Polyarylene sulfide

Abstract

Provided is a polyarylene sulfide that, when being added to a composition containing a silane coupling agent and a polyarylene sulfide produced by a conventional method, is capable of easily increasing the melt viscosity of said composition to a desired degree.　The present invention uses a polyarylene sulfide in which, in the result of a fluorescent X-ray analysis carried out by using a sample obtained by reacting the polyarylene sulfide with n-propyltriethoxysilane by using a prescribed method, the intensity ISi-Kα(kcps) of the Si-Kα line and the intensity IS-Kα(kcps) of the S-Kα line satisfy formula (1): (ISi-Kα / IS-Kα)×1000≥1.00.

Description

Polyarylene sulfide

[0001] This invention relates to polyarylene sulfide.

[0002] Polyarylene sulfides (hereinafter also referred to as "PAS"), typified by polyphenylene sulfide (hereinafter also referred to as "PPS"), are engineering plastics with excellent heat resistance, chemical resistance, flame retardancy, mechanical strength, electrical properties, and dimensional stability. PAS can be molded into various molded products, films, sheets, fibers, etc., by common melting processes such as extrusion molding, injection molding, and compression molding. For this reason, PAS is widely used in a wide range of technological fields, including electrical equipment, electronic equipment, automotive equipment, and packaging materials.

[0003] However, PAS has a problem in that it is prone to burr formation during molding due to its low melt viscosity. For this reason, it has been proposed to mix in an aminosilane coupling agent to prevent burr formation (see Patent Documents 1 and 2). As for PAS, PAS having amino groups or carboxyl groups as terminal groups is known. When such terminal groups react with a silane coupling agent such as an aminosilane coupling agent, the PAS becomes more viscous in the molten state.

[0004] Japanese Patent Publication No. 08-053592 Japanese Patent Publication No. 2004-244619

[0005] For PAS to thicken through reaction with a silane coupling agent, PAS needs to have a certain amount of reactive functional groups. However, as the molecular weight of PAS increases, the number of terminal groups decreases. In addition, in order to increase the molecular weight of PAS, side reactions in the polymerization of PAS are suppressed. As a result, the number of reactive functional groups originating from side reactions in PAS tends to decrease. Consequently, even when a silane coupling agent is mixed with PAS, the PAS often does not thicken easily in the molten state.

[0006] The present invention has been made in view of the above problems, and an object thereof is to provide a polyarylene sulfide which, when added to a composition containing a polyarylene sulfide produced by a conventional method and a silane coupling agent, can easily increase the melt viscosity of the composition to a desired level.

[0007] The present inventors found that, in the results of X-ray fluorescence analysis performed using a sample obtained by reacting polyarylene sulfide and n-propyltriethoxysilane by a predetermined method, the intensity I of Si-Kα line Ｓｉ－Ｋα (kcps) and the intensity I of S-Kα line Ｓ－Ｋα (kcps) satisfy the following formula (1): (I Ｓｉ－Ｋα / I Ｓ－Ｋα )×1000≧1.00 (1), the above object can be achieved by using the polyarylene sulfide satisfying the above formula, and thus the present invention has been completed. Specifically, the present invention is configured as the following [1] to [7].

[0008] [1] 3.0 g of polyarylene sulfide, 3.5 g of n-propyltriethoxysilane, and 1.4 g of 1,8-diazabicyclo[5.4.0]undec-7-ene are reacted in 45 g of N-methyl-2-pyrrolidone in an open system under a nitrogen gas flow at 120°C for 8 hours with stirring, thereby reacting the polyarylene sulfide with the n-propyltriethoxysilane; recovering the polyarylene sulfide (a) reacted with n-propyltriethoxysilane from the N-methyl-2-pyrrolidone; washing the recovered polyarylene sulfide (a) and then drying it at 80°C or lower to obtain a sample for X-ray fluorescence analysis; in the results of X-ray fluorescence analysis performed using the sample obtained by the method including the above steps, the intensity I of Si-Kα line Ｓｉ－Ｋα (kcps) and the intensity I of S-Kα line Ｓ－Ｋα (kcps) satisfy the following formula (1): (I Ｓｉ－Ｋα / I Ｓ－Ｋα )×1000≧1.00 (1), the polyarylene sulfide.

[0009] [2] A mixture of 10 mg of an extract extracted from said polyarylene sulfide by Soxhlet extraction using chloroform, 5.0 mg of 1,3,5-trimethoxybenzene, and 0.7 mL of deuterated chloroform, normalized such that the resonance peak based on chloroform in deuterated chloroform is 7.26 ppm １ When measured by 1H-NMR, when the integrated value of a peak observed within the range of 6.03 to 6.15 ppm is defined as Hs, and the integrated value of a peak observed within the range of 4.58 to 4.89 ppm is defined as Ha, the polyarylene sulfide according to [1], which satisfies the following formula (2): 1000 × (Ha) / (Hs / 3) ≧ 10 ... (2).

[0010] [3] The specific surface area measured by the BET method (single-point method) using a mixed gas composed of nitrogen and helium as the adsorption gas (nitrogen:helium = 30:70 (volume ratio)) is 5 m ２ / g or more, the polyarylene sulfide according to [1] or [2].

[0011] [4] The specific surface area measured by the BET method (single-point method) using a mixed gas composed of nitrogen and helium as the adsorption gas (nitrogen:helium = 30:70 (volume ratio)) is 5 m ２ / g or more, the melt viscosity measured under the conditions of a temperature of 310°C and a shear rate of 1200 sec －１ -1 is 1 Pa·s or more, the amount of functional groups reactive with epoxy groups is 14 μmol / g or more, and the sodium content is 800 mass ppm or less. A method for producing polyarylene sulfide, comprising: a mixing step of mixing untreated polyarylene sulfide and an epoxy group-containing compound; and a reaction step of reacting the mixture obtained in said mixing step under conditions of 30°C or higher and 230°C or lower, and substantially solvent-free.

[0012] [5] The method for producing polyarylene sulfide according to [4], wherein the amount of functional groups reactive with the epoxy group is a nitrogen atom content.

[0013] [6] The method for producing polyarylene sulfide according to [4] or [5], further comprising a step of washing the untreated polyarylene sulfide at a temperature below the glass transition temperature and / or drying it before the mixing step.

[0014] [7] A method for producing polyarylene sulfide according to any one of [4] to [6], wherein the amount of the epoxy group-containing compound is added in a manner that is 30 molar times or more relative to the amount of functional groups that react with the epoxy groups of the untreated polyarylene sulfide.

[0015] According to the present invention, a polyarylene sulfide can be added to a composition containing a polyarylene sulfide produced by a conventional method and a silane coupling agent, thereby easily increasing the melt viscosity of the composition to a desired degree.

[0016] The embodiments of the present invention will be described in detail below. The present invention is not limited to the embodiments described below, and can be modified as appropriate without altering the essence of the invention.

[0017] Furthermore, in this specification, numerical ranges expressed using "~" mean a range that includes the numbers written before and after "~" as the lower and upper limits, respectively, and "A~B" means A or greater and B or less. Also, unless otherwise specified in this specification, "room temperature" means 20°C or more and 25°C or less, and "melt viscosity" means at a temperature of 310°C and a shear rate of 1200 sec. －１ This refers to the melt viscosity of polyarylene sulfide measured under these conditions, and "under reduced pressure conditions" means an absolute pressure of 10 Torr or less.

[0018] An embodiment of the polyarylene sulfide (hereinafter also referred to as "E-PAS") according to the present invention will be described below. E-PAS has a structure in which an arylene group (hereinafter also referred to as "Ar") and a sulfide are bonded, and its main constituent is a repeating unit of -(Ar-S)-. Examples of Ar include p-phenylene group, m-phenylene group, o-phenylene group, substituted phenylene group, p,p'-diphenylene sulfone group, p,p'-biphenylene group, p,p'-diphenylene ether group, and naphthalene group.

[0019] E-PAS can be a homopolymer containing any of the repeating units described above individually, or a copolymer containing two or more of the repeating units described above. As the homopolymer, Ar is preferably a polyphenylene sulfide having a p-phenylene group.

[0020] In E-PAS, the Ar preferably consists of 50% by weight or more of any group selected from the group consisting of p-phenylene groups, m-phenylene groups, and o-phenylene groups, more preferably 80% by weight or more of p-phenylene groups, even more preferably 90% by weight or more, and particularly preferably 98% by weight or more. Such a structure is preferable in terms of the heat resistance and crystallinity of the resulting PAS.

[0021] The following describes the manufacturing method of E-PAS.

[0022] <Method for Producing E-PAS> One method for producing E-PAS is to react an untreated polyarylene sulfide (hereinafter also referred to as "untreated PAS") obtained by polymerizing a sulfur source and a dihalo-aromatic compound in N-methyl-2-pyrrolidone (hereinafter also referred to as "NMP") according to a well-known method with an epoxy group-containing compound. In this specification, polyarylene sulfide produced by conventional methods (hereinafter also referred to as "conventionally known PAS") and untreated PAS are distinguished. Conventionally known PAS refers to PAS produced by conventional methods, while untreated PAS refers to PAS that has the characteristics described below and serves as a raw material for E-PAS, among conventionally known PAS.

[0023] (Untreated PAS) Untreated PAS will be explained. Untreated PAS is measured by the BET method (single-point method) using a mixed gas of nitrogen and helium (nitrogen:helium = 30:70 (volume ratio)) as the adsorption gas, and has a specific surface area of ​​5 m². ２ It can be used without particular limitations as long as it has a concentration of 1 μmol / g or more, a melt viscosity of 1 Pa·s or more, a functional group that reacts with the epoxy group of 14 μmol / g or more, and a sodium content of 800 ppm by mass or less.

[0024] The specific surface area of ​​untreated PAS is 5 m². ２ It is 10.0 m or more per gram. ２ / g or more 120m ２ Preferably less than / g, and 15.0m ２ / g or more 100.0m ２ More preferably less than or equal to 20.0 m ２ / g or more 100.0m ２ It is even more preferable to have less than or equal to 30.0 m ２ / g or more 100.0m ２ A value of less than or equal to / g is particularly preferred. Within this range, the untreated PAS can react well with epoxy group-containing compounds under temperature conditions in which it does not melt or dissolve. Such a specific surface area can be obtained in the production of untreated PAS by slowly cooling and crystallizing the mixture in which the PAS has dissolved after the polymerization reaction (quench method), or by volatilizing the solvent from the mixture after the reaction at a high temperature and recovering it (flash method).

[0025] In this specification, "specific surface area" refers to the value measured by the BET method (single-point method) using a mixed gas of nitrogen and helium (nitrogen:helium = 30:70 (volume ratio)) as the adsorbent gas, in accordance with ISO 9277.

[0026] The melt viscosity of untreated PAS is 1 Pa·s or more, preferably 5 Pa·s to 250 Pa·s, more preferably 15 Pa·s to 250 Pa·s, even more preferably 20 Pa·s to 200 Pa·s, and particularly preferably 20 Pa·s to 150 Pa·s. Being within the above range distinguishes it from PAS mainly composed of low molecular weight components such as oligomers. Furthermore, the melt viscosity can be obtained by adjusting the amount of dihalo-aromatic compound relative to the amount of sulfur source.

[0027] Examples of functional groups that react with epoxy groups (hereinafter also referred to as "epoxy-reactive functional groups") include phenolic hydroxyl groups, mercapto groups, and MABA-terminated groups. Since MABA-terminated groups can be easily introduced into untreated PAS using NMP, it is preferable that the functional group that reacts with the epoxy group is an MABA-terminated group.

[0028] The "MABA-terminated group" is a by-product derived from the ring-opening of NMP, which is generated during polymerization side reactions in untreated PAS produced using NMP as a solvent. ３ -CH ２ CH ２ CH ２ This refers to the terminal group represented as "-COOH".

[0029] The amount of epoxy-reactive functional groups is 14 μmol / g or more, preferably 18 μmol / g to 93 μmol / g, and more preferably 36 μmol / g to 93 μmol / g. Having the amount of epoxy-reactive functional groups within this range allows the untreated PAS to react well with the epoxy group-containing compound, thus easily introducing alcoholic hydroxyl groups into the PAS.

[0030] Furthermore, the amounts of phenolic hydroxyl groups and mercapto groups can be measured, for example, by the purge-trap method, and the amount of MABA terminal groups is the same as the amount of nitrogen atoms in untreated PAS, so the nitrogen atom content can be treated as the amount of MABA terminal groups. In other words, the nitrogen atom content and the preferred range correspond to the amount of epoxy-reactive functional groups and the preferred range described above. The nitrogen atom content is determined by a method using a trace nitrogen analyzer. The unit of the nitrogen atom content obtained by this method is mass ppm, but this value can be converted to the amount of substance per gram of PAS (μmol / g) by dividing it by the atomic weight of nitrogen (14.00).

[0031] Examples of methods for producing untreated PAS having many MABA-terminated groups include, in the method for producing untreated PAS described later, using NMP as an organic polar solvent and carrying out polymerization under conditions where a sulfur source and dihalo-aromatic compounds are at high concentrations, and adjusting the amount of alkali metal hydroxide added.

[0032] A method for producing PAS having many phenolic hydroxyl groups includes, for example, a method of heating and mixing untreated PAS with an aromatic compound having phenolic hydroxyl groups and mercapto groups as substituents on the aromatic ring, and a basic compound such as an alkali metal hydroxide, in an organic solvent.

[0033] A method for producing PAS having many mercapto groups includes, for example, a method of heating and mixing untreated PAS with an alkali metal sulfide or an aromatic compound having two or more mercapto groups as substituents on the aromatic ring in an organic solvent.

[0034] The organic solvent used in the production of PAS having a large number of phenolic hydroxyl groups or mercapto groups is not particularly limited, as long as it is an organic polar solvent commonly used in the production of PAS.

[0035] The sodium content of untreated PAS (hereinafter also referred to as "Na content") is 800 ppm by mass or less, preferably greater than 0 ppm by mass and 800 ppm by mass or less, more preferably greater than 0 ppm by mass and 500 ppm by mass or less, and even more preferably greater than 0 ppm by mass and 200 ppm by mass or less. A Na content within the above range allows for good reaction with epoxy group-containing compounds. The Na content is measured by ICP emission spectroscopy using an ICP-AES (for example, Hitachi High-Tech Corporation's ICP emission spectrometer SPS3500DD) on a sulfuric acid-decomposed sample, as described in the examples. The Na content can be adjusted by washing the untreated PAS.

[0036] (Method for producing untreated PAS) Untreated PAS as described above can be obtained by a general manufacturing method comprising a preparation step of preparing a mixture containing NMP, alkali metal hydroxide, sulfur source, and dihalo-aromatic compound, and a polymerization step of heating the mixture to carry out a polymerization reaction (see, for example, Japanese Patent Publication No. 61-7332, Japanese Patent Publication No. 9-286861, etc.). In addition to the above preparation step and polymerization step, the method may also include a dehydration step to reduce the amount of water in the mixture, a post-treatment step, a pre-polymerization step to generate a PAS prepolymer, a phase separation step to add a phase separation agent to the mixture to form a phase-separated state, and a post-polymerization step to carry out a further polymerization reaction after phase separation.

[0037] (Sulfur source and dihalo-aromatic compound) The sulfur source and dihalo-aromatic compound are not particularly limited, and those commonly used in the production of PAS can be used. Each of the sulfur source and the dihalo-aromatic compound may be used alone, or two or more may be used in combination, provided that it is possible to produce a PAS having the desired chemical structure. In this specification and in the claims, "dihalo-aromatic compound" means an aromatic compound in which two hydrogen atoms directly attached to the aromatic ring are replaced by halogen atoms.

[0038] Examples of sulfur sources include alkali metal sulfides, alkali metal hydrosulfides, and hydrogen sulfide, with alkali metal sulfides and alkali metal hydrosulfides being preferred, and alkali metal hydrosulfides being more preferred. The sulfur source can be handled in either the form of an aqueous slurry or an aqueous solution, and from the viewpoint of handling, such as metering and transportability, it is preferable to be in the form of an aqueous solution. Examples of alkali metal sulfides include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, and cesium sulfide. Examples of alkali metal hydrosulfides include lithium hydrosulfide, sodium hydrosulfide, potassium hydrosulfide, rubidium hydrosulfide, and cesium hydrosulfide.

[0039] Examples of dihaloaromatic compounds include o-dihalobenzene, m-dihalobenzene, p-dihalobenzene, dihalotoluene, dihalonaphthalene, methoxy-dihalobenzene, dihalobiphenyl, dihalobenzoic acid, dihalodiphenyl ether, dihalodiphenyl sulfone, dihalodiphenyl sulfoxide, and dihalodiphenyl ketone. The halogen atoms refer to fluorine, chlorine, bromine, and iodine atoms, and two or more halogen atoms in a dihaloaromatic compound may be the same or different. Among these, p-dihalobenzene, m-dihalobenzene, and mixtures thereof are preferred in terms of availability and reactivity, with p-dihalobenzene being more preferred, and p-dichlorobenzene (hereinafter also referred to as "pDCB") being particularly preferred.

[0040] The amount of dihalo-aromatic compound used is preferably 0.90 moles to 1.50 moles, and more preferably 0.92 moles to 1.10 moles, per mole of sulfur source. When the amount used is within the above range, it is easy to generate high molecular weight polymers, and thus an untreated PAS with high melt viscosity can be obtained.

[0041] (NMP) From the viewpoint of the efficiency of the polymerization reaction, the amount of NMP used is preferably 1 mole to 30 moles, and more preferably 3 moles to 15 moles, per mole of sulfur source charged.

[0042] The sulfur source described above may be mixed with NMP and subjected to the dehydration process.

[0043] (Dehydration Process) The dehydration process is a process performed before the charging process in which at least a portion of the water-containing distillate is discharged from the system containing a mixture of NMP and a sulfur source. The mixture subjected to the dehydration process may optionally contain alkali metal hydroxides. The water to be dehydrated in the dehydration process includes water contained in each raw material charged in the dehydration process, the aqueous medium of the aqueous mixture, and water produced as a by-product of the reaction between the raw materials.

[0044] The heating temperature in the dehydration process is not particularly limited, but is preferably 300°C or lower, and more preferably 100°C to 250°C. It is desirable to dehydrate the mixture (described later) until the amount of water is 0.5 moles or more and 2.4 moles or less per 1.0 mole of the amount of sulfur source in the mixture (hereinafter also referred to as "fermented sulfur source"). If the amount of water becomes too low in the dehydration process, water can be added in the fermentation process to adjust it to the desired amount of water.

[0045] (Preparation Process) The preparation process is the process of preparing a mixture containing NMP, a sulfur source, a dihalo-aromatic compound, and an alkali metal hydroxide. The mixture prepared in the preparation process is also called the "preparation mixture."

[0046] When a dehydration process is performed, the sulfur source used in the brewing process can be calculated by subtracting the amount of hydrogen sulfide volatilized during the dehydration process from the amount of sulfur source added as a raw material.

[0047] As the alkali metal hydroxide, those commonly used in the production of PAS can be used. The alkali metal hydroxide may be used alone, or two or more types may be mixed together, as long as the combination allows for the production of PAS. Examples of alkali metal hydroxides include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide.

[0048] The number of moles of alkali metal hydroxide is calculated based on the number of moles of alkali metal hydroxide added as needed during the initial stage, the number of moles of alkali metal hydroxide added as needed during the dehydration stage (if applicable), and the number of moles of alkali metal hydroxide generated during the dehydration stage in conjunction with the generation of hydrogen sulfide. By adjusting the amount of alkali metal hydroxide in the initial mixture, the nitrogen atom content of the untreated PAS can be adjusted.

[0049] In the fermentation mixture, the amounts of NMP and dihalo-aromatic compounds used are set, for example, within the ranges indicated above for NMP and dihalo-aromatic compounds per mole of fermentation sulfur source.

[0050] (Polymerization Process) The polymerization process is a process in which the preparation mixture is heated to initiate the polymerization reaction and produce PAS. From the viewpoint of the efficiency of the polymerization reaction, the polymerization temperature is preferably 170°C to 300°C, and more preferably 180°C to 290°C. The temperature may be maintained at a constant level, or it may be raised or lowered in stages or continuously as needed. In order to obtain high molecular weight PAS, the polymerization reaction may be carried out in two or more stages. For example, when a phase separation agent described later is added during polymerization, the process is carried out in two or more stages, and the process of producing a prepolymer before the addition of the phase separation agent is called the pre-polymerization process, and the process of continuing the polymerization reaction after the addition of the phase separation agent is called the post-polymerization process. The mixture heated in the polymerization process is called the "reaction mixture".

[0051] The conversion rate of the dihalo-aromatic compound at the end of the preceding polymerization step is preferably 60 mol% to 98 mol%, more preferably 65 mol% to 98 mol%. The conversion rate of the dihalo-aromatic compound can be calculated by determining the amount of dihalo-aromatic compound remaining in the reaction mixture by gas chromatography, and then calculating the amount of dihalo-aromatic compound charged and the amount of sulfur source charged.

[0052] (Phase Separation Step) The phase separation step is the step of adding a phase separation agent to the starting mixture and / or reaction mixture. The phase separation agent can be one that is commonly used in the production of PAS. Examples of phase separation agents include water, metal organic carboxylates, metal organic sulfonic acid salts, alkali metal halides, etc. Among these, water and / or metal organic carboxylates are preferred, and water is more preferred. The amount of phase separation agent used varies depending on the type of compound used, but is preferably in the range of 0.01 moles to 20 moles per 1 kg of NMP, and when water is used as the phase separation agent, it is preferably 2 moles to 7 moles.

[0053] There is no specific timing for adding the phase separation agent; it may be added during the preparation process, at the start of polymerization, or in the middle of the polymerization process, with addition in the middle of the polymerization process being preferable. The presence of the phase separation agent allows the polymerization reaction to proceed in a phase-separated state. When the phase separation process is performed in the middle of the polymerization reaction, a state with a high concentration of prepolymer can be formed by liquid-liquid phase separation. This binds the prepolymers together, further growing the chains and yielding a high molecular weight polymer. Furthermore, when the phase separation agent is added in the middle of the polymerization process, the specific surface area of ​​the untreated PAS can be increased by reducing the amount of phase separation agent used within a range where phase separation is possible.

[0054] (Post-treatment and recovery steps) The untreated PAS produced by the method described above may be recovered through post-treatment and recovery steps. The post-treatment and recovery steps can be carried out by conventional methods. For example, by cooling the reaction mixture, a slurry containing granular polymer products can be obtained. The untreated PAS can be recovered by filtering the cooled product slurry as is, or after diluting it with water, and then repeatedly washing and filtering it to dry it.

[0055] By generating granular untreated PAS using the method described above, the granular untreated PAS can be separated from the reaction solution and recovered by, for example, sieving it using a 100-mesh screen (mesh opening diameter 150 μm). This allows for easy separation of the untreated PAS from by-products and oligomers.

[0056] Suitable washing solvents for untreated PAS include organic solvents such as NMP, ketones (e.g., acetone), and alcohols (e.g., methanol), as well as water, acids, and aqueous solutions containing salts such as ammonium chloride. It is preferable to use hot water (e.g., 170°C or higher) and / or an acidic aqueous solution as the washing solvent, and more preferably an acidic aqueous solution. In the polymerization of untreated PAS, sodium salts such as sodium chloride are produced as by-products, and may exist as "-COONa" where the hydrogen atom of the carboxyl group in the MABA terminal group is replaced by sodium. By treating untreated PAS with hot water and / or an acidic aqueous solution, the Na content is reduced, that is, the carboxyl group in the MABA terminal group can be acidified (-COOH), which facilitates the reaction with epoxy group-containing compounds.

[0057] Here, when a washing step (hereinafter also referred to as the "washing step") and / or a drying step (hereinafter also referred to as the "drying step") are performed on the untreated PAS, it is preferable that the temperature in these steps be below the glass transition temperature of the untreated PAS (for example, 93°C or below). By using such temperature conditions, the terminal groups of the untreated PAS remain on the outer surface of the PAS particles and become reactive terminal groups. The detailed mechanism is not clear, but it is thought to be as follows: In organic polar solvents, especially in NMP, the affinity between the organic polar solvent and the terminal functional groups of the untreated PAS is high. Therefore, even if the PAS is heated above the glass transition temperature (hereinafter also referred to as "Tg") where molecular motion is active, the terminal functional groups of the untreated PAS remain on the solvent side with high affinity, i.e., on the outer surface of the PAS. On the other hand, if the process includes contact with water or air, which has low affinity to the terminal functional groups, it is thought that the terminal functional groups will fold into the interior of the PAS, which has a higher affinity than water or air, and / or burrow inside. Therefore, it is desirable to process at a temperature in which molecular motion is not active. For PPS, a temperature of 93°C or lower, which is below the Tg, is preferable, and a temperature of 20°C to 93°C is more preferable.

[0058] Furthermore, even if the washing and / or drying processes are carried out at a temperature higher than Tg (e.g., above 93°C), the reactive end groups described above can be obtained by heating the untreated PAS in an organic polar solvent at a temperature above the Tg of the untreated PAS but at which the untreated PAS does not melt (e.g., 95 to 230°C), and drying it at a temperature below the Tg of the untreated PAS. On the other hand, as described later, there is a risk that the amount of PAS containing MABA end groups will decrease, so it is preferable to carry out the washing and drying processes of the untreated PAS at a temperature below Tg.

[0059] The organic polar solvent is not particularly limited as long as it is a solvent commonly used in PAS production, but organic amide solvents having an amide bond in their molecular structure are preferred, and amide compounds having an aliphatic cyclic structure such as N-methyl-ε-caprolactam, NMP, and N-cyclohexyl-2-pyrrolidone are more preferred, with NMP being particularly preferred.

[0060] By using reactive terminal groups, untreated PAS and epoxy group-containing compounds can be reacted well even under temperature conditions where the untreated PAS does not melt or dissolve, and even under substantially solvent-free conditions, as described later. The Tg of PAS can be measured by known methods. For example, it can be measured using a differential scanning calorimeter (DSC) in accordance with ISO 11357-2 (2020).

[0061] By the method described above, untreated PAS, which is the raw material for E-PAS, can be obtained.

[0062] (Method for producing E-PAS) E-PAS can be obtained by reacting the untreated PAS obtained as described above with an epoxy group-containing compound.

[0063] A preferred method for producing E-PAS includes a mixing step of mixing untreated PAS with an epoxy group-containing compound, and a reaction step of reacting the mixture obtained in the mixing step at a temperature of 30°C to 230°C under substantially solvent-free conditions. In addition to the above steps, the method may also include a washing step and / or drying step for the untreated PAS, and a washing step and / or drying step for the E-PAS, as described above.

[0064] (Epoxy group-containing compounds) Epoxy group-containing compounds are compounds that contain one or more epoxy groups in their molecule. Epoxy group-containing compounds are not particularly limited. They may be glycidyl group-containing compounds, or alicyclic epoxy group-containing compounds having an epoxy group composed of two adjacent carbon atoms and an oxygen atom constituting an alicyclic structure such as a cycloalkyl group.

[0065] The epoxy group-containing compound may be a monofunctional epoxy group-containing compound having one epoxy group in its molecule, a difunctional epoxy group-containing compound having two epoxy groups in its molecule, or a polyfunctional epoxy group-containing compound having three or more epoxy groups in its molecule, with monofunctional epoxy group-containing compounds being more preferred. Monofunctional epoxy group-containing compounds react better with the MABA terminal groups in untreated PAS. The reason is not clear, but it is thought that this is because their smaller molecular size allows them to penetrate more easily into the interior of the PAS. Furthermore, from the viewpoint of maintaining reactivity, it is preferable that the epoxy group-containing compound does not contain alkoxysilyl groups. Epoxy group-containing compounds containing alkoxysilyl groups may undergo self-condensation when reacted with untreated PAS, making it difficult to recover and reuse the unreacted epoxy group-containing compound.

[0066] Suitable examples of alicyclic epoxy group-containing compounds as monofunctional epoxy group-containing compounds include cyclohexene oxide, cyclopentene oxide, cycloheptene oxide, cyclooctenone oxide, 1,2-epoxy-4-vinylcyclohexane, and methyl methacrylate [(3,4-epoxycyclohexane)-1-yl]methyl.

[0067] Suitable examples of glycidyl group-containing compounds as monofunctional epoxy group-containing compounds include glycidyl esters such as glycidyl acetate, glycidyl propionate, glycidyl butanoate, glycidyl benzoate, glycidyl acrylate, and glycidyl methacrylate; and glycidyl ethers such as butyl glycidyl ether, glycidyl phenyl ether, and 2-ethylhexyl glycidyl phenyl ether.

[0068] Suitable examples of glycidyl group-containing compounds as bifunctional and polyfunctional epoxy group-containing compounds include: bifunctional epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD ​​type epoxy resin, naphthalene type epoxy resin, and biphenyl type epoxy resin; novolac epoxy resins such as phenol novolac type epoxy resin, brominated phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, and bisphenol AD ​​novolac type epoxy resin; cyclic aliphatic epoxy resins such as epoxy compounds of dicyclopentadiene type phenol resins; aromatic epoxy resins such as epoxy compounds of naphthalene type phenol resins; glycidylamine type epoxy resins such as tetraglycidylaminodiphenylmethane, triglycidyl-p-aminophenol, tetraglycidylmetaxylylenediamine, and tetraglycidylbisaminomethylcyclohexane; and heterocyclic epoxy resins such as triglycidyl isocyanurate.

[0069] A suitable example of a alicyclic epoxy group-containing compound having an alicyclic epoxy group such as an epoxycycloalkyl group, as a bifunctional epoxy group-containing compound, is the compound represented by the following formula (i).

[0070] In formula (i) above, X represents a single bond or a linking group. Preferred examples of linking groups include one or more selected from the group consisting of a divalent hydrocarbon group, an alkenylene group in which the carbon-carbon double bond is epoxidized (hereinafter also referred to as "epoxidized alkenylene group"), a carbonyl group, an ether bond, a carboxylic acid ester bond, a siloxane bond, a carbonate group, and a carboxylic acid amide group. Note that substituents such as alkyl groups may be attached to the cyclohexene oxide group in formula (i).

[0071] Examples of divalent hydrocarbon groups include linear or branched alkylene groups having 1 to 18 carbon atoms, and divalent alicyclic hydrocarbon groups.

[0072] Examples of linear or branched alkylene groups having 1 to 18 carbon atoms include the methylene group, methylmethylene group (ethane-1,1-diyl group), dimethylmethylene group (propane-2,2-diyl group), ethylene group, propylene group, and trimethylene group.

[0073] Examples of divalent alicyclic hydrocarbon groups include cycloalkylene groups such as 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylidene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, and cyclohexylidene, or cycloalkylidene groups.

[0074] Examples of alkenylene groups in epoxidized alkenylene groups include linear or branched alkenylene groups having 2 to 8 carbon atoms, such as vinylene group (ethylene-1,2-diyl group), 1-propene-1,3-diyl group, 1-propene-1,2-diyl group, 1-propene-2,3-diyl group, 1-butene-1,4-diyl group, 1-butene-1,3-diyl group, 1-butene-1,2-diyl group, 2-butene-1,4-diyl group, 2-butene-1,3-diyl group, 2-butene-1,2-diyl group, 1-pentene-1,5-diyl group, 1-hexene-1,6-diyl group, 1-heptene-1,7-diyl group, and 1-octene-1,8-diyl group. The epoxidized alkenylene group is preferably an alkenylene group having 2 to 4 carbon atoms in which the carbon-carbon double bond is epoxidized.

[0075] Examples of compounds represented by formula (i) include (3,4,3',4'-diepoxy)bicyclohexyl, bis(3,4-epoxycyclohexylmethyl) ether, 1,2-epoxy-1,2-bis(3,4-epoxycyclohexane-1-yl)ethane, 2,2-bis(3,4-epoxycyclohexane-1-yl)propane, and 1,2-bis(3,4-epoxycyclohexane-1-yl)ethane.

[0076] Examples of alicyclic epoxy group-containing compounds as bifunctional epoxy group-containing compounds include, in addition to the compound represented by formula (i) above, the following compounds, and compounds having both an alicyclic epoxy group and a glycidyl group, such as limonene dioxide.

[0077] Examples of alicyclic epoxy group-containing compounds, which are polyfunctional epoxy group-containing compounds, include, for example, the compounds represented by the following formulas (ii-1) to (ii-3). In the following formulas (ii-1) and (ii-2), n1 to n6 each independently represent an integer from 1 to 30.

[0078]

[0079] As the epoxy group-containing compound, alicyclic epoxy group-containing compounds are preferred, and epoxycycloalkanes are more preferred. By using alicyclic epoxy group-containing compounds, the reaction with untreated PAS with reduced Na content can be performed more effectively. The reaction between the epoxy group and the terminal groups of PAS, such as MABA terminal groups, is considered to be a nucleophilic substitution reaction. In the case of alicyclic epoxy group-containing compounds, S Ｎ Since the reaction is uniform, it is presumed that the acidic end, which can promote the cleavage of the alicyclic epoxy group, will react more favorably.

[0080] The amount of epoxy group-containing compound used is in a sufficiently excessive amount relative to the amount of epoxy-reactive functional groups in the untreated PAS. Preferably, the amount of epoxy group-containing compound added is 30 molar times or more relative to the amount of epoxy-reactive functional groups, and if a monofunctional epoxy group-containing compound is used, it is more preferably 200 molar times or more, and even more preferably 350 molar times or more. There is no particular upper limit, but it may be 1000 molar times or less.

[0081] The reaction temperature is not particularly limited as long as the PAS does not melt or dissolve. For example, a temperature of 30°C to 230°C is preferred, and a temperature of 60°C to 150°C is more preferred. Many epoxy group-containing compounds are prone to volatilization under high-temperature conditions (e.g., 200°C or higher). Therefore, when reacting PAS with an epoxy group-containing compound under conditions in which the PAS melts, it is difficult to recover the volatilized epoxy group-containing compound, requiring a large amount of the epoxy group-containing compound, which can easily lead to increased manufacturing costs and deterioration of the working environment.

[0082] Furthermore, under conditions where the PAS melts or dissolves, unreacted epoxy group-containing compounds may be incorporated into the particles during the granulation process after the reaction between the PAS and the epoxy group-containing compound. If a large amount of unreacted epoxy group-containing compounds are incorporated into the PAS particles, the epoxy group-containing compounds may act as plasticizers, potentially reducing the melt viscosity of the PAS or increasing volatile matter and / or mold deposits during melt molding. In addition, by carrying out the process under conditions where the untreated PAS does not melt or dissolve, the unreacted epoxy group-containing compounds can be removed by washing, and the epoxy group-containing compounds can be recovered from the solution after washing and reused as a raw material for reacting with the untreated PAS.

[0083] "Substantially solvent-free" means that the presence of inert gases or solids in the reaction system is not prevented, as long as they do not adversely affect the reaction and do not substantially reduce the substrate concentration. Specifically, this means that the total amount of untreated PAS and solvent substances other than the polyfunctional epoxy group-containing compound is 30% by weight or less and 10% by weight or less relative to the total amount of untreated PAS, polyfunctional epoxy group-containing compound, and solvent substances.

[0084] For example, PAS having MABA-terminated groups may have a low degree of polymerization. Therefore, when such PAS is reacted with an epoxy-containing compound in a solvent, the PAS may leach into the solvent and be difficult to recover. As a result, the amount of PAS that reacted with the epoxy-containing compound in the solids recovered after the reaction may be small, potentially reducing the effectiveness of the present invention. For this reason, it is preferable to carry out the reaction under substantially solvent-free conditions.

[0085] The reaction time is typically preferably 30 minutes to 24 hours, and more preferably 1 hour to 12 hours.

[0086] As described above, the untreated PAS is reacted with an epoxy group-containing compound, and the solids in the reaction solution are recovered by filtration. The recovered solids are then washed with an organic solvent, water, etc., and subsequently dried as necessary to obtain polyarylene sulfide corresponding to E-PAS.

[0087] Examples of organic solvents used for washing include organic polar solvents commonly used in the polymerization of untreated PAS, ketones (e.g., acetone), alcohols (e.g., methanol), ethers (e.g., diethyl ether), halogenated hydrocarbons (e.g., chloroform), etc. Ketones, alcohols, and ethers are preferred because they do not have too high an affinity for PAS but have a high affinity for polyfunctional epoxy group-containing compounds. Furthermore, in order to improve the recovery efficiency of E-PAS and the removal efficiency of unreacted epoxy group-containing compounds, the washing step of E-PAS is preferably carried out at 80°C or below, and more preferably at 10°C to 40°C. The drying step of E-PAS can be carried out in the same manner as in conventional methods for producing PAS, and is preferably carried out under reduced pressure.

[0088] <E-PAS> E-PAS is prepared by a method comprising: heating 3.0 g of E-PAS, 3.5 g of n-propyltriethoxysilane, and 1.4 g of 1,8-diazabicyclo[5.4.0]undec-7-ene (hereinafter referred to as "DBU") in 45 g of NMP with a nitrogen gas flow at 120°C for 8 hours while stirring to react polyarylene sulfide with n-propyltriethoxysilane; recovering the polyarylene sulfide (a) reacted with n-propyltriethoxysilane from the NMP; washing the polyarylene sulfide (a) recovered from the NMP and drying it at 80°C or below to obtain a sample for X-ray fluorescence analysis; and in the results of X-ray fluorescence analysis using the sample obtained by this method, the Si-Kα intensity I Ｓｉ－Ｋα (kcps) and the intensity I of S-Kα rays Ｓ－Ｋα (kcps) and are given by the following equation (1): (I Ｓｉ－Ｋα / I Ｓ－Ｋα It is a polyarylene sulfide that satisfies ) × 1000 ≥ 1.00 ... (1).

[0089] The reaction between E-PAS and n-propyltriethoxysilane is carried out in an open system under nitrogen gas flow. Furthermore, to prevent the inactivation of n-propyltriethoxysilane by moisture, the reaction vessel is thoroughly purged with nitrogen gas before the reaction begins. Here, "open system" means that the reaction vessel is not sealed. For example, a calcium chloride tube (e.g., a glass apparatus filled with absorbent cotton and calcium chloride in an L-shaped glass apparatus) may be used, or a reflux tubing may be used if the volatilization of NMP and n-propyltriethoxysilane is significant, or a combination of these may be used. The nitrogen gas flow rate is preferably 5 mL / min to 100 mL / min, and more preferably 10 mL / min to 50 mL / min. NMP and n-propyltriethoxysilane may be added entirely at the start of the reaction, or in multiple additions. If added in multiple additions, the entire amount should be added no later than two hours before the end of the reaction. When E-PAS reacts with n-propyltriethoxysilane, ethanol is produced. However, the reaction of ethanol with the functional group in E-PAS and n-propyltriethoxysilane can sometimes cause a reverse reaction, where the bond formed by the reaction can be cleaved. Therefore, it is necessary to remove ethanol from the reaction system between E-PAS and n-propyltriethoxysilane.

[0090] When measuring polyarylene sulfide (a), a reaction product of E-PAS and n-propyltriethoxysilane, by fluorescent X-ray, the polyarylene sulfide in NMP, which has completed the predetermined reaction and been allowed to cool to room temperature, shall be filtered using a membrane filter to separate the solid and liquid components, and then subjected to the washing and drying treatments described in (i) and (ii) below. This treatment removes unreacted n-propyltriethoxysilane. (i) The entire amount of solid on the membrane filter shall be washed with 50 mL of acetone while separating the solid and liquid components. The solid components after solid-liquid separation and 100 mL of acetone shall be placed in a 200 mL round-bottom flask, stirred at room temperature for 30 minutes, filtered using a membrane filter, and the solid components shall be recovered. (ii) The above operation (i) shall be repeated twice, and the obtained solid components shall be dried at a temperature of 80°C or lower under reduced pressure. The dried solid components shall be used as the fluorescent X-ray measurement sample. The lower limit of the drying temperature is not particularly limited and may be, for example, 0°C or higher. Furthermore, drying of the solids is continued until the weight of the solids no longer changes.

[0091] Si-Kα radiation intensity I Ｓｉ－Ｋα (kcps) refers to the silicon content in polyarylene sulfide (a). S-Kα ray intensity I Ｓ－Ｋα (kcps) relates to the sulfur content in polyarylene sulfide (a).

[0092] (I Ｓｉ－Ｋα / I Ｓ－ＫαA larger value of () × 1000 indicates that a large amount of silicon-containing groups derived from n-propyltriethoxysilane are introduced at the end of the E-PAS. The n-propyl group is generally known to be a functional group with low reactivity under basic conditions, such as when basic compounds like DBU are present, while alkoxy groups, such as ethoxy groups, are known to be highly reactive functional groups under basic conditions. Therefore, an E-PAS that satisfies formula (1) indicates that it has a functional group that reacts well with the ethoxy group in n-propyltriethoxysilane. Here, since n-propyltriethoxysilane is one of the silane coupling agents, a PAS that reacts well with n-propyltriethoxysilane can be said to react well even when silane coupling agents other than n-propyltriethoxysilane (hereinafter also referred to as "alkoxysilane compounds") are used.

[0093] Although the need to remove ethanol in the reaction between E-PAS and n-propyltriethoxysilane is mentioned, when E-PAS is added to a composition containing conventionally known PAS and an alkoxysilane compound, these are melt-kneaded. However, since the temperature at which the resin composition containing PAS is melt-kneaded is such that ethanol easily evaporates, the generation of ethanol does not need to be considered.

[0094] Examples of alkoxysilane compounds include epoxy group-containing alkoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; amino group-containing alkoxysilane compounds such as γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, and 3-aminopropyltrimethoxysilane; and isocyanate group-containing alkoxysilane compounds such as γ-isocyanatetopropyltriethoxysilane, γ-isocyanatetopropyltrimethoxysilane, γ-isocyanatetopropylmethyldimethoxysilane, γ-isocyanatetopropylmethyldiethoxysilane, γ-isocyanatetopropylethyldimethoxysilane, γ-isocyanatetopropylethyldiethoxysilane, and γ-isocyanatetopropyltrichlorosilane.

[0095] The functional groups known to exist in conventional PAS include amino groups, carboxyl groups, phenolic hydroxyl groups, and mercapto groups derived from MABA terminal groups. When conventional PAS and n-propyltriethoxysilane are melt-kneaded, there is almost no improvement in melt viscosity. Therefore, it is thought that the functional groups of conventional PAS hardly react with alkoxysilyl groups, or if they do react, they are rapidly eliminated. From the above, it is thought that conventional PAS introduces an alkoxysilane structure into the PAS by reacting with functional groups other than alkoxysilyl groups contained in alkoxysilane compounds (for example, amino groups contained in alkoxysilane compounds), and then the alkoxysilyl groups contained in the introduced alkoxysilane structure condense with each other, lengthening the molecular chain of the PAS and increasing its melt viscosity.

[0096] E-PAS can be obtained by reacting untreated PAS with an epoxy group-containing compound, and this reaction generates alcoholic hydroxyl groups. As described above, the phenolic hydroxyl groups contained in conventionally known PAS do not react well with alkoxysilyl groups, or if they do react, they are rapidly eliminated, but alcoholic hydroxyl groups react well with alkoxysilyl groups. Therefore, by adding E-PAS to a composition containing conventionally known PAS and an alkoxysilane compound (hereinafter also referred to as "alkoxysilane-containing composition"), the alkoxysilyl groups introduced into the PAS and the alcoholic hydroxyl groups in E-PAS react well, further extending the molecular chain of PAS and / or introducing a branched structure to the PAS molecule, which is presumed to increase the melt viscosity. As a result, by adding E-PAS to an alkoxysilane-containing composition, the melt viscosity of the composition can be increased.

[0097] (I Ｓｉ－Ｋα / I Ｓ－Ｋα The value of (I) × 1000 is preferably 1.00 or more and 7.00 or less, more preferably 1.50 or more and 7.00 or less, and even more preferably 3.00 or more and less than 7.00. By being within the above range, the melt viscosity of a composition containing a conventionally known PAS and a silane coupling agent can be increased by adding E-PAS to the composition. Ｓｉ－Ｋα / I Ｓ－Ｋα Methods to increase the value of ) × 1000 include increasing the amount of epoxy-reactive functional groups in the untreated PAS, and using alicyclic epoxy group-containing compounds as epoxy group-containing compounds.

[0098] In E-PAS, a mixture of 10 mg of the extract obtained by Soxhlet extraction using chloroform, 5.0 mg of 1,3,5-trimethoxybenzene, and 0.7 mL of deuterated chloroform was normalized so that the resonance peak based on chloroform in the deuterated chloroform was 7.26 ppm. １When measured by 1H-NMR (proton nuclear magnetic resonance), if Hs is the integral value of the peak observed in the range of 6.03 to 6.15 ppm and Ha is the integral value of the peak observed in the range of 4.58 to 4.89 ppm, it is preferable that the following equation (2) is satisfied: 1000 × (Ha) / (Hs / 3) ≥ 10 ... (2)

[0099] Ha is the integral value of the peak originating from the hydrogen atom bonded to the carbon atom bonded to the non-carbonyl oxygen atom in the ester bond (-O-CO-) in the group formed by the reaction of an alicyclic epoxy group and a MABA-terminated group. Ｓ This is the integral value of the peak originating from the hydrogen atoms bonded to the benzene ring in the reference substance, 1,3,5-trimethoxybenzene.

[0100] When an alicyclic epoxy group reacts with a MABA terminus, isomers may be formed. As a result, multiple peaks may be observed. Therefore, when multiple peaks are observed between 4.58 and 4.89 ppm, the sum of the integral values ​​of each peak is calculated, and the relative value of this sum is calculated with Hs set to 3000, and this is defined as Ha. Note that if the integral value of one peak is less than 0.1 with Hs set to 3000, it is determined that there is no structure associated with that peak, and the integral value is treated as 0.

[0101] Here, if formula (2) is satisfied, it indicates that the ratio of the integral value of the peak derived from a specific hydrogen atom in the functional group produced by the reaction between the alicyclic epoxy group and the MABA terminal group to the integral value of the peak derived from the hydrogen atom in the reference substance is high, and that the substance is rich in alcoholic hydroxyl groups produced by the reaction between the alicyclic epoxy group and the MABA terminal group. Therefore, when E-PAS satisfying formula (2) is added to an alkoxysilane-containing composition, the melt viscosity can be further increased.

[0102] As described above, compounds containing alicyclic epoxy groups react better with untreated PAS than compounds containing glycidyl groups, and the lower the Na content of the untreated PAS, the higher the reactivity. Therefore, PAS that satisfies formula (2) can also be determined to be PAS obtained by reacting PAS with a low Na content with an alicyclic epoxy group.

[0103] The upper limit of 1000 × (Ha) / (Hs / 3) is not particularly limited, but may be 50 or less, preferably 10 or more and less than 50, more preferably 10 or more and 30 or less, and even more preferably 15 or more and 30 or less.

[0104] １ The extracts used to prepare samples for 1H-NMR measurement are extracted by Soxhlet extraction using chloroform as the solvent. The Soxhlet extraction method is as follows: １ The method for obtaining 10 mg of sample for 1H-NMR measurement is not particularly limited, and can be carried out using the method described in the examples, for example, with a fully automated extraction apparatus. The extraction temperature should be the temperature at which chloroform refluxes.

[0105] "Extract" refers to the solid obtained after removing chloroform from E-PAS by heating the chloroform solution, which is acquired after Soxhlet extraction, at a temperature of 80°C or lower. Drying at room temperature and pressure or heated and reduced-pressure drying at a temperature of 80°C or lower (for example, solvent removal using an evaporator) may be combined. Chloroform removal is continued until the combined weight of the container and the extract inside the container no longer decreases.

[0106] The extract is washed and dried by the following method: The extract is ultrasonically washed for 10 minutes with acetone at a weight of 500 times or more the volume of the extract. The washed extract is then recovered by filtration using a membrane filter. Subsequently, the recovered material is washed on the membrane filter with acetone at a weight of 600 times or more the mass of the recovered extract, and this process is repeated five times. If the series of operations using ultrasonic washing and acetone at a weight of 600 times the mass of the extract is considered as one cycle, the above series of washing operations is repeated three times.

[0107] The specific surface area of ​​E-PAS is 5 m².​２ Preferably 10 m ２ / g or more 100m ２ Less than / g is more preferable, 15m ２ / g or more 100m ２ Less than / g is even more preferable, 20m ２ / g or more 80m ２ A value of less than or equal to / g is particularly preferred. The specific surface area of ​​E-PAS is 5 m². ２ When the concentration is 1 / g or higher, it becomes easier to uniformly disperse it in a composition containing untreated PAS and alkoxysilane compounds. Furthermore, its excellent washability makes it easy to remove unreacted epoxy group-containing compounds, preventing a decrease in physical properties due to the plasticizing effect derived from these compounds.

[0108] Specific surface area is 5 m ２ A value of 1 / g or more indicates that E-PAS is a microporous powder. Therefore, in the manufacturing method of E-PAS, it indicates that the untreated PAS was manufactured under conditions where it did not melt or dissolve, and it is also an indicator to distinguish it from E-PAS manufactured under conditions where it did melt or dissolve. The specific surface area of ​​E-PAS is usually adjusted by adjusting the specific surface area of ​​the untreated PAS.

[0109] The melt viscosity of E-PAS is not particularly limited, but is preferably 5 Pa·s to 250 Pa·s, more preferably 15 Pa·s to 250 Pa·s, and even more preferably 15 Pa·s to 200 Pa·s. Being within this range allows the melt viscosity of E-PAS to be easily increased to the desired level when added to an alkoxysilane-containing composition, resulting in a PAS with excellent mechanical strength and melt moldability.

[0110] When E-PAS was analyzed using X-ray fluorescence, the intensity of the Si-Kα rays was I. Ｓｉ－Ｋα（ｋｃｐｓ） And the intensity of S-Kα rays I Ｓ－Ｋα（ｋｃｐｓ） It is preferable that the relationship (6) is satisfied. Equation (6) indicates that E-PAS contains almost no Si. E-PAS exhibiting such a value can be obtained by using a compound that does not contain Si as the epoxy group-containing compound to be reacted with untreated PAS. Note that the measurement sample is PAS before reaction with n-propyltriethoxysilane. (IＳｉ－Ｋα / I Ｓ－Ｋα ) × 1000 ≤ 0.50 ... (6)

[0111] Furthermore, it is preferable that the melt viscosity of a mixture obtained by mixing E-PAS and linear untreated PAS having a melt viscosity equivalent to that of E-PAS in a weight ratio of 1:1 is less than 1.05 times the melt viscosity of E-PAS. Here, "melt viscosity equivalent to that of E-PAS" means that the difference from the melt viscosity of E-PAS is within ±5%. When a compound having two or more epoxy groups in its molecule is used as the epoxy group-containing compound, one or more epoxy groups may be introduced to at least one end of the PAS. The alcoholic hydroxyl group of E-PAS does not react when melt-kneaded with conventionally known PAS, but the epoxy group can react with the epoxy-reactive functional group of conventionally known PAS by melt-kneading. Therefore, E-PAS that satisfies the above range is PAS obtained from a monofunctional epoxy group-containing compound and untreated PAS, and it is judged that the E-PAS does not contain epoxy groups derived from the raw material epoxy group-containing compound.

[0112] The thickening properties of PAS are evaluated using mixture A, consisting of E-PAS, untreated PAS, and 3-aminopropyltriethoxysilane, and mixture B, consisting of untreated PAS and 3-aminopropyltriethoxysilane. Each mixture is placed in an antistatic polyethylene bag, and under conditions of room temperature and relative humidity of 50-70 RH%, the mixture is shaken by hand at least 60 times per minute while containing air. The melt viscosity of the mixture is measured, and the thickening ratio is calculated using the following formula (7). Note that one shake in one direction is counted as one shake. Thickening ratio [%] = Melt viscosity of mixture A [Pa·s] / Melt viscosity of mixture B [Pa·s] × 100 ... (7)

[0113] A thickening ratio exceeding 100% is considered to indicate a thickening effect, with 105% or higher being preferable, and 110% or higher being more preferable.

[0114] The present invention is not limited to the embodiments described above, and various modifications are possible. Embodiments obtained by appropriately combining the technical means disclosed in this specification are also included within the technical scope of the present invention. Furthermore, all documents cited in this specification are incorporated herein by reference.

[0115] The present invention will be described in more detail below with reference to examples and comparative examples. The methods for measuring various characteristics and physical properties are as follows.

[0116] <Various Measurement and Evaluation Methods> [Melting Viscosity Measurement] [Measurement Method] Melting viscosity was measured using a Capillograph F-1 manufactured by Toyo Seiki Co., Ltd. A 1 mmφ × 10 mm angled inlet die was used as the capillary. 20.0 g of PPS sample was placed in a barrel heated to 310°C and held for 5 minutes, then subjected to a shear rate of 1200 sec. －１ The melt viscosity was measured using the following method. Note that for the melt viscosities (M3) and (M4) described later, the PAS sample amount was set to 12.8 g.

[0117] [Measurement of melt viscosity when mixed with aminoalkoxysilane compounds] The formulations shown in Tables 3 and 4 below were placed in an antistatic polyethylene bag, and while air was incorporated, the mixture was shaken by hand for 1 minute at room temperature (23°C) and relative humidity of 63 RH%. The resulting mixture was used as the measurement sample. At this time, the number of shakes per minute was at least 60, and the number of shakes in one direction was counted as 1. In Tables 3 and 4, "Asi" refers to 3-aminopropyltriethoxysilane.

[0118] (Calculation of Thickening Ratio) The melt viscosity (M3) and (M4) of the obtained sample was measured under the same conditions as the measurement method described above. In addition, to evaluate the thickening effect, the thickening ratio of the melt viscosity was calculated from the following formula (7). Note that the melt viscosity of mixture A in formula (7) corresponds to M4 in Examples 1 to Comparative Example 5, and the melt viscosity of mixture B corresponds to M3 in Comparative Example 2. Thickening ratio [%] = Melt viscosity of mixture A [Pa·s] / Melt viscosity of mixture B [Pa·s] × 100 ... (7)

[0119] [Method for Measuring Specific Surface Area using the BET Method] Specific surface area was measured using the BET method (single-point method) in accordance with ISO 9277, using a specific surface area measuring device ("Monosorb®" manufactured by Anton Paar). 0.1 g of PPS sample was placed in a sample cell, and the sample was heated at 105°C for 3 hours while flowing a mixed gas of nitrogen and helium (nitrogen:helium = 30:70 (volume ratio)). After the heated sample cooled to room temperature (23°C), the sample cell was cooled with liquid nitrogen to adsorb nitrogen gas onto the sample. Adsorption was considered complete when the fluctuation of the nitrogen flow rate stopped. After adsorption was complete, cooling was stopped to desorb the nitrogen. Desorption was considered complete when the fluctuation of the nitrogen flow rate stopped. The specific surface area was calculated using the following formula (4): Specific surface area (m²) ２ / g) = Surface area of ​​the sample (m²) calculated from the nitrogen adsorption amount based on ISO 9277 ２ ) / Sample weight (weight after nitrogen gas desorption - container weight) (g) ... (4)

[0120] [Method for Measuring Extract Volume] The amount of extract obtained from 3.0 g of untreated PPS using chloroform was measured using a fully automatic Soxhlet extractor (Soxtherm 414) manufactured by Gerhardt Japan. The extraction conditions were a heating temperature of 170°C, a boiling extraction time of 60 minutes, and a washing extraction time of 90 minutes, with 150 mL of chloroform used as the solvent. The total extraction time was 2.5 hours, which is the sum of the boiling extraction time and the washing extraction time. After the extraction operation was completed, the glass container of the Soxhlet extractor containing the extract was left in a fume hood at room temperature for 15 hours to allow some of the chloroform to evaporate. Then, it was placed in a vacuum dryer and the extract was dried to dryness under reduced pressure at 80°C for 4 hours. After removing the glass container from the vacuum dryer, the temperature of the glass container was returned to room temperature in a desiccator. Subsequently, the total weight of the obtained extract and the glass container was measured. The weight of the extract obtained by the extraction procedure was calculated by subtracting the weight of the dry glass container stored in the desiccator, which was measured before the extraction procedure, from the total weight measured. The extract amount (weight %), which is the ratio of the weight of the extract to the weight of the untreated PPS used in the extraction procedure, was calculated using the following formula (5): Extract amount (weight %) = Weight of extract obtained by the extraction procedure (g) / Weight of sample used in the extraction procedure (g) × 100 ... (5)

[0121] [Method for measuring nitrogen atom content (Method for measuring MABA terminal group amount)] 10 mg of untreated PPS was accurately weighed, and the nitrogen atom content (mass ppm) was determined by elemental analysis using a trace nitrogen analyzer (TN-2100H, manufactured by Nitto Seiko Analytech Co., Ltd.). The amount of substance of the MABA terminal group was calculated by dividing the result by the atomic weight of nitrogen (14.00). The temperature of the sample injection section was set to 800°C, the temperature of the reaction section to 900°C, and the gas flow rate to 300 mL / min. A calibration curve was prepared using a toluene solution of pyridine with a known concentration.

[0122] [Method for measuring Na content] 0.5 g of untreated PAS, 5 mL of 96% by mass sulfuric acid, and 2 mL of 33±3% by mass hydrogen peroxide solution were added to a 30 mL Kelder flask and heated for 40 minutes. After heating, the entire volume was transferred to a 50 mL volumetric flask and diluted with pure water. The Na content of the obtained solution was determined using ICP-AES (Hitachi High-Tech Corporation, ICP emission spectrometer "SPS3500DD"). The Na content was determined by interpolation using a calibration curve prepared with commercially available standard solutions.

[0123] [Fluorescent X-ray Analysis 1: Evaluation using n-propyltriethoxysilane] [Preparation of Sample for Measurement] 3.0 g of PPS sample, 2.0 g of n-propyltriethoxysilane, 1.4 g of DBU, and 30 g of NMP were placed in a 200 mL round-bottom flask. The contents of the flask were stirred at 120°C for 8 hours in an open system under nitrogen gas flow. Considering the volatilization of NMP and n-propyltriethoxysilane, 5.0 g of NMP and 0.5 g of n-propyltriethoxysilane were added to the flask a total of three times, every two hours from the start of stirring. After the reaction, the contents of the flask were allowed to cool to room temperature. The solids were then recovered by filtration using a membrane filter. The recovered solids were separated from the liquid by washing with 50 mL of acetone on the membrane filter. The obtained solids and 100 mL of acetone were placed in a 200 mL round-bottom flask and stirred at room temperature for 30 minutes. The mixture was then filtered through a membrane filter to recover the solids. During stirring, care was taken to ensure that the entire solid was immersed in the 100 mL of acetone. The washing procedure using 50 mL of acetone and then 100 mL of acetone was repeated twice to recover the solids. The recovered solids were dried at 80°C for 4 hours under reduced pressure to obtain a sample for X-ray fluorescence analysis.

[0124] [Measurement Method] 2.1 g of the PPS sample for X-ray fluorescence analysis obtained above was weighed. The sample was placed in a circular mold with an inner diameter of 3.5 cm manufactured by Shimadzu Corporation, and the sample was compressed under a compression pressure of 20 MPa for 60 minutes to create a disk with a diameter of 3.5 cm, which was used as the measurement sample. The measurement was performed using an X-ray fluorescence analyzer (ZSX Primus IV) manufactured by Rigaku Corporation under the conditions of tube voltage 30 kV, tube current 80 mA, step 0.05 deg, and speed 400 deg / min, and the intensity of the S-Kα rays was measured. Ｓ－Ｋα (kcps) and Si-Kα radiation intensity I Ｓｉ－Ｋα (kcps) was calculated.

[0125] [ １ [H-NMR Measurement Method] [Preparation of Sample for Measurement] Soxhlet extraction with chloroform was performed under the same conditions as the extraction amount measurement method described above. After the extraction operation was completed, the glass container of the Soxhlet extractor containing the extract was left in a fume hood at room temperature for 15 hours to allow some of the chloroform to evaporate. Then, it was placed in a vacuum dryer and dried at 80°C under reduced pressure to dry the extract in the glass container. After removing the glass container from the vacuum dryer, the temperature of the glass container was returned to room temperature in a desiccator to obtain the dried extract.

[0126] 20 mg of the obtained Soxhlet extract and 10 g of acetone were added to a 30 mL vial, and ultrasonic washing was performed for 10 minutes. The washed extract was recovered by filtration through a membrane filter. With the suction filtration vial under atmospheric pressure, 60 g of acetone was added to the solids on the membrane filter, and after stirring with a spatula for 30 seconds, the suction filtration vial was reduced in pressure and the mixture was filtered. Furthermore, the ultrasonic washing, filtration, and washing on the membrane filter were repeated twice, and then the washed extract was obtained by drying at 80°C for 4 hours under reduced pressure. A mixture of 10 mg of the obtained extract, 7.0 mL of deuterated chloroform, and 5.0 mg of 1,3,5-trimethoxybenzene was prepared. １ The sample was prepared for 1H-NMR measurement.

[0127] [Measurement Method and Conditions] The measurement conditions were as follows. The results were analyzed using Delta for Windows v6.3.0 manufactured by JEOL Ltd. Furthermore, the chloroform-based resonance peak in deuterated chloroform was normalized to 7.26 ppm. １ Based on the 1H-NMR measurement results, the integral values ​​of the peaks observed in the range of 6.03 to 6.15 ppm were defined as Hs, the integral value of the peaks observed in the range of 4.58 to 4.89 ppm as Ha, and the integral value of the peaks observed in the range of 4.00 to 4.25 ppm as Hb. Equations (2) and (3) below were calculated and are shown in Table 1. Here, Hb originates from the hydrogen atom bonded to the carbon atom bonded to the non-carbonyl oxygen atom in the ester bond in the functional group produced by the reaction of the glycidyl group and the MABA terminal group. (Measurement conditions) Equipment: JNM-ECZ600R / S1 (manufactured by JEOL Ltd.) Resonance frequency: 600 MHz Measurement temperature: Room temperature (23°C: no temperature adjustment) Number of cumulative measurements: 8192 (Formula used for calculation) 1000 × (Ha) / (Hs / 3) ... (2) 1000 × (Hb / 2) / (Hs / 3) ... (3)

[0128] [Synthesis Example 1 (Untreated PPS-a)] 5000g of NMP was placed in a 20L autoclave. After creating a nitrogen gas atmosphere inside the autoclave, the NMP inside the autoclave was heated to 100°C over 1 hour while stirring at a stirrer speed of 250 rpm. After reaching 100°C, 1200g of a 74.0% by mass NaOH aqueous solution, 21.4 moles of NaSH, and Na were added. ２ 2000 g of an aqueous sulfur source solution containing 0.36 moles of sulfur, along with 1000 g of NMP, were added to an autoclave. The mixture in the autoclave was then gradually heated to 200°C over 2 hours. During the heating process to 200°C, 1028 g of water, 760 g of NMP, and 0.36 moles of hydrogen sulfide were discharged from the autoclave.

[0129] Next, the mixture in the autoclave was cooled to 170°C, and at the same temperature, 3359 g of p-DCB (p-dichlorobenzene), 2920 g of NMP, 173 g of water, and 5.9 g of NaOH at a concentration of 97% by mass were added to the autoclave. At the end of the addition, the temperature of the mixture in the autoclave was 130°C. Next, while stirring at a stirrer speed of 250 rpm, the mixture in the autoclave was heated to 180°C over 30 minutes, and then heated from 180°C to 220°C over 60 minutes. After that, the mixture in the autoclave was heated to 260°C over 90 minutes to carry out the preliminary polymerization.

[0130] After the initial polymerization stage was completed, the stirrer speed was increased to 400 rpm, and 443 g of water was injected into the autoclave as a phase-separating agent. After the injection of water, the temperature of the reaction solution was raised to 260°C in 0.5 hours, and the reaction was continued at the same temperature for 3 hours to carry out the subsequent polymerization stage.

[0131] After the subsequent polymerization was complete, the reaction mixture was cooled to near room temperature and then passed through a 100-mesh screen to recover granular polymer from the reaction mixture. The recovered granular polymer was washed three times with acetone, three times with water, once with a 0.3% by mass aqueous acetic acid solution, and four times with water, in that order at room temperature. All washing operations were carried out under conditions that the PPS was fully immersed in the washing solvent. The washed granular polymer was dried at 80°C (below the glass transition temperature of PPS) under reduced pressure for 4 hours to obtain untreated PPS-a.

[0132] [Synthesis Example 2 (Untreated PPS-b)] 5000 g of NMP was placed in a 20 L autoclave. After creating a nitrogen gas atmosphere inside the autoclave, the NMP in the autoclave was heated to 100°C over 1 hour while stirring at 250 rpm. After reaching 100°C, 1470 g of a 74.0 mass% NaOH aqueous solution, 2340 g of a 62.4 mass% NaSH aqueous solution, and 1000 g of NMP were added to the autoclave. The mixture in the autoclave was then gradually heated to 200°C over 2 hours. During the heating to 200°C, 1200 g of water, 800 g of NMP, and 0.36 moles of hydrogen sulfide were discharged from the autoclave.

[0133] Next, the mixture in the autoclave was cooled to 170°C, and at the same temperature, 3973 g of p-DCB, 2466 g of NMP, 26 g of water, and 2 g of NaOH at a concentration of 97% by mass were added to the autoclave. At the end of the addition, the temperature of the mixture in the autoclave was 130°C. Next, while stirring at a stirrer speed of 250 rpm, the mixture in the autoclave was heated to 180°C over 30 minutes, and then heated from 180°C to 220°C over 60 minutes. After that, the mixture in the autoclave was heated to 260°C over 90 minutes to carry out the preliminary polymerization.

[0134] After the initial polymerization stage was completed, the stirrer speed was increased to 400 rpm, and 443 g of water was injected into the autoclave as a phase-separating agent. After the injection of water, the temperature of the reaction solution was raised to 260°C in 0.5 hours, and the reaction was continued at the same temperature for 3 hours to carry out the subsequent polymerization stage.

[0135] The recovery and post-treatment steps following the subsequent polymerization were carried out in the same manner as in Synthesis Example 1 to obtain untreated PPS-b.

[0136] [Synthesis Example 3 (Untreated PPS-c)] Untreated PPS-c was obtained by using 3379 g of p-DCB as the starting material, and carrying out the recovery and post-treatment steps following the subsequent polymerization in the same manner as in Production Example 1, except that acetone washing was performed three times followed by water washing three times.

[0137] [Evaluation of physical properties of untreated PPS] For untreated PPS-a, untreated PPS-b, and untreated PPS-c obtained in Synthesis Examples 1 to 3, the melt viscosity, specific surface area, Soxhlet extract amount, nitrogen atom content, and Na content were measured using the method described above. The results are shown in Table 1.

[0138]

[0139] [Example 1] 16 g of untreated PPS-a obtained in Synthesis Example 1, 40 g of cyclohexene oxide (637 molar times the amount of MABA terminal group), and a stirring bar were placed in a 100 mL round-bottom flask. The contents of the round-bottom flask were stirred at 120°C for 8 hours to react the untreated PPS-a with the cyclohexene oxide. After the reaction, the mixture was allowed to cool to room temperature, and the solids were collected from the reaction solution in the round-bottom flask using filter paper (No. 5A). The collected solids were washed with 50 mL of acetone. Next, the washed solids and 100 mL of acetone were placed in a 200 mL round-bottom flask, and the contents of the round-bottom flask were stirred for 30 minutes to wash them. The solids were then collected by filtration using filter paper. At this time, the entire solid was immersed in 100 mL of acetone. The washing procedure was repeated using 50 mL of acetone and then 100 mL of acetone in the same manner, and the solids were recovered. The washed solids were dried at 80°C for 4 hours under reduced pressure to obtain PPS (modified PPS-A) with terminal modification by cyclohexene oxide.

[0140] [Example 2] PPS (modified PPS-B) was obtained in the same manner as in Example 1, except that cyclohexene oxide was replaced with tert-butylglycidyl ether.

[0141] [Example 3] Except that untreated PPS-a in Example 1 was changed to untreated PPS-b, terminally modified PPS (modified PPS-C) was obtained in the same manner as in Example 1.

[0142] [Example 4] PPS (modified PPS-D) was obtained in the same manner as in Example 2, except that untreated PPS-a was replaced with untreated PPS-b.

[0143] [Comparative Example 1] The procedure was the same as in Example 1, except that untreated PPS-c was used, to obtain terminally modified PPS (modified PPS-E) with cyclohexene oxide.

[0144] [Comparative Example 2] 16 g of untreated PPS-a, 40 g of cyclohexene oxide, 40 g of NMP, and a stirring bar were placed in a 200 mL round-bottom flask and reacted at 120°C for 8 hours. Recovery and washing after the reaction were carried out in the same manner as in Example 1 to obtain terminally modified PPS (modified PPS-F).

[0145] [Comparative Example 3] Untreated PPS-a obtained by the method described in Synthesis Example 1 was used.

[0146] [Evaluation of physical properties of modified PPS] For the modified PPS-A to modified PPS-F obtained in Examples 1 to 4 and Comparative Examples 1 to 2, and the untreated PPS-a of Comparative Example 2, the melt viscosity, specific surface area, X-ray fluorescence analysis, and the methods described above were used to evaluate the physical properties of modified PPS. １ 1H-NMR measurements were performed. The results are shown in Table 2.

[0147]

[0148] [Evaluation of PPS Thickening Properties 1] Using the method described above, the melt viscosity of mixtures consisting of 3-aminopropyltriethoxysilane and each of the modified PPS-A to modified PPS-E obtained in Examples 1 to 4 and Comparative Example 1, and the untreated PPS-a from Comparative Example 2 was measured. The results are shown in Table 3.

[0149]

[0150] [Evaluation of the thickening properties of modified PPS] Using the method described above, mixture A consisting of modified PPS-A to modified PPS-F obtained in Examples 1 to 4 and Comparative Examples 1 to 2, untreated PPS-a from Comparative Example 3, and 3-aminopropyltriethoxysilane, and mixture B consisting of untreated PPS-a from Comparative Example 2 and 3-aminopropyltriethoxysilane were prepared to obtain samples for measurement. From the melt viscosity measurement method and calculation of the thickening ratio described above, the thickening ratios of modified PPS-A to modified PPS-F obtained in Examples 1 to 4 and Comparative Examples 1 to 2, and untreated PPS-a from Comparative Example 3 were determined. The results are shown in Table 4. Comparative Examples 4 to 6 were carried out in the same manner as Comparative Example 2, except that the "type of epoxy compound" and / or "amount of epoxy compound used" were changed, as shown in Table 4.

[0151]

[0152] [Fluorescent X-ray Analysis 2: Evaluation of End-Treated PPS] Except for using 2.1 g of end-treated PPS obtained in Examples 1-4 and Comparative Examples 1-2 as the measurement sample, the measurements were performed under the same conditions as in Fluorescent X-ray Analysis 1 described above. As a result, all end-treated PAS showed (I Ｓｉ－Ｋα / I Ｓ－Ｋα The condition ) × 1000 ≤ 0.50 was satisfied.

[0153] According to Tables 2-4, the results of analyzing the PAS, which was reacted with n-propyltriethoxysilane under predetermined conditions and subjected to predetermined treatment, using X-ray fluorescence were (I Ｓｉ－Ｋα / I Ｓ－Ｋα The PPS of Examples 1 to 4, where ) × 1000 ≥ 1.00, can be seen to increase the melt viscosity when added to a composition containing PAS manufactured by a conventional method and a silane coupling agent.

[0154] [Discussion] Comparing Example 1 and Comparative Example 1, Example 1 is better at "(I Ｓｉ－Ｋα / I Ｓ－Ｋα The large value of ") × 1000" indicates that more alcoholic hydroxyl groups have been introduced. Since the only difference between Example 1 and Comparative Example 1 is the untreated PPS used in the examples, it is thought that washing with an acidic aqueous solution made the reactive end groups such as MABA end groups acidic end groups, which facilitated the reaction between the epoxy group-containing compound and the untreated PAS.

[0155] Comparing Example 1 with Comparative Example 3, it can be seen that the melt viscosity (M3) of Example 1 is smaller than that of Comparative Example 2, but the melt viscosity (M4) is larger than that of Comparative Example 2. From the viewpoint of reactivity with the amino groups contained in 3-aminopropyltriethoxysilane, the MABA terminal groups in PPS react well, but the alcoholic hydroxyl groups do not react, so it is presumed that M3 was larger in Comparative Example 2, which has more MABA terminal groups. On the other hand, from the viewpoint of reactivity with the alkoxysilyl groups contained in 3-aminopropyltriethoxysilane, the MABA terminal groups in PPS hardly react, or if they do react, they are rapidly eliminated. Therefore, it is thought that in Example 1, the coexistence of the MABA terminal groups in untreated PPS-a and the alcoholic hydroxyl groups in modified PPS-A allowed for good reaction with both the amino groups and alkoxysilyl groups contained in 3-aminopropyltriethoxysilane, resulting in a larger M4 than in Comparative Example 2.

[0156] Comparative Examples 3 to 6 show that, when measuring the melt viscosity (M4), the thickening ratio is less than 100% in all cases, despite the use of epoxy group-containing compounds. These results indicate that simply melt-mixing PPS, epoxy compounds, and silane coupling agents is insufficient. It is found that pre-reacting untreated PPS with epoxy group-containing compounds to introduce alcoholic hydroxyl groups to the terminal groups of PPS increases the melt viscosity when added to a composition containing PAS produced by a conventional method and a silane coupling agent. This is thought to be because, when the epoxy group-containing compound and the silane coupling agent are added simultaneously during melt-mixing, the reaction between the epoxy groups and the functional groups (in this case, amino groups) in the silane coupling agent proceeds preferentially, thereby inhibiting the reaction between the terminal groups of PPS and the silane coupling agent.

[0157] Furthermore, comparing Examples 1 and 3, Example 3 is better at "(I Ｓｉ－Ｋα / I Ｓ－ＫαIt can be seen that the value of ") × 1000" is larger. This is thought to be because the untreated PPS-b used in Example 3 has a higher nitrogen atom content (amount of MABA end groups) than the untreated PPS-a used as a raw material in Example 1, resulting in the introduction of more alcoholic hydroxyl groups to the ends of the PPS. Furthermore, comparing Example 1 and Example 2, it can be seen that the alicyclic epoxy group-containing compound has better reactivity with PPS than the glycidyl group-containing compound, allowing for the introduction of more alcoholic hydroxyl groups to the ends of the PPS and resulting in a higher viscosity ratio.

Claims

1. Reacting 3.0 g of polyarylene sulfide, 3.5 g of n-propyltriethoxysilane, and 1.4 g of 1,8-diazabicyclo[5.4.0]undec-7-ene in 45 g of N-methyl-2-pyrrolidone in an open system with nitrogen gas flow, stirring at 120°C for 8 hours, the polyarylene sulfide and the n-propyltriethoxysilane; recovering the polyarylene sulfide (a) that has reacted with the n-propyltriethoxysilane from the N-methyl-2-pyrrolidone; washing the recovered polyarylene sulfide (a) and drying it at 80°C or below to obtain a sample for X-ray fluorescence analysis; and in the results of X-ray fluorescence analysis performed using the sample obtained by the method, the Si-Kα intensity I Ｓｉ－Ｋα (kcps) and the intensity I of S-Kα rays Ｓ－Ｋα (kcps) and are given by the following equation (1): (I Ｓｉ－Ｋα / I Ｓ－Ｋα A polyarylene sulfide that satisfies ) × 1000 ≥ 1.00 ... (1).

2. A mixture of 10 mg of the extract obtained from the polyarylene sulfide by Soxhlet extraction using chloroform, 5.0 mg of 1,3,5-trimethoxybenzene, and 0.7 mL of deuterated chloroform was normalized to have a resonance peak based on chloroform in the deuterated chloroform of 7.26 ppm. １ When measured by 1H-NMR, if Hs is the integral value of the peak observed in the range of 6.03 to 6.15 ppm and Ha is the integral value of the peak observed in the range of 4.58 to 4.89 ppm, the polyarylene sulfide according to claim 1 satisfies the following equation (2): 1000 × (Ha) / (Hs / 3) ≥ 10 ... (2).

3. The specific surface area measured by the BET method (single-point method) using a mixed gas of nitrogen and helium (nitrogen:helium = 30:70 (volume ratio)) as the adsorption gas is 5 m². ２ The polyarylene sulfide according to claim 1, wherein the amount is 1 / g or more.

4. The specific surface area measured by the BET method (single-point method) using a mixed gas of nitrogen and helium (nitrogen:helium = 30:70 (volume ratio)) as the adsorption gas is 5 m². ２ The value is greater than or equal to / g, at a temperature of 310°C and a shear rate of 1200 sec. －１ A method for producing polyarylene sulfide, comprising: a mixing step of mixing an untreated polyarylene sulfide having a melt viscosity of 1 Pa·s or more as measured under certain conditions, a functional group that reacts with epoxy groups of 14 μmol / g or more, and a sodium content of 800 ppm by mass or less with an epoxy group-containing compound; and a reaction step of reacting the mixture obtained in the mixing step at a temperature of 30°C to 230°C under substantially solvent-free conditions.

5. The method for producing polyarylene sulfide according to claim 4, wherein the amount of functional group that reacts with the epoxy group is the nitrogen atom content.

6. A method for producing polyarylene sulfide according to claim 4 or 5, further comprising a step of washing the untreated polyarylene sulfide at a temperature below its glass transition temperature and / or drying it, prior to the mixing step.

7. The method for producing polyarylene sulfide according to claim 4 or 5, wherein the amount of the epoxy group-containing compound is added in such a way that it is 30 molar times or more relative to the amount of functional groups that react with the epoxy groups of the untreated polyarylene sulfide.

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