Method for manufacturing polyarylene sulfide, method for manufacturing polyarylene sulfide copolymer, and polyarylene sulfide

Abstract

The object of the present invention is to provide a method for producing polyarylene sulfide that can simply and efficiently provide polyarylene sulfide in which a large number of reactive functional groups are introduced into the molecular chain. The present invention is a method for producing polyarylene sulfide in which at least a dihalogenated aromatic compound, an inorganic sulfidizing agent, and a compound (A) are reacted in the presence of an alkali metal hydroxide in an organic polar solvent, wherein the compound (A) is present in a reaction vessel in a range of 0.04 moles or more and 0.5 moles or less per mole of inorganic sulfidizing agent, and the compound (A) has at least one aromatic ring, and on the one aromatic ring, at least one reactive functional group selected from an amino group, a carboxyl group, an acid anhydride group, an isocyanate group, an epoxy group, and a silanol group, and at least one functional group selected from a hydroxyl group, a salt of a hydroxyl group, a thiol group, and a salt of a thiol group.

Description

Technology Field

[0001] The present invention relates to a method for producing polyarylene sulfide having functional groups. Background Technology

[0002] Polyarylene sulfides, represented by polyphenylene sulfide (hereinafter abbreviated as PPS), possess desirable properties as engineering plastics, such as excellent heat resistance, barrier properties, moldability, chemical resistance, electrical insulation, and resistance to heat and humidity. They are used in various electrical and electronic components, mechanical parts, automotive parts, films, and fibers, primarily for injection molding and extrusion molding applications. Due to their excellent characteristics, the applications of polyarylene sulfides have been expanding in recent years.

[0003] On the other hand, polyarylene sulfide has few functional groups in its molecular chain and exhibits lower interaction and reactivity compared to other engineering plastics such as polyamides and polyesters, which has presented a challenge in achieving adhesion or composite formation with other materials.

[0004] For this reason, many studies have been conducted on introducing reactive functional groups into polyarylene sulfides. For example, Patent Document 1 discloses a method of introducing reactive functional groups into the main chain of polyarylene sulfide by polymerizing 2,4-dichlorobenzoic acid simultaneously with p-dichlorobenzene. Patent Document 2 discloses a method of introducing reactive functional groups to the terminals of polyarylene sulfide by reacting a monohalogenated compound containing a carboxylic acid with a metal hydroxide when preparing polyarylene sulfide. In addition, Patent Document 3 discloses a method of preparing polyarylene sulfide having reactive functional groups by heating cyclic arylene sulfide with a sulfur-containing compound having reactive functional groups, and Patent Document 4 discloses a method of preparing polyarylene sulfide having reactive functional groups using an aromatic thiol.

[0005] In addition, polyarylene sulfides having reactive functional groups are also useful as prepolymers for obtaining polyarylene sulfide copolymers, and Patent Document 5 discloses a polyarylene sulfide copolymer obtained by reacting a polyarylene sulfide having reactive functional groups with a rigid molecule. Prior art literature

[0006] Japanese Patent Publication No. Hei 4-283247 (Claims) Japanese Patent Publication No. 2017-066261 (Claims) International Publication No. 2012 / 057319 (Claims) Japanese Patent Publication No. 2020-084027 (Claims) International Publication No. 2019 / 151288 (Claims) The problem to be solved

[0007] However, in the method disclosed in Patent Document 1, since the reactive functional group is introduced into the main chain, the frequency of contact with the reaction target is reduced, making it impossible to utilize the reactivity, and thus it was not an optimal molecular design. In the method disclosed in Patent Document 2, reactive functional groups could be introduced into the polyarylene sulfide molecular chain, but there was a problem in that the amount of reactive functional groups introduced into the polyarylene sulfide molecular chain was small compared to the amount of reactive functional groups in the compound used as a raw material, resulting in a large amount of unreacted compounds becoming waste. In the method disclosed in Patent Document 3, reactive functional groups could be introduced into polyarylene sulfide, but it could not be considered simple due to the numerous processes. Furthermore, in the method disclosed in Patent Document 4, the amount of functional groups introduced into polyarylene sulfide was small and could not be considered a sufficient amount. In the method for manufacturing a polyarylene sulfide copolymer disclosed in Patent Document 5, there was a problem in that gas was generated during the heating process required for manufacturing the polyarylene sulfide copolymer because the polyarylene sulfide that becomes the prepolymer contained impurities.

[0008] The present invention aims to provide a polyarylene sulfide in which many reactive functional groups are introduced into the molecular chain in a simple and efficient manner. Furthermore, the present invention also aims to obtain a polyarylene sulfide containing reactive functional groups with low impurity content, and to obtain a method for manufacturing a polyarylene sulfide copolymer that generates less gas during heat processing by using the polyarylene sulfide as a prepolymer. means of solving the problem

[0009] The present invention is made to solve at least some of the above-mentioned problems, and can be realized by providing the following.

[0010] A method for producing polyarylene sulfide by reacting at least a dihalogenated aromatic compound, an inorganic sulfidizing agent, and a compound (A) in the presence of an alkali metal hydroxide in an organic polar solvent, wherein the compound (A) is present in a reaction vessel in a range of 0.04 moles or more and 0.5 moles or less per mole of inorganic sulfidizing agent, and the compound (A) has at least one aromatic ring, and on the one aromatic ring, at least one reactive functional group selected from an amino group, a carboxyl group, an acid anhydride group, an isocyanate group, an epoxy group, and a silanol group, and at least one functional group selected from a hydroxyl group, a salt of a hydroxyl group, a thiol group, and a salt of a thiol group.

[0011] In addition, the present invention includes a method for producing a polyarylene sulfide copolymer, wherein a polyarylene sulfide is obtained by the manufacturing method described above, and then at least one compound (B) selected from the following formulas (a) to (k) is mixed and further heated.

[0012] [Painting 1]

[0013]

[0014] (Here, X is any one selected from hydroxyl group, carboxyl group, silanol group, sulfonic acid group, amino group, acid anhydride group, acetamide group, sulfonamide group, cyano group, isocyanate group, aldehyde group, acetyl group, epoxy group, and alkoxysilane group. R, R 1 , and R 2 is a substituent selected from hydrogen, alkyl groups having 1 to 12 carbon atoms, aryl groups having 6 to 24 carbon atoms, and halogen groups, and R, R 1 , and R 2 It can be the same or different.)

[0015] In addition, the present invention is a polyarylene sulfide containing amino groups in the range of 400 μmol / g or more and 5,000 μmol / g or less, and having a weight loss rate of 5 wt% or less when heated from 30°C to 320°C at a heating rate of 10°C / min. Effects of the invention

[0016] According to the present invention, polyarylene sulfide having a large number of reactive functional groups introduced into the molecular chain can be efficiently provided by a simple method. Furthermore, the polyarylene sulfide having reactive functional groups produced by the manufacturing method of the present invention has the characteristic of producing a small amount of gas upon heating. When polyarylene sulfide is obtained by the manufacturing method of the present invention, mixed with a reactive compound, and further heated to produce a polyarylene sulfide copolymer, workability can be improved because the amount of gas produced during the heating process is suppressed. Specific details for implementing the invention

[0017] The embodiments of the present invention will be described in detail below.

[0018] Polyarylene sulfide in an embodiment of the present invention is a homopolymer or copolymer having a repeating unit of the formula -(Ar-S)- as a main constituent unit, preferably containing 70 mol% or more of said repeating unit. As Ar, there are units represented by the following formulas (l) to (v), etc., but among them, the unit represented by formula (l) is particularly preferred.

[0019] [Painting 2]

[0020]

[0021] (R 3 , R 4 is a substituent selected from hydrogen, alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, aryl groups having 6 to 24 carbon atoms, halogen groups, and reactive functional groups, and R 3 and R 4 It can be the same or different.)

[0022] As long as this repeating unit is used as the main constituent unit, it may include a small amount of branching units or crosslinking units represented by the following formulas (I) to (III), 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)- unit.

[0023] [Tuesday 3]

[0024]

[0025] (Here, Ar is the unit represented by the preceding equations (l) through (v).)

[0026] In addition, a polyarylene sulfide having a reactive functional group bonded to the above Ar can also be exemplified as a preferred form. The reactive functional group is a structure derived from compound (A), and details will be described later. The position of the reactive functional group may be within the main chain of the polyarylene sulfide or at the terminal, but in the case of the terminal, it is preferably at the p position with respect to S bonded to Ar.

[0027] In addition, the polyarylene sulfide in the embodiments of the present invention may be any of a random copolymer, a block copolymer, and a mixture thereof containing the repeating unit.

[0028] Representative examples of these include polyphenylene sulfide, polyphenylene sulfide sulfone, polyphenylene sulfide ketone, random copolymers and block copolymers thereof, and mixtures thereof. Particularly preferred polyarylene sulfide is a p-phenylene sulfide unit as the main constituent unit of the polymer.

[0029] [Painting 4]

[0030]

[0031] Examples include polyphenylene sulfide containing 80 mol% or more, particularly 90 mol% or more.

[0032] The method for manufacturing polyarylene sulfide according to the present invention is described in detail below, but is not limited to the following method.

[0033] First, I will explain the raw materials used in the manufacture of polyarylene sulfide.

[0034] [Inorganic Sulfide Agents]

[0035] The inorganic sulfidizing agent used in the method for manufacturing polyarylene sulfide of the present invention is any agent capable of introducing a sulfide bond to a dihalogenated aromatic compound, and examples include alkali metal sulfides, alkali metal hydrosulfides, and hydrogen sulfide.

[0036] Specific examples of alkali metal sulfides include, for instance, lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide, and mixtures of two or more of these. Among these, lithium sulfide and / or sodium sulfide is preferred, and sodium sulfide is more preferably used. These alkali metal sulfides can be used as hydrates or aqueous mixtures, or in the form of anhydrous compounds. Furthermore, an aqueous mixture refers to an aqueous solution, a mixture of an aqueous solution and a solid component, or a mixture of water and a solid component. Since generally available and inexpensive alkali metal sulfides are hydrates or aqueous mixtures, it is preferable to use alkali metal sulfides in this form.

[0037] Specific examples of alkali metal hydrosulfides include, for instance, lithium hydrosulfide, sodium hydrosulfide, potassium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide, and mixtures of two or more of these, among which lithium hydrosulfide and / or sodium hydrosulfide is preferred, and sodium hydrosulfide is more preferably used.

[0038] In addition, alkali metal sulfides prepared in a reaction system from alkali metal water sulfides and alkali metal hydroxides may also be used. Furthermore, alkali metal sulfides prepared by contacting alkali metal water sulfides and alkali metal hydroxides in advance may also be used. These alkali metal water sulfides and alkali metal hydroxides may be used as hydrates or aqueous mixtures, or in anhydrous form, and hydrates or aqueous mixtures are preferred in terms of ease of availability and cost.

[0039] In addition, alkali metal sulfides prepared within the reaction system from alkali metal hydroxides, such as lithium hydroxide and sodium hydroxide, and hydrogen sulfide may also be used. Furthermore, alkali metal sulfides prepared in advance by contacting alkali metal hydroxides, such as lithium hydroxide and sodium hydroxide, with hydrogen sulfide may also be used. It does not matter whether hydrogen sulfide is used in a gaseous, liquid, or aqueous solution state.

[0040] [Compound (A)]

[0041] The compound (A) used in the method for preparing polyarylene sulfide according to the present invention is a compound having at least one aromatic ring, and on the one aromatic ring, having at least one reactive functional group selected from an amino group, a carboxyl group, an acid anhydride group, an isocyanate group, an epoxy group, and a silanol group, and at least one functional group selected from a hydroxyl group, a salt of a hydroxyl group, a thiol group, and a salt of a thiol group. The compound (A) may be an aromatic compound having a hydroxyl group, a salt of a hydroxyl group, a thiol group, or a salt of a thiol group that reacts with the dihalogenated aromatic compound in the polymerization reaction process described later, and a reactive functional group introduced into the polyarylene sulfide. As for the reactive functional group, it is preferable to have an electron-donating amino group or an isocyanate group to improve the reactivity of the hydroxyl group or the thiol group. As specific examples, 2-aminophenol, 4-aminophenol, 3-aminophenol, o-hydroxybenzoic acid, p-hydroxybenzoic acid, m-hydroxybenzoic acid, 3-hydroxyphthalic acid, 4-hydroxyphthalic acid, 2-aminothiophenol, 4-aminothiophenol, 3-aminothiophenol, o-mercaptobenzoic acid, p-mercaptobenzoic acid, m-mercaptobenzoic acid, 3-mercaptophthalic acid, 4-mercaptophthalic acid, and compounds in which the hydroxyl groups and thiol groups of these compounds are salts of alkali metals or alkaline earth metals can be exemplified as preferred compounds. In terms of reactivity, 4-aminophenol, p-hydroxybenzoic acid, 4-aminothiophenol, and p-mercaptobenzoic acid can be exemplified as particularly preferred compounds. If the above characteristics are present, it is also possible to use a combination of two or more different types of compounds (A). When using a compound having a hydroxyl group or a thiol group as compound (A), it is a preferred embodiment to use an equal amount of alkali metal hydroxide simultaneously. In addition, when using a compound in which a hydroxyl group or a thiol group takes the form of a salt as compound (A), it is possible to form a salt in advance and then use it for the production of polyarylene sulfide, or to form a salt through a reaction in a reaction vessel.

[0042] The lower limit of the amount of compound (A) used is 0.04 moles or more per 1 mole of input inorganic sulfidizing agent, 0.06 moles or more is more preferable, and 0.08 moles or more is more preferable. It is desirable that the amount used is greater than this value because reactive functional groups can be sufficiently introduced into the polyarylene sulfide. In addition, the upper limit of the amount of compound (A) used is 0.5 moles or less per 1 mole of input inorganic sulfidizing agent, 0.45 moles or less is more preferable, and 0.4 moles or less is more preferable. It is desirable that the amount used is less than this value because it prevents a decrease in the molecular weight of the polyarylene sulfide and prevents a decrease in mechanical properties.

[0043] There is no specific time for adding compound (A), and it may be added at any point during the preceding process described later, at the start of polymerization, or during the polymerization reaction process, and it may also be added in multiple stages. However, from the perspective of efficiently reacting with the dihalogenated aromatic compound, it is more preferable to add it at the same stage as adding the dihalogenated aromatic compound to the reaction vessel.

[0044] [Dihalogenated aromatic compounds]

[0045] As dihalogenated aromatic compounds used in the method for preparing polyarylene sulfide of the present invention, dihalogenated benzenes such as p-dichlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dibromobenzene, o-dibromobenzene, m-dibromobenzene, 1-bromo-4-chlorobenzene, 1-bromo-3-chlorobenzene, and 1-methoxy-2,5-dichlorobenzene, 1-methyl-2,5-dichlorobenzene, 1,4-dimethyl-2,5-dichlorobenzene, 1,3-dimethyl-2,5-dichlorobenzene, 2,5-dichlorobenzoic acid, 3,5-dichlorobenzoic acid, 2,5-dichloroaniline, 3,5-dichloroaniline, and bis(4-chlorophenyl)sulfide, etc., other than halogens Examples include dihalogenated aromatic compounds containing substituents. Among these, dihalogenated aromatic compounds having p-dihalogenated benzene, represented by p-dichlorobenzene, as the main component are preferred. Particularly preferably, they contain 80 to 100 mol% of p-dichlorobenzene, and more preferably, 90 to 100 mol%. In addition, it is also possible to use a combination of two or more different types of dihalogenated aromatic compounds.

[0046] Although there is no specific lower limit for the amount of dihalogenated aromatic compound used, it is preferable to set the [monomer ratio] expressed in the following formula to 0.8 or higher, more preferable to set it to 0.9 or higher, and even more preferable to set it to 0.95 or higher. This is desirable because setting the [monomer ratio] within the above range stabilizes the polymerization reaction system and prevents side reactions. Additionally, although there is no specific upper limit for the amount used, it is preferable to set the [monomer ratio] to 1.2 or lower, more preferable to set it to 1.1 or lower, and even more preferable to set it to 1.05 or lower. This is desirable because setting the [monomer ratio] within the above range can reduce the amount of halogen remaining in the polyarylene sulfide. In addition, [amount of dihalogenated aromatic compound], [amount of inorganic sulfidizing agent], and [amount of compound (A)] in the following formula represent the amount of each compound used when manufacturing polyarylene sulfide.

[0047] [Monomer Ratio] = [Amount of Dihalogenated Aromatic Compound] / ([Amount of Inorganic Sulfide Agent] + [Amount of Compound (A)]).

[0048] [Organic polar solvents]

[0049] Organic amide solvents can be preferably exemplified as the organic polar solvent used in the method for preparing polyarylene sulfide according to the present invention. As specific examples, aprotic organic solvents represented by N-alkylpyrrolidones such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and N-cyclohexyl-2-pyrrolidone, caprolactams such as N-methyl-ε-caprolactam, 1,3-dimethyl-2-imidazolidinone, N,N-dimethylacetamide, N,N-dimethylformamide, and hexamethylphosphate triamide, as well as mixtures thereof, are preferably used because they provide high reaction stability. Among these, N-methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone are preferred, and N-methyl-2-pyrrolidone is more preferably used.

[0050] The amount of organic polar solvent used is preferably 2.0 moles or more, more preferably 2.2 moles or more, and more preferably 2.3 moles or more per 1 mole of input inorganic sulfidizing agent. It is desirable to use an amount greater than this value because it allows for the synthesis of polyarylene sulfide with good yield. Additionally, the amount of organic polar solvent used is preferably 6.0 moles or less per 1 mole of input inorganic sulfidizing agent, more preferably 5.0 moles or less, and more preferably 4.0 moles or less. It is desirable to use an amount less than this value because it allows for the reduction of gas generated when the obtained polyarylene sulfide is heated.

[0051] [Polymerization Preparation]

[0052] One of the preferred methods is to use a polymerization aid to obtain polyarylene sulfide with a relatively high degree of polymerization in a shorter time. Here, a polymerization aid refers to a substance that has the effect of increasing the viscosity of the polyarylene sulfide obtained. Specific examples of such polymerization aids include, for instance, organic carboxylates, water, alkali metal chlorides, organic sulfonates, alkali metal sulfates, alkaline earth metal oxides, alkali metal phosphates, and alkaline earth metal phosphates. These may be used individually or in combination of two or more. Among these, organic carboxylates, water, and alkali metal chlorides are preferred, and as organic carboxylates, alkali metal carboxylates are preferred, and as alkali metal chlorides, lithium chloride is preferred.

[0053] The above alkali metal carboxylate is the general formula R(COOM) nIt is a compound represented by (wherein R is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group, an alkylaryl group, or an arylalkyl group. M is an alkali metal selected from lithium, sodium, potassium, rubidium, and cesium. n is an integer from 1 to 3). Alkali metal carboxylates may also be used as hydrates, anhydrous forms, or aqueous solutions. Specific examples of alkali metal carboxylates include, for instance, lithium acetate, sodium acetate, potassium acetate, sodium propionate, lithium valerate, sodium benzoate, and mixtures thereof.

[0054] Alkali metal carboxylates may be synthesized by reacting an organic acid with one or more compounds selected from the group consisting of alkali metal hydroxide, alkali metal carbonate, and alkali metal bicarbonate, in roughly equal chemical equivalents. Among the above alkali metal carboxylates, lithium salts have high solubility in the reaction system and a large auxiliary effect, but they are expensive. On the other hand, since potassium, rubidium, and cesium salts are considered to have insufficient solubility in the reaction system, sodium acetate, which is inexpensive and has suitable solubility in the polymerization system, is most preferably used.

[0055] When these alkali metal carboxylates are used as polymerization aids, the amount used is typically in the range of 0.01 to 2 moles per 1 mole of input inorganic sulfidizing agent, and in order to obtain a higher degree of polymerization, a range of 0.1 to 0.6 moles is preferred, and a range of 0.2 to 0.5 moles is more preferred.

[0056] In addition, when water is used as a polymerization aid, the amount added is typically in the range of 0.3 moles to 15 moles per mole of input inorganic sulfidizing agent, and in order to obtain a higher degree of polymerization, a range of 0.6 moles to 10 moles is preferred, and a range of 1 mole to 5 moles is more preferred.

[0057] Of course, it is also possible to use two or more of these polymerization aids in combination. For example, if alkali metal carboxylates and water are used in combination, high molecular weight can be achieved with a smaller amount of alkali metal carboxylates and water.

[0058] There is no specific time for adding these polymerization aids; they may be added at any point during the preceding process, at the start of polymerization, or during the polymerization reaction process as described below, or added in multiple stages. When using alkali metal carboxylates as polymerization aids, it is more preferable to add them simultaneously with other additives at the start of the preceding process or at the start of polymerization, as this facilitates the addition process. Furthermore, when using water as a polymerization aid, it is effective to add it during the polymerization reaction process after the dihalogenated aromatic compound has been introduced.

[0059] [Polymerization Stabilizer]

[0060] Polymerization stabilizers may be used to stabilize the polymerization reaction system and prevent side reactions. Polymerization stabilizers contribute to the stabilization of the polymerization reaction system and suppress undesirable side reactions. One criterion for a side reaction is the formation of thiophenol. The formation of thiophenol can be suppressed by adding a polymerization stabilizer. 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 aforementioned alkali metal carboxylates also act as polymerization stabilizers and are therefore included as a type of polymerization stabilizer. Furthermore, while it has been stated above that it is particularly desirable to use alkali metal hydroxides simultaneously when using alkali metal hydrosulfides as inorganic sulfidizing agents, the alkali metal hydroxides that are in excess of the sulfidizing agent can also serve as polymerization stabilizers.

[0061] These polymerization stabilizers can be used individually or in combination of two or more types. It is preferable to use the polymerization stabilizer in a ratio of typically 0.02 to 0.2 moles, preferably 0.03 to 0.1 moles, and more preferably 0.04 to 0.09 moles per mole of input inorganic sulfidizing agent. If this ratio is too low, the stabilization effect is insufficient, and conversely, if it is too high, it is economically disadvantageous and tends to lower the polymer yield.

[0062] There is no specific time for adding the polymerization stabilizer; it may be added at any point during the preceding process, the start of polymerization, or the polymerization reaction process as described below, and may also be added in multiple stages. However, it is more preferable to add it simultaneously at the start of the preceding process or the start of polymerization, as this is easier.

[0063] Next, a preferred method for manufacturing polyarylene sulfide according to the present invention will be described in detail in the order of a pre-process, a polymerization reaction process, a recovery process, and a post-treatment process, but of course, it is not limited to this method.

[0064] [Full Process]

[0065] In a method for manufacturing polyarylene sulfide, the inorganic sulfidizing agent is typically used in the form of a hydrate; however, before adding the dihalogenated aromatic compound, it is preferable to heat a mixture containing an organic polar solvent and an inorganic sulfidizing agent to remove excess water from the system.

[0066] In addition, as described above, as an inorganic sulfidizing agent, an inorganic sulfidizing agent prepared from alkali metal hydrosulfides and alkali metal hydroxides in situ in the reaction system or in a vessel different from the polymerization vessel may be used. There are no particular limitations on this method, but preferably, an alkali metal hydrosulfide and an alkali metal hydroxide are added to an organic polar solvent under an inert gas atmosphere at room temperature to 150°C, preferably from room temperature to 100°C, and the temperature is raised to at least 150°C, preferably 180°C to 260°C, under atmospheric pressure or reduced pressure to remove moisture. A polymerization aid may be added at this stage. In addition, to promote the removal of moisture, the reaction may be carried out by adding toluene, etc.

[0067] At the end of the entire process, that is, before the polymerization reaction process, the amount of water in the system is preferably 0.3 moles to 10.0 moles per mole of the input sulfidizing agent. Here, the amount of water in the system is the amount obtained by subtracting the amount of water removed from the polymerization system from the amount of water input into the polymerization system. In addition, the water input may be in any form, such as water, aqueous solution, or crystal water.

[0068] [Polymerization Reaction Process]

[0069] Polyarylene sulfide is prepared by reacting an inorganic sulfidizing agent, a dihalogenated aromatic compound, and compound (A) in an organic polar solvent within a temperature range of 200°C or higher and less than 290°C.

[0070] Initiating the polymerization reaction process, preferably under an inert gas atmosphere, an organic polar solvent, a sulfidizing agent, and a dihalogenated aromatic compound are mixed at a temperature range of room temperature to 240°C, preferably 100°C to 230°C. At this stage, compound (A) and a polymerization aid may be added. The order of adding these raw materials may be different or may be simultaneous.

[0071] This mixture is typically heated to a range of 200°C to less than 290°C. There are no particular restrictions on the heating rate, but a rate of 0.01°C / min to 5°C / min is typically selected, and a range of 0.1°C / min to 3°C / min is more preferable.

[0072] Generally, the temperature is finally raised to a temperature of 250°C to less than 290°C, and the reaction is carried out at that temperature for typically 0.25 hours to 50 hours, preferably 0.5 hours to 20 hours.

[0073] In the step before reaching the final temperature, for example, a method of reacting at 200°C to 260°C for a certain period of time and then raising the temperature to less than 270°C to 290°C is effective in obtaining a higher degree of polymerization. At this time, the reaction time at 200°C to 260°C is typically selected in a range of 0.25 hours to 20 hours, and preferably in a range of 0.25 hours to 10 hours.

[0074] Additionally, to adjust the molecular weight of the polymer, it is possible to add compound (A) during polymerization, but from the perspective of efficient reaction of compound (A), it is more preferable to add at least a portion of compound (A) at the same stage as the dihalogenated aromatic compound.

[0075] [Recovery Process]

[0076] In a method for manufacturing polyarylene sulfide, solids are recovered from a polymerization reaction product containing a polymer, a solvent, etc., after the polymerization is completed. Any known method may be employed for the recovery method.

[0077] For example, a method of recovering particulate polymer by slow cooling after the polymerization reaction is completed may be used. There are no specific restrictions on the slow cooling rate at this time, but it is typically about 0.1°C / min to 3°C / min. It is not necessary to slow cool at the same rate throughout the entire slow cooling process; methods such as slow cooling at a rate of 0.1°C / min to 1°C / min until the polymer particles crystallize and precipitate, and then slow cooling at a rate of 1°C / min or higher thereafter may be adopted.

[0078] In addition, performing the above recovery under rapid cooling conditions is also one of the preferred methods. Among these recovery methods, the flash method is a preferred method. The flash method is a method of recovering polymerized reactants by flashing them into an atmosphere of atmospheric pressure or reduced pressure under high temperature and high pressure (typically 250°C or higher, 8 kg / cm² or higher) to recover the polymer in powder form simultaneously with the solvent recovery. The term "flash" as used here refers to ejecting the polymerized reactants from a nozzle. Specifically, the atmosphere used for flashing may be nitrogen or water vapor at atmospheric pressure, and the temperature is typically selected to be in the range of 150°C to 250°C.

[0079] [Post-processing]

[0080] Polyarylene sulfide may be produced through the above polymerization reaction process and recovery process, and then subjected to acid treatment, hot water treatment, washing with an organic solvent, or treatment with an alkali metal or alkaline earth metal.

[0081] Acid treatment is performed in the following cases. The acid used for acid treatment of polyarylene sulfide is not particularly limited as long as it does not have the function of decomposing polyarylene sulfide, and examples include acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid, and propyl acid. Among these, acetic acid and hydrochloric acid are more preferably used. On the other hand, it is not desirable to use acids that decompose or degrade polyarylene sulfide, such as nitric acid.

[0082] The acid treatment method may involve, for example, immersing the polyarylene sulfide in an acid or an aqueous solution of acid, and stirring or heating may also be performed as necessary. For example, when using acetic acid, sufficient effect is obtained by immersing the polyarylene sulfide powder in an aqueous acetic acid solution of pH 4 heated to 80°C to 200°C and stirring for 30 minutes. The pH after treatment may be 4 or higher, for example, approximately pH 4 to 8. To remove residual acid or salts from the acid-treated polyarylene sulfide, it is desirable to wash it several times with water or hot water. The water used for washing is preferably distilled water or deionized water so as not to impede the desired chemical modification effect of the polyarylene sulfide by acid treatment.

[0083] The case for performing hot water treatment is as follows. When treating polyarylene sulfide with hot water, it is preferable to set the temperature of the hot water to 100°C or higher, more preferably 120°C or higher, even more preferably 150°C or higher, and particularly preferably 170°C or higher. It is not desirable to set the temperature below 100°C because the effect of desirable chemical modification of polyarylene sulfide is small.

[0084] In order to achieve the desired chemical modification effect of polyarylene sulfide by hot water washing, it is preferable that the water used be distilled water or deionized water. There are no particular restrictions on the operation of the hot water treatment. It is carried out by methods such as adding a predetermined amount of polyarylene sulfide to a predetermined amount of water and heating and stirring it in a pressure vessel, or by continuously performing the hot water treatment. Regarding the ratio of PPS resin to water, it is preferable that water be abundant, but typically, a bath ratio (weight of washing solution relative to the weight of dry polyarylene sulfide) of 200g or less of polyarylene sulfide per 1 liter of water is selected.

[0085] In addition, to avoid undesirable decomposition of the terminal reactive functional groups, it is preferable to perform the treatment under an inert atmosphere. Furthermore, to remove residual components, it is preferable to wash the polyarylene sulfide, after this hot water treatment operation, several times with hot water.

[0086] The cases of cleaning with organic solvents are as follows. There are no particular restrictions on the organic solvent used for cleaning polyarylene sulfide, as long as it does not have the function of decomposing polyarylene sulfide. Examples of organic solvents used for cleaning polyarylene sulfides include nitrogen-containing polar solvents such as N-methyl-2-pyrrolidone, dimethylformamide, and dimethylacetamide; sulfoxide-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 solvents such as chloroform, methylene chloride, trichloroethylene, dichloroethylene, and perchloroethylene; alcohol solvents such as methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, and propylene glycol; and aromatic hydrocarbon solvents such as benzene, toluene, and xylene. Among these organic solvents, the use of N-methyl-2-pyrrolidone, acetone, dimethylformamide, and chloroform is particularly preferred. In addition, these organic solvents may be used as a single type or a mixture of two or more types, or may be used mixed with water.

[0087] As a method for cleaning with an organic solvent, for example, polyarylene sulfide can be immersed in an organic solvent, and stirring or heating can be performed appropriately as needed. There are no particular restrictions on the cleaning temperature when cleaning polyarylene sulfide with an organic solvent, and any temperature ranging from room temperature to approximately 300°C can be selected. Although cleaning efficiency tends to increase as the cleaning temperature rises, sufficient effect is typically obtained at a cleaning temperature ranging from room temperature to 150°C. It is also possible to perform cleaning under pressure in a pressure vessel at a temperature above the boiling point of the organic solvent. Furthermore, there are no particular restrictions on the cleaning time. Depending on the cleaning conditions, in the case of batch cleaning, sufficient effect is typically obtained by cleaning for at least 5 minutes. Continuous cleaning is also possible. For the post-treatment process, it is preferable to perform acid treatment, hydrothermal treatment, or cleaning with an organic solvent, and using two or more types of treatments in combination is desirable from the perspective of impurity removal.

[0088] Methods for treating alkali metals and alkaline earth metals include adding alkali metal salts or alkaline earth metal salts before, during, or after the aforementioned process; adding alkali metal salts or alkaline earth metal salts into the polymerization furnace before, during, or after the polymerization reaction process; or adding alkali metal salts or alkaline earth metal salts at the beginning, middle, or end of the aforementioned cleaning process. Among these, the easiest method is to add alkali metal salts or alkaline earth metal salts after removing residual oligomers or residual salts by organic solvent cleaning or hot water or hydrothermal cleaning. It is preferable to introduce alkali metals or alkaline earth metals into the polyarylene sulfide in the form of alkali metal ions or alkaline earth metal ions, such as acetates, hydroxides, or carbonates. Furthermore, it is preferable to remove excess alkali metal salts or alkaline earth metal salts by hot water cleaning or the like. When introducing the above alkali metal and alkaline earth metal, the concentration of alkali metal ions and alkaline earth metal ions is preferably 0.001 mmol or more per 1 g of polyarylene sulfide, and more preferably 0.01 mmol or more. As for the temperature, 50°C or higher is preferred, 75°C or higher is more preferred, and 90°C or higher is particularly preferred. There is no particular upper temperature limit, but from the perspective of operability, 280°C or lower is generally preferred. As for the bath ratio (weight of cleaning solution relative to weight of dry polyarylene sulfide), 0.5 or higher is preferred, 3 or higher is more preferred, and 5 or higher is more preferred.

[0089] [Thermal Oxidation Crosslinking Treatment]

[0090] In addition, the polyarylene sulfide in the present invention may be used after increasing its molecular weight by thermal oxidative crosslinking treatment by heating in an oxygen atmosphere or by adding a crosslinking agent such as a peroxide after the polymerization is completed. However, as will be described in detail later, the number average molecular weight is preferably 30,000 or less.

[0091] The polyarylene sulfide obtained by the manufacturing method of the present invention can be used as a raw material for resin compositions, polymer modification, copolymerization, etc. Since the preferred molecular weight varies depending on the application, it cannot be uniformly specified, but it is preferable that the number average molecular weight be 1,000 or more, and more preferably 2,000 or more. It is desirable that the number average molecular weight of the polyarylene sulfide be 1,000 or more because sufficient chemical resistance is obtained. In addition, the upper limit of the number average molecular weight of the polyarylene sulfide is preferably 50,000 or less, and more preferably 30,000 or less. It is desirable that the number average molecular weight of the polyarylene sulfide be 50,000 or less because the melt viscosity does not become too high and molding processing tends to be easy. In addition, the number average molecular weight Mn is a value calculated in polystyrene equivalent by gel permeation chromatography (GPC), which is a type of size exclusion chromatography (SEC).

[0092] The polyarylene sulfide obtained by the manufacturing method of the present invention preferably has reactive functional groups of 400 μmol / g or more, more preferably 500 μmol / g or more, more preferably 700 μmol / g or more, and even more preferably 1,000 μmol / g or more. It is preferable that the reactive functional groups are above the lower limit mentioned above, as this tends to sufficiently increase the glass transition point of the polyarylene sulfide copolymer when manufacturing the polyarylene sulfide copolymer described later. Additionally, it is preferable that the reactive functional groups are 5,000 μmol / g or less, more preferably 4,000 μmol / g or less, and more preferably 3,000 μmol / g or less. It is preferable that the reactive functional groups are below the upper limit mentioned above, as this prevents a decrease in the chemical resistance of the polyarylene sulfide copolymer when manufacturing the polyarylene sulfide copolymer described later.

[0093] Reactive functional groups in polyarylene sulfides are identified by FT-IR analysis of polyarylene sulfides, for example, 1900 cm⁻¹ derived from a benzene ring -1 It can be quantified by comparing the intensity of absorption derived from the reactive functional group with respect to absorption in the vicinity. For example, if it is a carboxyl group, it is 1730 cm⁻¹. -1 The absorption of, if it is an amino group, 3360 cm -1 The absorption of, if acid anhydrous, 1725 cm -1 Each of the absorptions can be utilized. Among them, it is preferable to have an amino group as a reactive functional group.

[0094] The halogen content of the polyarylene sulfide obtained by the manufacturing method of the present invention is preferably 8,000 ppm or less, more preferably 5,000 ppm or less, and even more preferably 3,000 ppm or less. It is desirable to prepare the polyarylene sulfide copolymer described below using the polyarylene sulfide with the halogen content within the above range, as high molecular weight polymers are easily obtained. Although the reason is not certain, it is thought that a low halogen content at the polymer ends increases the probability of functional groups existing at the ends, making copolymerization reactions easier to occur. There is no lower limit for the halogen content of the polyarylene sulfide, but, for example, 500 ppm or more can be exemplified. The halogen content in the polyarylene sulfide can be measured, for example, using a device combining a combustion device and ion chromatography. The halogen content of polyarylene sulfide is derived from the raw material, a dihalogenated aromatic compound, and can be controlled by increasing or decreasing the value of the [monomer ratio] described in the section on the dihalogenated aromatic compound.

[0095] The polyarylene sulfide obtained by the manufacturing method of the present invention preferably has a weight loss rate of 5 wt% or less when heated from 30°C to 320°C at a heating rate of 10°C / minute, more preferably 4 wt% or less, and even more preferably 3 wt% or less. A smaller weight loss rate is preferable, but, for example, 0.01 wt% or more can be exemplified. In the manufacturing method of the present invention, even if a large amount of functional groups are introduced into the polyarylene sulfide, unreacted monomers that are prone to becoming gaseous components upon heating tend to remain difficult to survive. Therefore, the weight loss rate can be reduced to 5 wt% or less.

[0096] The above weight loss rate can be determined by general thermogravimetric analysis. In this analysis, a non-oxidizing atmosphere at atmospheric pressure is typically used. A non-oxidizing atmosphere is an atmosphere in which the oxygen concentration in the gaseous phase in contact with the sample is 5 volume% or less, preferably 2 volume% or less, and more preferably does not contain oxygen substantially; it is preferable to use an inert gas atmosphere such as nitrogen, helium, or argon. Among these, a nitrogen atmosphere is particularly preferred in terms of economic efficiency and ease of handling. Furthermore, atmospheric pressure refers to atmospheric pressure, i.e., absolute pressure, and is a pressure condition of approximately 101.3 kPa.

[0097] In addition, for measuring the weight loss rate, thermogravimetric analysis is performed by increasing the temperature from room temperature to any temperature of 320°C or higher at a heating rate of 10°C / min. This temperature range is a frequently used temperature range when polyarylene sulfides, such as polyphenylene sulfide, are used in actual applications or when molten molding or reactions are performed. The weight loss rate in this actual application temperature range serves as an indicator of the amount of gas generated from the polyarylene sulfide during actual use and the degree of contamination of the equipment during molding, processing, or reaction. Therefore, polyarylene sulfide with a low weight loss rate in this temperature range can be considered a high-quality, excellent polyarylene sulfide.

[0098] [Method for manufacturing polyarylene sulfide copolymer]

[0099] A polyarylene sulfide copolymer may be prepared by obtaining a polyarylene sulfide containing a reactive functional group by the manufacturing method of the present invention, and by mixing it with at least one compound (B) selected from the following formulas (a) to (k) (hereinafter sometimes abbreviated as compound (B)) and heating.

[0100] [Tuesday 5]

[0101]

[0102] Here, X is any selected from a hydroxyl group, a carboxyl group, a silanol group, a sulfonic acid group, an amino group, an acid anhydride group, an acetamide group, a sulfonamide group, a cyano group, an isocyanate group, an aldehyde group, an acetyl group, an epoxy group, and an alkoxysilane group; from the perspective of reactivity with polyarylene sulfide, an amino group or an acid anhydride group is preferred. The aromatic ring of each compound represented by formulas (a) to (k) may be disubstituted or trisubstituted, and the plurality of substituents X substituted with a single aromatic ring may be the same or different. R, R 1 , and R 2 is a substituent selected from hydrogen, alkyl groups having 1 to 12 carbon atoms, aryl groups having 6 to 24 carbon atoms, and halogen groups, and R, R 1 , and R 2 It may be the same or different, and hydrogen, methyl, ethyl, or propyl groups are preferred due to ease of availability.

[0103] Specific examples of compound (B) include p-phenylenediamine, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 2,7-diaminofluorene, o-toluidine, 1,5-diaminonaphthalene, p-benzenediol, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, 2,7-dihydroxyfluorene, 4,4'-dihydroxybiphenyl, 1,5-dihydroxynaphthalene, Pyromellitic acid, 3,3',4,4'-thiodiphthalic acid, 3,3',4,4'-sulfonyldiphthalic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 3,3',4,4'-sulfinyldiphthalic acid, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-tetracarboxydiphenylmethane dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, pyromellitic anhydride, 3,3',4,4'-thiodiphthalic acid dianhydride, 3,3',4,4'-sulfonyldiphthalic acid dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, Examples include 3,3',4,4'-sulfinyldiphthalic anhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-tetracarboxydiphenylmethane dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 4,4'-thiodibenzoic acid, 4,4'-dicarboxybenzophenone, 4,4'-sulfinyldibenzoic acid, and 4,4'-dicarboxybiphenyl in terms of reactivity, and 4,4'-diaminodiphenylsulfone, 4,4'-diaminobenzophenone, 2,7-diaminofluorene, o-toluidine, and 3,3',4,4'-thiodiphthalic anhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3',4,4'-sulfinyl diphthalic acid dianhydride, 3,3',4,4'-biphenyl tetracarboxylic acid dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 4,4'-thiodibenzoic acid, 4,4'-dicarboxybenzophenone, 4,4'-sulfinyl dibenzoic acid, 4,4'-dicarboxybiphenylpyromellitic acid, and pyromellitic acid anhydride are preferably used.

[0104] The lower limit of the amount of compound (B) is preferably 0.5 mol% or more with respect to the sulfur atoms of polyarylene sulfide, more preferably 1 mol% or more, and more preferably 2 mol% or more. The upper limit is preferably 30 mol% or less with respect to the sulfur atoms in polyarylene sulfide, more preferably 20 mol% or less, and more preferably 15 mol% or less. By ensuring the amount added is greater than or equal to the lower limit above, the decrease in stiffness of the resulting polyarylene sulfide copolymer at high temperatures can be sufficiently suppressed. Furthermore, although the chemical resistance of the resulting polyarylene sulfide copolymer tends to decrease as the amount of compound (B) increases, by keeping the amount of compound (B) added within the above range, a polyarylene sulfide copolymer exhibiting sufficient mechanical properties or chemical resistance can be easily manufactured. Here, the heating temperature is selected to be 200°C or higher, preferably 230°C or higher, and more preferably 250°C or higher. As an upper limit for the heating temperature, 400°C or lower can be exemplified, preferably 380°C or lower, and more preferably 360°C or lower. It is desirable to heat the temperature to 200°C or higher so that the reaction between the polyarylene sulfide and the compound (B) can be easily promoted, and to heat it above the temperature at which the polyarylene sulfide melts so that the reaction can be completed in a shorter time. In addition, since the temperature at which the polyarylene sulfide melts varies depending on the composition and molecular weight of the polyarylene sulfide and the environment during heating, it cannot be expressed uniquely; however, for example, it is possible to determine the melting temperature by analyzing the polyarylene sulfide using a differential scanning calorimeter. However, if the temperature is too high, undesirable side reactions, such as cross-linking reactions or decomposition reactions between polyarylene sulfides, tend to occur easily, and the properties of the resulting polyarylene sulfide copolymer may deteriorate. Therefore, it is desirable to avoid temperatures at which such undesirable side reactions occur significantly.The time for heating described above cannot be expressed uniquely because it varies depending on the composition and molecular weight of the polyarylene sulfide and the environment during heating, but it is desirable to set the time so that the aforementioned undesirable side reaction does not occur as much as possible. As for the heating time, 0.01 to 100 hours can be exemplified, 0.1 to 20 hours is preferred, and 0.1 to 10 hours is more preferred. If the time is less than 0.01 hours, the reaction between the polyarylene sulfide and the compound (B) is likely to be insufficient, and if the time exceeds 100 hours, not only is there a higher tendency for adverse effects on the properties of the polyarylene sulfide copolymer obtained by undesirable side reactions to become apparent, but there may also be economic disadvantages.

[0105] In the method for preparing a polyarylene sulfide copolymer of the present invention, it is preferable to form an imide group by reacting the functional group of the polyarylene sulfide with X of the compound (B). As for the combination for forming the imide group, there are no particular limitations as long as the imide group is formed, but it is preferable that the functional group of the polyarylene sulfide and X of the compound (B) be a combination of an acid anhydride group and an amino group, or a combination of a carboxyl group and an amino group. It is particularly preferable that it be a combination of an acid anhydride group and an amino group.

[0106] In the method for manufacturing the polyarylene sulfide copolymer of the present invention, heating is preferably performed in the absence of a solvent to prevent contamination of the molded article by gases generated during molding processing. Furthermore, the method is not limited to the above, and it is also possible to perform the process in the presence of a solvent. As for the solvent, there are no particular restrictions as long as it does not substantially cause undesirable side reactions, such as decomposition or crosslinking of the generated polyarylene sulfide copolymer. The solvent may be used as one type or a mixture of two or more types.

[0107] In the method for manufacturing a polyarylene sulfide copolymer according to the present invention, heating can be performed not only by using a conventional polymerization reaction apparatus, but also within a mold for manufacturing a molded article, or by using an extruder or a melt mixer; any apparatus equipped with a heating mechanism can be used without particular limitation, and known methods such as batch methods and continuous methods can be employed.

[0108] In the method for manufacturing a polyarylene sulfide copolymer according to the present invention, it is preferable to perform the heating in a non-oxidizing atmosphere, and it is also preferable to perform it under reduced pressure conditions. Furthermore, when performing under reduced pressure conditions, it is preferable to first make the atmosphere within the reaction system a non-oxidizing atmosphere and then change it to a reduced pressure condition. Accordingly, there is a tendency to suppress the occurrence of undesirable side reactions, such as cross-linking reactions or decomposition reactions between polyarylene sulfides. In addition, a non-oxidizing atmosphere refers to an atmosphere in which the oxygen concentration in the gas phase is 5 volume% or less, preferably 2 volume% or less, and more preferably does not substantially contain oxygen, i.e., an inert gas atmosphere such as nitrogen, helium, or argon; among these, a nitrogen atmosphere is particularly preferred in terms of economic efficiency and ease of handling. In addition, a reduced pressure condition refers to the pressure within the reaction system being lower than atmospheric pressure; as an upper limit, it is preferable to be 50 kPa or less, more preferable to be 20 kPa or less, and even more preferable to be 10 kPa or less. As a lower limit, 0.1 kPa or more can be exemplified. By keeping the reduced pressure condition below the desirable upper limit, undesirable side reactions such as cross-linking reactions tend to be suppressed, while above the desirable lower limit, it is desirable because the load caused by reduced pressure is not placed on the reaction device more than necessary.

[0109] The glass transition point of the polyarylene sulfide copolymer obtained by the manufacturing method of the present invention is preferably 95°C or higher, more preferably 100°C or higher, and even more preferably 110°C or higher. It is desirable that the glass transition point be 95°C or higher because high rigidity is obtained under high temperature conditions. In addition, the glass transition point of the polyarylene sulfide copolymer is preferably 190°C or lower, more preferably 180°C or lower, and even more preferably 160°C or lower. It is desirable that the glass transition point be 190°C or lower because the chemical resistance of the molded article is maintained. Here, the glass transition point is defined as the inflection point of the baseline shift detected when the temperature is raised from 0°C to 340°C at a rate of 20°C / min using a differential scanning calorimeter. In addition, the polyarylene sulfide copolymer obtained by the manufacturing method of the present invention is preferably 300°C or lower, or has no melting point. Melt molding processing is facilitated by having a melting point of 300°C or lower, or by having no melting point. Here, the melting point is defined as the value of the melting peak temperature detected when using a differential scanning calorimeter to raise the temperature from 0°C to 340°C at a rate of 20°C / min, hold at 340°C for 1 minute, lower the temperature to 100°C at a rate of 20°C / min, hold at 100°C for 1 minute, and then raise the temperature again to 340°C at a rate of 20°C / min. "Having no melting point" is defined as not observing a clear melting peak when measurements are taken under the above conditions using a differential scanning calorimeter. The melting point can be adjusted by selecting the molecular weight of the arylene sulfide unit in the polyarylene sulfide copolymer.

[0110] The preferred molecular weight of the polyarylene sulfide copolymer obtained by the manufacturing method of the present invention is, in terms of weight average molecular weight, 10,000 or more, preferably 20,000 or more, more preferably 30,000 or more, even more preferably 40,000 or more, and even more preferably 45,000 or more. A weight average molecular weight of 10,000 or more is preferred because the toughness or mechanical strength of the polyarylene sulfide copolymer tends to be sufficiently high. Although there is no particular limit on the upper limit of the weight average molecular weight, less than 1,000,000 can be exemplified as a preferred range, more preferably less than 500,000, and even more preferably less than 200,000, and this range is preferred because the moldability is excellent.

[0111] In addition, the weight-average molecular weight can be obtained, for example, using SEC (size exclusion chromatography) equipped with a differential refractive index detector.

[0112] The polyarylene sulfide and polyarylene sulfide copolymer obtained by the manufacturing method of the present invention can be used as a polyarylene sulfide resin composition by mixing with fillers and other additives. Although the method of mixing in the manufacture of the resin composition is not particularly limited, representative examples include a method of feeding to a known melt mixer such as a single-screw or twin-screw extruder, a bomber mixer, a kneader, and a mixing roll, and mixing at a processing temperature of + 5 to 100°C of the melting peak temperature of the polyarylene sulfide copolymer.

[0113] For example, inorganic or organic fillers can be used as fillers.

[0114] Although the type of filler is not strictly specified, fibrous inorganic fillers such as glass fibers and carbon fibers are preferred when considering the reinforcing effect of the filler in the resin composition. Carbon fibers provide not only an effect of improving mechanical properties but also a lightweighting effect for the molded product. Furthermore, when the filler is carbon fiber, it is more preferable because the effect of improving the mechanical properties and chemical resistance of the resin composition is more significantly manifested.

[0115] The polyarylene sulfide and polyarylene sulfide copolymer obtained by the present invention have excellent heat resistance, chemical resistance, flame retardancy, electrical properties, and mechanical properties, and can be formed into extruded products such as sheets, films, fibers, and pipes by extrusion molding, as well as for use in injection molding, injection compression molding, and blow molding.

[0116] In addition, examples of uses for the resin composition using polyarylene sulfide and polyarylene sulfide copolymer obtained by the present invention include electrical and electronic components, voice device components, components for household and office electrical products, machine-related components, optical instruments, precision machine-related components, water section components, automobile and vehicle-related components, aerospace-related components, and various other applications.

[0117] Examples

[0118] The method of the present invention will be explained in more detail below through examples and comparative examples, but the present invention is not limited to these examples only.

[0119] [Analysis of Functional Group Content]

[0120] The amount of functional groups introduced into polyarylene sulfide was determined by measuring the amorphous film of polyarylene sulfide prepared by rapid cooling from a molten state using FT-IR (JASCO Corporation IR-810 infrared spectrophotometer), and the 1900 cm derived from the benzene ring -1It was estimated by comparing the absorption derived from each functional group with the absorption in the vicinity. For the amino group, 3360 cm -1 The absorption peak of in the acid anhydride group is 1725 cm⁻¹ -1 The absorption peaks of were each used in the calculation.

[0121] [Molecular Weight Measurement]

[0122] The number average molecular weight Mn of polyarylene sulfide and the weight average molecular weight Mw of the polyarylene sulfide copolymer were calculated in polystyrene equivalents by gel permeation chromatography (GPC), a type of size exclusion chromatography (SEC). The measurement conditions for GPC are shown below.

[0123] Device: Senshu Scientific co., ltd. SSC-7110

[0124] Column Name: Shodex UT806M×2

[0125] Eluent: 1-chloronaphthalene

[0126] Detector: Parallax refractive index detector

[0127] Column temperature: 210℃

[0128] Pre-constant bath temperature: 250℃

[0129] Pump constant temperature bath temperature: 50℃

[0130] Detector temperature: 210℃

[0131] Flow rate: 1.0 mL / min

[0132] Sample injection volume: 300μL.

[0133] [Analysis of Residual Amount of Functional Group-Containing Monomers]

[0134] The monomers containing reactive functional groups remaining in the polymerization reaction product obtained after the completion of the polymerization process of polyarylene sulfide were quantified using a gas chromatograph GC-2010 PLUS manufactured by Shimadzu Corporation, and the retention rate was calculated from the input amount.

[0135] [Measurement of weight loss rate upon heating]

[0136] The weight loss rate of polyarylene sulfide upon heating was determined using a thermogravimetric analyzer under the following conditions.

[0137] Device: TGA7 manufactured by PerkinElmer, Inc.

[0138] Measurement atmosphere: Under nitrogen stream

[0139] Sample input weight: Approx. 5 mg

[0140] Measurement conditions

[0141] (a) Maintain program temperature at 30℃ for 1 minute

[0142] (b) Program temperature increase from 30℃ to 340℃. During this process, the heating rate is 10℃ / min.

[0143] From the weight at 320℃ and the weight at 30℃ measured under the above conditions, the weight loss rate was calculated by the following formula.

[0144] Weight loss rate (%) = ((Weight at 30℃ (mg) - Weight at 320℃ (mg)) / Weight at 30℃ (mg)) × 100.

[0145] [Analysis of Halogen Content in Polymers]

[0146] Using an automatic sample combustion device AQF-100 manufactured by DIA Instruments Co. Ltd., 1 to 2 mg of polymer was combusted at a final temperature of 1000°C, the generated gas components were absorbed into 10 mL of water containing a dilute oxidizing agent, and the absorption solution was supplied to an ion chromatography system ICS1500 manufactured by DIONEX, which used a sodium carbonate / sodium bicarbonate mixed aqueous solution as the mobile phase, and the amount of halogen in the polymer was measured.

[0147] [Example 1]

[0148] 10.40 kg (88.0 mol) of 47.5% sodium hydrosulfide, 4.15 kg (99.6 mol) of 96% sodium hydroxide, 20.82 kg (210 mol) of N-methyl-2-pyrrolidone (NMP), and 5.96 kg of ion-exchanged water were added to a 70-liter autoclave equipped with a stirrer and a bottom plug valve. The mixture was then slowly heated to 225°C over approximately 3 hours while passing nitrogen through it at atmospheric pressure. Heating was stopped and cooling was initiated when 9.82 kg of water and 0.28 kg of NMP had been discharged. At this point, the amount of hydrogen sulfide released was 2.1 mol, so the amount of inorganic sulfidating agent in the system after this process was 85.9 mol.

[0149] After that, the mixture was cooled to 200°C, and 13.5 kg (91.8 mol) of p-dichlorobenzene (p-DCB), 1.46 kg (11.7 mol) of 4-aminothiophenol (4-ATP), and 7.93 kg (80.0 mol) of NMP were added. Then, the reaction vessel was sealed under nitrogen gas, the temperature was raised to 260°C at a rate of 0.6°C / min while stirring at 240 rpm, and the reaction was carried out at 260°C for 120 minutes.

[0150] After the reaction was finished, the autoclave bottom plug valve was immediately opened, and the contents were flashed into a stirrer attachment device, dried for 1.5 hours in a stirrer attachment device at 230°C, and the solid containing PPS and salts was recovered.

[0151] The obtained recovered material and ion-exchanged water were placed in an autoclave equipped with a stirrer, washed at 75°C for 15 minutes, and then filtered three times to obtain a cake. The cake and ion-exchanged water were placed in an autoclave equipped with a stirrer, the inside of the autoclave was purged with nitrogen, and the temperature was raised to 195°C. Afterward, the autoclave was cooled, and the contents were removed. The contents were filtered to obtain a cake. The obtained cake was dried at 120°C under a nitrogen stream to obtain dried PPS.

[0152] [Example 2]

[0153] 8.27 kg (70.0 mol) of 47.5% sodium hydrosulfide, 3.22 kg (77.3 mol) of 96% sodium hydroxide, 14.57 kg (147 mol) of N-methyl-2-pyrrolidone (NMP), and 4.47 kg of ion-exchanged water were added to a 70-liter autoclave equipped with a stirrer and a bottom plug valve. The mixture was then slowly heated to 225°C over approximately 3 hours while passing nitrogen through it at atmospheric pressure. Heating was stopped and cooling was initiated when 12.37 kg of water and 0.28 kg of NMP had been discharged. At this point, the amount of hydrogen sulfide released was 2.1 mol, so the amount of inorganic sulfidating agent in the system after this process was 67.9 mol.

[0154] After that, the mixture was cooled to 200°C, and 13.5 kg (72.63 mol) of p-dichlorobenzene (p-DCB), 0.86 kg (6.85 mol) of 4-aminothiophenol (4-ATP), and 5.55 kg (56.0 mol) of NMP were added. Then, the reaction vessel was sealed under nitrogen gas, the temperature was raised to 260°C at a rate of 0.6°C / min while stirring at 240 rpm, and the reaction was carried out at 260°C for 120 minutes.

[0155] After the reaction was finished, the autoclave bottom plug valve was immediately opened, and the contents were flashed into a stirrer attachment device, dried for 1.5 hours in a stirrer attachment device at 230°C, and the solid containing PPS and salts was recovered.

[0156] The obtained recovered material and ion-exchanged water were placed in an autoclave equipped with a stirrer, washed at 75°C for 15 minutes, and then filtered three times to obtain a cake. The cake and ion-exchanged water were placed in an autoclave equipped with a stirrer, the inside of the autoclave was purged with nitrogen, and the temperature was raised to 195°C. Afterward, the autoclave was cooled, and the contents were filtered to obtain a cake. The obtained cake was dried at 120°C under a nitrogen stream to obtain dried PPS.

[0157] [Example 3]

[0158] 11.1 kg (94.0 mol) of 47.5% sodium hydrosulfide, 4.15 kg (99.6 mol) of 96% sodium hydroxide, 20.82 kg (210 mol) of N-methyl-2-pyrrolidone (NMP), and 4.45 kg of ion-exchanged water were added to a 70-liter autoclave equipped with a stirrer and a bottom plug valve. The mixture was then slowly heated to 225°C over approximately 3 hours while passing nitrogen through it at atmospheric pressure. Heating was stopped and cooling was initiated when 10.07 kg of water and 0.27 kg of NMP had been discharged. At this point, the amount of hydrogen sulfide released was 2.2 mol, so the amount of inorganic sulfidating agent in the system after this process was 91.8 mol.

[0159] After that, the mixture was cooled to 200°C, and 13.9 kg (94.8 mol) of p-dichlorobenzene (p-DCB), 0.72 kg (5.88 mol) of 4-aminothiophenol (4-ATP), and 7.93 kg (80.0 mol) of NMP were added. Then, the reaction vessel was sealed under nitrogen gas, the temperature was raised to 260°C at a rate of 0.6°C / min while stirring at 240 rpm, and the reaction was carried out at 260°C for 120 minutes.

[0160] After the reaction was finished, the autoclave bottom plug valve was immediately opened, and the contents were flashed into a stirrer attachment device, dried for 1.5 hours in a stirrer attachment device at 230°C, and the solid containing PPS and salts was recovered.

[0161] The obtained recovered material and ion-exchanged water were placed in an autoclave equipped with a stirrer, washed at 75°C for 15 minutes, and then filtered three times to obtain a cake. The cake and ion-exchanged water were placed in an autoclave equipped with a stirrer, the inside of the autoclave was purged with nitrogen, and the temperature was raised to 195°C. Afterward, the autoclave was cooled, and the contents were filtered to obtain a cake. The obtained cake was dried at 120°C under a nitrogen stream to obtain dried PPS.

[0162] [Example 4]

[0163] 8.26 kg (70.0 mol) of 47.5% sodium hydrosulfide, 4.13 kg (99.1 mol) of 96% sodium hydroxide, 20.82 kg (210 mol) of N-methyl-2-pyrrolidone (NMP), and 4.43 kg of ion-exchanged water were added to a 70-liter autoclave equipped with a stirrer and a bottom plug valve. The mixture was then slowly heated to 225°C over approximately 3 hours while passing nitrogen through it at atmospheric pressure. Heating was stopped and cooling was initiated when 8.61 kg of water and 0.26 kg of NMP had been discharged. At this point, the amount of hydrogen sulfide released was 2.1 mol, so the amount of inorganic sulfidating agent in the system after this process was 67.9 mol.

[0164] After that, the mixture was cooled to 200°C, and 12.1 kg (82.6 mol) of p-dichlorobenzene (p-DCB), 3.64 kg (29.4 mol) of 4-aminothiophenol (4-ATP), and 7.93 kg (80.0 mol) of NMP were added. Then, the reaction vessel was sealed under nitrogen gas, the temperature was raised to 260°C at a rate of 0.6°C / min while stirring at 240 rpm, and the reaction was carried out at 260°C for 120 minutes.

[0165] After the reaction was finished, the autoclave bottom plug valve was immediately opened, and the contents were flashed into a stirrer attachment device, dried for 1.5 hours in a stirrer attachment device at 230°C, and the solid containing PPS and salts was recovered.

[0166] The obtained recovered material and ion-exchanged water were placed in an autoclave equipped with a stirrer, washed at 75°C for 15 minutes, and then filtered three times to obtain a cake. The cake and ion-exchanged water were placed in an autoclave equipped with a stirrer, the inside of the autoclave was purged with nitrogen, and the temperature was raised to 195°C. Afterward, the autoclave was cooled, and the contents were filtered to obtain a cake. The obtained cake was dried at 120°C under a nitrogen stream to obtain dried PPS.

[0167] [Example 5]

[0168] 7.22 kg (62.3 mol) of 48.4% sodium hydrosulfide, 2.90 kg (70.5 mol) of 97% sodium hydroxide, 14.57 kg (147 mol) of N-methyl-2-pyrrolidone (NMP), and 4.22 kg of ion-exchanged water were added to a 70-liter autoclave equipped with a stirrer and a bottom plug valve. The mixture was then slowly heated to 225°C over approximately 3 hours while passing nitrogen through it at atmospheric pressure. Heating was stopped and cooling was initiated when 7.95 kg of water and 0.072 kg of NMP had been discharged. At this point, the amount of hydrogen sulfide released was 1.4 mol, so the amount of inorganic sulfidating agent in the system after this process was 60.9 mol.

[0169] After that, the mixture was cooled to 200°C, and 9.51 kg (64.5 mol) of p-dichlorobenzene (p-DCB), 0.94 kg (7.55 mol) of a portion of 4-aminothiophenol (4-ATP), and 5.55 kg (56.0 mol) of NMP were added. Then, the reaction vessel was sealed under nitrogen gas, the temperature was raised to 260°C at a rate of 0.6°C / min while stirring at 240 rpm, and the reaction was carried out at 260°C for 120 minutes.

[0170] After reacting at 260°C for 120 minutes, the remaining 0.86 kg (0.69 mol) of 4-aminothiophenol (4-ATP) was pressed in together with 0.70 kg (7.06 mol) of NMP and reacted at 260°C for 60 minutes.

[0171] After the reaction was finished, the autoclave bottom plug valve was immediately opened, and the contents were flashed into a stirrer attachment device, dried for 1.5 hours in a stirrer attachment device at 230°C, and the solid containing PPS and salts was recovered.

[0172] The obtained recovered material and ion-exchanged water were placed in an autoclave equipped with a stirrer, washed at 75°C for 15 minutes, and then filtered three times to obtain a cake. The cake and ion-exchanged water were placed in an autoclave equipped with a stirrer, the inside of the autoclave was purged with nitrogen, and the temperature was raised to 195°C. Afterward, the autoclave was cooled, and the contents were filtered to obtain a cake. The obtained cake was dried at 120°C under a nitrogen stream to obtain dried PPS.

[0173] [Example 6]

[0174] 7.14 kg (61.6 mol) of 48.4% sodium hydrosulfide, 2.87 kg (69.3 mol) of 97% sodium hydroxide, 14.57 kg (147 mol) of N-methyl-2-pyrrolidone (NMP), and 4.18 kg of ion-exchanged water were added to a 70-liter autoclave equipped with a stirrer and a bottom plug valve. The mixture was then slowly heated to 225°C over approximately 3 hours while passing nitrogen through it at atmospheric pressure. Heating was stopped and cooling was initiated when 7.87 kg of water and 0.014 kg of NMP had been discharged. At this point, the amount of hydrogen sulfide released was 1.6 mol, so the amount of inorganic sulfidating agent in the system after this process was 60.0 mol.

[0175] After that, the mixture was cooled to 200°C, and 9.42 kg (64.1 mol) of p-dichlorobenzene (p-DCB), 1.02 kg (8.21 mol) of 4-aminothiophenol (4-ATP), and 13.2 kg (133.0 mol) of NMP were added. Then, the reaction vessel was sealed under nitrogen gas, the temperature was raised to 260°C at a rate of 0.6°C / min while stirring at 240 rpm, and the reaction was carried out at 260°C for 120 minutes.

[0176] After the reaction was finished, the autoclave bottom plug valve was immediately opened, and the contents were flashed into a stirrer attachment device, dried for 1.5 hours in a stirrer attachment device at 230°C, and the solid containing PPS and salts was recovered.

[0177] The obtained recovered material and ion-exchanged water were placed in an autoclave equipped with a stirrer, washed at 75°C for 15 minutes, and then filtered three times to obtain a cake. The cake and ion-exchanged water were placed in an autoclave equipped with a stirrer, the inside of the autoclave was purged with nitrogen, and the temperature was raised to 195°C. Afterward, the autoclave was cooled, and the contents were filtered to obtain a cake. The obtained cake was dried at 120°C under a nitrogen stream to obtain dried PPS.

[0178] [Example 7]

[0179] 7.14 kg (61.6 mol) of 48.4% sodium hydrosulfide, 2.87 kg (69.3 mol) of 97% sodium hydroxide, 14.57 kg (147 mol) of N-methyl-2-pyrrolidone (NMP), and 4.19 kg of ion-exchanged water were added to a 70-liter autoclave equipped with a stirrer and a bottom plug valve. The mixture was then slowly heated to 225°C over approximately 3 hours while passing nitrogen through it at atmospheric pressure. Heating was stopped and cooling was initiated when 7.88 kg of water and 0.039 kg of NMP had been discharged. At this point, the amount of hydrogen sulfide released was 1.4 mol, so the amount of inorganic sulfidating agent in the system after this process was 60.2 mol.

[0180] After that, the mixture was cooled to 200°C, and 9.45 kg (64.3 mol) of p-dichlorobenzene (p-DCB), 1.02 kg (8.23 mol) of 4-aminothiophenol (4-ATP), and 2.78 kg (28.0 mol) of NMP were added. Then, the reaction vessel was sealed under nitrogen gas, the temperature was raised to 260°C at a rate of 0.6°C / min while stirring at 240 rpm, and the reaction was carried out at 260°C for 120 minutes.

[0181] After the reaction was finished, the autoclave bottom plug valve was immediately opened, and the contents were flashed into a stirrer attachment device, dried for 1.5 hours in a stirrer attachment device at 230°C, and the solid containing PPS and salts was recovered.

[0182] The obtained recovered material and ion-exchanged water were placed in an autoclave equipped with a stirrer, washed at 75°C for 15 minutes, and then filtered three times to obtain a cake. The cake and ion-exchanged water were placed in an autoclave equipped with a stirrer, the inside of the autoclave was purged with nitrogen, and the temperature was raised to 195°C. Afterward, the autoclave was cooled, and the contents were filtered to obtain a cake. The obtained cake was dried at 120°C under a nitrogen stream to obtain dried PPS.

[0183] [Example 8]

[0184] 10.40 kg (88.0 mol) of 47.5% sodium hydrosulfide, 4.15 kg (99.6 mol) of 96% sodium hydroxide, 20.82 kg (210 mol) of N-methyl-2-pyrrolidone (NMP), and 5.96 kg of ion-exchanged water were added to a 70-liter autoclave equipped with a stirrer and a bottom plug valve. The mixture was then slowly heated to 225°C over approximately 3 hours while passing nitrogen through it at atmospheric pressure. Heating was stopped and cooling was initiated when 9.82 kg of water and 0.28 kg of NMP had been discharged. At this point, the amount of hydrogen sulfide released was 2.1 mol, so the amount of inorganic sulfidating agent in the system after this process was 85.9 mol.

[0185] After that, the mixture was cooled to 200°C, and 16.9 kg (114.8 mol) of p-dichlorobenzene (p-DCB), 1.46 kg (11.7 mol) of 4-aminothiophenol (4-ATP), and 7.93 kg (80.0 mol) of NMP were added. Then, the reaction vessel was sealed under nitrogen gas, the temperature was raised to 260°C at a rate of 0.6°C / min while stirring at 240 rpm, and the reaction was carried out at 260°C for 120 minutes.

[0186] After the reaction was finished, the autoclave bottom plug valve was immediately opened, and the contents were flashed into a stirrer attachment device, dried for 1.5 hours in a stirrer attachment device at 230°C, and the solid containing PPS and salts was recovered.

[0187] The obtained recovered material and ion-exchanged water were placed in an autoclave equipped with a stirrer, washed at 75°C for 15 minutes, and then filtered three times to obtain a cake. The cake and ion-exchanged water were placed in an autoclave equipped with a stirrer, the inside of the autoclave was purged with nitrogen, and the temperature was raised to 195°C. Afterward, the autoclave was cooled, and the contents were filtered to obtain a cake. The obtained cake was dried at 120°C under a nitrogen stream to obtain dried PPS.

[0188] [Example 9]

[0189] 10.40 kg (88.0 mol) of 47.5% sodium hydrosulfide, 4.15 kg (99.6 mol) of 96% sodium hydroxide, 20.82 kg (210 mol) of N-methyl-2-pyrrolidone (NMP), and 5.96 kg of ion-exchanged water were added to a 70-liter autoclave equipped with a stirrer and a bottom plug valve. The mixture was then slowly heated to 225°C over approximately 3 hours while passing nitrogen through it at atmospheric pressure. Heating was stopped and cooling was initiated when 9.82 kg of water and 0.28 kg of NMP had been discharged. At this point, the amount of hydrogen sulfide released was 2.1 mol, so the amount of inorganic sulfidating agent in the system after this process was 85.9 mol.

[0190] After that, the mixture was cooled to 200°C, and 13.5 kg (91.8 mol) of p-dichlorobenzene (p-DCB), 1.46 kg (11.7 mol) of 3-aminothiophenol (3-ATP), and 7.93 kg (80.0 mol) of NMP were added. Then, the reaction vessel was sealed under nitrogen gas, the temperature was raised to 260°C at a rate of 0.6°C / min while stirring at 240 rpm, and the reaction was carried out at 260°C for 120 minutes.

[0191] After the reaction was finished, the autoclave bottom plug valve was immediately opened, and the contents were flashed into a stirrer attachment device, dried for 1.5 hours in a stirrer attachment device at 230°C, and the solid containing PPS and salts was recovered.

[0192] The obtained recovered material and ion-exchanged water were placed in an autoclave equipped with a stirrer, washed at 75°C for 15 minutes, and then filtered three times to obtain a cake. The cake and ion-exchanged water were placed in an autoclave equipped with a stirrer, the inside of the autoclave was purged with nitrogen, and the temperature was raised to 195°C. Afterward, the autoclave was cooled, and the contents were filtered to obtain a cake. The obtained cake was dried at 120°C under a nitrogen stream to obtain dried PPS.

[0193] [Example 10]

[0194] 3 kg of dried PPS obtained in Example 7 and 30 kg of N-methyl-2-pyrrolidone (NMP) were placed in a container equipped with a stirrer and stirred at 50 rpm for 30 minutes, after which a cake was obtained by filtering. The obtained cake was washed with 30 liters of ion-exchanged water for 15 minutes and filtered three times, and then the obtained cake was dried at 120°C for 4 hours under a nitrogen stream to obtain dried PPS.

[0195] [Example 11]

[0196] 10.40 kg (88.0 mol) of 47.5% sodium hydrosulfide, 4.15 kg (99.6 mol) of 96% sodium hydroxide, 20.82 kg (210 mol) of N-methyl-2-pyrrolidone (NMP), and 5.96 kg of ion-exchanged water were added to a 70-liter autoclave equipped with a stirrer and a bottom plug valve. The mixture was then slowly heated to 225°C over approximately 3 hours while passing nitrogen through it at atmospheric pressure. Heating was stopped and cooling was initiated when 9.82 kg of water and 0.28 kg of NMP had been discharged. At this point, the amount of hydrogen sulfide released was 2.1 mol, so the amount of inorganic sulfidating agent in the system after this process was 85.9 mol.

[0197] After that, the mixture was cooled to 200°C, and 13.5 kg (91.8 mol) of p-dichlorobenzene (p-DCB), 1.28 kg (11.7 mol) of 4-aminophenol (4-AP), and 7.93 kg (80.0 mol) of NMP were added. Then, the reaction vessel was sealed under nitrogen gas, the temperature was raised to 260°C at a rate of 0.6°C / min while stirring at 240 rpm, and the reaction was carried out at 260°C for 120 minutes.

[0198] After the reaction was finished, the autoclave bottom plug valve was immediately opened, and the contents were flashed into a stirrer attachment device, dried for 1.5 hours in a stirrer attachment device at 230°C, and the solid containing PPS and salts was recovered.

[0199] The obtained recovered material and ion-exchanged water were placed in an autoclave equipped with a stirrer, washed at 75°C for 15 minutes, and then filtered three times to obtain a cake. The cake and ion-exchanged water were placed in an autoclave equipped with a stirrer, the inside of the autoclave was purged with nitrogen, and the temperature was raised to 195°C. Afterward, the autoclave was cooled, and the contents were filtered to obtain a cake. The obtained cake was dried at 120°C under a nitrogen stream to obtain dried PPS.

[0200] [Comparative Example 1]

[0201] 8.27 kg (70.0 mol) of 47.5% sodium hydrosulfide, 3.56 kg (85.5 mol) of 96% sodium hydroxide, 11.45 kg (115.50 mol) of N-methyl-2-pyrrolidone (NMP), and 5.50 kg of ion-exchanged water were added to a 70-liter autoclave equipped with a stirrer and a bottom plug valve. The mixture was then slowly heated to 225°C over approximately 3 hours while passing nitrogen through it at atmospheric pressure. Heating was stopped and cooling was initiated when 9.82 kg of water and 0.28 kg of NMP had been discharged. At this point, the amount of residual water in the system per mol of added alkali metal hydrosulfide was 1.01 mol, including the water consumed in the hydrolysis of NMP. Additionally, since the amount of hydrogen sulfide released was 1.4 mol, the amount of sulfidizing agent in the system after this process was 68.6 mol.

[0202] After that, the mixture was cooled to 200°C, and 9.28 kg (65.1 mol) of p-dichlorobenzene (p-DCB), 2.88 kg (15.8 mol) of 4-chlorophthalic anhydride (4-CPA), and 9.37 kg (94.50 mol) of NMP were added. Then, the reaction vessel was sealed under nitrogen gas, the temperature was raised to 275°C at a rate of 0.6°C / min while stirring at 240 rpm, and the reaction was carried out at 275°C for 60 minutes.

[0203] After the reaction was finished, the autoclave bottom plug valve was immediately opened, and the contents were flashed into a stirrer attachment device, dried for 1.5 hours in a stirrer attachment device at 230°C, and the solid containing PPS and salts was recovered.

[0204] The obtained recovered material and ion-exchanged water were placed in an autoclave equipped with a stirrer, washed at 75°C for 15 minutes, and then filtered three times to obtain a cake. The cake and ion-exchanged water were placed in an autoclave equipped with a stirrer, the inside of the autoclave was purged with nitrogen, and the temperature was raised to 195°C. Afterward, the autoclave was cooled, and the contents were filtered to obtain a cake. The obtained cake was dried at 120°C under a nitrogen stream to obtain dried PPS.

[0205] [Comparative Example 2]

[0206] 8.27 kg (70.0 mol) of 47.5% sodium hydrosulfide, 3.56 kg (85.5 mol) of 96% sodium hydroxide, 11.45 kg (115.50 mol) of N-methyl-2-pyrrolidone (NMP), and 5.50 kg of ion-exchanged water were added to a 70-liter autoclave equipped with a stirrer and a bottom plug valve. The mixture was then slowly heated to 225°C over approximately 3 hours while passing nitrogen through it at atmospheric pressure. Heating was stopped and cooling was initiated when 9.82 kg of water and 0.28 kg of NMP had been discharged. At this point, the amount of residual water in the system per mol of added alkali metal hydrosulfide was 1.01 mol, including the water consumed in the hydrolysis of NMP. Additionally, since the amount of hydrogen sulfide released was 1.4 mol, the amount of sulfidizing agent in the system after this process was 68.6 mol.

[0207] After that, the mixture was cooled to 200°C, and 9.28 kg (65.1 mol) of p-dichlorobenzene (p-DCB), 4.61 kg (25.3 mol) of 4-chlorophthalic anhydride, and 9.37 kg (94.50 mol) of NMP were added. Then, the reaction vessel was sealed under nitrogen gas, the temperature was raised to 275°C at a rate of 0.6°C / min while stirring at 240 rpm, and the reaction was carried out at 275°C for 120 minutes.

[0208] After the reaction was finished, the bottom plug valve of the autoclave was immediately opened, and the contents were flashed into a stirrer-equipped device. The mixture was dried for 1.5 hours in a stirrer-equipped device at 230°C until more than 95% of the NMP used during polymerization was volatilized, and the solid containing PPS and salts was recovered.

[0209] The obtained recovered material and ion-exchanged water were placed in an autoclave equipped with a stirrer, washed at 75°C for 15 minutes, and then filtered three times to obtain a cake. The cake and ion-exchanged water were placed in an autoclave equipped with a stirrer, the inside of the autoclave was purged with nitrogen, and the temperature was raised to 195°C. Afterward, the autoclave was cooled, and the contents were filtered to obtain a cake. The obtained cake was dried at 120°C under a nitrogen stream to obtain dried PPS.

[0210] [Comparative Example 3]

[0211] 8.27 kg (70.00 mol) of 47.5% sodium hydrosulfide, 2.96 kg (70.97 mol) of 96% sodium hydroxide, 11.4 kg (115.50 mol) of N-methyl-2-pyrrolidone (NMP), 2.58 kg (31.50 mol) of sodium acetate, and 10.5 kg of ion-exchanged water were added to a 70-liter autoclave equipped with a stirrer. The mixture was then slowly heated to 245°C over approximately 3 hours while passing nitrogen through it at atmospheric pressure, after which 14.8 kg of water and 280 g of NMP were discharged, and the reaction vessel was cooled to 160°C. The amount of residual water in the system per mole of the added alkali metal sulfide was 1.06 mol, including the water consumed in the hydrolysis of NMP. Additionally, the amount of hydrogen sulfide ejected was 0.02 mol per mole of the added alkali metal sulfide.

[0212] Next, 10.24 kg (69.63 mol) of p-dichlorobenzene and 9.01 kg (91.00 mol) of NMP were added, the reaction vessel was sealed under nitrogen gas, and the temperature was raised to 238°C at a rate of 0.6°C / min while stirring at 240 rpm. After carrying out the reaction at 238°C for 95 minutes, the temperature was raised to 270°C at a rate of 0.8°C / min. After carrying out the reaction at 270°C for 100 minutes, 1.26 kg (70 mol) of water was injected over 15 minutes while cooling to 250°C at a rate of 1.3°C / min. Afterward, it was cooled to 200°C at a rate of 1.0°C / min, and then rapidly cooled to near room temperature.

[0213] The contents were extracted, diluted with 26.3 kg of NMP, and the solvent and solids were separated using a sieve (80 mesh). The obtained particles were washed and filtered with 31.9 kg of NMP. This was washed and filtered several times with 56 kg of ion-exchanged water. After washing and filtering with 70 kg of ion-exchanged water, the obtained hydrated PPS particles were dried with hot air at 80°C and dried under reduced pressure at 120°C to obtain PPS.

[0214] 80g of the obtained PPS and 12g of 4,4'-thiodianiline (TDA) were placed into a glass test tube equipped with a stirring blade and capable of reduced pressure and nitrogen displacement, and the reduced pressure and nitrogen displacement inside the test tube were repeated three times. With the test tube filled with a nitrogen atmosphere, the temperature was controlled to 340°C, and heating was performed for 180 minutes while stirring to obtain polyarylene sulfide.

[0215] The analysis results of PPS obtained in the above Examples 1 to 11 and Comparative Examples 1 to 3 were as shown in Table 1.

[0216] [Table 1]

[0217]

[0218] [Examples 12–21, Comparative Examples 4–6]

[0219] The PPS obtained in Examples 1 to 10 and Comparative Examples 1 to 3, and a compound (B) weighed such that the functional group content as the copolymerizing partner is equivalent to that of the PPS, were introduced into a reaction vessel capable of reduced pressure and nitrogen substitution equipped with stirring blades, and the reduced pressure and nitrogen substitution within the reaction vessel were repeated three times. The reaction vessel was filled with a nitrogen atmosphere, heated for 20 minutes while stirring at a temperature of 320°C, and then cooled to room temperature to obtain a polyarylene sulfide copolymer. From the FT-IR spectrum, it was confirmed that the obtained polyarylene sulfide copolymer contains phenylene sulfide units as structural units and that imide groups derived from the copolymerizing components have been introduced. After removing the polyarylene sulfide copolymer from the reaction vessel, the degree of contamination of the reaction vessel by gas components generated during heating was determined according to the following criteria.

[0220] A: No cleaning operation required before inputting the next batch

[0221] B: Next batch can be fed by washing in NMP at room temperature.

[0222] C: The next batch requires cleaning by NMP reflux above the boiling point.

[0223] The results of determining the weight average molecular weight Mw, glass transition point Tg, melting point Tm, and contamination level of the reaction vessel of the polyarylene sulfide copolymer were as shown in Table 2.

[0224] [Table 2]

[0225]

[0226] In addition, the following compounds are indicated for the abbreviations of each compound in the table.

[0227] PDA: Pyromolit acid anhydride

[0228] DDS: 4,4'-Diaminodiphenylsulfone

[0229] As shown in Examples 1 to 11, according to the manufacturing method of the present invention, polyarylene sulfide containing functional groups and having a low amount of gas generated upon heating can be provided simply and efficiently.

[0230] In addition, as shown in Examples 12 to 21 of Table 2, according to the manufacturing method of the present invention, since contamination of the reaction vessel can be suppressed when manufacturing a polyarylene sulfide copolymer, it is possible to omit or simplify the cleaning process of the reaction vessel, thereby improving workability.

Claims

Claim 1 A method for producing polyarylene sulfide having a weight loss rate of 5 wt% or less when heated at a heating rate of 10°C / min from 30°C to 320°C, wherein at least a dihalogenated aromatic compound, an inorganic sulfidizing agent, and a compound (A) are reacted in the presence of an alkali metal hydroxide in an organic polar solvent, wherein the compound (A) is present in a range of 0.04 mol to 0.5 mol per 1 mol of inorganic sulfidizing agent in a reaction vessel, and the compound (A) has at least one aromatic ring and has at least one functional group selected from an amino group, a hydroxyl group, a salt of a hydroxyl group, a thiol group, and a salt of a thiol group on the one aromatic ring. Claim 2 A method for producing polyarylene sulfide according to claim 1, characterized in that at least a portion of compound (A) is added to a reaction vessel in the same step as adding a dihalogenated aromatic compound to a reaction vessel. Claim 3 A method for preparing a polyarylene sulfide copolymer, wherein a polyarylene sulfide is obtained by the manufacturing method described in claim 1 or 2, and then at least one compound (B) selected from the following formulas (a) to (k) is mixed and further heated. [Chemical 1] (Here, X is any one selected from hydroxyl group, carboxyl group, silanol group, sulfonic acid group, amino group, acid anhydride group, acetamide group, sulfonamide group, cyano group, isocyanate group, aldehyde group, acetyl group, epoxy group, and alkoxysilane group. R, R 1 , and R 2 is a substituent selected from hydrogen, alkyl groups having 1 to 12 carbon atoms, aryl groups having 6 to 24 carbon atoms, and halogen groups, and R, R 1 , and R 2 It can be the same or different.) Claim 4 Polyarylene sulfide containing amino groups in the range of 400 μmol / g or more and 5,000 μmol / g or less, and having a weight loss rate of 5 wt% or less when heated from 30°C to 320°C at a heating rate of 10°C / min.

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