JPH09241379A - Production of polyarylene sulfide modification, modification obtained thereby, and resin composition comprising the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyarylene sulfide modification enhanced in the affinity for fillers and improved in strength by depolymerizing a polyarylene sulfide(PAS), subjecting it to a substitution reaction with a halogenated arom. compd. to introduce arom. groups having a substituent into PAS to thereby modify PAS. SOLUTION: 100 to 1,000g of a polyarylene sulfide(PAS) is dissolved in 1l of an aprotic org. solvent, to which an alkali metal sulfide is then added in an amt. of 0.005 to 0.2mol per unit mol of PAS to effect a reaction, whereby PAS is depolymerized. Subsequently, the depolymn. product is subjected in the aprotic org. solvent to a substitution reaction with a halogenated arom. compd. of the formula (wherein X is halogen; R<1> is a 6-13C arom. group; Y is a hydroxyl, amino, dialkylamino, 1-2C alkoxyl, carboxyl, aldehyde, carboxylic ester, cyano, nitro or 1-30C alkyl group; and a and me are each 1 to 4), the amt. of which is 2 to 5 times as much as that of the alkali metal sulfide in the depolymn. reaction, whereby arom. groups having a substituent are introduced into PAS to obtain a modification thereof.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a modified polyarylene sulfide (hereinafter sometimes referred to as PAS), a modified product obtained by the production method, and a resin composition thereof.

[0002]

2. Description of the Related Art In recent years, since PAS resins have excellent heat resistance, mechanical properties, chemical resistance, etc., they have come to be widely used in various electric and electronic equipment parts, automobile equipment parts and the like. However, on the other hand, due to its low reactivity, it is difficult to react with the filler or its surface treatment agent, and there is a problem that the improvement of strength is insufficient.

In order to solve such a problem, a PAS resin having a functional group introduced is considered as a method for increasing the affinity with the filler or its surface treatment agent, and the following techniques have been disclosed in this regard. There is. For example, JP-A-61
-7248 discloses a PAS containing a disulfide bond.
Although a method in which a disulfide bond is cleaved and a functional group is introduced after the resin is produced is disclosed, there is a problem that the obtained PAS resin has a low molecular weight.

Further, JP-A-58-185625 discloses a combination of a halothiophenol compound having a functional group such as a nitro group, an amino group and a carboxyl group with a hydrogen halide scavenger, or a halothiophenol salt thereof. Although a method of producing a PAS resin by reacting in the presence of a catalyst such as a nickel compound or a divalent or zero-valent palladium complex compound is disclosed, it is industrialized because a raw material and a catalyst that are expensive and difficult to obtain are used. Is extremely disadvantageous.

Further, JP-A-57-90018 discloses a method of copolymerizing a halogenated aromatic compound having an electron-withdrawing substituent to introduce a functional group into a PAS resin. In the method, it is indispensable that the halogenated aromatic compound has an electron-withdrawing substituent, and the electron-donating substituent such as hydroxyl group and amino group is not described at all.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above problems, and a terminal of a polyarylene sulfide having a repeating unit represented by the structural formula -Ar-S- (Ar represents an arylene group). Another object of the present invention is to provide a method for producing a modified form of PAS, which is capable of quantitatively and effectively introducing an aromatic compound having a functional group in the chain. In addition, PAS, which has affinity with inorganic fillers and organic fillers, and whose addition improves the strength, is high.
It is an object of the present invention to provide a modified resin composition of the above.

[0007]

To achieve the above object, according to the present invention, the polyarylene sulfide is depolymerized by reaction with an alkali metal sulfide in an aprotic organic solvent, and then the obtained solution is obtained. The polymer has the general formula (I) X _n R ¹ Y _m ... (I) (wherein, X is a halogen group, R ¹ is an aromatic group having 6 to 13 carbon atoms, Y is a hydroxyl group, an amino group, Dialkylamino group,
An alkoxyl group having 1 or 2 carbon atoms, a carboxyl group,
It represents any substituent selected from the group consisting of an aldehyde group, a carboxylic acid ester group, a cyano group, a nitro group and an alkyl group having 1 to 30 carbon atoms, and when Y is plural, it may be the same or different. Good. n and m are integers of 1 to 4. ) A substituted aromatic compound having a substituent is introduced into the polyarylene sulfide by substitution reaction of the halogenated aromatic compound represented by the formula (1) in an aprotic organic solvent to prepare a modified polyarylene sulfide. A method is provided.

In a preferred embodiment, the reaction concentration of the polyarylene sulfide during the depolymerization reaction is 100 to 10 with respect to 1 liter of the aprotic organic solvent.
00g, the blending ratio of the alkali metal sulfide is 0.005 to 0.2 with respect to 1 basic mole of polyarylene sulfide.
It is molar, and the mixing ratio of the halogen aromatic compound at the time of the substitution reaction is 2 to 5 times the molar amount of the alkali metal sulfide used in the depolymerization reaction. A method of making a modified polyarylene sulfide is provided.

The structural formula obtained by the above method is
It is composed of a repeating unit represented by Ar-S- (Ar represents an arylene group) and has a logarithmic viscosity of 0.1 to 0.35.
Modified polyarylene sulfides are provided that are in the range of dl / g. In addition, the structural formula-Ar
An aromatic compound having a hydroxyl group as a substituent in a polyarylene sulfide composed of a repeating unit represented by —S— (Ar represents an arylene group) is added to the polyarylene sulfide at the end or in the chain of 0.05 per repeating unit.
-10 mol% is included, and its inherent viscosity is 0.1-0.3
A modified form of polyarylene sulfide in the range of 5 dl / g.

Further, 100 parts by weight of the modified polyarylene sulfide and 1 to 3 of the inorganic and / or organic fillers.
A resin composition comprising 400 parts by weight is provided.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. I. Method for producing modified polyarylene sulfide 1. Depolymerization Reaction In the present invention, first, a polyarylene sulfide and an alkali metal sulfide are depolymerized in an aprotic organic solvent. By this reaction, a polyarylene sulfide having an increased number of terminal alkali thiolate groups can be obtained. (1) Reaction component and its solvent Polyarylene sulfide The polyarylene sulfide used in the present invention is a polymer containing 70 mol% or more of the repeating unit represented by the structural formula —Ar—S— (Ar is an arylene group). The representative substance is structural formula -Ph-S- (Ph is a phenylene group).
Is a polyphenylene sulfide having 70 mol% or more of the repeating unit represented by. Among them, α-chloronaphthalene solution (concentration 0.4 g / dl), logarithmic viscosity at 206 ° C. is 0.1 to 0.5 (dl / g), preferably 0.1.
3 to 0.4 (dl / g), more preferably 0.15 to
Those in the range of 0.35 (dl / g) are suitable.
Further, those having a melt viscosity of 100 to 20,000 poises, particularly 100 to 5,000 poises, measured under conditions of a temperature of 300 ° C. and a shear rate of 1200 / sec are suitable. PAS is generally known to have a substantially linear molecular structure without a branched or crosslinked structure and a structure having a branched or crosslinked structure depending on the production method. Is also effective. The PAS preferable for use in the present invention is a homopolymer or copolymer containing 70 mol% or more, more preferably 80 mol% or more, of a paraphenylene sulfide unit as a repeating unit. If this repeating unit is less than 70 mol%, the original crystallinity, which is a characteristic of a crystalline polymer, tends to be low, and sufficient mechanical properties tend not to be obtained, which is not preferable.

Examples of the copolymer unit include a metaphenylene sulfide unit, an orthophenylene sulfide unit, a p, p'-diphenylene ketone sulfide unit,
p, p'-diphenylene sulfone sulfide unit, p,
Examples thereof include p'-biphenylene sulfide unit, p, p'-diphenylene ether sulfide unit, and 2,6-naphthalene sulfide unit. In addition, the PAS of the present invention
As the above, in addition to the above-mentioned substantially linear polymer, a branched or crosslinked polyarylene sulfide obtained by polymerizing by using a small amount of a monomer having three or more functional groups as a part of the monomer can also be used. It is preferable to use a compounded polymer blended with the above linear polymer. Furthermore, PAS as a component used in the present invention may be a polymer in which a linear polymer having a relatively low molecular weight is increased in logarithmic viscosity by oxidative crosslinking or thermal crosslinking to improve moldability. Alkali metal sulfide The alkali metal sulfide used in the present invention is not particularly limited, but preferred examples thereof include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide, and the like, and mixtures thereof. . Further, it may be either an anhydrate or a hydrate.

Aprotic organic solvent The aprotic organic solvent used in the present invention is generally an aprotic polar organic compound (eg, amide compound, lactam compound, urea compound, organic sulfur compound, cyclic organic phosphorus compound). Compound etc.) can be suitably used as a single solvent or as a mixed solvent.

Of these aprotic polar organic compounds, examples of the amide compound include N, N-
Dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dipropylacetamide, N,
N-dimethylbenzoic acid amide and the like can be mentioned.
Examples of the lactam compound include caprolactam, N-methylcaprolactam, N-ethylcaprolactam, N-isopropylcaprolactam, N-isobutylcaprolactam, N-normalpropylcaprolactam, N-normalbutylcaprolactam, N-cyclohexylcaprolactam and the like. N-alkylcaprolactams, N-methyl-2-pyrrolidone (NMP), N
-Ethyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-isobutyl-2-pyrrolidone, N-n-propyl-2-pyrrolidone, N-n-butyl-
2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-methyl-3-methyl-2-pyrrolidone, N-ethyl-3-methyl-2-pyrrolidone, N-methyl-3,
4,5-Trimethyl-2-pyrrolidone, N-methyl-2
-Piperidone, N-ethyl-2-piperidone, N-isopropyl-2-piperidone, N-methyl-6-methyl-
2-piperidone, N-methyl-3-ethyl-2-piperidone and the like can be mentioned.

Examples of the urea compound include:
Tetramethylurea, N, N'-dimethylethyleneurea,
N, N'- dimethyl propylene urea etc. can be mentioned. Examples of the organic sulfur compound include dimethyl sulfoxide, diethyl sulfoxide, diphenyl sulfone, 1-methyl-1-oxosulfolane, 1-ethyl-1-oxosulfolane, 1-phenyl-1-oxosulfolane, and the like. Examples of the cyclic organic phosphorus compound include 1-methyl-1-oxophosphorane, 1-normal-propyl-1-oxophosphorane, 1-phenyl-1-oxophosphorane and the like.

These various aprotic polar organic compounds may be used alone or in combination of two or more,
Further, it can be used as the aprotic organic solvent by mixing with another solvent component which does not disturb the object of the present invention. Among the various aprotic organic solvents,
Preferred are N-alkylcaprolactam and N-alkylpyrrolidone, particularly preferred are N-methyl-
2-pyrrolidone.

Alkali Metal Hydroxide In the present invention, an alkali metal hydroxide may be blended if necessary. Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide and cesium hydroxide. The addition of this alkali metal hydroxide has the effect of making it easier to maintain the alkalinity of the reaction solution. Water In the present invention, water may be added if necessary.
The solubility of the metal sulfide can be improved by adding water.

(2) Reaction conditions Reaction concentration and blending ratio (i) The reaction concentration of polyarylene sulfide is 100 to 1000 g per liter of aprotic organic solvent from the viewpoint of promoting reaction with halogenated aromatics. 200 to 400 g is more preferable. If it is less than 100 g, the productivity may decrease, and if it exceeds 1000 g, the reaction rate may decrease and a side reaction may occur. (Ii) The blending ratio of the alkali metal sulfide is preferably 0.005 to 0.2 mol based on 1 mol of PAS, and is 0.1.
01 to 0.1 mol is more preferable. If it is less than 0.005 mol, the desired effect may not be obtained,
If it exceeds 0.2 mol, the molecular weight may decrease excessively.

(Iii) The mixing ratio of the alkali metal hydroxide used as necessary is preferably 2 to 10 times the mol of the mixing amount of the alkali metal sulfide (B). If it is less than 2 times the molar amount, reaction active points remain and the thermal stability may decrease, and if it exceeds 10 times the molar amount, unreacted substances remain and gas is generated during molding, and the surface appearance and physical properties of the molded article are increased. May cause adverse effects such as a decrease in (Iv) The mixing ratio of water used as necessary is 0.1 to 10 mol per liter of the aprotic organic solvent,
It is preferably 1 to 5 mol. If it is less than 0.1 mol, the solubility of the alkali metal sulfide may be insufficient, and if it is more than 10 mol, depolymerization may be insufficient.

Reaction temperature The reaction temperature of the depolymerization reaction in the present invention is 30 ° C to 30 ° C.
0 degreeC is preferable and 100-250 degreeC is more preferable.
If the temperature is lower than 30 ° C, the reaction may be insufficient,
If it exceeds 300 ° C, side reactions may occur and the molecular weight may excessively decrease. Reaction time The reaction time of the depolymerization reaction in the present invention is 10 minutes to 25 minutes.
Time is preferable, and 10 minutes to 10 hours is more preferable.
If it is less than 10 minutes, the reaction may be insufficient,
If it exceeds 25 hours, productivity may be decreased and side reactions may occur, and the molecular weight may be excessively decreased.

2. Substitution Reaction (Introduction of Aromatic Compound Having Substituent) In the present invention, after the depolymerization reaction, the terminal alkali thiolate group contained in the residual liquid after completion of the reaction was increased. Halogen represented by the general formula (I) X _n R ¹ Y _m ... (I) (wherein X, R ¹ , Y, n and m are the same as described above) to be newly blended with the polyarylene sulfide. A substitution reaction is carried out with the aromatic compound. As the aprotic organic solvent, the same aprotic organic solvent used in the depolymerization reaction can be used. By this reaction, an aromatic group having a substituent is introduced into the polyarylene sulfide resin.

(1) Reaction Component Halogenated Aromatic Compound As the halogenated aromatic compound used in the substitution reaction in the present invention, those represented by the above general formula (I) can be mentioned. That is, X _n R ¹ Y _m (I) In the formula, X represents a halogen group, and when there are a plurality of Xs, they may be the same or different. It is preferably a chlorine atom or a bromine atom. n shows the integer of 1-4.

Y is a hydroxyl group, amino group, dialkylamino group, alkoxy group having 1 or 2 carbon atoms, carboxyl group, aldehyde group, carboxylic acid ester group, cyano group, nitro group and alkyl group having 1 to 30 carbon atoms. When any one of the substituents selected from the group consisting of groups is present and Y is plural, they may be the same or different. m shows the integer of 1-4.

R ¹ represents an aromatic group having 6 to 13 carbon atoms, and R ¹ Y _m is the following general formula (II) to (VI).

[0025]

Embedded image

It is shown by. Specific examples of the halogenated aromatic compound include o-chlorophenol and m-
Chlorophenol, p-chlorophenol, o-chlorobenzoic acid, m-chlorobenzoic acid, p-chlorobenzoic acid,
o-chloroaniline, m-chloroaniline, p-chloroaniline, o-chloro (dimethylamino) benzene, m
-Chloro (dimethylamino) benzene, p-chloro (dimethylamino) benzene, o-chloroanisole, m-
Chloroanisole, p-chloroanisole, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-
Chlorobenzaldehyde, ethyl o-chlorobenzoate,
Ethyl m-chlorobenzoate, ethyl p-chlorobenzoate, o-chlorobenzonitrile, m-chlorobenzonitrile, p-chlorobenzonitrile, o-chloronitrobenzene, m-chloronitrobenzene, p-chloronitrobenzene, chloronaphthol, Chloro, hydroxy-biphenyl, dichlorophenol, trichlorophenol, dichlorobenzoic acid, trichlorobenzoic acid, dichloroaniline, trichloroaniline, chloro-dihydroxybenzene, etc., and corresponding compounds containing bromine atom or fluorine atom instead of chlorine atom in these compounds The compound which does is mentioned. A compound containing a chlorine atom is preferable, and p-chlorophenol, p-chlorobenzoic acid and the like can be preferably used.

(2) Reaction conditions Blending ratio The blending ratio of the halogenated aromatic compound used in the present invention is 2 to 5 with respect to the blending molar amount of the alkali metal sulfide.
Double molar is preferred. If it is less than 2 times by mole, reaction active points remain and the thermal stability may be deteriorated, and if it exceeds 5 times by mole, gas is generated and adverse effects such as deterioration of surface appearance and physical properties of the molded product occur. There is.

Reaction temperature The reaction temperature of the substitution polymerization reaction in the present invention is 30 ° C to 3 ° C.
00 ° C is preferable, and 100 to 250 ° C is more preferable. If it is lower than 30 ° C, the reaction may be insufficient, and if it exceeds 300 ° C, a side reaction may occur and the molecular weight may decrease.

Reaction time The reaction time of the substitution reaction in the present invention is preferably 10 minutes to 10 hours, more preferably 10 minutes to 5 hours. 10
If it is less than minutes, the reaction may be insufficient, and 10
If the time is exceeded, productivity may decrease.

3. Post-treatment In the present invention, depolymerization reaction and substitution reaction are carried out continuously, after the completion of these reactions, as post-treatment, filtered,
And washed with water and organic solvent (acetone, alcohol),
By drying, a polyarylene sulfide into which an aromatic group having a substituent is introduced can be finally obtained. As described above, the halogenated aromatic compound can be reacted almost quantitatively by performing the substitution reaction with the polyarylene sulfide in which the alkali thiolate group is increased by depolymerization and the halogenated aromatic compound. In this method, a modified product mainly having a halogenated aromatic compound introduced at the terminal of polyarylene sulfide is different from the one obtained by reacting with an aromatic compound having a substituent in a conventional polymerization step, and , -Ar-S-, having a logarithmic viscosity of 0.1 at 206 ° C.
~ 0.35 dl / g, preferably 0.1-0.3 dl / g
g, more preferably a modified form of high molecular weight PAS in the range of 0.15-0.25 dl / g. 0.1 dl
If it is less than / g, sufficient mechanical properties cannot be obtained, and 0.
If it exceeds 35 dl / g, the moldability deteriorates.

Further, it is possible to introduce an aromatic compound having an electron-donating substituent, which has a bad influence on polymerization and which is difficult to undergo a substitution reaction, into the terminal or chain of the polyarylene sulfide resin. became. Above all, there is no example of a copolymer having an aromatic compound having a hydroxyl group and having a high molecular weight. Further, under appropriate depolymerization reaction conditions, the decrease in the molecular weight of the polyarylene sulfide is small, the desired physical properties, the molecular weight considered necessary from the fluidity, preferably, using a polyarylene sulfide having a molecular weight slightly higher than the desired molecular weight, After the polymerization reaction, it may be replaced with a desired halogenated aromatic compound, so that
A substantially linear polyarylene sulfide produced in a large amount can be used, which is extremely industrially advantageous.

II. Modified Polyarylene Sulfide and Resin Composition Thereof The modified polyarylene sulfide of the present invention can be obtained as polyarylene sulfide by the above-mentioned production method. Further, the resin composition of the present invention can be obtained by blending the above-mentioned modified product with an inorganic and / or organic filler. Inorganic or organic filler The filler used in the resin composition of the present invention may be an inorganic compound or an organic compound,
Each may be used alone or as a mixture. It may be fibrous or non-fibrous in shape.

Specifically, in order to obtain a molded product having excellent performance such as mechanical properties, heat resistance, dimensional stability (deformation resistance, warpage), and electrical properties, a fibrous or powdery material can be obtained. A granular or plate-shaped filler is used. Fibrous fillers include glass fiber, asbestos fiber, carbon fiber, silica fiber,
Inorganic fibrous materials such as silica / alumina fibers, zirconia fibers, boron nitride fibers, silicon nitride fibers, boron fibers, potassium titanate fibers, and fibrous materials of metals such as stainless steel, aluminum, titanium, copper and brass You can Particularly typical fibrous filler is glass fiber or carbon fiber. In addition, high-melting point organic fibrous substances such as aromatic polyamide, fluororesin, and acrylic resin can also be used. On the other hand, powdered and granular fillers include carbon black, fused or crystalline silica, quartz powder, glass beads, glass powder, calcium silicate, aluminum silicate, kaolin, talc, clay, diatomaceous earth, and wollastonite. Acid salt, iron oxide, titanium oxide, zinc oxide,
Oxides of metals such as alumina, calcium carbonate, carbonates of metals such as magnesium carbonate, calcium sulfate,
Metal sulfates such as barium sulfate, other silicon carbide,
Examples thereof include boron nitride and various metal powders. Also,
Examples of the plate-shaped filler include mica, glass flakes, various metal foils and the like. These inorganic fillers can be used alone or in combination of two or more. The combined use of fibrous fillers, particularly glass fibers or carbon fibers, with granular and / or plate-like fillers is a preferable combination particularly in terms of mechanical strength, dimensional accuracy, electrical properties and the like. When using these fillers, it is desirable to use a sizing agent or a surface treatment agent if necessary. Examples of this are functional compounds such as epoxy compounds, isocyanate compounds, silane compounds and titanate compounds. These compounds may be used by subjecting the filler to a surface treatment or a converging treatment in advance, or may be added at the same time when the material is prepared. The amount of the filler used is 400 parts by weight or less, preferably 10 to 300 parts by weight, per 100 parts by weight of the PAS. The lower limit is not particularly limited, but if it is less than 10 parts by weight, mechanical strength and rigidity may be poor depending on the use of the molded product. Moreover, when it exceeds 400 parts by weight,
The molding work becomes difficult and the mechanical properties of the molded product deteriorate.

In the resin composition of the present invention, as the base polymer, PAS is used within a range that does not impair its purpose.
Besides, it is also possible to supplementarily use a small amount of other thermoplastic resin. The other thermoplastic resin used here may be any thermoplastic resin that is stable at high temperatures. For example, aromatic dicarboxylic acids such as polyethylene terephthalate and polybutylene terephthalate, and aromatic polyester resins composed of diols or oxycarboxylic acids, nylon 6, nylon 6-6, and the like.
Polyamide-based resins such as nylon 6-10, nylon 12, nylon 46, olefin-based resins containing ethylene, propylene, butene, etc. as main components, polystyrene, polystyrene-acrylonitrile, styrene-based resins such as ABS,
Examples thereof include polycarbonate, polyphenylenoxide, polyalkyl acrylate, polyacetal, polysulfone, polyether sulfone, polyetherimide, polyether ketone, and fluororesin. Further, these thermoplastic resins may be used as a mixture of two or more kinds.

Further, in the resin composition of the present invention, known additives generally added to thermoplastic resins, that is, stabilizers such as antioxidants and ultraviolet absorbers, antistatic agents, flame retardants, dyes and pigments are included. Colorants such as, a lubricant, a release agent, etc. can be appropriately added depending on the required performance.

[0036]

EXAMPLES The present invention will be described in more detail below with reference to examples. The reaction components used in Examples 1 and 2 and Comparative Example 1 below are as follows, and the sample production and evaluation methods were performed as follows. <Reaction Component> As the polyarylene sulfide, one prepared as follows (PAS1) was used.

In a polymerization tank equipped with a stirrer, 833 mol of hydrous sodium sulfide (Na ₂ S.5H ₂ O) and LiCl 83
0 mol of N-methylpyrrolidrin (hereinafter referred to as NMP) (510 liters) was added, and dehydration treatment was performed for 1 hour while keeping the temperature at 145 ° C. under reduced pressure. Then, the reaction system was cooled to 45 ° C. and p-dichlorobenzene (hereinafter referred to as DCB) 8
57 mol was added and polymerization was carried out at 260 ° C. for 3 hours. Wash the contents 5 times with hot water, 1 time with NMP at 170 ° C, 3 times with water,
It was dried at 185 ° C. to obtain a linear polyarylene sulfide (PAS1). The logarithmic viscosity of the obtained PAS was 0.
23.

As the alkali metal sulfide, hydrous sodium sulfide (Na ₂ S.9H ₂ O) was used. Sodium hydroxide (NaOH) was used as the alkali metal hydroxide. As the halogenated aromatic compound, p-chlorophenol, p-chlorobenzoic acid and bromobenzene were used. As the inorganic filler, glass fiber (manufactured by Asahi Fiber Glass Co., Ltd., trade name: JAFT591) was used.

<Sample Production and Evaluation Method> (Kneading) Dry blending was carried out using a twin-screw extruder at a compounding ratio described below, and then melt-mixing was carried out at a resin temperature of 300 ° C. of the modified PAS1 to produce pellets. (Logarithmic Viscosity) The logarithmic viscosity IV was measured using an Ubbelobe viscometer from the relational expression of the following equation. IV = [ln (t ₁ / t ₀ )] / C (dl / g) t ₁ : Solution flowing time t ₀ : Solvent flowing time C: Solution concentration (g / dl) The measurement conditions are a temperature of 206 ° C. and a solution concentration. 0.4 g / d
1 and the solvent was α-chloronaphthalene. (Evaluation of physical properties) The pellets obtained above were subjected to various test pieces by a 50t injection molding machine (manufactured by JSW). Under neat conditions, the resin temperature of the modified PAS1 was 300 ° C, the composition containing the filler was 320 ° C, and the mold temperature was 135 ° C.
A test piece was prepared and Izod strength (ASTM D256
Physical properties such as flexural strength (ASTM D790 compliant) and tensile strength (ASTM D638 compliant) were evaluated.

Example 1 PAS prepared as described above
1, 1000 g, NMP 5.0 liters, 22 g (0.
09 mol of hydrous sodium sulfide (Na ₂ S.9H)
₂ O) and sodium hydroxide aqueous solution 8 g / 200 m
l (0.2 mol / 200 ml) to 10 liters of SUS
Put it in a polymerization tank and stir at 250 ° C for 1 hour, then p
-23.1 g (0.18 mol) of chlorophenol was added, and the mixture was stirred at 250 ° C for 0.5 hours, filtered, washed twice with acetone and twice with water, and dried at 120 ° C under reduced pressure. Then, a PAS copolymer was obtained. The logarithmic viscosity of this product is 0.
It was 18.

When the unreacted halogenated aromatic compound in the reaction residual liquid and the washing liquid, p-chlorophenol in this example, was quantitatively analyzed by gas chromatography, p-chlorophenol was found in the reaction residual liquid and the washing liquid. Was not detected, indicating that the aromatic group having a functional group was introduced almost quantitatively. Moreover, when the obtained modified form of PAS1 was subjected to infrared absorption spectrum analysis, as can be seen from FIG. 1 and FIG.
A wide absorption band of cm ^-1 (stretching vibration of OH group) is seen,
It was confirmed that an aromatic group having a hydroxyl group was introduced.

Example 2 Instead of p-chlorophenol in Example 1, p-chlorobenzoic acid was added to 28.
Example 1 was repeated except that 1 g (0.18 mol) was added. The inherent viscosity of this product was 0.18. As a result of analysis in the same manner as in Example 1, unreacted p-chlorobenzoic acid was not detected, and as shown in FIG. 3, strong absorption at 1680 to 1700 cm ⁻¹ which is not found in PAS1 (of C═O group). (Stretching vibration) and a wide and weak absorption band (stretching vibration of OH group) of 3500 to 3600 cm ⁻¹ , and it was confirmed that an aromatic group having a carbonyl group was introduced. [Comparative Example 1] The same procedure as in Example 1 was carried out except that 28.2 g (0.18 mol) of bromobenzene was used instead of p-chlorophenol in Example 1. The inherent viscosity of this product was 0.18.

[Example 3] PAS obtained in Example 1
67 parts by weight of glass fiber was added to 100 parts by weight of the modified product of Example 1, and the mixture was kneaded at 320 ° C. and pelletized as described above. This was used as a test piece by an injection molding machine to evaluate mechanical properties. The results are shown in Table 1. [Example 4] Modified form 1 of PAS1 obtained in Example 2
67 parts by weight of glass fiber was added to 00 parts by weight, and kneaded and pelletized at 320 ° C. as described above. This was used as a test piece by an injection molding machine to evaluate mechanical properties. The results are shown in Table 1. Examples 3 and 4 are PA
It can be seen that the mechanical properties are higher than those using S1 ([Comparative Example 2] shown below) and those introducing an aromatic group having no substituent ([Comparative Example 3] shown below).

Comparative Example 2 67 parts by weight of glass fiber was added to 100 parts by weight of PAS1, and the mixture was kneaded at 320 ° C. and pelletized as shown above. This was used as a test piece by an injection molding machine to evaluate mechanical properties. The result is
It is shown in Table 1. The mechanical properties are lower than those of Examples 3 and 4. [Comparative Example 3] 67 parts by weight of glass fiber was added to 100 parts by weight of the PAS resin obtained in Comparative Example 1, and the mixture was kneaded at 320 ° C as described above and pelletized. This was used as a test piece by an injection molding machine to evaluate mechanical properties. The results are shown in Table 1. The mechanical properties are lower than those of Examples 3 and 4.

[0045]

[Table 1]

[0046]

INDUSTRIAL APPLICABILITY The method for producing a modified polyarylene sulfide of the present invention comprises quantitatively producing a PAS containing an alkali thiolate group and then reacting it with a halogenated aromatic compound having a substituent. The aromatic group having a substituent can be introduced quantitatively and effectively.

The polyarylene sulfide modified product produced by the present invention is a modified product in which an aromatic group having a substituent is mainly introduced at the terminal of the PAS molecule and has affinity with the filler. The addition of the filler greatly increases the strength.

[Brief description of drawings]

FIG. 1 Infrared absorption spectrum of PAS1

FIG. 2 Infrared absorption spectrum of Example 1

FIG. 3 Infrared absorption spectrum of Example 2

Claims (5)

[Claims] 1. A polyarylene sulfide is depolymerized by a reaction with an alkali metal sulfide in an aprotic organic solvent, and the depolymerized product is then represented by the general formula (I) X _n R ¹ Y _m. (I) (In the formula, X is a halogen group, R ¹ is an aromatic group having 6 to 13 carbon atoms, Y is a hydroxyl group, an amino group, a dialkylamino group,
An alkoxyl group having 1 or 2 carbon atoms, a carboxyl group,
It represents any substituent selected from the group consisting of an aldehyde group, a carboxylic acid ester group, a cyano group, a nitro group and an alkyl group having 1 to 30 carbon atoms, and when Y is plural, it may be the same or different. Good. n and m are integers of 1 to 4. ) A halogenated aromatic compound represented by the formula (1) is substituted in an aprotic organic solvent to introduce an aromatic group having a substituent into the polyarylene sulfide, thereby producing a modified polyarylene sulfide. Method. 2. The reaction concentration of the polyarylene sulfide at the time of the depolymerization reaction is 100 to 1000 g with respect to 1 liter of the aprotic organic solvent, and the mixing ratio of the alkali metal sulfide is polyarylene sulfide. 1
It is 0.005 to 0.2 mol with respect to the basic mol, and the mixing ratio of the halogen aromatic compound at the time of the substitution reaction is
The method for producing a polyarylene sulfide modified product according to claim 1, wherein the amount is 2 to 5 times the molar amount of the alkali metal sulfide used in the depolymerization reaction. 3. A repeating unit represented by the structural formula —Ar—S— (Ar represents an arylene group) obtained by the method according to claim 1 or 2, and having a logarithmic viscosity of 0.1 to 0. A modified form of polyarylene sulfide in the range of 0.35 dl / g. 4. A polyarylene sulfide comprising a repeating unit represented by the structural formula —Ar—S— (Ar represents an arylene group), and an aromatic compound having a hydroxyl group as a substituent is added to the end or the chain of the polyarylene sulfide. A modified polyarylene sulfide containing 0.05 to 10 mol% of repeating units therein and having an inherent viscosity in the range of 0.1 to 0.35 dl / g. 5. 100 parts by weight of the modified polyarylene sulfide according to claim 3 and an inorganic filler and / or
Alternatively, a resin composition comprising 1 to 400 parts by weight of an organic filler.