Method for producing polyarylene sulfide resin

Abstract

To efficiently obtain a polyarylene sulfide resin that contains a large number of functional groups and is increased in molecular weight.SOLUTION: A method for producing a polyarylene sulfide resin includes the step of causing a reaction to occur between a polyarylene sulfide with a weight average molecular weight of 25000 or more and a halogenated compound having a functional group in a temperature range of 200°C or higher and lower than 290°C.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a method for producing a polyarylene sulfide resin having a high content of functional groups and a high molecular weight. More specifically, the present invention provides a method for producing a polyarylene sulfide resin having a high content of functional groups and a high molecular weight, the method including a step of reacting a polyarylene sulfide having a weight average molecular weight of 25,000 or more with a halogenated compound having a functional group. [Background technology]

[0002] Polyarylene sulfide (PAS) resin has excellent properties suitable for engineering plastics, such as excellent heat resistance, chemical resistance, and electrical insulation. For this reason, it is widely used in electrical and electronic parts, communication device parts, automotive materials, etc. However, it has a problem that it has low adhesion to different materials such as resins other than PAS resin, fillers, and metals, and the strength of composite materials made by combining PAS resin with different materials is low. In addition, problems such as the further decrease in strength and toughness of composite materials due to long-term hot water treatment and long-term dry heat treatment have been pointed out. In particular, with the recent market demand for low fuel consumption, light weight, and low cost of automobiles, there is a demand for excellent materials that have high strength due to improved adhesion with different materials and do not experience a decrease in strength or toughness even when subjected to long-term hot water treatment and long-term dry heat treatment.

[0003] In response to this, an improvement method has been reported in which other compounds are blended into the PAS resin to increase adhesion to different materials and maintain strength and toughness. For example, Patent Document 1 discloses a PAS resin composition obtained by blending a polyamide in addition to a PAS resin and glass fiber. Patent Document 2 discloses a PAS resin composition obtained by blending an epoxysilane with a PAS resin obtained by reacting a polyarylenesulfonium salt with an aliphatic amide compound.

[0004] However, the poor adhesion of the above-mentioned PAS resin to different materials has not been significantly improved, and the issue of how to meet market demands remains.

[0005] Therefore, several methods for improving PAS resins have been reported. For example, Patent Document 3 discloses a PAS resin in which a certain amount of thioether groups have been introduced by depolymerizing PAS in the presence of sodium hydrosulfide. Patent Document 4 discloses a polyphenylene sulfide resin in which a certain amount of carboxyl groups have been introduced to the terminals by reacting sodium hydrosulfide with paradichlorobenzene under specific conditions in the presence of NMP solvent. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2019-137868 A [Patent Document 2] JP 2016-147958 A [Patent Document 3] Japanese Patent Application Publication No. 5-5061 [Patent Document 4] JP 2012-177015 A Summary of the Invention [Problem to be solved by the invention]

[0007] However, although the PAS resin described in Patent Document 3 is expected to have a relatively high functional group content, it has an extremely low molecular weight, which causes a problem of low strength when processed into products.

[0008] The PAS resin described in Patent Document 4 has a relatively high molecular weight, but the functional group content is insufficient, and the strength is significantly reduced when subjected to a long-term hot water treatment or long-term dry heat treatment.

[0009] As described above, it is difficult for the PAS resins described in Patent Documents 3 and 4 to have both a high functional group content and a high molecular weight, and there is a problem that resin compositions obtained from such PAS resins cannot be used for electric / electronic components, communication device components, or automobile components. [Means for solving the problem]

[0010] Therefore, the inventors conducted intensive research to solve the above problems, and discovered that a PAS manufacturing method can efficiently produce a polyarylene sulfide resin having a high molecular weight and a large functional group content by including a step of reacting a PAS having a weight average molecular weight of 25,000 or more with a halogenated compound having a functional group within a temperature range of 200°C or more and less than 290°C, thereby arriving at the present invention.

[0011] That is, the present invention is as follows. 1. A method for producing a polyarylene sulfide resin, comprising the step of reacting a polyarylene sulfide having a weight average molecular weight of 25,000 or more with a halogenated compound having a functional group within a temperature range of 200°C or higher and lower than 290°C. 2. A method for producing the polyarylene sulfide resin described in 1, characterized in that in the step of reacting the polyarylene sulfide having a weight average molecular weight of 25,000 or more with a halogenated compound having a functional group, the reaction is carried out at a temperature range of 200°C or higher and lower than 290°C for 15 minutes to less than 3 hours. 3. The method for producing a polyarylene sulfide resin according to 1 or 2, characterized in that the halogenated compound having a functional group contains at least one functional group selected from the group consisting of a carboxyl group, an acid anhydride group, an amino group, a hydroxyl group and derivatives thereof. 4. The method for producing a polyarylene sulfide resin according to any one of 1 to 3, wherein the polyarylene sulfide resin has a weight average molecular weight of 45,000 or more. 5. The method for producing a polyarylene sulfide resin according to any one of 1 to 4, wherein the polyarylene sulfide resin has a functional group content of 100 μmol / g or more and less than 500 μmol / g. 6. A method for producing a polyarylene sulfide resin according to any one of 1 to 5, comprising the step of reacting a sulfidizing agent with a dihalogenated aromatic compound in an organic polar solvent in the presence of 1 mol or more and less than 1,000 mol of a polymerization aid per 100 mol of the sulfidizing agent within a temperature range of 200°C or more and less than 290°C. 7. The method for producing a polyarylene sulfide resin according to any one of 1 to 6, wherein the halogenated compound having a functional group is substantially free of water. Effect of the Invention

[0012] According to the present invention, a polyarylene sulfide resin having a large content of functional groups and a high molecular weight can be efficiently obtained. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] The PAS in the present invention is a homopolymer or copolymer whose main constituent unit is a repeating unit of the formula -(Ar-S)-, preferably containing 80 mol % or more of said repeating unit. Ar may be any of the units represented by the following formulae (A) to (K), with formula (A) being particularly preferred.

[0014] [ka]

[0015] (R1 and R2 are substituents selected from hydrogen, alkyl groups, alkoxy groups, and halogen groups, and R1 and R2 may be the same or different.)

[0016] As long as this repeating unit is the main constituent unit, it may contain a small amount of branching units or crosslinking units represented by the following formulas (L) to (N), etc. The copolymerization amount of these branching units or crosslinking units is preferably in the range of 0 to 1 mol % per 1 mol of -(Ar-S)- units.

[0017] [ka]

[0018] The PAS in the present invention may be any of a random copolymer, a block copolymer, and a mixture thereof, which contain the above repeating units.

[0019] Representative examples of these include polyphenylene sulfide, polyphenylene sulfide sulfone, polyphenylene sulfide ketone, random copolymers thereof, block copolymers thereof, and mixtures thereof. Particularly preferred PASs include those having the following p-phenylene sulfide unit as the main structural unit of the polymer:

[0020] [ka]

[0021] % or more, particularly 90 mol % or more of the above.

[0022] The method for producing the PAS resin of the present invention will be described below.

[0023] First, the details of the dihalogenated aromatic compound, sulfidizing agent, polymerization solvent, halogenated compound having a functional group, branching / crosslinking agent, polymerization aid, and polymerization stabilizer used in the production method will be described.

[0024] [Dihalogenated aromatic compound] The dihalogenated aromatic compound refers to a compound having two halogen atoms in one molecule. Specific examples include p-dichlorobenzene, m-dichlorobenzene, o-dichlorobenzene, 2,5-dichlorotoluene, 2,5-dichloro-p-xylene, 1,4-dibromobenzene, 1,4-diiodobenzene, and 1-methoxy-2,5-dichlorobenzene, and preferably p-dichlorobenzene is used. In addition, it is possible to combine two or more different dihalogenated aromatic compounds to form a copolymer, but it is preferable to use p-dihalogenated aromatic compounds as the main component.

[0025] In order to obtain a PAS resin with a viscosity suitable for processing, the amount of the dihalogenated aromatic compound used is, for example, in the range of 90 to 120 mol, preferably 95 to 110 mol, more preferably 99 to 105 mol, and even more preferably 100.5 to 103 mol per 100 mol of the sulfidizing agent.

[0026] [Sulfidizing agent] The sulfidizing agent includes alkali metal sulfides, alkali metal hydrosulfides, and hydrogen sulfide.

[0027] Specific examples of alkali metal sulfides include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide, and mixtures of two or more of these, with sodium sulfide being preferred. These alkali metal sulfides can be used as hydrates or aqueous mixtures, or in the anhydrous form.

[0028] Specific examples of the alkali metal hydrosulfide include sodium hydrosulfide, potassium hydrosulfide, lithium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide, and mixtures of two or more of these, with sodium hydrosulfide being preferred. These alkali metal hydrosulfides can be used as hydrates or aqueous mixtures, or in the anhydrous form.

[0029] In addition, an alkali metal sulfide prepared in situ in the reaction system from an alkali metal hydrosulfide and an alkali metal hydroxide can also be used.Alkali metal sulfide can also be prepared from an alkali metal hydrosulfide and an alkali metal hydroxide, and then transferred to a polymerization tank for use.

[0030] Alternatively, an alkali metal sulfide prepared in situ in the reaction system from an alkali metal hydroxide such as lithium hydroxide or sodium hydroxide and hydrogen sulfide can be used.Alkaline metal sulfides can also be prepared from an alkali metal hydroxide such as lithium hydroxide or sodium hydroxide and hydrogen sulfide, and then transferred to a polymerization tank for use.

[0031] When a part of the sulfidizing agent is lost before the start of the polymerization reaction due to a dehydration operation or the like, the amount of the charged sulfidizing agent means the remaining amount obtained by subtracting the lost amount from the actual charged amount.

[0032] It is also possible to use an alkali metal hydroxide and / or an alkaline earth metal hydroxide together with the sulfidizing agent.Specific examples of the alkali metal hydroxide include, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, and mixtures of two or more of these.Specific examples of the alkaline earth metal hydroxide include, for example, calcium hydroxide, strontium hydroxide, barium hydroxide, etc., and among these, sodium hydroxide is preferably used.

[0033] When an alkali metal hydrosulfide is used as the sulfidizing agent, it is particularly preferable to use an alkali metal hydroxide simultaneously. The amount of the alkali metal hydroxide used is, for example, in the range of 0.95 to 1.20 mol, preferably 1.00 to 1.15 mol, and more preferably 1.005 to 1.100 mol, per mol of the alkali metal hydrosulfide.

[0034] [Polymerization solvent] As the polymerization solvent, it is preferable to use an organic polar solvent. Specific examples include N-alkylpyrrolidones such as N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone, caprolactams such as N-methyl-ε-caprolactam, aprotic organic solvents such as 1,3-dimethyl-2-imidazolidinone, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphoric triamide, dimethylsulfone, and tetramethylene sulfoxide, and mixtures thereof. All of these polymerization solvents are preferably used because of their high reaction stability. Among these, N-methyl-2-pyrrolidone (hereinafter sometimes abbreviated as NMP) is particularly preferably used.

[0035] The amount of the organic polar solvent used is selected from the range of 20 to 1,000 moles, preferably 225 to 600 moles, more preferably 250 to 550 moles, per 100 moles of the sulfidizing agent.

[0036] [Halogenated compounds with functional groups] In the present invention, it is essential to use a halogenated compound having a functional group. Specifically, the halogenated compound having a functional group is a halogenated compound having at least one functional group selected from a carboxyl group, an acid anhydride group, a hydroxyl group, an amino group, an isocyanate group, an epoxy group, a nitro group, a thiol group, a sulfonamide group, an amide group, a sulfonic acid group, an acetyl group, a silanol group, an alkoxysilane group, and a derivative thereof. Among these, from the viewpoint of reactivity and handling, any one selected from a carboxyl group, an acid anhydride group, an amino group, a hydroxyl group, and a derivative thereof is preferable, and any one selected from a carboxyl group, an acid anhydride group, and a carboxylate is more preferable. These functional groups may be present in one molecule or two or more. In addition, one molecule may have a plurality of different functional groups.

[0037] In the present invention, the halogenated compound having a functional group is not particularly limited as long as it is a compound having one or more halogens in one molecule, and examples thereof include monohalogenated compounds, dihalogenated compounds, trihalogenated compounds, tetrahalogenated compounds, etc. From the viewpoint of obtaining excellent reactivity and a melt viscosity suitable for processing, monohalogenated compounds and dihalogenated compounds are preferred, and monohalogenated aromatic compounds and dihalogenated aromatic compounds are more preferred.

[0038] Examples of halogenated compounds having functional groups include 4-chloro-cyclohexane-1-carboxylic acid, 2-chloroaniline, 3-chloroaniline, 4-chloroaniline, 5-chlorobenzene-1,3-diamine, 2-chlorobenzoic acid, 3-chlorobenzoic acid, 4-chlorobenzoic acid, sodium 4-chlorobenzoate, 5-chlorobenzene-1,2,3-tricarboxylic acid, 3-chlorophthalic anhydride, 4-chlorophthalic anhydride, 5-chloroisophthalic acid, 4-chlorophthalic acid, sodium 2-carboxy-4-chlorobenzoate, 3-chlorophthalic acid disodium, 4-chlorophthalic acid disodium, 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, 3-chloroammonium chloride, 4-chlorobenzamide, 4-chlorobenzeneacetamide, 4-chlorobenzenesulfonyl. monohalogenated aromatic compounds such as 4-chlorobenzenesulfonic acid, 4-chlorobenzenethiol, 4'-chlorobenzophenone-2-carboxylic acid, 2-amino-5-chlorobenzophenone, 4'-chloro-[1,1'-biphenyl]-4-carboxylic acid, 4-((chlorophenyl)thio)aniline, 6-chloro-2-naphthoic acid, 6-chloronaphthalene-2-amine, 6-chloro-2-naphthol, 6-chloronaphtho[2,3-c]furan-1,3-dione, 4-bromobenzoic acid, 4-iodobenzoic acid, 4-chloronitrobenzene, and dihalogenated aromatic compounds such as 3,5-dichloroaniline, 2,5-dichlorophenol, 2,5-dichlorobenzoic acid, 4,7-dichloroisobenzofuran-1,3-dione, and disodium 3,6-dichlorophthalate.

[0039] Among these, from the viewpoints of handling and reactivity, 3,5-dichloroaniline, 4-chlorobenzoic acid, sodium 4-chlorobenzoate, 4-chlorophthalic anhydride, 4-chlorophthalic acid, disodium 4-chlorophthalate, 2-carboxy-sodium 4-chlorobenzoate, and 4-chlorophenol are preferred, and 4-chlorobenzoic acid, sodium 4-chlorobenzoate, 4-chlorophthalic anhydride, 4-chlorophthalic acid, disodium 4-chlorophthalate, and 2-carboxy-sodium 4-chlorobenzoate are more preferred.

[0040] In the present invention, when a halogenated compound having a functional group also falls under the category of a dihalogenated aromatic compound, it is treated as a halogenated compound having a functional group and not as a dihalogenated aromatic compound.

[0041] In the present invention, the amount of the halogenated compound having a functional group is preferably 0.05 mol or more and less than 15 mol, more preferably 0.1 mol or more and less than 10 mol, and even more preferably 2 mol or more and less than 5 mol, relative to 100 mol of the sulfidizing agent. If the amount of the halogenated compound having a functional group is less than 0.01 mol relative to 100 mol of the sulfidizing agent, the content of the functional group introduced is significantly reduced, which is not preferable. If the amount of the halogenated compound having a functional group is 40 mol or more relative to 100 mol of the sulfidizing agent, the amount of the halogenated compound having an unreacted functional group increases, which is not preferable in terms of increasing the load of the wastewater treatment. The halogenated compound having a functional group may be used alone or as a mixture of two or more different types.

[0042] The total amount of the halogenated compounds is preferably 98 mol or more and less than 108 mol per 100 mol of the sulfidizing agent. The halogenated compounds include not only the above-mentioned dihalogenated aromatic compounds and halogenated compounds having functional groups, but also halogenated compounds used in the branching / crosslinking agent described below.

[0043] In the present invention, it is preferable that the halogenated compound having a functional group does not substantially contain water. Substantially free of water means that the water content of the halogenated compound having a functional group is 5 wt% or less, more preferably 1 wt% or less, and even more preferably 0.1 wt%. If the water content of the halogenated compound having a functional group exceeds 5 wt%, it is not preferable because the reactivity with PAS is significantly reduced after being supplied to the polymerization system. The reason for this is unclear, but it is presumed that the interaction between the halogenated compound having a functional group and water is strong, which inhibits the reaction with PAS.

[0044] [Branching / Crosslinking Agents] In the present invention, a substantially linear PAS resin having a large content of functional groups and a high molecular weight can be obtained, but in order to form a branched or crosslinked polymer, a trihalogenated or higher polyhalogen compound (not necessarily an aromatic compound) can be used. Among these, polyhalogenated aromatic compounds are preferred, and specific examples include 1,3,5-trichlorobenzene, 1,2,4-trichlorobenzene, 1,2,4,5-tetrachlorobenzene, hexachlorobenzene, and 1,4,6-trichloronaphthalene, with 1,3,5-trichlorobenzene and 1,2,4-trichlorobenzene being preferred.

[0045] In the present invention, when a halogenated compound having a functional group also falls under the category of a trihalogenated compound, it is treated as a halogenated compound having a functional group and not as a trihalogenated aromatic compound.

[0046] [Polymerization aid] In order to obtain a PAS resin with a relatively high degree of polymerization in a short time, it is also a preferred embodiment to use a polymerization aid. Here, the polymerization aid means a substance that has the effect of increasing the viscosity of the resulting PAS resin. Specific examples of such polymerization aids include organic carboxylates, water, alkali metal chlorides, organic sulfonates, alkali metal sulfates, alkaline earth metal oxides, alkali metal phosphates, and alkaline earth metal phosphates.

[0047] These may be used alone or in combination of two or more. Among these, organic carboxylates, alkali metal chlorides, and water are preferred, and as the organic carboxylates, alkali metal carboxylates and as the alkali metal chlorides, lithium chloride are preferred.

[0048] The above alkali metal carboxylate has the general formula R(COOM) n (wherein R is an alkyl group, a cycloalkyl group, an aryl group, an alkylaryl group, or an arylalkyl group having 1 to 20 carbon atoms; M is an alkali metal selected from lithium, sodium, potassium, rubidium, and cesium; and n is an integer of 1 to 3). The alkali metal carboxylate can also be used as a hydrate, anhydride, or an aqueous solution. Specific examples of the alkali metal carboxylate include lithium acetate, sodium acetate, potassium acetate, sodium propionate, lithium valerate, sodium benzoate, sodium phenylacetate, potassium p-toluate, and mixtures thereof.

[0049] The alkali metal carboxylate may be formed by adding and reacting an organic acid with one or more compounds selected from the group consisting of alkali metal hydroxides, alkali metal carbonates, and alkali metal bicarbonates in approximately equal chemical equivalents. Among the above alkali metal carboxylates, lithium salts have high solubility in the reaction system and have a large auxiliary effect, but are expensive. On the other hand, potassium, rubidium, and cesium salts are thought to have insufficient solubility in the reaction system, so sodium acetate, which is inexpensive and has moderate solubility in the polymerization system, is most preferably used.

[0050] In the present invention, the amount of the polymerization aid added is preferably within a range of 1 mol to 1500 mol per 100 mol of the charged sulfidizing agent.

[0051] In the present invention, it is preferable to use an alkali metal carboxylate as a polymerization aid, and more preferably to use sodium acetate. In this case, from the viewpoint of obtaining a higher degree of polymerization, the amount of the alkali metal carboxylate used is preferably in the range of 1 mol to 200 mol, more preferably in the range of 10 mol to 100 mol, and even more preferably in the range of 20 mol to 50 mol, relative to 100 mol of the charged sulfidizing agent.

[0052] When water is used as a polymerization aid, the amount added is preferably in the range of 30 mol to 1500 mol relative to 100 mol of the charged sulfidizing agent, more preferably in the range of 60 mol to 1000 mol, and even more preferably in the range of 100 mol to 500 mol, in terms of obtaining a higher degree of polymerization.

[0053] Of course, two or more of these polymerization aids can be used in combination. For example, when an alkali metal carboxylate and water are used in combination, a higher molecular weight can be achieved with smaller amounts of the alkali metal carboxylate and water.

[0054] There is no particular designation for the timing of addition of these polymerization aids, and they may be added at any time during the pre-step, at the start of polymerization, or during the polymerization, as described below, or may be added in several batches. When an alkali metal carboxylate is used as the polymerization aid, it is more preferable to add it at the start of the pre-step or at the start of polymerization simultaneously with other additives, since it is easy to add. When water is used as the polymerization aid, it is effective to add it during the polymerization reaction after the polyhalogenated aromatic compound is charged.

[0055] [Polymerization stabilizer] A polymerization stabilizer can be used to stabilize the polymerization reaction system and prevent side reactions. The polymerization stabilizer contributes to the stabilization of the polymerization reaction system and suppresses undesirable side reactions. One indicator of side reactions is the generation of thiophenol. The addition of a polymerization stabilizer can suppress the generation of thiophenol. Specific examples of polymerization stabilizers include compounds such as alkali metal hydroxides, alkali metal carbonates, alkaline earth metal hydroxides, and alkaline earth metal carbonates. Among these, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide are preferred. The above-mentioned alkali metal carboxylates also act as polymerization stabilizers, and therefore are included as one of the polymerization stabilizers. In addition, as mentioned above, when an alkali metal hydrosulfide is used as a sulfidizing agent, it is particularly preferable to use an alkali metal hydroxide at the same time, but here, an alkali metal hydroxide that is in excess of the sulfidizing agent can also be a polymerization stabilizer.

[0056] These polymerization stabilizers can be used alone or in combination of two or more. The polymerization stabilizer is preferably used in a ratio of usually 0.02 mol to 0.2 mol, preferably 0.03 mol to 0.1 mol, more preferably 0.04 mol to 0.09 mol, per mol of the charged alkali metal sulfide. If this ratio is too small, the stabilizing effect is insufficient, and conversely, if it is too large, it is economically disadvantageous and the polymer yield tends to decrease.

[0057] The timing of adding the polymerization stabilizer is not particularly specified, and it may be added at any time during the pre-step described below, at the start of polymerization, or during the polymerization, or may be added in several divided portions. However, it is more preferable to add it simultaneously at the start of the pre-step or at the start of polymerization from the viewpoint of ease.

[0058] Next, a preferred method for producing the PAS resin of the present invention will be specifically described in order, including a pre-process, a polymerization reaction process, a recovery process, and a post-treatment process, although the present invention is not limited to this method.

[0059] [Pre-process] In the production method of PAS resin, the sulfidizing agent is usually used in the form of a hydrate, and it is preferable to heat the mixture containing the organic polar solvent and the sulfidizing agent and remove excess water from the system before adding the polyhalogenated aromatic compound.

[0060] As described above, the sulfidizing agent may be prepared in situ in the reaction system from an alkali metal hydrosulfide and an alkali metal hydroxide, or in a tank separate from the polymerization tank. There is no particular restriction on this method, but a preferable method is to add an alkali metal hydrosulfide and an alkali metal hydroxide to an organic polar solvent in an inert gas atmosphere at room temperature to 150°C, preferably from room temperature to 100°C, and then heat the mixture to at least 150°C or higher, preferably 180°C to 260°C, under normal pressure or reduced pressure, to distill off water. A polymerization aid may be added at this stage. Toluene or the like may be added to promote the distillation of water.

[0061] In the polymerization reaction, the amount of water in the polymerization system is preferably 0.3 mol to 10.0 mol per 1 mol of the charged sulfidizing agent. Here, the amount of water in the polymerization system is the amount of water charged to the polymerization system minus the amount of water removed from the polymerization system. The charged water may be in any form such as water, an aqueous solution, or crystal water.

[0062] [Polymerization reaction process] The PAS resin is produced by reacting a sulfidizing agent with a dihalogenated aromatic compound in an organic polar solvent at a temperature range of 200°C or higher and lower than 290°C.

[0063] When starting the polymerization reaction process, the organic polar solvent, the sulfidizing agent, and the dihalogenated aromatic compound are mixed, desirably in an inert gas atmosphere, at a temperature range of room temperature to 240°C, preferably 100°C to 230°C. A polymerization aid may be added at this stage. The order of charging these raw materials may be random, or they may be charged simultaneously.

[0064] The mixture is usually heated to a temperature in the range of 200° C. to less than 290° C. There are no particular limitations on the heating rate, but a rate of 0.01° C. / min to 5° C. / min is usually selected, and a range of 0.1° C. / min to 3° C. / min is more preferable.

[0065] In general, the temperature is finally raised to 250° C. to less than 290° C., and the reaction is carried out at that temperature for usually 0.25 hours to 50 hours, preferably 0.5 hours to 20 hours.

[0066] In order to obtain a higher degree of polymerization, it is effective to react at 200° C. to 260° C. for a certain period of time before the final temperature is reached, and then to raise the temperature to 270° C. to less than 290° C. In this case, the reaction time at 200° C. to 260° C. is usually selected within the range of 0.25 hours to 20 hours, and preferably 0.25 hours to 10 hours.

[0067] In order to obtain a polymer with a higher degree of polymerization, it may be effective to carry out the polymerization in multiple stages. When carrying out the polymerization in multiple stages, it is effective to carry out the polymerization when the conversion rate of the polyhalogenated aromatic compound in the system at 245°C reaches 40 mol% or more, preferably 60 mol%.

[0068] The conversion rate of polyhalogenated aromatic compounds (herein abbreviated as PHA) is a value calculated by the following formula: The amount of remaining PHA can usually be determined by gas chromatography. (A) When a polyhalogenated aromatic compound is added in excess of an alkali metal sulfide in terms of molar ratio Conversion rate = [PHA charge amount (mol) - PHA remaining amount (mol)] / [PHA charge amount (mol) - PHA excess amount (mol)] (B) Cases other than (A) above Conversion rate = [PHA charge amount (mol) - PHA remaining amount (mol)] / [PHA charge amount (mol)]

[0069] [A step of reacting a polyarylene sulfide having a weight average molecular weight of 25,000 or more with a halogenated compound having a functional group within a temperature range of 200° C. or more and less than 290° C.] In the present invention, it is essential to include a step (hereinafter sometimes referred to as step A) of reacting a polyarylene sulfide having a weight average molecular weight of 25,000 or more with a halogenated compound having a functional group within a temperature range of 200°C or more and less than 290°C.

[0070] Step A will be described in more detail. Step A includes, but is not limited to, (1) a method of reacting a sulfidizing agent with a dihalogenated aromatic compound, and after the weight average molecular weight reaches 25,000 or more, injecting a solution of a halogenated compound having a functional group into a high-temperature, high-pressure polymerization system to mix it, (2) a method of reacting a sulfidizing agent with a dihalogenated aromatic compound, and after the weight average molecular weight reaches 25,000 or more, cooling to 150°C or less, and mixing a halogenated compound having a functional group into the polymerization system, and (3) a method of dry-blending a polyarylene sulfide having a weight average molecular weight of 25,000 or more with a halogenated compound having a functional group and heating it. Preferred methods include (1) a method in which a sulfidizing agent is reacted with a dihalogenated aromatic compound, and after the weight average molecular weight reaches 25,000 or more, a solution of a halogenated compound having a functional group is pressurized into a high-temperature, high-pressure polymerization system to be blended; and (2) a method in which a sulfidizing agent is reacted with a dihalogenated aromatic compound, and after the weight average molecular weight reaches 25,000 or more, the mixture is cooled to 150°C or less and the halogenated compound having a functional group is blended into the polymerization system. More preferred methods include (1) a method in which a sulfidizing agent is reacted with a dihalogenated aromatic compound, and after the weight average molecular weight reaches 25,000 or more, a solution of a halogenated compound having a functional group is pressurized into a high-temperature, high-pressure polymerization system to be blended.

[0071] As a method for injecting a solution of a halogenated compound having a functional group into the polymerization system, a method in which the halogenated compound having a functional group is dissolved in an organic polar solvent and then injected is preferable, and a more preferable example is a method in which the halogenated compound is dissolved in 2-methylpyrrolidone and then injected.

[0072] The weight average molecular weight of PAS referred to here is a value measured by gel permeation chromatography (GPC) using 1-chloronaphthalene as an eluent at a column temperature of 210° C., and converted into a polystyrene standard.

[0073] In the present invention, it is preferable that the halogenated compound having a functional group reacted with the polyarylene sulfide having a weight average molecular weight of 25,000 or more does not substantially contain water. "Substantially free of water" means that the water content of the halogenated compound having a functional group is 5 wt% or less, more preferably 1 wt% or less, and even more preferably 0.1 wt%. If the water content of the halogenated compound having a functional group exceeds 5 wt%, that is, if it is reacted as an aqueous solution, it is not preferable because the reactivity with PAS is significantly reduced after being supplied to the polymerization system. The reason for this is unclear, but it is presumed that the strong interaction between the halogenated compound having a functional group and water inhibits the reaction with PAS.

[0074] In the present invention, from the viewpoint of improving the reaction rate of the halogenated compound having a functional group, in step A, the reaction is preferably carried out within a temperature range of 200° C. or more and less than 290° C. for 15 minutes or more and less than 3 hours, more preferably for 20 minutes or more and less than 2 hours, and even more preferably for 25 minutes or more and 90 minutes. If the reaction time within the temperature range of 200° C. or more and less than 290° C. is 15 minutes or more, the reaction between the PAS and the halogenated compound having a functional group proceeds sufficiently, which is preferable. In addition, if the reaction time in step A is 3 hours or more, the reaction between the PAS and the halogenated compound having a functional group may proceed sufficiently, but it is not preferable from the viewpoint of productivity.

[0075] [Recovery process] In the method for producing a PAS resin, after the polymerization is completed, a solid matter is recovered from the polymerization reaction product containing the polymer, the solvent, etc. As the recovery method, any known method may be adopted.

[0076] For example, after the polymerization reaction is completed, the polymer particles may be collected by gradually cooling. The cooling speed is not particularly limited, but is usually about 0.1°C / min to 3°C / min. It is not necessary to cool at the same speed throughout the entire cooling process, and a method of gradually cooling at a speed of 0.1°C / min to 1°C / min until the polymer particles crystallize and precipitate, and then at a speed of 1°C / min or more may be used.

[0077] Another preferred method is to carry out the above recovery under rapid cooling conditions. A preferred recovery method is the flash method. In the flash method, the polymerization reaction product is subjected to high temperature and high pressure (usually 250°C or higher, 8 kg / cm 2 This is a method in which the polymer is flashed from the above state into an atmosphere of normal pressure or reduced pressure, and the polymer is powdered and recovered while the solvent is recovered. Flashing here means that the polymerization reaction product is ejected from a nozzle. Specific examples of the flashing atmosphere include nitrogen or water vapor at normal pressure, and the temperature is usually selected in the range of 150°C to 250°C.

[0078] [Post-processing process] The PAS resin may be produced through the above-mentioned polymerization and recovery steps, and then subjected to acid treatment, hot water treatment, washing with an organic solvent, or treatment with an alkali metal or alkaline earth metal.

[0079] The acid treatment is carried out as follows. There are no particular limitations on the acid used in the acid treatment of the PAS resin, so long as it does not have the effect of decomposing the PAS resin, and examples of the acid include acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid, and propylic acid. Of these, acetic acid and hydrochloric acid are more preferably used. On the other hand, acids such as nitric acid that decompose and deteriorate the PAS resin are not preferred.

[0080] The acid treatment may be carried out, for example, by immersing the PAS resin in an acid or an aqueous solution of an acid, and stirring or heating may be performed as necessary. For example, when acetic acid is used, a sufficient effect can be obtained by immersing the PAS resin powder in an aqueous solution of acetic acid at pH 4 heated to 80°C to 200°C and stirring for 30 minutes. The pH after the treatment may be 4 or higher, for example, about pH 4 to 8. In order to remove residual acid or salt from the PAS resin that has been subjected to the acid treatment, it is preferable to wash the resin several times with water or hot water. The water used for washing is preferably distilled water or deionized water so as not to impair the effect of the preferable chemical modification of the PAS resin by the acid treatment.

[0081] The hot water treatment is carried out as follows: When treating the PAS resin with hot water, the temperature of the hot water is preferably 100° C. or higher, more preferably 120° C. or higher, even more preferably 150° C. or higher, and particularly preferably 170° C. or higher. Temperatures below 100° C. are not preferred because the desired chemical modification effect of the PAS resin is small.

[0082] In order to achieve the desired chemical modification effect of the PAS resin by hot water washing, it is preferable that the water used is distilled water or deionized water. There are no particular limitations on the procedure for hot water treatment. It can be carried out by adding a specified amount of PAS resin to a specified amount of water, heating and stirring in a pressure vessel, or by continuous hot water treatment. The ratio of PAS resin to water is preferably higher, but a bath ratio (weight of washing solution relative to the weight of dry PAS) of 200g or less of PAS resin per 1 liter of water is usually selected.

[0083] In addition, since decomposition of the terminal groups is undesirable, it is desirable to carry out the treatment in an inert atmosphere to avoid this. Furthermore, in order to remove any remaining components, it is preferable to wash the PAS resin after this hot water treatment operation several times with warm water.

[0084] When washing with an organic solvent, the procedure is as follows: There are no particular limitations on the organic solvent used for washing the PAS resin, so long as it does not have the effect of decomposing the PAS resin. Examples of organic solvents that can be used to wash PAS resin include nitrogen-containing polar solvents such as N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, 1,3-dimethylimidazolidinone, hexamethylphosphoramide, and piperazinones; sulfoxide and sulfone solvents such as dimethyl sulfoxide, dimethyl sulfone, and sulfolane; ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, and acetophenone; ether solvents such as dimethyl ether, dipropyl ether, dioxane, and tetrahydrofuran; halogen-based solvents such as chloroform, methylene chloride, trichloroethylene, ethylene dichloride, perchloroethylene, monochloroethane, dichloroethane, tetrachloroethane, perchloroethane, and chlorobenzene; alcohol and phenol solvents such as methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol, and polypropylene glycol; and aromatic hydrocarbon solvents such as benzene, toluene, and xylene. Among these organic solvents, it is particularly preferable to use N-methyl-2-pyrrolidone, acetone, dimethylformamide, chloroform, etc. Furthermore, these organic solvents are used alone or in combination of two or more kinds.

[0085] As a method of washing with an organic solvent, for example, there is a method of immersing the PAS resin in the organic solvent, and it is also possible to stir or heat it appropriately if necessary. There is no particular limit to the washing temperature when washing the PAS resin with an organic solvent, and any temperature from room temperature to about 300°C can be selected. The higher the washing temperature, the higher the washing efficiency tends to be, but usually, a washing temperature of room temperature to 150°C can be sufficiently effective. It is also possible to wash under pressure in a pressure vessel at a temperature above the boiling point of the organic solvent. There is also no particular limit to the washing time. Although it depends on the washing conditions, in the case of batch washing, a sufficient effect is usually obtained by washing for 5 minutes or more. It is also possible to wash in a continuous manner. The post-treatment step is preferably performed by any one of acid treatment, hot water treatment, and washing with an organic solvent, and it is preferable to use two or more types of treatments in combination from the viewpoint of removing impurities.

[0086] Examples of the method of treating with an alkali metal or alkaline earth metal include a method of adding an alkali metal salt or an alkaline earth metal salt before, during, or after the previous step, a method of adding an alkali metal salt or an alkaline earth metal salt into a polymerization vessel before, during, or after the polymerization step, or a method of adding an alkali metal salt or an alkaline earth metal salt at the beginning, middle, or end of the washing step. The easiest method among them is a method of adding an alkali metal salt or an alkaline earth metal salt after removing residual oligomers and residual salts by washing with an organic solvent or washing with warm or hot water. The alkali metal or alkaline earth metal is preferably introduced into the PAS in the form of an alkali metal ion or an alkaline earth metal ion such as an acetate, hydroxide, or carbonate. It is also preferable to remove excess alkali metal salt or alkaline earth metal salt by washing with warm water or the like. The concentration of the alkali metal ion or alkaline earth metal ion when introducing the alkali metal or alkaline earth metal is preferably 0.001 mmol or more per 1 g of PAS, more preferably 0.01 mmol or more. The temperature is preferably 50° C. or higher, more preferably 75° C. or higher, and particularly preferably 90° C. or higher. There is no particular upper limit to the temperature, but from the viewpoint of operability, it is usually preferable that the temperature is 280° C. or lower. The bath ratio (weight of cleaning solution to weight of dry PAS) is preferably 0.5 or higher, more preferably 3 or higher, and even more preferably 5 or higher.

[0087] [Thermal oxidation crosslinking treatment] In addition, the PAS resin in the present invention can also be used after being polymerized by a thermal oxidation crosslinking treatment, which involves heating in an oxygen atmosphere after polymerization or heating with the addition of a crosslinking agent such as a peroxide, to increase the molecular weight.

[0088] When dry heat treatment is performed for the purpose of increasing the molecular weight by thermal oxidation crosslinking, the temperature is preferably 160°C to 260°C, more preferably 170°C to 250°C. The oxygen concentration is desirably 5% by volume or more, more desirably 8% by volume or more. There is no particular upper limit to the oxygen concentration, but the limit is about 50% by volume. The treatment time is preferably 0.5 to 100 hours, more preferably 1 to 50 hours, and even more preferably 2 to 25 hours. The heat treatment device may be a normal hot air dryer or a rotary type or a heating device with an agitating blade. For efficient and more uniform treatment, it is preferable to use a rotary type or a heating device with an agitating blade.

[0089] Dry heat treatment can also be performed to suppress thermal oxidative crosslinking and remove volatiles. The temperature is preferably 130°C to 250°C, more preferably 160°C to 250°C. In this case, the oxygen concentration is preferably less than 5% by volume, and even more preferably less than 2% by volume. The treatment time is preferably 0.5 hours to 50 hours, more preferably 1 hour to 20 hours, and even more preferably 1 hour to 10 hours. The heat treatment device may be a normal hot air dryer or a rotary or stirring blade-equipped heating device. For efficient and more uniform treatment, it is more preferable to use a rotary or stirring blade-equipped heating device.

[0090] [Characteristics of PAS resin] In the manufacturing method of the present invention, by including a step of reacting a polyarylene sulfide having a weight average molecular weight of 25,000 or more with a halogenated compound having a functional group, a PAS resin having a high content of functional groups and a high molecular weight can be efficiently obtained.

[0091] The functional group content of the PAS resin obtained in the present invention is preferably 100 μmol / g or more, more preferably 130 μmol / g or more, and even more preferably 180 μmol / g or more. If the functional group content of the obtained PAS resin is less than 100 μmol / g, the adhesiveness to different materials is not sufficient, which is not preferable. There is no particular limit to the functional group content of the obtained PAS resin, but it is generally 500 μmol / g or less.

[0092] The functional group content of the PAS resin referred to here was measured according to the type of functional group as follows.

[0093] The content of carboxyl groups introduced into the PAS resin was measured by measuring the amorphous film of the PAS resin with FT-IR (IR-810 infrared spectrophotometer manufactured by JASCO Corporation) and measuring the 1,900 cm -1 The absorption at 1,730 cm originating from the carboxyl group -1 The absorption was estimated by comparing the absorption in the vicinity.

[0094] The acid anhydride content introduced into the PAS resin was measured by measuring the amorphous film of the PAS resin with FT-IR (IR-810 infrared spectrophotometer manufactured by JASCO Corporation) and detecting the 1,900 cm -1 The absorption at around 1,850 cm originates from the acid anhydride group. -1 The absorption was estimated by comparing the absorption in the vicinity.

[0095] The amino group content introduced into the PAS resin was measured by measuring the amorphous film of the PAS resin with FT-IR (IR-810 infrared spectrophotometer manufactured by JASCO Corporation) and determining the 1,900 cm -1 The absorption at around 3380 cm originates from the amino group. -1 The absorption was estimated by comparing the absorption in the vicinity.

[0096] The content of hydroxyl groups introduced into the PAS resin was measured by measuring the amorphous film of the PAS resin with FT-IR (IR-810 infrared spectrophotometer manufactured by JASCO Corporation) and detecting the 1,900 cm -1 The absorption at 3430 cm originating from the hydroxyl group -1 The absorption was estimated by comparing the absorption in the vicinity.

[0097] The PAS resin obtained in the present invention preferably has a weight average molecular weight of 40,000 or more, more preferably 45,000 or more, and even more preferably 50,000 or more. If the weight average molecular weight of the PAS resin is less than 30,000, the strength and toughness may be significantly impaired when molded, which is undesirable. There is no particular upper limit to the weight average molecular weight of the PAS resin, but if it exceeds 100,000, the fluidity decreases, which is undesirable in terms of molding and processing, which is undesirable.

[0098] The weight average molecular weight referred to here is a value measured by gel permeation chromatography (GPC) using 1-chloronaphthalene as an eluent at a column temperature of 210° C. and converted into a polystyrene standard.

[0099] [Characteristics of PAS resin composition] The PAS resin obtained in the present invention can be preferably used as a PAS resin composition obtained by melt-kneading with a filler. The filler referred to here is a fibrous filler such as glass fiber, carbon fiber, carbon nanotube, carbon nanohorn, potassium titanate whisker, zinc oxide whisker, calcium carbonate whisker, wollastonite whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, gypsum fiber, metal fiber, or a silicate such as fullerene, talc, wollastonite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, silica, bentonite, asbestos, alumina silicate, or a silicon oxide. Examples of fillers that can be used include metal compounds such as magnesium oxide, alumina, zirconium oxide, titanium oxide, and iron oxide; carbonates such as calcium carbonate, magnesium carbonate, and dolomite; sulfates such as calcium sulfate and barium sulfate; hydroxides such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide; glass beads, glass flakes, glass powder, ceramic beads, boron nitride, silicon carbide, carbon black, and non-fibrous fillers such as silica and graphite. Of these, fibrous fillers such as glass fiber, carbon fiber, ceramic fiber, and aramid fiber are preferred, and glass fiber is more preferred.

[0100] The upper limit of the filler content is preferably 30 parts by weight or more, more preferably 45 parts by weight or more, and even more preferably 60 parts by weight or more, relative to 100 parts by weight of PAS. The lower limit is preferably 150 parts by weight or less, more preferably 100 parts by weight or less, and even more preferably 80 parts by weight or less, relative to 100 parts by weight of PAS. If the filler content is less than 30 parts by weight relative to 100 parts by weight of PAS, the tensile strength of the molded product may be significantly reduced, which is not preferable. If the filler content exceeds 150 parts by weight relative to 100 parts by weight of PAS, the fluidity of the resulting PAS resin composition is significantly reduced, which is not preferable.

[0101] In the present invention, when the PAS resin and the filler are melt-kneaded, it is preferable to further add a silane coupling agent and melt-knead the mixture. The silane coupling agent here is preferably an alkoxysilane having a functional group. Specific examples include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N-phenylaminomethyltrimethoxysilane, N-phenylaminopropyl Preferred examples of the silane coupling agent include alkoxysilane, dimethoxymethyl-3-piperazinopropylsilane, 3-piperazinopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, 3-isocyanatopropylethyldimethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptomethyldimethoxysilane, and γ-ureidopropyltrimethoxysilane. Among them, alkoxysilane having at least one functional group selected from isocyanate group, epoxy group, and amino group is more preferred, and alkoxysilane having amino group is even more preferred. The upper limit of the amount of the silane coupling agent to be blended is preferably 0.1 parts by weight or more, more preferably 0.2 parts by weight or more, and even more preferably 0.3 parts by weight or more, based on 100 parts by weight of the PAS resin. The lower limit is preferably 5 parts by weight or less, more preferably 3 parts by weight or less, and even more preferably 1 part by weight or less, per 100 parts by weight of the PAS resin composition.If the amount of the silane coupling agent is less than 0.1 parts by weight, the tensile strength of the PAS resin composition is low, which is undesirable in practical use, whereas if the amount of the silane coupling agent is more than 5 parts by weight, the melt viscosity becomes significantly high, which is undesirable from the viewpoint of molding processability.

[0102] The PAS resin composition obtained by the above method has excellent tensile strength, and is characterized by excellent tensile strength after hydrolysis resistance test and strength retention after hydrolysis resistance test. In the present invention, the tensile strength is a value obtained by measuring a JIS K7161-2 1A type test piece obtained by injection molding using an AG-20kNx universal testing machine under the conditions of a tensile speed of 5mm / min, an atmospheric temperature of 23°C, and a relative humidity of 50% according to ISO527-1. In the present invention, the lower limit of the tensile strength is preferably 150MPa or more, more preferably 170MPa or more, and even more preferably 180MPa or more. If the tensile strength is less than 150MPa, it is not practical and is not preferable as a molded product. In the present invention, there is no upper limit to the tensile strength, but it is usually less than 500MPa.

[0103] In the present invention, the tensile strength after the hydrolysis resistance test can be determined as follows. The JIS K7161-2 1A type test piece obtained by injection molding is placed in an autoclave, and a solution of Toyota Super Long Life Coolant manufactured by Toyota and ion-exchanged water mixed at a weight ratio of 1:1 is poured into the autoclave until the test piece is fully immersed. The autoclave is then treated for 500 hours in a dryer heated to 150°C. After sufficient cooling, the test piece is taken out of the autoclave and the moisture is removed, and the tensile strength is measured according to ISO527-1 using an AG-20kNx universal testing machine under conditions of a tensile speed of 5mm / min, an atmospheric temperature of 23°C, and a relative humidity of 50%, and is defined as the tensile strength after the hydrolysis resistance test. The lower limit of the tensile strength after the hydrolysis resistance test is preferably 130MPa or more, more preferably 140MPa or more. If the tensile strength after the hydrolysis resistance test is less than 130MPa, it is not preferable because it may crack when used for a long time in an environment immersed in water. There is no upper limit to the tensile strength after the hydrolysis resistance test, but it is usually less than 300 MPa.

[0104] In the present invention, the strength retention rate after the hydrolysis resistance test is determined according to the following formula. Strength retention rate after hydrolysis resistance test (%) = tensile strength after hydrolysis resistance test (MPa) / tensile strength (MPa) × 100 (%)

[0105] The lower limit of the strength retention rate after the hydrolysis resistance test is preferably 70% or more, more preferably 80% or more. If the strength retention rate after the hydrolysis resistance test is less than 70%, it is not preferable because it may crack when used for a long time in an environment immersed in water. The upper limit of the strength retention rate after the hydrolysis resistance test is not particularly limited, but is usually less than 120%.

[0106] [Uses of PAS resin] The PAS resin obtained by the present invention is preferably used in applications requiring adhesion to different materials such as resins other than PAS resins, fillers, and metals, more preferably used in applications requiring adhesion to fillers, and more preferably used in applications requiring adhesion to glass fibers. The filler referred to here is the same as the filler added when melt-kneading the PPS resin described above. In addition, in order to introduce many functional groups to the filler surface, it is preferable to use the filler after preliminary treatment with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, and an epoxy compound.

[0107] In the present invention, the adhesion to the filler can be improved by forming a covalent bond between the PAS resin and the filler. Examples of the covalent bond formed between the PAS resin and the filler include an ether bond, a urethane bond, an ester bond, an amide bond, an esteramide bond, and an imide bond, and preferred examples of the covalent bond include an ether bond, an amide bond, and an imide bond.

[0108] As a method for mixing the PAS resin obtained in the present invention with a filler, it is possible to use a method such as production in a molten state or production in a solution state, but from the viewpoint of simplicity, it is preferable to use a method such as production in a molten state. For production in a molten state, it is possible to use melt kneading using an extruder or melt kneading using a kneader, but from the viewpoint of productivity, it is preferable to use a method such as melt kneading using an extruder that can be continuously produced. For melt kneading using an extruder, it is possible to use one or more extruders such as a single screw extruder, a twin screw extruder, a multi-screw extruder such as a four-screw extruder, or a twin-screw single screw composite extruder, but from the viewpoint of kneading property, reactivity, and productivity improvement, it is preferable to use a multi-screw extruder such as a twin screw extruder or a four-screw extruder, and it is most preferable to use a method such as melt kneading using a twin screw extruder.

[0109] The PAS resin obtained by the present invention has excellent heat resistance, chemical resistance, flame retardancy, electrical properties and mechanical properties, and can be used not only for injection molding, injection compression molding and blow molding, but also for extrusion molding into extrusion molded products such as sheets, films, fibers and pipes.

[0110] The applications of the PAS resin of the present invention include, for example, electrical and electronic components such as sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, optical pickups, oscillators, various terminal boards, transformers, plugs, printed circuit boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, semiconductors, liquid crystal, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, and computer-related components; VTR components, television components, irons, hair dryers, rice cooker components, microwave oven components, audio components, and the like. Audio equipment parts such as audio, laser discs (registered trademark), and compact discs; lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, and other household and office electrical appliance parts; office computer related parts, telephone related parts, facsimile related parts, copier related parts, cleaning tools, motor parts, lighters, typewriters, and other machine related parts; optical equipment and precision machinery related parts such as microscopes, binoculars, cameras, and clocks; water faucet tops, mixer faucets, pump parts, pipe joints, water flow control valves, relief valves, water temperature sensors, water flow sensors, water meter housings, and other plumbing parts;Valve alternator terminals, alternator connectors, IC regulators, potentiometer bases for light dimmers, various valves such as exhaust gas valves, various pipes for fuel, exhaust system and intake system, air intake nozzle snorkels, intake manifolds, fuel pumps, engine coolant joints, carburetor main bodies, carburetor spacers, exhaust gas sensors, coolant sensors, oil temperature sensors, throttle position sensors, crankshaft position sensors, air flow meters, brake pad wear sensors, thermostat bases for air conditioners, heating hot air flow control valves, brush holders for radiator motors, water pump impellers, turbine vanes, Examples of applications include automobile and vehicle-related parts such as wiper motor-related parts, distributors, starter switches, starter relays, transmission wire harnesses, windshield washer nozzles, air conditioner panel switch boards, fuel-related electromagnetic valve coils, fuse connectors, horn terminals, electrical component insulating plates, step motor rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters, ignition device cases, vehicle speed sensors, cable liners, engine control unit cases, engine driver unit cases, condenser cases, motor insulating materials, and hybrid car control system part cases, as well as various other applications. Among these, the material is particularly suitable for applications that may come into contact with hot water or cooling water for long periods of time, such as automobile cooling modules, automobile piping, residential piping, and water heater parts.

[0111] As a method for producing a PAS film using the PAS resin obtained by the present invention, a known melt film-forming method can be used, for example, a method in which the PAS resin is melted in a single-screw or twin-screw extruder, extruded through a film die, and cooled on a cooling drum to produce a film, or a biaxial stretching method in which the film thus produced is stretched vertically and horizontally using a roller-type vertical stretching device and a horizontal stretching device called a tenter, but the method is not limited to these.

[0112] The PAS film obtained in this manner has excellent mechanical properties, electrical properties, and heat resistance, and can be suitably used for a variety of applications, such as as a dielectric film for film capacitors and chip capacitors, or as a release film.

[0113] As a method for producing PAS fibers using the PAS resin obtained by the present invention, a known melt spinning method can be applied. For example, a method can be adopted in which the raw material PAS resin chips are fed into a single-screw or twin-screw extruder while being kneaded, and then the material is extruded from a spinneret through a polymer flow line exchanger and a filtration layer installed at the tip of the extruder, and then cooled, stretched, and heat-set. However, the method is not limited to this.

[0114] The PAS monofilaments or short fibers thus obtained can be suitably used for various applications such as papermaking dryer canvases, net conveyors, and bag filters. EXAMPLES

[0115] The method of the present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. Here, Examples 2 to 5, 7 to 9, 13 and 14 are examples of the present invention, and the rest are reference examples. The various measurement methods are as follows.

[0116] [Weight average molecular weight of polymer] The weight average molecular weight (Mw) of the polymer was calculated in terms of polystyrene by gel permeation chromatography (GPC) under the following conditions. Equipment: SSC-7100 (Sensyu Science) Column name: GPC3506 (Senshu Kagaku) Eluent: 1-chloronaphthalene Detector: Differential refractive index detector Column temperature: 210℃ Pre-thermostat temperature: 250℃ Pump thermostatic chamber temperature: 50℃ Detector temperature: 210℃ Flow rate: 1.0mL / min Sample injection volume: 300 μL (slurry: approximately 0.2% by weight).

[0117] [Functional group content] The functional group content of the PAS resin was measured according to the type of functional group as follows.

[0118] The content of carboxyl groups introduced into the PAS resin was measured by measuring the amorphous film of the PAS resin with FT-IR (IR-810 infrared spectrophotometer manufactured by JASCO Corporation) and determining the 1,900 cm -1 The absorption at 1,730 cm originating from the carboxyl group -1 The absorption was estimated by comparing the absorption in the vicinity.

[0119] The acid anhydride content introduced into the PAS resin was measured by measuring the amorphous film of the PAS resin with FT-IR (IR-810 infrared spectrophotometer manufactured by JASCO Corporation) and determining the 1,900 cm -1 The absorption at around 1,850 cm originates from the acid anhydride group. -1 The absorption was estimated by comparing the absorption in the vicinity.

[0120] The amino group content introduced into the PAS resin was measured by measuring the amorphous film of the PAS resin with FT-IR (IR-810 infrared spectrophotometer manufactured by JASCO Corporation) and determining the 1,900 cm -1 The absorption at around 3380 cm originates from the amino group. -1 The absorption was estimated by comparing the absorption in the vicinity.

[0121] The content of hydroxyl groups introduced into the PAS resin was measured by measuring the amorphous film of the PAS resin with FT-IR (IR-810 infrared spectrophotometer manufactured by JASCO Corporation) and determining the 1,900 cm -1 The absorption at 3430 cm originating from the hydroxyl group -1 The absorption was estimated by comparing the absorption in the vicinity.

[0122] [Injection molding] The PAS resin composition was molded into JIS K7161-2 1A type test pieces using a Sumitomo Heavy Industries SE75-DUZ injection molding machine under conditions of a resin temperature of 310°C and a mold temperature of 140°C.

[0123] [Tensile strength] The tensile strength of the JIS K7161-2 1A type test pieces obtained by injection molding was measured in accordance with ISO527-1 using an AG-20kNx universal testing machine under conditions of a tensile speed of 5mm / min, an atmospheric temperature of 23°C, and a relative humidity of 50%, and the average value of five measurements was calculated.

[0124] [Tensile strength after hydrolysis resistance test] The JIS K7161-2 1A type test piece obtained by injection molding was placed in an autoclave, and a solution of Toyota Super Long Life Coolant (product number 08889-01005) manufactured by Toyota Motor Corporation and ion-exchanged water mixed at a weight ratio of 1:1 was poured into the autoclave until the test piece was fully immersed. The autoclave was then treated for 500 hours in a dryer heated to 150°C. After sufficient cooling, the test piece was removed from the autoclave and the moisture was removed. The tensile strength was measured according to ISO527-1 using an AG-20kNx universal testing machine under conditions of a tensile speed of 5mm / min, an atmospheric temperature of 23°C, and a relative humidity of 50%, and the average value of five measurements was calculated to determine the tensile strength after the hydrolysis resistance test.

[0125] [Strength retention after hydrolysis resistance test] The strength retention rate after the hydrolysis resistance test was determined according to the following formula. Strength retention rate after hydrolysis resistance test (%) = tensile strength after hydrolysis resistance test (MPa) / tensile strength (MPa) × 100 (%)

[0126] The following compounds were used in the examples.

[0127] [Reference Example 1] Glass fiber Glass fiber-1: Glass fiber (Nippon Electric Glass "T760H")

[0128] [Reference Example 2] Silane coupling agent Silane coupling agent - 1: 3-aminopropyltriethoxysilane (Shin-Etsu Silicone "KBE903")

[0129] [Example 1] In a 70-liter autoclave equipped with a stirrer and a bottom plug valve, 8.26 kg (70.00 mol) of 47.5% sodium hydrosulfide, 3.19 kg (76.65 mol) of 96% sodium hydroxide, 14.57 kg (147.00 mol) of N-methyl-2-pyrrolidone (NMP), 1.89 kg (23.1 mol) of sodium acetate, and 5.78 kg of ion-exchanged water were charged, and the mixture was gradually heated to 245°C over about 3 hours while passing nitrogen through it at normal pressure. When 9.70 kg of water and 0.28 kg of NMP were distilled, heating was stopped and cooling was started. At this point, the amount of water remaining in the system per mole of the charged alkali metal hydrosulfide was 1.01 mol, including the water consumed in the hydrolysis of NMP. In addition, the amount of hydrogen sulfide scattered was 1.4 mol, so the amount of sulfidizing agent in the system after this process was 68.6 mol.

[0130] After that, it was cooled to 200°C, 10.08 kg (69.29 mol) of p-dichlorobenzene (p-DCB) and 5.55 kg (56.00 mol) of NMP were added, and the reaction vessel was sealed under nitrogen gas and heated from 200°C to 276°C at a rate of 0.6°C / min while stirring at 240 rpm, and then reacted at 276°C for 50 minutes. The bottom plug valve was slightly opened to collect a small amount of the content, and it was confirmed that the weight average molecular weight (Mw) was 30,000.

[0131] Next, 0.38 kg (2.06 mol) of 4-chlorophthalic anhydride and 2.07 kg (16.1 mol) of NMP were pressure-fed into the reaction vessel and further reacted at 276°C for 60 minutes. After that, the bottom plug valve of the autoclave was opened and the contents were flushed into a vessel equipped with a stirrer over 15 minutes while pressurizing with nitrogen, and most of the NMP was removed by stirring for a while at 250°C.

[0132] The obtained solid matter and 76 L of ion-exchanged water were placed in an autoclave equipped with a stirrer, washed at 70° C. for 30 minutes, and then suction filtered through a glass filter. Next, 76 L of ion-exchanged water heated to 70° C. was poured into the glass filter, and suction filtered to obtain a cake.

[0133] The obtained cake and 90 liters of ion-exchanged water were charged into an autoclave equipped with a stirrer, and acetic acid was added to adjust the pH to 4. After the inside of the autoclave was replaced with nitrogen, the temperature was raised to 192°C and maintained at that temperature for 30 minutes. The autoclave was then cooled and the contents were removed.

[0134] The contents were filtered through a glass filter under suction, and then 76 liters of 70°C ion-exchanged water was poured into the mixture and filtered under suction to obtain a cake. The cake was dried at 120°C under a nitrogen stream to obtain a dried PAS. The functional group content and weight-average molecular weight of the obtained PAS are shown in Table 1.

[0135] [Example 2] Polymerization and washing were carried out in the same manner as in Example 1, except that the reaction time at 276° C. after the temperature was raised from 240° C. to 276° C. at a rate of 0.8° C. / min was 90 minutes.

[0136] [Example 3] Polymerization and washing were carried out in the same manner as in Example 1, except that the reaction time at 276° C. after the temperature was raised from 240° C. to 276° C. at a rate of 0.8° C. / min was set to 75 minutes.

[0137] [Example 4] Polymerization and washing were carried out in the same manner as in Example 3, except that the amount of 96% sodium hydroxide was changed to 3.08 kg (73.85 mol) and the amount of 4-chlorophthalic anhydride injected was changed to 0.13 kg (0.69 mol).

[0138] [Example 5] Polymerization and washing were carried out in the same manner as in Example 3, except that the amount of 96% sodium hydroxide was changed to 3.37 kg (80.85 mol) and the amount of 4-chlorophthalic anhydride injected was changed to 0.75 kg (4.12 mol).

[0139] [Example 6] After the pressure introduction of 4-chlorophthalic anhydride, polymerization and washing were carried out in the same manner as in Example 3, except that the reaction time at 276° C. was changed to 10 minutes.

[0140] [Example 7] After the pressure introduction of 4-chlorophthalic anhydride, polymerization and washing were carried out in the same manner as in Example 3, except that the reaction time at 276° C. was changed to 120 minutes.

[0141] [Example 8] Polymerization and washing were carried out in the same manner as in Example 3, except that the amount of sodium acetate used was 2.87 kg (35.00 mol).

[0142] [Example 9] Polymerization and washing were carried out in the same manner as in Example 3, except that the amount of 96% sodium hydroxide was changed to 3.11 kg (74.55 mol) and 4-chlorophthalic anhydride was changed to 0.32 kg (2.06 mol) of 4-chlorobenzoic acid.

[0143] [Example 10] Polymerization and washing were carried out in the same manner as in Example 3, except that the amount of 96% sodium hydroxide was changed to 3.19 kg (76.65 mol), 4-chlorophthalic anhydride was changed to 0.64 kg (4.12 mol) of 4-chlorobenzoic acid, and the reaction time at 276°C after injection was changed to 120 minutes.

[0144] [Example 11] Polymerization and washing were carried out in the same manner as in Example 3, except that the amount of 96% sodium hydroxide was changed to 3.11 kg (74.55 mol) and 4-chlorophthalic anhydride was changed to 0.26 kg (2.06 mol) of 4-chlorophenol.

[0145] [Example 12] Polymerization and washing were carried out in the same manner as in Example 3, except that the amount of 96% sodium hydroxide was changed to 3.02 kg (72.45 mol) and 4-chlorophthalic anhydride was changed to 0.33 kg (2.06 mol) of 3,5-dichloroaniline.

[0146] [Example 13] In a 70-liter autoclave equipped with a stirrer and a bottom plug valve, 8.26 kg (70.00 mol) of 47.5% sodium hydrosulfide, 3.02 kg (72.45 mol) of 96% sodium hydroxide, 14.57 kg (147.00 mol) of N-methyl-2-pyrrolidone (NMP), 1.89 kg (23.1 mol) of sodium acetate, and 5.78 kg of ion-exchanged water were charged, and the mixture was gradually heated to 245°C over about 3 hours while passing nitrogen through it at normal pressure. When 9.70 kg of water and 0.28 kg of NMP were distilled, heating was stopped and cooling was started. At this point, the amount of water remaining in the system per mole of the charged alkali metal hydrosulfide was 1.01 mol, including the water consumed in the hydrolysis of NMP. In addition, the amount of hydrogen sulfide scattered was 1.4 mol, so the amount of sulfidizing agent in the system after this process was 68.6 mol.

[0147] After that, it was cooled to 200°C, 10.08 kg (69.29 mol) of p-dichlorobenzene (p-DCB) and 5.55 kg (56.00 mol) of NMP were added, and the reaction vessel was sealed under nitrogen gas and heated from 200°C to 276°C at a rate of 0.6°C / min while stirring at 240 rpm, and then reacted at 276°C for 50 minutes. The bottom plug valve was slightly opened to collect a small amount of the content, and it was confirmed that the weight average molecular weight (Mw) was 40,000.

[0148] Next, 0.55 kg (2.06 mol) of disodium 4-chlorophthalic anhydride was supplied to the reaction vessel, and the temperature was raised to 200°C, and then raised to 276°C at 2°C / min. After reacting at 276°C for 60 minutes, the bottom plug valve of the autoclave was opened, and the contents were flushed into a vessel equipped with a stirrer over 15 minutes while pressurizing with nitrogen, and the contents were stirred for a while at 250°C to remove most of the NMP.

[0149] The subsequent washing was carried out in the same manner as in Example 1 to obtain a dry PAS resin.

[0150] [Example 14] In a 70-liter autoclave equipped with a stirrer and a bottom plug valve, 8.26 kg (70.00 mol) of 47.5% sodium hydrosulfide, 3.19 kg (76.65 mol) of 96% sodium hydroxide, 14.57 kg (147.00 mol) of N-methyl-2-pyrrolidone (NMP), 1.89 kg (23.1 mol) of sodium acetate, and 5.78 kg of ion-exchanged water were charged, and the mixture was gradually heated to 245°C over about 3 hours while passing nitrogen through it at normal pressure. When 9.70 kg of water and 0.28 kg of NMP were distilled, heating was stopped and cooling was started. At this point, the amount of water remaining in the system per mole of the charged alkali metal hydrosulfide was 1.01 mol, including the water consumed in the hydrolysis of NMP. In addition, the amount of hydrogen sulfide scattered was 1.4 mol, so the amount of sulfidizing agent in the system after this process was 68.6 mol.

[0151] After that, it was cooled to 200°C, 10.08 kg (69.29 mol) of p-dichlorobenzene (p-DCB) and 5.55 kg (56.00 mol) of NMP were added, and the reaction vessel was sealed under nitrogen gas and heated from 200°C to 276°C at a rate of 0.6°C / min while stirring at 240 rpm, and then reacted at 276°C for 50 minutes. The bottom plug valve was slightly opened to collect a small amount of the content, and it was confirmed that the weight average molecular weight (Mw) was 40,000. Next, 0.50 kg (2.06 mol) of disodium 4-chlorophthalic anhydride and 0.84 kg (46.9 mol) of water were mixed and dissolved, and the mixture was pressurized into a reaction vessel and reacted at 276°C for 60 minutes. After that, the bottom plug valve of the autoclave was opened, and the contents were flushed into a vessel equipped with a stirrer over 15 minutes while pressurizing with nitrogen, and the mixture was stirred for a while at 250°C to remove most of the NMP.

[0152] The subsequent washing was carried out in the same manner as in Example 1 to obtain a dry PAS resin.

[0153] [Comparative Example 1] In a 70-liter autoclave equipped with a stirrer and a bottom plug valve, 8.26 kg (70.00 mol) of 47.5% sodium hydrosulfide, 3.19 kg (76.65 mol) of 96% sodium hydroxide, 14.57 kg (147.00 mol) of N-methyl-2-pyrrolidone (NMP), and 3.14 kg of ion-exchanged water were charged, and the mixture was gradually heated to 245°C over about 3 hours while passing nitrogen through it at normal pressure. After distilling 9.70 kg of water and 0.28 kg of NMP, the reaction vessel was cooled to 200°C. The amount of water remaining in the system per mole of charged alkali metal sulfide was 1.01 mol, including the water consumed in the hydrolysis of NMP. In addition, the amount of hydrogen sulfide scattered was 1.4 mol, so the amount of sulfidizing agent in the system after this step was 68.6 mol.

[0154] Then, 9.48 kg (65.17 mol) of p-dichlorobenzene, 0.38 kg (2.06 mol) of 4-chlorophthalic anhydride, and 5.55 kg (56.00 mol) of NMP were added, the reaction vessel was sealed under nitrogen gas, and the temperature was increased from 200°C to 270°C at a rate of 0.6°C / min while stirring at 240 rpm. After reacting for 60 minutes at 270°C, the bottom plug valve of the autoclave was opened, and the contents were flushed into a vessel equipped with a stirrer over 15 minutes while pressurizing with nitrogen, and most of the NMP was removed by stirring for a while at 250°C.

[0155] The subsequent washing was carried out in the same manner as in Example 1 to obtain a dry PAS resin.

[0156] [Comparative Example 2] Polymerization and washing were carried out in the same manner as in Comparative Example 1, except that the amount of 96% sodium hydroxide was changed to 3.11 kg (74.55 mol) and 4-chlorophthalic anhydride was changed to 0.32 kg (2.06 mol) of 4-chlorobenzoic acid.

[0157] [Comparative Example 3] Polymerization and washing were carried out in the same manner as in Example 3, except that the reaction time at 276°C after raising the temperature from 240°C to 276°C at a rate of 0.8°C / min was 15 minutes and the weight average molecular weight of the PAS was 12,000.

[0158] [Comparative Example 4] Polymerization and washing were carried out in the same manner as in Example 3, except that the reaction time at 276°C after the temperature was raised from 240°C to 276°C at a rate of 0.8°C / min was set to 15 minutes, the weight average molecular weight of PAS was set to 12,000, and then 4-chlorophthalic anhydride was injected. The reaction time at 250°C was set to 300 minutes.

[0159] [Comparative Example 5] In a 70-liter autoclave equipped with a stirrer and a bottom plug valve, 8.26 kg (70.00 mol) of 47.5% sodium hydrosulfide, 3.02 kg (72.45 mol) of 96% sodium hydroxide, 14.57 kg (147.00 mol) of N-methyl-2-pyrrolidone (NMP), and 5.78 kg of ion-exchanged water were charged, and the mixture was gradually heated to 245°C over about 3 hours while passing nitrogen through it at normal pressure. When 9.70 kg of water and 0.28 kg of NMP were distilled, heating was stopped and cooling was started. At this point, the amount of water remaining in the system per mole of the charged alkali metal hydrosulfide was 1.01 mol, including the water consumed in the hydrolysis of NMP. In addition, the amount of hydrogen sulfide scattered was 1.4 mol, so the amount of sulfidizing agent in the system after this process was 68.6 mol.

[0160] After that, it was cooled to 200°C, 10.08 kg (69.29 mol) of p-dichlorobenzene (p-DCB) and 5.55 kg (56.00 mol) of NMP were added, and the reaction vessel was sealed under nitrogen gas and heated from 200°C to 220°C at a rate of 1.0°C / min while stirring at 240 rpm. The reaction was carried out at 220°C for 4.5 minutes. The bottom plug valve was slightly opened to collect a small amount of the content, and it was confirmed that the weight average molecular weight (Mw) was 20,000.

[0161] Next, 0.50 kg (2.06 mol) of disodium 4-chlorophthalic anhydride and 0.84 kg (46.9 mol) of water were mixed and dissolved, and the mixture was pressurized into a reaction vessel and reacted at 255°C for 300 minutes. After that, the bottom plug valve of the autoclave was opened, and the contents were flushed into a vessel equipped with a stirrer over 15 minutes while pressurizing with nitrogen, and the mixture was stirred for a while at 230°C to remove most of the NMP.

[0162] The subsequent washing was carried out in the same manner as in Example 1 to obtain a dry PAS.

[0163] The results of the above-mentioned Examples and Comparative Examples will be compared and explained.

[0164] In Examples 1 to 14, a PAS resin having a high content of functional groups and a high molecular weight was obtained by including a step of mixing a polyarylene sulfide having a weight average molecular weight of 25,000 or more with a halogenated compound having a functional group.

[0165] In particular, in Examples 1 to 5 and 7 to 14, after mixing a polyarylene sulfide having a weight average molecular weight of 25,000 or more with a halogenated compound having a functional group, the mixture was further reacted for 30 minutes to less than 3 hours within a temperature range of 200°C or more and less than 290°C, thereby obtaining a PAS resin that had both a high molecular weight and a functional group content.

[0166] In addition, in Examples 2 to 5, 7 to 9, 13 and 14, the weight average molecular weight of the polyarylene sulfide resin was 45,000, and therefore the PAS resin obtained had excellent initial strength when molded into a molded article.

[0167] Furthermore, in Examples 2 to 5, 7 to 9, and 13, the halogenated compound having a functional group was substantially free of water, and thus PAS resins having both a high functional group content and a high molecular weight were obtained.

[0168] Comparative Examples 1 and 2 did not include a process of mixing a polyarylene sulfide having a weight average molecular weight of 25,000 or more with a halogenated compound having a functional group, and therefore the molecular weight of the obtained PAS resin was low and the initial strength of the molded product was extremely low.

[0169] In Comparative Examples 3 and 4, polyarylene sulfide having a weight average molecular weight of less than 25,000 was mixed with a halogenated compound having a functional group, and as a result, the molecular weight of the obtained PAS resin was low.

[0170] Comparative Example 5 did not include a step of mixing a polyarylene sulfide having a weight average molecular weight of 25,000 or more with a halogenated compound having a functional group, and in addition, the halogenated compound having a functional group contained water. As a result, the molecular weight of the obtained PAS resin was significantly high, but the functional group content of the obtained PAS resin was extremely low.

[0171] [Reference examples 3~6] Next, 100 parts by weight of PAS obtained in the examples or comparative examples were dry-blended with a silane coupling agent in advance in the ratio shown in Table 3, and then the mixture was fed into a TEX30α type twin-screw extruder equipped with a vacuum vent (manufactured by Japan Steel Works, Ltd.: L / D=30, of the 11 cylinder blocks, the two in contact with the die tip were set to 300°C, and the remaining nine (Tc: cylinder temperature) were set to 280°C for melt-kneading). Furthermore, glass fiber was fed from the side feeder of the twin-screw extruder in the ratio shown in Table 3. The gut obtained by melt-kneading was pelletized with a strand cutter and dried overnight at 130°C. The pellets were subjected to injection molding, and the tensile strength, tensile strength after hydrolysis resistance test, and tensile strength retention rate after hydrolysis resistance test were evaluated for the obtained molded products. The results were as shown in Table 3.

[0172] [Table 1]

[0173] [Table 2]

[0174] [Table 3]

Claims

1. A method for producing a polyarylene sulfide resin having a weight average molecular weight of 45,000 or more, comprising the step of reacting a polyarylene sulfide having a weight average molecular weight of 25,000 or more with a halogenated compound having at least one functional group selected from the group consisting of a carboxyl group, an acid anhydride group, an amino group, a hydroxyl group, and derivatives thereof, within a temperature range of 200°C or more and less than 290°C.

2. The method for producing a polyarylene sulfide resin according to claim 1, characterized in that in the step of reacting the polyarylene sulfide having a weight average molecular weight of 25,000 or more with a halogenated compound having at least one functional group selected from the group consisting of a carboxyl group, an acid anhydride group, an amino group, a hydroxyl group and derivatives thereof, the reaction is carried out within a temperature range of 200°C or more and less than 290°C for 15 minutes to less than 3 hours.

3. 3. The method for producing a polyarylene sulfide resin according to claim 1, wherein the content of at least one functional group selected from the group consisting of a carboxyl group, an acid anhydride group, an amino group, a hydroxyl group, and derivatives thereof in the polyarylene sulfide resin is 100 μmol / g or more and less than 500 μmol / g.

4. The method for producing the polyarylene sulfide resin according to any one of claims 1 to 3, further comprising a step of reacting a sulfidizing agent with a dihalogenated aromatic compound in an organic polar solvent in the presence of 1 mol or more and less than 1000 mol of a polymerization aid relative to 100 mol of the sulfidizing agent within a temperature range of 200°C or more and less than 290°C.

5. The method for producing a polyarylene sulfide resin according to any one of claims 1 to 4, characterized in that the halogenated compound having at least one functional group selected from the group consisting of a carboxyl group, an acid anhydride group, an amino group, a hydroxyl group, and derivatives thereof does not substantially contain water.

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