JPH05301962A - Production of new polyarylene sulfide - Google Patents

Abstract

PURPOSE:To efficiently obtain the subject polymer, excellent in heat and chemical resistance and fluidity and useful as a member, etc., for electrical and electronic devices in a short time by carrying out the thermal ring opening polymerization of a specific cyclic arylene sulfide oligomer in the presence of a specific ionic compound and a Lewis acid. CONSTITUTION:A cyclic arylene sulfide oligomer expressed by formula I (Ar is 6-24C arylene; R is 1-12C alkyl, 1-12C alkoxy, 6-24C arylene or primary, secondary or tertiary amino; n is 2-50; m is 0-15) is subjected to the thermal ring opening polymerization in the coexistence of an ionic compound expressed by formula II (R' is H, 1-12C alkyl, 1-12C alkoxy, 6-24C arylene, etc.; B is 1-24C organic group; D<-> is anionic species such as S or O; M<+> is monovalent metallic ion, bivalent metallic monohalide ion, etc.; p is 0-15; q is 1-15) in an amount of preferably 0.01-10mol% (based on 1mol oligomer) and a Lewis acid such as copper chloride in an amount of preferably 0.001-100mol% (based on 1mol oligomer) to afford the objective polymer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyarylene sulfide excellent in mechanical properties, heat resistance and chemical resistance, and more particularly to a polyarylene sulfide oligomer characterized by ring-opening polymerization. The present invention relates to a method for producing arylene sulfide.

Polyarylene sulfide has been attracting attention as a member for electric / electronic equipment and a member for automobile equipment due to its excellent heat resistance and chemical resistance. Also injection molding,
It can be molded into various molded parts, films, sheets, fibers, etc. by extrusion molding and is widely used in fields where heat resistance and chemical resistance are required.

[0003]

2. Description of the Related Art As a method for producing polyarylene sulfide, as disclosed in Japanese Patent Publication No. 45-3368, a dihaloaromatic compound and an alkali such as sodium sulfide are used in an organic amide solvent such as N-methylpyrrolidone. Desalting polycondensation by a nucleophilic substitution reaction with a metal compound is general.

However, since this production method uses a nucleophilic aromatic nucleophilic substitution reaction having low reactivity, it requires a reaction under high temperature and high pressure, and in addition, an expensive high boiling point polar solvent such as N-methylpyrrolidone is used. It requires a large amount of energy and requires a large amount of cost for solvent recovery, and requires a large amount of process cost.

Further, since the obtained polymer has a low molecular weight, a step of heating and oxidative crosslinking in air to make a high molecular weight is further required for use in molding and processing, which complicates the process and lowers productivity. Will be invited.

Therefore, a method for obtaining a high molecular weight polyarylene sulfide has been proposed. As a typical example, a method of adding a polymerization aid (Japanese Patent Publication No. 52-12240, US Pat. No. 4,038,263), a method of controlling the polymerization temperature and the amount of water in the system (Japanese Patent Laid-Open No. 61- 7332
JP-A No. 62-149725) and the like. However, there are drawbacks such as a large amount of expensive polymerization aid, a long polymerization time, increased cost, and reduced productivity. Have

Recently, a new method for producing polyarylene sulfide which has solved such a problem has been attracting attention.
As a typical example, a method of cationically oxidatively polymerizing diphenyl disulfide or thiophenol using a Lewis acid (Japanese Patent Laid-Open No. 63-213526, 63-63).
No. 213527), similarly, a method in which diphenyl disulfide or thiophenol is subjected to oxidative coupling polymerization with oxygen using a catalyst in the presence of an acid (JP-A-2-
169626) has been proposed. However, in these methods, polyphenylene sulfide without branching can be obtained in high yield under mild conditions.
Since the obtained polyphenylene sulfide has a low melting point and is a low molecular weight substance, it is difficult to use it as it is for applications such as injection molding. Further, there are problems that a large amount of expensive Lewis acid and oxidizing agent are required and that the reaction takes a long time, which results in an increase in manufacturing cost and is industrially disadvantageous.

By the way, poly (phenylene sulfide)
It is known that an oligomer can be effectively used by curing it to obtain a useful product (US Pat.
046,749). This method is characterized by performing heat treatment at high temperature in the presence of oxygen gas, and the product is partially oxygen-crosslinked. Further, the obtained product does not show a clear melting point, but is inferior in fluidity and color tone of the molded product.

On the other hand, a method for producing an engineering plastic by ring-opening polymerization of a cyclic oligomer is generally known. A method for producing nylon 6 by ring-opening polymerization of ε-caprolactam is already known.

Recently, macrocyclic condensation oligomers
Manufacturing method, polymerization method and composite material of the obtained polymer
There are reports on the application of. For example, polycar
Bonate (ACS Polym. Prepr.Thirty
[2], 569 (1989)), polyarylate (AC
S Polym. Prepr.Thirty[2], 579
(1989)), polyether sulfone (ACS Po
lym. Prepr.Thirty[2], 581 (198
9)), polyimide siloxane (Macromolec)
ules,23, 4341 (1990); ibid. ，
23, 4514 (1990)), aromatic polyethers
(J. Chem. Soc. Chem. Comm.
un. 1990, 336); JP-A-3-88828
News) etc.

[0011]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems and is a polyarylene sulfide excellent in heat resistance, chemical resistance, various mechanical characteristics, electrical characteristics, fluidity, moldability, etc. In particular, the present invention provides a novel production method by which a high-molecular weight polyarylene sulfide that is essentially linear and has a low proportion of cross-linked polymer can be obtained in a short time, almost quantitatively, and easily.

[0012]

Means for Solving the Problems That is, the present invention provides the following general formula (1):

[0013]

[Chemical 2] (Here, S represents a sulfur atom, Ar represents a carbon number of 6 to 24.
R is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an arylene group having 6 to 24 carbon atoms, a primary, secondary or tertiary amino group.
Ar and R may have the same structure or different structures. Moreover, n is an integer of 2 to 50 and m is an integer of 0 to 15. In the case of ring-opening polymerization of the cyclic arylene sulfide oligomer represented by the formula (1), as a ring-opening polymerization catalyst, the following general formula (2) (R ') _p- B- (D ^- M ⁺ ) _q (2) (where R' Is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an arylene group having 6 to 24 carbon atoms, a primary, secondary or tertiary amino group, a carboxyl group and its ester, a cyano group , A sulfonic acid group, a halogen atom, B represents an organic group having 1 to 24 carbon atoms, D ⁻ represents an anion species of sulfur or oxygen, M
⁺ Represents a monovalent metal ion, a divalent metal monohalide ion, an ammonium ion, or a phosphonium ion, p is an integer of 0 to 15, and q is an integer of 1 to 15. The present invention relates to a method for producing a polyarylene sulfide, which comprises performing ring-opening polymerization by heating in the presence of an ionic compound represented by the formula (1) and a Lewis acid.

The details will be described below.

Ar in the cyclic arylene sulfide oligomer of the formula (1) used in the present invention has an Ar content of 6 to
It is an arylene group having 24 carbon atoms and at least one aromatic ring, and examples thereof include phenylene, biphenylene, naphthalene ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, benzotriazole ring and phthalimide ring. Of these, preferred arylene groups are phenylene, biphenylene, naphthalene ring and benzimidazole ring.

R in the formula (1) is an alkyl group having 1 to 12 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group. , Sec-butoxy group, ter
Examples thereof include an alkoxy group having 1 to 12 carbon atoms such as t-butoxy group, an arylene group having 6 to 24 carbon atoms such as phenyl, biphenyl, and naphthyl group, a primary, secondary, or tertiary amino group. Further, R is a carboxyl group and its ester, a cyano group, a sulfonic acid group, a fluorine atom, a chlorine atom,
It may be a halogen atom such as a bromine atom or an iodine atom. Among these, alkyl groups such as methyl group and ethyl group, alkoxy groups such as methoxy group and ethoxy group,
A cyclic arylene sulfide oligomer having an amino group or an unsubstituted cyclic arylene sulfide oligomer is preferably used.

In the above formula (1), n is an integer of 2 to 50, but it is preferably 2 to 35, and more preferably 2 to 25 for lowering the melting point.

The polymerizable cyclic arylene sulfide oligomer may be either a single compound having a single degree of polymerization or a mixture of cyclic oligomers having different degrees of polymerization. It may also be a mixture of cyclic oligomers having different repeating units. Mixtures of cyclic oligomers are preferred because oligomer mixtures with different degrees of polymerization have lower melting points than single compounds with a single degree of polymerization.

The cyclic oligomer mixture may contain a small amount of a linear oligomer or a compound having a very small amount of an arylene sulfide unit. It may also contain a linear or cyclic polymer having a low viscosity at a temperature at which these oligomers are liquid.

In the present invention, various ionic compounds are used as the ring-opening polymerization catalyst.

As the ionic compound which can serve as a ring-opening polymerization catalyst, various metal salts, ammonium salts, phosphonium salts and the like can be mentioned. For example, mono- or divalent metal monohalide aryl or alkyl, aryl or alkyl oxide, hydroxide, amide, hydride, sulfide, halide, cyanide, carboxylate, carbonate. , Hydrogencarbonate, ammonium salt, phosphonium salt, tertiary amine and the like. Among them, the ionic compounds represented by the above formula (2) which generate a sulfur anion species and an oxygen anion species are preferable.

R'in the above formula (2) is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a sec-butyl group, a tert-butyl group, or methoxy. Group, ethoxy group, propoxy group, isopropoxy group, butoxy group, sec-butoxy group, ter
C1-C12 alkoxy group such as t-butoxy group, C6-C24 arylene group such as phenyl, biphenyl and naphthyl group, primary, secondary or tertiary amino group, carboxyl group and ester thereof, nitro Group, cyano group, sulfonic acid group and the like. Among them, lower alkyl groups such as hydrogen atom, methyl group, ethyl group, propyl group, butyl group, sec-butyl group, tert-butyl group, methoxy group, ethoxy group, propoxy group, isopropoxy group,
A lower alkoxy group such as butoxy group, sec-butoxy group and tert-butoxy group, an amino group and the like are preferable.

R'is an electron-donating group such as an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an arylene group having 6 to 24 carbon atoms, 1, 2 or a tertiary amino group. If so, the ring-opening polymerization catalyst can be highly activated.

B in the above formula (2) is an organic group having 1 to 24 carbon atoms, and is an arylene group having 6 to 24 carbon atoms or a pyridine ring, a pyrimidine ring, an imidazole ring, a benzimidazole ring, a benzoxazole ring. It means that even a heterocyclic compound such as a benzothiazole ring may be used. Among them, phenylene, biphenylene, naphthalene ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, benzotriazole ring, phthalimide ring and the like, which are excellent in stability at high temperature, are preferable. More preferably phenylene, biphenylene,
A naphthalene ring and a benzimidazole ring.

D ⁻ in the above formula (2) is either a sulfur anion species or an oxygen anion species, and a sulfur anion species having a high nucleophilicity is preferable.

M ⁺ in the above formula (2) is a monovalent metal ion, a divalent metal monohalide ion, an ammonium ion, or a phosphonium ion. Metal ions and divalent metal monohalide ions are preferred. Further, by changing the monovalent metal ion and the divalent metal monohalide ion, it becomes possible to improve the activity and increase the molecular weight of the produced polymer. For example, a ring-opening polymerization catalyst having a metal ion having a smaller ionic radius such as lithium ion than sodium ion has higher activity, and a ring-opening polymerization catalyst having a larger ionic radius such as potassium is used to produce a polymer. It is possible to achieve a higher molecular weight.

The examples of the ring-opening polymerization catalyst used in the present invention are shown below, but the present invention is not limited thereto.

As a ring-opening polymerization catalyst for producing a sulfur anion species, thiophenol, 1,2-benzenedithiol,
1,3-benzenedithiol, 1,4-benzenedithiol, 2-thiocresol, 3-thiocresol, 4-
Thiocresol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 2-methoxybenzenethiol, 3-methoxybenzenethiol, 4-methoxybenzenethiol, 4-nitrothiophenol, 4-tert-butyl Thiophenol, 3-
Dimethylaminothiophenol, 4-dimethylaminothiophenol, 2-chlorothiophenol, 3-chlorothiophenol, 4-chlorothiophenol, 2-bromothiophenol, 3-bromothiophenol, 4-bromothiophenol, 4- tert-butyl-1,2-
Examples thereof include lithium salts such as benzenedithiol, mercaptoimidazole, mercaptobenzimidazole, mercaptobenzoxazole, mercaptobenzothiazole and mercaptopyrimidine, and alkali metal salts such as sodium salt or potassium salt.

As the ring-opening polymerization catalyst for generating oxygen anion species, phenol, 1,2-benzenediol, 1,3
-Benzenediol, 1,4-benzenediol, 2-
Cresol, 3-cresol, 4-cresol, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol, 4-nitrophenol, 4-tert-butylphenol , 3-dimethylaminophenol, 4-dimethylaminophenol, 2-
Examples thereof include lithium salts such as chlorophenol, 3-chlorophenol, 4-chlorophenol, 2-bromophenol, 3-bromophenol, 4-bromophenol, and alkali metal salts such as sodium salt and potassium salt.

These ring-opening polymerization catalysts may be used alone or in combination of two or more.

The concentration of the ring-opening polymerization catalyst used varies depending on the molecular weight of the target polyarylene sulfide and the kind of the ring-opening polymerization catalyst, but is usually 0 with respect to the cyclic oligomer (the number of moles per unit of arylene sulfide). 0.001 to 20 mol%, preferably 0.005 to 15
Mol%, and more preferably 0.01 to 10 mol%.

The Lewis acid that can be used together with the ring-opening polymerization catalyst used in the present invention is not particularly limited,
Preferably zinc, copper (I), copper (II), iron (II),
Iron (III), cobalt, nickel, lead, tin, silver,
Gold, thallium (I), thallium (III), palladium, cadmium, platinum (II), platinum (I
V), mercury (I), mercury (II), gallium, tellurium,
Antimony, bismuth, rhodium, iridium, ruthenium, osmium, hydrogen, lithium, sodium, potassium, beryllium, aluminum, manganese, magnesium, calcium, titanium fluorides, chlorides, bromides, iodides, alkylates, alkoxides, etc. Can be mentioned.

These Lewis acids may be used alone or in combination of two or more.

There is no problem if the concentration of the Lewis acid used is 0.001 to 100 mol% based on the cyclic oligomer (the number of moles per unit of arylene sulfide), but the same range as the above ring-opening polymerization catalyst is used. It is preferably within.

When the ring-opening polymerization catalyst or Lewis acid is added, it may be added as it is, or the cyclic oligomer may be dissolved in a suitable solvent, preferably methylene chloride,
A method of adding a predetermined amount of a ring-opening polymerization catalyst and / or a Lewis acid thereto and then removing the solvent may be adopted.

The temperature used for the ring-opening polymerization of the present invention is preferably not higher than the melting temperature of the cyclic oligomer mixture and the decomposition temperature of the ring-opening polymerization catalyst, Lewis acid or cyclic oligomer used. Further, if the polymerization temperature is too high, the possibility of side reaction such as curing reaction of the cyclic oligomer increases. Usually in the range of 150 to 400 ° C, 180 to 37
The range of 0 ° C. is preferable, and more preferably 200 to 35.
It is in the range of 0 ° C.

The reaction time varies depending on the conditions such as the ring-opening polymerization catalyst used, the type of Lewis acid, the polymerization temperature, etc., but it is preferable to set the conditions so as to suppress the curing reaction as much as possible, usually 0.1 to 100 hours. It is preferable to carry out in the range of.

The above-mentioned polymerization may be carried out not only in an ordinary polymerization reaction tank, but also in a mold for producing a molded article, or as an extrudate for producing a polyarylene sulfide. The polymerization may be carried out in the machine.

The polyarylene sulfide such as polyphenylene sulfide obtained in the present invention is excellent in heat resistance, chemical resistance, various mechanical characteristics and electrical characteristics. Further, it has an advantage that the proportion of the cross-linked polymer is extremely low, the polymer is essentially linear, and the flowability and moldability are excellent. Furthermore, in the present invention, by adjusting the amount of ring-opening polymerization catalyst used, the amount of Lewis acid,
It becomes possible to control the molecular weight of the polyarylene sulfide, and normally, a polyarylene sulfide having a higher molecular weight than the polyarylene sulfide obtained by polycondensation can be easily obtained.

The polyarylene sulfide obtained as described above can be melt-mixed with various polymers and is expected to have improved physical properties as a polymer alloy.

Specific examples of blendable polymers include polyethylene, polybutadiene, polyisoprene,
Polychloroprene, polystyrene, polybutene, poly α
-Methyl styrene, polyvinyl acetate, polyvinyl chloride,
Polyacrylic acid ester, polymethacrylic acid ester,
Polyacrylonitrile, nylon 6, nylon 66, nylon 610, nylon 12, nylon 11, nylon 46 and other polyamides, polyethylene terephthalate,
Polybutylene terephthalate, polyester such as polyarylate, polyurethane, polyacetal, polycarbonate, polyphenylene oxide, polysulfone, polyether sulfone, polyallyl sulfone, polyphenylene sulfide sulfone, polyether ketone, polyether ether ketone, polyphenylene sulfide ketone, polyimide, polyamideimide , Homopolymers such as epoxy resins, silicone resins, phenoxy resins, and fluororesins, random or block, graft copolymers, and mixtures thereof.

If necessary, reinforcing fibers such as glass fibers, carbon fibers, ceramic fibers such as alumina fibers, aramid fibers, wholly aromatic polyester fibers, metal fibers, potassium titanate whiskers, calcium carbonate, mica, Talc, silica, barium sulfate, calcium sulfate, kaolin, clay, pyroferrite, bentonite, serisanite, zeolite, nepheline sinite, attapulgite, wollastonite, ferrite, calcium silicate, magnesium carbonate, dolomite, antimony trioxide, zinc oxide. , Titanium oxide, magnesium oxide, iron oxide, molybdenum disulfide, graphite, gypsum, glass beads, glass powder, glass balloon,
Inorganic fillers such as quartz and quartz glass and organic and inorganic pigments can also be blended.

Further, a releasing agent, a silane type or titanate type coupling agent, a lubricant, a heat resistance stabilizer, a weather resistance stabilizer, a crystal nucleating agent, a foaming agent, a rust preventive agent, an ion trap agent, a flame retardant,
A flame retardant aid or the like may be added if necessary.

As described above, the polyarylene sulfide obtained by the above-mentioned production method is used alone or in combination with the above-mentioned polymer, reinforcing filler, inorganic filler and the like, and various molded articles and films are obtained by injection molding and extrusion molding. It can be molded into sheets, pipes, fibers, etc.

[0045]

The present invention will be described below with reference to examples. These examples are illustrative and not limiting.

The cyclic oligomer mixture used in each of the examples was a cyclic phenylene sulfide oligomer having a degree of polymerization of 7 to 15 and substantially no linear phenylene sulfide oligomer. The molecular weight was calculated in terms of polystyrene by gel permeation chromatography (GPC). The measurement conditions of GPC are shown below.

Eluent: 1-chloronaphthalene Temperature: 210 ° C. Detector: UV detector 360 nm Flow rate: 1.0 ml / min Injection volume: 200 μl (slurry form: 0.2% by weight) Melting point: DSC (Seiko Denshi) ) Is used, the temperature is maintained at 340 ° C. for 5 minutes and then cooled to 50 ° C.
Measured in minutes.

The melt viscosity was measured using a Koka type flow tester at 300 ° C., a load of 10 kg, a die diameter of 0.5 mm,
The length was measured using a die of 2.0 mm.

Reference Example 1 (Method for recovering cyclic phenylene sulfide oligomer) The cyclic phenylene sulfide oligomer used in each example was recovered by the following procedure.

A 15 l reactor equipped with a stirrer, a dehydration tower and a jacket was charged with N-methyl-2-pyrrolidone (N
MP) 5 l and sodium sulfide (purity: Na ₂ S 6
0.4%) 1872.5 g was charged, and the mixture was heated with a jacket while stirring and dehydrated through a dehydration tower until the internal temperature reached about 205 ° C. At this time, 420 g of effluent mainly consisting of water was distilled off. Then, 2153 g of p-dichlorobenzene was added, the temperature was raised to 250 ° C., and the reaction was carried out for 3 hours. After the reaction was completed, the reaction mixture was cooled to about 100 ° C., the pressure inside the reactor was reduced, and then the mixture was reheated to distill off 5200 g of an effluent mainly composed of NMP through the dehydration tower. The pressure in the reactor system was returned to normal pressure, 8 l of water was added to form a water slurry, and the mixture was heated and stirred at 80 ° C. for 15 minutes, then the water slurry was extracted from the outlet at the bottom of the reactor and centrifuged to recover a polymer. .. Further, the polymer was returned to the reactor, 8 liters of water was added, the mixture was heated and stirred at 180 ° C. for 30 minutes, and after cooling, the water slurry was extracted from the outlet of the lower part of the reactor and centrifuged to recover the polymer. The obtained polymer was transferred to a ribbon blender with a jacket and dried. The polymer obtained was 1450 g and had a melt viscosity of 240 poise.

Then, this polyphenylene sulfide 2
Soxhlet extraction was carried out using 00 g of methylene chloride as a solvent. Then, the saturated methylene chloride extract was added to methanol, and the precipitate was filtered and dried to obtain 1.2 g of a cyclic phenylene sulfide oligomer mixture. From the results of mass spectrum and high performance liquid chromatography, it was confirmed that this cyclic oligomer mixture was substantially a 7 to 15-mer cyclic phenylene sulfide oligomer. The melting point was 260 ° C.

Example 1 540 mg of the cyclic phenylene sulfide oligomer obtained in Reference Example 1 and sodium salt of thiophenol 6.6.
mg and 7.2 mg of copper (II) chloride were charged into a 10 ml test tube for polymerization, the atmosphere was replaced with nitrogen, and the tube was sealed under reduced pressure at 300 ° C.
Was immersed in the molten salt bath for 30 minutes. The obtained off-white product was cooled to room temperature, then pulverized, and redissolved in 250 ml of 1-chloronaphthalene at 230 ° C. A white precipitate was obtained upon cooling to room temperature. The precipitate was filtered, washed (methylene chloride, methanol) and dried to obtain 533 mg of white powder. The yield was 99% and the melting point was 283 ° C. The weight average molecular weight of the obtained polymer was 60,000.

Examples 2 and 3 The same as Example 1 except that the copper (II) chloride used in Example 1 was replaced with 5.3 mg and 6.6 mg of copper (I) chloride and zinc chloride, respectively. Polymerization was performed under the conditions. In both cases, a white powder was obtained with a yield of 98%. The weight average molecular weight was 53,000 and 49,000, respectively.

Example 4 Polymerization was carried out under the same conditions as in Example 1 except that the sodium salt of thiophenol and copper (II) chloride used in Example 1 were changed to 1.8 mg each. Yield 98
% A white powder is obtained with a weight average molecular weight of 9800
It was 0.

Comparative Example 1 Polyphenylene sulfide was obtained in the same manner as in Reference Example 1. The obtained polyphenylene sulfide has a melting point of 280 ° C.
The weight average molecular weight was 28,000, which was a low molecular weight as compared with the examples.

Comparative Example 2 540 mg of the cyclic phenylene sulfide oligomer obtained in Reference Example 1 was placed under the same conditions as in Example 1 in the absence of a ring-opening polymerization catalyst. The black product obtained is 230 ° C.
It was a cross-linked polymer partially insoluble in 1-chloronaphthalene. In addition, the 1-chloronaphthalene soluble component also has a melting point of 265.
It was shown to be ° C and was a highly crosslinked polymer.

[0057]

As is apparent from the above description, according to the present invention, a high-molecular weight polyarylene sulfide having a low proportion of crosslinked polymer and having an essentially linear structure can be quantitatively determined in a short time. Therefore, it can be easily obtained.

Claims (2)

[Claims] 1. The following general formula (1): (Here, S represents a sulfur atom, Ar represents a carbon number of 6 to 24.
R is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an arylene group having 6 to 24 carbon atoms, a primary, secondary or tertiary amino group.
Ar and R may have the same structure or different structures. Moreover, n is an integer of 2 to 50 and m is an integer of 0 to 15. In the case of ring-opening polymerization of the cyclic arylene sulfide oligomer represented by the formula (1), as a ring-opening polymerization catalyst, the following general formula (2) (R ') _p- B- (D ^- M ⁺ ) _q (2) (where R' Is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an arylene group having 6 to 24 carbon atoms, a primary, secondary or tertiary amino group, a carboxyl group and its ester, a cyano group , A sulfonic acid group, a halogen atom, B represents an organic group having 1 to 24 carbon atoms, D ⁻ represents an anion species of sulfur or oxygen, M
⁺ Represents a monovalent metal ion, a divalent metal monohalide ion, an ammonium ion, or a phosphonium ion, p is an integer of 0 to 15, and q is an integer of 1 to 15. ] The ring-opening polymerization by heating is carried out in the coexistence of the ionic compound represented by the above) and a Lewis acid. 2. The method for producing a polyarylene sulfide according to claim 1, wherein a ring-opening polymerization catalyst in which R'in the general formula (2) is an electron-donating group is used.