TW201736444A - Polyarylene sulfide resin and method for producing same - Google Patents

Abstract

Disclosed is a polyarylene sulfide resin having a main chain including a structural unit represented by general formula (1.1). No absorption peak derived from the S=O stretching vibration of a sulfonyl group is observed in the infrared absorption spectrum of the polyarylene sulfide resin. In general formula (1.1), Ar1 and Ar2b each independently represent an optionally substituted arylene group, and the two Ar1 may be the same or different.

Description

Polyarylene sulfide resin and method of producing the same

The present invention relates to a polyarylene sulfide resin having a biphenyl skeleton having a biphenyl skeleton or the like and a method for producing the same. Further, the present invention relates to a compound which can be used to produce the polyarylene sulfide resin and a method for producing the same.

A polyarylene sulfide resin (hereinafter abbreviated as "PAS resin"), which is a polyphenylene sulfide resin (hereinafter referred to as "PPS resin"), is excellent in heat resistance and chemical resistance, and is widely used in electrical and electronic parts. , automotive parts, water heater parts, fiber, film applications, etc.

Conventionally, a polyphenylene sulfide resin is produced, for example, by p-dichlorobenzene, sodium sulfide, or sodium hydrosulfide, and sodium hydroxide as a raw material, and is subjected to solution polymerization in a polymerization reaction in an organic polar solvent (for example, refer to a patent). Document 1). Polyphenylene sulfide resins currently on the market are generally produced by this method.

However, in this method, since dichlorobenzene is used in a single system, the concentration of halogen remaining in the synthesized resin tends to be high. Further, since it is necessary to carry out a polymerization reaction under a severe environment of a so-called high-temperature high-pressure ‧ strong alkali, it is necessary to use a polymerization container which is expensive and difficult to process titanium, chromium or zirconium in contact with the liquid.

Thus, a method of producing a polyarylene sulfide resin under mild polymerization conditions without using dichlorobenzene as a polymerization monomer is known. For example, Patent Document 2 discloses a solvent-soluble poly(arylsulfonium salt) as a precursor for synthesizing a polyarylene sulfide resin. Poly(aryl) salt is a homopolymerized by a hydrazine group having a sulfinyl group such as methylphenylarylene (hereinafter sometimes referred to as "monofunctional fluorene") in the presence of an acid. The method is manufactured (for example, refer to Patent Document 2 and Non-Patent Document 1).

Prior technical literature Patent literature

Patent Document 1 US Patent No. 3,354,129

Patent Document 2 Japanese Patent Laid-Open No. Hei 10-182825

Non-patent literature

Non-Patent Document 1 JOURNAL OF MACROMOLECULAR SCIENCE Part A-Pure and Applied Chemistry, Volume 40, Issue 4, p.415-423

The above-mentioned polyphenylene sulfide resin is mainly used as an engine surround part of an automobile because of its dimensional stability due to high heat resistance and crystallinity. However, in recent years, as parts have become smaller and smaller, dimensional stability has been demanded, and it has been desired to develop a resin having heat resistance and dimensional stability beyond the polyphenylene sulfide resin.

Further, in the polymerization reaction shown in Non-Patent Document 1, trifluoromethanesulfonic acid is generally used as a solvent; however, since the above-mentioned acid has strong corrosiveness, it is required to be lowered based on a safety surface and an industrial viewpoint. A method for preparing acidity in a polymerization solution.

Accordingly, an object of the present invention is to provide a polyarylene sulfide resin having crystallinity and high heat resistance which satisfies the above characteristics, and a method for producing the same.

As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention have found that the above problem can be solved by substantially eliminating sulfonyl groups from a polyarylene sulfide resin having a biphenyl skeleton having a biphenyl skeleton or the like.

That is, the present invention relates to a polyarylene sulfide resin having a main chain comprising a constituent unit represented by the following formula (1.1). In the infrared absorption spectrum of the polyarylene sulfide resin, no absorption peak derived from the sulfonyl group was observed.

In the formula, Ar ¹ and Ar ^2b each independently represent an extended aryl group which may have a substituent.

Another aspect of the present invention relates to a poly(arylsulfonium salt) having a main chain comprising a constituent unit represented by the following formula (2.1).

In the formula, Ar ¹ and Ar ^2b each independently represent an extended aryl group which may have a substituent, and R ¹ represents an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms as a substituent. An aryl group, X ^- represents an anion.

Still another aspect of the invention relates to an anthraquinone compound which is represented by the following formula (3.1).

In the formula, Ar ¹ represents an extended aryl group which may have a substituent, Ar ^2a represents an aryl group which may have a substituent, R ¹ represents an alkyl group having 1 to 10 carbon atoms, or may have an alkyl group having 1 to 10 carbon atoms. An aryl group as a substituent.

Still another aspect of the invention relates to a thioether compound represented by the following formula (4.1).

Ar ^2a -S-Ar ¹ -Ar ¹ -SR ¹ (4.1)

In the formula, Ar ¹ represents an extended aryl group which may have a substituent, Ar ^2a represents an aryl group which may have a substituent, R ¹ represents an alkyl group having 1 to 10 carbon atoms, or may have an alkyl group having 1 to 10 carbon atoms. An aryl group as a substituent.

Still another aspect of the invention relates to an anthraquinone compound which is represented by the following formula (8.1).

In the formula, Ar ¹ represents an extended aryl group which may have a substituent, R ¹ represents an alkyl group having 1 to 10 carbon atoms, or an aryl group which may have an alkyl group having 1 to 10 carbon atoms as a substituent, and Y ¹ represents Halogen ion.

Still another aspect of the present invention relates to a molded article comprising the aforementioned polyarylene sulfide resin.

According to the present invention, it is possible to provide a polyarylene sulfide resin having a high degree of freedom in designing a constituent unit and having a high melting point, and a method for producing the same. According to several forms of the method, a very high molecular weight polyarylene sulfide resin can be easily obtained.

Fig. 1 is an infrared absorption spectrum of poly(p-phenylphenylthio-p,p'-extended biphenyl sulfide) obtained in Example 5-2.

Fig. 2 is an infrared absorption spectrum of poly(p-phenylphenylthio-p,p'-extended biphenyl sulfide) obtained in Example 6.

Fig. 3 is an infrared absorption spectrum of poly(p-phenylphenylthio-p,p'-extended biphenyl sulfide) obtained in Example 7.

Fig. 4 is an infrared absorption spectrum of poly(p-phenylphenylthio-p,p'-extended biphenyl sulfide) obtained in Example 8-2.

Fig. 5 is an infrared absorption spectrum of poly(p-phenylphenylthio-p,p'-extended biphenyl sulfide) obtained in Comparative Example 1-2.

Form of implementing the invention

Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

<Polyarylene sulfide resin>

The polyarylene sulfide resin according to the embodiment is a polymer having a main chain comprising a constituent unit represented by the following formula (1.1). The main chain of the polyarylene sulfide resin can be substantially constituted only by the constituent units represented by the general formula (1.1). More specifically, the ratio of the constituent units represented by the formula (1.1) in the main chain of the polyarylene sulfide resin may be 95 to 100% by mass or 98 to 100% by mass.

In the formula, Ar ¹ and Ar ^2b each independently represent an extended aryl group which may have a substituent, and two Ar ^{1 's} may be the same or different.

The bonding form of Ar ¹ and Ar ^2b is not particularly limited, but Ar ¹ and Ar ^{2b are} preferably bonded to S and Ar ¹ at a distant position in the extended aryl group. For example, when Ar ¹ and Ar ^2b are a phenylene group, Ar ¹ and Ar ^{2b are} preferably a unit bonded in the para position (1,4-phenylene group) or a unit bonded at a meta position (1, 3-phenylene), more preferably a unit bonded by a para position. In terms of heat resistance and crystallinity of the polyarylene sulfide resin, Ar ¹ and Ar ^{2b are} preferably composed of units bonded in the para position.

Examples of the substituent which the aryl group represented by Ar ¹ or Ar ^2b may have include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, and an anthracene group. An alkyl group having 1 to 10 carbon atoms, a hydroxyl group, an amine group, a thiol group, an ester group, and a carboxyl group.

In general, in the polyarylene sulfide resin having such a main chain, a small amount of a sulfonyl group derived from an anthracene compound described later may remain, but the polyarylene sulfide resin of the present embodiment does not substantially contain Sulfonyl. According to the findings of the inventors of the present invention, a polyarylene sulfide resin having a high melting point can be obtained by substantially eliminating the sulfonyl group. The reason for this is that the proportion of the amorphous portion derived from the residual sulfonyl group is small.

In the infrared absorption spectrum of the polyarylene sulfide resin, the absorption peak derived from the S=O stretching vibration of the sulfonyl group was not observed, reflecting that the polyarylene sulfide resin substantially did not contain a sulfonyl group. The absorption peak derived from the S=O stretching vibration of the sulfonyl group is usually observed in the region of the wave number of 1170 to 1140 cm ^-1 . In the present specification, the term "absorption peak derived from the S=O stretching vibration of the sulfonyl group is not observed" means that the S=O of the sulfonyl group is not observed in the region of the wave number of 1170 to 1140 cm ^-1 . The absorption peak derived from the stretching vibration. Here, in the region where the wave number is 1170 to 1140 cm ^-1 , the maximum value of the minimum value or the flat portion is present, and the minimum value or the height of the flat portion to the maximum value, and the wave number is 1200 to 1170 cm ^{- one} of the observed absorption peak height ratio of minimum to maximum value of 0.1 or less were deemed nor peak. The measurement of the infrared absorption spectrum can be carried out, for example, by using an amorphous film prepared by heating a polyarylene sulfide resin by heating at 400 ° C on a hot plate and quenching it.

The polyarylene sulfide resin of one embodiment preferably has a weight average molecular weight of 8,000 or more, more preferably 10,000 or more. When the weight average molecular weight is in this range, the polyarylene sulfide resin can be more excellent. Heat resistance and mechanical properties. In the present specification, "weight average molecular weight" means a value measured according to gel permeation chromatography (calculated according to standard polystyrene). The measurement conditions of the gel permeation chromatography can be appropriately set within a range that does not substantially affect the measured value of the weight average molecular weight.

The glass transition temperature of the polyarylene sulfide resin of one embodiment is preferably from 70 to 200 ° C, more preferably from 80 to 180 ° C, and still more preferably from 120 to 180 ° C. The glass transition temperature of the polyarylene sulfide resin can be determined by differential scanning calorimetry (DSC).

The melting point of the polyarylene sulfide resin of one embodiment is preferably from 100 to 450 ° C, more preferably from 180 to 420 ° C, still more preferably from 280 to 400 ° C, and still preferably from 330 to 380 ° C. The melting point of the polyarylene sulfide resin can be determined by differential scanning calorimetry (DSC).

The 5% thermal decomposition temperature (T _5%d ) of the polyarylene sulfide resin of one embodiment is preferably 200 to 800 ° C, more preferably 300 to 650 ° C, and still more preferably 350 to 600 ° C. The 5% thermal decomposition temperature of the polyarylene sulfide resin means a value measured by thermogravimetric ‧ differential thermal analysis (TG-DTA).

<Method of Producing Polyarylene Sulfide Resin>

The above polyarylene sulfide resin can be produced, for example, by a method comprising the steps of: polymerizing a fluorene compound represented by the following formula (3.1) in the presence of an acid to have a pass a step of forming a poly(arylsulfonium salt) of a main chain of the unit represented by the formula (2.1);

The poly(arylene salt) is subjected to dealkylation or dearomatization to form a polyarylene sulfide resin having a main chain comprising the constituent unit represented by the above formula (1.1). The method for obtaining the fluorene compound represented by the formula (3.1) will be described later.

Ar ¹ and Ar ^2b in the equation are defined in the same manner as Ar ¹ and Ar ^2b in the formula (1.1). R ¹ represents an alkyl group having 1 to 10 carbon atoms, or an aryl group which may have an alkyl group having 1 to 10 carbon atoms as a substituent, and X ^- represents an anion. Ar ^2a represents an aryl group which may have a substituent, which is an aryl group corresponding to Ar ^2b in the formula (1.1). The aryl group represented by Ar ^2a may have the same substituent as Ar ^2b .

Examples of R ¹ include an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group or a fluorenyl group, and the like. An aryl group having a structure such as a phenyl group, a naphthyl group or a biphenyl group. The aryl group may have a methyl group number of 1 to 10 in a range of 1 to 4, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group or a fluorenyl group. The alkyl group serves as a substituent bonded to the aromatic ring.

Examples of the anion of X ⁻ include a sulfonate group, a carboxylate group, a phosphate ion, a perchloric acid ion, a hexafluorophosphate ion, and a halogen ion.

The polymerization of the fluorene compound represented by the formula (3.1) can be carried out in a reaction liquid containing an acid. The acid may be any of an organic acid or an inorganic acid. Examples of the acid include non-acid acids such as hydrochloric acid, hydrobromic acid, hydrocyanic acid, and tetrafluoroboric acid; sulfuric acid, phosphoric acid, perchloric acid, bromic acid, nitric acid, carbonic acid, boric acid, molybdic acid, and homopolymeric acid. Inorganic oxyacids such as heteropolyacids; partial or partial esters of sulfuric acid such as sodium hydrogen sulfate, sodium dihydrogen phosphate, proton residual heteropolyacid salts, monomethylsulfuric acid, trifluoromethanesulfuric acid; formic acid, acetic acid, a mono- or polycarboxylic acid such as propionic acid, butyric acid, succinic acid, benzoic acid or phthalic acid; halogen of monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, monofluoroacetic acid, difluoroacetic acid or trifluoroacetic acid a carboxylic acid; a mono- or poly-sulfonic acid of methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, benzenedisulfonic acid, etc.; a partial metal salt of a polysulfonic acid such as sodium benzenedisulfonate ; Lewis acid such as antimony pentachloride, aluminum chloride, aluminum bromide, titanium tetrachloride, tin tetrachloride, zinc chloride, copper chloride or ferric chloride. Among these acids, trifluoromethanesulfonic acid and methanesulfonic acid are preferably used from the viewpoint of reactivity, and methanesulfonic acid is more preferable from the viewpoint of easily obtaining a polyaromatic resin containing no sulfonyl group. These acids may be used alone or in combination of two or more.

The amount of the acid used in the polymerization reaction is preferably from 100 to 2,000 parts by mass, more preferably from 200 to 1,000 parts by mass, per 100 parts by mass of the ytterbium compound represented by the formula (3.1).

The polymerization of the fluorene compound represented by the formula (3.1) can also be carried out in the presence of a dehydrating agent in common with an acid. The use of a dehydrating agent can also contribute to the formation of a sulfonyl group-free polyarylene sulfide resin. Examples of the dehydrating agent include phosphoric acid anhydrides such as phosphorus oxide and phosphorus pentoxide; sulfonic acid anhydrides such as benzenesulfonic anhydride, methanesulfonic anhydride, trifluoromethanesulfonic anhydride, and p-toluenesulfonic anhydride; acetic anhydride and fluoroacetic anhydride; A carboxylic acid anhydride such as trifluoroacetic anhydride; anhydrous magnesium sulfate, zeolite, cerium oxide gel, calcium chloride. These dehydrating agents can be used separately One type or two or more types may be used in combination. In order to obtain a polyarylene sulfide resin containing no sulfonyl group, a combination of methanesulfonic acid and phosphorus pentoxide is particularly preferred.

The amount of the dehydrating agent used in the polymerization reaction is preferably from 5 to 150 parts by mass, more preferably from 30 to 100 parts by mass, per 100 parts by mass of the ytterbium compound represented by the formula (3.1).

The reaction liquid of the polymerization reaction may contain a solvent. The combination of an acid and a solvent can also contribute to the formation of a sulfonyl group-free polyarylene sulfide resin. The solvent may, for example, be an alcohol-based solvent such as methanol, ethanol, propanol or isopropanol; a ketone-based solvent such as acetone, methyl ethyl ketone or methyl isobutyl ketone; or a nitrile-based solvent such as acetonitrile; a halogen-containing solvent such as dichloromethane (chloromethylene) or chloroform; a saturated hydrocarbon solvent such as n-hexane, cyclohexane, n-heptane or cycloheptane; dimethylformamide or dimethylamine a guanamine-based solvent such as guanamine or N-methyl-2-pyrrolidone; a sulfur-containing solvent such as cyclobutyl hydrazine or DMSO; tetrahydrofuran, An ether-based solvent such as an alkane. These solvents may be used alone or in combination of two or more. When trifluoromethanesulfonic acid is used, in order to obtain a polyarylene sulfide resin containing no sulfonyl group, a combination of trifluoromethanesulfonic acid and dichloromethane or acetonitrile is preferred.

The amount of the solvent in the case where the acid and the solvent are used in the polymerization reaction is preferably 50 to 5000 parts by mass, more preferably 100 to 1000 parts by mass, per 100 parts by mass of the acid. When the amount of the solvent is within the above range, the acidity in the polymerization reaction is lowered, and the resulting polyarylene sulfide resin tends to be less likely to contain a sulfonyl group.

The reaction temperature of the polymerization reaction is preferably from -30 to 150 ° C, more preferably from 0 to 100 ° C.

The poly(arylene salt) produced by the polymerization reaction is subjected to a dealkylation or dearomatization reaction, and can be efficiently carried out in a reaction liquid containing a dealkylation agent or a dearomatization agent. Examples of dealkylating agents or de-agglomerating agents include nucleophiles and reducing agents. Examples of the nucleophilic agent include a nitrogen-containing aromatic compound, an amine compound, and a guanamine compound. Examples of the reducing agent include potassium metal, sodium metal, potassium chloride, sodium chloride, and barium. These compounds may be used alone or in combination of two or more. The amount of the deaminating agent or the de-aromatic agent may be set so as to be appropriately carried out in the reaction, and is usually set in the range of 100 to 50,000 parts by mass based on 100 parts by mass of the poly(arylene salt).

Examples of the nitrogen-containing aromatic compound include pyridine, quinoline, and aniline. Among these compounds, preferred are pyridines which are widely used compounds.

The amine compound may, for example, be a trialkylamine or ammonia.

The guanamine compound may be an aromatic guanamine compound or an aliphatic guanamine compound. The aliphatic guanamine compound is represented, for example, by the following formula (9).

In the formula (9), R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ¹¹ and R ¹³ may be bonded to each other to form a cyclic structure. Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, and a decyl group.

The aliphatic guanamine compound is more highly soluble than the aromatic guanamine compound and water, and can be easily removed by washing with water of the reaction mixture. Therefore, when an aliphatic guanamine compound is used, the residual amount of the aliphatic guanamine compound in the polyarylene sulfide resin can be more reduced than when an aromatic guanamine compound is used.

By using an aliphatic guanamine compound as a dealkylating agent or a de-aromatic agent, it is possible to suppress gas generation during resin processing, and to improve the quality of the polyarylene sulfide resin molded article and improve the working environment, and even further improve the mold. Maintenance, so it is better. Since the aliphatic guanamine compound is also excellent in solubility of the organic compound, the oligomer component of the polyarylene sulfide can be easily removed from the reaction mixture by using the aliphatic guanamine compound. As a result, the oligomer component which may be one of the causes of gas generation is removed by the aliphatic guanamine compound, whereby the quality of the obtained polyarylene sulfide resin can be multiplied.

The aliphatic guanamine compound may be selected from a primary guanamine compound such as formamide or a secondary guanamine compound such as β-indoleamine, N-methyl-2-pyrrolidone or dimethylformamide. A tertiary amide compound such as diethylformamide, dimethylacetamide or tetramethylurea. The aliphatic guanamine compound preferably contains an aliphatic tertiary sulfonamide compound in which R ¹² and R ¹³ are aliphatic groups, and a tertiary decylamine based on solubility to poly(aryl sulfonium salt) and solubility in water. Among the compounds, N-methyl-2-pyrrolidone is preferred.

The aliphatic guanamine compound can be used as a reaction solvent in addition to its function as a dealkylating agent or a deagulating agent because of its excellent solubility. As the reaction solvent, only an aliphatic guanamine compound may be used, and another solvent such as toluene may be used in combination therewith.

The reaction temperature of the dealkylation or dearomatization of the poly(arylene salt) can be appropriately adjusted so that the reaction proceeds appropriately, and for example, it can be 50 to 250 ° C or 80 to 230 ° C.

The method for producing a polyarylene sulfide resin may further comprise the step of washing the polyarylene sulfide resin formed by dealkylation or dearomatization of the poly(arylene salt) with water, a water-soluble solvent or a mixed solvent thereof. By this washing step, the residual amount of the dealkylating agent or the dearomatizing agent contained in the polyarylene sulfide resin can be more reliably reduced. This tendency is particularly remarkable when the dealkylating agent or the dearomatizing agent is an aliphatic guanamine compound.

The residual amount of the dealkylating agent or the dearomatizing agent in the polyarylene sulfide resin is preferably 1000 ppm or less based on the mass of the entire resin including the polyarylene sulfide resin and other components such as a dealkylating agent or a deaminating agent. More preferably, it is 700 ppm or less, and further preferably 100 ppm or less. When the residual amount of the dealkylating agent or the degranating agent in the resin is 1000 ppm or less, the substantial influence on the quality of the polyarylene sulfide resin can be further reduced.

The solvent used in the washing step is not particularly limited, and is preferably one which can dissolve unreacted materials. Examples of the solvent include an acidic aqueous solution such as water, hydrochloric acid, an aqueous acetic acid solution, an aqueous oxalic acid solution, or a nitric acid aqueous solution; an aromatic hydrocarbon solvent such as toluene or xylene; and an alcohol system such as methanol, ethanol, propanol or isopropanol. a solvent; a ketone solvent such as acetone, methyl ethyl ketone or methyl isobutyl ketone; a nitrile solvent such as acetonitrile; tetrahydrofuran; An ether-based solvent such as an alkane; a guanamine-based solvent such as dimethylacetamide or N-methyl-2-pyrrolidone; a halogen-containing solvent such as dichloromethane or chloroform; These solvents may be used alone or in combination of two or more. Among these solvents, water or N-methyl-2-pyrrolidone is preferred from the viewpoint of removing the reaction reagent and removing the oligomer component of the resin.

The polyarylene sulfide resin as a reaction product may be subjected to alkali treatment by contact with an aqueous solution containing a basic compound as needed. The hydroxyl group or the carboxyl group present in the molecular structure of the polyarylene sulfide resin can be converted into a metal salt by alkali treatment.

Examples of the basic compound used for the alkali treatment include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide; and sodium carbonate. ; calcium carbonate; sodium phosphate and the like.

<Method of producing an ytterbium compound represented by the formula (3.1)> (method 1)

The hydrazine compound represented by the formula (3.1) can be obtained, for example, by a method comprising the following steps: a diaryl disulfide represented by the following formula (5.1) and the following formula (6.1) a reaction of the thioether compound shown to form a thioether compound represented by the following formula (4.1); and Ar ^2a -SS-Ar ^2a (5.1)

Y ¹ -Ar ¹ -Ar ¹ -SR ¹ (6.1)

Ar ^2a -S-Ar ¹ -Ar ¹ -SR ¹ (4.1)

The step of oxidizing the thioether compound represented by the formula (4.1) to form a hydrazine compound represented by the formula (3.1).

(Method 2)

Alternatively, the sulfonium compound represented by the formula (3.1) can be obtained by a method comprising the step of oxidizing a thioether compound represented by the following formula (6.1) to give the following formula (8.1). The step of the hydrazine compound shown; and Y ¹ -Ar ¹ -Ar ¹ -SR ¹ (6.1)

The step of producing a fluorene compound represented by the formula (3.1) by reacting a fluorene compound represented by the formula (8.1) with a diaryl disulfide represented by the following formula (5.1).

Ar ^2a -SS-Ar ^2a (5.1)

In the equation, Ar ¹ , Ar ^2a , and R ¹ are defined in the same manner as in the formula (3.1). The two Ar ^2a in the formula (5.1) may be the same or different. Y ¹ represents a halogen atom. Y ¹ may be a chlorine atom, a bromine atom or an iodine atom, preferably a bromine atom.

The reaction of the diaryl disulfide represented by the formula (5.1) and the thioether compound represented by the formula (6.1) in the method 1 can be carried out in a suitable solvent. The solvent used in this reaction can be suitably selected from the above. The reaction temperature may be, for example, -100 to 100 ° C or -78 to 10 ° C.

Specific examples of the diaryl disulfide represented by the formula (5.1) include unsubstituted diaryl disulfides such as diphenyl disulfide and dinaphthyl disulfide; and bis (2-hydroxyl) groups. Substituted diaryl disulfide such as phenyl) disulfide, bis(2-aminophenyl) disulfide, bis(2-carboxyphenyl) disulfide; 2,2'-diphenyl A diaryl disulfide having a heterocyclic ring such as a thiazolyl disulfide.

The thioether compound represented by the formula (6.1) can be, for example, made by the following formula (7.1) Y ¹ -Ar ¹ -Ar ¹ -Y ² (7.1)

The aromatic compound shown is obtained by reacting a halogenated hydrocarbon represented by the formula R ¹ Y ² in the presence of sulfur. Examples of R ¹ include an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group or a fluorenyl group, and the like. An aryl group having a structure such as a phenyl group, a naphthyl group or a biphenyl group. The aryl group may have a methyl group number of 1 to 10 in a range of 1 to 4, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group or a fluorenyl group. The alkyl group serves as a substituent bonded to the aromatic ring. Y ² may be a chlorine atom, a bromine atom or an iodine atom, and a combination of R ¹ and Y ² may be appropriately selected from the above description. In the formula (7.1), Ar Ar ¹ based formula (6.1) ¹ defined in the same manner. Y ¹ and Y ² represent a halogen atom, and Y ¹ and Y ² may be the same or different from each other.

Examples of the aromatic compound represented by the formula (7.1) include 4-bromo-4'-iodobiphenyl, 4,4'-dibromobiphenyl, 4,4'-dibromobina, and 10,10. Unsubstituted aromatic compounds such as '-dibromo-9,9'-biindole; 4,4'-dibromo-2-benzidine, 4,4'-dibromo-2,2'-biphenyldiamine An aromatic compound having a substituent.

The reaction of the thioether compound represented by the formula (6.1) with a halogenated hydrocarbon can be carried out in a reaction liquid containing a solvent selected from the above-mentioned solvent.

The thioether compound represented by the formula (4.1) can be oxidized in a reaction liquid containing an oxidizing agent. The oxidizing agent is not particularly limited and may be selected, for example, from potassium permanganate, oxygen, ozone, organic peroxide, hydrogen peroxide, nitric acid, and m-chlorochloride. Peroxybenzoic acid, Oxone (registered trademark), osmium tetroxide. This reaction can be carried out in a suitably selected solvent. The reaction temperature may be appropriately set, and may be, for example, -20 to 100 ° C or 0 to 70 ° C.

The respective reactions constituting the method 2 can also be carried out in the same manner as the respective reactions constituting the method 1. For example, the oxidation reaction of the thioether compound represented by the formula (6.1) can be carried out in the presence of an oxidizing agent under the same conditions as those of the thioether compound represented by the formula (4.1).

<Polyarylene sulfide resin composition>

The polyarylene sulfide resin can be used in combination with other components as a polyarylene sulfide resin composition. As the other component, for example, an inorganic filler can be used.

Examples of the inorganic filler include powdery fillers such as carbon black, calcium carbonate, cerium oxide, and titanium oxide; plate-shaped fillers such as talc and mica; glass beads, cerium oxide beads, and glass balloons. Granular filler; fibrous filler of glass fiber, carbon fiber, ash stone fiber, etc.; and glass cullet. These inorganic fillers may be used alone or in combination of two or more. By blending an inorganic filler, a composition having high rigidity and high heat resistance stability is easily obtained. The polyarylene sulfide resin composition particularly preferably contains at least one inorganic filler selected from the group consisting of glass fibers, carbon fibers, carbon black, and calcium carbonate.

The content of the inorganic filler is preferably from 1 to 300 parts by mass, more preferably from 5 to 200 parts by mass, even more preferably from 15 to 150 parts by mass, per 100 parts by mass of the polyarylene sulfide resin. When the content of the inorganic filler is in the above range, a more excellent effect can be obtained in terms of maintaining the mechanical strength of the molded article.

The polyarylene sulfide resin composition may further contain a resin other than the polyarylene sulfide resin selected from the group consisting of a thermoplastic resin, an elastomer, and a crosslinkable resin. These resins can also be combined with inorganic fillers.

Examples of the thermoplastic resin other than the polyarylene sulfide resin which may be contained in the composition of the polyarylene sulfide resin include polyester, polyamine, polyimine, polyetherimide, polycarbonate, and polyphenylene ether. , polyfluorene, polyether oxime, polyether ether ketone, polyether ketone, polyethylene, polypropylene, polytetrafluoroethylene, polytetrafluoroethylene, polystyrene, ABS resin, polyoxyl resin and liquid crystal polymer (liquid crystal Polyester, etc.). The thermoplastic resin may be used alone or in combination of two or more.

The content of the thermoplastic resin other than the polyarylene sulfide resin is preferably from 1 to 300 parts by mass, more preferably from 3 to 100 parts by mass, even more preferably from 5 to 45 parts by mass, per 100 parts by mass of the polyarylene sulfide resin. When the content of the thermoplastic resin other than the polyarylene sulfide resin is in the above range, the effect of further improving heat resistance, chemical resistance, and mechanical properties can be obtained.

The elastomer which the polyarylene sulfide resin composition may contain is usually a thermoplastic elastomer. Examples of the thermoplastic elastomer include a polyolefin elastomer, a fluorine elastomer, and a polyoxynene elastomer. In the present specification, the thermoplastic elastomer system is classified into an elastomer instead of the aforementioned thermoplastic resin.

In the case of an elastomer (especially a thermoplastic elastomer), when the polyarylene sulfide resin has a functional group such as a carboxyl group, it preferably has a functional group reactive therewith. Thereby, a resin composition which is particularly excellent in adhesion and impact resistance can be obtained. Examples of the functional group include an epoxy group, an amine group, a hydroxyl group, a carboxyl group, a thiol group, and an isocyanate group. An oxazoline group and a group represented by the formula: R(CO)O(CO)- or R(CO)O- (wherein R represents an alkyl group having 1 to 8 carbon atoms). The thermoplastic elastomer having the functional group can be obtained, for example, by copolymerization of an α-olefin and a vinyl polymerizable compound having the aforementioned functional group. The α-olefin may, for example, be an α-olefin having 2 to 8 carbon atoms such as ethylene, propylene or 1-butene. Examples of the vinyl polymerizable compound having the functional group include α,β-unsaturated carboxylic acids such as (meth)acrylic acid and (meth)acrylate, and alkyl esters thereof; maleic acid and fumar Acid, itaconic acid and other α,β-unsaturated dicarboxylic acids having 4 to 10 carbon atoms and derivatives thereof (mono or diesters, their anhydrides, etc.); glycidyl (meth)acrylate, etc. . Among these, it is selected from the group consisting of an epoxy group, a carboxyl group, and a formula of R(CO)O(CO)- or R(CO)O- (wherein R represents an alkyl group having 1 to 8 carbon atoms). The ethylene-propylene copolymer and the ethylene-butene copolymer of at least one functional group in the group are preferably improved from the further improvement in toughness and impact resistance.

The content of the elastomer varies depending on the type and use, and therefore cannot be uniformly defined. The content of the elastomer is, for example, preferably from 1 to 300 parts by mass, more preferably from 3 to 100 parts by mass, even more preferably from 5 to 45 parts by mass, per 100 parts by mass of the polyarylene sulfide resin. When the content of the elastomer is in the above range, a more excellent effect can be obtained in securing the heat resistance and toughness of the molded article.

The crosslinkable resin which the polyarylene sulfide resin composition can contain has two or more crosslinkable functional groups. Examples of the crosslinkable functional group include an epoxy group, a phenolic hydroxyl group, an amine group, a decylamino group, a carboxyl group, an acid anhydride group, and an isocyanate group. Examples of the crosslinkable resin include an epoxy resin, a phenol resin, and a urethane resin.

As the epoxy resin, an aromatic epoxy resin is preferred. The aromatic epoxy resin may have a halogen group, a hydroxyl group or the like. Examples of preferred aromatic epoxy resins include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, biphenyl epoxy resin, and tetramethyl linkage. Benzene type epoxy resin, phenol novolak type epoxy resin, cresol novolac type epoxy resin, bisphenol A phenolic type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, two Cyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolac type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol copolyphenol type ring Oxygen resin, naphthol-cresol copolyphenol type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type epoxy resin, and diphenol aldehyde type epoxy resin. These aromatic epoxy resins may be used alone or in combination of two or more. Among these aromatic epoxy resins, in particular, those having excellent compatibility with other resin components are preferably phenolic epoxy resins, more preferably cresol novolac epoxy resins.

The content of the crosslinkable resin is preferably from 1 to 300 parts by mass, more preferably from 3 to 100 parts by mass, even more preferably from 5 to 30 parts by mass, per 100 parts by mass of the polyarylene sulfide resin. When the content of the crosslinkable resin is in the above range, the effect of improving the rigidity and heat resistance of the molded article can be particularly remarkable.

The polyarylene sulfide resin composition may contain a decane compound having a functional group. The decane compound may, for example, be γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropyltriethoxydecane or β-(3,4-epoxycyclohexyl). a decane coupling agent such as ethyltrimethoxydecane, γ-glycidoxypropylmethyldiethoxydecane or γ-glycidoxypropylmethyldimethoxydecane.

For example, the content of the decane compound is 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass, per 100 parts by mass of the polyarylene sulfide resin. By the content of the decane compound being in the above range, the effect of further improving the compatibility of the polyarylene sulfide resin with other components can be obtained.

The polyarylene sulfide resin composition may further contain other additives such as a release agent, a colorant, a heat stabilizer, an ultraviolet stabilizer, a foaming agent, a rust preventive, a flame retardant, and a lubricant. For example, the content of the additive is from 1 to 10 parts by mass relative to 100 parts by mass of the polyarylene sulfide resin.

The polyarylene sulfide resin composition can be obtained in the form of a pellet-shaped composite or the like by melt-kneading the polyarylene sulfide resin and other components. The temperature of the melt-kneading is, for example, 300 to 450 °C. The time of melt kneading is, for example, 5 to 30 seconds. Melt kneading can be carried out using a twin-screw extruder or the like.

The polyarylene sulfide resin composition can be processed into heat resistance, moldability, dimensional stability by various melt processing methods such as injection molding, extrusion molding, compression molding, and blow molding, alone or in combination with other materials. Such excellent molded products. The polyarylene sulfide resin obtained by the production method of the present embodiment or the resin composition containing the same can be easily produced into a high-quality molded article because the amount of gas generated when heated is small.

The polyarylene sulfide resin obtained by the production method of the present embodiment or the resin composition containing the resin also has various properties such as heat resistance and dimensional stability originally possessed by the polyarylene sulfide resin. Therefore, the polyarylene sulfide resin or the resin composition containing the resin is widely used as an electric ‧ electronic component, a lamp reflector, and various electrical components, such as a connector, a printed circuit board, and a seal molded product. Parts, various construction Interior molding materials such as buildings, aircrafts, and automobiles, or injection molding or compression molding of precision parts such as office automation equipment parts, camera parts, and watch parts, or extrusion molding of composites, sheets, tubes, etc., or Various materials for forming processing such as pultrusion, or materials for fibers or films.

[Examples]

Hereinafter, the present invention will be more specifically described by way of examples. However, the invention is not limited by the examples.

Evaluation method 1-1. Identification method (NMR measurement)

The compound was dissolved in various heavy solvents by a device of DPX-400 manufactured by BRUKER, and various NMRs were measured.

1-2. Identification method (quality analysis)

The molecular weight of the compound was determined using MS-700T manufactured by JEOL.

1-3. Identification method (elemental analysis)

The ratio of the elements constituting the compound was measured using MT-5 manufactured by Yanaco.

1-4. Infrared absorption spectrum

The infrared absorption spectrum was measured using "FT/IR-6100" manufactured by JASCO Corporation. An amorphous film obtained by heating a synthetic resin by heating on a hot plate of 400 ° C and quenching it was used as a measurement sample.

1-5. Glass transition temperature (Tg)

The glass transition temperature was determined by using a PerkinElmer DSC apparatus Pyris Diamond under a nitrogen gas flow of 50 mL/min at a temperature rise of 20 ° C /min to 40 to 400 ° C.

1-6. Melting point (Tm)

The melting point was determined by using a Pyrite Diamond DSC apparatus manufactured by PerkinElmer under a nitrogen gas flow of 50 mL/min under the temperature rising condition of 20 ° C /min to 40 to 400 ° C.

1-7.5% thermal decomposition temperature (T _5%d )

Using a TG-DTA apparatus (Rigaku Co., Ltd. TG-8120), the measurement was performed at a temperature elevation rate of 20 ° C /min under a nitrogen gas flow of 20 mL / minute, and the temperature at which the weight loss was 5% was measured.

2. Synthesis of monomers

In the examples shown below, the following reagents were used:

4-Bromo-4'-iodobiphenyl: Tokyo Chemical Industry Co., Ltd., purity >98%

Methyl iodide: Kanto Chemical Co., Ltd., special grade

Copper iodide: Kanto Chemical Co., Ltd., purity >99%

Sulfur: Kanto Chemical Co., Ltd.

Potassium carbonate: Nacalai Tesque Co., Ltd., Nacalai specification

N,N-dimethylformamide (dehydrated): Kanto Chemical Co., Ltd., special grade

Sodium borohydride: Kanto Chemical Co., Ltd.

Zeolite: Wako Pure Chemical Industries Co., Ltd., No. 503

n-Bromobutane: Tokyo Chemical Industry Co., Ltd., purity >98%

n-Bromooctane: Tokyo Chemical Industry Co., Ltd., purity >98%

Tertiary butyl lithium: Kanto Chemical Co., Ltd.

Tetrahydrofuran (dehydration): Kanto Chemical Co., Ltd.

Diphenyl disulfide: Kanto Chemical Co., Ltd., special grade

Ammonium chloride: Nacalai Tesque Co., Ltd., Nacalai specification

Nitric acid (1.38): Wako Pure Chemical Industries Co., Ltd., special grade reagent, content 60~61%, density 1.38g/mL

Dichloromethane: Kanto Chemical Co., Ltd., special grade

Trifluoromethanesulfonic acid: Wako Pure Chemical Industries Co., Ltd., and light special grade

Pyridine: Wako Pure Chemical Industries Co., Ltd., and light special grade

Methanesulfonic acid: Heguang Pure Pharmaceutical Industry Co., Ltd., and light special grade

Phosphorus pentoxide: Heguang Pure Pharmaceutical Industry Co., Ltd., and light special grade

(Example 1-1)

Synthesis of 4-bromo-4'-(methylthio)biphenyl

The three-necked flask was charged with 100 parts by mass of 4-bromo-4'-iodobiphenyl, 10 parts by mass of copper iodide, 300 parts by mass of sulfur, and 1,700 parts by mass of potassium carbonate, and the inside of the flask was purged with nitrogen. After adding 20,000 parts by mass of N,N-dimethylformamide (dehydrated) to the flask, the mixture was stirred at 100 ° C for 17 hours. Thereafter, 400 parts by mass of sodium borohydride was added at 0 ° C, and the mixture was stirred at 50 ° C for 6 hours. Then, 900 parts by mass of methyl iodide was added at 0 ° C, and the mixture was stirred at 25 ° C for 20 hours. After stirring, the reaction solution was poured into 10% hydrochloric acid to stop the reaction, and the mixture was filtered through celite, extracted with dichloromethane and separated, and then the organic layer was dried over anhydrous magnesium sulfate. After filtration, the solvent was removed from the filtrate by a rotary evaporator, and dried under reduced pressure to give a crude product. The crude product was separated by column chromatography using hexane as a solvent. A solution containing the product of the separation purpose is recovered. The solvent was removed from the solution by a rotary evaporator, and dried under reduced pressure to give 4-bromo-4'-(methylthio)biphenyl in a yield of 43%. The product was confirmed by ¹ H-NMR and ¹³ C-NMR.

¹ H-NMR (solvent CDCl ₃ ): 2.52, 7.32, 7.43, 7.48, 7.54 [ppm]

¹³ C-NMR (solvent CDCl ₃ ): 15.9, 121.5, 127.0, 127.4, 128.5, 132.0, 136.8, 138.4, 139.6 [ppm]

(Example 1-2)

Synthesis of 4-methylthio-4'-(phenylthio)biphenyl

To a nitrogen-substituted three-necked flask, 100 parts by mass of 4-bromo-4'-(methylthio)biphenyl and 4000 parts by mass of tetrahydrofuran (dehydrated) were added. 400 parts by mass of tertiary butyl lithium was added to the reaction solution at -78 ° C, and the mixture was stirred for 1 hour. Next, 100 parts by mass of diphenyl disulfide was added to the reaction solution, and the mixture was stirred at 25 ° C for 3 hours. Thereafter, the reaction solution was poured into an aqueous ammonium chloride solution to stop the reaction, and extraction and separation were carried out using diethyl ether, and then the organic layer was dried over anhydrous magnesium sulfate. After filtration, the solvent was removed from the filtrate by a rotary evaporator, and dried under reduced pressure to give a crude product. The crude product was separated by column chromatography using hexane as a developing solvent, and a solution containing the desired product was collected. The solvent was removed from the solution by a rotary evaporator, and dried under reduced pressure to give 4-methylthio-4'-(phenylthio)biphenyl in a yield of 73%. The product was confirmed by ¹ H-NMR, ¹³ C-NMR, EI-MS, and elemental analysis.

¹ H-NMR (solvent CDCl ₃ ): 2.52, 7.24-7.28, 7.30-7.34, 7.39, 7.50 [ppm]

¹³ C-NMR (solvent CDCl ₃ ): 15.9, 127.0, 127.3, 127.4, 127.6, 129.4, 131.3, 131.5, 135.0, 135.8, 137.1, 138.1, 139.4 [ppm]

EI-MS: m/z 308 (M ⁺ )

Elemental analysis (calculated value): C 73.98 (73.70), H 5.23 (5.23)

(Example 1-3)

Synthesis of 4-methylsulfinyl-4'-(phenylthio)biphenyl

The eggplant type flask was charged with 100 parts by mass of 4-methylthio-4'-(phenylthio)biphenyl, 2000 parts by mass of dichloromethane, and further 40 parts by mass of nitric acid. The reaction solution was stirred at 25 ° C for 3 hours, neutralized with a saturated aqueous solution of potassium carbonate, and the reaction was stopped. Thereafter, after extraction and liquid separation using dichloromethane, the organic layer was dried over anhydrous magnesium sulfate. After filtration, the solvent was removed from the filtrate by a rotary evaporator, and dried under reduced pressure to give a crude product. The crude product was separated by column chromatography using chloroform as a developing solvent, and a solution containing the desired product was recovered. The solvent was removed from the solution by a rotary evaporator, and dried under reduced pressure to give 4-methylsulfinyl-4'-(phenylthio)biphenyl in a yield of 72%. The product was confirmed by ¹ H-NMR, ¹³ C-NMR, EI-MS, and elemental analysis.

¹ H-NMR (solvent CDCl ₃ ): 2.77, 7.30, 7.35, 7.39, 7.43, 7.52, 7.71 [ppm]

¹³ C-NMR (solvent CDCl ₃ ): 44.1, 124.3, 127.7, 128.0, 128.0, 129.5, 130.9, 132.0, 135.0, 136.9, 143.4, 144.8 [ppm]

EI-MS: m/z 324 (M ⁺ )

Elemental analysis (calculated values): C 70.33 (70.19), H 4.97 (4.98)

(Example 2-1)

Synthesis of 4-bromo-4'-(methylsulfinyl)biphenyl

The eggplant type flask was charged with 100 parts by mass of 4-bromo-4'-(methylthio)biphenyl, 2000 parts by mass of dichloromethane, and further 50 parts by mass of nitric acid. The reaction solution was stirred at 25 ° C for 3 hours, neutralized with a saturated aqueous solution of potassium carbonate, and the reaction was stopped. Thereafter, the reaction solution was extracted with dichloromethane and separated, and then dried over anhydrous magnesium sulfate. After the dehydrated reaction solution was filtered, the solvent was removed from the filtrate by a rotary evaporator, and dried under reduced pressure to give a crude product. The crude product was separated by column chromatography using chloroform as a developing solvent, and a solution containing the desired product was recovered. The solvent was removed from the solution by a rotary evaporator, and dried under reduced pressure to give 4-bromo-4'-(methylsulfinyl)biphenyl in a yield of 83%. The product was confirmed by ¹ H-NMR.

¹ H-NMR (solvent CDCl ₃ ): 2.77, 7.48, 7.61, 7.71 [ppm]

(Example 2-2)

Synthesis of 4-methylsulfinyl-4'-(phenylthio)biphenyl

To a nitrogen-substituted three-necked flask, 100 parts by mass of 4-bromo-4'-(methylsulfinyl)biphenyl and 4000 parts by mass of tetrahydrofuran (dehydrated) were added. To the reaction solution, 400 parts by mass of tertiary butyl lithium was added at -78 ° C, and the mixture was stirred for 1 hour. Next, 100 parts by mass of diphenyl disulfide was added to the reaction solution, and the mixture was stirred at 25 ° C for 3 hours. Thereafter, the reaction solution was poured into an aqueous ammonium chloride solution to stop the reaction, and extraction and separation were carried out using diethyl ether, and then the organic layer was dried over anhydrous magnesium sulfate. After the dehydrated reaction solution was filtered, the solvent was removed from the filtrate by a rotary evaporator, and dried under reduced pressure to give a crude product. The crude product was separated by column chromatography using hexane as a developing solvent, and a solution containing the desired product was collected. The solvent was removed from the solution by a rotary evaporator, and dried under reduced pressure to give 4-methylsulfinyl-4'-(phenylthio)biphenyl in a yield of 68%. The product was confirmed by ¹ H-NMR.

¹ H-NMR (solvent CDCl ₃ ): 2.77, 7.30, 7.36, 7.39, 7.43, 7.52, 7.71 [ppm]

(Example 3-1)

Synthesis of 4-n-butylthio-4'-(phenylthio)biphenyl

The same operation as in Example 1-1 was carried out except that 700 parts by mass of n-bromobutane was used instead of methyl iodide to obtain 4-bromo-4'-(n-butylthio)biphenyl in a yield of 72%. Thereafter, the same operation as in Example 2 was carried out to obtain 4-n-butylthio-4'-(phenylthio)biphenyl in a yield of 72%. The product was confirmed by ¹ H-NMR, ¹³ C-NMR, EI-MS, and elemental analysis.

¹ H-NMR (solvent CDCl ₃ ): 0.94, 1.47, 1.67, 2.96, 7.24-7.28, 7.31, 7.34-7.40, 7.49, 7.51 [ppm]

¹³ C-NMR (solvent CDCl ₃ ): 13.8, 22.1, 31.3, 33.2, 127.3, 127.4, 127.7, 129.0, 129.4, 131.3, 131.4, 135.7, 136.7, 137.6, 139.3 [ppm]

EI-MS: m/z 350 (M ⁺ )

Elemental analysis (calculated values): C 75.21 (75.38), H 6.35 (6.33)

(Example 3-2)

Synthesis of 4-n-butylsulfinyl-4'-(phenylthio)biphenyl

The same operation as in Example 1-3 was carried out except that 4-n-butylthio-4'-(phenylthio)biphenyl was used instead of 4-methylthio-4'-(phenylthio)biphenyl. 4-n-butylsulfinyl-4'-(phenylthio)biphenyl was obtained in a yield of 85%. The product was confirmed by ¹ H-NMR, ¹³ C-NMR, EI-MS, and elemental analysis.

¹ H-NMR (solvent CDCl ₃ ): 0.93, 1.42-1.50, 1.59-1.78, 2.83, 7.29-7.43, 7.53, 7.69 [ppm]

¹³ C-NMR (solvent CDCl ₃ ): 13.8, 22.0, 24.3, 57.2, 124.7, 127.6, 127.8, 128.0, 129.5, 130.9, 131.8, 135.0, 136.7, 138.3, 143.0, 143.1 [ppm]

EI-MS: m/z 366 (M ⁺ )

Elemental analysis (calculated values): C 72.09 (72.12), H 6.05 (6.10)

(Example 4-1)

Synthesis of 4-n-octylthio-4'-(phenylthio)biphenyl

The same operation as in Example 1-1 was carried out except that 1000 parts by mass of n-bromooctane was used instead of methyl iodide to obtain 4-bromo-4'-(n-octylthio)biphenyl in a yield of 77%. Thereafter, the same operation as in Example 1-2 was carried out to obtain 4-n-octylthio-4'-(phenylthio)biphenyl in a yield of 73%. The product was confirmed by ¹ H-NMR, ¹³ C-NMR, HR-MS, and elemental analysis.

¹ H-NMR (solvent CDCl ₃ ): 0.88, 1.26-1.29, 1.43, 1.66, 2.94, 7.26, 7.31, 7.35-7.39, 7.48, 7.50 [ppm]

¹³ C-NMR (solvent CDCl ₃ ): 14.4, 23.0, 29.2, 29.4, 29.5, 29.5, 32.1, 33.8, 127.5, 127.6, 127.8, 129.3, 129.6, 131.5, 131.6, 135.2, 136.0, 136.9, 137.8, 139.6 [ Ppm]

HR-MS (calculated value): 406.1789 (406.1956)

Elemental analysis (calculated values): C 76.54 (76.29), H 7.42 (7.44)

(Example 4-2)

Synthesis of 4-n-octylsulfinyl-4'-(phenylthio)biphenyl

The same operation as in Example 1-3 was carried out except that 4-n-octylthio-4'-(phenylthio)biphenyl was used instead of 4-methylthio-4'-(phenylthio)biphenyl. 4-n-octylsulfinyl-4'-(phenylthio)biphenyl was obtained in a yield of 72%. The product was confirmed by ¹ H-NMR, ¹³ C-NMR, HR-MS, and elemental analysis.

¹ H-NMR (solvent CDCl ₃ ): 0.87, 1.23-1.31, 1.40-1.45, 1.64-1.77, 2.80-2.83, 7.29, 7.35, 7.38, 7.53, 7.67, 7.71 [ppm]

¹³ C-NMR (solvent CDCl ₃ ): 14.4, 22.3, 22.5, 29.0, 29.3, 29.5, 32.0, 57.8, 125.0, 127.9, 128.0, 128.2, 129.7, 131.1, 132.1, 135.2, 136.9, 138.5, 142.4, 142.4 [ Ppm]

HR-MS (calculated value): 422.1738 (422.1365)

Elemental analysis (calculated value): C 73.89 (73.60), H 7.15 (7.17)

(Example 5-1)

Synthesis of poly{methanesulfonate methyl 4-[4-(phenylthio)phenyl]phenylhydrazine}

To the separable flask, 100 parts by mass of 4-methylsulfinyl-4'-(phenylthio)biphenyl, 50 parts by mass of phosphorus pentoxide, and 500 parts by mass of methanesulfonic acid were further dropped at 0 ° C. . After the reaction solution was stirred at 25 ° C for 20 hours, it was poured into acetone to stop the reaction. The precipitated solid was taken out by filtration and washed with acetone. Thereafter, the washed solid was dried under reduced pressure to obtain poly{methanesulfonate methyl 4-[4-(phenylthio)phenyl]phenylhydrazine} in a yield of 93%. The product was confirmed by ¹ H-NMR.

¹ H-NMR (solvent DMSO-d ₆ ): 3.84, 7.63, 7.87, 8.04, 8.15 [ppm]

(Example 5-2)

Synthesis of poly(p-phenylphenyl-p,p'-extended biphenyl sulfide)

100 parts by mass of the obtained poly{methanesulfonate methyl 4-[4-(phenylthio)phenyl]phenylhydrazine}, 2000 parts by mass of N-methyl-2-pyrrolidone were added to the flask. The reaction solution was stirred at 25 ° C for 30 minutes and then stirred at 120 ° C for 20 hours. The reaction solution was poured into water to stop the reaction, and the precipitate was filtered by filtration. Next, the precipitate was washed with chloroform, NMP, and water, and the obtained solid was dried under reduced pressure to give poly(p-phenylphenylthio-p,p'-extended biphenyl sulfide) in a yield of 43%. .

As a result of thermal analysis of the obtained poly(p-phenylphenylthio-p,p'-extended biphenyl sulfide), the glass transition temperature (T _g ) was 164 ° C, the melting point was 347 ° C, and 5% thermal decomposition was carried out. The temperature (T _5%d ) was 507 °C. Fig. 1 is an infrared absorption spectrum of the obtained poly(p-phenylphenylthio-p,p'-extended biphenyl sulfide). In the infrared absorption spectrum of Fig. ¹ , no absorption peak derived from the stretching vibration of S=O of the sulfonyl group was observed in the vicinity of the wave number of 1160 cm ^-1 . This indicates that the obtained poly(p-phenylphenylthio-p,p'-extended biphenyl sulfide) has substantially no sulfonyl group.

(Example 6)

Poly{n-butyl methanesulfonate 4-[4-(phenylthio)phenyl]phenylhydrazine}, and poly(p-phenylphenylthio-p,p'-extended biphenyl sulfide) synthesis

Except that 4-n-butyl sulfinothinyl-4'-(phenylthio)biphenyl was used instead of 4-methylsulfinyl-4'-(phenylthio)biphenyl and Example 5-1 was used. In the same manner, poly{n-butyl methanesulfonate 4-[4-(phenylthio)phenyl]phenylhydrazine} was obtained in a yield of 95%. The product was confirmed by ¹ H-NMR.

¹ H-NMR (solvent DMSO-d ₆ ): 0.81, 1.40, 1.54, 4.31, 7.40, 7.82, 7.99, 8.04, 8.15 [ppm]

The same operation as in Example 5-2 was carried out except that the obtained poly{n-butyl methanesulfonate 4-[4-(phenylthio)phenyl]phenylhydrazine} was used, and poly( P-phenylphenyl-p,p'-extended biphenyl sulfide).

As a result of thermal analysis of the obtained poly(p-phenylphenylthio-p,p'-extended biphenyl sulfide), the glass transition temperature (T _g ) was 159 ° C, the melting point was 348 ° C, and 5% thermal decomposition. The temperature (T _5%d ) was 507 °C. Fig. 2 is a graph showing the infrared absorption spectrum of the obtained poly(p-phenylphenylthio-p,p'-extended biphenyl sulfide). In the infrared absorption spectrum of Fig. 2, the absorption peak derived from the S=O stretching vibration of the sulfonyl group was not observed in the vicinity of the wave number of 1160 cm ^-1 .

(Example 7)

Poly{n-octyl methanesulfonate 4-[4-(phenylthio)phenyl]phenylhydrazine}, and poly(p-phenylphenylthio-p,p'-extended biphenyl sulfide) synthesis

Except that 4-n-octylsulfinyl-4'-(phenylthio)biphenyl was used instead of 4-methylsulfinyl-4'-(phenylthio)biphenyl and Example 5-1 was used. The same operation gave poly{n-octyl methanesulfonate 4-[4-(phenylthio)phenyl]phenylhydrazine} in a yield of 91%. The product was confirmed by ¹ H-NMR.

¹ H-NMR (solvent DMSO-d ₆ ): 0.82, 1.19-1.24, 1.44, 1.63, 4.35, 7.50, 7.67, 7.91, 8.09, 8.20 [ppm]

The same procedure as in Example 5-2 was carried out except that the obtained poly{n-octylsulfonate 4-[4-(phenylthio)phenyl]phenylhydrazine} was used, and poly(() was obtained in a yield of 32%. P-phenylphenyl-p,p'-extended biphenyl sulfide).

As a result of thermal analysis of the obtained poly(p-phenylphenylthio-p,p'-extended biphenyl sulfide), the glass transition temperature (T _g ) was 158 ° C, the melting point was 349 ° C, and 5% thermal decomposition was carried out. The temperature (T _5%d ) was 520 °C. Fig. 3 is a graph showing the infrared absorption spectrum of the obtained poly(p-phenylphenylthio-p,p'-extended biphenyl sulfide). In the infrared absorption spectrum of Fig. 3, the absorption peak derived from the S=O stretching vibration of the sulfonyl group was not observed in the vicinity of the wave number of 1160 cm ^-1 .

(Example 8-1)

Synthesis of poly(p-phenylphenyl-p,p'-extended biphenyl sulfide)

To the separable flask, 100 parts by mass of 4-methylsulfinyl-4'-(phenylthio)biphenyl, 2,500 parts by mass of dichloromethane, and 600 parts by mass of trifluoromethanesulfonic acid were dropped at 0 °C. After the reaction solution was stirred at 25 ° C for 20 hours, it was poured into water to stop the reaction. The precipitated solid was taken out by filtration and washed with water. Thereafter, the washed solid was dried under reduced pressure to obtain poly{trifluoromethanesulfonate 4-[4-(phenylthio)phenyl]phenylhydrazine} in a yield of 98%. The product was confirmed by ¹ H-NMR.

¹ H-NMR (solvent CD ₃ CN): 3.58, 7.45, 7.66, 7.76, 7.94

(Example 8-2)

Synthesis of poly(p-phenylphenyl-p,p'-extended biphenyl sulfide)

100 parts by mass of poly{trifluoromethanesulfonate 4-[4-(phenylthio)phenyl]phenylhydrazine} obtained in Example 8-1, 5000 parts by mass of pyridine was added to the eggplant flask in. The reaction solution was stirred at 25 ° C for 30 minutes and then stirred at 110 ° C for 20 hours. The reaction solution was poured into water to stop the reaction, and the precipitate was filtered by filtration. Next, the precipitate was washed with chloroform, NMP, and water, and the obtained solid was dried under reduced pressure to obtain poly(p-phenylphenylthio-p,p'-extended biphenyl sulfide) in a yield of 48%. .

As a result of thermal analysis of the obtained poly(p-phenylphenylthio-p,p'-extended biphenyl sulfide), the glass transition temperature (T _g ) was 159 ° C, the melting point was 336 ° C, and 5% thermal decomposition was carried out. The temperature (T _5%d ) was 511 °C. Figure 4 is a graph showing the infrared absorption spectrum of the obtained poly(p-phenylphenylthio-p,p'-extended biphenyl sulfide). In the infrared absorption spectrum of Fig. 4, the absorption peak derived from the S=O stretching vibration of the sulfonyl group was not observed in the vicinity of the wave number of 1160 cm ^-1 .

(Comparative Example 1-1)

Synthesis of poly{methyl trifluoromethanesulfonate 4-[4-(phenylthio)phenyl]phenylhydrazine}

To the separable flask, 100 parts by mass of 4-methylsulfinyl-4'-(phenylthio)biphenyl and 600 parts by mass of trifluoromethanesulfonic acid were dropped at 0 °C. After the reaction solution was stirred at 25 ° C for 20 hours, it was poured into water to stop the reaction. The precipitated solid was taken out by filtration and washed with water. Thereafter, the washed solid was dried under reduced pressure to give poly{trifluoromethanesulfonate 4-[4-(phenylthio)phenyl]phenylhydrazine} in a yield of 95%. The product was confirmed by ¹ H-NMR.

¹ H-NMR (solvent CD ₃ CN): 3.57, 7.45, 7.66, 7.77, 7.95 [ppm]

(Comparative Example 1-2)

Synthesis of poly(p-phenylphenyl-p,p'-extended biphenyl sulfide)

100 parts by mass of poly{trifluoromethanesulfonate 4-[4-(phenylthio)phenyl]phenylhydrazine} obtained in Comparative Example 1-1, 5000 parts by mass of pyridine was added to the eggplant type flask in. The reaction solution was stirred at 25 ° C for 30 minutes and then stirred at 110 ° C for 20 hours. The reaction solution was poured into water to stop the reaction, and the precipitate was filtered by filtration. Next, the precipitate was washed with chloroform, NMP, and water, and the obtained solid was dried under reduced pressure to obtain poly(p-phenylphenylthio-p,p'-extended biphenyl sulfide) in a yield of 48%. .

As a result of thermal analysis of the obtained poly(p-phenylphenylthio-p,p'-extended biphenyl sulfide), the glass transition temperature (T _g ) was 160 ° C, no melting point was detected, and 5% thermal decomposition was observed. The temperature (T _5%d ) was 465 °C. Fig. 5 is a graph showing the infrared absorption spectrum of the obtained poly(p-phenylphenylthio-p,p'-extended biphenyl sulfide). In the infrared absorption spectrum of Fig. 5, an absorption peak derived from the S=O stretching vibration of the sulfonyl group was observed in the vicinity of the wave number of 1160 cm ^-1 . This indicates that the obtained poly(p-phenylphenylthio-p,p'-extended biphenyl sulfide) has a trace amount of a sulfonyl group.

Synthesis of PPS without biphenyl skeleton

(Comparative Example 2)

To the separable flask, 100 parts by mass of methyl 4-(phenylthio)phenylarylene, 70 parts by mass of phosphorus pentoxide was added, and 700 parts by mass of methanesulfonic acid was dropped at 0 °C. The reaction solution was stirred at 25 ° C for 20 hours, after which the reaction was stopped with 10,000 parts by mass of acetone. Regression by filtration The solid was removed and washed with acetone. The washed solid was dried under reduced pressure to give poly[methylsulfonate 4-(phenylthio)phenylhydrazine] in a yield of 98%.

100 parts by mass of the obtained poly[methylsulfonate 4-(phenylthio)phenylhydrazine] and 5000 parts by mass of N-methyl-2-pyrrolidone were added to an eggplant type flask. The reaction solution was stirred at 25 ° C for 30 minutes and then stirred at 110 ° C for 20 hours. The reaction solution was poured into water to stop the reaction, and the precipitate was filtered by filtration. Then, the precipitate was washed with chloroform, NMP, and water, and the obtained solid was dried under reduced pressure to give poly(p-phenylene sulfide) in a yield of 63%. As a result of thermal analysis of the obtained poly(p-phenylene sulfide), the glass transition temperature (T _g ) was 99 ° C, the melting point was 260 ° C, and the 5% thermal decomposition temperature (T _{5% d} ) was 485 ° C.

Claims (13)

A polyarylene sulfide resin having a polyarylene sulfide resin having a main chain represented by the following formula (1.1), in which no sulfonate is observed in the infrared absorption spectrum of the polyarylene sulfide resin An absorption peak derived from the S=O stretching vibration of the thiol group; In the general formula (1.1), Ar ¹ and Ar ^2b each independently represent an extended aryl group which may have a substituent, and two Ar ^{1 's} may be the same or different. A method for producing a polyarylene sulfide resin according to claim 1, which comprises subjecting a poly(arylsulfonium salt) having a main chain comprising a structural unit represented by the following formula (2.1) to dealkylation or dearomatization. And the step of producing the aforementioned polyarylene sulfide resin; [wherein, Ar ¹ and Ar ^2b each independently represent an extended aryl group which may have a substituent, R ¹ represents an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms as a substituent; The aryl group, X ^- represents an anion, and 2 Ar ¹ may be the same or different]. The method of claim 2, further comprising: a step of polymerizing a sulfonium compound represented by the following formula (3.1) in the presence of an acid to form the poly(arylene salt); [wherein, Ar ¹ represents an extended aryl group which may have a substituent, Ar ^2a represents an aryl group which may have a substituent, R ¹ represents an alkyl group having 1 to 10 carbon atoms, or may have a carbon number of 1 to 10 The alkyl group is an aryl group as a substituent, and two Ar ^{1 's} may be the same or different. A poly(arylsulfonium salt) having a main chain comprising a constituent unit represented by the following formula (2.1); [wherein, Ar ¹ and Ar ^2b each independently represent an extended aryl group which may have a substituent, R ¹ represents an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms as a substituent; The aryl group, X ^- represents an anion, and 2 Ar ¹ may be the same or different]. A method for producing a poly(aryl sulfonium salt) according to claim 4, which comprises polymerizing a fluorene compound represented by the following formula (3.1) in the presence of an acid to form the above poly(aryl sulfonium salt) Steps; [wherein, Ar ¹ represents an extended aryl group which may have a substituent, Ar ^2a represents an aryl group which may have a substituent, R ¹ represents an alkyl group having 1 to 10 carbon atoms, or may have a carbon number of 1 to 10 The alkyl group is an aryl group as a substituent, and two Ar ^{1 's} may be the same or different. An anthraquinone compound represented by the following formula (3.1); [wherein, Ar ¹ represents an extended aryl group which may have a substituent, Ar ^2a represents an aryl group which may have a substituent, R ¹ represents an alkyl group having 1 to 10 carbon atoms, or may have a carbon number of 1 to 10 The alkyl group is an aryl group as a substituent, and two Ar ^{1 's} may be the same or different. A method for producing a hydrazine compound according to claim 6, which comprises the step of oxidizing a thioether compound represented by the following formula (4.1) to form the aforementioned hydrazine compound; Ar ^2a -S-Ar ¹ -Ar ¹ -SR ¹ (4.1) [wherein, Ar ¹ represents an extended aryl group which may have a substituent, Ar ^2a represents an aryl group which may have a substituent, R ¹ represents an alkyl group having 1 to 10 carbon atoms, or may have The alkyl group having 1 to 10 carbon atoms may be the aryl group of the substituent, and the two Ar ^{1 's} may be the same or different. A thioether compound represented by the following formula (4.1); Ar ^2a -S-Ar ¹ -Ar ¹ -SR ¹ (4.1) wherein Ar ¹ represents an exoaryl group which may have a substituent, Ar ^2a An aryl group which may have a substituent, R ¹ represents an alkyl group having 1 to 10 carbon atoms, or an aryl group which may have an alkyl group having 1 to 10 carbon atoms as a substituent, and two Ar ^{1 's} may be the same or different ]. A method for producing a thioether compound according to claim 8, which comprises a diaryl disulfide represented by the following formula (5.1) and a thioether compound represented by the following formula (6.1) a step of reacting to form the aforementioned thioether compound; Ar ^2a -SS-Ar ^2a (5.1) Y ¹ -Ar ¹ -Ar ¹ -SR ¹ (6.1) [In the formula (5.1), Ar ^2a represents a substituent which may have a substituent The aryl group, the two Ar ^2a may be the same or different, in the formula (6.1), Ar ¹ represents a aryl group which may have a substituent, R ¹ represents an alkyl group having 1 to 10 carbon atoms, or may have carbon An alkyl group having an atomic number of 1 to 10 is an aryl group as a substituent, and Y ¹ represents a halogen ion, and two Ar ^{1 's} may be the same or different. A method for producing a sulfonium compound according to claim 6, which comprises a diaryldisulfide represented by the following formula (5.1) and an anthracene compound represented by the following formula (8.1) a step of reacting to form an anthracene compound represented by the above formula (3.1); Ar ^2a -SS-Ar ^2a (5.1) [In the formula (5.1), Ar ^2a represents an aryl group which may have a substituent, and two Ar ^2a may be the same or different. In the formula (8.1), Ar ¹ represents an exoaryl group which may have a substituent, R ¹ An alkyl group having 1 to 10 carbon atoms or an aryl group having an alkyl group having 1 to 10 carbon atoms as a substituent, Y ¹ represents a halogen ion, and two Ar ^{1 's} may be the same or different. An anthraquinone compound represented by the following formula (8.1); [wherein, Ar ¹ represents an extended aryl group which may have a substituent, R ¹ represents an alkyl group having 1 to 10 carbon atoms, or an aryl group which may have an alkyl group having 1 to 10 carbon atoms as a substituent, and Y ¹ Indicates a halogen ion, and two Ar ^{1 's} may be the same or different. A method for producing a hydrazine compound according to claim 11, which comprises the step of oxidizing a thioether compound represented by the following formula (6.1) to form the aforementioned hydrazine compound; Y ¹ -Ar ¹ -Ar ¹ - SR ¹ (6.1) [wherein, Ar ¹ represents an extended aryl group which may have a substituent, R ¹ represents an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms as a substituent. An aryl group, Y ¹ represents a halogen ion, and two Ar ^{1 's} may be the same or different. A molded article comprising the polyarylene sulfide resin of claim 1.