阅读说明：本技术 聚芳硫醚的制备方法 (Process for producing polyarylene sulfide ) 是由 朴银珠 金汉率 韩仲镇 柳昡旭 郑权洙 张容溱 于 2018-11-23 设计创作，主要内容包括：本公开内容涉及聚芳硫醚的制备方法,并且该方法可以通过除现有材料之外添加脂族氨基酸盐酸盐以用于脱水来以高产率生产具有等于或高于常规方法的聚芳硫醚的特性的聚芳硫醚。(The present disclosure relates to a method for preparing polyarylene sulfide, and the method can produce polyarylene sulfide having characteristics equal to or higher than those of conventional methods in high yield by adding an aliphatic amino acid hydrochloride in addition to existing materials for dehydration.)

1. A method of preparing a polyarylene sulfide, comprising:

by combining in water and amide-based compoundsIn a mixed solvent of the above components in the presence of an alkali metal organic acid salt and C_1-20A first step of dehydrating an alkali metal hydrosulfide and an alkali metal hydroxide in the presence of an aliphatic amino acid hydrochloride to prepare a mixed solvent comprising water and an amide-based compound, and a sulfur source of the alkali metal sulfide; and

a second step of adding a dihalo-aromatic compound and an amide-based compound to a reactor containing the sulfur source and carrying out a polymerization reaction to produce a polyarylene sulfide.

2. The method for producing polyarylene sulfide according to claim 1, wherein the aliphatic amino acid hydrochloride is used in an amount of 0.01 to 0.50 equivalent based on 1 equivalent of the sulfur source.

3. The method for producing polyarylene sulfide according to claim 1, wherein the aliphatic amino acid hydrochloride is at least one selected from the group consisting of (methylamino) butyric acid hydrochloride, (methylamino) propionic acid hydrochloride, and (methylamino) acetic acid hydrochloride.

4. The method for producing polyarylene sulfide according to claim 1, wherein water in the first step is used in an amount of 1 to 8 equivalents based on 1 equivalent of the amide-based compound.

5. The method for producing polyarylene sulfide according to claim 1, wherein the alkali metal organic acid salt is used in an amount of 0.01 to 1.0 equivalent based on 1 equivalent of the alkali metal hydrosulfide.

6. The method for producing polyarylene sulfide according to claim 1, wherein the alkali metal organic acid salt includes lithium acetate, sodium acetate or a mixture thereof.

7. The method for producing polyarylene sulfide according to claim 1, wherein a dehydration reaction is performed at a temperature of 130 ℃ to 205 ℃ in the first step.

8. The method for producing polyarylene sulfide according to claim 1, wherein the dihalo-aromatic compound includes at least one selected from the group consisting of: o-dihalobenzene, m-dihalobenzene, p-dihalobenzene, dihalotoluene, dihalonaphthalene, dihalobiphenyl, dihalobenzoic acid, dihalodiphenyl ether, dihalodiphenyl sulfone, dihalodiphenyl sulfoxide and dihalobenzophenone.

9. The method for producing polyarylene sulfide according to claim 1, wherein the dihalo-aromatic compound is used in an amount of 0.8 to 1.2 equivalents based on 1 equivalent of the sulfur source.

10. The method for producing polyarylene sulfide according to claim 1, wherein the polyarylene sulfide is produced at a yield of 66.5% or more and has a melting point (T) of 270 ℃ to 300 ℃_m) And a crystallization point (T) of 200 ℃ to 250 ℃_c)。

11. The method for producing polyarylene sulfide according to claim 1, further comprising a step of reducing the temperature of the reactor containing the sulfur source to a temperature of 150 ℃ to 200 ℃ before the second step.

12. The method for producing polyarylene sulfide according to claim 1, further comprising a cooling step of adding water in an amount of 3 to 5 equivalents based on 1 equivalent of sulfur to the reaction mixture after the second step.

13. The method for producing polyarylene sulfide according to claim 12, further comprising a step of washing the reaction mixture with water and an amide-based compound and then drying the reaction mixture after the cooling step.

Technical Field

Cross Reference to Related Applications

This application claims the benefit of korean patent application No. 10-2017-0158921, filed 24.11.2017 to the korean intellectual property office, the disclosure of which is incorporated herein by reference in its entirety.

The present disclosure relates to a method for producing a polyarylene sulfide having a high polymerization degree and exhibiting excellent strength, heat resistance, flame retardancy, and processability when processed into a molded product with high yield.

Background

Polyarylene sulfide (PAS) represented by polyphenylene sulfide (PPS) is widely used for automobiles, electric and electronic products, machinery, and the like to replace metals, particularly die cast metals such as aluminum and zinc, due to its excellent strength, heat resistance, flame retardancy, and processability. In particular, since the PPS resin has excellent fluidity, it is suitable for use as a composite by kneading it with a filler such as glass fiber or a reinforcing agent.

Generally, PAS is prepared by polymerizing a sulfur source and a dihalo-aromatic compound in the presence of an amide-based compound such as N-methylpyrrolidone (NMP). Optionally, a molecular weight regulator such as an alkali metal salt may be further used.

As PAS is widely used for various purposes, particularly as a molded product by melt processing, PAS having excellent product characteristics and moldability (e.g., high degree of polymerization, particularly high melt viscosity) is required. As the demand for PAS increases, there is also a need to improve the yield of PAS production. For example, japanese patent No. 5623277 discloses a process for producing granular PAS, which comprises: a step of adding aromatic compounds such as dihalo-aromatic compounds and trihaloaromatic compounds to a liquid phase in a polymerization reaction system after a phase separation polymerization process, and a step of cooling the liquid phase, and which can produce a granular PAS in a high yield while maintaining a high level of melt viscosity. There is a need for a process capable of further improving the yield of PAS having a high degree of polymerization.

Therefore, in a process for producing polyarylene sulfide in which a sulfur source and a dihalo-aromatic compound are subjected to a polymerization reaction in the presence of an amide-based compound, research into a method of producing polyarylene sulfide having a high polymerization degree with high yield is required.

Disclosure of Invention

Technical problem

The present disclosure is directed to providing a method for preparing polyarylene sulfide having excellent strength, heat resistance, flame retardancy, processability, etc. in high yield by adding aliphatic amino acid hydrochloride in a dehydration reaction for preparing a sulfur source.

Technical scheme

According to one embodiment of the present disclosure, there is provided a method for preparing polyarylene sulfide, including: by dissolving an alkali metal organic acid salt and C in a mixed solvent of water and an amide-based compound_1-20A first step of dehydrating an alkali metal hydrosulfide and an alkali metal hydroxide in the presence of an aliphatic amino acid hydrochloride to prepare a mixed solvent comprising water and an amide-based compound, and a sulfur source of the alkali metal sulfide; and a second step of adding the dihalo-aromatic compound and the amide-based compound to a reactor containing a sulfur source and carrying out a polymerization reaction to produce the polyarylene sulfide.

In the present disclosure, polyarylene sulfide may be produced in a yield of about 66.5% or more, and may have a melting point (T) of 270 ℃ to 300 ℃_m) And a crystallization point (T) of 200 ℃ to 250 ℃_c)。

Advantageous effects

According to the present disclosure, a polyarylene sulfide having excellent strength, heat resistance, flame retardancy, processability, and the like can be produced in high yield by additionally introducing an aliphatic amino acid hydrochloride into a dehydration reaction of a sulfur source used in polymerization for producing the polyarylene sulfide.

Drawings

Fig. 1 is a schematic illustration of a process for preparing polyarylene sulfide according to example 1 of one embodiment of the present disclosure.

Fig. 2 is a schematic view of a process for preparing polyarylene sulfide according to comparative example 1 of the prior art.

Detailed Description

In the present disclosure, the terms "first", "second", and the like are used to describe various components, and these terms are used only to distinguish one component from another component.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular forms are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms "comprises," "comprising," "has," "having," or "having," when used in this specification, specify the presence of stated features, integers, steps, components, or groups thereof, but do not preclude the presence or addition of one or more other features, integers, steps, components, or groups thereof.

While the invention is amenable to various modifications and alternative forms, specifics thereof have been shown by way of example and will be described in detail. However, it is not intended to limit the invention to the particular forms disclosed, and it should be understood that the invention includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

Hereinafter, the present disclosure will be described in detail.

According to an embodiment of the present disclosure, there is provided a method for producing a polyarylene sulfide, in which the polyarylene sulfide is provided in high yield by a polymerization reaction additionally introducing an aliphatic amino acid hydrochloride, a sulfur source and a dihalo-aromatic compound into a dehydration reaction for producing the sulfur source.

The preparation method of the polyarylene sulfide comprises the following steps: by dissolving an alkali metal organic acid salt and C in a mixed solvent of water and an amide-based compound_1-20Preparation of water and acyl radicals by dehydration of alkali metal hydrosulfides and alkali metal hydroxides in the presence of aliphatic amino acid hydrochloridesA first step of mixing a solvent mixture of an amine compound and a sulfur source of an alkali metal sulfide; and a second step of adding the dihalo-aromatic compound and the amide-based compound to a reactor containing a sulfur source and carrying out a polymerization reaction to produce the polyarylene sulfide.

In particular, the present disclosure can readily produce polyarylene sulfides that are capable of providing a final polymer product having thermal properties equal to or higher than those of conventional polymer products, via the promotion of the formation of sodium (4-methylamino) butyrate (SMAB) known to contribute to the polymerization reaction by the addition of an aliphatic amino acid hydrochloride in the dehydration to produce a sulfur source to be subjected to the polymerization reaction with a dihaloaromatic compound to produce the polyarylene sulfide. The method of preparing polyarylene sulfide of the present disclosure can also improve the yield and increase the amount of the final product.

First, the respective steps of the method for producing polyarylene sulfide according to one embodiment of the present disclosure will be described.

The first step described above is the preparation of a sulfur source.

The sulfur source is prepared by dehydrating an alkali metal hydrosulfide, an alkali metal hydroxide and an aliphatic amino acid hydrochloride in a mixed solvent of water and an amide-based compound. Thus, the sulfur source may comprise a mixed solvent of water and the amide-based compound remaining after the dehydration, and an alkali metal sulfide prepared by reacting the alkali metal hydrosulfide with an alkali metal hydroxide.

In addition, the present disclosure may facilitate the formation of SMAB, which is known to contribute to the polymerization of polyarylene sulfides, by adding an aliphatic amino acid hydrochloride, such as (methylamino) butyrate hydrochloride, in the preparation of the sulfur source. Thereafter, in the present disclosure, polyarylene sulfide is prepared in high yield by continuously polymerizing a sulfur source, a dihalo-aromatic compound and an amide-based compound.

The aliphatic amino acid hydrochloride may be linear or cyclic C_1-20Hydrochloride salts of aliphatic amino acids, linear or cyclic C_1-12Hydrochloride of aliphatic amino acid, or linear or cyclic C_1-6Hydrochloride salts of aliphatic amino acids. Here, the aliphatic amino acids may have side chains, for exampleC_1-4Alkyl radical, C_6-14Aryl, combinations thereof, C_1-4alkylthio-C_1-4Alkyl, or up to three C containing a heteroatom such as N, O or S_6-14A heterocyclic substituent. The amino group of the aliphatic amino acid may be NH₂NRH or NR₂In which R is alkyl, preferably C_1-4An alkyl group. Two R groups may form a ring together with the NH group as both ends of an alkylene chain containing a carboxyl group as a side chain. The amino group may be attached to an alpha-, beta-, gamma-or epsilon-carbon. The hydrochloride salt of an aliphatic amino acid may be a hydrochloride salt of a diamino acid or an amino dicarboxylic acid.

For example, the aliphatic amino acid hydrochloride salt may be a salt of Via C_1-4Alkyl substituted C_1-6Hydrochloride salts of aliphatic amino acids.

Specifically, the aliphatic amino acid hydrochloride may be at least one selected from the group consisting of (methylamino) butyric acid hydrochloride, (methylamino) propionic acid hydrochloride, and (methylamino) acetic acid hydrochloride. For example, the aliphatic amino acid hydrochloride may be 4- (methylamino) butanoic acid & HCl (MAB & HCl), 3- (methylamino) butanoic acid & HCl, 2- (methylamino) butanoic acid & HCl, 3- (methylamino) propanoic acid & HCl, or 2- (methylamino) ethanoic acid & HCl. The use of an aliphatic amino acid hydrochloride can increase the yield of polyarylene sulfide and can enhance ease of use. More preferably, 4- (methylamino) butanoic acid & HCl (MAB & HCl) or the like can be used.

The aliphatic amino acid hydrochloride may be used in an amount of about 0.01 to 0.50 equivalent based on 1 equivalent of the sulfur source, which is about 1 to 50 mol% based on 100 mol% of the sulfur source. More specifically, the aliphatic amino acid hydrochloride salt may be used in an amount of about 0.05 equivalents or more, about 0.05 equivalents to about 0.45 equivalents, about 0.15 equivalents or more, about 0.15 equivalents to about 0.40 equivalents, about 0.20 equivalents or more, or about 0.20 equivalents to about 0.30 equivalents. The aliphatic amino acid hydrochloride salt may be used in an amount of about 0.01 equivalent or more to improve the yield. In addition, when the aliphatic amino acid hydrochloride is used in an amount exceeding about 0.50 equivalent, the polymerization of the polyarylene sulfide may be inhibited, and the yield may be decreased.

Meanwhile, the alkali metal sulfide may be determined according to the type of the alkali metal hydrosulfide used in the reaction. Specific examples thereof include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, and cesium sulfide, and any one thereof or a mixture of two or more thereof may be used.

Specific examples of the alkali metal hydrosulfide that can be used in the production of the sulfur source by reacting the alkali metal hydrosulfide with the alkali metal hydroxide include lithium hydrosulfide, sodium hydrosulfide, potassium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide and the like. Either one or a mixture of two or more thereof may be used, and an anhydride or hydrate thereof may be used.

Specific examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide and the like, and any one or a mixture of two or more thereof may be used. 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 more specifically 1.0 to 1.2 equivalents, based on 1 equivalent of the alkali metal hydrosulfide.

In the present disclosure, an equivalent (eq.) refers to a molar equivalent (eq/mol).

Further, in the preparation of the sulfur source by reacting the alkali metal hydrosulfide with the alkali metal hydroxide, an alkali metal organic acid salt capable of promoting the polymerization reaction and increasing the polymerization degree of the polyarylene sulfide in a short period of time may be added as a polymerization assistant. Specific examples of the alkali metal organic acid salt include lithium acetate, sodium acetate, and the like, and either one or a mixture of two or more thereof may be used. The alkali metal organic acid salt may be used in an amount of about 0.01 to 1.0 equivalent, specifically about 0.01 to 0.8 equivalent, and more specifically about 0.05 to 0.5 equivalent, based on 1 equivalent of the alkali metal hydrosulfide.

The reaction between the alkali metal hydrosulfide and the alkali metal hydroxide may be performed in a mixed solvent of water and the amide-based compound. Specific examples of the amide-based compound include: amide compounds such as N, N-dimethylformamide or N, N-dimethylacetamide; pyrrolidone compounds such as N-methyl-2-pyrrolidone (NMP) or N-cyclohexyl-2-pyrrolidone; caprolactam compounds, such as N-methyl-epsilon-caprolactam; imidazolidinone compounds such as 1, 3-dialkyl-2-imidazolidinone; urea compounds such as tetramethylurea; phosphoric acid amide compounds such as hexamethylphosphoric acid triamide; and the like, and either one or a mixture of two or more thereof may be used. Among them, the amide-based compound may be preferably N-methyl-2-pyrrolidone (NMP) in view of reaction efficiency and co-solvent effect as a polymerization solvent for preparing polyarylene sulfide.

Water may be used in an amount of about 1 to 8 equivalents, specifically about 1.5 to 5 equivalents, and more specifically about 2.5 to 5 equivalents, based on 1 equivalent of the amide-based compound.

Meanwhile, in the first step, the alkali metal sulfide may be prepared by dehydrating a reactant including the alkali metal hydrosulfide, the alkali metal hydroxide, or the like. Here, the dehydration reaction may be performed by stirring at about 100 to 500rpm at a temperature of about 130 to 205 ℃. More specifically, the dehydration reaction may be performed by stirring at about 100rpm to 300rpm at a temperature of about 175 ℃ to 200 ℃. The dehydration reaction may be carried out for about 30 minutes to 6 hours, or about 1 hour to 3 hours.

During the dehydration reaction, the solvent such as water in the reactants may be removed by distillation or the like, and some of the amide-based compound may be discharged together with water. In addition, some of the sulfur contained in the sulfur source may react with water due to the heat during the dehydration reaction and may volatilize as hydrogen sulfide gas.

As a result of the reaction of the alkali metal hydrosulfide, the alkali metal hydroxide, and the alkali metal salt, the alkali metal sulfide is precipitated in a solid phase in a mixed solvent of water and the amide-based compound. Therefore, when a sulfur source prepared by reacting an alkali metal hydrosulfide with an alkali metal hydroxide is used as the sulfur source in the preparation of polyarylene sulfide according to the present disclosure, the molar ratio of the sulfur source refers to the molar ratio of the alkali metal hydrosulfide introduced during the reaction.

Subsequently, in order to remove the solvent such as water from the reaction product containing the alkali metal sulfide produced as a result of the above reaction, a dehydration process is performed. The dehydration process may be carried out according to methods well known in the art. The conditions are not particularly limited, and specific process conditions are as described above.

Further, during the dehydration reaction, sulfur contained in the sulfur source reacts with water to produce hydrogen sulfide and an alkali metal hydroxide, and the produced hydrogen sulfide volatilizes. Therefore, the amount of sulfur in the sulfur source remaining in the system after the dehydration reaction may be reduced due to hydrogen sulfide volatilized away from the system during the dehydration reaction. For example, when a sulfur source mainly comprising an alkali metal hydrosulfide is used, the amount of sulfur remaining in the system after the dehydration reaction is equal to the molar amount of sulfur in the introduced sulfur source minus the molar amount of hydrogen sulfide volatilized out from the system. Therefore, it is necessary to quantify the amount of available sulfur contained in the sulfur source remaining in the system after the dehydration reaction from the amount of hydrogen sulfide volatilized out from the system. Specifically, the dehydration reaction is carried out until the molar ratio of water to 1mol of available sulfur is 1 to 5, specifically 1.5 to 4, more specifically 1.75 to 3.5. When the water content in the sulfur source is excessively reduced due to the dehydration reaction, water may be added before the polymerization process to adjust the water content.

Therefore, the sulfur source prepared by the reaction and dehydration of the alkali metal hydrosulfide with the alkali metal hydroxide as described above may contain a mixed solvent of water and the amide-based compound and the alkali metal sulfide, and water may be contained in a molar ratio of 1.75 to 3.5 based on 1mol of sulfur contained in the sulfur source. In addition, the sulfur source may also comprise an alkali metal hydroxide prepared by the reaction of sulfur with water.

According to one embodiment of the present disclosure, the second step is to polymerize the sulfur source with the dihalo-aromatic compound to produce the polyarylene sulfide.

Dihalogenated aromatic compounds useful for preparing polyarylene sulfides are compounds in which two hydrogen atoms of the aromatic ring are substituted with halogen atoms. Specific examples thereof include: o-dihalobenzene, m-dihalobenzene, p-dihalobenzene, dihalotoluene, dihalonaphthalene, dihalobiphenyl, dihalobenzoic acid, dihalodiphenyl ether, dihalodiphenyl sulfone, dihalodiphenyl sulfoxide and dihalobenzophenone, and any one thereof or a mixture of two or more thereof may be used. In the dihalo-aromatic compound, the halogen atom may be fluorine, chlorine, bromine or iodine. Among them, p-dichlorobenzene (p-DCB) can be preferably used in order to improve reactivity and suppress side reactions in the production of polyarylene sulfide.

The dihalo-aromatic compound may be added in an amount of about 0.8 to 1.2 equivalents based on 1 equivalent of the sulfur source. When the dihalo-aromatic compound is added within the above range, a polyarylene sulfide having excellent physical properties can be obtained without lowering the melt viscosity of the polyarylene sulfide produced and without increasing the content of chlorine present in the polyarylene sulfide. The dihalo-aromatic compound may be added in an amount of about 0.9 to 1.1 equivalents in view of excellent effect of controlling the addition amounts of the sulfur source and the dihalo-aromatic compound.

In addition, a step of reducing the temperature of the reactor containing the sulfur source to a temperature of about 150 ℃ to 200 ℃ may be further included before the second step to prevent vaporization of the dihalo-aromatic compound.

Further, the polymerization reaction of the sulfur source and the dihalo-aromatic compound may be carried out in a solvent of the amide-based compound which is a polar aprotic organic solvent and is stable to alkali at high temperature.

Specific examples of the amide-based compound are as described above, and in view of reaction efficiency, pyrrolidone compounds such as N-methyl-2-pyrrolidone (NMP) or N-cyclohexyl-2-pyrrolidone are preferable.

Since the amide-based compound contained in the sulfur source in the first step functions as a co-solvent, the amide-based compound in the second step may be about 0.85 or more of water (H) present in the polymerization system₂O) to the amide-based compound (water/amide-based compound ratio).

During the polymerization reaction, other additives for controlling the polymerization reaction or molecular weight, such as a molecular weight regulator, a crosslinking agent, etc., may be further added in an amount that does not reduce the physical properties and yield of the finally prepared polyarylene sulfide.

The polymerization of the sulfur source and the dihaloaromatic compound may be carried out at about 200 ℃ to 300 ℃. Alternatively, the polymerization reaction may be carried out in a plurality of steps while changing the temperature within the above-mentioned temperature range. Specifically, after the first polymerization reaction at about 200 ℃ or more and less than 250 ℃, the second polymerization reaction may be carried out at a temperature higher than that of the first polymerization reaction, specifically at about 250 ℃ to 300 ℃.

The reaction product produced as a result of the above polymerization reaction is separated into an aqueous phase and an organic phase, and the polyarylene sulfide as a product of the polymerization reaction is dissolved in the organic phase. Therefore, a process for precipitating and separating the polyarylene sulfide produced can be selectively performed.

In particular, the precipitation of polyarylene sulfide can be carried out by adding water in an amount of 3 to 5 equivalents based on 1 equivalent of sulfur to the reaction mixture, followed by cooling. When water is added within the above range, the polyarylene sulfide can be precipitated with excellent efficiency.

The precipitated polyarylene sulfide may optionally be further subjected to washing, filtration and drying according to a conventional method.

As a specific production method of polyarylene sulfide, the following examples can be referred to. However, the method for producing the polyarylene sulfide is not limited to this description. The preparation method may further include steps generally performed in the technical field of the present invention, and the steps of the preparation method may be changed by generally changeable steps.

Meanwhile, the method for preparing polyarylene sulfide according to one embodiment of the present disclosure as described above can easily produce polyarylene sulfide having thermal characteristics equal to or higher than those of conventional methods with excellent yield.

Specifically, the polyarylene sulfide can be produced in a yield of about 66.5% or more, or about 70% or more, or about 74% or more by the above production method.

In N₂The polyarylene sulfide was melted under an atmosphere and frequency scanned using an ARES-G2 rheometer to determine the viscosity change. The value at a frequency of 0.10Hz is referred to as melt viscosity (m.v.). The melt viscosity (m.v.) may be up to about 60PaS or higher, or from about 60PaS to 400 PaS. Poly(s) are polymerizedThe arylsulfonyl ethers can have a high melt viscosity of about 79PaS or greater, about 79PaS to 400PaS, about 89PaS or greater, about 89PaS to 400PaS, about 260PaS or greater, or about 260PaS to 400 PaS.

The melting point (Tm) of the polyarylene sulfide can be about 270 ℃ to 300 ℃, about 275 ℃ to 295 ℃, about 277 ℃ to 290 ℃, or about 280 ℃ to 285 ℃. The polyarylene sulfide may have a crystallization point (Tc) of about 200 ℃ to 250 ℃, about 210 ℃ to 245 ℃, about 215 ℃ to 235 ℃, or about 220 ℃ to 232 ℃. Further, the weight average molecular weight (Mw) of the polyarylene sulfide may be about more than 10000g/mol and 30000g/mol or less. Here, the melting point (Tm) and the crystallization point (Tc) of the polyarylene sulfide can be measured using a differential scanning calorimeter (DSC, manufactured by TA instrument, TA Q2000). Since the measurement method is well known in the art, a detailed description thereof will be omitted.

The Cl content of the polyarylene sulfide measured using a dispersive X-ray fluorescence spectrometer (ED-XRF) can be about 3200ppm or less, about 2000ppm to 3200ppm, about 3000ppm or less, about 2100ppm to 3000ppm, about 2985ppm or less, or about 2143ppm to 2985ppm, based on the total weight of the polyarylene sulfide.

Hereinafter, the present invention will be described in more detail with reference to the following preferred examples. However, these examples are for illustrative purposes only, and the present invention is not intended to be limited by these examples.

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