KR20210052074A - Manufacturing Method of Polyarylene Sulfide Having Hydrophilic Functional Group - Google Patents

Abstract

The present invention relates to a method for manufacturing polyarylene sulfide having a hydrophilic functional group introduced therein, comprising: a first step of manufacturing sulfide of an alkali metal; a second step of manufacturing slurry containing polyarylene sulfide; and a third step of manufacturing the polyarylene sulfide into which the hydrophilic functional group is introduced. In the method for manufacturing polyarylene sulfide according to an exemplary embodiment of the present invention, it is possible to provide the polyarylene sulfide into which the hydrophilic functional group is introduced having excellent thermal stability.

Description

Manufacturing Method of Polyarylene Sulfide Having Hydrophilic Functional Group}

The present invention relates to a method for producing polyarylene sulfide into which a hydrophilic functional group is introduced, and more particularly, to a method for producing polyarylene sulfide into which a hydrophilic functional group having excellent kneaability with a coupling agent, glass fiber, etc. is introduced.

Polyarylene sulfide (PAS) is a material that replaces metals, especially 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 workability. It is widely used. Meanwhile, since polyphenylene sulfide (PPS) has good fluidity, it is preferable to mix it with a filler or reinforcing agent such as glass fiber.

Typically, PAS is prepared by polymerization of an alkali metal sulfide and a dihalogenated aromatic compound under polymerization conditions in the presence of a polar organic compound such as N-methyl pyrrolidone (NMP). The reaction product obtained as a result of the polymerization reaction includes an aqueous phase and an organic phase, and the PAS produced is mainly dissolved and contained in the organic phase. Accordingly, a process for recovering only PAS is additionally performed, mainly after cooling the reaction product to precipitate PAS, performing repeated washing and filtration processes at normal pressure using water and a polar organic solvent, and performing a drying process. Method is used.

However, since the PAS obtained by the above method has strong hydrophobic properties, kneading properties are inferior when mixed with a coupling agent or glass fiber. Therefore, when a molded article is manufactured using the PAS obtained by the conventional method, there is a problem that the mechanical properties of the molded article are deteriorated.

Accordingly, there is a need for a method of manufacturing a PAS having excellent kneading properties with a coupling agent and glass fiber.

The technical problem to be achieved by the present invention is to provide a method for producing polyarylene sulfide into which a hydrophilic functional group having excellent kneaability with a coupling agent, glass fiber, etc. is introduced.

However, the problem to be solved by the present invention is not limited to the above-mentioned problems, and other problems that are not mentioned will be clearly understood by those skilled in the art from the following description.

An exemplary embodiment of the present invention is to react an alkali metal hydrosulfide and an alkali metal hydroxide in a mixed solvent of water and an amide-based compound in the presence of an alkali metal organic acid salt, followed by dehydration, and the alkali metal sulfide A first step of manufacturing; A second step of adding a dihalogenated aromatic compound and an amide compound to the reactor containing the sulfide of the alkali metal and performing a polymerization reaction to prepare a slurry containing polyarylene sulfide; And washing the slurry with water, followed by washing with an amide compound or an amide compound, followed by washing with water, washing with an acidic aqueous solution at high temperature and high pressure, and further washing with water to prepare a polyarylene sulfide having a hydrophilic functional group introduced therein. It provides a method for producing polyarylene sulfide into which a hydrophilic functional group is introduced, including a third step.

The manufacturing method of polyarylene sulfide according to an exemplary embodiment of the present invention can provide a polyarylene sulfide into which a hydrophilic functional group having excellent kneading properties with a coupling agent, glass fiber, and the like is introduced.

In addition, the method for producing polyarylene sulfide according to an exemplary embodiment of the present invention may provide a polyarylene sulfide into which a hydrophilic functional group having excellent thermal stability is introduced.

Further, the method for producing polyarylene sulfide according to an exemplary embodiment of the present invention enables a substitution reaction that is more effective than conventional pickling under high temperature and high pressure conditions, so that even when a low concentration of acid is used, the same as that of using a high concentration of acid. You can get the effect of pickling.

In addition, the method for producing polyarylene sulfide according to an exemplary embodiment of the present invention may provide a polyarylene sulfide into which a hydrophilic functional group having a small amount of total volatile organic compound (tVOC) is introduced.

In the present specification, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components unless otherwise stated.

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

An exemplary embodiment of the present invention is to react an alkali metal hydrosulfide and an alkali metal hydroxide in a mixed solvent of water and an amide-based compound in the presence of an alkali metal organic acid salt, followed by dehydration, and the alkali metal sulfide A first step of manufacturing; A second step of adding a dihalogenated aromatic compound and an amide compound to the reactor containing the sulfide of the alkali metal and performing a polymerization reaction to prepare a slurry containing polyarylene sulfide; And washing the slurry with water, followed by washing with an amide compound or an amide compound, followed by washing with water, washing with an acidic aqueous solution at high temperature and high pressure, and further washing with water to prepare a polyarylene sulfide having a hydrophilic functional group introduced therein. It provides a method for producing polyarylene sulfide into which a hydrophilic functional group is introduced, including a third step.

Hereinafter, a method for producing polyarylene sulfide into which a hydrophilic functional group is introduced according to an exemplary embodiment of the present invention will be described in more detail for each step.

The method for preparing polyarylene sulfide into which a hydrophilic functional group is introduced according to an exemplary embodiment of the present invention may be to prepare a polyarylene sulfide by reacting a reactant in a stoichiometric equivalent.

An exemplary embodiment of the present invention is to react an alkali metal hydrosulfide and an alkali metal hydroxide in a mixed solvent of water and an amide-based compound in the presence of an alkali metal organic acid salt, followed by dehydration, and the alkali metal sulfide It includes a first step of manufacturing.

The alkali metal hydrosulfide may be one or more of lithium hydrogen sulfide, sodium hydrogen sulfide, potassium hydrogen sulfide, rubidium hydrogen sulfide and cesium hydrogen sulfide, and the hydroxide of the alkali metal is lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide. There may be more than one type. The alkali metal hydroxide may be used in an amount of 0.90 to 2.0 equivalents, more specifically 1.0 to 1.5 equivalents, and even more specifically 1.0 to 1.1 equivalents based on 1 equivalent of alkali metal hydrosulfide.

The organic acid salt of the alkali metal is a compound capable of accelerating the polymerization reaction in the second step, and may be at least one of lithium acetate and sodium acetate, and may be 0.01 to 1.0 equivalent, more specifically, based on 1 equivalent of hydrosulfide of the alkali metal. May be used in an amount of 0.01 to 0.8 equivalents, more specifically 0.05 to 0.5 equivalents.

The reaction of an alkali metal hydrosulfide and an alkali metal hydroxide may be carried out in a mixed solvent of water and an amide compound, and specific examples of the amide compound include N,N-dimethylformamide or N,N-dimethyl Amide compounds such as acetamide; Pyrrolidone compounds such as N-methyl-2-pyrrolidone (NMP) or N-cyclohexyl-2-pyrrolidone; Caprolactam compounds such as N-methyl-ε-caprolactam; Imidazolidinone compounds such as 1,3-dialkyl-2-imidazolidinone; Urea compounds such as tetramethyl urea; Or phosphoric acid amide compounds such as hexamethylphosphoric acid triamide, and the like, and any one or a mixture of two or more of them may be used. Among these, the amide-based compound may be more specifically N-methyl-2-pyrrolidone (NMP) when considering the reaction efficiency and the co-solvent effect as a polymerization solvent during polymerization for the production of polyarylene sulfide. Meanwhile, the water may be used in an amount of 1 to 8 equivalents per 1 equivalent of the amide-based compound, more specifically 1.5 to 5 equivalents, and even more specifically 2.5 to 4.5 equivalents.

As a result of the reaction of alkali metal hydrosulfide and alkali metal hydroxide as described above, alkali metal sulfide is precipitated as a solid in the mixed solvent of water and amide compound, and some unreacted alkali metal hydrosulfide remains in the reaction system. can do.

The dehydration reaction in the first step is performed to remove a solvent such as water from among the reaction products including sulfides of alkali metals. According to an exemplary embodiment of the present invention, the dehydration reaction in the first step is performed in the range of 180° C. to 200° C. It may be performed at temperature. Specifically, the dehydration reaction may be performed at a temperature of 180°C to 190°C, 190°C to 200°C, or 185°C to 195°C. When the temperature at which the dehydration reaction is performed is within the above range, the sulfide of the alkali metal and the amide compound used in the second step may be minimized while removing an appropriate amount of water. According to an exemplary embodiment of the present invention, after the dehydration reaction is terminated, the amide compound in the reactor may be present in an amount of 3 to 4 moles per 1 mole of sulfur (S), and water is 1 per 1 mole of sulfur. It may be present in an amount of moles to 2 moles.

According to an exemplary embodiment of the present invention, before performing the second step, it may further include lowering the temperature of the reactor including the sulfide of the alkali metal to a temperature of 150 ℃ to 180 ℃.

An exemplary embodiment of the present invention includes a second step of adding a dihalogenated aromatic compound and an amide-based compound to a reactor containing a sulfide of an alkali metal, followed by polymerization to prepare a slurry containing polyarylene sulfide.

The dihalogenated aromatic compound is a compound in which two hydrogens in the aromatic ring are substituted with halogen atoms, specific examples are o-dihalobenzene, m-dihalobenzene, p-dihalobenzene, dihalotoluene, dihalonaphthalene, Dihalobiphenyl, dihalobenzoic acid, dihalodiphenyl ether, dihalodiphenylsulfone, dihalodiphenylsulfoxide, dihalodiphenyl ketone, and the like, and any one or a mixture of two or more of them may be used. In the dihalogenated aromatic compound, the halogen atom may be fluorine, chlorine, bromine or iodine. Among them, p-dichlorobenzene (p-DCB) may be used in consideration of the reactivity and the effect of reducing side reactions when preparing polyarylene sulfide.

The dihalogenated aromatic compound may be added in an equivalent amount of 0.8 to 1.2 based on 1 equivalent of hydrosulfide of the alkali metal. When added within the above content range, polyarylene sulfide having excellent physical properties can be prepared without fear of lowering the melt viscosity of the produced polyarylene sulfide and increasing the chlorine content present in the polyarylene sulfide. have. Considering the excellence of the improvement effect by controlling the addition amount of the alkali metal sulfide and the dihalogenated aromatic compound, more specifically, the dihalogenated aromatic compound may be added in an equivalent amount of 0.8 to 1.1 based on 1 equivalent of the alkali metal hydrosulfide. have.

The polymerization reaction of the sulfide of an alkali metal and a dihalogenated aromatic compound is an aprotic polar organic solvent, and may be carried out in a solvent of an amide-based compound that is stable against alkali at high temperature. Specific examples of the amide-based compound are as described above, and in consideration of reaction efficiency among the exemplified compounds, more specifically, the amide-based compound is N-methyl-2-pyrrolidone (NMP) or N-cyclo It may be a pyrrolidone compound such as hexyl-2-pyrrolidone.

During the polymerization reaction, other additives for controlling the polymerization reaction or molecular weight, such as a molecular weight control agent and a crosslinking agent, may be further added in an amount within a range that does not degrade the physical properties and production yield of the finally produced polyarylene sulfide.

The polymerization reaction of the alkali metal sulfide and the dihalogenated aromatic compound may be performed at 200°C to 300°C. Alternatively, it may be performed in multiple steps by changing the temperature within the above-described temperature range. Specifically, after the first polymerization reaction at 200°C to less than 250°C, the secondary polymerization reaction may be carried out at a temperature higher than the temperature during the first polymerization reaction, specifically at 250°C to 300°C. .

In an exemplary embodiment of the present invention, the slurry is washed with water and then washed with an amide compound or an amide compound and then washed with water, washed with an acidic aqueous solution at high temperature and high pressure, and then washed with water, whereby a hydrophilic functional group is introduced. And a third step of preparing polyarylene sulfide.

The third step includes washing the slurry at least four times. Specifically, it includes a step of sequentially washing the slurry with water, an amide compound, an acidic aqueous solution, and water, or sequentially washing the slurry with an amide compound, water, an acidic aqueous solution, and water.

The process of washing the slurry with water according to an exemplary embodiment of the present invention is to remove sodium chloride (NaCl) and a base component, which are by-products generated when preparing a slurry containing polyarylene sulfide. According to an exemplary embodiment of the present invention, the third step of washing with water may be performed at a temperature of 80°C to 90°C. When the temperature at the time of washing with water is within the above range, the solubility of by-products generated during the production of polyarylene sulfide in water may be increased to maximize the removal of by-products such as sodium chloride.

According to an exemplary embodiment of the present invention, the washing with the amide-based compound in the third step may be performed at a temperature of 140°C to 160°C. When the temperature at the time of washing with the amide compound is within the above range, the solubility of the by-product generated during the production of polyarylene sulfide in water can be increased to maximize the removal of the by-product.

The present invention can introduce a hydrophilic functional group to the polyarylene sulfide, including the step of washing the slurry with an acidic aqueous solution at high temperature and high pressure in the third step. Accordingly, the polyarylene sulfide prepared according to an exemplary embodiment of the present invention may have increased hydrophilicity, thereby increasing kneading properties with a coupling agent, glass fiber, and the like. That is, the polyarylene sulfide prepared according to the manufacturing method of the present invention may have improved reactivity when mixed with a coupling agent, glass fiber, or the like. Therefore, a molded article made of a composition including a polyarylene sulfide, a coupling agent, and glass fiber into which a hydrophilic functional group prepared according to an exemplary embodiment of the present invention is introduced may have excellent mechanical properties, for example, strength. .

According to an exemplary embodiment of the present invention, washing with an acidic aqueous solution at high temperature and high pressure in the third step may be performed at a pressure of more than 1 bar and less than or equal to 15 bar. Specifically, the pressure when washing with an acidic aqueous solution at high temperature and high pressure may be 2 bar to 14 bar, 3 bar to 13 bar, 4 bar to 12 bar, 5 bar to 11 bar, or 6 bar to 10 bar. When the pressure when washing with an acidic aqueous solution at high temperature and high pressure is within the above range, the washing effect of residual by-products may be increased. Accordingly, it is possible to provide a polyarylene sulfide into which a hydrophilic functional group having a small amount of total volatile organic compound (tVOC) is introduced. And, it is possible to provide a polyarylene sulfide into which a hydrophilic functional group having excellent thermal stability is introduced.

According to an exemplary embodiment of the present invention, washing with an acidic aqueous solution at high temperature and high pressure in the third step may be performed at a temperature of more than 90° C. and 200° C. or less. Specifically, the temperature when washing with an acidic aqueous solution at high temperature and high pressure is 100°C to 190°C, 110°C to 180°C, 120°C to 190°C, 130°C to 180°C, 140°C to 170°C, or 150°C to 160°C. ℃ Can be When the temperature at the time of washing with an acidic aqueous solution at high temperature and high pressure is within the above range, the polyarylene sulfide slurry exhibits appropriate fluidity, so that the acid substitution reaction of the end group of the polyarylene sulfide can occur effectively. Specifically, if the temperature exceeds 200 ℃, dissociation reaction may occur due to acid, and the time and cost required to increase the temperature increase, thus preventing an increase in manufacturing cost. In addition, it can withstand high temperature and high pressure conditions. It is possible to prevent the problem of increasing the cost of equipment due to the need for a reactor that is equipped with, and it is possible to prevent the problem of increasing the acid corrosion rate of the reactor. Eventually, the amount of acid used can be reduced, and the process of washing the acid by washing with water can be simplified or eliminated.

According to an exemplary embodiment of the present invention, washing with an acidic aqueous solution at high temperature and high pressure in the third step may be performed in washing water having a pH of 5 to 6. When the pH of the washing water is within the above range, an acid substitution reaction of the end group of polyarylene sulfide may occur effectively. Accordingly, the hydrophilicity of the polyarylene sulfide is increased, so that kneading properties with a coupling agent, glass fiber, and the like may be increased.

The third step according to an exemplary embodiment of the present invention does not include a process of washing with a separate organic solvent after the process of washing with an acidic aqueous solution. According to an exemplary embodiment of the present invention, the process of washing with an acidic aqueous solution and then additionally washing with water in the third step is a process for neutralizing acid, and may be, for example, washing twice with water.

According to an exemplary embodiment of the present invention, the hydrophilic functional group may be at least one of a carboxyl group, a hydroxy group, and an amine group. The hydrophilic functional group may preferably be a carboxyl group.

As described above, the polyarylene sulfide having a hydrophilic functional group introduced according to the manufacturing method of the present invention has a hydrophilic functional group, for example, a carboxy group, at the terminal, and thus has excellent kneading properties with a coupling agent, glass fiber, etc. , As a result, it is possible to provide a molded article having excellent quality. Accordingly, the present invention may be useful in the manufacture of a molded article for metal replacement in automobiles, electrical and electronic products, or mechanical parts, particularly in the manufacture of reflectors, base plates, and the like for automobile lamps that require excellent mechanical properties.

According to an exemplary embodiment of the present invention, the polyarylene sulfide into which the hydrophilic functional group is introduced may be produced in a yield of 85% or more.

_{Reactivity (MFR pps} / MFR _{pps - ca} ) of the polyarylene sulfide prepared according to an exemplary embodiment of the present invention to a coupling agent into which a hydrophilic functional group is introduced may be 2.3 or more. For example, the reactivity of the polyarylene sulfide into which the hydrophilic functional group is introduced may be 2.32 or more. When the reactivity of the polyarylene sulfide into which the hydrophilic functional group is introduced is within the above range, a molded article having excellent mechanical properties may be provided by using the polyarylene sulfide prepared according to an exemplary embodiment of the present invention.

_{The reactivity (MFR pps} / MFR _{pps - gf} ) of the polyarylene sulfide prepared according to an exemplary embodiment of the present invention to the glass fiber into which the hydrophilic functional group is introduced may be 12 or more. For example, the reactivity of the polyarylene sulfide into which a hydrophilic functional group is introduced may be 13 or more or 13.06 or more. When the reactivity of the polyarylene sulfide into which the hydrophilic functional group is introduced is within the above range, a molded article having excellent mechanical properties may be provided by using the polyarylene sulfide prepared according to an exemplary embodiment of the present invention.

_{Melt stability (MFR pps} / MFR _{pps , 20min} ) of the polyarylene sulfide prepared according to an exemplary embodiment of the present invention, the hydrophilic functional group is introduced may be 1 to 1.20. Therefore, the polyarylene sulfide prepared according to an exemplary embodiment of the present invention may have excellent thermal stability.

Hereinafter, examples will be described in detail in order to describe the present invention in detail. However, the embodiments according to the present invention may be modified in various forms, and the scope of the present invention is not construed as being limited to the embodiments described below. The embodiments of the present specification are provided to more completely describe the present invention to those of ordinary skill in the art.

Example One

In a 30 L reactor (manufacturer, product name), 1 equivalent of sodium hydrogen sulfide (NaSH) and 1.05 equivalents of sodium hydroxide (NaOH) were added 4.72 equivalents of DI water and 1.65 equivalents of N-methyl-2-pyrroleone ( NMP) was reacted in the presence of 0.44 equivalents of sodium acetate (NaOAc) in a mixed solvent, followed by dehydration, to prepare _{sodium sulfide (Na 2 S).}

To the reactor containing sodium sulfide, 1.04 equivalents of p-dichlorobenzene (p-DCB) and 1.65 equivalents of NMP were added, the temperature was raised to 230 degrees, and the temperature was maintained for 3 hours, followed by polymerization reaction, and then 260 degrees. After raising the temperature to, a polymerization reaction was carried out while maintaining the temperature for 1 hour to prepare a slurry containing polyphenylene sulfide (PPS).

The PPS slurry was washed at 90° C. with water (5 times the amount of PPS slurry) for 30 minutes, and then washed with NMP at 150° C. for 30 minutes, and acetic acid contained 0.4 wt% at 150° C.·3.5 bar to 4.5 bar. After washing with an aqueous acetic acid solution for 30 minutes, it was further washed twice with water, and dried in a vacuum oven (150° C. for 8 hours) to prepare a polyarylene sulfide into which a carboxy group was introduced.

Example 2

Instead of washing for 30 minutes with an acetic acid aqueous solution containing 0.4 wt% of acetic acid at 150° C.·3.5 bar to 4.5 bar conditions in Example 1, 0.4 wt% of acetic acid was included at 120° C.·1.5 bar to 2.5 bar conditions. Polyarylene sulfide was prepared in the same manner as in Example 1, except that it was washed with an aqueous acetic acid solution for 30 minutes.

Comparative example One

In Example 1, instead of washing with an acetic acid aqueous solution containing 0.4 wt% of acetic acid at 150° C.·3.5 bar to 4.5 bar for 30 minutes, except for washing with deionized water at 90° C.·1 bar for 30 minutes Then, polyarylene sulfide was prepared in the same manner as in Example 1.

Comparative example 2

Instead of washing for 30 minutes with an acetic acid aqueous solution containing 0.4 wt% acetic acid at 150° C.·3.5 bar to 4.5 bar conditions in Example 1, an acetic acid aqueous solution containing 0.4 wt% acetic acid at 90° C.·1 bar condition was used. Polyarylene sulfide was prepared in the same manner as in Example 1, except for washing for 30 minutes.

Comparative example 3

In Example 1, instead of washing with an acetic acid aqueous solution containing 0.4 wt% of acetic acid at 150° C.·3.5 bar to 4.5 bar for 30 minutes, an acetic acid aqueous solution containing 0.8 wt% of acetic acid at 90° C.·1 bar was used. Polyarylene sulfide was prepared in the same manner as in Example 1, except for washing for 30 minutes.

Comparative example 4

In Example 1, instead of washing with an acetic acid aqueous solution containing 0.4 wt% of acetic acid at 150° C.·3.5 bar to 4.5 bar for 30 minutes, an acetic acid aqueous solution containing 0.4 wt% of acetic acid at 210° C.·18 bar was used. Polyarylene sulfide was prepared in the same manner as in Example 1, except for washing for a minute.

Test example One

_{MFR (MFR pps} ) of each of the PPS prepared in Examples 1 and 2 and Comparative Examples 1 to 4; _{MFR (MFR pps - ca} ) after stirring each of 50 g of PPS prepared in Examples 1 and 2 and Comparative Examples 1 to 4 with 0.25 g of A-187 (manufacturer), a silane-based coupling agent; _{And MFR (MFR pps-gf} ) after compounding each of 4000 g of PPS prepared in Examples 1 and 2 and Comparative Examples 1 to 4 with 1600 g of glass fiber (ECS390C, CPIC); MI-4 (Gotffert) ) Using ASTM D1238-04 conditions (5kg, 315 ℃, 4 minutes),

_{After measuring the MFR (MFR pps, 20min} ) of each of the PPSs prepared in Examples 1 and 2 and Comparative Examples 1 to 4 using MI-4 (Gotffert) under (5kg, 315°C, 4 minutes) conditions,

The reactivity of the PPS to the coupling agent and the reactivity to the glass fiber and melt stability were calculated as shown in Equations 1 to 3 below, and the results are shown in Table 1 below.

[Equation 1]

PPS reactivity to coupling agent = MFR _pps / MFR _{pps - ca}

[Equation 2]

Reactivity of PPS to Glass Fiber = MFR _pps / MFR _{pps - gf}

[Equation 3]

Melt Stability = MFR _pps / MFR _{pps , 20min}

Test example 2

1uL of 1.7ug/uL of toluene standard solution prepared by diluting 17mg of toluene in 10ml methanol was injected into a test tube, and a chromatogram was obtained at 320℃/10 minutes using Purge&Trap sampler-GC/MS (JTD-505, JAI). _{, The peak area (A std} ) of the chromatogram of the toluene standard solution was confirmed. In addition, 20 mg of PPS prepared in Examples 1 and 2 and Comparative Examples 1 to 4 were respectively injected into a test tube, and the upper part of the test tube was closed with glass wool, and then Purge&Trap sampler-GC/MS (JTD-505, JAI company) was used. The chromatogram was obtained under the condition of 320° C./10 minutes, and the sum of the peak areas of the chromatogram of volatile substances present in the measurement sample was _{confirmed (A compound} ).

The tVOC content was calculated according to Equation 4 below, and the results are shown in Table 1 below.

[Equation 4]

tVOC _compound = [(A _compound /A _std )*C _std ]/W _sample

tVOC _compound : The content of volatile substances present in 1 g of the measurement sample (ug/g)

A _compound : Sum of peak areas of chromatogram of volatile substances present in the measurement sample

A _std : Peak area of chromatogram of toluene standard solution

C _std : Mass of toluene injected using standard toluene solution (ug)

Wsample: weight of the measurement sample (g)

Reactivity of PPS to the coupling agent (MFR _pps / MFR _pps-ca ) Reactivity of PPS to glass fibers (MFR _pps / MFR _pps-gf ) Melt Stability (MFR _pps /MFR _{pps, 20min} ) tVOC (ppm) Example 1 2.38 13.06 1.2 540 Example 2 2.24 12.08 1.18 580 Comparative Example 1 1.12 5.45 1.54 1020 Comparative Example 2 1.61 10.55 1.23 780 Comparative Example 3 1.87 11.32 1.22 640 Comparative Example 4 2.12 11.54 1.87 1240

Referring to Table 1 above, the PPS prepared in Examples 1 and 2 includes the process of washing the PPS slurry with an acidic aqueous solution at high temperature and high pressure, and the reactivity of PPS to the coupling agent and the reactivity of PPS to the glass fiber It was confirmed that all are superior to Comparative Examples 1 to 4.

In addition, Examples 1 and 2 have a melt stability value close to 1 compared to Comparative Examples 1 to 4, and the difference between the MFR value after standing at a high temperature (315 °C) for 20 minutes and the MFR value after standing for 4 minutes It was confirmed that the is not large. Accordingly, it was found that the method for producing polyarylene sulfide into which a hydrophilic functional group was introduced according to an exemplary embodiment of the present invention provides a polyarylene sulfide having excellent kneading properties with a coupling agent and glass fiber, and excellent thermal stability. I can.

And, it was confirmed that the amount of total volatile organic compounds (tVOC) present in the PPS prepared in Examples 1 and 2 was less than the amount of tVOC present in the PPS prepared in Comparative Examples 1 to 4, from which the present invention It can be seen that the method for producing polyarylene sulfide according to an exemplary embodiment of can provide a polyarylene sulfide into which a hydrophilic functional group having a small amount of total volatile organic compound (tVOC) is introduced.

Therefore, it can be seen that when a molded article is manufactured using the polyarylene sulfide manufactured according to an exemplary embodiment of the present invention, a molded article having excellent mechanical properties can be provided.

Claims (12)

A first step of reacting a hydrosulfide of an alkali metal and a hydroxide of an alkali metal in a mixed solvent of water and an amide compound in the presence of an organic acid salt of an alkali metal and then performing dehydration to prepare a sulfide of an alkali metal;
A second step of adding a dihalogenated aromatic compound and an amide compound to the reactor containing the sulfide of the alkali metal and performing a polymerization reaction to prepare a slurry containing polyarylene sulfide; And
Washing the slurry with water, followed by washing with an amide compound or with an amide compound, followed by washing with water, washing with an acidic aqueous solution at high temperature and high pressure, and further washing with water to prepare a polyarylene sulfide having a hydrophilic functional group introduced therein. Including a third step;
A method for producing polyarylene sulfide into which a hydrophilic functional group is introduced. The method of claim 1,
The dehydration reaction of the first step is carried out at a temperature of 180 ℃ to 200 ℃
A method for producing polyarylene sulfide into which a hydrophilic functional group is introduced. The method of claim 1,
Before performing the second step, further comprising the step of lowering the temperature of the reactor containing the sulfide of the alkali metal to a temperature of 150 ℃ to 180 ℃
A method for producing polyarylene sulfide into which a hydrophilic functional group is introduced. The method of claim 1,
Washing with water in the third step is performed at a temperature of 80 ℃ to 90 ℃
A method for producing polyarylene sulfide into which a hydrophilic functional group is introduced. The method of claim 1,
Washing with the amide-based compound in the third step is performed at a temperature of 140°C to 160°C.
A method for producing polyarylene sulfide into which a hydrophilic functional group is introduced. The method of claim 1,
Washing with an acidic aqueous solution at high temperature and high pressure in the third step is performed at a pressure of more than 1 bar and less than 15 bar.
A method for producing polyarylene sulfide into which a hydrophilic functional group is introduced. The method of claim 1,
Washing with an acidic aqueous solution at high temperature and high pressure in the third step is performed at a temperature of more than 90 ℃ and not more than 200 ℃.
A method for producing polyarylene sulfide into which a hydrophilic functional group is introduced. The method of claim 1,
Washing with an acidic aqueous solution at high temperature and high pressure in the third step is performed in washing water having a pH of 5 to 6
A method for producing polyarylene sulfide into which a hydrophilic functional group is introduced. The method of claim 1,
The hydrophilic functional group is at least one of a carboxyl group, a hydroxy group, and an amine group.
A method for producing polyarylene sulfide into which a hydrophilic functional group is introduced. The method of claim 1,
The polyarylene sulfide into which the hydrophilic functional group is introduced is produced in a yield of 85% or more.
A method for producing polyarylene sulfide into which a hydrophilic functional group is introduced. The method of claim 1,
The reactivity of the polyarylene sulfide into which the hydrophilic functional group is introduced to the coupling agent (MFR _pps / MFR _pps-ca ) is 2.3 or more.
A method for producing polyarylene sulfide into which a hydrophilic functional group is introduced. The method of claim 1,
The reactivity of the polyarylene sulfide into which the hydrophilic functional group is introduced to the glass fiber (MFR _pps / MFR _pps-gf ) is 12 or more.
A method for producing polyarylene sulfide into which a hydrophilic functional group is introduced.