JP5760756B2 - Polyarylene sulfide and process for producing the same - Google Patents

Description

  The present invention relates to a method for efficiently producing a polyarylene sulfide having a high melt fluidity and a small amount of volatile components and a small chlorine content, and having high reactivity and excellent mechanical strength.

  Polyarylene sulfide (hereinafter abbreviated as PAS) typified by polyphenylene sulfide (hereinafter abbreviated as PPS) has excellent properties as engineering plastics such as excellent heat resistance, barrier properties, chemical resistance, electrical insulation properties, and heat and humidity resistance. It is used for various electric / electronic parts, machine parts and automobile parts, films, fibers, etc. mainly for injection molding and extrusion molding. In particular, PAS with high melt flowability can cope with molding of a complicated shape accompanying reduction in size and weight of a molded product, and a resin composition using the PAS can be filled with a large amount of inorganic filler, and has heat resistance. It has the advantage that dimensional stability and the like can be improved, and in recent years, the needs for the PAS are very high. However, since PAS with high melt flowability generally contains a large amount of low molecular weight components, the amount of volatile components at the time of melting tends to be high, which tends to cause a problem that mold vent clogging and production efficiency deteriorate. . In addition, PAS originally has low adhesiveness and adhesion to inorganic fillers and has a problem in mechanical strength. For this reason, there has been a strong demand for a PAS that has high melt fluidity and a small amount of volatile components, yet has high reactivity and excellent mechanical strength.

  In the field of electrical and electronic parts, the trend toward reducing the halogen content has become active as an environmental measure, and PAS that can obtain sufficient flame retardancy without a halogen-based flame retardant has been attracting attention. However, when a dihalogenated aromatic compound, which is a general PAS production method, is used as a raw material, the halogen derived from the dihalogenated aromatic compound is present at an arbitrary ratio at the molecular chain end, so that a high halogen content is obtained. In the case of using dichlorobenzene as the dihalogenated aromatic compound, the chlorine content becomes high. In particular, the above-described PAS having high melt fluidity generally has a low molecular weight, and therefore, there are more molecular chain ends than PAS having a high molecular weight, and the chlorine content tends to increase. Therefore, PAS that has a low volatile component amount and a low chlorine content while having a high melt fluidity, and that is highly reactive and excellent in mechanical strength, is an epoch-making that can satisfy environmental impact reduction and good physical properties. It is particularly strongly desired as PAS, and the present invention has found a production method thereof.

  As a typical production method of PAS, a sulfidizing agent such as sodium sulfide and a dihalogenated aromatic compound such as p-dichlorobenzene in an organic polar solvent such as N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) A method of reacting is known. As a method for reducing the amount of volatile components generated when PAS is melted, a method of washing the PAS slurry obtained after the reaction with an organic solvent such as acetone or NMP is generally known. Since the low molecular weight substance which is the main component of the sex component is removed by washing and the oligomer is also removed, the fluidity when PAS is melted tends to be lowered. Therefore, studies have been made to reduce the amount of volatile components in a state where a specific amount of oligomer is included and high melt fluidity is ensured. For example, in Patent Document 1, a polyhalogen aromatic compound and a sulfidizing agent are reacted in a polar organic solvent and then recovered by a flash method, and the resulting polymer is acid-treated at pH = 2-8 and 80-200 ° C. In addition, a method is disclosed in which the obtained PPS is heat-treated at 160 to 270 ° C. for 0.2 to 50 hours in an atmosphere having an oxygen concentration of 2% by volume or more. In Patent Document 1, by controlling the heat treatment condition to a specific condition, both high melt fluidity and a small amount of volatile components are compatible, but since a specific amount of oligomer having chlorine as a molecular chain end is included, There was a problem that the chlorine content of the obtained PAS was high. Patent Document 2 discloses a method for obtaining PAS that achieves both high melt fluidity and a small amount of volatile components by controlling the temperature and time during polymerization. Since a specific amount of the oligomer at the chain end is included, there is a problem that the chlorine content of the obtained PAS is high.

  Patent Document 3 uses specific amounts of dihalogenated aromatic compounds and monohalogenated compounds as a PAS that combines high melt flowability, a small amount of volatile components, and a small amount of chlorine. However, in this document, functional groups are not actively introduced and only a low-reactivity PAS can be obtained. .

  As PASs in which functional groups are actively introduced to improve the reactivity, Patent Documents 4 to 6 disclose dihalogenated aromatic compounds having reactive functional groups or monohalogenated aromatic compounds having reactive functional groups during polymerization. A method of adding is disclosed. Certainly, functional groups having reactivity have been introduced into PPS, but all have been polymerized for a long time at a polymerization temperature of 250 ° C. or higher for 2 hours or longer, so that reactive functional groups introduced into PAS have been introduced. Can be predicted that the reactivity and mechanical strength of PAS are insufficient, but the influence of polymerization conditions such as polymerization temperature and time on the functional groups introduced into PAS is not disclosed. In addition, due to polymerization at a high temperature for a long time, an increase in volatile components and a decrease in mechanical strength associated with the main chain decomposition of PAS due to heat are expected.

JP 2009-144141 A (Claims, Examples) International Publication No. 2011/024879 (Claims, Examples) JP 2010-053335 A (Claims, Examples) Japanese Patent Laid-Open No. 02-296829 (Claims, Examples) JP 2007-106834 A (Claims, Examples) International Publication No. 2008/020554 (Claims, Examples)

  The present invention has been achieved as a result of studying as an object to efficiently obtain a PAS having both a high volatile component amount and a low chlorine content while having a high melt flowability, and having high reactivity and excellent mechanical strength. Is.

  In the present invention, as a result of intensive studies to solve such problems, PAS is obtained by reacting a sulfidizing agent, a dihalogenated aromatic compound, and a monohalogenated aromatic compound having a reactive functional group in an organic polar solvent. When obtained, by reacting for a specific time under specific temperature conditions, the main chain decomposition of PAS and the thermal decomposition of the reactive functional group introduced into PAS are suppressed, and high reactivity is exhibited and high melt fluidity is achieved. It has been found that a PAS having a small amount of volatile components and a small amount of chlorine can be obtained while having it, and has led to the present invention.

That is, the present invention is as follows.
(1) A monohalogenated aromatic compound having a reactive functional group represented by a sulfidizing agent, a dihalogenated aromatic compound and the following formula (A) within a temperature range of 200 ° C. or higher and lower than 280 ° C. in an organic polar solvent In the method for producing polyarylene sulfide in which is reacted in the presence of an alkali metal hydroxide, at least the following steps 1 and 2 are performed.
Step 1: In a temperature range of 230 ° C. or higher and lower than 245 ° C., the polymerization time (T1a) including the temperature rise / fall time is 30 minutes or longer and less than 3.5 hours, and the conversion rate of the dihalogenated aromatic compound at the end of the step Is a process in which a polyarylene sulfide prepolymer is produced by reacting so as to be 70 to 98 mol%. In a temperature range of 245 ° C. or more and less than 280 ° C., a polymerization time (T2) including a temperature increase / decrease time is A step of reacting in 5 minutes or more and less than 1 hour to obtain polyarylene sulfide.

(X is a halogen group. At least one of R1 to R9 is amino group, amide group, acetamide group, sulfonamide group, sulfonic acid group, carboxyl group, hydroxyl group, thiol group, cyano group, isocyanate group, aldehyde group, acetyl group. A functional group selected from a group, an anhydride group, an epoxy group, a silanol group, an alkoxysilane group, or a derivative thereof, and when two or more of these functional groups are contained, they may be the same or different. A linking group selected from oxygen, carbonyl, amide, ester, sulfonyl and sulfoxide, n is an integer of 0 to 10.)
(2) The ratio (T1a / T2) of the polymerization time (T1a) from 230 ° C. to less than 245 ° C. in the step 1 and the polymerization time (T2) in the step 2 is 0.5 or more (1) A process for producing the polyarylene sulfide as described.
(3) The polymerization time (T1) including the temperature increasing / decreasing time in the temperature range of 200 ° C. or more and less than 245 ° C. including the step 1 is 1.5 hours or more and less than 4 hours (1) or (2) The method for producing a polyarylene sulfide according to (2).
(4) The ratio (T1 / T2) of the polymerization time (T1) between 200 ° C. and less than 245 ° C. and the polymerization time (T2) in step 2 is 1.2 or more, A process for producing arylene sulfide.
(5) The reaction amount of the monohalogenated aromatic compound having a reactive functional group with respect to 100 mol of the sulfidizing agent is 0.1 mol or more and less than 20 mol, any of (1) to (4) A process for producing a polyarylene sulfide as described above.
(6) The reaction amount of the monohalogenated aromatic compound having a reactive functional group with respect to 100 mol of the sulfidizing agent is 0.1 mol or more and less than 6 mol, any of (1) to (4) A process for producing a polyarylene sulfide as described above.
(7) The method for producing polyarylene sulfide according to any one of (1) to (6), wherein the dihalogenated aromatic compound includes a dihalogenated aromatic compound having a reactive functional group.
(8) The method for producing polyarylene sulfide according to any one of (1) to (7), wherein the polyarylene sulfide is recovered by a flash method.
(9) The amount of volatile components that volatilize when heated and melted under vacuum at 320 ° C. for 2 hours is 1.0 wt% or less, and the melt viscosity (measured at a temperature of 300 ° C. and a shear rate of 1216 sec ⁻¹ ) is 2 Pa · s to 100 Pa. -Less than s, chlorine content is less than 3500ppm, and 0.5 parts by weight of epoxy silane coupling agent is added to 100 parts by weight of polyarylene sulfide , and the mixture is melted and stirred for 5 minutes in a test tube at 315 ° C. was charged into a cylinder set at 300 ° C. the 20g obtained after keeping 5 minutes, when measured at a shear rate of 1216 sec ^-1, epoxy for melt viscosity prior to reaction with the epoxy silane coupling agent (MV1) polyarylene the ratio of melt viscosity after the silane coupling agent reaction (MV2) (MV2 / MV1) is equal to or less than 25 3.5 or higher Nsurufido.
(10) The polyarylene sulfide according to (9), wherein the amount of chloroform extracted is 1.0% by weight or more.

  According to the present invention, it is possible to efficiently obtain a PAS having both a low volatile component amount and a low chlorine content while having a high melt fluidity and a high reactivity and an excellent mechanical strength.

  The PAS in the present invention is a homopolymer or copolymer having a repeating unit of the formula, — (Ar—S) —, as a main constituent unit, and preferably containing 80 mol% or more of the repeating unit. Ar includes units represented by the following formulas (B) to (L), among which the formula (B) is particularly preferable.

(R1 and R2 are substituents selected from hydrogen, an alkyl group, an alkoxy group, and a halogen group, and R1 and R2 may be the same or different).

  As long as this repeating unit is a main structural unit, it can contain a small amount of branching units or crosslinking units represented by the following formulas (M) to (O). The amount of copolymerization of these branched units or cross-linked units is preferably in the range of 0 to 1 mol% with respect to 1 mol of-(Ar-S)-units.

  The PAS in the present invention may be any of a random copolymer, a block copolymer and a mixture thereof containing the above repeating unit.

  Typical examples of these include polyphenylene sulfide, polyphenylene sulfide sulfone, polyphenylene sulfide ketone, random copolymers thereof, block copolymers, and mixtures thereof. Particularly preferred PASs include p-phenylene sulfide units as the main structural unit of the polymer.

Is polyphenylene sulfide containing 80 mol% or more, particularly 90 mol% or more.

  In the reaction of obtaining PAS using a sulfidizing agent, a dihalogenated aromatic compound and a monohalogenated aromatic compound having a reactive functional group in an organic polar solvent of the present invention, the monohalogenated aromatic having a reactive functional group is used. When the halogen group of the group compound reacts with the end of PAS, the molecular chain end of the obtained PAS does not have a halogen group but has a structure having a reactive functional group. In order to obtain a PAS having a low chlorine content and a high reactivity, the terminal structure having a reactive functional group and not having a halogen group should have 10 to 100% of all molecular chain terminals of PAS. preferable.

  Regarding the method for producing PAS in the present invention, sulfidizing agent, organic polar solvent, dihalogenated aromatic compound, monohalogenated aromatic compound having a reactive functional group, polymerization aid, branching / crosslinking agent, polymerization stability The agent, the pre-process, the polymerization reaction process, the polymer recovery, other post-treatments, the produced PAS, and the use will be described in detail in this order.

(1) Sulfiding agent Examples of the sulfiding agent used in the present invention include alkali metal sulfides, alkali metal hydrosulfides, and hydrogen sulfide.

  Specific examples of the alkali metal sulfide include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide and a mixture of two or more of these, and sodium sulfide is preferably used. These alkali metal sulfides can be used as hydrates or aqueous mixtures or in the form of anhydrides.

  Specific examples of the alkali metal hydrosulfide include, for example, sodium hydrosulfide, potassium hydrosulfide, lithium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide and a mixture of two or more of these. Preferably used. These alkali metal hydrosulfides can be used as hydrates or aqueous mixtures or in the form of anhydrides.

  A sulfidizing agent prepared in situ in a reaction system from an alkali metal hydrosulfide and an alkali metal hydroxide can also be used. Further, a sulfidizing agent can be prepared from an alkali metal hydrosulfide and an alkali metal hydroxide, and transferred to a polymerization tank for use.

  Alternatively, a sulfidizing agent prepared in situ in a reaction system from an alkali metal hydroxide such as lithium hydroxide or sodium hydroxide and hydrogen sulfide can also be used. Further, a sulfidizing agent can be prepared from an alkali metal hydroxide such as lithium hydroxide or sodium hydroxide and hydrogen sulfide, and transferred to a polymerization tank for use.

  In the present invention, the amount of the sulfidizing agent means a residual amount obtained by subtracting the loss from the actual charge when there is a partial loss of the sulfidizing agent before the start of the polymerization reaction due to dehydration operation or the like. Shall.

  An alkali metal hydroxide and / or an alkaline earth metal hydroxide can be used in combination with the sulfidizing agent. Specific examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, and a mixture of two or more thereof. Specific examples of the metal hydroxide include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, and the like. Among them, sodium hydroxide is preferably used.

  When an alkali metal hydrosulfide is used as the sulfiding agent, it is particularly preferable to use an alkali metal hydroxide at the same time, and the amount used is 90 mol or more and less than 120 mol with respect to 100 mol of the alkali metal hydrosulfide, The range is preferably 95 mol or more and less than 115 mol, more preferably 95 mol or more and less than 110 mol. By setting it within this range, PAS having a small amount of polymerization by-products can be obtained without causing decomposition.

(2) Organic polar solvent In this invention, an organic polar solvent is used as a polymerization solvent. Specific examples include N-alkylpyrrolidones such as N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone, caprolactams such as N-methyl-ε-caprolactam, and 1,3-dimethyl-2-imidazolide. Non-, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, dimethyl sulfone, tetramethylene sulfoxide, and other aprotic organic solvents, and mixtures thereof have high reaction stability. Are preferably used. Of these, N-methyl-2-pyrrolidone (NMP) is particularly preferably used.

  In the present invention, the amount of the organic polar solvent used as the polymerization solvent for PAS is not particularly limited, but from the viewpoint of stable reactivity and economy, 250 mol or more and less than 550 mol, preferably 250 mol, per 100 mol of the sulfidizing agent. A range of not less than 500 mol and more preferably not less than 250 mol and less than 450 mol is selected.

(3) Dihalogenated aromatic compound The dihalogenated aromatic compound used in the present invention is dihalogenated benzene such as p-dichlorobenzene, m-dichlorobenzene, o-dichlorobenzene, p-dibromobenzene, or 2,3-dichlorobenzoic acid. Acid, 2,4-dichlorobenzoic acid, 2,5-dichlorobenzoic acid, 2,6-dichlorobenzoic acid, 3,4-dichlorobenzoic acid, 3,5-dichlorobenzoic acid and salts thereof, and 2,3 -Dichlorophenol, 2,4-dichlorophenol, 2,5-dichlorophenol, 2,6-dichlorophenol, 3,4-dichlorophenol, 3,5-dichlorophenol and their salts, 2,3-dichloroaniline 2,4-dichloroaniline, 2,5-dichloroaniline, 2,6-dichloroaniline, 3,4-dichloro In order to produce a PAS copolymer, aniline, 3,5-dichloroaniline, dihalogenated benzene having a reactive functional group such as 4-amino-2,5-dichlorobenzoic acid and its salt, and the like can be mentioned. It is also possible to use two or more different dihalogenated aromatic compounds in combination. Especially, the dihalogenated aromatic compound which has p-dihalogenated benzene represented by p-dichlorobenzene as a main component is preferable.

  In the present invention, the polymerization time at high temperature is short, and the thermal decomposition of the reactive functional group is suppressed, so that a highly reactive PAS can be obtained. Therefore, it is suitable for production of copolymer PAS using a dihalogenated aromatic compound having a reactive functional group as a copolymer component.

  The purpose of the present invention is to obtain a PAS having a small amount of chlorine, and it is not preferable to use a dihalogenated aromatic compound as a chlorine source in a large excess because the amount of chlorine is increased. On the other hand, when the amount of the dihalogenated aromatic compound is too small, the reaction system becomes rich in a sulfur source and causes a decomposition reaction. For this reason, the amount of the dihalogenated aromatic compound needs to be 95 to 105 moles per 100 moles of the sulfidizing agent, preferably 96 to 104 moles, particularly preferably 97 to 103 moles. it can.

(4) Monohalogenated aromatic compound having a reactive functional group The reactive functional group of the monohalogenated aromatic compound having a reactive functional group of the present invention is an aminosilane coupling agent, an epoxysilane coupling agent, or an isocyanate. It is a functional group that reacts with an additive having reactivity during melt-kneading, such as a reactive coupling agent such as a silane coupling agent or a resin having a glycidyl group. The PAS obtained by using the monohalogenated aromatic compound having a reactive functional group under specific polymerization conditions according to the present invention is, for example, mechanical strength of a resin composition obtained by melt-kneading with a coupling agent. Is significantly improved, and is effective in reducing burrs in injection molding.

  The monohalogenated aromatic compound having a reactive functional group necessary in the present invention is represented by the following formula (P).

(X is a halogen group. At least one of R1 to R9 is amino group, amide group, acetamide group, sulfonamide group, sulfonic acid group, carboxyl group, hydroxyl group, thiol group, cyano group, isocyanate group, aldehyde group, acetyl group. A functional group selected from a group, an anhydride group, an epoxy group, a silanol group, an alkoxysilane group, or a derivative thereof, and when two or more of these functional groups are contained, they may be the same or different. A linking group selected from oxygen, carbonyl, amide, ester, sulfonyl and sulfoxide, n is an integer of 0 to 10.)

  Specifically, 2-chloroaniline, 3-chloroaniline, 4-chloroaniline, 2-bromoaniline, 3-bromoaniline, 4-bromoaniline, 2-chlorobenzoic acid, 3-chlorobenzoic acid, 4-chloro Benzoic acid, 2-bromobenzoic acid, 3-bromobenzoic acid, 4-bromobenzoic acid, 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, 2-bromophenol, 3-bromophenol, 4-bromophenol Halogen such as 4-chlorobenzamide, 4-chlorobenzeneacetamide, 4-chlorobenzenesulfonamide, 4-chlorobenzenesulfonic acid, 4-chlorobenzenethiol, 4'-chlorobenzophenone-2-carboxylic acid, 2-amino-5-chlorobenzophenone Monohalogen containing one reactive functional group other than And aromatic compounds and their salts. In addition, monohalogenated aromatic compounds containing two or more reactive functional groups such as 3,5-diaminochlorobenzene, 4-chlorophthalic acid, 4-chlorophthalic anhydride, and 5-chloroisophthalic acid, and salts thereof. Can do. Of these, 4-chlorobenzoic acid, 4-chlorophthalic acid or a salt thereof, and 4-chloroaniline are preferable from the viewpoint of reactivity and economy. It is also possible to use a combination of two or more different monohalogenated aromatic compounds having a reactive functional group.

  Reactions of 2-chloropyrrole, 2-chloroimidazole, 2-chloro-4,6-dimercaptotriazine, 2-chloro-4,6-diaminototriazine, 2-chloro-4,6-dimercaptotriazine, etc. It is also possible to use a monohalogenated heterocyclic compound having a reactive functional group, a monohalogenated naphthalene having a reactive functional group, a monohalogenated anthracene having a reactive functional group, or the like.

  Since these monohalogenated aromatic compounds having reactive functional groups can be introduced arbitrarily at the end of PAS, they can also be used as molecular weight regulators. As the amount used increases, the molecular weight decreases and the melt fluidity decreases. Although it tends to improve, when used excessively, the molecular weight becomes too low, the processability is lowered and the amount of volatile components is also increased. Moreover, excessive use is not preferable from the viewpoint of economy. The object of the present invention is to obtain a PAS having both a low volatile component amount and a low chlorine content while having a high melt fluidity suitable for processing, and having a high reactivity and excellent mechanical strength. The amount of the monohalogenated aromatic compound having a functional group is required to be 0.01 mol or more and less than 15 mol, preferably 0.1 mol or more and less than 10 mol, more preferably 0.1 mol, per 100 mol of the sulfidizing agent. The range is 5 mol or more and less than 5 mol, particularly preferably 1.0 mol or more and less than 5 mol.

  In addition, as described above, the dihalogenated aromatic compound and the monohalogenated aromatic compound having a reactive functional group can be used in an amount of too much or too little, while having the high melt fluidity of the present invention. It is not preferable for obtaining a PAS having both a small amount of volatile components and a small amount of chlorine. Therefore, the total amount of halogenated compounds such as dihalogenated aromatic compounds and monohalogenated aromatic compounds having a reactive functional group is preferably within a specific range, and the total amount of halogenated compounds with respect to 100 mol of the sulfidizing agent. The amount is preferably 98 mol or more and less than 108 mol, more preferably 100 mol or more and less than 105 mol, and even more preferably 101 mol or more and less than 103 mol. The halogenated compounds include not only the above-mentioned dihalogenated aromatic compounds and monohalogenated aromatic compounds having a reactive functional group, but also polyhalogenated compounds of trihalogenated or higher used in the branching / crosslinking agent described later. Including.

  There is no particular limitation on the addition timing of the monohalogenated aromatic compound having a reactive functional group, and it may be added at any time during the previous step, at the start of polymerization, or during polymerization, which will be described later, or divided into multiple times. However, if it is added during the previous step, a reflux device is required so that the monohalogenated aromatic compound having a reactive functional group does not volatilize during the previous step, or during polymerization (pressurized state) A press-fitting device is required to add in the above. In order to add a monohalogenated aromatic compound having a reactive functional group by a simple operation, it is preferably added at the start of polymerization or during polymerization.

  For the purpose of adjusting the molecular weight, it is also possible to use a monohalogenated aromatic compound having no reactive functional group such as chlorobenzene and 1-chloronaphthalene.

(5) Polymerization aid In the present invention, it is one of preferred embodiments to use a polymerization aid. One purpose of using the polymerization aid is to adjust the PAS to a desired melt viscosity, but another purpose is to reduce the amount of volatile components. Specific examples of such polymerization aids include, for example, organic carboxylic acid metal salts, water, alkali metal chlorides (excluding sodium chloride), organic sulfonic acid metal salts, alkali metal sulfates, alkaline earth metal oxidations. Products, alkali metal phosphates and alkaline earth metal phosphates. These may be used alone or in combination of two or more. Of these, organic carboxylic acid metal salts and / or water are preferably used.

  The organic carboxylic acid metal salt is a general formula R (COOM) n (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. Is an alkali metal selected from lithium, sodium, potassium, rubidium, and cesium, and n is an integer of 1 to 3). The organic carboxylic acid metal salt can also be used as a hydrate, an anhydride or an aqueous solution. Specific examples of the organic carboxylic acid metal salt include, for example, lithium acetate, sodium acetate, potassium acetate, magnesium acetate, calcium acetate, sodium propionate, lithium valerate, sodium benzoate, sodium phenylacetate, potassium p-toluate, And a mixture thereof. The organic carboxylic acid metal salt is obtained by adding an organic acid and one or more compounds selected from the group consisting of an alkali metal hydroxide, an alkali metal carbonate and an alkali metal bicarbonate, and adding them to each other at approximately equal chemical equivalents. You may form by. Among the above organic carboxylic acid metal salts, lithium salts are highly soluble in the reaction system and have a large auxiliary effect, but are expensive, and potassium, rubidium and cesium salts are insufficiently soluble in the reaction system. Sodium acetate, which has been estimated and is inexpensive and has adequate solubility in the reaction system, is preferably used.

  The amount used in the case of using the above organic carboxylic acid metal salt as a polymerization aid is preferably in the range of 1 mol or more and less than 70 mol, more preferably in the range of 2 mol or more and less than 60 mol, relative to 100 mol of the charged sulfidizing agent. The range of 2 mol or more and less than 55 mol is more preferable.

  When using an organic carboxylic acid metal salt as a polymerization aid, the addition timing is not particularly limited, and it may be added at any time during the previous step, at the start of polymerization, or during polymerization, which will be described later, or multiple times. However, from the viewpoint of ease of addition, it is preferable to add them at the start of the previous step or at the start of polymerization.

  When water is used as a polymerization aid, it is possible to use water alone, but it is preferable to use an organic carboxylic acid metal salt at the same time, which can further enhance the effect as a polymerization aid and reduce polymerization. There is a tendency that a PAS having a desired melt viscosity can be obtained in a short time even with the use amount of the auxiliary agent. In this case, the preferable range of the amount of water in the polymerization system is 80 to 300 mol, and more preferably 85 to 180 mol with respect to 100 mol of the sulfidizing agent. If the amount of water is too large, the internal pressure of the reactor is greatly increased, and a reactor having high pressure resistance is required, which tends to be unfavorable in terms of economy and safety. The conversion rate of the dihalogenated aromatic compound at the stage of setting the water content in the polymerization system to the above range is 60 mol% or more, preferably 70% or more, more preferably 80% or more, and still more preferably 90%, as described later. The above is preferable. Water produced as a by-product during polymerization can also serve as a polymerization aid.

  In addition, it is one of preferable modes to add water after polymerization. The preferable range of the water content in the polymerization system after adding water after the polymerization is 100 to 1500 mol, more preferably 150 to 1000 mol, relative to 100 mol of the sulfidizing agent.

(6) Branching / crosslinking agent In the present invention, it is possible to obtain a PAS in which the chlorine content of the substantially linear PAS having high melt flowability is reduced and the amount of volatile components is reduced. Alternatively, in order to form a crosslinked polymer and adjust the melt viscosity to a desired value, a polyhalogen compound that is trihalogenated or higher (not necessarily an aromatic compound), an active hydrogen-containing halogenated aromatic compound, and a halogenated aromatic nitro compound. It is also possible to use a branching / crosslinking agent such as a compound in combination. As the polyhalogen compound, a commonly used compound can be used. Among them, polyhalogenated aromatic compounds are preferable, and specific examples include 1,3,5-trichlorobenzene, 1,2,4-trichlorobenzene, Examples include 1,2,4,5-tetrachlorobenzene, hexachlorobenzene, 1,4,6-trichloronaphthalene, and among them, 1,3,5-trichlorobenzene and 1,2,4-trichlorobenzene are preferable. Examples of the active hydrogen-containing halogenated aromatic compound include halogenated aromatic compounds having functional groups such as amino group, mercapto group, and hydroxyl group. Specific examples include 2,5-dichloroaniline, 2,4-dichloroaniline, 2,3-dichloroaniline, 2,4,6-trichloroaniline, 2,2′-diamino-4,4′-dichlorodiphenyl ether, 2 , 4′-diamino-2 ′, 4-dichlorodiphenyl ether, and the like. Examples of the halogenated aromatic nitro compound include 2,4-dinitrochlorobenzene, 2,5-dichloronitrobenzene, 2-nitro-4,4′-dichlorodiphenyl ether, and 3,3′-dinitro-4,4′-. Examples include dichlorodiphenyl sulfone, 2,5-dichloro-2-nitropyridine, 2-chloro-3,5-dinitropyridine, and the like.

(7) Polymerization stabilizer In the production of the PAS of the present invention, a polymerization stabilizer can also be used in order to stabilize the polymerization reaction system and prevent side reactions. The polymerization stabilizer contributes to stabilization of the polymerization reaction system and suppresses undesirable side reactions. One measure of the side reaction is the generation of thiophenol, and the addition of a polymerization stabilizer can suppress the generation of thiophenol. Specific examples of the polymerization stabilizer 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 preferable. Since the aforementioned organic carboxylic acid metal salt also acts as a polymerization stabilizer, it is one of the polymerization stabilizers used in the present invention. In addition, when an alkali metal hydrosulfide is used as a sulfidizing agent, it has been described above that it is particularly preferable to use an alkali metal hydroxide at the same time. Oxides can also be polymerization stabilizers.

  These polymerization stabilizers can be used alone or in combination of two or more. The polymerization stabilizer is desirably used in a proportion of usually 1 to 20 mol, preferably 3 to 10 mol, per 100 mol of the sulfidizing agent in the reaction system before the start of the polymerization reaction. If this ratio is too large, it tends to be economically disadvantageous and the polymer yield tends to decrease. In addition, when a part of alkali metal sulfide decomposes | disassembles at the time of reaction and hydrogen sulfide generate | occur | produces, the alkali metal hydroxide produced | generated as a result can also become a polymerization stabilizer.

  The addition timing of the polymerization stabilizer is not particularly specified. The polymerization stabilizer may be added at any time during the previous step, the start of polymerization, or during the polymerization described later, or may be added in a plurality of times.

(8) Pre-process In the PAS production method of the present invention, the sulfiding agent is usually used in the form of a hydrate, but a dihalogenated aromatic compound or a monohalogenated aromatic compound having a reactive functional group is added. It is preferable to raise the temperature of the mixture containing the organic polar solvent and the sulfidizing agent before removing the excess water out of the system. In addition, when water is removed excessively by this operation, it is preferable to add and replenish the deficient water.

  Further, as described above, an alkali metal sulfide prepared from an alkali metal hydrosulfide and an alkali metal hydroxide in situ in the reaction system or in a tank different from the polymerization tank is also used as the sulfidizing agent. be able to. Although there is no particular limitation on this method, desirably, an alkali metal hydrosulfide and an alkali metal hydroxide are added to the organic polar solvent in an inert gas atmosphere at a temperature ranging from room temperature to 150 ° C., preferably from room temperature to 100 ° C. In addition, a method of raising the temperature to at least 150 ° C. or more, preferably 180 ° C. to 260 ° C. under normal pressure or reduced pressure, and distilling off the water can be mentioned. A polymerization aid may be added at this stage. Moreover, in order to accelerate | stimulate distillation of a water | moisture content, you may react by adding toluene etc.

  The amount of water in the system at the stage where the pre-process is completed is preferably 90 to 110 mol per 100 mol of the charged sulfidizing agent. Here, the amount of water in the system is an amount obtained by subtracting the amount of water removed from the system from the amount of water charged in the previous step. In addition, the water to be charged may be in any form such as water, an aqueous solution, and crystal water.

  After completion of the previous step, the reaction product prepared in the previous step is brought into contact with the dihalogenated aromatic compound and the monohalogenated aromatic compound having a reactive functional group in an organic polar solvent. The polymerization reaction step described later may be performed in the same reactor as the step, or the polymerization reaction step may be performed after the reactant prepared in the previous step is transferred to a reaction vessel different from the previous step.

(9) Polymerization reaction step In order to obtain a PAS having a high melt fluidity and a low volatile component amount and a low chlorine content, and having a high reactivity and excellent mechanical strength, It is necessary to go through the polymerization step. The polymerization step is a reaction of a sulfidizing agent with a predetermined amount of a dihalogenated aromatic compound and a monohalogenated aromatic compound having a reactive functional group in an organic polar solvent within a temperature range of 200 ° C. or higher and lower than 280 ° C. Let's get a PAS
<Step 1> Within a temperature range of 230 ° C. or more and less than 245 ° C., the polymerization time (T1a) including the temperature rising / falling time is 30 minutes or more and less than 3.5 hours, and the dihalogenated aromatic compound at the end of the step A step of producing a prepolymer of PAS by reacting such that the conversion is 70 to 98 mol%, and <Step 2> in a temperature range from 245 ° C. to less than 280 ° C. A step of reacting T2) for 5 minutes to less than 1 hour to obtain PAS;
That is. By passing through this step, the PAS of the present invention can be efficiently obtained in a short time.

  Hereinafter, Step 1 and Step 2 will be described in detail.

  <Step 1> In the present invention, in an organic polar solvent, when a sulfidizing agent, a dihalogenated aromatic compound and a monohalogenated aromatic compound having a functional group are polymerized in a temperature range of 200 ° C. or higher and lower than 280 ° C., It is necessary to perform step 1 in which the polymerization time (T1a) including the temperature raising and lowering time is 30 minutes or more and less than 3.5 hours within a temperature range of 230 ° C. or more and less than 245 ° C. In order to obtain a PAS having a small amount of volatile components at the time of melting according to the present invention, it is preferable to carry out step 2 after sufficiently increasing the conversion rate of the dihalogenated aromatic compound at a low temperature, but the polymerization temperature is less than 230 ° C. In the reaction, since the reaction rate is slow, the conversion rate of the dihalogenated aromatic compound is hardly increased, and the melt viscosity of PAS obtained through Step 2 is too low, and the melt fluidity suitable for injection molding tends not to be obtained. In addition, a long reaction time is required to increase the conversion rate of the dihalogenated aromatic compound by a reaction of less than 230 ° C., which is not preferable in terms of production efficiency. Therefore, in a temperature range of 230 ° C. or higher and lower than 245 ° C. where the reaction rate is relatively high, it is 30 minutes or longer and shorter than 3.5 hours, preferably 40 minutes or longer and shorter than 3.5 hours, more preferably 1 hour or longer and shorter than 3 hours, even more preferable. It is preferable to carry out the reaction for 1.5 hours or more and less than 3 hours. In the present invention, since the conversion rate of the dihalogenated aromatic compound is increased in a temperature range of 230 ° C. or higher and lower than 245 ° C., which has a relatively high reaction rate, the production efficiency is reduced by shortening the polymerization time in the temperature range of less than 230 ° C. The polymerization time in the temperature range of 200 ° C. or more and less than 230 ° C. is preferably within 2 hours, and more preferably within 1 hour can be exemplified. Furthermore, the polymerization time (T1) including the temperature increase / decrease time within the temperature range of 200 ° C. or more and less than 245 ° C. including Step 1 is preferably 1.5 hours or more and less than 4 hours, and 1.5 hours or more and 3 Less than 5 hours is more preferable, and 2 hours or more and 3.5 hours or less is more preferable. When T1 is less than 1.5 hours, the conversion rate of the dihalogenated aromatic compound described later is too low, so that the unreacted sulfiding agent causes decomposition of the prepolymer in Step 2, and the obtained PAS is heated and melted. Volatile components tend to increase. Moreover, when T1 exceeds 4 hours, it will lead to a reduction in production efficiency.

The average rate of temperature increase within the polymerization temperature range is preferably 0.1 ° C./min or more. The average rate of temperature increase is the time m required to raise the temperature section (provided that t2 <t1) from a certain temperature t2 (° C.) to a certain temperature t1 (° C.). From (minutes), the following average heating rate (° C./minute)=[t1 (° C.) − T2 (° C.)] / M (minutes)
Is the average speed calculated by Therefore, if it is within the range of the above average heating rate, it is not always necessary to have a constant rate, there may be a constant temperature section, and there is no problem even if the temperature is raised in multiple stages, and the essence of the present invention is impaired. As long as there is not, there may be a section which becomes a negative temperature rising rate temporarily.

  The average temperature rising rate is preferably 2.0 ° C./min or less, and more preferably 1.5 ° C./min or less. If the average heating rate is too high, it may be difficult to control the reaction, and more energy tends to be required to raise the temperature. When a vigorous reaction occurs at the initial stage of the reaction, it is preferable to carry out the reaction by a method in which the reaction is carried out to some extent at 240 ° C. or lower and then heated to a temperature exceeding 240 ° C.

In the present invention, it is necessary to react so that the conversion rate of the dihalogenated aromatic compound at the end of Step 1 is 70 to 98 mol% to form a PAS prepolymer, preferably 75 mol% or more, The reaction is more preferably performed at 80 mol% or more, more preferably 90 mol% or more. When the process proceeds to step 2 with such a low conversion rate, the unreacted sulfidizing agent causes decomposition of the prepolymer, and the amount of volatile components tends to increase when the obtained PAS is heated and melted. In addition, if the reaction is carried out until the conversion rate in Step 1 exceeds 98 mol%, a long polymerization time is required, leading to a decrease in production efficiency, and at the same time, a PAS having a high melt fluidity according to the present invention can be obtained. Absent. The conversion rate of the dihalogenated aromatic compound (hereinafter abbreviated as DHA) is a value calculated by the following formula. The remaining amount of DHA can be usually determined by gas chromatography.
(A) When dihalogenated aromatic compound is added excessively in a molar ratio with respect to the sulfidizing agent, conversion rate = [[DHA charge (mol) -DHA remaining amount (mol)] / [DHA charge (mol)- DHA excess (mole)]] × 100%
(B) In cases other than (a) above, conversion rate = [[DHA charge (mol) −DHA remaining amount (mol)] / [DHA charge (mol)]] × 100%.

  <Step 2> In the present invention, a sulfidizing agent, a dihalogenated aromatic compound and a monohalogenated aromatic compound having a reactive functional group are polymerized in an organic polar solvent in a temperature range of 200 ° C. or higher and lower than 280 ° C. At the same time, it is necessary to carry out the step 2 of obtaining the PAS by reacting the polymerization time (T2) including the temperature rising / falling time within 5 minutes to less than 1 hour within the temperature range of 245 ° C. or more and less than 280 ° C. It is. The final temperature in step 2 is preferably 275 ° C. or lower, and more preferably 270 ° C. or lower. If the polymerization is terminated only in step 1 without passing through step 2, or if the polymerization time in step 2 is extremely short, the melt viscosity of PAS tends to be too low and the strength of the molded product tends to decrease, which is suitable for injection molding. PAS having high melt fluidity cannot be obtained, and the reaction rate of monohalogenated aromatic compounds having a reactive functional group is reduced, so the effect of reducing the amount of terminal chlorine in PAS is small, and the reactivity of PAS Will be insufficient. Further, when the flash method is used in the polymer recovery step described later, since the flash energy becomes small when the temperature of the polymer is low, there is a problem that the heat of vaporization of the polymerization solvent is reduced and the flash recovery cannot be efficiently performed. When the final temperature of Step 2 reaches 280 ° C. or higher, the melt viscosity of PAS becomes too high and the internal pressure of the reactor tends to increase, which may require a reactor with high pressure resistance. It is not preferable in terms of economy and safety. Further, as the polymerization temperature increases, the reactive functional group introduced into the PAS is thermally decomposed, and the reactivity with the coupling agent or the like tends to decrease.

  The polymerization time (T2) of step 2 in the present invention needs to be 5 minutes or more and less than 1 hour, preferably 10 minutes or more and less than 40 minutes, and preferably 10 minutes or more and less than 30 minutes. Even more preferable. When a sulfiding agent, a dihalogenated aromatic compound and a monohalogenated aromatic compound having a reactive functional group are reacted in the presence of an alkali metal hydroxide in an organic polar solvent, an organic polar solvent such as NMP and an alkali metal water are reacted. The alkali metal alkylaminoalkylcarboxylate produced by the reaction with the oxide contributes as a side reaction during the polymerization reaction. If the polymerization time (T2) in step 2 is 1 hour or longer, the side reaction proceeds. Remarkably, when the obtained PAS is melted and heated, the amount of volatile components derived from by-products tends to increase. In addition, a long polymerization time causes problems such as a decrease in production efficiency and an increase in the melt viscosity of PAS. At the same time, a reactive functional group introduced into PAS is thermally decomposed to reduce the reactivity with a coupling agent and the like. There is a tendency. In addition, the main chain of PAS is decomposed by heat, and the mechanical strength is reduced accordingly.

  The reaction in step 2 may be a one-step reaction performed at a constant temperature, a multi-step reaction in which the temperature is raised stepwise, or a reaction in which the temperature is continuously changed.

  In order to obtain a PAS having a high melt fluidity, a small amount of volatile components, a small chlorine content, and a high reactivity according to the present invention, the polymerization time in step 1 (T1a) and the polymerization time in step 2 (T2) The ratio (T1a / T2) is preferably 0.5 or more. The higher the ratio, the more sufficient the polymerization time in Step 1 and the higher the conversion rate of the dihalogenated aromatic compound and the monohalogenated aromatic compound having a reactive functional group. At the same time, the polymerization time in Step 2 In a short time, high melt fluidity, a small amount of volatile components, and a small chlorine content can be secured. Moreover, since thermal decomposition of the reactive functional group introduce | transduced into PAS can also be suppressed by suppressing reaction at high temperature like process 2 for a short time, high reactivity can be expressed. Therefore, T1a / T2 is more preferably 1 or more, more preferably 2 or more, and even more preferably 5 or more. The upper limit of T1a / T2 is not particularly limited, but is preferably 25 or less, more preferably 20 or less, in order to obtain a PAS having preferable melt fluidity.

  In addition, it is preferable that the ratio (T1 / T2) of the polymerization time (T1) in the temperature range including Step 1 to 200 ° C. or more and less than 245 ° C. to the polymerization time (T2) in Step 2 is 1.2 or more. The higher the ratio, the more sufficient the polymerization time at a low temperature and the higher the conversion rate of the dihalogenated aromatic compound or the monohalogenated aromatic compound having a reactive functional group, and at the same time, the polymerization time in step 2 In a short time, high melt fluidity, a small amount of volatile components, a small chlorine content, and high reactivity can be secured. Therefore, T1 / T2 is more preferably 3 or more, and even more preferably 5 or more. The upper limit of T1 / T2 is not particularly limited, but is preferably 30 or less, more preferably 25 or less, in order to obtain a PAS having preferable melt fluidity.

  Furthermore, in order to obtain the PAS of the present invention, the total reaction time (T1 + T2) from the start of step 1 to the end of step 2 is preferably less than 5 hours, more preferably less than 4 hours, and 3.5 hours. It is more preferable to make it less than. Prolonging the polymerization time leads to a decrease in production efficiency, and also tends to cause an increase in the amount of volatile components at the time of melting, a deterioration in melt fluidity, and a decrease in reactivity due to thermal decomposition of reactive end groups.

  For the polymerization of the present invention, known polymerization methods such as a batch method and a continuous method can be employed. Further, the atmosphere during polymerization is preferably a non-oxidizing atmosphere, preferably carried out in an inert gas atmosphere such as nitrogen, helium, and argon, and nitrogen is particularly preferred from the viewpoint of economy and ease of handling. . The reaction pressure is not particularly limited because it cannot be defined unconditionally depending on the type and amount of the raw material and solvent used, or the reaction temperature.

  In order to further reduce the amount of volatile components of PAS, it is preferable to perform at least a part of the entire polymerization step in the presence of the polymerization aid described above. There is no particular limitation on the timing of addition of the polymerization aid, but it may be added at any time before the start of the previous step, at the start of step 1, during the step 1, at the start of step 2, or during the step 2, Further, although it may be added in a plurality of times, it is possible to further reduce the amount of volatile components of PAS by performing at least step 2 in the presence of a polymerization aid. The polymerization aid may be added in any form, such as an anhydride, hydrate, aqueous solution or mixture with an organic polar solvent. However, when the polymerization aid to be added contains water and at the start of step 2 Or when adding in the middle of the process 2, the water content in the reaction system at the stage where the addition of the polymerization aid has been completed is 80 to 300 mol, more preferably 85 to 180 mol, relative to 100 mol of the sulfidizing agent. preferable.

  The amount of the monohalogenated aromatic compound having a reactive functional group introduced into the PAS at the stage of completing the polymerization reaction step is, for example, a functional group direct analysis in solid NMR, an absorption derived from a benzene ring in FT-IR. Can be evaluated by a relative amount by comparing absorption derived from the functional group and a reaction amount calculated by subtracting the residual amount from the charged amount of the reactive functional group-containing monohalogenated aromatic compound before or during the polymerization. .

  The reaction amount of the monohalogenated aromatic compound having a reactive functional group is preferably 0.1 mol or more and less than 20 mol, more preferably 1.0 mol or more and less than 6 mol, more preferably 1.5 mol per 100 mol of sulfidation. More preferably less than 5 mol. The reaction amount in the present invention is the amount of the reactive functional group-containing monohalogenated aromatic compound remaining in the sample sampled after the completion of the polymerization step, and quantitatively determined with a gas chromatograph (GC-14B, manufactured by Shimadzu Corporation). Or it is a value calculated by subtracting the remaining amount from the charged amount during polymerization. This means that the greater the reaction amount, the greater the amount of reactive functional groups introduced to the PAS end and the higher the reactivity. However, when the reaction amount is 20 moles or more per 100 moles of the sulfidizing agent, This results in a PAS having a high molecular weight and a high molecular weight, leading to a significant decrease in mechanical strength due to the low molecular weight. On the other hand, when the reaction amount is less than 0.1 mol, the reactivity of PAS is low, leading to a decrease in mechanical strength.

(10) Polymer Recovery In the production of the PAS of the present invention, PAS is recovered from the polymerization reaction product containing the PAS component and solvent obtained in the polymerization step after the polymerization step is completed. As a recovery method, for example, a flash method, that is, a polymerization reaction product is flashed from a high-temperature and high-pressure (normally 250 ° C. or higher, 0.8 MPa or higher) state to an atmosphere of normal pressure or reduced pressure, and the polymer is powdered simultaneously with solvent recovery. Or the quenching method, that is, the polymerization reaction product is gradually cooled from a high temperature and high pressure state to precipitate the PAS component in the reaction system, and is filtered off at a temperature of 70 ° C. or higher, preferably 100 ° C. or higher. Thus, a method of recovering a solid containing a PAS component can be used.

  The present invention is limited to either the quench method or the flash method as long as it has a high melt fluidity and has a low volatile component amount and a low chlorine content, and a PAS having high reactivity and excellent mechanical strength can be obtained. Although it is not, the flash method is economical because it can recover solids at the same time as the solvent recovery, the recovery time is relatively short, and the amount of recovered material is large compared to the quench method. It is an excellent recovery method, and the PAS obtained by the flash method contains a large amount of oligomer components such as the chloroform extraction component, so it has a melt flowability compared to the PAS obtained by the quench method. This is a preferred recovery method in the present invention because it is easy to obtain a high PAS. A preferable amount of chloroform extracted for obtaining high melt fluidity is 1.0% by weight or more, and more preferably 2.0% by weight or more.

  As a preferred embodiment of the flash method, a method in which the high-temperature and high-pressure polymerization reaction product obtained in the polymerization step is ejected from a nozzle into an atmosphere such as nitrogen or water vapor at normal pressure. In the flash method, the solvent can be efficiently recovered by utilizing the heat of vaporization of the solvent when the polymerization reaction product is flushed from the high temperature and high pressure state to the normal pressure state. Efficiency decreases and productivity deteriorates. Therefore, the temperature in the polymerization system when flushing, that is, the temperature of the polymerization reaction product is preferably 250 ° C. or higher, and more preferably 255 ° C. or higher. The temperature of the atmosphere such as nitrogen or water vapor when flushing under normal pressure is usually selected from 150 to 250 ° C. If the solvent recovery from the polymerization reaction product is insufficient, nitrogen or water vapor at 150 to 250 ° C. after flushing, etc. Heating may be continued under the atmosphere of

  Since the PAS obtained by such a flash method contains ionic impurities such as alkali metal halides and alkali metal organic substances, which are polymerization by-products, washing is usually performed. The cleaning conditions are not particularly limited as long as the conditions are sufficient to remove such ionic impurities. Examples of the cleaning liquid include a method of cleaning using water or an organic solvent, and water is used in terms of obtaining PAS simply and inexpensively, and by adding an oligomer component in PAS to provide high melt fluidity. Washing can be exemplified as a preferred method. In order to obtain a PAS having a low volatile component and a low chlorine content according to the present invention, the temperature of water is preferably 80 ° C. or higher, and hot water, an acid or acid aqueous solution, an alkali metal salt or an alkaline earth is preferred. The treatment of immersing in any liquid of an aqueous solution of a metal salt is preferably performed once or more.

  Furthermore, it is preferable to perform the dipping treatment at a temperature of 80 ° C. or more twice or more, and the first dipping treatment is performed in any one of hot water, an alkali metal salt or an alkaline earth metal salt solution. It is preferable. Of course, when performing the process of immersing twice or more, the cleaning temperature in each process may be different, and it is also possible to use a combination of processes immersed in two or more different liquids. It is more preferable to pass a filtration step for separating the polymer and the cleaning liquid between them.

  In the treatment of immersing PAS in an acid or an acid aqueous solution, the pH of the treated liquid is preferably 2 to 8. An acid or an aqueous solution of an acid is an acid obtained by adding an organic acid, an inorganic acid, or the like to an organic acid, an inorganic acid, or the above-described water. Examples of the organic acid and inorganic acid to be used include acetic acid, propionic acid, hydrochloric acid, sulfuric acid, phosphoric acid, formic acid and the like, but are not limited thereto, but acetic acid and hydrochloric acid are preferable.

  The amount of the alkali metal salt or alkaline earth metal salt in the aqueous solution used for the treatment of immersing the PAS in the aqueous solution of the alkali metal salt or alkaline earth metal salt is preferably 0.01 to 5% by weight relative to the PAS. 1 to 0.7% by weight is more preferable. An aqueous solution of an alkali metal salt or alkaline earth metal salt is obtained by adding an alkali metal salt, an alkaline earth metal salt, or the like to the water and dissolving it. Examples of the alkali metal salt and alkaline earth metal salt used include, but are not limited to, calcium salts, potassium salts, sodium salts and magnesium salts of the above organic acids.

  The washing temperature when washing PAS with liquid is preferably 80 ° C. or more and 200 ° C. or less, more preferably 150 ° C. or more and 200 ° C. or less, and more preferably 180 ° C. or more and 200 ° C. or less in terms of obtaining PAS with less ionic impurities. preferable. The treatment operation with a liquid of 100 ° C. or higher is usually performed by charging a predetermined amount of PAS with a predetermined amount of liquid, and heating and stirring at normal pressure or in a pressure vessel.

  The water used for the hot water, the acid aqueous solution, the alkali metal salt or alkaline earth metal salt aqueous solution is preferably distilled water or deionized water. The ratio of PAS and liquid is preferably higher in liquid, and usually a bath ratio of 10 to 500 g of PAS is preferably selected with respect to 1 liter of liquid, and more preferably 50 to 200 g.

  As long as a PAS excellent in melt fluidity according to the present invention can be obtained, any cleaning additive may be used. However, when treated with an acid, higher melt fluidity is obtained, and at the same time, the obtained PAS is converted to 550 ° C. Since the ash content when ashing is low and the characteristics of exhibiting excellent performance in applications requiring electrical insulation are exhibited, it can be exemplified as a suitable method. From the viewpoint of electrical insulation, the ash content is preferably 0.5% by weight or less, and more preferably 0.3% by weight or less.

  The cleaning additive may be used at any stage of the cleaning process. However, in order to efficiently perform the cleaning with a small amount of additive, the solid collected by the flash method is heated to 80 ° C. or higher and 200 ° C. or lower. A method in which the PAS is immersed in an acid or an aqueous solution of acid at 150 ° C. or higher after the treatment of immersing and filtering several times is preferably performed.

(11) Other post-treatments The PAS thus obtained is dried under normal pressure and / or under reduced pressure. The drying temperature is preferably in the range of 120 to 280 ° C, more preferably in the range of 140 to 250 ° C. The drying atmosphere may be an inert atmosphere such as nitrogen, helium or reduced pressure, an oxidizing atmosphere such as oxygen or air, or a mixed atmosphere of air and nitrogen, but an inert atmosphere is preferred from the viewpoint of melt viscosity. The drying time is preferably 0.5 to 50 hours, preferably 1 to 30 hours, and more preferably 1 to 20 hours.

  The PAS obtained in the present invention can be treated at a temperature of 130 to 260 ° C. in an oxygen-containing atmosphere in order to remove volatile components or to adjust to a preferred melt viscosity by increasing the cross-linking molecular weight. It is.

  When dry heat treatment is performed for the purpose of suppressing cross-linking high molecular weight and removing volatile components, the heat treatment may be performed in a high oxygen concentration atmosphere or a low oxygen concentration atmosphere as long as the heat treatment temperature and heat treatment time are within a specific range. .

  As conditions for a high oxygen concentration atmosphere, the oxygen concentration is preferably 2% by volume or more, the heat treatment temperature is preferably 160 to 270 ° C., and the heat treatment time is preferably 0.1 to 20 hours. However, although the reduction rate of the volatile component is fast under the condition where the oxygen concentration is high, the melt flowability tends to decrease because the oxidative crosslinking proceeds at the same time. Therefore, it is generally preferable to perform the heat treatment at a low temperature / long time or at a high temperature / short time. Specific conditions for the heat treatment at low temperature and long time are preferably 160 ° C. or higher and 210 ° C. or lower and 1 hour or longer and 20 hours or shorter, more preferably 170 ° C. or higher and 200 ° C. or lower and 1 hour or longer and 10 hours or shorter. When the heat treatment is performed at a temperature lower than 160 ° C., the effect of reducing volatile components is small. Even at low temperatures, when the heat treatment time exceeds 20 hours under conditions where the oxygen concentration is 2% by volume or more, the melt fluidity tends to decrease. Specific conditions for the high temperature and short time heat treatment are preferably higher than 210 ° C. and lower than 270 ° C. for 0.1 hour or longer and shorter than 1 hour, more preferably 220 ° C. or higher and 260 ° C. or lower for 0.2 to 0.8 hours. When the heat treatment temperature exceeds 270 ° C., the oxidative crosslinking proceeds rapidly and the melt fluidity tends to decrease. Moreover, even if the temperature is high, the effect of reducing volatile components is small when the heat treatment time is less than 0.1 hour under the condition where the oxygen concentration is 2% by volume or more.

  As conditions for the low oxygen concentration atmosphere, the oxygen concentration is preferably less than 2% by volume, the heat treatment temperature is preferably 210 to 270 ° C., and the heat treatment time is preferably 0.2 to 50 hours. Since the reduction effect of volatile components tends to decrease when the oxygen concentration is low, it is generally preferable to perform the heat treatment at a high temperature for a long time, and more preferably for 2 to 20 hours under a heat treatment temperature condition of 220 ° C. to 260 ° C. . When the heat treatment time is less than 210 ° C., volatile components are difficult to reduce, and when the heat treatment time exceeds 50 hours, the productivity is lowered.

  When dry-type heat treatment is performed for the purpose of adjusting to a high melt viscosity by crosslinking, the temperature is preferably from 160 to 260 ° C, more preferably from 170 to 250 ° C. Further, it is desirable that the oxygen concentration is 2% by volume or more, more preferably 8% by volume or more. The treatment time is preferably 1 to 100 hours, more preferably 2 to 50 hours, and even more preferably 3 to 25 hours.

  The heat treatment apparatus may be a normal hot air dryer or a heating apparatus with a rotary type or a stirring blade. However, for efficient and more uniform processing, a heating apparatus with a rotary type or a stirring blade is used. More preferably it is used.

  In developing the PAS obtained by the present invention into various uses described later, the design is an important factor. In order to provide high designability, the PAS should have a high whiteness, and the L value indicating the high whiteness is preferably 80 or more, more preferably 83 or more. Usually, when heat treatment is performed in the post-treatment of PAS, there is a tendency to color due to heat history or oxidative crosslinking. Therefore, when post-treatment is performed, it is preferably performed within a range in which such whiteness can be maintained.

(12) Generated PAS
According to the present invention, it is possible to obtain a PAS which has a high melt fluidity and has a small amount of volatile components and a small chlorine content, and which has high reactivity and excellent mechanical strength. By obtaining the PAS of the present invention, it is possible to drastically improve mold contamination and mold vent clogging that lead to deterioration of production efficiency, and it is possible to cope with complicated shaped injection molded products that require high melt fluidity. Further, the adhesiveness and adhesion between the PAS and the filler in the resin composition in which the amount of the inorganic filler is increased to improve the heat resistance and dimensional stability can be improved, and the environmental load is reduced. That is, it is possible to achieve both a reduction in environmental load and good physical properties that could not be achieved in the past.

The amount of the volatile component of the PAS obtained in the present invention is the amount of the component that volatilizes when heated and melted at 320 ° C. for 2 hours under vacuum, preferably 1.0% by weight or less, more preferably 0.1% by weight. % To 0.9% by weight. Higher melt fluidity of PAS is preferable, but too high, that is, too low polymerization degree leads to deterioration of mechanical properties. Therefore, PAS having high melt fluidity has a melt viscosity of 2 Pa · s or more and less than 100 Pa · s, preferably 3 Pa · s or more and less than 60 Pa · s, more preferably 4 Pa · s or more and less than 20 Pa · s, More preferably, it is 4 Pa · s or more and less than 8 Pa · s. PAS of less than 2 Pa · s leads to a significant decrease in mechanical properties. The preferable chlorine content in the present invention is 3500 ppm or less, and more preferably 3300 ppm or less. The preferable reactivity in the present invention is that the ratio (MV2 / MV1) of the melt viscosity (MV2) after the coupling agent reaction to the melt viscosity (MV1) before the reaction with the coupling agent is 3.5 or more and less than 25. , Preferably 3.5 or more and less than 10. If the PAS reactivity is too low, the mechanical strength of the resin obtained by reacting with a reactive substance such as a coupling agent will decrease, while if the PAS reactivity is too high, the resin obtained after the reaction will melt. The fluidity is remarkably lowered, and troubles such as short shots are likely to occur in molding of a complicated shape. Coupling agent used is Ru et Po silane coupling agent der.

  The amount of the volatile component means the amount of the adhering component in which the component that volatilizes when the PAS is heated and melted under vacuum is cooled and liquefied or solidified. It is measured by heating in a tubular furnace. As the shape of the glass ampule, the abdomen is 100 mm × 25 mm, the neck is 255 mm × 12 mm, and the wall thickness is 1 mm. As a specific measurement method, only the body of a glass ampoule in which PAS is vacuum-sealed is inserted into a 320 ° C. tubular furnace and heated for 2 hours, so that a volatile gas is generated at the neck of the ampoule not heated by the tubular furnace. Is cooled and adheres. After the neck is cut out and weighed, the attached volatile components are dissolved in chloroform and removed. The neck is then dried and weighed again. The amount of volatile components is determined from the weight difference between the ampoule necks before and after removing the volatile components, and is calculated as a percentage of the weight of PAS used for the measurement.

The melt viscosity means a melt viscosity detected when a specific shear rate is applied to a PAS melted at a specific temperature. Specifically, the pore length is 10.00 mm, the hole diameter is 0.00. The melt viscosity is detected when a capillary rheometer equipped with a 50 mm die is used, PAS is put into a cylinder set at 300 ° C., held for 5 minutes, and then measured at a shear rate of 1216 sec ⁻¹ .

  The above-mentioned reactivity means the melt viscosity (MV2) after the coupling agent reaction with respect to the melt viscosity (MV1) before the reaction when 0.5 parts by weight of the epoxysilane coupling agent is added to 100 parts by weight of PAS and reacted. ) Ratio (MV2 / MV1), and a larger MV2 / MV1 means a higher viscosity due to the reaction with the coupling agent and a higher reactivity PAS.

(13) Applications The PAS obtained according to the present invention is excellent in heat resistance, chemical resistance, flame retardancy, electrical properties and mechanical properties, and is used not only for injection molding, injection compression molding and blow molding, but also for extrusion molding. Can be formed into extruded products such as sheets, films, fibers and pipes, but is particularly suitable for injection molding applications. As its injection molding applications, for example, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, optical pickups, oscillators, various terminal boards, transformers, plugs, printed boards, Electric / electronic parts such as tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer-related parts, VTR parts , TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio equipment parts such as audio / compact discs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts Home, office electrical product parts represented by word processor parts, etc .; office computer-related parts, telephone-related parts, facsimile-related parts, copier-related parts, cleaning jigs, motor parts, lighters, typewriters, etc. Machine-related parts: Optical instruments such as microscopes, binoculars, cameras, watches, precision machine-related parts; water taps, mixing faucets, pump parts, pipe joints, water flow control valves, relief valves, hot water temperature sensors, water flow Water-related parts such as sensors and water meter housings; valve alternator terminals, alternator connectors, IC regulators, light dimmer potentiometer bases, various valves such as exhaust gas valves, fuel-related / exhaust / intake system pipes, air intake nozzles snorkel For intake manifold, fuel pump, engine coolant joint, carburetor main body, carburetor spacer, exhaust gas sensor, coolant sensor, oil temperature sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake pad wear sensor, for air conditioner Thermostat base, heating hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, distributor, starter switch, starter relay, transmission wire harness, window washer nozzle, air conditioner panel switch Board, fuel-related electromagnetic valve coil, fuse connector, horn -Insulator, electrical component insulation plate, step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, solenoid bobbin, engine oil filter, ignition device case, vehicle speed sensor, cable liner, engine control unit case, engine driver unit case, Examples include condenser cases, motor insulating materials, automobile / vehicle-related parts such as hybrid car control system parts cases, and other various uses.

  Hereinafter, the method of the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. Various measurement methods are as follows.

[Melt viscosity]
A capilograph 1C manufactured by Toyo Seiki Co., Ltd. was used, and a die having a hole length of 10.00 mm and a hole diameter of 0.50 mm was used. About 20 g of the sample was put into a cylinder set at 300 ° C. and held for 5 minutes, and then the melt viscosity (MV1) was measured at a shear rate of 1216 sec ⁻¹ .

[Amount of volatile components]
A sample 3 g was weighed into a glass ampoule having an abdomen of 100 mm × 25 mm, a neck of 255 mm × 12 mm, and a wall thickness of 1 mm, and then vacuum-sealed. Only the barrel of this glass ampoule was inserted into a ceramic electric tubular furnace ARF-30K manufactured by Asahi Rika Seisakusho and heated at 320 ° C. for 2 hours. After the ampoule was taken out, the ampoule neck which was not heated by the tubular furnace and was attached with volatile components was cut out with a file and weighed. Next, the adhering gas was dissolved and removed with 5 g of chloroform, dried for 1 hour in a glass dryer at 60 ° C., and then weighed again. The weight difference between the ampoule neck before and after the removal of the volatile component was defined as the amount of volatile component (% by weight based on the polymer).

[Chlorine content of polymer]
Using an automatic sample combustor AQF-100 manufactured by Dia Instruments, 1 to 2 mg of polymer is burned at a final temperature of 1000 ° C., and the generated gas component is absorbed in 10 mL of water containing a dilute oxidant, and the absorbing solution is carbonated. The total chlorine content in the polymer was measured using an ion chromatography system ICS1500 manufactured by DIONEX with a sodium / sodium hydrogen carbonate mixed aqueous solution as a mobile phase.

[Reactivity of polymer]
0.5 parts by weight of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (hereinafter abbreviated as “epoxysilane”) was added to 100 parts by weight of the polymer, and was thoroughly dry blended. Then, the blend was melted and stirred for 5 minutes in a test tube at 315 ° C., and the obtained 20 g was measured for melt viscosity under the same conditions as for the melt viscosity measurement. The reactivity of the polymer is determined by the ratio (MV2 / MV1) of the melt viscosity (MV2) of the polymer after reaction with epoxysilane to the melt viscosity (MV1) of the polymer measured without reacting with epoxysilane (MV1). evaluated. Higher ratios indicate higher polymer reactivity.

[Example 1]
In a 70 liter autoclave equipped with a stirrer and a bottom plug valve, 8.26 kg (70.00 mol) of 47.5% sodium hydrosulfide, 2.94 kg (70.63 mol) of 96% sodium hydroxide, N-methyl-2 -Charge 11.45 kg (115.50 mol) of pyrrolidone (NMP) and 5.50 kg of ion-exchanged water, gradually heat to 225 ° C. over about 3 hours while passing nitrogen at normal pressure, 9.82 kg of water and NMP0 When the 28 kg was distilled, the heating was finished and the cooling was started. The residual water content in the system per mole of the alkali metal hydrosulfide charged at this time was 1.01 moles including the water consumed for the hydrolysis of NMP. Moreover, since the amount of hydrogen sulfide scattered was 1.4 mol, the sulfiding agent in the system after this dehydration step was 68.6 mol. As the hydrogen sulfide is scattered, 1.4 mol of sodium hydroxide is newly generated in the system.

  Thereafter, the mixture was cooled to 200 ° C., p-dichlorobenzene (p-DCB) 10.19 kg (69.29 mol), 4-chlorobenzoic acid 0.188 kg (1.20 mol), NMP 9.37 kg (94.50 mol). After adding the reaction vessel, the reaction vessel was sealed under nitrogen gas, and Step 1 and Step 2 were performed under the following reaction conditions while stirring at 240 rpm.

  <Step 1> The temperature was raised from 200 ° C. to 230 ° C. at 0.8 ° C./min over 38 minutes, and subsequently from 230 ° C. to 238 ° C. was raised at 0.6 ° C./min over 13 minutes. After performing the reaction for 128 minutes at a constant temperature of 238 ° C., the temperature was raised from 238 ° C. to 245 ° C. at 0.8 ° C./min for 9 minutes. The polymerization time in Step 1 was 188 minutes for (T1) and 150 minutes for (T1a). The reaction product was sampled at the end of Step 1, and the amount of p-DCB remaining in the sample was quantified with a gas chromatograph. The consumption rate of p-DCB, that is, the conversion rate, was calculated to be 94.5%. .

  <Step 2> Subsequent to Step 1, the temperature was raised from 245 ° C. to 255 ° C. at 0.8 ° C./min over 12 minutes. The polymerization time (T2) in Step 2 was 12 minutes. When the reaction product was sampled at the end of step 2, the amount of 4-chlorobenzoic acid remaining in the sample was quantified with a gas chromatograph, and the reaction amount of 4-chlorobenzoic acid was calculated by subtracting the residual amount from the charged amount. The reaction amount was 1.16 mol per 100 mol of the sulfidizing agent.

  Immediately after the end of step 2, the bottom valve of the autoclave is opened, the contents are flushed to a device with a stirrer, and in a device with a stirrer at 230 ° C. until 95% or more of NMP used during polymerization is volatilized and removed. The mixture was dried for 1.5 hours to recover a solid containing PPS and salts.

  The obtained recovered product and 74 liters of ion-exchanged water were placed in an autoclave equipped with a stirrer, washed at 75 ° C. for 15 minutes, and then filtered through a filter to obtain a cake. The obtained cake was washed with ion exchange water at 75 ° C. for 15 minutes and filtered three times, and then 74 liters of cake and ion exchange water and 0.4 kg of acetic acid were placed in an autoclave equipped with a stirrer, and the inside of the autoclave was filled with nitrogen. After the replacement, the temperature was raised to 195 ° C. Thereafter, the autoclave was cooled and the contents were taken out. The contents were filtered through a filter to obtain a cake. The obtained cake was dried at 120 ° C. under a nitrogen stream to obtain dry PPS.

[Example 2]
Polymerization and washing were carried out in the same manner as in Example 1 except that 4-chlorobenzoic acid used in the polymerization was changed to 0.198 kg (0.89 mol) of sodium 4-chlorophthalate. The conversion rate of p-DCB at the end of Step 1 was 94.5%, and the reaction amount of sodium 4-chlorophthalate at the end of Step 2 was 1.15 mol with respect to 100 mol of the sulfidizing agent.

[Example 3]
The amount of 4-chlorobenzoic acid used in the polymerization was 0.177 kg (1.13 mol), and the same operation as in Example 1 was performed except that Steps 1 and 2 were performed under the following reaction conditions.

  <Step 1> The temperature was raised from 200 ° C. to 230 ° C. at 0.8 ° C./min over 38 minutes, and subsequently from 230 ° C. to 238 ° C. was raised at 0.6 ° C./min over 13 minutes. The reaction was performed at a constant temperature of 238 ° C. for 89 minutes, and then the temperature was increased from 238 ° C. to 245 ° C. at 0.8 ° C./min for 9 minutes. T1 was 149 minutes and T1a was 111 minutes. The conversion rate of p-DCB was 91%.

  <Step 2> Subsequent to Step 1, the temperature was raised from 245 ° C. to 270 ° C. at 0.8 ° C./min for 31 minutes. T2 was 31 minutes. The reaction amount of 4-benzoic acid was 1.15 mol with respect to 100 mol of the sulfidizing agent.

[Example 4]
Polymerization and washing were carried out in the same manner as in Example 1 except that 9.68 kg (65.86 mol) of p-DCB used at the time of polymerization and 1.074 kg (6.86 mol) of 4-chlorobenzoic acid were used. The conversion rate of p-DCB at the end of Step 1 was 89%, and the reaction amount of 4-chlorobenzoic acid at the end of Step 2 was 6.62 mol with respect to 100 mol of the sulfidizing agent.

[Comparative Example 1]
Polymerization and washing were carried out in the same manner as in Example 1 except that 4-chlorobenzoic acid was not used. The conversion rate of p-DCB at the time of completion of Step 1 was 94.5%.

[Comparative Example 2]
Polymerization and washing were performed in the same manner as in Example 1 except that 4-chlorobenzoic acid used in the polymerization was changed to 0.270 kg (2.40 mol) of chlorobenzene. The conversion rate of p-DCB at the end of Step 1 was 94.5%, and the reaction amount of chlorobenzene at the end of Step 2 was 1.11 mol with respect to 100 mol of the sulfidizing agent.

[Comparative Example 3]
Step 1 was performed under the following reaction conditions, and the same operation as in Example 1 was performed except that the flash operation was performed without performing Step 2 after Step 1 was completed. After flushing, 95% or more of NMP used at the time of polymerization was evaporated and removed in an apparatus with a stirrer at 230 ° C. for 3 hours to recover a solid containing PPS and salts.

  <Step 1> The temperature was raised from 200 ° C. to 230 ° C. at 0.8 ° C./min over 38 minutes, and subsequently from 230 ° C. to 238 ° C. was raised at 0.6 ° C./min over 13 minutes. The reaction was carried out at a constant temperature of 238 ° C. for 149 minutes. T1 was 200 minutes and T1a was 162 minutes. The conversion rate of p-DCB at the end of Step 1 was 95%, and the reaction amount of 4-chlorobenzoic acid was 1.05 mol with respect to 100 mol of the sulfidizing agent.

[Comparative Example 4]
The same operation as in Example 1 was performed except that Step 1 and Step 2 were performed under the following reaction conditions.

  <Step 1> The temperature was raised from 200 ° C to 220 ° C at 0.8 ° C / min for 25 minutes. After 131 minutes of reaction at a constant temperature of 220 ° C., the temperature was raised from 220 ° C. to 245 ° C. at 0.8 ° C./min for 31 minutes. T1 was 188 minutes and T1a was 19 minutes. The conversion rate of p-DCB was 90%.

  <Step 2> Subsequent to Step 1, the temperature was raised from 245 ° C. to 255 ° C. at 0.8 ° C./min over 12 minutes. T2 was 12 minutes. The reaction amount of 4-chlorobenzoic acid was 0.90 mol with respect to 100 mol of the sulfidizing agent.

[Comparative Example 5]
The amount of 4-chlorobenzoic acid used in the polymerization was 0.140 kg (0.89 mol), and the same operation as in Example 1 was performed except that Steps 1 and 2 were performed under the following reaction conditions.

  <Step 1> The temperature was raised from 200 ° C. to 230 ° C. at 0.8 ° C./min over 38 minutes, and subsequently from 230 ° C. to 245 ° C. was raised at 0.6 ° C./min over 25 minutes. T1 was 63 minutes and T1a was 25 minutes. The conversion rate of p-DCB was 65%.

  <Step 2> Subsequent to Step 1, the temperature was increased from 245 ° C. to 276 ° C. at 0.6 ° C./min over 52 minutes, and then reacted at a constant temperature of 276 ° C. for 65 minutes. T2 was 117 minutes. The reaction amount of 4-chlorobenzoic acid was 1.17 mol with respect to 100 mol of the sulfidizing agent.

[Comparative Example 6]
The amount of 4-chlorobenzoic acid used in the polymerization was 0.136 kg (0.87 mol), and the same operation as in Example 1 was performed except that Steps 1 and 2 were performed under the following reaction conditions.

  <Step 1> The temperature was raised from 200 ° C. to 230 ° C. at 0.8 ° C./min over 38 minutes, and subsequently from 230 ° C. to 235 ° C. was raised at 0.6 ° C./min over 8 minutes. After performing the reaction at a constant temperature of 235 ° C. for 60 minutes, the temperature was raised from 235 ° C. to 245 ° C. at 0.8 ° C./min over 13 minutes. T1 was 119 minutes and T1a was 81 minutes. The conversion rate of p-DCB was 65%.

  <Step 2> Subsequent to Step 1, the temperature was raised from 245 ° C. to 265 ° C. at 0.6 ° C./min over 25 minutes, and then reacted at a constant temperature of 265 ° C. for 120 minutes. T2 was 145 minutes. The reaction amount of 4-chlorobenzoic acid was 1.20 mol with respect to 100 mol of the sulfidizing agent.

  Table 1 shows the melt viscosity, volatile component amount, chlorine content, and polymer reactivity measurement results of the obtained PAS.

  In Example 1 and Example 3, the polymerization time (T2) in the comparative example 5 and the comparative example 6 comparison step 2 is significantly short, and the side reaction is suppressed by the short polymerization time at high temperature. Therefore, the gas is low while maintaining the melt viscosity equivalent to that of Comparative Example 5. In addition, although Examples 1, 3 and 5 and 6 have almost the same amount of 4-chlorobenzoic acid reacted at the time of polymerization, the reactivity of PAS is Example 1 and Example 3. It can be considered that the thermal decomposition of the reactive functional group introduced into the PAS was suppressed. In Example 2, the reactivity of the polymer is further improved by using a monohalogenated aromatic compound containing two reactive functional groups. In Example 4, the amount of reacted 4-chlorobenzoic acid is large, and the reactivity is remarkably improved. On the other hand, since Comparative Example 1 does not use a monohalogenated aromatic compound having a reactive functional group, the reactivity of PAS compared to Example 1 is low and the amount of chlorine is large. Since Comparative Example 2 uses chlorobenzene having no reactive functional group, although the amount of chlorine is reduced to the same level as in Example 1, the reactivity of PAS is low. Comparative Example 3 does not perform Step 2 which is polymerization at a high temperature, and Comparative Example 4 has a short polymerization time in the polymerization time (T1a) of 230 ° C. or more and less than 245 ° C. in Step 1, and the reaction proceeds slowly. Since the polymerization time at a temperature of not lower than 230 ° C. and longer than 230 ° C. is long, the polymerization does not proceed and the melt viscosity is significantly low.

  As described above, by reacting a monohalogenated aromatic compound having a reactive functional group under specific polymerization conditions, it has a low amount of chlorine and a high reactivity while having a high melt fluidity and a small amount of volatile components. It turns out that PAS which has can be obtained.

Claims (10)

In an organic polar solvent, a sulfidizing agent, a dihalogenated aromatic compound, and a monohalogenated aromatic compound having a reactive functional group represented by the following formula (A) within a temperature range of 200 ° C. or higher and lower than 280 ° C. are alkali metals. In the method for producing polyarylene sulfide to be reacted in the presence of a hydroxide, at least the following steps 1 and 2 are performed.
Step 1: In a temperature range of 230 ° C. or higher and lower than 245 ° C., the polymerization time (T1a) including the temperature rise / fall time is 30 minutes or longer and less than 3.5 hours, and the conversion rate of the dihalogenated aromatic compound at the end of the step Is a process in which a polyarylene sulfide prepolymer is produced by reacting so as to be 70 to 98 mol%. In a temperature range of 245 ° C. or more and less than 280 ° C., a polymerization time (T2) including a temperature increase / decrease time is A step of reacting in 5 minutes or more and less than 1 hour to obtain polyarylene sulfide.

(X is a halogen group. At least one of R1 to R9 is amino group, amide group, acetamide group, sulfonamide group, sulfonic acid group, carboxyl group, hydroxyl group, thiol group, cyano group, isocyanate group, aldehyde group, acetyl group. A functional group selected from a group, an anhydride group, an epoxy group, a silanol group, an alkoxysilane group, or a derivative thereof, and when two or more of these functional groups are contained, they may be the same or different. A linking group selected from oxygen, carbonyl, amide, ester, sulfonyl and sulfoxide, n is an integer of 0 to 10.) 2. The poly of claim 1, wherein a ratio (T1a / T2) of a polymerization time (T1a) of 230 ° C. to less than 245 ° C. in the step 1 and a polymerization time (T2) of the step 2 is 0.5 or more. A process for producing arylene sulfide. The polymerization time (T1) including a temperature rising and falling time in a temperature range of 200 ° C. or more and less than 245 ° C. including the step 1 is 1.5 hours or more and less than 4 hours. A method for producing polyarylene sulfide. 4. The polyarylene sulfide according to claim 3, wherein a ratio (T1 / T2) of the polymerization time (T1) between 200 ° C. and less than 245 ° C. and the polymerization time (T2) in step 2 is 1.2 or more. Production method. The polyarylene according to any one of claims 1 to 4, wherein the reaction amount of the monohalogenated aromatic compound having a reactive functional group is 0.1 mol or more and less than 20 mol with respect to 100 mol of the sulfidizing agent. A method for producing sulfide. The polyarylene according to any one of claims 1 to 4, wherein the reaction amount of the monohalogenated aromatic compound having a reactive functional group is 1.0 mol or more and less than 6 mol with respect to 100 mol of the sulfidizing agent. A method for producing sulfide. The method for producing a polyarylene sulfide according to any one of claims 1 to 6, wherein the dihalogenated aromatic compound contains a dihalogenated aromatic compound having a reactive functional group. The method for producing polyarylene sulfide according to any one of claims 1 to 7, wherein the polyarylene sulfide is recovered by a flash method. The amount of volatile components that volatilizes when heated and melted under vacuum at 320 ° C. for 2 hours is 1.0% by weight or less, and the melt viscosity (measured at a temperature of 300 ° C. and a shear rate of 1216 sec ⁻¹ ) is 2 Pa · s or more and less than 100 Pa · s. The chlorine content is less than 3500 ppm, and 0.5 parts by weight of an epoxy silane coupling agent is added to 100 parts by weight of polyarylene sulfide , and melted and stirred in a test tube at 315 ° C. for 5 minutes. of 20g was charged into a cylinder set at 300 ° C., was maintained 5 minutes, when measured at a shear rate of 1216 sec ^-1, epoxysilane coupling to the melt viscosity prior to reaction with the epoxy silane coupling agent (MV1) Polyarylene characterized in that the ratio (MV2 / MV1) of melt viscosity (MV2) after agent reaction is 3.5 or more and less than 25 Fido. The polyarylene sulfide according to claim 9, wherein the amount of chloroform extracted is 1.0% by weight or more.