JP3050568B2 - Method for producing arylene thioether polymer - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel method for producing polyarylene thioether. More specifically, polyarylene thioether (hereinafter abbreviated as PATE) is depolymerized to produce a prepolymer having an alkali thiolate group at a terminal, and then the prepolymer is reacted with a specific dihalogen-substituted aromatic compound to produce a prepolymer. The present invention relates to a method for producing an arylene thioether polymer having excellent melt stability and low ionic impurities by polymerization.

According to the present invention, an off-spec (non-standard) polymer or oligomer in the production of PATE, or molding waste of PATE or waste plastic can be used as a raw material.

[Conventional technology]

Conventionally, PATE has been produced mainly by a method of reacting a dihalogen-substituted aromatic compound with an alkali metal sulfide in a polar organic solvent (for example, Japanese Patent Publication No. 45-3368,
JP-B-53-25589, U.S. Pat. No. 3,919,177, U.S. Pat. No. 4,645,826, etc.).

 This reaction is represented by the following equation.

n (X-Ar-X) + nM ₂ S → Ar-S _n + 2nMX (where Ar is an aromatic residue, M is an alkali metal, and X is a halogen atom) In this production method, dihalogen-substituted aromatic Along with the reaction of the compound with the alkali metal sulfide at a high temperature, phenols and amines are produced as by-products, which adversely affect the degree of polymerization and the melt stability of the produced PATE.

In addition, in the conventional production method, a relatively large amount of oligomers may be produced as by-products, and so-called off-spec products having a melt viscosity out of the standard may be generated, which causes a reduction in yield.

On the other hand, it is desired to reuse such oligomers, off-spec products, debris generated during molding of PATE, and used molded products (waste plastic) from the viewpoint of effective use of resources. No effective use has been proposed yet.

By the way, as another production method of PATE, a method of reacting a dihalogen-substituted aromatic compound with an aromatic dithiol or an alkali metal salt thereof (alkali thiolate) has been proposed (JP-B-45-19713, JP-B-46-19763). 4398
No., JP-A-61-197634, JP-A-61-200127, JP-A-Showa
62-529, JP-A-62-530, JP-A-62-91530, JP-A-62-20530, etc.).

 This reaction is represented by the following two equations.

According to this production method, the reactivity is good, but the aromatic dithiol and alkali thiolate as raw materials are easily oxidized, so that purification and handling thereof are difficult, production costs are high, and industrial implementation is difficult. is there.

[Problems to be solved by the invention]

An object of the present invention is to provide a method for producing PATE by using oligomers or off-spec products generated during PATE production, or molding waste or waste plastic of PATE as a raw material.

The present inventors have conducted intensive studies to overcome the problems of the prior art, and found that when an alkali metal sulfide was allowed to act on PATE, the main chain of PATE was cut and depolymerized, resulting in one end. Alternatively, they have found that a compound (prepolymer) having an alkali thiolate group at both ends can be easily obtained.

Then, it was found that when the prepolymer having an alkali thiolate group at its terminal was reacted with a dihalogen-substituted aromatic compound in a water-containing polar organic solvent, the prepolymer had a polymerization reaction again to increase the degree of polymerization. Moreover, this prepolymer is
It was found that the polymerization reaction system had excellent stability. That is, it is possible to take advantage of only the advantages of the PATE production method using the above-described aromatic dithiol or alkali thiolate having good reactivity as a raw material.

In addition, according to this method, a polymer having a uniform composition and excellent melt stability can be obtained, and the amount of salt formed in the reaction system can be reduced, so that ionic impurities in the obtained polymer can be reduced. Can be done.

According to this method, PATE from a low-polymerized oligomer to a high-polymerized polymer can be depolymerized into a prepolymer, and oligomers, off-spec products, molded waste, used molded products, etc. By using as a raw material, a polymer having excellent melt stability and excellent powder handling properties can be obtained.

The present invention has been completed based on these findings.

[Means for solving the problem]

Thus, according to the present invention, in a hydrated polar organic solvent,
Repeating unit [I] [However, R ¹ represents an alkyl group having 1 to 6 carbon atoms;
Represents 0 or an integer of 1 to 4. ] As a main constituent polyarylene thioether (A)
A prepolymer (B) having an alkali thiolate group at at least one end obtained by depolymerization by the action of an alkali metal sulfide; [However, R ² represents at least one or more substituents selected from an alkyl group, an aryl group, and an alkoxy group, j represents 0 or an integer of 1 to 4, and X represents a halogen atom. ] The polymerization reaction of the dihalogen-substituted aromatic compound represented by these in a water-containing polar organic solvent is provided, The manufacturing method of the arylene thioether type polymer (C) provided.

 Hereinafter, the present invention will be described in detail.

[Raw material PATE (A)]

In the present invention, PATE (A) as a raw material for depolymerization
Is a repeating unit [I] [However, R ¹ represents an alkyl group having 1 to 6 carbon atoms;
Represents 0 or an integer of 1 to 4. ] As a main constituent polyarylene thioether (A)
It is. Here, the term “main constituent” means that the polymer contains the repeating unit in an amount of 50 mol% or more.

Further, PATE (A) used as a raw material in the present invention includes:
Melt viscosity of about 10 ⁶ poise (310 ° C, shear rate 1200sec ^-1
) To oligomers having a low degree of polymerization of several, preferably about tens of repeating units. Furthermore, off-spec products, molding waste, waste plastics and the like can also be used.

The method for producing such a raw material PATE (A) is not particularly limited, but is usually obtained by reacting a dihalogen-substituted aromatic compound with an alkali metal sulfide. For example, as disclosed in the aforementioned U.S. Pat.Nos. 3,919,177 and 4,645,826, an alkali metal sulfide and a dihalogen-substituted aromatic compound are dissolved in a polar organic solvent such as N-methylpyrrolidone in water. Can be obtained by heating and polymerizing in the presence of

Furthermore, in the present invention, the compound represented by the general formula [III] Wherein X represents a halogen atom, R ¹ represents an alkyl group having 1 to 6 carbon atoms, and ¹ represents 0 or an integer of 1 to 4. 0.9 to 1.1 mol, more preferably 0.95 to 1.05 mol, even more preferably 0.97 to 1.03 mol of a compound represented by the following formula as a main component, obtained by a polymerization reaction in a water-containing polar organic solvent. PATE can be suitably used.

Examples of the compound represented by the general formula [III] include p-dichlorobenzene, m-dichlorobenzene,
2,6-dichlorotoluene, 2,5-dichlorotoluene, p-
Examples thereof include dihalogen-substituted aromatic compounds such as dibromobenzene. Also, 2,6-dichloronaphthalene, 1-methoxy-2,5-dichlorobenzene, 4,4′-dichlorobiphenyl, 3,5-dichlorobenzoic acid, p, p′-dichlorodiphenyl ether, Other dihalogen-substituted aromatic compounds such as 4-dichlorodiphenylsulfone, 4,4'-dichlorodiphenylsulfoxide, 4,4'-dichlorodiphenylketone can be used as minor components of less than 50 mol%. .

The PATE thus obtained may be used separately from the reaction mixture, or the reaction mixture may be directly subjected to depolymerization. In particular, when reducing ionic impurities,
Separating the polymer from the polymerization mixture as PATE (A)
Those purified by washing or the like are preferred.

Incidentally, the polar organic solvent and water contained in the reaction solution,
It is used as it is as a part of the components in the depolymerization step. Further, PATE may be obtained by cooling and depositing the reaction solution.

(Alkali metal sulfide)

Examples of the alkali metal sulfide used for depolymerization of PATE (A) include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide, and a mixture thereof.

Further, an alkali metal sulfide prepared in situ from an alkali hydrosulfide and an alkali hydroxide in a reaction system can also be used.

(Dihalogen-substituted aromatic compound)

Prepolymer (B) having an alkali thiolate group at at least one terminal obtained by depolymerizing PATE (A)
The dihalogen-substituted aromatic compound to be reacted with the general formula (II) [However, R ² represents at least one or more substituents selected from an alkyl group, an aryl group, and an alkoxy group, j represents 0 or an integer of 1 to 4, and X represents a halogen atom. ] It is a compound represented by these.

The halogen atom X is selected from fluorine, chlorine, bromine or iodine, and may be the same or different from each other.
In particular, those selected from chlorine or bromine are preferable.

Such dihalogen-substituted aromatic compounds include, for example, p-dichlorobenzene, m-dichlorobenzene,
Examples thereof include dihalogen-substituted aromatic compounds such as 2,5-dichlorotoluene and p-dibromobenzene.

Further, for example, an oligomer or a polymer produced by the reaction of the above-mentioned dihalogen-substituted aromatic compound with an alkali metal sulfide, a compound having a halogen atom at its terminal, and an oligomer or polymer of PATE, further comprising Compounds having a halogen atom can also be used.

(Polar Organic Solvent) As the polar organic solvent, for example, N-alkylpyrrolidone such as N-methylpyrrolidone, 1,3-dialkyl-
An aprotic organic amide solvent typified by 2-imidazolidinone, tetraalkyl urea, hexaalkyl phosphoric triamide and the like is preferable because the stability of the reaction system is high and a high molecular weight polymer can be obtained.

(Production Method) The method for producing the arylene thioether polymer (C) of the present invention comprises a prepolymer having an alkali thiolate group at at least one terminal by depolymerizing by reacting an alkali metal sulfide on PATE (A). Step of obtaining B) (depolymerization step or alkali thiolate formation step)
And reacting the produced prepolymer (B) with the dihalogen-substituted aromatic compound to cause a polymerization reaction again (polymerization step or repolymerization step).

Depolymerization Step The prepolymer (B) having an alkali thiolate group on at least one end is usually (a) a water-containing polar organic solvent containing 0.1 to 20 mol of water per 1 kg of a polar organic solvent, (b) 1 kg of a polar organic solvent At a temperature of 200 to 300 ° C. and 0.1 to 5 mol of PATE (A), and (c) 0.01 to 1 mol of alkali metal sulfide per 1 mol of PATE (A). It can be suitably obtained by performing a depolymerization reaction for 30 hours.

The reaction temperature is usually 200 to 300 ° C., preferably 220 to 280
° C, more preferably 230-280 ° C. If the temperature is lower than 200 ° C., the depolymerization and alkali thiolate formation become insufficient or the reaction time becomes too long. If the temperature exceeds 300 ° C., the decomposition reaction is liable to occur, and both are not preferred.

The reaction time is generally 0.1 to 30 hours, more preferably 0.5 to 30 hours.
~ 20 hours. If the time is less than 0.1 hour, the reaction may be insufficient, and if it exceeds 30 hours, it is economically disadvantageous.

The coexisting amount of water in the depolymerization step is in the range of 0.1 to 20 mol, preferably 0.2 to 10 mol, per kg of the polar organic solvent. If it is less than 0.1 mol or more than 20 mol, undesirable side reactions may occur.

The amount of PATE (A) to be used for depolymerization is 1 kg of polar organic solvent
The preferred range is from 0.1 to 5 base moles, preferably from 0.2 to 4 base moles. If the amount is less than 0.1 basic mol, the productivity is lowered. On the other hand, if it exceeds 5 basic mol, the viscosity of the reaction system increases, and both are not preferred.

The “basic mole number” in the present invention refers to a mole number calculated assuming that the total atomic weight of the atoms constituting the repeating unit [I] of PATE is 1 gram molecule.

The amount of the alkali metal sulfide is desirably in the range of 0.01 to 1 mol, preferably 0.02 to 1 mol, and more preferably 0.05 to 1 mol, per 1 mol of PATE (A). As the amount of the alkali metal sulfide increases, the average molecular weight of the depolymerized product decreases, so that the average molecular weight of the depolymerized product can be controlled by this amount. Is useful as, for example, a prepolymer for a PATE block of a thioether block copolymer in addition to the present invention. If the amount is less than 0.01 mol, the formation of alkali thiolate may be insufficient, while if it exceeds 1 mol, it is not economically preferable.

The mixture containing the water-containing polar organic solvent, the polyarylene thioether (A) and the alkali metal sulfide is adjusted so that the pH value of an aqueous solution obtained by diluting the mixture with 100 times (weight ratio) water becomes 9 or more, preferably 10 or more. It is desirably alkaline. When the pH value is less than 9, depolymerization and alkali thiolate conversion may be insufficient.

To make the mixture desired alkaline, PATE (A)
0.001-1 mol, preferably 0.01-0.5, per 1 mol.
Molar basic compounds can be added.

Examples of such a basic compound include at least one compound selected from hydroxides, oxides, and carbonates of alkali metals or alkaline earth metals.

Thus, a prepolymer (B) having an alkali thiolate group at at least one terminal is obtained. It is considered that such a prepolymer (B) usually has mainly an alkali thiolate group at both terminals.

In addition, the degree of polymerization of the prepolymer (B) is based on the raw material PATE
Depending on the reaction conditions such as the degree of polymerization of (A) and the amount of alkali metal sulfide used for depolymerization, the repeating unit [I] ranges from one to several oligomers to those having a relatively high degree of polymerization. The material used in the present invention can be used without any particular limitation, and may be of any degree of polymerization or a mixture thereof.

The prepolymer (B) having an alkali thiolate group at at least one end can be used as a component for the next polymerization step with good stability as a reaction mixture (reaction liquid) containing the prepolymer (B). . Further, if necessary, the prepolymer (B) can be once separated from the reaction solution under non-oxidation conditions and used as a component in the next polymerization step.

After the prepolymer (B) having an alkali thiolate group at the terminal is produced by depolymerization with an alkali metal sulfide, the reaction system does not need to be strongly alkaline. Rather, strong alkalinity may inhibit the polymerization reaction.

Therefore, when the produced prepolymer (B) is used for the next polymerization reaction without separation from the reaction solution after the alkali thiolate reaction, it can be partially neutralized with an acidic substance. However, making the reaction solution acidic is not preferable because the alkali thiolate group is easily decomposed.

As the neutralizing agent, a salt composed of a protonic acid and / or a strong acid and a weak base is used, and a salt composed of a strong acid and a weak base is particularly preferred. Specific examples include ammonium halides, dilute mineral acids, and organic carboxylic acids.

Polymerization Step The polymerization reaction between the prepolymer (B) having at least one terminal having an alkali thiolate group and the dihalogen-substituted aromatic compound represented by the general formula [II] is usually carried out by: (a) 0.5 kg of water per 1 kg of polar organic solvent; (B) a prepolymer having an alkali thiolate group at at least one end with respect to 1 kg of the polar organic solvent.
0.05 to 5 base moles, and (c) 1 mole of the prepolymer (B) [not mean the base mole. Substantially the same as 1 mol of the alkali metal sulfide used in producing the prepolymer (B). To a mixture containing 0.7 to 1.3 mol of a dihalogen-substituted aromatic compound represented by the general formula (II) at 80 to 300 ° C. for 0.1 to 30 hours. .

The polymerization reaction temperature is usually 80 to 300 ° C., more preferably 1 to 300 ° C.
00-280 ° C. If the reaction temperature is lower than 80 ° C., the polymerization reaction may be insufficient, while if it exceeds 300 ° C., the decomposition reaction may occur.

The polymerization time is usually 0.1 to 30 hours, more preferably 0.5 to 30 hours.
~ 20 hours. If the reaction time is less than 0.1 hour, the polymerization reaction may be insufficient, and if it exceeds 30 hours, the productivity may be poor.

In addition, a polymer having a higher molecular weight can be easily obtained in a shorter time by performing a polymerization reaction by raising the temperature in two or more stages. For example, there is a method in which first-stage polymerization is performed at a temperature up to 235 ° C., and then second-stage polymerization is performed by raising the temperature to 245 ° C. or higher.

The amount of water in the reaction system in this polymerization step is desirably 0.5 to 30 mol, preferably 1 to 25 mol, and more preferably 5 to 20 mol per kg of the polar organic solvent. A part of the water may be added during the polymerization reaction. In particular,
When the polymerization reaction is carried out by raising the temperature to 245 ° C. or higher in the latter half of the polymerization step, adding water before and after this temperature raising step,
An arylene thioether-based polymer (C) having a higher molecular weight and more excellent melt stability can be easily obtained.

If the amount of water is less than 0.5 mol or more than 30 mol, undesirable side reactions and the like are likely to occur, and it is difficult to obtain a high molecular weight polymer.

The amount of prepolymer (B) is per 1 kg of polar organic solvent
A range of 0.05 to 5 base moles, preferably 0.1 to 4 base moles is desirable. If it is less than 0.05 basic mol, it is disadvantageous in terms of productivity, and if it exceeds 5 basic mol, the viscosity of the reaction system becomes high, and both are not preferred. Here, the basic mole number of the prepolymer (B) means the mole number calculated by assuming that the total atomic weight of the atoms constituting the repeating unit [I] is 1 gram molecule.

The amount of the dihalogen-substituted aromatic compound is from 0.7 to 1.3 mol, preferably from 0.9 to 1.3 mol, per mol of the prepolymer (B).
A range of ~ 1.1 moles is desirable. If it is less than 0.7 mol or more than 1.3 mol, it is difficult to obtain a high molecular weight polymer.

When an alkali metal sulfide is used in the step of polymerizing the prepolymer (B) and the dihalogen-substituted aromatic compound, this amount is also included in the alkali metal sulfide. On the other hand, when the prepolymer is separated from the reaction mixture and then polymerized with the dihalogen-substituted aromatic compound, the amount of the alkali metal sulfide lost in the separation step is subtracted or the amount obtained by supplementing the amount is added to the alkali metal sulfide. It is the amount of metal sulfide.

〔The invention's effect〕

According to the present invention, it is possible to provide an arylene thioether polymer having a high degree of polymerization, excellent melt stability, and low ionic impurities.

Further, according to the present invention, since a by-product oligomer or an off-spec product in a PATE production process can be used as a raw material, the product yield in PATE production can be improved.

Furthermore, it is possible to recycle PATE molding waste and used waste plastic, which contributes to effective use of resources and reduction of plastic waste.

The arylene thioether-based polymer (C) obtained by the production method of the present invention is a resin having excellent heat resistance, flame retardancy, chemical resistance, mechanical strength, workability, and the like, for example, an injection molded product, an extruded product. , Films (oriented or unoriented), sheets, sealing materials, etc.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to Examples and Reference Examples, but the present invention is not limited to only these Examples.

 In addition, the measuring method of physical properties is as follows.

Measurement of number average molecular weight: Sample the sample reaction solution (including alkali thiolate), add a large excess of methyl iodide and stir for 24 hours to change the terminal alkali thiolate group to methyl thioether group and stabilize the terminal. It was made. This was poured into a large amount of water to neutralize it, washed sufficiently with water, and dried under vacuum to prepare a sample sample. The raw material PATE polymer was used as a sample as it was.

The number average molecular weight was determined by a gel permeation chromatography (GPC method).

 The measurement conditions are as follows.

Column: SHODEX AT 80 M / S 2 in series Solvent: α-chloronaphthalene Flow rate: 0.7 ml / min Temperature: 220 ° C Sample concentration: 0.05% by weight Injection volume: 200μ Detector: Flame ionization detector (FID) Molecular weight calibration : Standard polystyrene and Data processing: SIC 7000B (manufactured by System Instruments) Measurement of the melting point of the polymer: The melting point (Tm) and glass transition temperature (Tg) are determined by hot pressing the polymer at about 320 ° C and quenching it to a thickness of about 0.5 mm. And heated using a differential scanning calorimeter (DSC) at a rate of 10 ° C./min from room temperature in a nitrogen atmosphere.

For the melt crystallization temperature (Tc), the sheet was measured at 340 ° C. to 10 ° C./min in a nitrogen atmosphere using a DSC.

Amount of sodium ions: After decomposing the polymer in heated concentrated sulfuric acid, a sample solution was prepared by treating with hydrogen peroxide solution, and quantified by an ion chromatography method.

Melt viscosity (η ^* ): Measured at 310 ° C. and a shear rate of 1200 sec ⁻¹ .

Melt stability of the polymer: DSC, the polymer powder in a nitrogen gas atmosphere, 4
The crystallization enthalpy ΔHmc (0 min) when the temperature is rapidly raised to 00 ° C. and then immediately decreased at a rate of 10 ° C./min, and the temperature is rapidly raised to 400 ° C. and then maintained at 400 ° C. for 10 minutes. The rate of decrease in the crystallization enthalpy ΔHmc (10 minutes) when the temperature was lowered at a rate of 10 ° C./min was calculated and evaluated according to the following equation.

Polymers with higher melt stability at 400 ° C. have a smaller rate of reduction, and conversely, polymers with lower melt stability have a greater rate of reduction. Those with low melt stability are in the molten state (40
(0 ° C.), causing cross-linking and the like, reducing or losing crystallinity.

[Reference Example 1] <Preparation of Raw Material PATE> 7.0 kg of N-methylpyrrolidone (NMP) and 3.03 kg (18.02 mol, 53.6% by weight of water) of hydrous sodium sulfide were charged into a titanium-lined autoclave, and replaced with nitrogen gas.
While gradually raising the temperature to 200 ° C, an NMP solution containing 1.32 kg of water
2.02 kg and 0.41 mol of hydrogen sulfide were distilled off.

Next, a mixed solution of 2.65 kg (18.03 mol) of p-dichlorobenzene, 0.24 kg (13.22 mol) of water and 3.70 kg of NMP was supplied, and the mixture was reacted at 220 ° C. for 5 hours.
2 kg (40.00 mol) was injected, the temperature was raised to 255 ° C., and the reaction was carried out for 3 hours.

The obtained reaction mixture was sieved with a screen to separate a granular polymer, washed with acetone and washed with water three times each, dehydrated, and dried at 100 ° C. to obtain white granular PATE (A).
-1) was obtained.

 Physical properties of PETE (A-1) were as described below.

Reduction rate of ΔHmc = 17% Tm = 281 ° C. Tg = 86 ° C. Tc = 203 ° C. η ^* = 2200 poise Number average molecular weight = about 11000 Sodium ion = 450 ppm [Example 1] <Depolymerization and alkali thiolate reaction> Titanium lining In an autoclave, 150.0 g (1.39 basic mol) of PATE (A-1) prepared in Reference Example 1, 1.5 kg of NMP,
Hydrous sodium sulfide 53.3 g (0.317 mol, water 53.6 wt%), calcium hydroxide 2.0 g (0.027 mol), and water 2
6.0 g (1.44 mol) of the mixture was stirred to prepare a mixture.

The pH value of an aqueous solution obtained by diluting a trace sample of this mixed solution with 100-fold (weight ratio) water was 11.6.

While stirring this mixture under a nitrogen gas atmosphere,
The mixture was heated at 240 ° C. for 2 hours to carry out a depolymerization and an alkali thiolate reaction to obtain a reaction solution (A).

<Analysis of Alkali Thiolate> The reaction solution (A) prepared in the same manner as above was diluted with 10 times the volume of water, and the pH was adjusted to 3 with hydrochloric acid. Thus, a thiol compound was obtained.

The thiolated product had a thiophenol odor. The infrared absorption spectrum shows that the raw material PATE (A-
Absorption near 2560 cm ^-1 derived from the thiol group, which was not observed in 1), was observed.

The melt viscosity of this thiol product is 50 poise or less,
No more accurate measurements could be made. On the other hand, the sulfur content of the methylthioetherified compound was increased to 32.20% by weight as compared with the theoretical value of 29.60% by weight of PATE, and its number average molecular weight was about 550.

<Polymerization reaction> The reaction solution (A) obtained above and p-dichlorobenzene
47.5g (0.323mol) in titanium lined autoclave
After reacting at 160 ° C. for 1 hour, 135 g (7.49 mol) of water was injected under pressure and reacted at 270 ° C. for 1 hour.

The resulting reaction mixture was sieved with a screen to separate a granular polymer, washed with acetone and washed with water three times each, dehydrated, and dried at 100 ° C. to obtain a white granular polymer (polymer P ₁ ). Was obtained in 87% yield.

<Physical Properties of Polymer> The resulting physical properties of the polymer P ₁ was as follows.

ΔHmc reduction rate = 6% Tm = 284 ℃ Tg = 81 ℃ Tc = 235 ℃ η * = 230 poise sodium ion = 65 ppm In addition, the polymer P _1, the composition of the polymer calculated from elemental analysis of sulfur, and infrared absorption The spectra were all the same as PATE (A-1).

Sodium ions are greatly reduced, and it can be seen that ionic impurities can be reduced according to the method of the present invention. Furthermore, it turns out that the polymer of this invention is also excellent in melt stability.

Example 2 Depolymerization and Alkali Thiolation Reaction In a titanium-lined autoclave, 43.2 g (0.40 basic mol) of PATE (A-1) prepared in Reference Example 1, 500 g of NMP, 16.5 g of hydrous sodium sulfide (0.098 mol) , Water 53.6% by weight), calcium hydroxide 1.0 g (0.013 mol), and water
9.0 g (0.5 mol) was charged to prepare a mixed solution. The pH value of an aqueous solution obtained by diluting a trace sample of this mixed solution with 100 times (weight ratio) water was 11 or more. After the mixed solution was replaced with nitrogen gas, the mixture was heated to 240 ° C. with stirring and reacted for 1.5 hours to perform depolymerization and alkali thiolate reaction.

The melt viscosity of this thiol product is 50 poise or less,
No more accurate measurements could be made. The number average molecular weight was about 500.

<Polymerization reaction> 14.7 m-dichlorobenzene was added to the reaction solution obtained above.
g (0.1 mol) and reacted at 160 ° C for 1 hour.
54.2 g (3.01 mol) of water was injected and reacted at 270 ° C. for 1 hour.

The resulting reaction mixture was sieved with a screen to separate a granular polymer, washed with acetone and washed with water three times each, dehydrated, and dried at 100 ° C. to obtain a white granular polymer (polymer P ₂ ). Was obtained in 84% yield.

The resulting physical properties of the polymer P ₂ were as follows.

Tm = 220 ° C. Tg = 70 ° C. η ^* = 140 poise Sodium ion = 55 ppm [Example 3] <Preparation of raw material PATE slurry> A titanium lined autoclave was charged with NMP 4000 g and hydrous sodium sulfide 1680 g (9.99 mol, water 53.6 wt%). After purging with nitrogen gas, 1700 g of an NMP solution containing 600 g of water and 0.23 mol of hydrogen sulfide were distilled out while gradually raising the temperature to 203 ° C.

Subsequently, a mixed solution of 1442 g (9.81 mol) of p-dichlorobenzene and 100 g of NMP2 was supplied and reacted at 220 ° C. for 10 hours to obtain a PATE (A-2) slurry. The number average molecular weight of PATE (A-2) was about 4500.

<Depolymerization and Alkali Thiolation Reaction> A portion of 1042 g (containing 1.36 basic moles of PATE) of a uniform slurry obtained by sufficiently stirring this PATE (A-2) slurry was dispersed in a titanium-lined autoclave, and then NM
P810g, hydrous sodium sulfide 53.3g (0.317 mol, moisture 53.
6% by weight) and 2.0 g (0.027 mol) of calcium hydroxide to prepare a mixed solution. Take a small sample of this mixture for 10
The pH value of the aqueous solution diluted with 0-fold (weight ratio) water was 11.6. Next, this mixture was heated to 250 ° C. while stirring in a nitrogen gas atmosphere, and reacted for 2 hours to perform depolymerization and alkali thiolate formation. At 100 ° C., no PATE (A-2) particles were observed in the mixed solution after the reaction, and the mixture was in a substantially uniform solution state.

<Polymerization reaction> 47.2 g of p-dichlorobenzene was added to the reaction solution obtained above.
(0.321 mol), and reacted at 160 ° C. for 1 hour.
135 g (7.49 mol) was injected and reacted at 270 ° C. for 1 hour.

The obtained reaction mixture was treated in the same manner as in Example 1 to obtain a white granular polymer (polymer P ₃ ) in a yield of 84%.

The properties of the obtained polymer P ₃ were as follows.

Reduction rate of ΔHmc = 8% Tm = 284 ° C. Tg = 80 ° C. Tc = 215 ° C. η ^* = 150 poise sodium ion = 340 ppm [Example 4] Extrude the granular PATE (A-1) prepared in Reference Example 1. After molding into pellets with a machine, the resin temperature is measured using an injection molding machine.
A plate was formed at 321 ° C. PATE cut this board
Except that was used instead of (A-1) in the same manner as in Example 1 to obtain a white granular polymer (Polymer P ₄₎ in 86% yield.

The properties of the obtained polymer P ₄ were as follows.

Reduction rate of ΔHmc = 10% Tm = 283 ° C. Tg = 80 ° C. Tc = 230 ° C. η ^* = 200 poise sodium ion = 65 ppm [Example 5] Poly-p-phenylene thioether having a number average molecular weight of about 7000 by GPC (off- Spec product) 108 g (1.0 basic mol), NMP 1000 g, hydrous sodium sulfide 20.2 g (0.12 mol, water 53.6 wt%), calcium hydroxide 2.0 g (0.027
Mol), replace with nitrogen gas, and stir with 245
The reaction was carried out at 2 ° C. for 2 hours to cause depolymerization and alkali thiolate reaction. 17.8 g (0.121 mol) of p-dichlorobenzene was added to the reaction solution obtained above and reacted at 180 ° C. for 2 hours. 135 g (7.49 mol) of water was injected, and the mixture was reacted at 260 ° C. for 2 hours. Was.

The obtained reaction mixture was treated in the same manner as in Example 1,
White granular polymer (Polymer P ₅₎ was obtained in 80% yield.

The properties of the obtained polymer P ₅ was as follows.

Tm = 282 ° C Tg = 80 ° C η ^* = 120 poise Sodium ion = 60ppm

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08G 75/00-75/04

Claims (8)

(57) [Claims] 1. A repeating unit [I] in a water-containing polar organic solvent. [However, R ¹ represents an alkyl group having 1 to 6 carbon atoms;
Represents 0 or an integer of 1 to 4. ] As a main constituent polyarylene thioether (A)
A prepolymer (B) having an alkali thiolate group at at least one end obtained by depolymerization by the action of an alkali metal sulfide; [However, R ² represents at least one or more substituents selected from an alkyl group, an aryl group, and an alkoxy group, j represents 0 or an integer of 1 to 4, and X represents a halogen atom. ] A method for producing an arylene thioether-based polymer (C), which comprises subjecting a dihalogen-substituted aromatic compound represented by the following formula to a polymerization reaction in a water-containing polar organic solvent. 2. A prepolymer (B) having an alkali thiolate group at at least one terminal, comprising: (a) a water-containing polar organic solvent containing 0.1 to 20 mol of water per 1 kg of a polar organic solvent; (b) 1 kg of a polar organic solvent On the other hand, 0.1 to 5 basic moles of polyarylene thioether (A) (however, the basic mole number is the mole number calculated as the total amount of atoms constituting the repeating unit [I] as one gram molecule), and c) A mixture obtained by subjecting a mixture containing 0.01 to 1 mol of an alkali metal sulfide to a basic mol of polyarylene thioether (A) to a depolymerization reaction at 200 to 300 ° C. for 0.1 to 30 hours. The method according to claim 1. 3. The pH value of an aqueous solution obtained by diluting the mixture containing water-containing polar organic solvent, polyarylene thioether (A) and alkali metal sulfide with 100-fold (by weight) water becomes 9 or more. 3. The production method according to claim 2, which is alkaline. 4. The mixture according to claim 1, wherein the mixture further contains a basic compound so that the pH of an aqueous solution obtained by diluting the mixture with 100-fold (by weight) water becomes 9 or more. 3. The production method according to 3. 5. The basic compound is at least one selected from hydroxides, oxides and carbonates of alkali metals or alkaline earth metals, and one basic mole of polyarylene thioether (A). 0.001 to 1
The production method according to claim 4, wherein the compound is contained in a molar range. 6. A prepolymer (B), which is subjected to a polymerization reaction of a dihalogen-substituted aromatic compound represented by the general formula [II] in a hydrous polar organic solvent, comprises a prepolymer (B) as a prepolymer (B). In which a polyarylene thioether (A) is allowed to react with an alkali metal sulfide to cause a depolymerization reaction, and then a prepolymer (B) is separated from the reaction mixture under non-oxidizing conditions, or The method according to any one of claims 1 to 5, wherein the reaction mixture containing (B) is used as it is. 7. A polyarylene thioether (A) is reacted with an alkali metal sulfide in a water-containing polar organic solvent to cause a depolymerization reaction.
The method according to claim 6, wherein the reaction mixture partially neutralized by adding a salt of a strong acid and a weak base is used as it is. 8. The polyarylene thioether (A) to be subjected to depolymerization is prepared by reacting an alkali metal sulfide with a compound represented by the general formula [III]: Wherein X represents a halogen atom, R ¹ represents an alkyl group having 1 to 6 carbon atoms, and ¹ represents 0 or an integer of 1 to 4. Is obtained by a polymerization reaction of 0.9 to 1.1 mol of a dihalogen-substituted aromatic compound containing a compound represented by the following formula in a water-containing polar organic solvent. From the reaction mixture, a polyarylene thioether (A) is produced. The method according to any one of claims 1 to 7, wherein the reaction mixture is separated or the reaction mixture is used as it is.