JP2001040090A - Polyarylene sulfide, method for producing the same, and polyarylene sulfide composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a high-molecular weight polyarylene sulfide(PAS) having many functional groups having reactivity with an acid or an alkali and useful as a material, etc., for molding processing of electrical components, etc., by carrying out a reaction of a specific amide compound with a specified aromatic compound and a sulfidation agent. SOLUTION: This polyarylene sulfide(PAS) has a structure of the formula (R is H, a 1-18C alkyl group or a functional group exhibiting reactivity with an acid or an alkali; n is 0-4) as a repeating unit and 400-1,500 poises melt viscosity at 300 deg.C and comprises functional groups exhibiting the reactivity with the acid or the alkali in an amount so as to provide 10-50 μmol/g. The PAS is preferably obtained by hydrolyzing an alicyclic amide compound in the presence of a polyhaloaromatic compound (e.g. p-dichlorobenzene), the alicyclic amide compound, an alkali metal hydroxide and water and then carrying out a reaction while adding a sulfidation agent into the system.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyphenylene sulfide having a relatively high molecular weight and having a large number of functional groups reactive with an acid or an alkali in a resin structure, a method for producing the same, and silane based on these structural characteristics. The present invention relates to a polyphenylene sulfide composition which can dramatically improve mechanical strength typified by toughness when used in combination with a coupling agent and can be widely used for molded articles such as electric / electronic parts and automobile parts.

[0002]

2. Description of the Related Art Polyarylene sulfide typified by polyphenylene sulfide has excellent heat resistance, chemical resistance and the like, and is widely used in molded products such as electric and electronic parts and automobile parts. However, polyarylene sulfides generally have the disadvantage of low toughness and very brittleness.

[0003] For example, Japanese Patent Application Laid-Open No. Hei 6-237131 discloses a reaction mixture containing an alkali metal hydrosulfide and / or a hydrous sulfidizing agent comprising an alkali metal sulfide in a mixture containing an organic polar solvent and a polyhaloaromatic compound. Discloses a technique for producing a high-molecular-weight, linear polyarylene sulfide and improving the toughness of the polyarylene sulfide by introducing the reaction at a rate at which water can be removed therefrom.

[0004]

However, Japanese Patent Application Laid-Open No.
The polyarylene sulfide obtained by the method of JP-A-237131 has a high molecular weight and some improvement in toughness, but is not yet sufficient. In order to improve the toughness of polyarylene sulfide, a method of modifying with a silane coupling agent is also known. However, the molecular weight of polyarylene sulfide obtained by the method of JP-A-6-237131 is increased. However, since it has few active sites for reaction with acids or alkalis, it is difficult to modify it with a coupling agent such as a silane coupling agent, and as a result, practical toughness cannot be obtained.

An object of the present invention is to provide a novel polyarylene sulfide having a high molecular weight, a large number of functional groups reactive with an acid or an alkali, and having a good affinity for a silane coupling agent, and a novel polyarylene sulfide. It is an object of the present invention to provide a novel polyarylene sulfide composition that can dramatically improve the toughness of a molded product and a production method.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, have found that a polyarylene sulfide which can exhibit excellent performance can be obtained when used in combination with a silane coupling agent. Thus, the present invention has been completed.

That is, the present invention provides the following structure

Embedded image (Wherein, R is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or a functional group reactive with an acid or an alkali, n
Is an integer of 0 to 4. ) Is a repeating unit, and the melt viscosity at 300 ° C. is 400 to 1500.
A polyarylene sulfide, which is a poise and contains a functional group having a reactivity with an acid or an alkali at a rate of 10 to 50 μmol / g;

In a process for producing a polyarylene sulfide by reacting an alicyclic amide compound, a polyhalo aromatic compound and a sulfidizing agent, Step 1: a polyhalo aromatic compound, an alicyclic amide compound,
A method for producing a polyarylene sulfide, comprising hydrolyzing the alicyclic amide compound in the presence of an alkali metal hydroxide and water, and then performing a reaction while adding a sulfidizing agent into the system. ,

In the production of a polyarylene sulfide polymer in which an alicyclic amide compound, a dihalo-aromatic compound and a sulfidizing agent are reacted, Step 1: a step of adding a sulfidizing agent to a mixture containing the alicyclic amide compound and the dihalo-aromatic compound While continuously or intermittently adding, the reaction is carried out such that the water content in the system is maintained in the range of 0.01 to 0.3 mol per 1 mol of the alicyclic amide compound. A method for producing a polyarylene sulfide polymer, wherein an alkali metal hydroxide is added to the reaction system to further react, and the polyarylene sulfide and the silane coupling agent as essential components And a polyarylene sulfide composition characterized by the following:

The polyarylene sulfide of the present invention has various molecular structures derived from the structure of the polyhaloaromatic compound. As described above, the polyarylene sulfide has reactivity with an acid or alkali despite its high molecular weight. It has a structural feature that many functional groups are shown. Due to this feature, an unprecedented remarkable effect of improving the toughness when used in combination with the silane coupling agent is exhibited.

Specifically, the following structural formula

Embedded image (Wherein, R is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or a functional group reactive with an acid or an alkali, n
Is an integer of 0 to 4. ) Is a repeating unit, and the melt viscosity at 300 ° C. is 400 to 1500.
It is a polyarylene sulfide (hereinafter abbreviated as "PAS of the present invention") which is a poise and contains a functional group having a reactivity with an acid or an alkali at a ratio of 10 to 50 mol / g.

Here, the term "functional group having reactivity with acid or alkali" specifically means a functional group having reactivity with alkali after acid treatment, and the amount thereof can be measured by the following method.

That is, 10 g of the polymer to be measured is added to 1 g of the polymer.
Add 10 ml of mol / l hydrochloric acid, stir, and then filter. Then, the washing with water is repeated until hydrochloric acid is no longer detected (silver nitrate solution is added and the solution does not become cloudy). The obtained polymer is dispersed again in distilled water, and 10 ml of 1 mol / l sodium hydroxide is added thereto and stirred. After stirring, the mixture is filtered, and washed repeatedly with water until sodium hydroxide is no longer detected (the phenolphthalein solution is added to prevent red coloration). Collect all the filtrate used in the water washing, titrate sodium hydroxide in the filtrate with hydrochloric acid, determine the amount of sodium hydroxide consumed, and the number of moles of sodium hydroxide consumed is contained in the polymer. It is the number of moles of the functional group.

The PAS of the present invention cannot improve the toughness if the functional group reactive with acid or alkali is less than 10 μmol / g.
If the ratio exceeds the above range, the problem that the moldability is lowered occurs.

The functional group reactive with an acid or an alkali is
Although the specific structure is not specified, it is particularly preferable that a carboxyalkylamino group, which is a structure obtained by hydrolyzing an alicyclic amide compound, is contained because the effect of the present invention becomes remarkable. Preferably, the PAS of the present invention contains a carboxyalkylamino group in the range of 10 to 50 μmol / g. Further, the carboxyl group represented by the carboxyalkylamino group may form a metal salt.

In the present invention, the content of the above-mentioned carboxyl group or its metal salt among the functional groups reactive with an acid or an alkali can be specifically measured by the following method. That is, 10 g of the polymer was wetted with a small amount of methanol, and 100 ml of water was added thereto to form a slurry.
The slurry was acidified by adding 5 ml of diluted hydrochloric acid thereto.
Next, filtration was performed, washing with water was repeated until hydrochloric acid was not detected in the filtrate, and the dried polymer was pressed into a disk shape with a press machine, and measured with a microscope FT-IR apparatus. It determined the relative intensity of the absorption of 1700 cm ^-1 for absorption of 2666cm ^-1 of absorption, while performs FT-IR measurement by adding a predetermined amount of p- chlorophenyl acetate as a standard substance, the absorption described above relative to the addition amount By obtaining a relative intensity, a calibration curve is prepared, and the content of the carboxy group or the metal salt of the polymer can be determined from the calibration curve.

In the PAS of the present invention, the structure represented by the above structural formula is used as a repeating unit, but all of the structure may be constituted by the structure, or a part of the structure is described above. As the polyhalo aromatic compound, a structure obtained by partially using another compound of dihalobenzene may be used, or two or more kinds of dihalobenzenes may be used in combination. It is preferable to use dihalobenzene in a proportion of 70 mol% or more, preferably 90 mol% or more, more preferably 99 mol% or more, from the viewpoint of excellent toughness improving effect.

The method for producing the PAS of the present invention is not particularly limited, but specifically, the following method and the method are preferred because the PAS having the intended molecular structure can be easily boiled. .

[Method] In a method for producing a polyarylene sulfide by reacting an alicyclic amide compound, a polyhalo aromatic compound and a sulfidizing agent, Step 1: a polyhalo aromatic compound, an alicyclic amide compound,
Step 2: hydrolyzing the alicyclic amide compound in the presence of an alkali metal hydroxide and water, and then performing a reaction while adding a sulfidizing agent into the system.

[Method] In the production of a polyarylene sulfide polymer in which an alicyclic amide compound and a dihalo-aromatic compound are reacted with a sulfidizing agent, Step 1: a sulfide is added to a mixture containing the alicyclic amide compound and the dihalo-aromatic compound Carrying out the reaction while adding the agent continuously or intermittently and maintaining the water content in the system in the range of 0.01 to 0.3 mol per 1 mol of the alicyclic amide compound. 2: Next, a method in which an alkali metal hydroxide is added to the reaction system to carry out a further reaction.

Hereinafter, the method and the method will be described in detail in this order. First, in the method for producing a polyarylene sulfide, which comprises reacting an alicyclic amide compound, a polyhaloaromatic compound, and a sulfidizing agent, first, step 1
The alicyclic amide compound is hydrolyzed in the presence of a polyhalo aromatic compound, an alicyclic amide compound, an alkali metal hydroxide and water, and then the reaction is carried out in step 2 while adding a sulfidizing agent into the system. It is a way to make it.

That is, in step 1, the alicyclic amide compound is hydrolyzed in advance in the presence of an alkali metal hydroxide before step 2, so that the desired polyarylene sulfide is reacted with an acid or alkali. The number of functional groups shown can be increased, and the toughness can be improved by using the silane coupling agent in combination.

The amount of the alkali metal hydroxide used in this step 1 is not particularly limited, but it should be 0.01 to 1 mol% with respect to 1 mol of the sulfidizing agent used. It is preferable because the effects of the invention become remarkable.

The alkali metal hydroxide and water can be used as an alkali metal aqueous solution, and the concentration thereof is 1
The range which becomes 0 to 50 weight% is preferable. In this case, the water used is preferably water from which anions and cations that inhibit the reaction have been removed, such as distilled water and ion-exchanged water.

Here, as the alicyclic amide compound, N
-Methylpyrrolidone (NMP), N-cyclohexylpyrrolidone (NCP), N-methylcaprolactam and the like. Among them, N-methylpyrrolidone (NMP) is preferable in that it has good reactivity with an alkali metal hydroxide.

In the method, the alicyclic amide compound also functions as a reaction solvent. The amount used depends on the type of the solvent to be used and the amount of water with respect to the solvent in the system, and is not particularly limited, but the viscosity of the reaction system capable of performing a uniform polymerization reaction is maintained. In order to maintain the productivity of the sulfidizing agent, the amount is preferably in the range of 1.0 to 6.0 mol per 1 mol of the sulfur source in the sulfidizing agent used for the polymerization. Further, in order to further enhance the productivity, 1.0 mol per mol of sulfur source in the sulfidizing agent is required.
Is preferably in the range of 1.2 to 3.5 mol per mol of sulfur source in the sulfidizing agent used for the polymerization.

Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide. These may be used alone or in combination of two or more. May be used in combination. Among the above alkali metal hydroxides, lithium hydroxide, sodium hydroxide and potassium hydroxide are preferable, and sodium hydroxide is particularly preferable because hydrolysis of the alicyclic amide compound is easy. The alkali metal hydroxide may be any of an anhydride, a hydrate, and an aqueous solution, but is preferably used in the form of an aqueous solution in order to facilitate dissolution in an organic polar solvent as described above.

The polyhalo aromatic compound used in Step 1 is
Although not particularly limited, for example, p-dihalobenzene, m-dihalobenzene, o-dihalobenzene,
2,3-trihalobenzene, 1,2,4-trihalobenzene, 1,3,5-trihalobenzene, 1,2,3,4
-Tetrahalobenzene, 1,2,3,5-tetrahalobenzene, 1,2,4,5-tetrahalobenzene, 2,5
-Dihalotoluene, 1,4-dihalonaphthalene, 1-methoxy-2,5-dihalobenzene, 4,4'-dihalobiphenyl, 3,5-dihalobenzoic acid, 2,4-dihalobenzoic acid, 2,5- Dihalonitrobenzene, 2,4-dihalonitrobenzene, 2,4-dihaloanisole, p,
p′-dihalodiphenyl ether, 4,4′-dihalobenzophenone, 4,4′-dihalodiphenylsulfone,
4,4'-dihalodiphenylsulfoxide, 4,4'-
Dihalodiphenyl sulfide and the like.

Of these, p-dihalobenzene,
m-Dihalobenzene, 4,4'-dihalobenzophenone and 4,4'-dihalodiphenylsulfone are preferred, and p-dihalobenzene and m-dihalobenzene are particularly preferred.

Here, as the dihalobenzene such as p-dihalobenzene and m-dihalobenzene, those having an alkyl group having 1 to 18 carbon atoms as a substituent on the aromatic ring can be preferably used. Further, the halogen atom in each of the above polyhalo aromatic compounds is preferably a chlorine atom or a bromine atom.

Further, a copolymer containing two or more different reaction units can be obtained by an appropriate combination of dihaloaromatic compounds. The specific combination is not particularly limited, and 2 is arbitrarily selected from those described above.
More than one species can be appropriately combined, but specifically, it is toughness to use a combination of p-dichlorobenzene and 4,4′-dichlorobenzophenone or 4,4′-dichlorophenylsulfone. In addition, it is preferable because other mechanical strength can be improved.

When two or more dihaloaromatic compounds are used with p-dihalobenzene as a component, 70 mol% or more, preferably 90 mol% or more, more preferably 90 mol% or more of p-dihalobenzene in the polyhaloaromatic compound. Is 9
It is preferable to use it in a proportion of 9 mol% or more, since the toughness improving effect is excellent.

The amount of the polyhalo aromatic compound used is 0.8 to 0.8 per mol of the sulfur source in the sulfidizing agent used.
The range of 1.3 mol is desirable, and the range of 0.9 to 1.10 mol is particularly preferable because a polymer having excellent physical properties, that is, a polyarylene sulfide having a higher molecular weight can be obtained.

In this step 1, a monohalo compound may be used together with a polyhalo aromatic compound in order to form a terminal of the produced polymer or to control a polymerization reaction or a molecular weight.

The reaction conditions in step 1 may be either open or closed, but the productivity is good if the reaction is carried out in a closed system in the presence of an inert gas followed by the reaction in step 2. Preferred from the point. As the temperature conditions,
Although not particularly limited, it is preferably in the range of 100 to 230 ° C., and at this time, the amount of water in the system is 0.01 to 0.5 with respect to 1 mol of the alicyclic amide compound used.
It is preferable to dehydrate to a molar ratio. The amount of the alicyclic amide compound used was 0.1 to 1 mol.
The ratio of 01 to 0.5 mol is not based on the total amount of the alicyclic amide compound present in the system, but on the basis of the total amount of the alicyclic amide compound used at the time of charging. It refers to the amount of water in the system per mole.

Next, as step 2, the reaction is carried out while adding a sulfidizing agent into the system. The sulfidizing agent that can be used here is not particularly limited, and includes an alkali metal sulfide or a hydrate thereof, or an alkali metal hydrosulfide or a hydrate thereof, each of which may be used alone or as an aqueous solution. Can be added into the system.

Examples of the alkali metal sulfides or hydrates thereof include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide and cesium sulfide, and hydrates thereof. Or a mixture of two or more.
In the case where an anhydride is used, the alkali metal sulfide may be used as an aqueous solution. Among the above alkali metal sulfides, sodium sulfide and potassium sulfide are preferable, and sodium sulfide is particularly preferable. These alkali metal sulfides can be obtained by reacting an alkali metal hydrosulfide with an alkali metal base or hydrogen sulfide with an alkali metal base, but those prepared outside the reaction system may be used.

Examples of the alkali metal hydrosulfide or its hydrate include lithium bisulfide, sodium bisulfide, potassium bisulfide, rubidium bisulfide and cesium bisulfide, and hydrates thereof. These may be used alone or in combination of two or more. Among these alkali metal hydrosulfides, sodium bisulfide and potassium bisulfide are preferred, and sodium bisulfide is particularly preferred. In this adjustment, a small excess of an alkali metal base may be added in order to remove a small amount of impurities present in the alkali metal sulfide and the alkali metal hydrosulfide.

The alkali metal hydrosulfide can be obtained by reacting hydrogen sulfide with an alkali metal base, but a product prepared in advance outside the reaction system may be used. Examples of the alkali metal base include an alkali metal hydroxide. Examples of the alkali metal hydroxide include, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, and the like.
Two or more kinds may be used as a mixture. Among the above alkali metal hydroxides, lithium hydroxide, sodium hydroxide and potassium hydroxide are preferred, and sodium hydroxide is particularly preferred. In this adjustment, a small excess of an alkali metal base may be added to remove a small amount of impurities present in the alkali metal sulfide and alkali metal hydrosulfide.

The sulfidizing agent used in step 2 is
As described above, the sulfidizing agent can be used alone or as an aqueous solution, but in the present invention, it is liquid, specifically, used as an aqueous solution, is easily introduced into the system, It is preferable that the reaction rate be increased, so that anhydrous or hydrated water is prepared in advance, such as distilled water, ion-exchanged water, etc. Is preferably used after being melted by heating to form an aqueous solution.

The reaction in the step 2 is a reaction solution obtained by hydrolyzing the alicyclic amide compound in the presence of the polyhalo aromatic compound, the alicyclic amide compound, the alkali metal hydroxide and water in the step 1, preferably a reaction solution. After heating the system to 120 to 200 ° C. to dry the inside of the system, the reaction is carried out while adding the sulfidizing agent. At this time, the amount of water in the system is controlled by the alicyclic type used in step 1. It is preferable to carry out the reaction while maintaining the range of 0.01 to 0.5 mol per 1 mol of the amide compound. That is, when the water content is in the range of 0.01 mol% or more, the number of functional groups exhibiting reactivity with acid or alkali in the polyarylene sulfide increases. On the other hand, in the range of 0.5 mol% or less, the reaction rate increases. And the molecular weight of the polyarylene sulfide increases. Here, the amount of water in the system is not based on the total amount of the alicyclic amide compound actually present in the system, but on the basis of the total amount of the alicyclic amide compound used at the time of preparation in Step 1. It means the amount of water in the system with respect to 1 mole of the solution.

That is, in the present invention, the sulfidizing agent is introduced into the system as an aqueous solution, and the water content in the system with respect to the charged alicyclic amide compound is maintained at 0.01 to 0.5 mol%. By performing the reaction while dehydrating, it is possible to dramatically increase the molecular weight while maintaining a high number of functional groups exhibiting reactivity with the acid or alkali of the product.

The amount of water in the system does not need to be maintained at 0.01 to 0.5 mol until the end of the reaction.
Specifically, it is preferable to maintain the range of the water content until the conversion of the dihalo aromatic compound becomes 50%, preferably 70%.

Here, the conversion of the dihalo aromatic compound is represented by the following formula. Conversion rate (%) = (feed amount-remaining amount) / feed amount × 100

In order to maintain the water content in the system within the above range, the concentration of the aqueous solution of the sulfidizing agent, the addition rate, the reaction temperature, and the dehydration conditions may be appropriately selected.

That is, the aqueous solution of the sulfidizing agent preferably has a concentration of 20 to 80% by weight.

In this case, the reaction conditions in step 2 are not particularly limited, but may be 200 to 300 ° C., preferably 21 to 200 ° C.
It is preferable to carry out the reaction while performing dehydration at a temperature of 0 to 280 ° C, more preferably 215 to 260 ° C. Also,
In the present invention, the reaction may be carried out while maintaining the temperature conditions until the water content in the system has completely disappeared even after the addition of the sulfidizing agent. Here, Step 1 and Step 2 may be performed at a constant temperature, the reaction may be performed by increasing the temperature stepwise, or the reaction may be performed by continuously changing the temperature. .

The rate of addition of the sulfidizing agent is not particularly limited, but is preferably added at such a rate that the amount of water in the system can maintain the above range.

In step 2, the dehydration method for maintaining the water content in the system is not particularly limited, and can be performed by controlling the temperature and pressure of the reaction system. , Water, solvent, temperature to be controlled by each vapor pressure curve of the polyhalo aromatic compound,
There is a method of estimating the pressure and adjusting the pressure and temperature conditions to a desired water content in the system.

Next, the method for producing the PAS comprises reacting an alicyclic amide compound, a dihalo-aromatic compound and a sulfidizing agent with each other. A group compound and a sulfidizing agent are reacted so as to maintain the water content in the system in the range of 0.01 to 0.3 mol per 1 mol of the alicyclic amide compound, thereby obtaining a high molecular weight PAS. Get
By adding an alkali metal hydroxide in step 2 to hydrolyze the alicyclic amide compound, and continuously subjecting the hydrolyzate and the high molecular weight PAS obtained in step 1 to substitution reaction, High molecular weight, and
A group reactive with an acid or an alkali, preferably a carboxyl group or an alkali metal salt thereof, is introduced into the molecular structure to increase the number of functional groups.

Here, at the time of the polymerization in the step 1, the water to be present in the system is, as described above, the amount of water in the system is 0.01 to 0.5 with respect to 1 mol of the alicyclic amide compound. Range of moles. That is, when the amount exceeds 0.5 mol, a hydrolysis reaction and the like occur simultaneously, while when the amount is less than 0.01, a problem that the reaction rate is remarkably reduced occurs.
Therefore, in the polymerization reaction of step 1 of the method, the amount of water to be present in the reaction system is 0.01 to 0.01 mol per mol of the alicyclic amide compound until the conversion of the dihalo aromatic compound becomes 70% or more. 0.5 mol, preferably 0.05-0.
It is adjusted to a range of 2 mol, and after completion of the introduction of the sulfidizing agent, the range is preferably 0.1 mol or less, more preferably 0.05 mol or less, per 1 mol of the alicyclic amide compound.

As the sulfidizing agent used in step 1 of the method, any of those exemplified in the method can be used, but in the method, it is necessary to add sufficient water to the system to hydrolyze the alicyclic amide compound. On the other hand, from the viewpoint of increasing the molecular weight of PAS, it is necessary to adjust the water content in the system to a necessary minimum. In order to introduce the water required for the hydrolysis, for example, water is added to the system before introducing the sulfidizing agent, an anhydride of the sulfidizing agent is introduced, or the system is sufficiently dried. Examples include a method of dropping an aqueous solution of a sulfidizing agent.In the method of the present invention, a method of sufficiently drying the system and dripping an aqueous solution of a sulfidizing agent into the system from the viewpoint of easy adjustment of the water content. preferable.

That is, it is preferable to use the sulfidizing agent in a liquid state, specifically, as an aqueous solution, since it can be easily introduced into the system and the reaction rate is increased. Therefore, in advance, anhydrous, hydrated, distilled water, ion-exchanged water, etc., to adjust the water and aqueous solution except the anions and cations that inhibit the reaction, or by heating and melting the hydrated aqueous solution Preferably, it is used.

As the dihalo aromatic compound corresponding to the monomer to form the skeleton of the aromatic sulfide polymer used in step 1 of the method, any of those exemplified in the method can be used. The amount of the dihaloaromatic compound used in the process is determined by the sulfur source 1 in the sulfidizing agent used.
It is preferably in the range of 0.8 to 1.3 mol per mol, and particularly preferably in the range of 0.9 to 1.1 mol to obtain a polymer having excellent physical properties, that is, a polymer having a higher molecular weight.

In the present invention, a monohalo compound (not necessarily an aromatic compound) may be used in combination for forming the terminal of the PAS-forming polymer or for controlling the polymerization reaction or the molecular weight. Further, a polyhalo compound of trihalo or higher (not necessarily an aromatic compound) may be used in combination to form a branched or crosslinked polymer. Further, the amount of the monohalo or polyhalo compound used is different depending on the purpose or reaction conditions and cannot be unconditionally specified, but is preferably 0.1 mol or less, more preferably 0.0 mol or less, per 1 mol of the dihalo aromatic compound.
It is preferably at most 5 mol.

As the alicyclic amide compound used in the method, any of those exemplified in the method can be used, but NMP is preferred because of its good reactivity with alkali metal hydroxide.
Is preferred. In the method, the alicyclic amide compound also functions as a reaction solvent. The amount of the alicyclic amide compound used is not particularly limited, but varies depending on the type of the solvent used and the amount of water to the solvent in the system, but maintains the viscosity of the reaction system capable of uniform polymerization reaction. In addition, in order to maintain a certain level of productivity, the range is preferably 1.0 to 6 mol per 1 mol of the sulfur source in the sulfidizing agent used for the polymerization. Further, when productivity is further taken into consideration, the sulfur source 1
The range of 1.0 to 4.0 mol per mol is preferable,
It is preferably from 1.2 to 3.5 mol.

In step 1 of the method, first, an alicyclic amide compound and a dihaloaromatic compound are mixed, and the mixture is heated to preferably 120 ° C. or more, more preferably 150 ° C. or more, to remove water in the system. After removal, a temperature at which the polymerization reaction can proceed substantially, 200 to 300 ° C., preferably 21 to
The mixture of the alicyclic amide compound and the dihaloaromatic compound is heated to a temperature of 0 to 280 ° C., more preferably 215 to 260 ° C., and the water content in the reaction system is reduced by the alicyclic amide compound 1
A method in which the aqueous solution of the sulfidizing agent is introduced at a rate that can be controlled in the range of 0.01 to 0.5 mol per mol. At this time, the aqueous solution of the sulfidizing agent is
It is preferable that the material is obtained by heating and melting a hydrate.

The amount of water to be controlled and the temperature and pressure at the time of introduction vary depending on the water content of the aqueous solution of the sulfidizing agent, and cannot be unconditionally specified. It is preferable to introduce the reaction solution over a period of 0.5 to 10 hours, since the amount of water or the temperature of the reaction system can be easily controlled and the productivity can be improved.

Next, after introducing the sulfidizing agent, water is further removed from the polymerization mixture (including the solvent, water, unreacted raw materials and polymer), and the water content in the reaction system is reduced to the alicyclic amide compound 1
Adjusted to a range of 0.05 mol or less with respect to
To 300 ° C., preferably heated to a temperature of 210 to 280 ° C. for 0.1 to 40 hours, preferably 0.5 to 20 hours,
More preferably, a method of heating for 1 to 10 hours is preferable.

At this time, from the viewpoint of increasing the molecular weight of the produced PAS, the timing of adjusting the water content in the reaction system to 0.05 mol or less per 1 mol of the alicyclic amide compound is as described above. , The conversion of the dihalo-aromatic compound is 70
%, More preferably 90% or more. Thus, finally, the conversion of the dihalo aromatic compound is 90% or more, preferably 95% or more.
% Or more.

As a method for removing water in step 1, a method for controlling the temperature and pressure of the reaction system is preferable.

That is, the temperature and pressure to be controlled can be easily analogized from the vapor pressure curves of water, the solvent and the dihaloaromatic compound, and the desired amount of water in the system can be obtained by controlling the temperature and pressure. .

The temperature adjustment in step 1 may be a multi-step reaction in which the temperature is increased stepwise, or may be a reaction in which the temperature is continuously changed.

By introducing the hydrous sulfidizing agent at such a rate that water can be removed from the reaction mixture, the water content in the reaction system is reduced to 0.01 to 1 mol per mol of the alicyclic amide compound.
A hydrous sulfidizing agent is introduced while controlling the amount within a range of 0.3 mol, and after the introduction is completed, the water content in the reaction system is controlled within a range of 0.1 mol or less per 1 mol of the alicyclic amide compound. Then, the process proceeds until the conversion of the dihalo aromatic compound becomes 90% or more. Further, in step 2, the alkali metal hydroxide is added to continue the reaction.

In the process step 2, 0.01 to 0.5 mol of an alkali metal hydroxide is added to the polymerization mixture obtained in the step 1 with respect to 1 mol of the hydrated sulfidizing agent introduced into the system. Done. As for the method of addition, the addition may be carried out by lowering the reaction temperature once, but it is preferable to continue the polymerization by keeping the temperature as it is while taking the productivity into consideration. Next, as the alkali metal hydroxide used in step 2 of the method, any of the above-mentioned alkali metal hydroxides can be used, but among them, lithium hydroxide, sodium hydroxide and potassium hydroxide are preferable, and sodium hydroxide is particularly preferable. The addition amount is preferably in the range of 0.01 to 0.3 mol per 1 mol of the introduced sulfidizing agent.

The alkali metal hydroxide to be added is
A solid state, an aqueous state, or a solution separately dissolved in an alicyclic amide compound may be added.
However, when the amount of water in the system increases, the high molecular weight P
Since AS is easily decomposed, it is preferably added in a solid state. In step 2 of the method, an alkali metal hydroxide is added to the system,
A method in which polymerization is carried out by heating at a temperature of 10 to 270 ° C. for 0.1 to 40 hours, preferably 0.1 to 10 hours, more preferably 0.1 to 10 hours, is a method of reacting with an acid or alkali. It is preferable because the amount of the group increases.

As a method and a reaction apparatus in the reaction of the method described in detail above, a polymerization vessel whose liquid contact part is made of titanium, chromium, zirconium, or the like is used.
It is preferable to carry out the reaction in an atmosphere of an inert gas such as nitrogen, helium, argon or the like. In particular, nitrogen is preferable in terms of economy and ease of handling.

Next, the method or the polymer obtained by the method is as follows: ~ 3. It can be recovered by the method described above. That is, 1. At the end of the reaction, first, the reaction mixture is left as it is, or after adding an acid or a base, the mixture is heated under reduced pressure or normal pressure to distill off only the solvent, and then the solid residue is washed with water, acetone, methyl ethyl ketone, alcohols or the like. 1. a method of washing once or twice or more with a solvent, followed by neutralization, washing with water, filtration and drying, and After the completion of the reaction, the reaction mixture is mixed with a solvent such as water, acetone, methyl ethyl ketone, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons, aliphatic hydrocarbons, etc. 2. A method in which a solid product such as a polymer or an inorganic salt is precipitated by adding a sedimentation agent thereto, which is a poor solvent for the polymer), followed by filtration, washing and drying; After completion of the reaction, a reaction solvent (or an organic solvent having the same solubility in a low-molecular polymer) is added to the reaction mixture, and the mixture is stirred. After filtration to remove the low-molecular polymer, water,
Washing is carried out once or twice or more with a solvent such as acetone, methyl ethyl ketone, alcohols, etc., followed by neutralization, washing with water, filtration and drying.

The above 1 .. ~ 3. In each of the recovery methods described above, drying may be performed under vacuum, or may be performed in air or under an inert gas atmosphere such as nitrogen.

The polyarylene sulfide of the present invention thus obtained can be used as it is for various molding materials, but can be thickened by heat treatment in air or oxygen-enriched air or under reduced pressure. After performing such a thickening operation as necessary, the composition may be used for various molding materials.

The heat treatment temperature varies depending on the treatment time and the atmosphere in which the treatment is carried out, so that it cannot be specified unconditionally, but it is usually preferable to carry out the treatment at 180 ° C. or higher.
If the heat treatment temperature is lower than 180 ° C., the rate of thickening is extremely slow, and the productivity is poor, which is not preferable. The heat treatment may be performed in a molten state at a temperature higher than the melting point of the polymer using an extruder or the like. However, from the possibility of polymer deterioration or workability, melting point plus 1
It is preferable to carry out at a temperature of not higher than 00 ° C.

The polyarylene sulfide thus obtained has a structural feature that, as described above, it has many functional groups which are reactive with an acid or an alkali despite having a high molecular weight.

The polyarylene sulfide described in detail above can be formed into a molded product excellent in heat resistance, molding processability, dimensional stability and the like by various melt processing methods such as injection molding, extrusion molding, compression molding and blow molding. However, when used in combination with a silane coupling agent, the toughness of a molded product can be dramatically improved.

The silane coupling agent which can be used herein is not particularly limited, but vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, epoxycyclohexyltrimethoxysilane, glycidoxypropylmethylethoxysilane And aminopropyltrimethoxysilane.

The amount of the silane coupling agent to be used is not particularly limited. However, since the effect of improving the toughness of the molded product is remarkable, the amount of the silane coupling agent is 0.0
A ratio of 1 to 2% by weight is preferable.

The composition using the above-mentioned polyarylene sulfide in combination with a silane coupling agent further improves the performance such as strength, heat resistance and dimensional stability, so that the object of the present invention is not impaired. Can be used in combination with various fillers.

Examples of the filler include a fibrous filler and an inorganic filler. As the fibrous filler, glass fiber, carbon fiber, silane glass fiber, ceramic fiber, aramid fiber, metal fiber, potassium titanate, silicon carbide,
Fibers such as calcium sulfate and calcium silicate, and natural fibers such as wollastonite can be used. Examples of the inorganic filler include barium sulfate, calcium sulfate, clay, viroferrite, bentonite, sericite, zeolite, mica, mica, talc, atalpargite, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, and glass beads. Can be used.

In addition, a small amount of a releasing agent, a coloring agent, a heat-resistant stabilizer, an ultraviolet light stabilizer, a foaming agent, a rust preventive, a flame retardant, etc. Lubricants can be included. Further, similarly, the following synthetic resins and elastomers can be mixed and used.
These synthetic resins include polyester, polyamide,
Polyimide, polyetherimide, polycarbonate,
Polyphenylene ether, polysulfone, polyethersulfone, polyetheretherketone, polyetherketone, polyarylene, polyethylene, polypropylene, polytetrafluoroethylene, polydifluoroethylene, polystyrene, ABS resin, epoxy resin, silicone resin, phenol Resins, urethane resins, liquid crystal polymers and the like can be mentioned, and elastomers include polyolefin-based rubber, fluorine rubber, silicone rubber and the like.

The polyarylene sulfide obtained by the production method of the present invention, the PAS of the present invention and the composition containing the silane coupling agent and the PAS of the present invention have various properties such as heat resistance and step stability inherent to polyarylene sulfide. Since it also has performance, for example, electrical or electronic parts such as connectors, printed circuit boards and encapsulation molded articles, automobile parts such as lamp reflectors and various electric parts, various building materials, interior materials such as aircraft and automobiles Or injection molding or compression molding of precision parts such as OA equipment parts, camera parts and watch parts, or composites, sheets,
It is useful as a material for various forming processes such as extrusion or drawing of pipes, or as a material for fibers or films.

[0080]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

(Measurement of Melt Viscosity) The melt viscosities (η) of the polymers obtained in the respective Examples and Comparative Examples were measured using a Koka type flow tester (300 ° C., shear rate 100 /
Second, nozzle hole diameter 0.5 mm, length 1.0 mm). (Evaluation of Toughness) The toughness of the polymer obtained in each of Examples and Comparative Examples was evaluated by a bending test. Specifically, 1% by weight of an aminosilane coupling agent (KBM, manufactured by Shin-Etsu Silicone Co., Ltd.) based on the polymers obtained in Examples and Comparative Examples.
603) was added and mixed well using a Henschel mixer. After melt-kneading the mixed polymer at 300 ° C. using a small extruder and forming pellets, using a small injection molding machine, a sample having a thickness of 2.0 mm, a width of 10.0 mm, and a length of 60.0 mm was used. A piece was prepared, and a bending test was performed using this sample piece. Bending test is for span length 3
The test was performed at a speed of 0.0 mm and a test speed of 1.5 mm / min.

(Analysis of Functional Group Reactive with Acid or Alkali) 10 g of the polymer obtained in each of the Examples and Comparative Examples is wetted with a small amount of acetone, and distilled water is added thereto and dispersed. Next, 10 ml of 1 mol / l hydrochloric acid is added and stirred. After stirring, the mixture is filtered, and washed repeatedly with water until hydrochloric acid is no longer detected (the silver nitrate solution is added to make the solution no more cloudy). The obtained polymer is again dispersed in distilled water, and 1 mol thereof is added thereto.
/ L sodium hydroxide 10 ml and stirred. After stirring, the mixture was filtered, and washed repeatedly with water until sodium hydroxide was no longer detected (the phenolphthalein solution was added to prevent red coloration). All filtrates used in the water washing were collected, and sodium hydroxide in the filtrate was removed with hydrochloric acid. And the amount of sodium hydroxide consumed was determined.

Example 1 A stainless steel (titanium-lined) 4-liter autoclave with stirring blades connected to a temperature sensor, a cooling tower, a dropping tank, a dropping pump, and a distillate separation tank. Step 1: Paradichlorobenzene (hereinafter referred to as p-DCB) Omitted)
735.0 g (5.0 mol), 1240 g (12.5 mol) of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP),
17 g (0.2 mol) of 48% sodium hydroxide are charged at room temperature, and the temperature is increased to 100 ° C. under a nitrogen atmosphere with stirring.
Then, the system is heated and the system is closed, and the temperature is further raised to 220 ° C. over 50 minutes. Step 2: Then, while dehydrating at that temperature, sodium sulfide 9-hydrate (hereinafter abbreviated as Na2S.9H2O) 1200
g (5.0 mol) was heated to 120 ° C. to make a 33% by weight aqueous solution, and the solution was added dropwise over 4 hours. The pressure of the reaction system during the dropwise addition was 0.1 MPa. The p-DCB distilled azeotropically with water during the dropwise addition was continuously returned to the autoclave. When the distillate during dropping was analyzed, water was found to be 8%.
05 g and NMP 21 g. After the completion of the dropping of the aqueous solution of Na2S, the space between the separation layer and the autoclave is shut off (the valve between the separation layer and the autoclave body is closed), and the temperature is raised from 220 ° C. to 250 over 1 hour. The reaction was terminated after holding for a time.

The pressure condition and temperature condition in this reaction are the amount of water in the system with respect to 1 mol of NMP used.
It is set so as to be always 0.2 mol. The slurry obtained after cooling is poured into 20 liters of water and
After stirring for 1 hour, the mixture was filtered. The cake was again stirred and washed with 5 liters of hot water for 1 hour, and then filtered. This operation was repeated four times. After filtration, the mixture was dried overnight (12
(0 ° C.) to obtain 508 g (94% yield) of a white powdery polymer. The melt viscosity of the obtained polymer is 121.
0 poise and the amount of reactive terminal groups were 12.8 μmol / g. FIG. 1 shows an IR chart of the obtained polymer. A bending test was performed using this polymer, and the results are shown in Table 1.

Example 2 In step 2, 83 g of 48% sodium hydroxide added was added.
(1.0 mol) and carried out in the same manner as in Example 1 (implementing such that the amount of water in the system was 0.2 mol per 1 mol of NMP used). The resulting polymer (93% yield) had a melt viscosity of 1040 poise and a reactive terminal group content of 19.1.
μmol / g. A bending test was performed in the same manner as in Example 1. The results are shown in Table 1.

Example 3 In step 2, 166 g of 48% sodium hydroxide added was added.
(2.0 mol) and carried out in the same manner as in Example 1 (the amount of water in the system was 0.04 per mol of NMP used).
Mol%). The obtained polymer (yield 94
%) Has a melt viscosity of 910 poise and a reactive terminal group content of 2
It was 8.8 μmol / g. A bending test was performed in the same manner as in Example 1. The results are shown in Table 1.

Example 4 In step 2, 332 g of 48% sodium hydroxide added was added.
(4.0 mol) and carried out in the same manner as in Example 1 (implementing such that the amount of water in the system was 0.2 mol per 1 mol of NMP used). The resulting polymer (94% yield) has a melt viscosity of 720 poise and a reactive terminal group content of 34.1 μm.
mol / g. A bending test was performed in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1 The procedure of Example 1 was repeated, except that 48% sodium hydroxide was not added.
The amount of water in the system was 0.04 mol% with respect to the above), and the melt viscosity of the obtained polymer was 1460 poise.
The reactive terminal group amount was 7.7 μmol / g. Also,
A bending test was performed in the same manner as in Example 1, and the results are shown in Table 2.

[0089]

[Table 1]

Example 5 Instead of the Na2S aqueous solution in Step 1, NaSH.H
370 g (5.0 mol) of 2O was heated to 120 ° C.
The same procedure as in Example 1 was carried out using a solution prepared as a weight% aqueous solution (the water content in the system relative to the NMP used was 0.0
4 mol%). The melt viscosity was 610 poise and the amount of reactive terminal groups was 18.5 μmol / g. Also,
A bending test was performed in the same manner as in Example 1, and the results are shown in Table 2.

Example 6 417 g of 48% sodium hydroxide added in Step 2
(3.0 mol) in the same manner as in Example 6 (implemented such that the amount of water in the system was 0.2 mol% with respect to 1 mol of NMP used). The melt viscosity was 830 poise and the amount of reactive terminal groups was 24.5 μmol / g. A bending test was performed in the same manner as in Example 1. The results are shown in Table 2.

Example 7 417 g of 48% sodium hydroxide added in Step 2
(5.0 mol) in the same manner as in Example 6 (implemented such that the amount of water in the system was 0.2 mol per 1 mol of NMP used). The melt viscosity was 790 poise and the amount of reactive terminal groups was 38.1 μmol / g. Table 2 summarizes the results of Examples 5 to 7. A bending test was performed in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 2 The same procedure as in Example 6 was carried out except that 48% sodium hydroxide was not added (the amount of water in the system was 0.2 mol per 1 mol of NMP used). (Execution) However, the obtained polymer had a low yield of 40%, a melt viscosity of 70 poise and a reactive terminal group content of 5.3 μmol / g. A bending test was performed in the same manner as in Example 1. The results are shown in Table 2.

[0094]

[Table 2]

Next, in Examples 8 to 12 and Comparative Examples 3 to 5, the amount of a carboxyl group or a metal salt thereof as a functional group having reactivity with an acid or an alkali was determined by the following method.

(Measurement of Carboxyl Group or Its Metal Salt Amount) 10 g of the polymer obtained in each of the examples and comparative examples was wetted with a small amount of methanol, and 100 ml of water was added thereto to form a slurry. The slurry was acidified by adding 5 ml of diluted hydrochloric acid thereto. Next, filtration was carried out, washing with water was repeated until hydrochloric acid was not detected in the filtrate, and the dried polymer was pressed into a disk shape by a press machine.
-Measurement was performed with an IR device. 2666 of these absorptions
The relative intensity of the absorption at 1700 cm ^-1 relative to the absorption at cm ^-1 was determined.

On the other hand, a predetermined amount of p-chlorophenylacetic acid was added as a standard substance to the PAS obtained in Comparative Example 3, and FT-IR measurement was performed. Was prepared, and the content of the carboxyl group and its alkali metal salt in the measurement sample was determined.

Example 8 A stainless steel (titanium-lined) 4-liter autoclave equipped with stirring blades connected to a temperature sensor, a cooling tower, a dropping tank, a dropping pump, and a distillate separation tank. Step 1: p-dichlorobenzene (hereinafter referred to as DCB) Omitted) 73
5 g (5.0 mol), 1980 g (20.0 mol) of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), water 2
7.0 g (1.5 mol) was charged at room temperature, the temperature was raised to 100 ° C. over 30 minutes in a nitrogen atmosphere with stirring, the system was closed, and the temperature was further raised to 220 ° C. over 60 minutes. At that temperature, the system was opened, dehydration was performed while adjusting the pressure of the reaction system to 0.1 MPa, and the amount of water in the system was adjusted (temperature at this time-
The amount of water is 0.02 mol per 1 mol of NMP in the system due to the pressure.) Under this condition, 1200 g (5.0 mol) of Na ₂ S.9H ₂ O melted by heating to 120 ° C. was added dropwise over 5 hours. The pressure of the reaction system during the dropwise addition was kept at 0.1 MPa. During the dropwise addition, p-DCB distilled azeotropically with water was continuously returned to the autoclave. After the dropping of Na ₂ S.9H ₂ O was completed, the temperature was raised from 220 ° C. to 230 ° C. over 3 hours while maintaining the pressure (also at this time, azeotropic distillation with water was performed as in the dropping). P-DCB was continuously returned to the autoclave). From the relationship between the temperature and the pressure after the completion of the heating, the amount of water was 0.01 mol per 1 mol of NMP in the system. The system was then closed and kept at that temperature for 3 hours. By sampling 20 g of the reaction slurry and using gas chromatography,
The calculated conversion of DCB was 99%. Step 2: After completion of step 1, 82 g of sodium hydroxide (0.41 mol per 1 mol of the sulfidizing agent) was added, and the mixture was kept at that temperature for 2 hours to terminate the reaction. The reaction slurry obtained is poured into 20 liters of water and the mixture
After stirring for an hour, the mixture was filtered. The cake was again stirred and washed with 5 liters of hot water for 1 hour, and then filtered. This operation was repeated four times. After filtration, the mixture was dried overnight (120
C) and dried to obtain a white powdery polymer. The melt viscosity of the obtained polymer was 1310 poise, and the amount of the carboxyl group or its alkali metal salt was 34 μmol / g. A bending test was performed using this polymer, and the results are shown in Table 3.

Example 9 Example 9 was carried out in the same manner as in Example 8, except that the amount of sodium hydroxide added in Step 2 was changed to 48 g (0.24 mol per mol of sulfidizing agent). The conversion of DCB was 99% at the end of step 1. The melt viscosity of the obtained polymer was 1150 poise, and the amount of the carboxyl group or its alkali metal salt was 27 μmol / g. Example 8
A bending test was performed in the same manner as in Example 1 and the results are shown in Table 3.

Example 10 The same procedure as in Example 8 was carried out except that the amount of sodium hydroxide added in Step 2 was changed to 16 g (0.08 mol per 1 mol of the sulfidizing agent). The conversion of DCB was 99% at the end of step 1. The melt viscosity of the obtained polymer was 1220 poise, and the amount of the carboxyl group or its alkali metal salt was 19 μmol / g. Example 8
A bending test was performed in the same manner as in Example 1 and the results are shown in Table 3.

Example 11 The same operation as in Example 8 was carried out except that the pressure of the system in Step 1 was changed to 0.25 MPa. From the temperature-pressure relationship after the completion of the temperature increase, the amount of water was 0.08 mol per 1 mol of NMP in the system. The conversion of DCB was 97% at the end of step 1. The melt viscosity of the obtained polymer is 830 poise, and the amount of the carboxyl group or its alkali metal salt is 39 μm.
ol / g. A bending test was performed in the same manner as in Example 8, and the results are shown in Table 3.

Example 12 Example 12 was carried out in the same manner as in Example 8, except that the pressure of the system in Step 1 was changed to 0.35 MPa. From the relationship between the temperature and the pressure after the completion of the heating, the amount of water was 0.14 mol per 1 mol of NMP in the system. The conversion of DCB was 95% at the end of step 1. The melt viscosity of the obtained polymer is 530 poise, and the amount of the carboxyl group or its alkali metal salt is 44 μm.
ol / g. A bending test was performed in the same manner as in Example 8, and the results are shown in Table 3.

Comparative Example 3 The same procedure as in Example 8 was carried out except that sodium hydroxide was not added in Step 2. The melt viscosity of the obtained polymer was 1420 poise, and no carboxyl group or alkali metal salt thereof could be detected. A bending test was performed in the same manner as in Example 8, and the results are shown in Table 4.

Comparative Example 4 The same operation as in Example 8 was carried out except that the amount of sodium hydroxide added in Step 2 was changed to 2 g (0.01 mol per 1 mol of the sulfidizing agent). The conversion of DCB was 99% at the end of the first step. The melt viscosity of the obtained polymer was 1340 poise, and the amount of the carboxyl group or its alkali metal salt was 5 μmol / g. A bending test was performed in the same manner as in Example 8, and the results are shown in Table 4.

Comparative Example 5 The procedure of Example 8 was repeated except that the amount of sodium hydroxide added in step 2 was changed to 140 g (0.7 mol per 1 mol of the sulfidizing agent). The conversion of DCB was 99% at the end of the first step. The melt viscosity of the obtained polymer was 230 poise, and the amount of the carboxyl group or its alkali metal salt was 63 μmol / g. Example 8
A bending test was performed in the same manner as described above, and the results are shown in Table 4. Table 3 shows the results of Examples 7 to 12 described above, and Comparative Examples 3 to 5
Table 4 shows the results.

[0106]

[Table 3]

[0107]

[Table 4]

[0108]

According to the present invention, a novel polyarylene sulfide having a high molecular weight, a large number of constant functional groups reactive with an acid or an alkali, and a good affinity with a silane coupling agent, and its production. A method and a novel polyarylene sulfide composition capable of dramatically improving the toughness of a molded product can be provided.

[0109]

[Brief description of the drawings]

FIG. 1 is an IR chart of the novel polyarylene sulfide produced in Example 1.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J002 CN011 EX016 EX036 EX066 EX076 FD010 GM00 GN00 GQ00 4J030 BA03 BA05 BA49 BB29 BC08 BC12 BC18 BF10 BG10 BG27

Claims (11)

[Claims] 1. The following structure: (Wherein, R is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or a functional group reactive with an acid or an alkali, n
Is an integer of 0 to 4. ) Is a repeating unit, and the melt viscosity at 300 ° C. is 400 to 1500.
A polyarylene sulfide, which is a poise and contains a functional group having a reactivity with an acid or an alkali at a ratio of 10 to 50 μmol / g. 2. A method for producing a polyarylene sulfide by reacting an alicyclic amide compound, a polyhaloaromatic compound, and a sulfidizing agent, comprising the steps of: Step 1: polyhaloaromatic compound, alicyclic amide compound,
A method for producing polyarylene sulfide, comprising hydrolyzing the alicyclic amide compound in the presence of an alkali metal hydroxide and water, and then reacting while adding a sulfidizing agent into the system. . 3. The reaction of step 2 is carried out in such a manner that the amount of water in the system is 0.02 to 1 mol of the alicyclic amide compound used.
3. The method according to claim 2, wherein the dehydration is carried out so as to have a ratio of 0.5 mol. 4. The amount of the alkali metal hydroxide used in the step 1 is based on 1 mol of the sulfidizing agent used.
The production method according to claim 2 or 3, wherein the ratio is 0.01 to 1 mol. 5. A process for producing a polyarylene sulfide polymer by reacting an alicyclic amide compound, a dihalo-aromatic compound and a sulfidizing agent, comprising the steps of: Step 1: preparing a mixture containing an alicyclic amide compound and a dihalo-aromatic compound; Carrying out the reaction while adding the agent continuously or intermittently and maintaining the water content in the system in the range of 0.01 to 0.3 mol per 1 mol of the alicyclic amide compound. 2: A method for producing a polyarylene sulfide polymer, wherein an alkali metal hydroxide is then added to the reaction system to carry out a further reaction. 6. The production method according to claim 5, wherein the reaction in the step 1 is performed until the conversion of the dihalo aromatic compound becomes 90% or more. 7. The method according to claim 5, wherein the amount of the alicyclic amide compound used is in the range of 1.0 to 6 mol per 1 mol of the hydrosulfide agent. 8. A hydrous sulfidizing agent is used as the sulfidizing agent used in step 1, and the amount of water in the system is 0.05 to 0.5 with respect to 1 mol of the alicyclic amide compound.
8. The production method according to claim 5, wherein the reaction is carried out while removing water in the system so as to maintain the molar range. 9. In the step 1, after the introduction of the hydrous sulfidizing agent, the reaction is further carried out while maintaining the water content in the reaction system within a range of 0.05 mol or less based on 1 mol of the alicyclic amide compound. 9. The production method according to claim 8, which is continued. 10. The amount of the alkali metal hydroxide added in Step 2 is 0.01 to 0.5 mol with respect to 1 mol of the sulfidizing agent introduced into the system in Step 1. 10. The production method according to any one of items 9 to 9. 11. The following structure: (Wherein, R is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or a functional group reactive with an acid or an alkali, n
Is an integer of 0 to 4. ) Is a repeating unit, and the melt viscosity at 300 ° C. is 400 to 1500.
A polyarylene sulfide characterized by comprising a polyarylene sulfide which is a poise and contains a functional group reactive with an acid or an alkali at a ratio of 10 to 50 μmol / g, and a silane coupling agent as essential components. Composition.