JP6830617B2 - Polyarylene sulfide resin having a biphenyl skeleton and its manufacturing method - Google Patents

Description

The present invention relates to a polyarylene sulfide resin having a biphenyl skeleton and a method for producing the same. The present invention also relates to a compound that can be used for producing the polyarylene sulfide resin and a method for producing the same.

Polyphenylene sulfide resin (hereinafter sometimes abbreviated as "PAS resin") represented by polyphenylene sulfide resin (hereinafter sometimes abbreviated as "PPS resin") has excellent heat resistance, chemical resistance and the like, and is electrically charged. It is widely used in electronic parts, automobile parts, water heater parts, textiles, film applications, etc.

Conventionally, a polyphenylene sulfide resin has been produced, for example, by solution polymerization in which p-dichlorobenzene, sodium sulfide or sodium hydrosulfide, and sodium hydroxide are polymerized in an organic polar solvent (for example, patent). Reference 1). Currently commercially available polyphenylene sulfide resins are generally produced by this method.

However, since this method uses dichlorobenzene as a monomer, the concentration of halogen remaining in the resin after synthesis tends to be high. In addition, since it is necessary to carry out the polymerization reaction in a harsh environment of high temperature and high pressure and strong alkali, it is necessary to use a polymerization container using expensive and difficult-to-process titanium, chromium or zirconium for the wetted part.

Therefore, there is known a method for producing a polyarylene sulfide resin without using dichlorobenzene as a polymerization monomer and under mild polymerization conditions. For example, Patent Document 2 discloses a solvent-soluble poly (arylene sulfonium salt) as a precursor for synthesizing a polyarylene sulfide resin. Poly (arylene sulfonium salt) is produced by a method of homopolymerizing sulfoxide having one sulfinyl group such as methylphenyl sulfoxide (hereinafter, may be referred to as "monofunctional sulfoxide") in the presence of an acid ( For example, see Patent Document 2 and Non-Patent Document 1).

U.S. Pat. No. 3,354,129 Japanese Unexamined Patent Publication No. 10-182825

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 a component around an automobile engine because of its high heat resistance and dimensional stability based on crystallinity. However, in recent years, with the miniaturization of parts, a higher degree of dimensional stability has been required, and it is desired to develop a resin having heat resistance and dimensional stability exceeding that of polyphenylene sulfide resin.

Further, in the polymerization reaction shown in Non-Patent Document 1, it is common to use trifluoromethanesulfonic acid as a solvent, but since the above acid has strong corrosiveness, it is contained in the polymerization solution from the viewpoint of safety and industry. There is a need for a manufacturing method that reduces the acidity of the solvent.

Therefore, an object to be solved by the present invention is to provide a crystalline polyarylene sulfide resin having a high degree of heat resistance, which satisfies the above characteristics, and a method for producing the same.

As a result of diligent research to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by substantially eliminating the sulfonyl group with respect to the polyarylene sulfide resin having a biphenyl skeleton.

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

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

Yet another aspect of the present invention relates to a poly (arylene sulfonium salt) having a main chain containing a structural unit represented by the following general formula (2.1).

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

Yet another aspect of the present invention relates to a sulfoxide compound represented by the following general formula (3.1).

In the formula, Ar ¹ represents an arylene group which may have a substituent, Ar ^2a represents an aryl group which may have a substituent, and R ¹ is an alkyl group having 1 to 10 carbon atoms. Alternatively, it represents an aryl group which may have an alkyl group having 1 to 10 carbon atoms as a substituent.

Yet another aspect of the present invention relates to a sulfide compound represented by the following general formula (4.1).

In the formula, Ar ¹ represents an arylene group which may have a substituent, Ar ^2a represents an aryl group which may have a substituent, and R ¹ is an alkyl group having 1 to 10 carbon atoms. Alternatively, it represents an aryl group which may have an alkyl group having 1 to 10 carbon atoms as a substituent.

Yet another aspect of the present invention relates to a sulfoxide compound represented by the following general formula (8.1).

In the formula, Ar ¹ represents an arylene group which may have a substituent, and R ¹ has an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms as a substituent. It represents an aryl group which may be used, and Y ¹ represents a halogen atom.

Yet another aspect of the present invention relates to a molded article containing the 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 structural unit and having a high melting point, and a method for producing the same. According to the methods according to some forms, a polyarylene sulfide resin having a sufficiently high molecular weight can be easily obtained.

It is an infrared absorption spectrum of the poly (p-phenylenethio-p, p'-biphenylylene sulfide) obtained in Example 5-2. 6 is an infrared absorption spectrum of the poly (p-phenylenethio-p, p'-biphenylene sulfide) obtained in Example 6. 6 is an infrared absorption spectrum of the poly (p-phenylenethio-p, p'-biphenylene sulfide) obtained in Example 7. It is an infrared absorption spectrum of the poly (p-phenylenethio-p, p'-biphenylylene sulfide) obtained in Example 8-2. It is an infrared absorption spectrum of the poly (p-phenylenethio-p, p'-biphenylylene sulfide) obtained in Comparative Example 1-2.

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 one embodiment is a polymer having a main chain containing a structural unit represented by the following general formula (1.1). The main chain of the polyarylene sulfide resin may be substantially composed of only the structural units represented by the general formula (1.1). More specifically, the proportion of the structural unit represented by the general 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.

Wherein each Ar ¹ and Ar ^2b are independently have a substituent represents also arylene group, the two Ar ¹ s may be the same or different.

The mode of bonding 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 arylene group. For example, when Ar ¹ and Ar ^2b are phenylene groups, Ar ¹ and Ar ^2b are a unit that binds at the para position (1,4-phenylene group) or a unit that binds at the meta position (1,3-phenylene group). ), And more preferably a unit that binds at the para position. In terms of heat resistance and crystallinity of the polyarylene sulfide resin, Ar ¹ and Ar ^2b are preferably composed of units that are bonded at the para position.

Examples of the substituent that the arylene group represented by Ar ¹ or Ar ^2b can 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 nonyl group and a decyl group. Examples thereof include an alkyl group having 1 to 10 carbon atoms such as a group, a hydroxy group, an amino group, a mercapto group, an ester group, and a carboxy group.

In general, a small amount of sulfonyl group which is considered to be derived from a sulfoxide compound described later may remain in the polyarylene sulfide resin having such a main chain, but the polyarylene sulfide resin according to the present embodiment has , Substantially free of sulfonyl groups. According to the findings of the present inventors, a polyarylene sulfide resin having a high melting point can be obtained by substantially eliminating the sulfonyl group. It is presumed that this is because the proportion of the amorphous portion due to the remaining sulfonyl group becomes small.

Reflecting that the polyarylene sulfide resin does not substantially contain a sulfonyl group, no absorption peak due to the S = O stretching vibration of the sulfonyl group is observed in the infrared absorption spectrum of this polyarylene sulfide resin. Absorption peaks derived from the S = O stretching vibration of the sulfonyl group are usually observed in the region of wavenumber 1170 to 1140 cm- ¹ . In the present specification, "the absorption peak derived from the S = O stretching vibration of the sulfonyl group is not observed" means that the absorption peak derived from the S = O stretching vibration of the sulfonyl group is observed in the region of wave number 1170 to 1140 cm ^-1. It means that the top is not observed. Here, even if there is a minimum value or a maximum value sandwiched between flat portions in the region of wave number 1170 to 1140 cm ^-1 , the height of the maximum value from the minimum value or flat portion and the wave number 1200 to 1200 to If the ratio of the absorption peak observed at 1170 cm ^-1 to the height of the maximum value from the minimum value is 0.1 or less, it is not considered as a peak. The infrared absorption spectrum is measured, for example, by using an amorphous film prepared by heating a polyarylene sulfide resin on a hot plate at 400 ° C. to melt it and quenching it as a measurement sample.

The weight average molecular weight of the polyarylene sulfide resin according to one embodiment is preferably 8,000 or more, and more preferably 10,000 or more. When the weight average molecular weight is in such a range, the polyarylene sulfide resin can exhibit more excellent heat resistance and mechanical properties. In the present specification, "weight average molecular weight" means a value measured by gel permeation chromatography (converted value using standard polystyrene). The measurement conditions of 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 according to one embodiment is preferably 70 to 200 ° C., more preferably 80 to 180 ° C., and even more preferably 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 according to one embodiment is preferably 100 to 450 ° C., more preferably 180 to 420 ° C., further preferably 280 to 400 ° C., and 330 to 380 ° C. It is more preferable to have. 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 according to one embodiment is preferably 200 to 800 ° C., more preferably 300 to 650 ° C., and 350 to 600 ° C. Is even more preferable. The 5% thermal decomposition temperature of the polyarylene sulfide resin indicates a value measured by thermogravimetric analysis (TG-DTA).

<Method of manufacturing polyarylene sulfide resin>
The polyarylene sulfide resin as described above is, for example,
The following general formula (3.1):

The sulfoxide compound represented by is polymerized in the presence of an acid, and the following general formula (2.1):

A step of producing a poly (arylene sulfonium salt) having a main chain containing a structural unit represented by
By a method including a step of dealkylating or dearyllating poly (arylene sulfonium salt) to produce a polyarylene sulfide resin having a main chain containing a structural unit represented by the above formula (1.1). Can be manufactured. The method for obtaining the sulfoxide compound represented by the formula (3.1) will be described later.

Ar ¹ and ^{Ar 2b} in these formulas are defined as Ar ¹ and ^{Ar 2b} in 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 substituent that the aryl group represented by Ar ^2a can have is the same as that of Ar ^2b .

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

X ^- include the anion, for example, sulfonate, carboxylate, phosphate ion, perchlorate ion, hexafluorophosphate ion, and halogen ions, and the like.

The polymerization reaction of the sulfoxide compound represented by the formula (3.1) can be carried out in a reaction solution containing an acid. The acid may be either an organic acid or an inorganic acid. Acids include, for example, non-oxygenic acids such as hydrochloric acid, hydrobromic acid, blue acid, tetrafluoroboric acid; sulfuric acid, phosphoric acid, perchloric acid, bromic acid, nitrate, carbonic acid, boric acid, molybdic acid, isopolyic acid, heteropoly Inorganic oxo acids such as acids; partial salts or esters of sulfuric acids such as sodium hydrogen sulfate, sodium dihydrogen phosphate, proton residual heteropolyate, monomethyl sulfate, trifluoromethane sulfate; formic acid, acetic acid, propionic acid, butanoic acid, succinic acid Monovalent or polyvalent carboxylic acids such as acids, benzoic acids and phthalates; halogen-substituted carboxylic acids such as monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, monofluoroacetic acid, difluoroacetic acid and trifluoroacetic acid; methanesulfonic acid and ethanesulfone. Monovalent or polyvalent sulfonic acid such as acid, propanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, benzenedisulfonic acid; partial metal salt of polyvalent sulfonic acid such as sodium benzenedisulfonic acid; antimony pentachloride, aluminum chloride , Lewis acids such as aluminum bromide, titanium tetrachloride, tin tetrachloride, zinc chloride, copper chloride, iron chloride and the like. Of these acids, trifluoromethanesulfonic acid and methanesulfonic acid are preferable from the viewpoint of reactivity, and methanesulfonic acid is more preferable from the viewpoint that a polyarylene resin containing no sulfonyl group can be easily obtained. When trifluoromethanesulfonic acid is used as the acid, it is preferably used together with a solvent described later. 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 100 to 2000 parts by mass, and more preferably 200 to 1000 parts by mass with respect to 100 parts by mass of the sulfoxide compound represented by the formula (3.1).

The polymerization reaction of the sulfoxide compound represented by the formula (3.1) may be carried out in the presence of a dehydrating agent together with an acid. The use of dehydrating agents can also contribute to the production of sulfonyl group-free polyarylene sulfide resins. Examples of the dehydrating agent include phosphate anhydrides such as phosphorus oxide and diphosphorus pentoxide; sulfonic acids such as benzenesulfonic anhydride, methanesulfonic anhydride, trifluoromethanesulfonic anhydride, and paratoluenesulfonic anhydride. Anhydrides; carboxylic acid anhydrides such as anhydrous acetic acid, anhydrous fluoroacetic anhydride, and anhydrous trifluoroacetic anhydride; anhydrous magnesium sulfate, zeolite, silica gel, calcium chloride and the like can be mentioned. These dehydrating agents may be used alone or in combination of two or more. A combination of methanesulfonic acid and diphosphorus pentoxide is particularly preferred in order to obtain a sulfonyl group-free polyarylene sulfide resin.

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

The reaction solution of the polymerization reaction can contain a solvent. The combined use of acid and solvent can also contribute to the production of sulfonyl group-free polyarylene sulfide resins. Examples of the solvent include alcohol solvents such as methanol, ethanol, propanol and isopropyl alcohol; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; nitrile solvents such as acetonitrile; and dichloromethane (methylene chloride) and chloroform. Halogen-based solvent; Saturated hydrocarbon-based solvent such as normal hexane, cyclohexane, normal heptane, cycloheptane; Amido-based solvent such as dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone; Sulfur-containing solvent such as sulfolane, DMSO ; Examples include ether solvents such as tetrahydrofuran and dioxane. These solvents may be used alone or in combination of two or more. When trifluoromethanesulfonic acid is used, a combination of trifluoromethanesulfonic acid and dichloromethane or acetonitrile is preferable in order to obtain a polyarylene sulfide resin containing no sulfonyl group.

The amount of the solvent when the acid and the solvent are used in combination in the polymerization reaction is preferably 50 to 5000 parts by mass, more preferably 100 to 1000 parts by mass with respect to 100 parts by mass of the acid. When the amount of the solvent is within the above range, the acidity during the polymerization reaction becomes low, and the produced polyarylene sulfide resin is less likely to contain a sulfonyl group.

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

The reaction of dealkylating or dearylting the poly (arylene sulfonium salt) produced by the polymerization reaction can be efficiently carried out in a reaction solution containing a dealkylating agent or a dearylling agent. Examples of dealkylating or dearylting agents include nucleophiles and reducing agents. Examples of the nucleophile include nitrogen-containing aromatic compounds, amine compounds, amide compounds and the like. Examples of the reducing agent include metallic potassium, metallic sodium, potassium chloride, sodium chloride, hydrazine and the like. These compounds may be used alone or in combination of two or more. The amount of the dealkylating agent or the dearylling agent may be set so that the reaction proceeds appropriately, but is usually 100 to 50,000 parts by mass with respect to 100 parts by mass of poly (arylene sulfonium salt). Set in range.

Examples of the nitrogen-containing aromatic compound include pyridine, quinoline, and aniline. Of these compounds, pyridine, which is a general-purpose compound, is preferable.

Examples of the amine compound include trialkylamine and ammonia.

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

In the general 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 are bonded to form a cyclic structure. May be. 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 nonyl group, and a decyl group.

The aliphatic amide compound is more miscible with water than the aromatic amide compound, and can be easily removed by washing the reaction mixture with water. Therefore, when the aliphatic amide compound is used, the residual amount of the aliphatic amide compound in the polyarylene sulfide resin can be further reduced as compared with the case where the aromatic amide compound is used.

The use of an aliphatic amide compound as a dealkylating agent or a dearylling agent suppresses gas generation during resin processing, improves the quality of polyarylene sulfide resin molded products, improves the working environment, and further molds. It is preferable because the maintainability of the above can be further improved. Since the aliphatic amide compound is also excellent in the solubility of the organic compound, the use of the aliphatic amide compound also makes it possible to easily remove the oligomer component of polyarylene sulfide from the reaction mixture. As a result, the quality of the obtained polyarylene sulfide resin can be synergistically improved by removing the oligomer component, which can contribute to gas generation, with the aliphatic amide compound.

The aliphatic amide compound is, for example, a primary amide compound such as formamide, a secondary amide compound such as β-lactam, and a tertiary amide compound such as N-methyl-2-pyrrolidone, dimethylformamide, diethylformamide, dimethylacetamide, and tetramethylurea. It can be selected from amide compounds. The aliphatic amide compound preferably contains an aliphatic tertiary amide compound in which R ¹² and R ¹³ are aliphatic groups from the viewpoint of the solubility of poly (arylene sulfonium salt) and the solubility in water. Among the tertiary amide compounds, N-methyl-2-pyrrolidone is preferable.

The aliphatic amide compound functions as a dealkylating agent or a dearylling agent, and can also be used as a reaction solvent because of its excellent solubility. Only the aliphatic amide compound may be used as the reaction solvent, or this may be used in combination with another solvent such as toluene.

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

The method for producing a polyarylene sulfide resin further comprises a step of washing the polyarylene sulfide resin produced by dealkylation or dearyllation of poly (arylene sulfonium salt) with water, a water-soluble solvent or a mixed solvent thereof. It may be. By this cleaning step, the residual amount of the dealkylating agent or the dearylling agent contained in the polyarylene sulfide resin can be more reliably reduced. This tendency is particularly remarkable when the dealkylating agent or dearylting agent is an aliphatic amide compound.

The residual amount of the dealkylating agent or dearylling agent in the polyarylene sulfide resin is based on the mass of the entire resin containing the polyarylene sulfide resin and other components such as the dealkylating agent or the dearylting agent. It is preferably 1000 ppm or less, more preferably 700 ppm or less, and even more preferably 100 ppm or less. When the residual amount of the dealkylating agent or the dearylling 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, but it is preferably one that dissolves the unreacted product. Examples of the solvent include acidic aqueous solutions such as water, hydrochloric acid, acetic acid aqueous solution, oxalic acid aqueous solution, and nitrate aqueous solution; aromatic hydrocarbon solvents such as toluene and xylene; alcohol solvents such as methanol, ethanol, propanol, and isopropyl alcohol; Ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran and dioxane; amide solvents such as dimethylacetamide and N-methyl-2-pyrrolidone; dichloromethane, chloroform and the like Halogen-containing solvent and the like can be mentioned. These solvents may be used alone or in combination of two or more. Of these solvents, water or N-methyl-2-pyrrolidone is preferable from the viewpoint of removing the reaction reagent and the oligomer component of the resin.

If necessary, the polyarylene sulfide resin as a reaction product may be base-treated by contact with an aqueous solution containing a basic compound. By base treatment, the hydroxy group or carboxy group present in the molecular structure of the polyarylene sulfide resin can be converted into a metal salt.

Examples of the basic compound used for the base 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; sodium carbonate. ; Potassium carbonate; sodium phosphate.

<Method of producing a sulfoxide compound represented by the formula (3.1)>
(Method 1)
The sulfoxide compound represented by the formula (3.1) is, for example,
The following general formula (5.1):

Diaryl disulfide represented by and the following general formula (6.1):

Depending on the reaction with the sulfide compound represented by, the following general formula (4.1):

The process of producing the sulfide compound represented by
It can be obtained by a method including a step of oxidizing a sulfide compound represented by the formula (4.1) to produce a sulfoxide compound represented by the formula (3.1).

(Method 2)
Alternatively, the sulfoxide compound represented by the formula (3.1) is
The following general formula (6.1):

Oxidize the sulfide compound represented by the following general formula (8.1):

The process of producing the sulfoxide compound represented by
The sulfoxide compound represented by the formula (8.1) and the following general formula (5.1):

It can also be obtained by a method including a step of producing a sulfoxide compound represented by the formula (3.1) by a reaction with a diallyl disulfide represented by.

In these equations, Ar ¹ , Ar ^2a , and R ¹ are defined in the same manner as in equation (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, and is preferably a bromine atom.

In Method 1, the reaction of the diallyl disulfide represented by the formula (5.1) with the sulfide compound represented by the formula (6.1) can be carried out in a suitable solvent. The solvent used for this reaction can be appropriately selected from those described 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; bis (2-hydroxyphenyl) disulfide, bis (2-aminophenyl) disulfide, and bis. Diaryl disulfide having a substituent such as (2-carboxyphenyl) disulfide; diaryl disulfide having a heterocycle such as 2,2'-dibenzothiazolyl disulfide and the like can be mentioned.

The sulfide compound represented by the formula (6.1) is, for example, the following general formula (7.1):

An aromatic compound represented in the formula: and a halogenated hydrocarbon represented by R ¹ Y ^2, can be obtained by reacting in the presence of sulfur. Examples of R ¹ include alkyl groups having 1 to 10 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group, and Examples thereof include an aryl group having a structure such as phenyl, naphthyl, and biphenyl. The aryl group comprises 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 nonyl group and a decyl group in an aromatic ring. It may have in the range of 1 to 4 as a bonded substituent. Further, Y ² may be a chlorine atom, a bromine atom, or an iodine atom, and the combination of R ¹ and Y ² can be appropriately selected from the above description. Wherein (7.1), Ar ¹ is defined as in Ar ¹ of formula (6.1). Y ¹ and Y ² represent halogen atoms, 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'-dibromobinaphthyl, and 10,10'-dibromo. Unsubstituted aromatic compounds such as -9,9'-bianthracene; aromatics having substituents such as 4,4'-dibromo-2-biphenylamine, 4,4'-dibromo-2,2'-biphenyldiamine Compounds, etc. can be mentioned.

The reaction between the sulfide compound represented by the formula (6.1) and the halogenated hydrocarbon can be carried out in a reaction solution containing a solvent selected from the above-mentioned solvents.

The sulfide compound represented by the formula (4.1) can be oxidized in a reaction solution containing an oxidizing agent. The oxidizing agent is not particularly limited, and may be selected from, for example, potassium permanganate, oxygen, ozone, organic peroxide, hydrogen peroxide, nitric acid, m-chloroperoxybenzoic acid, oxone (registered trademark), and osminium tetraoxide. Can be done. This reaction can be carried out in a solvent of choice. The reaction temperature may be appropriately set, but may be, for example, -20 to 100 ° C. or 0 to 70 ° C.

Each reaction constituting the method 2 can be carried out in the same manner as each elementary reaction constituting the method 1. For example, the oxidation reaction of the sulfide compound represented by the formula (6.1) can be carried out in the presence of an oxidizing agent under the same conditions as the sulfide compound represented by the formula (4.1).

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

Examples of the inorganic filler include powder fillers such as carbon black, calcium carbonate, silica and titanium oxide; plate-like fillers such as talc and mica; granular fillers such as glass beads, silica beads and glass balloons; glass. Fibrous fillers such as fibers, carbon fibers, wollastonite fibers; and glass flakes. These inorganic fillers can be used alone or in combination of two or more. By blending an inorganic filler, it is easy to obtain a composition having high rigidity and high heat resistance stability. It is particularly preferable that the polyarylene sulfide resin composition contains at least one inorganic filler selected from the group consisting of glass fiber, carbon fiber, carbon black and calcium carbonate.

The content of the inorganic filler is preferably 1 to 300 parts by mass, more preferably 5 to 200 parts by mass, and further preferably 15 to 150 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin. When the content of the inorganic filler is in these ranges, a better effect can be obtained in terms of maintaining the mechanical strength of the molded product.

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

Examples of the thermoplastic resin that can be contained in the polyarylene sulfide resin composition include polyester, polyamide, polyimide, polyetherimide, polycarbonate, polyphenylene ether, polysulfone, polyethersulfone, polyetheretherketone, polyetherketone, polyethylene, and the like. Examples thereof include polypropylene, polytetrafluorinated ethylene, polydifluorinated ethylene, polystyrene, ABS resin, silicone resin and liquid crystal polymer (liquid crystal polyester and the like). As the thermoplastic resin, one type can be used alone, or two or more types can be used in combination.

The content of the thermoplastic resin is preferably 1 to 300 parts by mass, more preferably 3 to 100 parts by mass, and further preferably 5 to 45 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin. When the content of the thermoplastic resin other than the polyarylene sulfide resin is within these ranges, the effect of further improving the heat resistance, chemical resistance and mechanical properties can be obtained.

The elastomer that can be contained in the polyarylene sulfide resin composition is often a thermoplastic elastomer. Examples of the thermoplastic elastomer include polyolefin-based elastomers, fluorine-based elastomers, and silicone-based elastomers. In the present specification, the thermoplastic elastomer is classified as an elastomer instead of the thermoplastic resin.

When the polyarylene sulfide resin has a functional group such as a carboxy group, the elastomer (particularly a thermoplastic elastomer) preferably has a functional group capable of reacting with the functional group. As a result, a resin composition particularly excellent in terms of adhesiveness, impact resistance and the like can be obtained. Such functional groups include an epoxy group, an amino group, a hydroxyl group, a carboxy group, a mercapto group, an isocyanate group, an oxazoline group, and a formula: R (CO) O (CO)-or R (CO) O- (in the formula, R represents an alkyl group having 1 to 8 carbon atoms.). The thermoplastic elastomer having such a functional group can be obtained, for example, by copolymerizing an α-olefin with the vinyl polymerizable compound having the functional group. Examples of the α-olefin include α-olefins having 2 to 8 carbon atoms such as ethylene, propylene and 1-butene. Examples of the vinyl polymerizable compound having a functional group include α, β-unsaturated carboxylic acids such as (meth) acrylic acid and (meth) acrylic acid ester, and alkyl esters thereof, maleic acid, fumaric acid, itaconic acid and the like. Other examples include α, β-unsaturated dicarboxylic acid having 4 to 10 carbon atoms and its derivative (mono or diester, acid anhydride thereof, etc.), glycidyl (meth) acrylate and the like. Among these, an epoxy group, a carboxy group, and a formula: R (CO) O (CO)-or R (CO) O- (in the formula, R represents an alkyl group having 1 to 8 carbon atoms). An ethylene-propylene copolymer and an ethylene-butene copolymer having at least one functional group selected from the group consisting of the represented groups are preferable from the viewpoint of further improving toughness and impact resistance.

The content of the elastomer varies depending on the type and application, and cannot be unconditionally specified. For example, the content of the elastomer is preferably 1 to 300 parts by mass, more preferably 3 to 100 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin. , More preferably 5 to 45 parts by mass. When the content of the elastomer is within these ranges, a further excellent effect can be obtained in terms of ensuring the heat resistance and toughness of the molded product.

The crosslinkable resin that can be contained in the polyarylene sulfide resin composition has two or more crosslinkable functional groups. Examples of the crosslinkable functional group include an epoxy group, a phenolic hydroxyl group, an amino group, an amide group, a carboxy group, an acid anhydride group and an isocyanate group. Examples of the crosslinkable resin include epoxy resin, phenol resin and urethane resin.

As the epoxy resin, an aromatic epoxy resin is preferable. The aromatic epoxy resin may have a halogen group, a hydroxyl group, or the like. Examples of suitable aromatic epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, phenol novolac type epoxy resin, and cresol novolac. Type epoxy resin, bisphenol A novolak type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolac type epoxy resin, naphthol aralkyl Examples thereof include type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolak type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type epoxy resin, and biphenyl novolac type epoxy resin. These aromatic epoxy resins can be used alone or in combination of two or more. Among these aromatic epoxy resins, a novolac type epoxy resin is preferable, and a cresol novolac type epoxy resin is more preferable, because it is excellent in compatibility with other resin components.

The content of the crosslinkable resin is preferably 1 to 300 parts by mass, more preferably 3 to 100 parts by mass, and further preferably 5 to 30 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin. When the content of the crosslinkable resin is in these ranges, the effect of improving the rigidity and heat resistance of the molded product is particularly remarkable.

The polyarylene sulfide resin composition can contain a silane compound having a functional group. Examples of such silane compounds include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ-glycidoxypropylmethyl. Examples thereof include silane coupling agents such as diethoxysilane and γ-glycidoxypropylmethyldimethoxysilane.

The content of the silane compound is, for example, 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin. When the content of the silane compound is in these ranges, the effect of further improving the compatibility between the polyarylene sulfide resin and other components can be obtained.

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

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

The polyarylene sulfide resin composition can be subjected to various melt processing methods such as injection molding, extrusion molding, compression molding and blow molding, alone or in combination with other materials, to achieve heat resistance, molding processability, dimensional stability, etc. It can be processed into an excellent molded product. Since the polyarylene sulfide resin or the resin composition containing the polyarylene sulfide resin obtained by the production method according to the present embodiment has a small amount of gas generated when heated, it is possible to easily produce a high-quality molded product.

The polyarylene sulfide resin obtained by the production method of the present embodiment or a resin composition containing the resin also has various performances such as heat resistance and dimensional stability inherent in the polyarylene sulfide resin. Therefore, the polyarylene sulfide resin or the resin composition containing the resin is, for example, electric / electronic parts such as connectors, printed substrates and sealed molded products, automobile parts such as lamp reflectors and various electrical component parts, and various buildings. Various molding processes such as injection molding or compression molding of interior materials for aircraft and automobiles, or precision parts such as OA equipment parts, camera parts and clock parts, extrusion molding of composites, sheets, pipes, etc., or drawing molding. It is widely useful as a material for fibers or as a material for fibers or films.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

1. 1. Evaluation method 1-1. Identification method (NMR measurement)
The compound was dissolved in various deuterated solvents by the apparatus of DPX-400 manufactured by BRUKER, and various NMR measurements were performed.
1-2. Identification method (mass spectrometry)
The molecular weight of the compound was measured using MS-700T manufactured by JEOL.
1-3. Identification method (elemental analysis)
Using MT-5 manufactured by Yanaco, the ratio of the elements constituting the compound was measured.
1-4. Infrared absorption spectrum The infrared absorption spectrum was measured using "FT / IR-6100" manufactured by JASCO Corporation. An amorphous film prepared by heating the synthesized resin on a hot plate at 400 ° C. to melt it and quenching it was used as a measurement sample.
1-5. Glass transition temperature (Tg)
Using a PerkinElmer DSC device, Pyris Diamond, measurements were taken from 40 to 400 ° C. under a nitrogen flow of 50 mL / min and a temperature rise condition of 20 ° C./min to determine the glass transition temperature.
1-6. Melting point (Tm)
Using a PerkinElmer DSC device, Pyris Diamond, measurements were taken from 40 to 400 ° C. under a nitrogen flow of 50 mL / min and a temperature rise condition of 20 ° C./min to determine the melting point.
1-7.5% pyrolysis temperature (T _{5% d} )
Using a TG-DTA device (Rigaku TG-8120 Co., Ltd.), measurements were taken at a temperature rise rate of 20 ° C./min under a nitrogen flow of 20 mL / min, and a 5% weight loss temperature was measured.

2. 2. Monomer Synthesis In the examples shown below, the following reagents were used.
4-Bromo-4'-iodobiphenyl: Tokyo Chemical Industry Co., Ltd., purity> 98%
Iodomethane: Kanto Chemical Co., Inc., special grade copper iodide: Kanto Chemical Co., Inc., purity> 99%
Sulfur: Kanto Chemical Co., Inc. Potassium carbonate: Nacalai Tesque Co., Ltd., Nakarai Standard Special Grade N, N-Dimethylformamide (dehydration): Kanto Chemical Co., Ltd., Special Grade Boron Borone Hydrogenide: Kanto Chemical Co., Ltd. , No. 503
n-Butyl bromide: Tokyo Chemical Industry Co., Ltd., purity> 98%
n-octyl bromide: Tokyo Chemical Industry Co., Ltd., purity> 98%
t-Butyl Lithium: Kanto Chemical Co., Inc. tetrahydrofuran (dehydration): Kanto Chemical Co., Inc. Diphenyl disulfide: Kanto Chemical Co., Inc., special grade ammonium chloride: Nacalai Tesque Co., Ltd., Nakarai standard special grade nitrate (1.38): Wako Pure Chemical Industries (1.38) Made by Co., Ltd., special grade reagent, content 60-61%, density 1.38 g / mL
Dichloromethane: Kanto Chemical Co., Ltd., special grade trifluoromethanesulfonic acid: Wako Pure Chemical Industries, Ltd., Wako special grade pyridine: Wako Pure Chemical Industries, Ltd., Wako special grade methanesulfonic acid: Wako Pure Chemical Industries, Ltd., Wako special grade diphosphorus pentoxide : Wako Pure Chemical Industries, Ltd., Wako Special Grade

(Example 1-1)
Synthesis of 4-bromo-4'-(methylthio) biphenyl

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 were placed in a three-necked flask, and the inside of the flask was replaced 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. Then, 400 parts by mass of sodium borohydride was added at 0 ° C., and the mixture was stirred at 50 ° C. for 6 hours. Subsequently, 900 parts by mass of iodomethane 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 after filtration through Celite, extraction with dichloromethane and liquid separation, the organic layer was dehydrated with anhydrous magnesium sulfate. After filtration, the solvent was removed from the filtrate with a rotary evaporator, and the mixture was dried under reduced pressure to obtain a crude product. The crude product was separated by column chromatography using hexane as a developing solvent. The solution containing the separated target product was recovered, the solvent was removed with a rotary evaporator, and the mixture was dried under reduced pressure to obtain 4-bromo-4'-(methylthio) biphenyl in a yield of 43%. ^The product was confirmed by ^{1 1} H-NMR and ¹³ C-NMR.
^{1 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 t-butyllithium was added to the reaction solution at −78 ° C., and the mixture was stirred for 1 hour. Subsequently, 100 parts by mass of diphenyl disulfide was added to the reaction solution, and the mixture was stirred at 25 ° C. for 3 hours. Then, the reaction solution was poured into an aqueous ammonium chloride solution to stop the reaction, and after extraction and separation with diethyl ether, the organic layer was dehydrated with anhydrous magnesium sulfate. After filtration, the solvent was removed from the filtrate with a rotary evaporator, and the mixture was dried under reduced pressure to obtain a crude product. The crude product was separated by column chromatography using hexane as a developing solvent, the solution containing the target product was recovered, and the solvent was removed with a rotary evaporator to obtain 4-methylthio-4'-(phenylthio) biphenyl in a yield of 73. Obtained in%. ^The product was confirmed by ^{1 1} H-NMR, ¹³ C-NMR, EI-MS and elemental analysis.
^{1 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

100 parts by mass of 4-methylthio-4'-(phenylthio) biphenyl and 2000 parts by mass of dichloromethane were placed in an eggplant flask, and 40 parts by mass of nitric acid was added. The reaction solution was stirred at 25 ° C. for 3 hours, neutralized with saturated aqueous potassium carbonate solution, and the reaction was stopped. Then, after extraction with dichloromethane and liquid separation, the organic layer was dehydrated with anhydrous magnesium sulfate. After filtration, the solvent was removed from the filtrate with a rotary evaporator, and the mixture was dried under reduced pressure to obtain a crude product. The crude product is separated by column chromatography using chloroform as a developing solvent, the solution containing the target product is recovered, the solvent is removed with a rotary evaporator, and the mixture is dried under reduced pressure to 4-methylsulfinyl-4'-(phenylthio). ) Biphenyl was obtained in a yield of 72%. ^The product was confirmed by ^{1 1} H-NMR, ¹³ C-NMR, EI-MS and elemental analysis.
^{1 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 value): C 70.33 (70.19), H 4.97 (4.98)

(Example 2-1)
Synthesis of 4-bromo-4'-(methylsulfinyl) biphenyl

In an eggplant flask, 100 parts by mass of 4-bromo-4'-(methylthio) biphenyl and 2,000 parts by mass of dichloromethane were placed, and 50 parts by mass of nitric acid was added. The reaction solution was stirred at 25 ° C. for 3 hours, neutralized with saturated aqueous potassium carbonate solution, and the reaction was stopped. Then, after extraction with dichloromethane from the reaction solution and liquid separation, it was dehydrated with anhydrous magnesium sulfate. After filtering the dehydrated reaction solution, the solvent was removed from the filtrate with a rotary evaporator, and the mixture was dried under reduced pressure to obtain a crude product. The crude product was separated by column chromatography using chloroform as a developing solvent, and the solution containing the target product was recovered. The solvent was removed with a rotary evaporator and the mixture was dried under reduced pressure to obtain 4-bromo-4'-(methylsulfinyl) biphenyl in a yield of 83%. ^{1 The} product was confirmed by ¹ H-NMR.
^{1 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 4,000 parts by mass of tetrahydrofuran (dehydrated) were added. The reaction solution was added with 400 parts by mass of t-butyllithium at −78 ° C. and stirred for 1 hour. Subsequently, 100 parts by mass of diphenyl disulfide was added to the reaction solution, and the mixture was stirred at 25 ° C. for 3 hours. Then, the reaction solution was poured into an aqueous ammonium chloride solution to stop the reaction, and after extraction and separation with diethyl ether, the organic layer was dehydrated with anhydrous magnesium sulfate. The dehydrated reaction solution was filtered, the solvent was removed from the filtrate with a rotary evaporator, and the solution was dried under reduced pressure to obtain a crude product. The crude product was separated by column chromatography using hexane as a developing solvent, and the solution containing the target product was recovered. The solvent was removed with a rotary evaporator and dried under reduced pressure to obtain 4-methylsulfinyl-4'-(phenylthio) biphenyl in a yield of 68%. ^{1 The} product was confirmed by ¹ H-NMR.
^{1 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 procedure as in Example 1-1 was carried out except that 700 parts by mass of n-butyl bromide was used instead of iodomethane to obtain 4-bromo-4'-(n-butylthio) biphenyl in a yield of 72%. .. Then, 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 1} H-NMR, ¹³ C-NMR, EI-MS and elemental analysis.
^{1 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 value): C 75.21 (75.38), H 6.35 (6.33)

(Example 3-2)
Synthesis of 4-n-butylsulfinyl-4'-(phenylthio) biphenyl

4-n- was carried out in the same manner as in Examples 1-3 except that 4-n-butylthio-4'-(phenylthio) biphenyl was used instead of 4-methylthio-4'-(phenylthio) biphenyl. Butylsulfinyl-4'-(phenylthio) biphenyl was obtained in a yield of 85%. ^The product was confirmed by ^{1 1} H-NMR, ¹³ C-NMR, EI-MS and elemental analysis.
^{1 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 value): C 72.09 (72.12), H 6.05 (6.10)

(Example 4-1)
Synthesis of 4-n-octylthio-4'-(phenylthio) biphenyl

4-Bromo-4'-(n-octylthio) biphenyl was obtained in a yield of 77% by performing the same operation as in Example 1-1 except that 1000 parts by mass of n-octylbromid was used instead of iodomethane. It was. Then, 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 1} H-NMR, ¹³ C-NMR, HR-MS and elemental analysis.
^{1 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 value): C 76.54 (76.29), H 7.42 (7.44)

(Example 4-2)
Synthesis of 4-n-octylsulfinyl-4'-(phenylthio) biphenyl

4-n- was carried out in the same manner as in Example 1-3 except that 4-n-octylthio-4'-(phenylthio) biphenyl was used instead of 4-methylthio-4'-(phenylthio) biphenyl. Octylsulfinyl-4'-(phenylthio) biphenyl was obtained in 72% yield. ^The product was confirmed by ^{1 1} H-NMR, ¹³ C-NMR, HR-MS and elemental analysis.
^{1 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 {methyl methanesulfonate 4- [4- (phenylthio) phenyl] phenylsulfonium}

To a separable flask, 100 parts by mass of 4-methylsulfinyl-4'-(phenylthio) biphenyl and 50 parts by mass of diphosphorus pentoxide were added, and 500 parts by mass of methanesulfonic acid was further added dropwise at 0 ° C. The reaction solution was stirred at 25 ° C. for 20 hours and then poured into acetone to stop the reaction. The precipitated solid was removed by filtration and washed with acetone. Then, the washed solid was dried under reduced pressure to obtain poly {methyl methanesulfonate 4- [4- (phenylthio) phenyl] phenylsulfonium} in a yield of 93%. ^{1 The} product was confirmed by ¹ H-NMR.
^{1 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-phenylenethio-p, p'-biphenylylene sulfide)

100 parts by mass of the obtained poly {methyl methanesulfonate 4- [4- (phenylthio) phenyl] phenylsulfonium} and 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 at 120 ° C. for 20 hours. The reaction solution was poured into water to stop the reaction, and the precipitate was filtered off by filtration. Subsequently, the precipitate was washed with chloroform, NMP, and water, and the obtained solid was dried under reduced pressure to obtain poly (p-phenylenethio-p, p'-biphenylylene sulfide) in a yield of 43%. It was.

As a result of thermal analysis of the obtained poly (p-phenylenethio-p, p'-biphenylene sulfide), the glass transition temperature (T _g ) was 164 ° C, the melting point was 347 ° C, and the 5% thermal decomposition temperature (T). _{5% d} ) was 507 ° C. FIG. 1 shows an infrared absorption spectrum of the obtained poly (p-phenylenethio-p, p'-biphenylylene sulfide). In the infrared absorption spectrum of FIG. 1, no absorption peak due to the expansion and contraction 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-phenylenethio-p, p'-biphenylylene sulfide) has substantially no sulfonyl group.

(Example 6)
Synthesis of poly {n-butyl 4-[4- (phenylthio) phenyl] phenylsulfonium} and poly (p-phenylenethio-p, p'-biphenylylene sulfide)

The same procedure as in Example 5-1 was carried out except that 4-n-butylsulfinyl-4'-(phenylthio) biphenyl was used instead of 4-methylsulfinyl-4'-(phenylthio) biphenyl. N-Butyl 4- [4- (phenylthio) phenyl] phenylsulfonium} methanesulfonate was obtained in a yield of 95%. ^{1 The} product was confirmed by ¹ H-NMR.
^{1 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]

Poly (p-phenylenethio) was obtained by performing the same operation as in Example 5-2 except that the obtained poly {n-butyl 4- [4- (phenylthio) phenyl] phenylsulfonium} was used. -P, p'-biphenylylene sulfide) was obtained in a yield of 56%.

As a result of thermal analysis of the obtained poly (p-phenylenethio-p, p'-biphenylene sulfide), the glass transition temperature (T _g ) was 159 ° C, the melting point was 348 ° C, and the 5% thermal decomposition temperature (T). _{5% d} ) was 507 ° C. FIG. 2 shows an infrared absorption spectrum of the obtained poly (p-phenylenethio-p, p'-biphenylylene sulfide). In the infrared absorption spectrum of FIG. 2, no 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 .

(Example 7)
Synthesis of poly {n-octyl methanesulfonate 4- [4- (phenylthio) phenyl] phenylsulfonium} and poly (p-phenylenethio-p, p'-biphenylylene sulfide)

The same procedure as in Example 5-1 was performed except that 4-n-octylsulfinyl-4'-(phenylthio) biphenyl was used instead of 4-methylsulfinyl-4'-(phenylthio) biphenyl. N-octyl methanesulfonate 4- [4- (phenylthio) phenyl] phenylsulfonium} was obtained in a yield of 91%. ^{1 The} product was confirmed by ¹ H-NMR.
^{1 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]

Poly (p-phenylenethio) was carried out in the same manner as in Example 5-2 except that the obtained poly {n-octyl 4- [4- (phenylthio) phenyl] phenylsulfonium} was used. -P, p'-biphenylylene sulfide) was obtained in a yield of 32%.

As a result of thermal analysis of the obtained poly (p-phenylenethio-p, p'-biphenylene sulfide), the glass transition temperature (T _g ) was 158 ° C, the melting point was 349 ° C, and the 5% thermal decomposition temperature (T). _{5% d} ) was 520 ° C. FIG. 3 shows an infrared absorption spectrum of the obtained poly (p-phenylenethio-p, p'-biphenylylene sulfide). In the infrared absorption spectrum of FIG. 3, an absorption peak derived from the S = O expansion and contraction 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-phenylenethio-p, p'-biphenylylene sulfide)

To a 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 added dropwise at 0 ° C. The reaction solution was stirred at 25 ° C. for 20 hours and then poured into water to stop the reaction. The precipitated solid was removed by filtration and washed with water. Then, the washed solid was dried under reduced pressure to obtain poly {methyl trifluoromethanesulfonate 4- [4- (phenylthio) phenyl] phenylsulfonium} in a yield of 98%. ^{1 The} product was confirmed by ¹ H-NMR.
^{1 1} H-NMR (solvent CD ₃ CN): 3.58, 7.45, 7.66, 7.76, 7.94

(Example 8-2)
Synthesis of poly (p-phenylenethio-p, p'-biphenylylene sulfide)

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

As a result of thermal analysis of the obtained poly (p-phenylenethio-p, p'-biphenylylene sulfide), the glass transition temperature (T _g ) was 159 ° C, the melting point was 336 ° C, and the 5% thermal decomposition temperature (T). _{5% d} ) was 511 ° C. FIG. 4 shows an infrared absorption spectrum of the obtained poly (p-phenylenethio-p, p'-biphenylylene sulfide). In the infrared absorption spectrum of FIG. 4, no 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 .

(Comparative Example 1-1)
Synthesis of poly {methyl trifluoromethanesulfonate 4- [4- (phenylthio) phenyl] phenylsulfonium}

To a separable flask, 100 parts by mass of 4-methylsulfinyl-4'-(phenylthio) biphenyl and 600 parts by mass of trifluoromethanesulfonic acid were added dropwise at 0 ° C. The reaction solution was stirred at 25 ° C. for 20 hours and poured into water to stop the reaction. The precipitated solid was removed by filtration and washed with water. Then, the washed solid was dried under reduced pressure to obtain poly {methyl trifluoromethanesulfonate 4- [4- (phenylthio) phenyl] phenylsulfonium} in a yield of 95%. ^{1 The} product was confirmed by ¹ H-NMR.
^{1 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-phenylenethio-p, p'-biphenylylene sulfide)

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

As a result of thermal analysis of the obtained poly (p-phenylenethio-p, p'-biphenylylene sulfide), the glass transition temperature (T _g ) was 160 ° C., the melting point was not detected, and the 5% thermal decomposition temperature (T). _{It was 5% d} ) 465 ° C. FIG. 5 shows an infrared absorption spectrum of the obtained poly (p-phenylenethio-p, p'-biphenylylene sulfide). In the infrared absorption spectrum of FIG. 5, an absorption peak derived from the expansion and contraction vibration of S = O of the sulfonyl group was observed near the wave number of 1160 cm ^-1 . This indicates that the obtained poly (p-phenylenethio-p, p'-biphenylylene sulfide) has a trace amount of sulfonyl group.

Synthesis of PPS without biphenyl skeleton (Comparative Example 2)
To a separable flask, 100 parts by mass of methyl 4- (phenylthio) phenyl sulfoxide and 70 parts by mass of diphosphorus pentoxide were added, and 700 parts by mass of methanesulfonic acid was added dropwise at 0 ° C. The reaction solution was stirred at 25 ° C. for 20 hours, after which the reaction was stopped with 10000 parts by mass of acetone. The precipitated solid was collected by filtration and washed with acetone. The washed solid was dried under reduced pressure to obtain poly [methyl 4- (phenylthio) phenylsulfonium methanesulfonate] in a yield of 98%.

100 parts by mass of the obtained poly [methyl 4- (phenylthio) phenylsulfonium methanesulfonate] and 5000 parts by mass of N-methyl-2-pyrrolidone were added to the eggplant flask. The reaction solution was stirred at 25 ° C. for 30 minutes and then at 110 ° C. for 20 hours. The reaction solution was poured into water to stop the reaction, and the precipitate was filtered off by filtration. Subsequently, the precipitate was washed with chloroform, NMP, and water, and the obtained solid was dried under reduced pressure to obtain 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. It was.

Claims (13)

A polyarylene sulfide resin having a main chain containing a structural unit represented by the following general formula (1.1).
The proportion of the structural unit represented by the general formula (1.1) in the main chain of the polyarylene sulfide resin is 95 to 100% by mass.
A polyarylene sulfide resin in which an absorption peak derived from S = O expansion and contraction vibration of a sulfonyl group is not observed in the infrared absorption spectrum of the polyarylene sulfide resin.

[In the general formula (1.1), Ar ^2b represents a phenylene group which may have a substituent, Ar ¹ represents an arylene group which may have a substituent, and two Ar ¹ are the same. But it may be different. ] The method for producing the polyarylene sulfide resin according to claim 1.
A method comprising a step of dealkylating or dearylting a poly (arylene sulfonium salt) having a main chain containing a structural unit represented by the following general formula (2.1) to produce the polyarylene sulfide resin.

[In the formula, Ar ^2b represents a phenylene group which may have a substituent, Ar ¹ represents an arylene group which may have a substituent, and R ¹ is an alkyl group having 1 to 10 carbon atoms. or have an alkyl group having 1 to 10 carbon atoms as a substituent represent an aryl group, X ^- represents an anion, two Ar ¹ may be the same or different. ] The method according to claim 2, further comprising a step of polymerizing a sulfoxide compound represented by the following general formula (3.1) in the presence of an acid to produce the poly (arylene sulfonium salt).

[In the formula, Ar ¹ represents an arylene group which may have a substituent, Ar ^2a represents a phenyl group which may have a substituent, and R ¹ is an alkyl group having 1 to 10 carbon atoms. or have an alkyl group having 1 to 10 carbon atoms as a substituent represent an aryl group, two Ar ¹ may be the same or different. ] A poly (arylene sulfonium salt) having a main chain containing a structural unit represented by the following general formula (2.1).

[In the formula, Ar ¹ and Ar ^2b each independently represent an arylene group which may have a substituent, and R ¹ is an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms. It represents an aryl group which may have a, X ^- represents an anion, two Ar ¹ may be the same or different. ] The method for producing a poly (arylene sulfonium salt) according to claim 4.
A method comprising a step of polymerizing a sulfoxide compound represented by the following general formula (3.1) in the presence of an acid to produce the poly (arylene sulfonium salt).

[In the formula, Ar ¹ represents an arylene group which may have a substituent, Ar ^2a represents an aryl group which may have a substituent, and R ¹ is an alkyl group having 1 to 10 carbon atoms. or have an alkyl group having 1 to 10 carbon atoms as a substituent represent an aryl group, two Ar ¹ may be the same or different. ] A sulfoxide compound represented by the following general formula (3.1).

[In the formula, Ar ¹ represents an arylene group which may have a substituent, Ar ^2a represents an aryl group which may have a substituent, and R ¹ is an alkyl group having 1 to 10 carbon atoms. or have an alkyl group having 1 to 10 carbon atoms as a substituent represent an aryl group, two Ar ¹ may be the same or different. ] The method for producing a sulfoxide compound according to claim 6.
A method comprising a step of oxidizing a sulfide compound represented by the following general formula (4.1) to produce the sulfoxide compound.

[In the formula, Ar ¹ represents an arylene group which may have a substituent, Ar ^2a represents an aryl group which may have a substituent, and R ¹ is an alkyl group having 1 to 10 carbon atoms. or have an alkyl group having 1 to 10 carbon atoms as a substituent represent an aryl group, two Ar ¹ may be the same or different. ] A sulfide compound represented by the following general formula (4.1).

[In the formula, Ar ¹ represents an arylene group which may have a substituent, and Ar ^2a is selected from an alkyl group having 1 to 10 carbon atoms, a hydroxy group, an amino group, a mercapto group, an ester group, and a carboxy group. Represents an aryl group which may have a substituent, and R ¹ may have an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms as a substituent. the stands, two Ar ¹ may be the same or different. ] The method for producing the sulfide compound according to claim 8.
A method comprising a step of producing the sulfide compound by reacting a diaryldisulfide represented by the following general formula (5.1) with a sulfide compound represented by the following general formula (6.1).


[In the general formula (5.1), Ar ^2a may have a substituent selected from an alkyl group having 1 to 10 carbon atoms, a hydroxy group, an amino group, a mercapto group, an ester group, and a carboxy group. Representing a group, the two Ar ^2a may be the same or different
In the general formula (6.1), Ar ¹ represents an arylene group which may have a substituent, and R ¹ is an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms as a substituent. represents an aryl group which may have an alkyl group, Y ¹ represents a halogen atom, two Ar ¹ may be the same or different. ] The method for producing a sulfoxide compound according to claim 6.
The sulfoxide compound represented by the general formula (3.1) is produced by the reaction of the diallyl disulfide represented by the following general formula (5.1) with the sulfoxide compound represented by the following general formula (8.1). A method that comprises a process.


[In the general formula (5.1), Ar ^2a represents an aryl group which may have a substituent, and the two Ar ^2a may be the same or different.
In the general formula (8.1), Ar ¹ represents an arylene group which may have a substituent, and R ¹ is an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms as a substituent. represents an aryl group which may have an alkyl group, Y ¹ represents a halogen atom, two Ar ¹ may be the same or different. ] A sulfoxide compound represented by the following general formula (8.1).

[In the formula, Ar ¹ represents an arylene group which may have a substituent, and R ¹ is an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group or a decyl group. or have an alkyl group having 1 to 10 carbon atoms as a substituent represent an aryl group, Y ¹ represents a halogen atom, two Ar ¹ may be the same or different. ] The method for producing a sulfoxide compound according to claim 11.
A method comprising a step of oxidizing a sulfide compound represented by the following general formula (6.1) to produce the sulfoxide compound.

[In the formula, Ar ¹ represents an arylene group which may have a substituent, and R ¹ is an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group or a decyl group. or have an alkyl group having 1 to 10 carbon atoms as a substituent represent an aryl group, Y ¹ represents a halogen atom, two Ar ¹ may be the same or different. ] A molded product containing the polyarylene sulfide resin according to claim 1.