KR102690259B1 - Surface-modified polyphenylene sulfide, method for preparing the same and surface-modified polyphenylene sulfide solution comprising the same - Google Patents

Abstract

The present invention relates to surface-modified polyphenylene sulfide, a method for producing the same, and a surface-modified polyphenylene sulfide solution containing the same. More specifically, the present invention relates to a surface-modified polyphenylene sulfide solution containing the same, and more specifically, to adjust the molecular weight of the polyphenylene sulfide by doping an organic receptor into the polyphenylene sulfide. By reducing , the solubility of the polyphenylene sulfide in the organic solvent can be improved, thereby improving process convenience.

Description

Surface-modified polyphenylene sulfide, manufacturing method thereof, and surface-modified polyphenylene sulfide solution containing the same {SURFACE-MODIFIED POLYPHENYLENE SULFIDE, METHOD FOR PREPARING THE SAME AND SURFACE-MODIFIED POLYPHENYLENE SULFIDE SOLUTION COMPRISING THE SAME}

The present invention relates to surface-modified polyphenylene sulfide, a method for producing the same, and a surface-modified polyphenylene sulfide solution containing the same.

Recently, the demand for thermoplastic resins with high heat resistance and good chemical resistance has been increasing as materials for electrical and electronic device parts and chemical device parts. Polyphenylene sulfide (PPS), one of these thermoplastic resins, is a material that replaces die casting metals such as aluminum or zinc in automobiles, electrical and electronic products, and machinery due to its excellent strength, heat resistance, flame retardancy, and processability. is in the spotlight.

POLYPHENYLENESULFIDE (PPS), also known as polyarylene sulfide, is a high-performance engineering thermoplastic material that can be heated and formed into desired shapes for a variety of manufacturing, sales and consumption applications. PPS can be used in the manufacture of fibers, films, coatings, injection molding compounds, and fiber-reinforced composites, and is well suited for demanding applications in the appliance, automotive, and electrical/electronic industries. PPS can be incorporated as a manufacturing component, either alone or mixed with other materials such as elastomeric materials, copolymers, resins, reinforcing agents, additives, other thermoplastic materials, etc.

Polyphenylene sulfide has little solubility in organic solvents and shows a solubility of less than 10% near the boiling point of the solvent.

Referring to US Patent No. 5,043,112, it can be seen that the solubility of polyphenylene sulfide in NMP (N-Methyl-2-pyrrolidinone), an organic solvent, is 10% or less at 203°C.

As such, polyphenylene sulfide has a problem of poor process convenience due to its low solubility in organic solvents.

Korean Patent Publication No. 1998-024567 provides polyphenylene sulfoxide obtained by oxidizing polyphenylene sulfide, and discloses that the polyphenylene sulfoxide exhibits the property of being completely soluble in NMP, but still contains polyphenylene sulfide. There is no solution to the low solubility problem.

Accordingly, there is a need to improve the convenience of processes using polyphenylene sulfide through the development of technology that can improve the solubility of polyphenylene sulfide in organic solvents.

US Patent No. 5,043,112 Korean Patent Publication No. 1998-024567

The present inventors conducted various studies to solve the above problems, and as a result, by reducing the molecular weight of polyphenylene sulfide through surface modification of polyphenylene sulfide, polyphenylene sulfide with improved solubility in organic solvents and the same The object is to provide a polyphenylene sulfide solution containing.

To achieve the above object, the present invention provides surface-modified polyphenylene sulfide doped with an organic receptor.

The organic receptor may be a quinone-based dopant.

The quinone-based dopants include chloranyl (tetrachloro-1,4-benzoquinone), DDQ (2,3-Dichloro-5,6-dicyano-1,4-benzoquinone), and TCNQ (7,7,8,8-Tetracyanoquinodimethane) ) and TCNE (Tetracyanoethylene).

The organic receptor may be doped at 1 to 50% by weight based on the total weight of the surface-modified polyphenylene sulfide.

The molecular weight of the surface-modified polyphenylene sulfide may be 100 g/min or less based on MFR.

The solubility of the surface-modified polyphenylene sulfide in an organic solvent may be 10 to 100.

The organic solvent is N-methylpyrrolidone (NMP), 1,3-dimethyl-2-imidazolidinone (DMI), dimethyl sulfoxide (DMSO), dimethylacetamide (DMAc), and dimethylformamide (DMF). , N-methylformamide (NMF), tetramethylene sulfone, butyl diglycol (BDG), ethyl diglycol (EDG), methyl diglycol (MDG), triethylene glycol , TEG), diethylene glycol monoethyl ether (DEM), and diethylene glycol monobutyl ether (diethylene glycol monoethylether).

The present invention also provides a method for producing surface-modified polyphenylene sulfide, comprising reacting polyphenylene sulfide powder and an organic receptor at high temperature.

The reaction may be gas phase doping at a high temperature of 150 to 220°C.

The present invention also provides a surface-modified polyphenylene sulfide solution in which the surface-modified polyphenylene sulfide is dissolved in an organic solvent.

The present invention also includes the step of (S1) dissolving the surface-modified polyphenylene sulfide of any one of claims 1 to 7 in an organic solvent; and (S2) heat treating the product of step (S1); A method for producing a surface-modified polyphenylene sulfide solution comprising a is provided.

The heat treatment in step (S2) may be performed at 150 to 250°C.

According to the present invention, the molecular weight of polyphenylene sulfide surface-modified with an organic receptor can be reduced and the solubility in organic solvents can be improved.

In this way, the process using polyphenylene sulfide with improved solubility in organic solvents has the effect of improving convenience.

Figure 1 shows photographs of a surface-modified polyphenylene sulfide solution and a polyphenylene sulfide solution before and after heat treatment in Example 1 and Comparative Example 1.

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

Surface modified polyphenylene sulfide

The present invention relates to surface-modified polyphenylene sulfide (PPS), and the surface-modified polyphenylene sulfide may be polyphenylene sulfide doped with an organic acceptor (dopant).

In the surface-modified polyphenylene sulfide according to the present invention, the polyphenylene sulfide polymer backbone is charged as a charge transfer complex is formed by doping polyphenylene sulfide with an organic acceptor. By changing into an ion-like form, the solubility in organic solvents can increase.

In addition, the surface-modified polyphenylene sulfide according to the present invention may have an increased solubility in organic solvents due to a decrease in molecular weight due to high-temperature doping when the organic receptor is doped into polyphenylene sulfide.

For example, the following Chemical Formula 1 shows surface-modified polyphenylene sulfide in the form of a charge transfer complex formed by doping the polyphenylene sulfide backbone (+) with Chloranil (-), a quinone-based dopant.

<Formula 1>

In the present invention, the organic receptor may be a quinone-based dopant. The quinone-based dopant has high oxidation properties and may be advantageous for charge formation in PPS.

In addition, the quinone-based dopants include chloranyl (tetrachloro-1,4-benzoquinone), DDQ (2,3-Dichloro-5,6-dicyano-1,4-benzoquinone), and TCNQ (7,7,8,8- It may contain one or more selected from the group consisting of Tetracyanoquinodimethane (TCNE) and Tetracyanoethylene (TCNE), and preferably may be Chloranil.

The organic receptor may be doped at 1 to 50% by weight, preferably 3 to 50% by weight, and more preferably 10 to 40% by weight, based on the total weight of the surface-modified polyphenylene sulfide. If it is less than the above range, it may be difficult to form a charge transfer complex of the polyphenylene sulfide, or the molecular weight reduction effect may be minimal, and if it is more than the above range, unreacted organic receptors may remain and the PPS doping effect may be lost.

In the present invention, the molecular weight of the surface-modified polyphenylene sulfide is 100 g/min or less, preferably more than 30 g/min, 90 g/min or less, more preferably 40 g/min based on MFR (Melt Flow Rate). min and may be less than or equal to 80 g/min, and within the above range, the smaller the molecular weight, the better the solubility improvement effect of the surface-modified polyphenylene sulfide in the organic solvent. If the above range is exceeded, the solubility of the surface-modified polyphenylene sulfide in the organic solvent may be reduced. At this time, the MFR refers to the melt mass-flow rate (MFR, 316°C/5.0kg).

In the present invention, the solubility of the surface-modified polyphenylene sulfide in an organic solvent may be 10 to 100, preferably 20 to 95, and more preferably 30 to 90. If it is below the above range, the solubility may be low and it may be difficult to proceed with a process such as a solution process, and if it is above the above range, the characteristics such as strength and heat resistance inherent to polyphenylene sulfide may not be expected. At this time, the solubility may mean solubility at the boiling point of the organic solvent.

In the present invention, the organic solvent is N-methylpyrrolidone (NMP), 1,3-dimethyl-2-imidazolidinone (DMI), dimethyl sulfoxide (DMSO), dimethylacetamide (DMAc), dimethyl Formamide (DMF), N-methylformamide (NMF), tetramethylenesulfone, butyl diglycol (BDG), ethyl diglycol (EDG), methyl diglycol (MDG), triglyceride It may be one or more selected from the group consisting of ethylene glycol (TEG), diethylene glycol monoethylether (DEM), and diethylene glycol monobutyl ether, but is not limited thereto, and is preferred. It could be NMP.

The surface-modified polyphenylene sulfide as described above is doped with an organic dopant and becomes charged as a charge transfer complex is formed, increasing its solubility in organic solvents. Additionally, as it is doped with the organic dopant, its molecular weight is reduced, resulting in an organic Solubility in solvents may be increased.

Additionally, as the solubility of the surface-modified polyphenylene sulfide increases, processes such as solution processes can proceed smoothly.

Method for producing surface-modified polyphenylene sulfide

The present invention also relates to a method for producing surface-modified polyphenylene sulfide, which may include reacting polyphenylene sulfide powder and an organic receptor at high temperature. Specifically, the reaction may be gas phase doping at high temperature.

The high temperature heat treatment can reduce the molecular weight of the surface-modified polyphenylene sulfide doped with the organic receptor.

The high temperature reaction step may be 150 to 220°C, preferably 180 to 210°C, and more preferably 190 to 205°C. If it is less than the above range, the reduction in the molecular weight of polyphenylene sulfide due to organic receptor doping may be minimal, and if it is more than the above range, polyphenylene sulfide may be denatured.

In addition, the reaction may preferably be carried out under a N ₂ atmosphere and in a vacuum of 10 ^-3 to 0 ^-1 torr.

In addition, the vapor phase doping may proceed through a mechanism in which the dopant is vaporized at high temperature and then reacts and dopes the polymer surface.

Additionally, the polyphenylene sulfide powder may have an average diameter of 5 to 15 ㎛, preferably 8 to 12 ㎛. The powder-type polyphenylene sulfide has a large surface area, so doping efficiency can be excellent and uniformity can be high.

Surface modified polyphenylene sulfide solution

The present invention also relates to a surface-modified polyphenylene sulfide solution containing the surface-modified polyphenylene sulfide and an organic solvent as described above.

Since the solubility of the surface-modified polyphenylene sulfide is high in organic solvents, the sulfur derived from the surface-modified polyphenylene sulfide may be dissolved, thereby increasing the sulfur content in the surface-modified polyphenylene sulfide solution.

Method for producing surface-modified polyphenylene sulfide solution

The present invention also includes the step of (S1) dissolving the surface-modified polyphenylene sulfide of any one of claims 1 to 7 in an organic solvent; and (S2) heat treating the product of step (S1); It relates to a method for producing a surface-modified polyphenylene sulfide solution containing.

The surface-modified polyphenylene sulfide may be in powder form.

The heat treatment in step (S2) may be performed at 150 to 250°C, preferably 170 to 130°C, and more preferably 190 to 210°C. If it is less than the above range, it may be difficult to completely dissolve the surface-modified polyphenylene sulfide powder in an organic solvent, and if it is more than the above range, the surface-modified polyphenylene sulfide may be denatured. Additionally, the organic solvent is the same as previously described.

Additionally, the surface-modified polyphenylene sulfide solution can be purified to improve purity.

Preferred examples are presented below to aid understanding of the present invention. However, the following examples are merely illustrative of the present invention, and it is obvious to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention. It is natural that changes and modifications fall within the scope of the attached patent claims.

Example 1

(1) Manufacturing of surface-modified polyphenylene sulfide

In a high pressure reactor of 10 ^-2 torr, under high temperature conditions of 200°C, 66% by weight of polyphenylene sulfide powder and 34% by weight of chloranil, an organic acceptor, are reacted, and the chloranil is vapor-doped into the polyphenylene sulfide. , surface-modified polyphenylene sulfide in powder form was prepared.

(2) Preparation of surface-modified polyphenylene sulfide solution

50 mg of the surface-modified polyphenylene sulfide powder was added to 50 ml of NMP, an organic solvent, and dissolved at 203°C for 24 hours, then purified using a micro filter to prepare a surface-modified polyphenylene sulfide solution.

Comparative Example 1

50 mg of polyphenylene sulfide powder was added to 50 ml of NMP, an organic solvent, and dissolved at 203°C for 24 hours, then purified using a microfilter to prepare a surface-modified polyphenylene sulfide solution.

Experimental Example 1: Observation of polyphenylene sulfide solution before and after heat treatment

Figure 1 shows photographs of a surface-modified polyphenylene sulfide solution and a polyphenylene sulfide solution before and after heat treatment in Example 1 and Comparative Example 1.

Referring to Figure 1, the color of the surface-modified polyphenylene sulfide solution of Example 1 is dark even before heat treatment, so the solubility of the surface-modified polyphenylene sulfide in NMR is good, and after heat treatment, the color of the solution becomes darker and the solubility increases. It can be seen that is further improved.

In addition, since the polyphenylene sulfide solution of Comparative Example 1 was transparent before heat treatment, it can be seen that polyphenylene sulfide that was not surface-modified was hardly dissolved in NMP. In addition, after heat treatment of the polyphenylene sulfide solution, the color of the solution is relatively darker than before heat treatment, but is not relatively dark compared to Example 1, so polyphenylene sulfide without surface modification has poor solubility in NMP. can be seen.

Experimental Example 2: Measurement of sulfur content in polyphenylene sulfide solution

In a polyphenylene sulfide solution containing an organic solvent, sulfur derived from the polyphenylene sulfide is dissolved in the organic solvent, so the solubility of the polyphenylene sulfide in the organic solvent can be determined by the sulfur content.

Accordingly, the content of sulfur contained in the surface-modified polyphenylene sulfide solution and the polyphenylene sulfide solution prepared in Example 1 and Comparative Example 1, respectively, was analyzed. In addition, the sulfur content in NMP used as an organic solvent as a control (Ref.) was also analyzed.

The sulfur content was analyzed by X-Ray Fluorescence (XRF, ED-XRF Semi-Quant, NEX CG, Rigaku), and the results are shown in Table 1 below.

division Sulfur content (ppm) Ref. 4.19 Comparative Example 1 99 Example 1 633

Referring to Table 1, it can be seen that the sulfur content in the surface-modified polyphenylene sulfide solution of Example 1 is significantly higher than the sulfur content in the NMP of Ref. or the polyphenylene sulfide solution of Comparative Example 1. At this time, the sulfur detected in the NMP of Ref. was measured due to the equipment error range of ±10 ppm.

From these results, polyphenylene sulfide doped with an organic receptor, that is, surface-modified polyphenylene sulfide, has high solubility in organic solvents, and when the surface-modified polyphenylene sulfide is dissolved in an organic solvent and then heat-treated It can be seen that solubility is further improved.

Although the present invention has been described above with limited examples and drawings, the present invention is not limited thereto, and the technical idea of the present invention and the following description will be provided by those skilled in the art in the technical field to which the present invention pertains. Of course, various modifications and variations are possible within the scope of equivalence of the patent claims.

Claims (12)

A surface-modified polyphenylene sulfide doped with an organic receptor,
The organic receptor is a quinone-based dopant,
The organic receptor is doped at 10 to 40% by weight based on the total weight of the surface-modified polyphenylene sulfide,
The surface-modified polyphenylene sulfide is manufactured by gas phase doping of polyphenylene sulfide powder and an organic receptor at 190 to 205°C. delete According to paragraph 1,
The quinone-based dopants include chloranyl (tetrachloro-1,4-benzoquinone), DDQ (2,3-Dichloro-5,6-dicyano-1,4-benzoquinone), and TCNQ (7,7,8,8-Tetracyanoquinodimethane). and TCNE (Tetracyanoethylene), which includes at least one selected from the group consisting of surface-modified polyphenylene sulfide. delete delete According to paragraph 1,
The surface-modified polyphenylene sulfide has a solubility in an organic solvent of 10 to 100. According to clause 6,
The organic solvent is N-methylpyrrolidone (NMP), 1,3-dimethyl-2-imidazolidinone (DMI), dimethyl sulfoxide (DMSO), dimethylacetamide (DMAc), and dimethylformamide (DMF). , N-methylformamide (NMF), tetramethylene sulfone, butyl diglycol (BDG), ethyl diglycol (EDG), methyl diglycol (MDG), triethylene glycol , TEG), surface-modified polyphenylene sulfide, at least one selected from the group consisting of diethylene glycol monoethylether (DEM) and diethylene glycol monobutyl ether. A method for producing the surface-modified polyphenylene sulfide of claim 1, comprising reacting polyphenylene sulfide powder and an organic receptor at 190 to 205°C. delete A surface-modified polyphenylene sulfide solution comprising the surface-modified polyphenylene sulfide of any one of claims 1, 3, 6, and 7 and an organic solvent. (S1) dissolving the surface-modified polyphenylene sulfide of any one of claims 1, 3, 6, and 7 in an organic solvent; and
(S2) heat treating the product of step (S1);
Method for producing a surface-modified polyphenylene sulfide solution comprising. According to clause 11,
A method for producing a surface-modified polyphenylene sulfide solution, wherein the heat treatment in step (S2) is performed at 150 to 250 ° C.