 One 0.9 DIBP 0.1 실리콘 油 230 nitrogen 106 29.1 Example 8 One 0.9 DIBA 0.1 실리콘 油 230 nitrogen 101 28.5

T _g (glass transition temperature): DSC Q1000 (TA Instrument), heating rate: 10 ° C / min, cooling rate: 5 ° C / min

* Analysis of elemental analysis (EA, C, H, N, S) (equipment name: FLASH 2000 Organic Elemental Analyzer,

* Structure analysis (FT-IR, Fourier transform Infrared) A2 Technologies EXOSCAN

Figure 1 shows FT-IR spectra of para-diiodobenzene and sulfur polymers according to one embodiment of the invention. As can be seen from FIG. 1, the reaction of para-diiodobenzene and the sulfur polymer proceeded effectively, and a peak was observed at 3060 cm ^-1 (CH) and 1080 cm ^-1 (CS). Further, when 1320 cm ^-1 (S = O) of Example 6 and 730 cm ^-1 (biphenyl) of Example 7 were observed, the polyphenylene sulfide copolymer was also well formed Respectively.

The content of sulfur in the solution polymerization of polyphenylene sulfide was confirmed by elemental analysis. The sulfur content of the polymer increased with the addition amount of sulfur, but it was confirmed that up to 6 sulfur per benzene was contained And it is inefficient to polymerize using more sulfur.

The polyphenylene sulfide polymer according to the present invention was found to be able to control the content of sulfur up to six per benzene ring during polymerization, and such a high sulfur content polyphenylene sulfide copolymer can be used as a positive electrode active material of a lithium- It is possible to use as material of.

The polyphenylene sulfide polymer produced according to the method of the present invention can be used as a cathode active material for a lithium sulfur battery together with a carbon-based material, and also can be used for the production of a lithium sulfur battery including a cathode including the cathode active material, .

<Evaluation of self-healing function>

A powder sample prepared according to Example 5 of the present invention was placed on a polyimide film (Kapton), and the upper portion was covered with another polyimide film, followed by hot pressing at 100 ° C for 1 minute to obtain a film-like polyphenylene sulfide A polymer film was prepared.

The upper Kapton film was removed, the polyphenylene sulfide polymer film thus prepared was subjected to scratching using a knife, and the scratch-formed film was heat-treated in an oven at 180 ° C to visually observe the self-healing function of the scratch. Is shown in Fig.

3, since the polyphenylene sulfide polymer film produced according to the present invention has a high sulfur content, surface scratches originating from the outside are formed by a mechanism of forming a thermoreversible disulfide bond (SS bond) It has a function of self-healing.

Claims (10)

Preparing elemental sulfur (S);
Preparing an aromatic dihalogen compound having two halogen groups in a molecular structure;
Mixing the aromatic dihalogen compound and sulfuric acid sulfur in a silicone oil to prepare a mixed solution; And
And heating the mixed solution to form a polymer. The polyphenylene sulfide solution polymerization method according to claim 1, The method according to claim 1,
Wherein the aromatic dihalogen compound having two halogen groups in the molecular structure is a compound having a chemical structure represented by the following Chemical Formula 1:
&Lt; Formula 1 >

In the above formula (1), X is any one of Cl, Br and I. The method according to claim 1,
Wherein the aromatic dihalogen compound having two halogen groups in the molecular structure is a compound having a chemical structure represented by the following Chemical Formula 2:
(2)
X-Aryl-X
In Formula 2, X is any one of Cl, Br, and I, Aryl is

,

,

&Lt; / RTI > The method according to claim 1,
Wherein the mixing ratio of the aromatic dihalogen compound and the elemental sulfur in the mixed solution is 1: 1 to 1: 6 in a molar ratio. The method according to claim 1,
Wherein the step of forming the polymer comprises heating the mixed solution to 150 to 250 ^° C. The method according to claim 1,
Further comprising the step of purifying the polymer produced using toluene after the step of forming the polymer. 6. A process for producing a polyurethane foam, which is produced by the process of any one of claims 1 to 6,
And a sulfur content of 33 to 71% by weight in the polymer, polyphenylene sulfide polymer, characterized in that the glass transition temperature (T _g) of 21 to 106 ℃. A polyphenylene sulfide polymer of claim 7; And
Wherein the positive electrode active material is a carbonaceous material. A cathode comprising the cathode active material of claim 8; cathode; And an electrolyte. A polyphenylene sulfide polymer comprising the polyphenylene sulfide polymer of claim 7,
Wherein the surface scratches derived from the outside have a self-healing function by a thermoreversible disbonding (SS bond) formation mechanism.

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